Quantitative determination of surface carboxyl groups in vinyl acid modified styrene/butadiene copolymer latexes

Greene, B.W

doi:10.1016/0021-9797(73)90390-1

Cited by 67 publications

(25 citation statements)

References 18 publications

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“…The distribution of acid groups was completely differ- Figure 6 Amount of surface acid groups as a function of the total surface area of the swollen latex particles per unit volume of the aqueous phase at X ov ϭ 0 in the seeded-batch-emulsion polymerization of styrene and acrylic acid at pH 2.5 for all the initiator concentrations and temperature listed in Table III. ent at pH 2.5 and 7 and was qualitatively in good agreement with the work of several authors. 25,33,34 All these authors reported that a high pH retains the dissociated carboxylic groups in the water phase, whereas a lower pH increases the AA concentration in the organic phase. This can explain the difference in the amount of buried acid groups (assuming that the amount of buried groups is related to the partition coefficient) at different pH values.…”

Section: Discussionmentioning

confidence: 97%

Seeded emulsion polymerization of styrene: influence of acrylic acid on the particle growth process

Slawinski

Schellekens

Meuldijk

et al. 2000

J. Appl. Polym. Sci.

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ABSTRACT:The seeded batch emulsion copolymerization of styrene and acrylic acid was studied. The polymerization rate was investigated with pH as the main parameter. Some attempts were made to evaluate the average number of growing chains per particle during Stage II of the emulsion polymerization process. The final latex products were characterized by means of conductometric aqueous titration and potentiometric titration in an organic solvent mixture. The distribution of the acid groups over the aqueous phase, the particle surface, and the interior of the particles together with the kinetic results provided insight into important features governing the incorporation of acrylic acid. The results indicate that pH is the dominating parameter for the incorporation process. An optimal incorporation on the surface of the particles is observed for a low value of pH. In that case, all the acid groups are protonated.

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Section: Discussionmentioning

confidence: 97%

Seeded emulsion polymerization of styrene: influence of acrylic acid on the particle growth process

Slawinski

Schellekens

Meuldijk

et al. 2000

J. Appl. Polym. Sci.

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“…a combination of turbidimetric titration and neutron activation analysis [1] or, more common used, conductometric and potentiometric titration combined with ion exchange and dialysis [2], rather easily give the distribution of the acid in the water and the polymer phase. The separation of the carboxylic groups in the polymer phase into surface and "buried" groups, on the contrary, seems to be more difficult.…”

Section: Introductionmentioning

confidence: 99%

Chemical heterogeneity in emulsion copolymers of carboxylic monomers

Zosel

Heckmann

Ley

et al. 1987

Colloid & Polymer Sci

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Copolymer latices of butylacrylate (BA) with acrylic and methacrylic acid (AA and MAA) were prepared by batch type emulsion polymerization, and, for comparison, copolymers with identical monomer composition were prepared by batch type solution polymerization.The distribution of the carboxylic monomers in the latex particles and the serum was studied by density gradient and sedimentation experiments with the analytical ultracentrifuge. Dynamic mechanical measurements of films of these copolymers were used to determine the storage and loss moduli as a function of temperature. From these measurements the position and extension of the glass transition range on the temperature scale is obtained. For heterogeneous emulsion copolymers with two glass transition temperatures the distribution of the carboxylic monomer units in the different copolymer phases can be determined. Electron microscopy of ultra thin cross-sections of stained films gave further insight into the film morphology.The combination of the results obtained with the different methods gives rise to the following dues: In the BA/AA latices about 40 % (by weight) of the total AA used in the recipe are found in the serum as a water soluble polymer, about 50 % are found to increase the glass transition temperature Tg of the bulk of the BA copolymer and, therefore, are thought to be incorporated into the interior of the latex particles, and the remaining 10 % are, conclusively, located on the particle surface.In the BA/MAA latices no water soluble copolymer could be detected in the serum, about 90 % of the MAA used is found in the bulk of the copolymer, and about 10 % form a second hard phase on the surface of the latex particles.Dynamic mechanical measurements on the copolymer latex films show at least two phases with different glass transition temperatures: the bulk of the copolymer with a relatively low content of (M)AA units and a glass transition range at low temperatures, and a second (M)AA rich phase with a high Tg.The latter phase forms a honeycomb-llke structure surrounding the packed latex particles. That results in a three-dimensional network of polymer with a high Tg extending throughout the latex film. In spite of the fact that this phase is built from a small fraction of the total copolymer only, it has a very pronounced influence on the performance behaviour of latex films.

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“…[9] The total amount of carboxyl could be achieved by neutronactivation method while the amount on the surface of the particle could not be determined. [6] Both potentiometric titration and surfactant titration methods have a problem that it is difficult to find the endpoint of the titration. [7,9] The conductometric titration method has become the most popular method to determine the amount of carboxyl groups on the particle surface owing to its advantages such as simple operation, clear endpoint of titration and high sensitivity.…”

Section: Introductionmentioning

confidence: 99%

“…It is very important to quantitate the amount of surface carboxyl groups, because it has great impact on some key properties of the particles such as colloid stability, viscosity and bio-coupling efficiency. [1 -5] The traditional quantitative methods include neutron-activation [6] , potentiometric titration [7] , surfactant titration [8] , and conductometric titration methods. [9] The total amount of carboxyl could be achieved by neutronactivation method while the amount on the surface of the particle could not be determined.…”

Section: Introductionmentioning

confidence: 99%

Phenanthroline method for quantitative determination of surface carboxyl groups on carboxylated polystyrene particles with high sensitivity

Dai¹,

Liu²,

Li³

et al. 2009

Surface & Interface Analysis

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This study developed a phenanthroline method for quantitative determination of surface carboxyl groups on carboxylated polystyrene (PS-COOH) particles based on the coordination between the carboxyl groups and Fe 2+ . The ratio of the carboxyl groups, which is determined by conductometric titration method, to Fe 2+ coordinated with the particles, which is determined by phenanthroline method, is 4.7, i.e. n COOH = 4.7 × n Fe 2+ . The Lambert-Beer law is obeyed in the range of 0-60 × 10 −9 mol/ml for the amount of surface carboxyl on the particles. The detection limit of the method is 2 nmol COOH/ml. The average standard deviation of the experiments is 4.4%. The relative deviation of the data obtained with this method is lower than 7% compared with that obtained with the conductometric titration method. The weight of the sample necessary for phenanthroline method is only about 0.1% of that necessary for conductometric titration method. It has been demonstrated that the phenanthroline method is suitable for quantitative determination of low amount of surface carboxyl groups on PS-COOH particles due to its high sensitivity.

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Quantitative determination of surface carboxyl groups in vinyl acid modified styrene/butadiene copolymer latexes

Cited by 67 publications

References 18 publications

Seeded emulsion polymerization of styrene: influence of acrylic acid on the particle growth process

Seeded emulsion polymerization of styrene: influence of acrylic acid on the particle growth process

Chemical heterogeneity in emulsion copolymers of carboxylic monomers

Phenanthroline method for quantitative determination of surface carboxyl groups on carboxylated polystyrene particles with high sensitivity

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