Other Polymerizations

The importance of coordination polymerization of alkenes and dienes is evident when it is noted that more than 40 billion pounds of polymers were produced by this route in the United States in 2001. This corresponds to 35 10% of the total industrial production of polymers from monomers containing carbon-carbon double bonds. 

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In estimating the enthalpy of polymerization, the physical state of both starting monomer and polymer must be specified. Changes in state are accompanied by ethalpy changes. Therefore, they also affect the level of the polymerization enthalpy. The AfT forN ylylene previously mentioned is apphcable to the monomer as an ideal gas. To make comparisons with other polymerization processes, most of which start with condensed monomer, a heat of vaporization for N ylylene is needed. It is assumed herein that it is the same as that for N ylene, 42.4 kJ /mol (10.1 kcal/mol). Thus the AfT of the hquid monomer -xylylene is 192.3 kJ/mol (46.0 kcal /mol). 

SAN resins themselves appear to pose few health problems in that they have been approved by the EDA for beverage botde use (149). The main concern is that of toxic residuals, eg, acrylonitrile, styrene, or other polymerization components such as emulsifiers, stabilizers, or solvents. Each component must be treated individually for toxic effects and safe exposure level. 

Phosphate Esters. The principal advantage of phosphate esters is the improved fire retardancy relative to phthalates. The fire performance of PVC itself, relative to other polymeric materials, is very good due to its high halogen content, but the addition of plasticizers reduces this. Consequendy there is a need, in certain demanding appHcations, to improve the fire-retardant behavior of dexible PVC. 

Many other polymerization processes have been patented, but only some of them appear to be developed or under development ia 1996. One large-scale process uses an acid montmorrillonite clay and acetic anhydride (209) another process uses strong perfiuorosulfonic acid reski catalysts (170,210). The polymerization product ia these processes is a poly(tetramethylene ether) with acetate end groups, which have to be removed by alkaline hydrolysis (211) or hydrogenolysis (212). If necessary, the product is then neutralized, eg, with phosphoric acid (213), and the salts removed by filtration. Instead of montmorrillonite clay, other acidic catalysts can be used, such as EuUer s earth or zeoHtes (214—216). 

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. 

Dimethyl sulfoxide can also be used as a reaction solvent for other polymerizations. Ethylene oxide is rapidly and completely polymerized in DMSO (85). Diisocyanates and polyols or polyamines dissolve and react in DMSO to form solutions of polyurethanes (86) (see Solvents, industrial). 

Stannic chloride is also used widely as a catalyst in Eriedel-Crafts acylation, alkylation and cycHzation reactions, esterifications, halogenations, and curing and other polymerization reactions. Minor uses are as a stabilizer for colors in soap (19), as a mordant in the dyeing of silks, in the manufacture of blueprint and other sensitized paper, and as an antistatic agent for synthetic fibers (see Dyes, application and evaluation Antistatic agents). 

Addition of one mole of P,P -dipheny1methy1enediphosphinic acid to tetraisopropyl titanate gives a chelated product, the solutions of which can be used as a primer coat for metals to enhance the adhesion of topcoats, eg, alkyds, polyalkyl acylates, and other polymeric surface coating products, and improve the corrosion resistance of the metal to salt water (102). 

Hindered Amines. Hiadered amines are extremely effective ia protecting polyolefins and other polymeric materials against photodegradation. They usually are classified as light stabilizers rather than antioxidants. 

Silicone—Fluorosilicone Lenses. Sdicone mbber has long been considered a unique contact lens material (55), and the development of sdicone mbber lenses has been reviewed in earHer editions of the Eniyclopedia. The oxygen permeabdity of sdicone mbber, >300 barrers, is virtually unsurpassed by any other polymeric material considered for contact lens appHcations. 

Other Polymerization Methods. Although none has achieved commercial success, there are a number of experimental alternatives to clay-catalyzed or thermal oligomeriza tion of dimer acids. These iaclude the use of peroxides (69), hydrogen fluoride (70), a sulfonic acid ion-exchange resia (71), and corona discharge (72) (see Initiators). 

Rubber base adhesives develop strength faster than most other polymeric types. Fig. 1 [3J shows the differences in the development of peel strength for several rubber polymers (without additional additives, except an antioxidant). Natural... 

