Acid acceptor

When pure needle-like crystals of -aminobenzoyl chloride are polymerized in a high temperature, nonsolvent process, or alow temperature, slurry process, polymer is obtained which maintains the needle-like appearance of monomer. PBA of inherent viscosity, 4.1 dL/g, has been obtained in a hexane slurry with pyridine as the acid acceptor. Therefore PBA of fiber-forming molecular weight can be prepared in the soHd state. 

An alternative polymerization process utilizes a slurry of calcium chloride in NMP as the polymerization medium. The solubiHty of calcium chloride is only 6% at 20°C however, the salt continues to dissolve as conversion of monomers to polymer proceeds and calcium chloride/polyamide complexes are formed. Polymer molecular weight is further increased by the addition of /V, /V- dim ethyl a n i1 in e as an acid acceptor. This solvent system produces fiber-forming polymer of molecular weights comparable to that formed in HMPA/NMP. 

These oxazolines have cationic surface-active properties and are emulsifying agents of the water-in-oil type. They ate acid acceptors and, in some cases, corrosion inhibitors (see Corrosion). Reaction to oxazoline also is useful as a tool for determination of double-bond location in fatty acids (2), or for use as a protective group in synthesis (3). The oxazolines from AEPD and TRIS AMINO contain hydroxyl groups that can be esterified easily, giving waxes (qv) with saturated acids and drying oils (qv) with unsaturated acids. 

Pyrrohdinone can be alkylated by reaction with an alkyl haUde or sulfate and an alkaline acid acceptor (63,64). This reaction can be advantageously carried out with a phase-transfer catalyst (65). Alkylation can also be accompHshed with alcohols and either copper chromite or heterogenous acid catalysts... 

Magnesium oxide is a typical acid scavenger for chlorinated mbbers. Compounds containing zinc oxide or magnesium oxide may tend to swell upon immersion in water. These inorganic salts have some water solubiHty and osmotic pressure causes the vulcanizates to imbibe water to equalize pressure (8,9). As such, vulcanizates tend to sweU more in fresh (distilled) water than in salt water. To minimize water sweU, insoluble salts such as lead oxides can be substituted. Because of the health concerns associated with lead, there is much mbber industry interest in other acid acceptors, such as synthetic... 

Amine Cross-Linking. Two commercially important, high performance elastomers which are not normally sulfur-cured are the fluoroelastomers (FKM) and the polyacrylates (ACM). Polyacrylates typically contain a small percent of a reactive monomer designed to react with amine curatives such as hexamethylene-diamine carbamate (Diak 1). Because the type and level of reactive monomer varies with ACM type, it is important to match the curative type to the particular ACM ia questioa. Sulfur and sulfur-beating materials can be used as cure retarders they also serve as age resistors (22). Fluoroelastomer cure systems typically utilize amines as the primary cross-linking agent and metal oxides as acid acceptors. 

As in dry compounding, acid acceptors must be incorporated into neoprene latices because of the wide use of these latices in coating fabrics and metals. The hydrochloric acid that forms during service life has a particularly destmetive effect on coated cotton fabrics that are not adequately protected. High zinc oxide concentration (ca 15 parts) and use of 0.4 parts AJ-phenyl-AT(p-toluenesulfonyl)-/)-phenylenediamine (Aranox, Uniroyal) as an antioxidant provides adequate protection. 

Chloroformates are reactive intermediates that combine acid chloride and ester functions. They undergo many reactions similar to those of acid chlorides however, the rates are usually slower (4—8). Those containing smaller organic (hydrocarbon) substituents react faster than those containing large organic (hydrocarbon) substituents (3). Reactions of chloroformates and other acid chlorides proceed faster with better yields when alkaU hydroxides or tertiary amines are present to react with the HCl as it forms. These bases act as stoichiometric acid acceptors rather than as tme catalysts. 

Heterocyclic Alcohols. Thek reactions with chloroformates lead to carbonates. Thus furan- and tetrahydrofuran-derived alcohols give the corresponding carbonates in 75% yield (15). Inorganic bases and tertiary amines as acid acceptors increase the rate and yield in this reaction. 

