Brassylic acid

Brass plating Brass wool Brassylic acid [505-52-2] Brassylic acid [505-55-2]... 

Brassylic Acid. This acid is commercially available from Nippon Mining Company (Tokyo, Japan). It is made by a fermentation process (76). Several years ago, Emery Group, Henkel Corp. (Cincinnati, Ohio) produced brassyUc acid via ozonization of emcic acid primarily for captive use in making dimethyl brassylate and ethylene brassylate. A pilot-scale preparation based on ozonization of emcic acid has been described in which brassyUc acid yields of 72—82% were obtained in purities of 92—95%. Recrystallization from toluene gave purities of 99% (77). 

Oxidation of -paraffins to C13 brassylic acid (dicarboxylic acid)... 

Coatings Based on Brassylic Acid (An Erncic Acid Derivative)... 

Erucic acid, H00C(CH2) CH=CH(CH2)jCH, can be economically obtained from rapeseed ana crambe abyssinica oils and is potentially a major source of industrial materials. It can be ozonized to brassylic acid, HOOCCCH ), COOH, which is known to impart flexibility and moisture resistance to nylons. Here preliminary results of a study of brassylic acid as a monomer for polyester resin/melamine resin coatings are described. It is demonstrated that brassylic acid imparts good flexibility to such coatings. It is also shoim that brassylic acid is polymorphic. 

Beside being a source of C-22 chemicals, erucic acid is a natural source of C-13 and C-9 chemicals made by cleavage at the site of the double bond. Ozonolysis of erucic acid followed by oxidative cleavage of the ozonide to form brassylic acid (BA) and pelargonic acid (Chart I) has been demonstrated on the pilot plant scale.[2,3] Yield of 99% pure brassylic acid was 72 to 82% of theoretical. 

Possible alternatives to the ozonolysis process for production of brassylic acid include oxidation with nitric acid or with potassium permanganate these routes are feasible,[5] but yields were inferior to ozonolysis. 

Several polymer-related uses of brassylic acid (BA) have been investigated. For example, a BA/l,3-butanediol/lauric acid oligomer is an effective plasticizer for poljrvinyl chloride,[6] BA/ethylene glycol and BA/propylene glycol polymers function as polyester based polyurethane elastomers,[7] and BA has been patented as a cross-linker for glycidyl methacrylate copolymer powder coatings.[8] However, the most detailed studies have involved polyamides selected data from these studies are summarized in Table I. 

Thus our first objective was to learn how BA polyesters could be designed to make resins which will perform as well as commercial polyesters and the second was to find ways in which they might be superior. Here we present initial results of our project, showing how BA polyesters can be designed for good performance in industrial coatings. We also demonstrated, apparently for the first time, that brassylic acid is polymorphic, undergoing phase transitions at about 112 °C and 114 °C. 

Brassylic acid for polymerization was recrystallized twice from 50/50 v/v ethanol/water this material had two melting points in the range 111-113.5 C by DSC at a heating rate of 1 C/min. Brassylic acid for melting point studies (see below) was recrystallized twice from toluene (91% overall recovery) or twice from from ethyl acetate (84% overall recovery). 

Synthesis of CHDM/BA and CHDM/PDA Polyester Resins Described in Tables III and IV. CHDM, brassylic acid (or dodecandioic acid) and "Fascat 4100 in a mol ratio of 2/1/0.005 and 5 wt % of xylene were placed in a three-necked, 250-mL round-bottomed flask fitted with line, a thermometer, an Ace temperature controller, a heating mantle, a mechanical stirrer, a steam-heated Allihn partial condenser with a xylene-filled Barrett moisture test receiver below the Allihn condenser and a total condenser above it. The mixture was heated to about 140 without stirring to melt the reactants and stirring was started. Heating was continued to 205 C. A slow N sweep was maintained throughout the reaction. About 95 to 100% of the theoretical water was collected in the Barrett receiver. Upon cooling the reaction mixtures partially solidified to white waxy solids which liquified when heated to about 40 C. Acid numbers were < 1 mg of KOH/g of resin. 

Analogous oligomers were made from dodecanedioic acid (DDA, n=10) and for brassylic acid (BA, n=ll) for comparison studies. Resins made from the oligomeric diols derived from DDA and BA were made into similar coatings in which the diol/HMMM ratio was varied from 68/32 to 53/47 with p-TSA catalyst. The coated panels were baked at 133 °C for 15 min and, in the case of the n = 11 materials at 150 C for 30 min. Results are provided in Tables III and IV. 

Table III PROPERTIES OF COATINGS BASED ON BRASSYLIC ACID AT VARIOUS HMMM LEVELS, BAKED AT 133 °C AND 150 °C ...

Table V MELTING POINTS, C, OF BRASSYLIC ACID MEASURED DIFFERENTIAL SCANNING CALORIMETRY...

It was concluded that brassylic acid is inherently polymorphic, with melting points at about 112 and 114 C. VHiile several other diacids in the series HOOC(CH ) COOH have been reported to exist in more than one crystal form,[17] polymorphism of brassylic acid has no to our knowledge been reported. A recent study demonstrated that erucic acid itself is polymorphic.[18]... 

Our results indicate that brassylic acid has potential utility as a monomer for polyester resins designed for industrial coatings. 

Financial support by the U.S. Department of Agriculture Alternative Crops Program is gratefully acknowledged. Very helpful discussions with Dr. K. D. Carlson of the U.S.D.A. Regional Laboratory at Peoria. IL are appreciated Dr. Carlson also helped by providing the brassylic acid used in this work. 

Nylon-13,13 and Nylon-13. The ingredients for nylon-13,13 [26796-68-9], [26796-70-3] and nylon-13 [14465-66-8], [26916-48-3] and their copolymers have become available in developmental quantities from a natural source, crambe and rapeseed oil (176). Emcic acid [112-86-7] is obtained in high yield approaching 50 wt % from the oil and oxidatively cleaved to produce the dicarboxylic acid, brassylic acid [505-55-2] and pelargonic acid ... 

Then in a series of chemical transformations the diamine or lactam can be prepared from brassylic acid (177,178). The diamine is formed as described above for the 12-carbon diamine, ie, diacid —> diamide —> dinitrile — diamine. The lactam is made from the dinitrile as follows. 

Fatty acids have been used previously in the development of polymers for biomedical applications as they are considered to be inert, inexpensive and biocompatible. The main fatty acids which are used as a base for synthesis of biomedical polymers (polyanhydrides) are stearic acid (/), erucic acid (C22 unsaturated fatty acid) dimer (2), bile acid dimer (i), ricinoleic acid 4) and other fatty acids (5), middle long carbon chain (C12 - 15) dibasic acids, such as dodecanedioic, brassylic acid, tetradecandioic acid and pentadecandioic acid (/). 

---