Radical polymerization of acrylic and fluoracrylic acids in various solvents

Gal'perina, N.I.; Gugunava, T.A.; Громов, В. Ф.; Khomikovskii, P.M.; Abkin, A.D.

doi:10.1016/0032-3950(75)90169-0

Cited by 13 publications

(8 citation statements)

References 8 publications

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“…The rotating sector technique has been applied to deduce individual rate coefficients of propagation, k p , and of termination, k t , for AA and MAA in aqueous phase at different degrees of ionization, a. [8] A minor lowering in k t , by less than a factor of 2, was observed between a ¼ 0 and 1, [8,9] whereas k p was found to decrease by about a factor of 50 within the same range. It should be noted that the absolute k p values for non-ionized AA, [9] which underline the literature statement on the changes of k p , are about one order of magnitude below the corresponding value Summary: Propagation rate coefficients, k p , for acrylic acid (AA) polymerization at 6 8C in aqueous solution were measured via pulsed laser polymerization (PLP) with the degree of ionization, a, varied over the entire range between 0 and 1.…”

Section: Introductionmentioning

confidence: 99%

“…[8,9,13,14] To provide a better understanding of aqueous-phase AA and MAA free-radical polymerization kinetics, advanced laser-assisted techniques such as PLP-SEC need to be applied. Recently, [10,11] we succeeded in measuring k p with pulsed laser polymerization (PLP) in conjunction with size-exclusion chromatography (SEC) in the aqueous phase for non-ionized AA at various concentrations, up to 40 wt.-%, and temperatures between 2 and 25 8C.…”

Section: Introductionmentioning

confidence: 99%

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PLP‐SEC Study into the Free‐Radical Propagation Rate Coefficients of Partially and Fully Ionized Acrylic Acid in Aqueous Solution

Lacı́k

Beuermann

Buback

2004

Macro Chemistry & Physics

114

165

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Summary: Propagation rate coefficients, kp, for acrylic acid (AA) polymerization at 6 °C in aqueous solution were measured via pulsed laser polymerization (PLP) with the degree of ionization, α, varied over the entire range between 0 and 1. These measurements were carried out in conjunction with aqueous‐phase size‐exclusion chromatography (SEC). Strictly speaking, the reported kp's are “apparent” propagation rate coefficients deduced from the PLP‐SEC data under the assumption that the local monomer concentration at the radical site is identical to overall monomer concentration. At an AA concentration of 0.69 mol · L−1, the apparent kp decreases from 111 000 L · mol−1 · s−1 at α = 0 to 13 000 L · mol−1 · s−1 at α = 1.0. The significant lowering of kp with higher α is attributed to the repulsion between both monomer molecules and macroradicals becoming negatively charged. Addition of up to 10 mol‐% (with respect to AA) sodium hydroxide to the fully ionized aqueous AA solution leads to an enhancement of kp up to 57 000 L · mol−1 · s−1.Dependence of apparent kp values on the degree of ionization of acrylic acid (a) and on pH (b) for aqueous polymerizations of acrylic acid.imageDependence of apparent kp values on the degree of ionization of acrylic acid (a) and on pH (b) for aqueous polymerizations of acrylic acid.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

PLP‐SEC Study into the Free‐Radical Propagation Rate Coefficients of Partially and Fully Ionized Acrylic Acid in Aqueous Solution

Lacı́k

Beuermann

Buback

2004

Macro Chemistry & Physics

114

165

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“…Many studies have been performed on the effect of the solvent in free radical polymerization, Gal'Perina et al 38 studied this for the acrylic acid polymerization (see Table 2). As can be seen from their results, the $k_{\rm p}/\sqrt{k_{\rm te}}$ ratio was found to decrease in going from aqueous media to organic media in agreement with our previous work 21…”

Section: Resultsmentioning

confidence: 99%

Telomerization of acrylic acid with mercaptans: Part 2. Kinetics of the synthesis of star‐shaped macromolecules of acrylic acid

