MONOMERS AND POLYMERS FROM BIODERIVED CARBON

• US 20090018300A1
• Filed: 07/08/2008
• Published: 01/15/2009
• Est. Priority Date: 07/11/2007
• Status: Abandoned Application

• Current Assignee: Archer Daniels Midland Company
• Original Assignee: Archer Daniels Midland Company
• Inventors: Venkitasubramanian, Padmesh, Bloom, Paul D.
• Application Number:
  US12/169,248
• Publication Number:
  US 20090018300A1
• Time in Patent Office: Days
• US Class Current: 527/102
• CPC Class Codes: C08G 2261/334 containing heteroatoms
• CPC Class Codes: C08G 2261/418 Ring opening metathesis polymerisation [ROMP]
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule

Abstract

The present disclosure provides compositions including biobased monomers derived from biological sources for the synthesis of polymers from bioderived carbon. The monomers and resulting polymers are comparable to petroleum derived monomers and polymers, but have a carbon isotope ratio characteristic of bioderived materials. Methods for synthesizing polymers having 100% biobased materials are also disclosed.

Claims

1-27. -27. (canceled)

28. A polymer comprising:

a product from a metathesis polymerization reaction of a bioderived olefin and an acrylate ester of a bioderived alcohol,

wherein the acrylate ester is produced by reacting the bioderived alcohol with at least one equivalent of acrylic acid produced from bioderived glycerol,

wherein the polymer is 100% biobased as determined by ASTM International Radioisotope Method D 6866.

29. The polymer of claim 28, wherein the bioderived diol is selected from the group consisting of isosorbide, 2,5-bishydroxymethyltetrahydrofuran, 2,5-bishydroxymethylfuran, a diol produced from the hydrogenation of a hydroformylated fatty acid, a diol produced from the hydrogenation of an epoxidized fatty acid ester or fatty acid alcohol, a diol produced from the reduction of an a,o)-dicarboxylic acid, and mixtures thereof.

30. The polymer of claim 28, wherein the bioderived olefin is a bioderived cyclic olefin and the metathesis polymerization reaction is a ring opening metathesis polymerization reaction.

31. The polymer of claim 30, wherein the polymer is an AB alternating polymer.

32. The polymer of claim 28, wherein the product is from an acyclic diene metathesis polymerization reaction and wherein the bioderived olefin is an acyclic diene derived from a bioderived fatty acid.

33. The polymer of claim 28, wherein the bioderived glycerol is produced from a triacylglycerol selected from the group consisting of corn oil, soybean oil, canola oil, vegetable oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, sesame oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, tallow, beef tallow, butter, chicken fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil miscella, used cooking oil, yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of these oils, conjugated derivatives of these oils, and mixtures of any thereof.

34. The polymer of claim 28, wherein the bioderived olefin is selected from the group consisting of monoacrylates, diacrylates, and allyl esters.

35. A polymer comprising:

a product of an acyclic diene metathesis polymerization reaction of a bioderived acyclic diene, wherein the bioderived acyclic diene is made from a bioderived fatty acid and the polymer is 100% biobased as determined by ASTM international Radioisotope Method D 6866.

36. The polymer of claim 35, wherein the polymer has a polydispersity index from 1 to 3.

37. The polymer of claim 35, wherein the polymer is further functionalized in a reaction selected from the group consisting of hydroformylation, hydroxylation, epoxidation, hydrogenation, and heat-bodied polymerization.

38. A method for producing a bioderived polymer, the method comprising:

reacting a compound selected from the group consisting of bioderived diols, bioderived amino alcohols, bioderived diamines, and combinations of any thereof with at least two equivalents of acrylic acid to yield a diacryl monomer product, wherein the acrylic acid is produced from bioderived glycerol; and

reacting the diacryl monomer product with a bioderived olefin in a metathesis polymerization reaction to form a bioderived polymer, wherein the bioderived polymer is 100% biobased as determined by ASTM Method International Radioisotope Method D 6866.

