1,1,1-Trimethylolpropane

Carboxylic acids react with butadiene as alkali metal carboxylates. A mixture of isomeric 1- and 3-acetoxyoctadienes (39 and 40) is formed by the reaction of acetic acid[13]. The reaction is very slow in acetic acid alone. It is accelerated by forming acetate by the addition of a base[40]. Addition of an equal amount of triethylamine achieved complete conversion at 80 C after 2 h. AcONa or AcOK also can be used as a base. Trimethylolpropane phosphite (TMPP) completely eliminates the formation of 1,3,7-octatriene, and the acetoxyocta-dienes 39 and 40 are obtained in 81% and 9% yields by using N.N.N M -tetramethyl-l,3-diaminobutane at 50 in a 2 h reaction. These two isomers undergo Pd-catalyzed allylic rearrangement with each other. 

TMPP trimethylolpropane phosphite or 4-ethyl-2.6.7-trioxa-1 -phospho-... 

EPM/EPDM compounding pLASTOTffiRS, SYNTHETIC - ETHYLENE-PROPYLENE-DIENE RUBBER] (Vol 8) Trimethylolpropane trimethacrylate [3290-92-4]... 

Pentaerythritol and trimethylolpropane are classified as nuisance particulate and dust, respectively. They are both nontoxic to animals by ingestion or inhalation and are essentially nonirritating to the skin or eyes (2,74). 

Pentaerythritol and trimethylolpropane acryUc esters are usefiti in solventiess lacquer formulations for radiation curing (qv), providing a cross-linking capabihty for the main film component, which is usually an acryUc ester of urethane, epoxy, or polyester. Some specialty films utilize dipentaerythritol and ditrimethylolpropane (94,95). 

Titanium dioxide pigment coated with pentaerythritol, trimethylolpropane, or trim ethyl ol eth an e exhibits improved dispersion characteristics when used in paint or plastics formulations. The polyol is generally added at levels of 0.1—0.5% (96). 

One noteworthy neurotoxic response was demonstrated in laboratory pyrolysis studies using various types of phosphoms flame retardants in rigid urethane foam, but the response was traced to a highly specific interaction of trimethylolpropane polyols, producing a toxic bicycHc trimethylolpropane phosphate [1005-93-2] (152). Formulations with the same phosphoms flame retardants but other polyols avoided this neurotoxic effect completely. 

Polyols. Several important polyhydric alcohols or polyols are made from formaldehyde. The principal ones include pentaerythritol, made from acetaldehyde and formaldehyde trimethylolpropane, made from -butyraldehyde and formaldehyde and neopentyl glycol, made from isobutyraldehyde and formaldehyde. These polyols find use in the alkyd resin (qv) and synthetic lubricants markets. Pentaerythritol [115-77-5] is also used to produce rosin/tall oil esters and explosives (pentaerythritol tetranitrate). Trimethylolpropane [77-99-6] is also used in urethane coatings, polyurethane foams, and multiftmctional monomers. Neopentyl glycol [126-30-7] finds use in plastics produced from unsaturated polyester resins and in coatings based on saturated polyesters. 

The formaldehyde demands for pentaerythritol, trimethylolpropane, and neopentyl glycol are about 7, 2, and 1%, respectively, of production. 

Polyol Esters. Polyol esters are formed by the reaction of an alcohol having two or more hydroxyl groups, eg, a polyhydric alcohol and a monobasic acid. In contrast to the diesters, the polyol in the polyol esters forms the backbone of the stmcture and the acid radicals are attached to it. The physical properties maybe varied by using different polyols or acids. Trimethylolpropane [77-99-6] C H O, and pentaerythritol [115-77-5] are... 

Polyol ester turbine oils currendy achieve greater than 10,000 hours of no-drain service in commercial jet aircraft with sump temperatures ranging to over 185°C. Polyol esters are made by reacting a polyhydric alcohol such as neopentyl glycol, trimethylol propane, or pentaerythritol with a monobasic acid. The prominent esters for automotive appfications are diesters of adipic and a2elaic acids, and polyol esters of trimethylolpropane and pentaerythritol (34). 

