Carboxylic emulsion polymers

Techniques for Measuring Particle Swelling of Carboxylic Emulsion Polymers... 

Central to any investigation of particle swelling is the use of a reliable method of measuring the size of the particles undergoing expansion. A sedimentation method was described previously (5) which can be used to explore the expansion characteristics of carboxylic emulsion polymers. In the present report, we present a comparison of sedimentation results with those obtained with two... 

This simplification was used by Ottewill and Walker (7) in their study of the adsorption of a nonionic surfactant onto polystyrene latex in aqueous sodium chloride. In the case of carboxylated emulsion polymers, evidence from conductometric titrations suggests that the carboxyl groups are generally concentrated near the particle surface. The resultant model of an expanded particle is that of a hydrated acid-rich shell surrounding a compact polymer core. The hydrated shell may be viewed as a dilute polymer solution where the density is close to that of water, i.e., Pe= P0. With this assumption, Equation 1 reduces to the form ... 

Photon correlation spectroscopy, carried out under very dilute conditions, has unambiguously demonstrated the expansion of carboxylic emulsion polymers at high pH, but it may not always be useful in predicting properties of practical interest. Of special concern is the apparent decrease in the intrinsic ionization constant of surface carboxyls at very low concentration. Since most uses of emulsion polymer occur at high concentrations, the measurement of particle-particle interactions is of great practical importance (21J. It has been found that the sedimentation and viscometric techniques closely reflect viscosity changes in latexes at much higher solids. Extension of the PCS approach to more concentrated systems is underway but not without problems (22). 

The results are generally consistent with a broader treatment of the techniques for measuring particle swelling of carboxylic emulsion polymer latexes reported elsewhere in this Monograph (9). The broader study, which was carried out independently but concurrently, has shown that the magnitude and pH of maximum expansion depends on dilution and ionic strength. Studies of the concentration dependence in the dilute regime and more concentrated systems are underway. 

Figure 13. The effect of nonuniform polymerization on the expansion behavior of carboxylic emulsion polymers. The power feed example was prepared using the monomer feed profile illustrated in Figure 12 ((%) uniform feed power feed).

Bassett, B.R., and Hoy, K.L., The Expansion Characteristics of Carboxylic Emulsion Polymers. I. Particle Expansion Bet-ermined by Sedimentation in Polymer Colloids II. 

Bassett, D.R. and Hoy, K.L (1980) The expansion characteristics of carboxylic emulsion polymers 1. Particle expansion determined by sedimentation. In R.M. Fitch (ed.). Polymer Colloids 11. Plenum Press, New York, p. 1. 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

Water-Based Inks. Approximately 50% of all flexographic inks use water as their primary solvent and diluent. They contain vehicles based on either acrylic emulsions, or hydrosols or an alkali-soluble rosin ester having a high acid number such as partially esterified fiimurated rosin and shellac. Carboxylated acrylic polymers, usually containing some styrene, have largely replaced natural resins because they provide better abrasion and water resistance. Ammonia or other volatile amines are used to solubilize these carboxylated resins and form resin salts. The volatile alkali evaporates from the ink film, rendering the printed matter water resistant. 

While most studies of particle swelling have dealt with emulsion polymers containing high acid levels, we have restricted our attention to latexes containing relatively low incorporated acid (ca.2-3%) to avoid substantial solubilization of the particles. Questions under current consideration are related to the location of incorporated carboxyl groups within the latex particles, the morphology of expanded particles, and the detailed mechanism of expansion. Information of this type is valuable not only from a fundamental standpoint but is essential in the investigation of very practical problems such as the viscosity stability of latex formulations. 

It is possible to convert a carboxyl-containing emulsion polymer which is not F/T stable to one which is stable by the addition of surfactant. 

The thickening mechanisms of linear carboxyl-containing emulsion polymers have been studied in considerable detail. The polymer molecules of AST emulsions are initially in a coiled configuration within individual latex particles of submicrometer size, and the viscosity of the diluted latex emulsion is similar to that of water prior to neutralization. On the addition of base, the carboxyl groups are ionized, and hydrophilic polymer is formed within the particles. Depending on various factors, which will be elaborated on later in this chapter under the section entitled Factors Affecting the Swelling Dissolution Behavior of Conventional ASTs , the particles may only swell or dissolve completely, or the surface polymer may dissolve and leave swollen cores. 