39. The method of claim 38, wherein the bioderived diol is selected from the group consisting of isosorbide, 2,5-bishydroxymethyltetrahydrofuran, 2,5-bishydroxymethylfuran, a diol produced from the hydrogenation of a hydroformylated fatty acid, a diol produced from the hydrogenation of an epoxidized fatty acid ester, a diol produced from the reduction of an α

,ω

-dicarboxylic acid, and mixtures thereof.

40. The method of claim 38, wherein the bioderived diamine is selected from the group consisting of bis-amino isosorbide, 2,5-bisaminomethyltetrahydrofuran, 2,5-bisaminomethylfuran, and mixtures thereof.

41. The method of claim 38, wherein the bioderived olefin is a cyclic olefin and the metathesis polymerization reaction is a ring opening metathesis polymerization reaction.

42. The method of claim 41, wherein the polymer is an AB alternating polymer.

43. The method of claim 41, wherein the cyclic olefin is produced from an anodic coupling of a monounsaturated long chain dicarboxylic acid derived from a bioderived fatty acid.

44. The method of claim 38, wherein the bioderived olefin is an acyclic diene derived from a bioderived fatty acid and wherein the metathesis polymerization reaction is an acyclic diene metathesis polymerization reaction.

45. The method of claim 38, wherein the bioderived glycerol is produced from a triacylglycerol selected from the group consisting of corn oil, soybean oil, canola oil, vegetable oil, safflower oil, sunflower oil, nasturtium seed oil, mustard seed oil, olive oil, sesame oil, peanut oil, cottonseed oil, rice bran oil, babassu nut oil, castor oil, palm oil, palm kernel oil, rapeseed oil, low erucic acid rapeseed oil, lupin oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, tallow, beef tallow, butter, chicken fat, lard, dairy butterfat, shea butter, biodiesel, used frying oil, oil miscella, used cooking oil, yellow trap grease, hydrogenated oils, derivatives of these oils, fractions of these oils, conjugated derivatives of these oils, and mixtures of any thereof.

46. A polymer composition comprising:

a monomer unit having an electrophilic reactive group and a nucleophilic reactive group, wherein the electrophilic reactive group is selected from the group consisting of an aldehyde, an aldimine, an α

,β

-unsaturated carbonyl, and an α

,β

-unsaturated nitrile and the nucleophilic reactive group is selected from the group consisting of an α

,β

-unsaturated ester, α

,β

-unsaturated amide, α

,β

-unsaturated aldehyde, an α

,β

-unsaturated ketone, an α

,β

-unsaturated sulfone, an α

,β

-unsaturated sulfonate, α

,β

-unsaturated nitrile, and an α

,β

-unsaturated phosphate,

wherein the nucleophilic reactive group reacts with the electrophilic reactive group via a Baylis-Hillman type reaction to form a polymer.

47. An AB alternating condensation polymer comprising:

a first monomer unit comprising a first electrophilic reactive group and a second electrophilic reactive group, wherein the first electrophilic reactive group and the second electrophilic reactive group are each independently selected from the group consisting of an aldehyde, an aldimine, an α

,β

-unsaturated carbonyl, and an α

,β

-unsaturated nitrile; and

a second monomer unit comprising a first nucleophilic reactive group and a second nucleophilic reactive group, wherein the first nucleophilic reactive group and the second nucleophilic reactive group are each independently selected from the group consisting of an α

,β

-unsaturated ester, an α

,β

-unsaturated amide, an α

,β

-unsaturated aldehyde, an α

,β

-unsaturated ketone, an α

,β

-unsaturated sulfone, an α

,β

-unsaturated sulfonate, an α

,β

-unsaturated nitrile, and an α

,β

-unsaturated phosphate,

wherein the first monomer unit reacts with the second monomer unit via a Baylis-Hillman type reaction to form a polymer.