Loubat¹,

Boutevin²

2001

Polymer International

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The telomerization of acrylic acid with a polyfunctional transfer agent initiated by 2,2'azobisisobutyronitrile, was ®rst investigated in an organic medium (THF) at 65°C. Transfer constants (C T ) for three mercaptans, ethylene glycol bisthioglycolate, trimethylolpropane tris(2-mercaptoacetate) and pentaerythritol tetrakis(3-mercaptopropionate) of about 6.1, 6.3 and 7.3, respectively, were determined. From these results, it followed that a well-de®ned star poly(acrylic acid) could not be synthesized via telomerization of acrylic acid in THF. Nevertheless, the same study was performed with the tetrafunctional transfer agent in water/THF mixtures. This work emphasized that the nature of the solvent plays an important role in determining the transfer constant. Thus, the value of C T for the tetrafunctional transfer agent decreased from 7.3 in THF to 1, the`ideal' case for telomerization (C T % 1), for the mixture of solvents water/THF (80%, 20%, v/v). With this route, it seems that acrylic acid star-shaped macromolecules could be synthesized via telomerization.

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“…This agrees well with the cryoscopically assessed amount of dimerized AA in DMSO solutions. 24 The decrease of a on addition of a certain amount of water into solution means that part For 25% solution of AA in mixture of 75% DMS0-25% H20 the equilibrium between complexes IV and III can be defined using constant K 3 :::::0.4. However, this system may contain complexes of other types, therefore the given equilibrium is not unique and our attempts at describing it are speculative.…”

Section: Discussion and Resultsmentioning

confidence: 99%

“…However, it is quite possible that the activity of the acid radical in DMSO may be decreased by some other causes, e.g., a de-crease in spin density of the unpaired electron due to the formation of n-complex with the solvent, as proposed in this work. 24 Thus, a significant decrease in the polymerization activity of unsaturated acids in strong electron-donor solvents (e.g., DMSO) mainly depends on two simultaneously occurring effects: the formation of H-complexes between acid molecules and the solvent, and ncomplexes between acid radicals and solvent molecules. Introduction of water into reaction mixture increases the activity of acid molecules in H -complexes and decreases the probability for the formation of n-complexes which promote the rate of polymerization.…”

Section: Discussion and Resultsmentioning

confidence: 99%

Peculiarities of Radical Homo- and Copolymerization of Acrylic, Methacrylic and Itaconic Acids in Complexing Solutions

Bajoras

Makuška

1986

Polym J

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Using the method of IR spectroscopy a study was made of complexation in the systems of acrylic, methacrylic and itaconic acids-dimethyl sulphoxide-water. Quantitative assessment was done on the number of acid molecules entering the H-bonds with DMSO using different amounts of water in the systems. Calculations were performed on the parameters of electron structure of itaconic acid, establishing higher acidity of the oc-carboxylic group. Reactivity of methacrylic acid in different complexes was assessed according to the redistribution of electron density in monomer molecules and in acid radicals during complexation. Copolymerization of acrylic, methacrylic and itaconic acids with acrylo-and methacrylonitriles in solutions of dimethyl sulphoxide-water was investigated as well. Peculiarities and differences of copolymerization of itaconic acid and monocarboxylic acids in binary solvents are thoroughly discussed here.

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Radical polymerization of acrylic and fluoracrylic acids in various solvents

Cited by 13 publications

References 8 publications

PLP‐SEC Study into the Free‐Radical Propagation Rate Coefficients of Partially and Fully Ionized Acrylic Acid in Aqueous Solution

PLP‐SEC Study into the Free‐Radical Propagation Rate Coefficients of Partially and Fully Ionized Acrylic Acid in Aqueous Solution

Telomerization of acrylic acid with mercaptans: Part 2. Kinetics of the synthesis of star‐shaped macromolecules of acrylic acid

Peculiarities of Radical Homo- and Copolymerization of Acrylic, Methacrylic and Itaconic Acids in Complexing Solutions

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