Dispersant, polymers

The phenomena we discuss, phase separation and osmotic pressure, are developed with particular attention to their applications in polymer characterization. Phase separation can be used to fractionate poly disperse polymer specimens into samples in which the molecular weight distribution is more narrow. Osmostic pressure experiments can be used to provide absolute values for the number average molecular weight of a polymer. Alternative methods for both fractionation and molecular weight determination exist, but the methods discussed in this chapter occupy a place of prominence among the alternatives, both historically and in contemporary practice. 

Table 9,4 Data for the Analysis of the Gel Permeation Chromatogram of a Poly disperse Polymer Used in Example 9.7...

Salts are made by reaction of acryhc acid with an appropriate base in aqueous medium. They can serve as monomers and comonomers in water-soluble or water-dispersible polymers for floor pohshes and flocculants. 

Emulsion Polymerization. Emulsion polymerization is the most important industrial method for the preparation of acryhc polymers. The principal markets for aqueous dispersion polymers made by emulsion polymerization of acryhc esters are the paint, paper, adhesives, textile, floor pohsh, and leather industries, where they are used principally as coatings or binders. Copolymers of either ethyl acrylate or butyl acrylate with methyl methacrylate are most common. 

Potential health and safety problems of acryflc polymers occur in their manufacture (159). During manufacture, considerable care is exercised to reduce the potential for violent polymerizations and to reduce exposure to flammable and potentially toxic monomers and solvents. Recent environmental legislation governing air quality has resulted in completely closed ketde processes for most acryflc polymerizations. Acryflc solution polymers are treated as flammable mixtures. Dispersion polymers are nonflammable. 

Since polymer swelling is poor and the aqueous solubiUty of acrylonitrile is relatively high, the tendency for radical capture is limited. Consequentiy, the rate of particle nucleation is high throughout the course of the polymerization, and particle growth occurs predominantiy by a process of agglomeration of primary particles. Unlike emulsion particles of a readily swollen polymer, such as polystyrene, the acrylonitrile aqueous dispersion polymer particles are massive agglomerates of primary particles which are approximately 100 nm in diameter. 

Nonaqueous Dispersion Polymerization. Nonaqueous dispersion polymers are prepared by polymerizing a methacryhc monomer dissolved in an organic solvent to form an insoluble polymer in the presence of an amphipathic graft or block copolymer. This graft or block copolymer, commonly called a stabilizer, lends coUoidal stabiUty to the insoluble polymer. Particle sizes in the range of 0.1—1.0 pm were typical in earlier studies (70), however particles up to 15 pm have been reported (71). 

Table 11. Examples of Methacrylic Nonaqueous Dispersion Polymers...

FIFE is made commercially by two major processes, one leading to the so called granular polymer and the second leading to a dispersion of polymer of much finer particle size and lower molecular weight. One method of producing the latter involved the use of a 0.1 % aqueous disuccinic acid peroxide solution. The reactions were carried out at temperatures up to 90°C. It is understood that the Du Pont dispersion polymers, at least, are produced by methods based on the patent containing the above example. 

Dispersion polymer obtained by coagulation of a dispersion. It consists of agglomerates with an average diameter of 450 pm made up of primary particles 0.1 pm in diameter. 

Dispersion polymer, which leads to products with improved tensile strength and flex life, is not easily fabricated by the above techniques. It has, however, been found possible to produce preforms by mixing with 15-25% of a lubricant, extruding and then removing the lubricant and sintering. Because of the need to remove the lubricant it is possible to produce only thin-section extrudates by this method. 

In a typical process a preform billet is produced by compacting a mixture of 83 parts PTFE dispersion polymer and 17 parts of petroleum ether (100-120°C fraction). This is then extmded using a vertical ram extruder. The extrudate is subsequently heated in an oven at about 105°C to remove the lubricant, this being followed by sintering at about 380°C. By this process it is possible to produce thin-walled tube with excellent flexing fatigue resistance and to coat wire with very thin coatings or polymer. 

PTFE is used for lining chutes and coating other metal objects where low coefficients of friction or non-adhesive characteristics are required. Because of its excellent flexing resistance, inner linings made from dispersion polymer are used in flexible steam hose. A variety of mouldings are used in aircraft and missiles and also in other applications where use at elevated temperatures is required. 

Data of Figs 8-10 give a simple pattern of yield stress being independent of the viscosity of monodisperse polymers, indicating that yield stress is determined only by the structure of a filler. However, it turned out that if we go over from mono- to poly-disperse polymers of one row, yield stress estimated by a flow curve, changes by tens of times [7]. This result is quite unexpected and can be explained only presumably by some qualitative considerations. Since in case of both mono- and polydisperse polymers yield stress is independent of viscosity, probably, the decisive role is played by more fine effects. Here, possibly, the same qualitative differences of relaxation properties of mono- and polydisperse polymers, which are known as regards their viscosity properties [1]. 

There are two types of multicomponent mixtures which occur In polymer phase equilibrium calculations solutions with multiple solvents or pol ers and solutions containing poly-disperse polymers. We will address these situations In turn. 

As emulsion polymerisation proceeds, like the suspension technique but unlike either the bulk or the solution techniques, there is almost no increase in viscosity. The resulting dispersed polymer is not a true emulsion any more, but instead has become a latex. The particles of the latex do not interact with the water hence viscosity is not found to change significantly up to about 60% solids content. 

Resin cements or polymer cements have been reviewed by Chandra, Justnes, and Ohama [343]. Polymer cements are materials made by replacing the cement at least partly with polymers. Cements can be modified by latex, dispersions, polymer powders, water-soluble polymers, liquid resins, and monomers. 

Special polymerization techniques are described [298] in which the polymerization is performed in an aqueous solution together with a polyvalent anionic salt in the presence of a water-soluble cationic polymer acting as a dispersant polymer. Furthermore, a seed polymer that is water soluble and a cationic polymer that is insoluble in the aqueous solution of the polyvalent anionic salt are present. 

In most enzymatic syntheses of polyesters, the polymerization was carried out in organic solvents or bulk. Using supercritical fluoroform as solvent, the polymerization of bis(2,2,2-trichloroethyl) adipate and 1,4-butanediol was demonstrated [60]. The molecular weight increased as a function of the pressure. By changing the pressure, the low-dispersity polymer fractions were separated. 

The rheological properties of insitu polymerized nanocomposites with end-tethered polymer chains were first described by Krisnamoorti and Giannelis [33]. The flow behavior of PCL- and Nylon 6-based nanocomposites differed extremely from that of the corresponding neat matrices, whereas the thermorheological properties of the nanocomposites were entirely determined by the behavior of the matrices [33]. The slope of G (co) and G"(co) versus flxco is much smaller than 2 and 1, respectively. Values of 2 and 1 are expected for linear mono-dispersed polymer melts, and the large deviation, especially in the presence of a very small amount of layered silicate loading, may be due to the formation of a network structure in the molten... 

PVAc, PVA and PVB are used in a vast number of different applications [19]. The most common use of PVAc-based dispersions and dispersible polymer powders is in the construction and adhesives industry. The polymeric binders are used as... 

Fundamental studies of the effects of sodium polyacrylate have shown it to be an electrosteric dispersant, for which the steric component of interparticle repulsion is the dominant one at the typical dose rates used commercially. In such dispersions the main contributor to solution ionic strength is unadsorbed polyacrylate. As well as representing a waste of valuable dispersant polymer, this unadsorbed material also reduces the effectiveness of the adsorbed material as a steric dispersant by compressing the conformation of the adsorbed layer. 

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