Vinyl polymerization using metallocomplexes commonly proceeds by a radical pathway and rarely involves an ionic mechanism. For instance, metal chelates in combination with promoters (usually halogenated hydrocarbons) are known as initiators of homo- and copolymerization of vinylacetate. Similar polymer-bound systems are also known [3]. The polymerization mechanism is not well understood, but it is believed to be not exclusively radical or cationic (as polymerization proceeds in water). The macrochelate of Cu with a polymeric ether of acetoacetic acid effectively catalyzes acrylonitrile polymerization. Meanwhile, this monomer is used as an indicator for the radical mechanism of polymerization. Mixed-ligand manganese complexes bound to carboxylated (co)polymers have been used for emulsion polymerization of a series of vinyl monomers. Macromolecular complexes of Cu(N03)2 and Fe(N03)3 with diaminocellulose in combination with CCI4 are active in polymerization of MMA, etc. 

The main source of hydroxyl groups in the adhesive is usually the PVA, but hydroxyl and other functional groups such as carboxyl groups and amines on the emulsion polymer chain can also react with the isocyanate, provided that they are physically available. In addition, the hydroxyl groups in the wood may take part in... 

A conventional emulsion polymer based on vinyl acetate has been modified by carboxylation (92). The carboxylated ethylene-vinyl acetate adhesive increases the adhesion to metal and polymer surfaces and the resistance to oil, grease, and water. The films are also acid, alkali, and UV resistant. Furthermore, the polymers are cross-linkable through the carboxylic groups. These adhesives can react with aminoplasts, phenolics, and epoxy resins for increased water and creep resistance. 

As noted in Section 6.5.2, the hydrolysis resistance of latex films from emulsion polymers prepared from the vinyl acetate (VA) monomer is marginal for ontdoor use. In Europe and recently in the United States, vinyl versatate (II) (Ri = —CH2CH2CH2CH2CH2CH2CH3 and R2 = R3 = —CH3) has been introduced for use along with vinyl acetate for improved outdoor performance of latex coatings. Vinyl versatate is the vinyl ester of versatic acid, a 10-carbon carboxylic acid of the highly branched structure sometimes called neo ... 

In a procedure described in Ref. [474], sodium orthosilicate was added to the reaction medium to raise the polymer yield to 95%. The initiator was ammonium persulfate with a special emulsifier that is believed to be perfluorinated carboxylated emulsifier from 3M Corp [458]. Other initiators used are redox systems such as potassium persulfate-sodium metabisulfite or ammonium persulfate-sodium sulfite [475]. Different initiators are also of some interest because they affect the particle diameter of the emulsion. Polymer particles formed with a diameter between 0.36 and 18 pm, depending on the initiator system and the polymerization procedures, are reported [458]. In a patent of Dynamit Nobel [476], iodine-containing compounds such as ammonium iodide or isopropyl iodide are used. These compounds give rise to polymers of improved thermal stability and resistance to color deterioration. The procedure did not require the use of an emulsifier. After 150 min the internal pressure of the autoclave dropped from 2 x 10 to 3 X 10 Pa and a conversion to polymer of 86% was found. More recently Uschold [477] describes also an emulsion polymerization of PVF in high yields and having excellent color. 

Thickening agents based on aqueous emulsion polymer chemistry were first developed [9] in the late 1950s and represent another important class of thickening agents. In this physical form, a monomer composition is chosen that provides a balance between the hydrophilic nature of a carboxylic acid monomer (such as acrylic, or more usually methacrylic acid) and a hydrophobic alkyl (meth)acrylate monomer (such as methyl methacrylate, ethyl acrylate, butyl acrylate or mixtures of such species). Whilst the carboxylic acid is in the free-acid form the overall composition is balanced to sufficiently hydrophobic to be water immiscible. This allows the monomer mixture to be reacted using a conventional oil-in-water emulsion polymerisation technique. 

Maleate esters such as dimethyl maleate, diethyl maleate and dibutyl maleate are extensively used in the production of latex emulsion polymers, thermoplastic and thermosetting plastics. Dimethyl maleate has found use in applications where improvement in hardness and toughness of polymer films are desired. This includes, in particular, the improvement of anti-blocking properties of copolymers of vinyl acetate with dimethyl maleate. It is also used as an internal modifier to increase the glass transition temperature of styrene or vinyl chloride polymer. The intermediate in esterification of maleic acid with methanol, monomethyl maleate provides plastsizing effect, as well as promotion of improved polymer adhesion due to the carboxylic group. It can be copolymerized with a variety of vinyl and acrylic monomers to provide coatings with improved stiffness and adhesion and reduced tackiness or tendency to block. Monoesters of maleates are used to provide carboxylic acid functionality in emulsions and water-soluble polymers. 

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