Polymerization and anionic

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. 

Formaldehyde polymerizes by both anionic and cationic mechanisms. Strong acids are needed to initiate cationic polymerization and anionic polymerization is initiated by relatively weak bases (e.g., pyridine). Boron trifluoride (BF3) or other Lewis acids are used to promote polymerization where trioxane is the raw material. 

U.S. 5,167,872 (1992) Pancheri et al. (Procter Gamble) Polymeric and anionic surfactants forming complexes High sudsing improved grease efficacy... 

Table 4 Block copolymers prepared by sequential controlled free radical polymerization and anionic polymerization... 

In addition polymerization, simple molecules or monomers are added to each other to form long-chain molecules (polymers) without by-products, thus yielding a polymeric product in which the molecular formula of the repeating unit is identical to that of the monomer. The molecular weight of the polymer so formed is thus the total of the molecular weights of all of the combined monomer units. There are three commonly used types of addition polymerization free-radical polymerization, cationic polymerization, and anionic polymerization, which are described below. An example of addition polymerization is given by ... 

Most Probable (Flory) Distribution The most probable or Rory distribution is described by the following equations. For polymerization problems. Equation 16.53 is appropriate, since chains of length zero are not considered Equation 16.52 is included for completeness only. It is a single-parameter distribution, with the shape of the distribution dependent only on the value of a. The Rory distribution describes the NCLD for a number of kinetic schemes, including batch condensation polymerization and anionic polymerization in a CSTR ... 

Introduction to Carbanions, Living Polymerization, and Anionic Polymerization 559... 

These conditions are applicable not only to cationic polymerization but also to radical polymerization and anionic polymerization. The polymer produced under these conditions being satisfied will have a narrow distribution of molecular weights, with the molecular weights being controlled. These conditions can also allow the polymer end to contain a functional group, or can also allow block copolymerization. 

As discussed earlier, ionic polymerization ean be eategorized according to the nature of the growing polymer centers, whieh yields the classifications cationic polymerization and anionic polymerization... 

Ionic polymerizations, whether anionic or cationic, should not be judged to be unimportant merely because our treatment of them is limited to two sections in this text. Although there are certain parallels between polymerizations which occur via free-radical and ionic intermediates, there are also numerous differences. An important difference lies in the more specific chemistry of the ionic mechanism. While the free-radical mechanism is readily discussed in general terms, this is much more difficult in the ionic case. This is one of the reasons why only relatively short sections have been allotted to anionic and cationic polymerizations. The body of available information regarding these topics is extensive enough to warrant a far more elaborate treatment, but space limitations and the more specific character of the material are the reasons for the curtailed treatment. 

The principal differences between cationic and anionic polymerizations center around the following points ... 

The point at which two polymeric chains are joined together by a cross-linker such as divinylbenzene, or sites where tertiary hydrogens are located in the stmcture, are other locations for oxidative attack. In both cation- and anion-exchange resins, oxidative attack results in the removal of cross-linking. 

The chemistry of polymerization of the oxetanes is much the same as for THE polymerization. The ring-opening polymerization of oxetanes is primarily accompHshed by cationic polymerization methods (283,313—318), but because of the added ring strain, other polymerization techniques, eg, iasertion polymerization (319), anionic polymerization (320), and free-radical ring-opening polymerization (321), have been successful with certain special oxetanes. 

Group-Transfer Polymerization. Du Pont has patented (29) a technique known as group-transfer polymerization and appHed it primarily to the polymerization of acrylates and methacrylates. It is mechanistically similar to anionic polymerization, giving living chains, except that chain transfer can occur (30). 

Polymerization and depolymerization of sihcate anions and their interactions with other ions and complexing agents are of great interest in sol—gel and catalyst manufacture, detergency, oil and gas production, waste management, and limnology (45—50). The complex silanol condensation process may be represented empirically by... 

There are two problems in the manufacture of PS removal of the heat of polymeriza tion (ca 700 kj /kg (300 Btu/lb)) of styrene polymerized and the simultaneous handling of a partially converted polymer symp with a viscosity of ca 10 mPa(=cP). The latter problem strongly aggravates the former. A wide variety of solutions to these problems have been reported for the four mechanisms described earlier, ie, free radical, anionic, cationic, and Ziegler, several processes can be used. Table 6 summarizes the processes which have been used to implement each mechanism for Hquid-phase systems. Free-radical polymerization of styrenic systems, primarily in solution, is of principal commercial interest. Details of suspension processes, which are declining in importance, are available (208,209), as are descriptions of emulsion processes (210) and summaries of the historical development of styrene polymerization processes (208,211,212). 

Proliferous Polymerization. Eady attempts to polymerize VP anionicaHy resulted in proliferous or "popcorn" polymerization (48). This was found to be a special form of free-radical addition polymerization, and not an example of anionic polymerization, as originally thought. VP contains a relatively acidic proton alpha to the pyrroHdinone carbonyl. In the presence of strong base such as sodium hydroxide, VP forms cross-linkers in situ probably by the following mechanism ... 

This conceptual link extends to surfaces that are not so obviously similar in stmcture to molecular species. For example, the early Ziegler catalysts for polymerization of propylene were a-TiCl. Today, supported Ti complexes are used instead (26,57). These catalysts are selective for stereospecific polymerization, giving high yields of isotactic polypropylene from propylene. The catalytic sites are beheved to be located at the edges of TiCl crystals. The surface stmctures have been inferred to incorporate anion vacancies that is, sites where CL ions are not present and where TL" ions are exposed (66). These cations exist in octahedral surroundings, The polymerization has been explained by a mechanism whereby the growing polymer chain and an adsorbed propylene bonded cis to it on the surface undergo an insertion reaction (67). In this respect, there is no essential difference between the explanation of the surface catalyzed polymerization and that catalyzed in solution. 

Alkyl cyanoacrylate monomers have been copolymerized with a variety of monomers, both by radical and anionic initiation. The radical-initiated copolymerization with acrylic monomers was performed with a sufficient amount of an acid stabilizer present to suppress polymerization by anionic means [19]. This investigation has been covered extensively elsewhere. 

Arsenites of the alkali metals are very soluble in water, those of the alkaline earth metals less so, and those of the heavy metals are virtually insoluble. Many of the salts are obtained as meta-arsenites, e.g. NaAs02, which comprises polymeric chain anions formed by comer linkage of pyramidal ASO3 groups and held together by Na ions ... 

NaAs03 has an infinite polymeric chain anion similar to that in diopside (pp. 349, 529) but with a trimeric repeat unit LiAs03 is similar but with a dimeric repeat unit whereas /6-KASO3 appears to have a cyclic trimeric anion As309 which resembles the cyc/o-trimetaphosphates (p. 530). There is thus a certain structural similarity between arsenates and phosphates, though arsenic acid and the arsenates show less tendency to catenation (p. 526). The tetrahedral As 04) group also resembles PO4) in forming the central unit in several heteropoly acid anions (p. 1014). 

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