Reactions with Nitrogen Compounds. The reaction with ammonia is the classical method for preparing primary carbamates. Excess ammonia is used as an acid acceptor to remove the HCI formed (see Carbamic acid). 

Amines. Primary and secondary aUphatic amines also yield carbamates in the presence of excess amine or other acid acceptors such as inorganic bases. Aromatic primary and secondary amines and heterocycHc amines react similarly, although slowly. 

The yields of primary chloroformates are usually well above 90%. The secondary chloroformates give yields of 80—90%. In cases where the alcohols are most unreactive, an acid acceptor may be used to drive the reaction. Commercial processes are usually mn neat, although solvents such as chloroform, toluene, dioxane, or THE are sometimes used to dissolve the starting alcohol or the product chloroformate as maybe necessary. 

Commercial use of many chlorinated derivatives imposes stress on the stabHity of the solvent. Inhibitors classified as antioxidants (qv), acid acceptors, and metal stabilizers are added to minimize these stresses. AH the chloriaated derivatives hydrolyze at a slow but finite rate when dissolved ia water. Hydrolysis of chloriaated solvents typicaHy Hberates hydrogen chloride that can corrode storage containers and commercial metal-cleaning equipment. The Hberated hydrogen chloride can be neutralized by an appropriate epoxide to form noncorrosive chlorohydrins (qv). 

Peroxide curing systems are generally the same for CSM as for other elastomers but large amounts of acid acceptor must be present to complete the cure. A small amount of a polyfunctional alcohol, ie, pentaerythritol (PER) in the compound significantly reduces the amount of base required by acting as a solubiHzer. TriaHyl cyanurate [101-37-17 is an additional cure promoter and leads to higher cross-link density. 

The carboxylated latexes are formulated to use a reduced amount of a less reactive 2inc complex. Special resin blends provide an optimum balance of film tack and strength, and are coUoidaHy compatible with the carboxylated latexes (158). Epon resins may also be used as an acid acceptor in place of 2inc oxide (160). 

The principal mechanism of polymer degradation during aging is the acid-catalyzed cleavage of the ether linkage in the backbone. The acid acceptor. 

The common acid acceptors, red lead oxide and barium carbonate, are both toxic when inhaled or ingested. They are, and should be, used in industry as dispersions in EPDM and ECO. SuppHers of red lead oxide include Polymeries, Inc., Rhein Chemie Corp., and Akrochem Co., Akron, Ohio. Barium carbonate in an ECO binder is available from Rhein Chemie Corp. and Synthetic Products Co. 

The acetal polymers are probably never supplied for use without any additives being incorporated. As mentioned in Section 19.3.1 antioxidants of the phenol alkane type are present in both homopolymers and copolymers. Acid acceptors are also believed to be widely used to absorb traces of acidic materials which attack the acetal linkage. Epoxides, nitrogen compounds and basic salts have been successfully employed. 

Reaction of dihydroxy compounds with phosgene in the presence of acid acceptors. 

The hydrohalide is liable to dehydrochlorination, particularly when moist acid is used in its preparation, so that hydrochloric acid acceptors such as lead carbonate are useful stabilisers. Dibutyl phthalate and tritolyl phosphate are effective plasticisers. Rubber hydrochloride is used as a packaging film (Pliofilm) and as a rubber-to-metal bonding agent (e.g. Typly). 

Acid acceptor. This is the main function of metal oxides in CR adhesive formulations. Upon age, small amounts of hydrochloric acid are released which may cause discolouration and substrate degradation. Magnesium oxide (4 phr) and zinc oxide (5 phr) act synergistically in the stabilization of solvent-borne polychloroprene adhesives against dehydrochlorination. 

Metal oxides. Zinc oxide is the most effective metal oxide. The zinc oxide should have a low lead content. Zinc oxide has three main functions (a) promote cure (b) improves ageing, heat and weathering resistance (c) acid acceptor. In general, 2-5 phr zinc oxide is added in latex formulations. 

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