Polymerization of hydrolysis

Concentration dependence, polymerization of hydrolysis products with uranyl nitrate.231, 237-39... 

PHOST is often prepared by polymerization of 4-acetoxystyrene followed by base-catalyzed hydrolysis (Fig. 29). The acetoxystyrene monomer s stabihty and polymerization kinetics allow production of PHOST of higher quaUty than is easily obtained by direct radical polymerization of HOST. The PHOST homopolymer product is then partially or fully derivatized with an acid-cleavable functionaUty to produce the final resist component. 

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

PVA used for the manufacture of fiber generally has a degree of polymerization of about 1700 and, for general-purpose fiber, a high degree of hydrolysis of vinyl acetate units of at least 99 mol %. 

On the other hand, water-soluble PVA fibers are available on the market. They are stable in cool water but shrink in warm water and dissolve at 40 to 90°C. The dissolution temperature is controlled by the degree of polymerization and hydrolysis of PVA, he at-treatment conditions after spinning, etc. 

A freshly made solution behaves as a strong monobasic acid. Neutralized solutions slowly become acidic because of hydrolysis to monofluorophosphoric acid and hydrofluoric acid. The anhydrous acid undergoes slow decomposition on distillation at atmospheric pressure, reacts with alcohols to give monofluorophosphoric acid esters, and is an alkylation (qv) and a polymerization catalyst. 

The mechanism of oxidative dyeing involves a complex system of consecutive, competing, and autocatalytic reactions in which the final color depends on the efficiency with which the various couplers compete with one another for the available diimine. In addition, hydrolysis, oxidation, or polymerization of diimine may take place. Therefore, the color of a mixture caimot readily be predicted and involves trial and error. Though oxidation dyes produce fast colors, some off-shade fading does occur, particularly the development of a red tinge by the slow transformation of the blue indamine dye to a red phenazine dye. 

The polymerization of A/-(2-tetrahydropyranyl)aziridine with subsequent hydrolysis of the resulting polymers has been described as an alternative route for the synthesis of linear polyethyleneimine (359). Linear polyethyleneimine, in contrast to branched polyethyleneimines, is only sparingly soluble in water at room temperature. 

Hydrolysis and Polycondensation. One of the key properties of polyamides relates to the chemical equihbrium set up when the material is polymerized. The polymerization of nylon is a reversible process and the material can either hydrolyze or polymerize further, depending on the conditions. 

Hydrolysis and Polycondensation. As shown in Figure 1, at gel time (step C), events related to the growth of polymeric chains and interaction between coUoids slow down considerably and the stmcture of the material is frozen. Post-gelation treatments, ie, steps D—G (aging, drying, stabilization, and densification), alter the stmcture of the original gel but the resultant stmctures aU depend on the initial stmcture. Relative rates, of hydrolysis, (eq. 2), and condensation, (eq. 3), determine the stmcture of the gel. Many factors influence the kinetics of hydrolysis and... 

In 1967, a polyglycoUc acid [26124-68-5] suture (17) made by the ring-opening polymerization of glycoUde (2), the cycUc dimer of glycoUc acid, was invented. PolyglycoUc acid sutures are degraded by hydrolysis more rapidly than polylactic acid. 

Besides direct hydrolysis, heterometaHic oxoalkoxides may be produced by ester elimination from a mixture of a metal alkoxide and the acetate of another metal. In addition to their use in the preparation of ceramic materials, bimetallic oxoalkoxides having the general formula (RO) MOM OM(OR) where M is Ti or Al, is a bivalent metal (such as Mn, Co, Ni, and Zn), is 3 or 4, and R is Pr or Bu, are being evaluated as catalysts for polymerization of heterocychc monomers, such as lactones, oxiranes, and epoxides. An excellent review of metal oxoalkoxides has been pubUshed (571). 

Buffers are frequently added to emulsion recipes and serve two main purposes. The rate of hydrolysis of vinyl acetate and some comonomers is pH-sensitive. Hydrolysis of monomer produces acetic acid, which can affect the initiator, and acetaldehyde which as a chain-transfer agent may lower the molecular weight of the polymer undesirably. The rates of decomposition of some initiators are affected by pH and the buffer is added to stabilize those rates, since decomposition of the initiator frequently changes the pH in an unbuffered system. Vinyl acetate emulsion polymerization recipes are usually buffered to pH 4—5, eg, with phosphate or acetate, but buffering at neutral pH with bicarbonate also gives excellent results. The pH of most commercially available emulsions is 4—6. 

The kinetics of vinyl acetate emulsion polymeriza tion in the presence of alkyl phenyl ethoxylate surfactants of various chain lengths indicate that part of the emulsion polymerization occurs in the aqueous phase and part in the particles (115). A study of the emulsion polymerization of vinyl acetate in the presence of sodium lauryl sulfate reveals that a water-soluble poly(vinyl acetate)—sodium dodecyl sulfate polyelectrolyte complex forms, and that latex stabihty, polymer hydrolysis, and molecular weight are controlled by this phenomenon (116). 

Syn- and anti-orientations are possible and there is evidence that the anti-orientation does not favor orbital overlap such an orientation is favored with larger branched-chain substituents. A C-nmr study found that the TT-electron density on the vinyl P-carbon is lower as the reactivity of the monomer increases (20). Methyl vinyl ether exists almost entirely ia the syn-stmcture, a favorable orbital overlap situation, and MVE for this reason is less reactive to both polymerization and hydrolysis (21). 

Zirconium [7440-67-7] is classified ia subgroup IVB of the periodic table with its sister metallic elements titanium and hafnium. Zirconium forms a very stable oxide. The principal valence state of zirconium is +4, its only stable valence in aqueous solutions. The naturally occurring isotopes are given in Table 1. Zirconium compounds commonly exhibit coordinations of 6, 7, and 8. The aqueous chemistry of zirconium is characterized by the high degree of hydrolysis, the formation of polymeric species, and the multitude of complex ions that can be formed. 

Although equation 9 is written as a total oxidation of sugar, this outcome is never realized. There are many iatermediate oxidation products possible. Also, the actual form of chromium produced is not as simple as that shown because of hydrolysis, polymerization, and anion penetration. Other reduciag agents are chosen to enhance the performance of the product. 

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