Acid strength loss

Chemical Properties. The hydrolysis of PET is acid- or base-catalyzed and is highly temperature dependent and relatively rapid at polymer melt temperatures. Treatment for several weeks in 70°C water results in no significant fiber strength loss. However, at 100°C, approximately 20% of the PET tenacity is lost in one week and about 60% is lost in three weeks (47). In general, the hydrolysis and chemical resistance of copolyester materials is less than that for PET and depends on both the type and amount of comonomer. 

At room temperature, PET is resistant to organic and moderate strength mineral acids. At elevated temperatures, PET strength loss in moderate strength acids can be appreciable. Strong acids such as concentrated sulfuric acid dissolve and depolymerize PET. 

N,]S7-bis(methoxymethyl)uron was first isolated and described in 1936 (41), but was commercialized only in 1960. It is manufactured (42) by the reaction of 4 mol of formaldehyde with 1 mol of urea at 60°C under highly alkaline conditions to form tetramethylolurea [2787-01-1]. After concentration under reduced pressure to remove water, excess methanol is charged and the reaction continued under acidic conditions at ambient temperatures to close the ring and methylate the hydroxymethyl groups. After filtration to remove the precipitated salts, the methanolic solution is concentrated to recover excess methanol. The product (75—85% pure) is then mixed with a methylated melamine—formaldehyde resin to reduce fabric strength losses in the presence of chlorine, and diluted with water to 50—75% soHds. Uron resins do not find significant use today due to the greater amounts of formaldehyde released from fabric treated with these resins. 

In order to become useful dmg delivery devices, biodegradable polymers must be formable into desired shapes of appropriate size, have adequate dimensional stability and appropriate strength-loss characteristics, be completely biodegradable, and be sterilizahle (70). The polymers most often studied for biodegradable dmg delivery applications are carboxylic acid derivatives such as polyamides poly(a-hydroxy acids) such as poly(lactic acid) [26100-51-6] and poly(glycolic acid) [26124-68-5], cross-linked polyesters poly(orthoesters) poly anhydrides and poly(alkyl 2-cyanoacrylates). The relative stabiUty of hydrolytically labile linkages ia these polymers (70) is as follows ... 

Unfortunately, it is not easy to measure acid strengths of very weak acids like the conjugate acids of simple unsubstituted carbanions. There is little doubt that these carbanions are very unstable in solution, and in contrast to the situation with carbocations, efforts to prepare solutions in which carbanions such as ethyl or isopropyl exist in a relatively free state have not yet been successful. Nor has it been possible to form these carbanions in the gas phase. Indeed, there is evidence that simple carbanions such as ethyl and isopropyl are unstable toward loss of an electron, which converts them to radicals. Nevertheless, there have been several approaches to the problem. Applequist and O Brien studied the position of equilibrium for the reaction... 

Loss of H+ by a neutral acid molecule (H2S03) reduces acid strength. Thus, H2S03 is a stronger acid than HS03 . 

Progress has recently been made at successfully retarding this adhesion strength loss mechanism for the case of aluminum oxide through the use of a phosphoric acid anodizing pretreatment or special inhibitors86). These pretreatments are analyzed in Section 6.2. 

Figure 3. Temperature dependence of rate of wet-strength loss caused by dry heat in joints of yellow birch and Douglas-fir with acidic and nonacidic adhesives (48).

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