The principal valeraldehyde derivatives, -amyl and 2-methylbutyl alcohols, are used predominandy to make ziac diamyldithiophosphate lube oil additives (see Amyl alcohols Lubrication and lubricants), which are employed primarily in automotive antiwear appHcations. Similady, the / -valerate and 2-methylbutyrate esters of pentaerythritol and trimethylolpropane are used ia aeromotive synlube formulations and as refrigerant lubricants. 

Cy—oxo-derived acids are the principal derivatives of the C —oxo aldehydes, and ia analogy to oxo aldehyde market appHcations, are used chiedy to make neopolyol esters, ie, those based on neopentyl glycol, trimethylolpropane, or pentaerythritol. These synlubes are employed almost entirely ia aeromotive appHcations. Heptanoic acid is also employed to make tetraethylene glycol diheptanoate, a plasticizer used with poly(vinyl butyral). 

Trimethylolpropane inNlkyd Coating Resins, Celanese Chemical Co., New York, 1961, p. 4. 

Condensation. The neopentyl trimethylolpropane carbonate [65332-76-5] formed from condensation of the trischloroformate of trimethylolpropane and neopentyl alcohol, is a clear yellow oil, useful as lubricant (77). 

Photopolymerizable compositions based on monomeric acryflc or other ethylenicaHy unsaturated acid derivatives are becoming increasingly popular. When multiftmctional derivatives are employed, three-dimensional networks having high strength and abrasion resistance are possible on exposure to light. A typical composition may contain an ethoxylated trimethylolpropane triacrylate monomer, a perester phenacjhdene initiator (69), and an acryflc acid—alkyl methacrylate copolymer as binder. 

The newer HFC refrigerants are not soluble in or miscible with mineral oils or alkylbenzenes. The leading candidates for use with HFC refrigerants are polyol ester lubricants. These lubricants are derived from a reaction between an alcohol and a normal or branched carboxyflc acid. The most common alcohols used are pentaerythritol, trimethylolpropane, neopentjlglycol, and glycerol. The acids are usually selected to give the correct viscosity and fluidity at low temperatures. 

Polyurethane foams are formed by reaction with glycerol with poly(propylene oxide), sometimes capped with poly(ethylene oxide) groups with a reaction product of trimethylolpropane and propylene oxide or with other appropriate polyols. A typical reaction sequence is shown below, in which HO—R—OH represents the diol. If a triol is used, a cross-linked product is obtained. 

Powder coatings are formulated from the reaction product of trimethylolpropane and IPDI, blocked with caprolactam, and polyester polyols. The saturated polyester polyols are based on aromatic acid diols, neopentyl glycol, and trimellitic anhydride for further branching. To avoid the release of caprolactam in the curing reaction, systems based on IPDI dimer diols are used. 

The remaining (8%) //-butyraldehyde production of the United States goes into (in decreasing order) poly(vinyl butyral), 2-ethyIhexanal, trimethylolpropane, methyl amyl ketone, and butyric acid. 

Trimethylolpropane (TMP), the reduced crossed aldol condensation product of //-butyraldehyde and formaldehyde, competes in many of the same markets as glycerol (qv) and pentaerythritol. The largest market for TMP is as a precursor in unsaturated polyester resins, short-oil alkyds, and urethanes for surface coatings (see Alkyd resins). 

The most active -butyraldehyde derivatives are expected to be PVB, as more regions require automotive safety glass, and trimethylolpropane. Overall annual growth in -butyraldehyde through 1993 is expected to be 0.9% in the United States and 1.2% in Japan. No growth in -butyraldehyde consumption is expected in Western Europe through 1993. 

C H NO, and drying oil acid amides with hexamethoxymethylmelamine [3089-11-OJ, C H qN O, (23,24), and trimethylolpropane triacrylate [37273-47-17, been recommended. Such reactive diluents give solutions of higher viscosity, ie, lower alkyd concentration at the same... 

Q 2(S 2 trimethylolpropane (TMP) (2-ethyl-2-(hydroxymethyl)-l,3-propanediol) [77-99-6] more hydrolytically stable than esters of... 

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