Methods for producing biosourced dodecanedioic acid and compositions comprising biosourced dodecanedioic acid are provided. In some embodiments, the method comprises first forming muconic acid biologically from a renewable carbon source, reducing the muconic acid to hexenedioic acid, and then reacting the hexenedioic acid with an unsaturated fatty acid, typically a Δ9 unsaturated fatty acid, in a metathesis reaction to produce dodecenedioic acid. Dodecenedioic acid is then reduced to dodecanedioic acid. Dodecanedioic acid is can be used to form polymers, such as polyamides. Examples of polyamides include nylon, such as nylon 6,12. Nylon 6,12 can be formed by reacting dodecanedioic acid with 1,6-hexamethylene diamine.
C07C 51/353 - Preparation of carboxylic acids or their salts, halides, or anhydrides by reactions not involving formation of carboxyl groups by isomerisationPreparation of carboxylic acids or their salts, halides, or anhydrides by reactions not involving formation of carboxyl groups by change of size of the carbon skeleton
C07C 51/36 - Preparation of carboxylic acids or their salts, halides, or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
C08G 69/26 - Polyamides derived from amino carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
C07C 69/34 - Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
C07C 69/593 - Dicarboxylic acid esters having only one carbon-to-carbon double bond
C07C 67/08 - Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
C07C 67/303 - Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
C07C 67/343 - Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisationPreparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by change of size of the carbon skeleton by increase in the number of carbon atoms
2.
MONOMERS DERIVED FROM ALPHA-OR BETA-AMINO-E-CAPROLACTAM AND POLYMERS MADE THEREFROM
The invention relates to monomers that are derived from α- and β-amino-ε-caprolactam and to polymers (e.g., homopolymers and copolymers) prepared from these monomers. In many embodiments, the α-amino-ε-caprolactam or β-amino-ε-caprolactam is manufactured from a renewable starting material, for example, biomass. In one aspect, the invention relates to polyamide polymers that are prepared by the polymerization of α-amido-ε-caprolactam monomer, β-amido-ε-caprolactam monomer, or a mixture thereof. In some embodiments, the monomers have the structures shown in Structure I and the polyamide polymers of the invention have the structure as shown in Structure II.
C07D 223/12 - Nitrogen atoms not forming part of a nitro radical
C07D 403/04 - Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group containing two hetero rings directly linked by a ring-member-to-ring- member bond
3.
METHODS OF MAKING CYCLIC AMIDE MONOMERS, AND RELATED DERIVATIVES AND METHODS
The present invention relates to methods of making a cyclic amide. The methods include the step of heating a fermentation broth in a manner effective to produce a cyclic amide (e.g., α-amino-ε-caprolactam), wherein the fermentation broth includes an amino acid or salt thereof (e.g., lysine (e.g., L-α-lysine, D-α-lysine, L-β-lysine, and D-β-lysine) or a salt thereof). The cyclic amide monomers can be polymerized in a manner effective to form a polyamide. For example, a method of making polycaprolactam (e.g., nylon 6) includes the steps of (a) heating a fermentation broth in a manner effective to produce α-amino-ε- caprolactam, wherein the fermentation broth includes lysine or a salt thereof; (b) removing (deaminating) the α-amino group from the α-amino-ε-caprolactam in a manner effective to produce a plurality of ε-caprolactam monomers; and (c) polymerizing the plurality of ε-caprolactam monomers in a manner effective to produce polycaprolactam. One advantage of the present invention is that lysine and/or salt thereof can be heated to form α-amino-ε-caprolactam while the lysine is still in the fermentation broth and in the presence of one or more additional amino acids and/or other products of fermentation. The lysine and/or salt thereof do not need to be purified from the fermentation broth prior to being heated to form α-amino-ε-caprolactam. For example, the fermentation broth does not need to be subjected to an ion exchange process prior to being heated to form α-amino-ε-caprolactam. Avoiding such an ion exchange process can substantially reduce manufacturing costs.
The invention relates to caprolactam monomers and to copolymers prepared from these monomers. In many embodiments, the caprolactam monomers are derived from α- amino-ε-caprolactam, β-amino-ε-caprolactam, or a mixture thereof. In many embodiments, the α-amino-ε-caprolactam or β-amino-ε-caprolactam is manufactured from a renewable starting material, for example, biomass (see, U.S. Patent Publication No. 2007/149777 (Frost)). In some embodiments, the invention relates to caprolactam monomers, for example, bis-α-amido-ε-caprolactam monomers and bis-β-amido-ε-caprolactam monomers. In many embodiments, the caprolactam monomers of the invention have the structure shown in structure I. where A is independently selected from formula (II), and where R1 is a linear alkyl, branched alkyl, aryl, or aralkyl group containing about 3 to about 34 carbon atoms.
C07D 403/12 - Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group containing two hetero rings linked by a chain containing hetero atoms as chain links
C08G 69/00 - Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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