Dibutyltins

The physical properties of polyurethane adhesives result from a special form of phase separation which occurs in the cross-linked polyurethane stmcture. The urethane portions of polyurethanes tend to separate from the polyol portion of the resin, providing good shear strength, good low temperature flexibiUty, and high peel strength. Catalysts such as dibutyltin dilaurate [77-58-7], stannous octoate [1912-83-0], l,4-diazabicyclo[2.2.2]octane... 

Polyhydric alcohol mercaptoalkanoate esters are prepared by reaction of the appropriate alcohols and thioester using -toluenesulfonic acid catalyst under nitrogen and subsequent heating (16,17). Organotin mercapto esters are similarly produced by reaction of the esters with dibutyltin oxide (18). Pentaerythritol can be oxidized to 2,2-bis(hydroxymethyl)hydracryhc acid [2831-90-5] C H qO, ... 

Chemical Properties. Trimethylpentanediol, with a primary and a secondary hydroxyl group, enters into reactions characteristic of other glycols. It reacts readily with various carboxyUc acids and diacids to form esters, diesters, and polyesters (40). Some organometaUic catalysts have proven satisfactory for these reactions, the most versatile being dibutyltin oxide. Several weak bases such as triethanolamine, potassium acetate, lithium acetate, and borax are effective as stabilizers for the glycol during synthesis (41). 

Following this work, the y -12F-diol was used for the direct reaction with hexamethylene-1,6-diisocyanate in the presence of dibutyltin dilaurate to produce a cross-linked elastomer or a reactive prepolymer which was terminated with either isocyanate or hydroxyl groups, depending on which reactant was in excess (142,143). 

Condensation cure can also be carried out ia emulsions (200—209). In this case, the cross-linker and polydimethylsiloxanediol are emulsified usiag anionic, cationic, or nonionic surfactants ia water, and a condensation catalyst such as dibutyltin dilaurate is added. The polymer can then undergo cross-linking, forming a continuous film when the water is evaporated. 

Mercaptides are unchallenged as the ligand of choice for the other entities bonded to the tin, but carboxylates can also be used. Whereas a variety of mercaptans are used, the thioglycolic acid derivatives remain the largest single mercaptan. Dibutyltin bis(isooctyl thioglycolate) [25168-24-5] and butyltin tris(isooctyl thioglycolate) [25852-70A] are two common examples. These materials are produced by the reaction of the appropriate alkyl tin chloride or oxide, and the mercaptan. 

Of the large volume of tin compounds reported in the Hterature, possibly only ca 100 are commercially important. The most commercially significant inorganic compounds include stannic chloride, stannic oxide, potassium staimate, sodium staimate, staimous chloride, stannous fluoride, stannous fluoroborate, stannous oxide, stannous pyrophosphate, stannous sulfate, stannous 2-ethyUiexanoate, and stannous oxalate. Also important are organotins of the dimethyl tin, dibutyltin, tributyltin, dioctyltin, triphenyl tin, and tricyclohexyltin families. 

Prepa.ra.tlon, Diorganotin dichlorides are the usual precursors for all other diorganotin compounds three primary methods of manufacture are practiced. Dibutyltin dichloride is manufactured by Kocheshkov redistribution from cmde tetrabutyltin and stannic chloride and usually is cataly2ed with a few tenths of a percent aluminum trichloride ... 

Other. Dibutyltin dilaurate [77-58-7] has been successfully used for many years as a coccidiostat in the treatment of intestinal worm infections in chickens and turkeys (see Antiparasitic agents). 

Dibutyltin and dioctyltin diacetate, dilaurate, and di-(2-ethylhexanoate) are used as catalysts for the curing of room-temperature-vulcanized (RTV) sihcone elastomers to produce flexible siUcone mbbers used as sealing compounds, insulators, and in a wide variety of other appHcations. Diorganotin carboxylates also catalyze the curing of thermosetting siHcone resins, which are widely used in paper-release coatings. 

In the presence of the organic siHcate, the heavy-metal salts trigger the chain extension and cross-linking reactions that lead to siHcone mbber and volatile ethanol as a byproduct. Useful metal soaps iaclude stannous octanoate [1912-83-0], ziac octanoate [557-09-5], dibutyltin dilaurate [77-58-7], and dibutyltin diacetate [1067-33-0]. The reactivity of the different salts varies considerably. Stannous octanoate effects a cure ia 0.5—2 min ziac octanoate may require 24—96 h the dibutyltin dilaurate, 10—20 min. Heat and moisture accelerate the curing rate, but to a lesser degree than ia the case of the polysulfide mbbers. 

Other Octoate Uses. Metal octoates are also used as driers in printing inks. Another appHcation of octoates includes the use of the aluminum salt to gel paint. Stannous, dibutyltin, and bismuth carboxylates find appHcation as catalysts in polyurethane foam appHcations in order to obtain a reaction efficiency suitable for industrial production. In polyurethane foam manufacture the relative rate of polymeriza tion and gas foaming reactions must be controlled so that the setting of the polymer coincides with the maximum expansion of the foam. 

Initially, the water slowly reacts with the isocyanate. However, the reaction can be catalyzed with an appropriate catalyst, such as dibutyltin dilaurate or a morpholine tertiary amine catalyst. The isocyanate will react with water to form a carbamic acid, which is unstable and splits off carbon dioxide, to produce a terminal amine end group (see p. 76 in [6]). This amine then reacts with more isocyanate-terminated prepolymer, as shown above, to form a polyurea. This process repeats itself, building up molecular weight and curing to become a polyurea-polyurethane adhesive. 

The most common catalyst used in urethane adhesives is a tin(lV) salt, dibutyltin dilaurate. Tin(IV) salts are known to catalyze degradation reactions at high temperatures [30J. Tin(II) salts, such as stannous octoate, are excellent urethane catalysts but can hydrolyze easily in the presence of water and deactivate. More recently, bismuth carboxylates, such as bismuth neodecanoate, have been found to be active urethane catalysts with good selectivity toward the hydroxyl/isocyanate reaction, as opposed to catalyzing the water/isocyanate reaction, which, in turn, could cause foaming in an adhesive bond line [31]. 

Catalysts serve a dual purpose in one-component moisture-curing urethanes. The first purpose is to accelerate the prepolymer synthesis. The second purpose is to catalyze the curing reaction of the adhesive with moisture. The most common catalysts used to promote both prepolymer formation (NCO/OH) and later the adhesive curing reaction (NCO/H2O) are dibutyltin dilaurate and DMDEE ((tertiary amine. A stabilizer such as 2,5-pentanedione is sometimes added when tin is used, but this specific stabilizer has fallen from favor in recent years, due to toxicity concerns. DMDEE is commonly used in many one-component moisture-curing urethanes. DMDEE is one of the few tertiary amines with a low alkalinity and a low vapor pressure. The latter... 

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