Nitrile rubber adhesives. The main application corresponds to laminating adhesives. PVC, polyvinyl acetate and other polymeric films can be laminated to several metals, including aluminium and brass, by using NBR adhesives. NBR adhesives can also be used to join medium-to-high polarity rubbers to polyamide substrates. The adhesive properties of NBR rubbers can be further improved by chemical modification using polyisocyanate or by grafting with methyl methacrylate. 

Tannins are polyhydroxyphenols. They are soluble in water, aleohols and aeetone and ean eoagulate proteins. They are yielded by extraetion from wood substanee, bark, leaves and fruits. Other components of the extraction solutions are sugars, pectins and other polymeric carbohydrates, amino acids and other substances. The content of non-tannins can reduce wood failure and water resistance of glued bonds. The polymeric carbohydrates especially increase the viscosity of the extracts. 

The polymerization in method [III] will probably be unsuitable for industrial production due to the heat of polymerization, but it can be used to produce a freeze-thaw stable adhesive with rapid drying and good adhesion to paper, which cannot be obtain by other polymerization methods. However, the water resistance of the latex film is not improved. 

Polymers obtained by the bulk technique are usually pure due to the absence of a solvent. The purity of the final polymer depends on the purity of the monomers. Heat and viscosity are not easily controlled, as in other polymerization techniques, due to absence of a solvent, suspension, or emulsion medium. This can be overcome by carrying the reaction to low conversions and strong agitation. Outside cooling can also control the exothermic heat. 

Klos et at.2is6 described a range of polymerizable benzoin derivatives as photoinitiators (e.g. 83, 84). These and other polymeric photoinitiators have advantages as initiators over low molecular weight analogs in circumstances where migratory stability is a problem.287"2 ... 

It seems likely that other polymerizations will be found to depart from Bemoullian statistics as the precision of tacticity measurements improves. One study12 indicated that vinyl chloride polymerizations are also more appropriately described by first order Markov statistics. However, there has been some reassignment of signals since that time. 4 25... 

Starnes et al.hl have also suggested that the head adduct may undergo p-scission to eliminate a chlorine atom which in turn adds VC to initiate a new polymer chain. Kinetic data suggest that the chlorine atom does not have discrete existence. This addition-elimination process is proposed to he the principal mechanism for transfer to monomer during VC polymerization and it accounts for the reaction being much more important than in other polymerizations. The reaction gives rise to terminal chloroallyl and 1,2-dichlorocthyl groups as shown in Scheme 4.8. 

Viswanadhan and Matticc278 carried out calculations aimed at rationalizing the relative frequency of backbiting in these and other polymerizations in terms of the ease of adopting the required conformation for intramolecular abstraction (see 2.4.4), More recent theoretical studies generally support these conclusions and provide more quantitative estimates of the Arrhenius parameters for the... 

The role of oxygen in radical and other polymerizations has been reviewed by Rhanu and Kishore.187 Rate constants for the reaction of carbon-centered radicals with oxygen are extremely fast, generally - 1 d" M 1 s 1.181,188 The initially formed... 

The dependence of the transfer constant on the Z substituent, summarized in Figure 9.4, is largely based on studies of the apparent transfer constants of benzyl and cyanoisopropyl RAFT agents in S polymerization 4 409 and qualitative observations of other polymerizations/97... 

What can ADMET offer in terms of tailoring the properties of a given polymer The answer lies in the clean chemistry of metathesis. If a metathesis active a,co-diene can be synthesized, then a known polymer can be produced. Few other polymerization techniques are so versatile, yet so precise. In recent years, our group has focused attention toward modeling polymers and copolymers made from ethylene in particular, we have been examining the effect of precise placement of alkyl and polar branches sequentially along tire backbone of polyethylene. 

Complete characterization of arylboronic acids is often difficult because they are readily transformed into stable cyclic anhydrides called boroxines5 and other polymeric species. Arylboronic acids are also known to be hygroscopic. Thus, arylboronic acids are often prepared and used directly as a mixture of different entities. Commercial arylboronic acids will very often contain varying amount of anhydrides. 

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