Processing hydroxy-carboxylic acids to polymers

Patent metadata

Field	Value
Publication number	US-10174160-B2
Application number	US-201414786299-A
Country	US
Kind code	B2
Filing date	Apr 25, 2014
Priority date	Apr 26, 2013
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

Biomass (e.g., plant biomass, animal biomass, and municipal waste biomass) is processed to produce useful intermediates and products, such as aliphatic hydroxy-carboxylic acid and hydroxyl-carboxylic acid derivatives. These aliphatic hydroxy-carboxylic acids are, in turn, polymerized. The polymerization is carried out using a thin film evaporator or a thin film polymerization/devolatilization device. Conversion of lactic acid to poly lactic acid is an especially useful product to this process.

First claim

The invention claimed is:

1. A method of processing hydroxy-carboxylic acids, the method comprising
irradiating a biomass to reduce the recalcitrance of the biomass;
saccharifying the biomass to form a saccharified biomass comprising glucose and xylose;
selectively fermenting the glucose, while the xylose is not consumed, to produce a hydroxy-carboxylic acid;
producing a poly hydroxy-carboxylic acid from the hydroxy-carboxylic acid;
transferring the poly hydroxy-carboxylic acid to a surface of a thin film evaporator; and
evaporating water as it is formed during condensation of a hydroxy-carboxylic acid polymer as it traverses a surface of the thin film evaporator.

2. The method of claim 1 , where the thin film evaporator comprises a thin film polymerization/devolatilization device.

3. The method of claim 2 , where an extruder is in fluid communication with the thin film polymerization/devolatilization device and the effluent of the extruder is the poly hydroxy-carboxylic acid polymer or effluent of the extruder is recycled to the thin film evaporator.

4. The method of claim 3 , where the extruder is a twin screw extruder.

5. The method of claim 1 , wherein the hydroxy-carboxylic acid is selected from the monomer group consisting of glycolic acid, D-lactic acid and/or L-lactic acid, D-malic acid, L-malic acid, citric acid, L-tartaric acid and D-tartaric acid and mixtures thereof.

6. The method of claim 5 , wherein the hydroxy-carboxylic acid is D-lactic acid and/or L-lactic acid.

7. The method of claim 1 , where at least a part of the thin film evaporator operates at a temperature of 100 to 260° C.

8. The method of claim 1 , where at least a part of the thin film evaporator operates at a pressure of 0.0001 torr or lower.

9. The method of claim 2 , where prior to transferring the poly hydroxy-carboxylic acid to a thin film polymerization/devolatilization device or during operation of the thin film polymerization/devolatilization device a catalyst deactivator and/or stabilizer agent is added, thereby forming a deactivated catalyst and/or a stabilized catalyst.

10. The method of claim 2 , where cyclic dimers derived from hydroxy-carboxylic acid is less than 5 weight percent based on the total mass of the hydroxy-carboxylic monomers, oligomers and polymers.

11. The method of claim 2 , where an aliphatic or aromatic dicarboxylic acid and an aliphatic or aromatic diol are added just prior to transferring the poly hydroxy-carboxylic acid to the thin film polymerization/devolatilization device.

12. The method of claim 11 , where the mole ratio of the aliphatic or aromatic dicarboxylic acid to the aliphatic or aromatic diol is 0.95:1 to 1.05:1.

13. The method of claim 11 , where the mole ratio of the sum of the aliphatic or aromatic dicarboxylic acid and the aliphatic or aromatic diol to the hydroxy-carboxylic acid monomer of the poly hydroxy-carboxylic acid is 0.1 or less.

14. The method of claim 11 , where the mole ratio of the sum of the aliphatic or aromatic dicarboxylic acid and the aliphatic or aromatic diol to the hydroxy-carboxylic acid monomer of the poly hydroxy-carboxylic acid is 0.05 or less.

15. The method of claim 1 , where a polymerization catalyst is added to the poly hydroxy-carboxylic acid and the polymerization catalyst is selected from the group consisting of protonic acids, H 3 PO 4 , H 2 SO 4 , methane sulfonic acid, p-toluene sulfonic acid, polymerically supported sulfonic acid, metals, Mg, Al, Ti, Zn, Sn, metal oxides, TiO 2 , ZnO, GeO 2 , ZrO 2 , SnO, SnO 2 , Sb 2 O 3 , metal halides, ZnCl 2 , SnCl 2 , SnCl 4 , Mn(AcO) 2 , Fe 2 (LA) 3 , Co(AcO) 2 , Ni(AcO) 2 , Cu(OA) 2 , Zn(LA) 2 , Y(OA) 3 , Al(i-PrO) 3 , Ti(BuO) 4 , TiO(acac) 2 , (Bu) 2 SnO, Sn(II)octoate, Li carbonate, Zn diacetate dehydrate, Ti tetraisopropoxide, potassium carbonate, tin powder, solvates of any of these and mixtures of any of these.

16. The method of claim 2 , where at least a part of the thin film polymerization/devolatilization device operates at a pressure of less than about 0.001 torr.

17. The method of claim 2 , where at least a part of the thin film polymerization/devolatilization device operates at a pressure of less than about 0.01 torr.

18. The method of claim 2 , where at least a part of the thin film polymerization/devolatilization device operates at a pressure of less than about 0.1 torr.

19. The method of claim 2 , where at least a part of the thin film polymerization/devolatilization device operates at a pressure of less than about 1 torr.

20. The method of claim 1 , further comprising branching or cross linking the poly hydroxy-carboxylic acid.

21. The method of claim 20 , wherein a branching or cross linking agent is utilized to cross link the poly hydroxy-carboxylic acid and the cross-linking agent selected from the group consisting of 5,5′-bis(oxepane-2-one)(bis-8-caprolactone)), spiro-bis-dimethylene carbonate, peroxides, dicumyl peroxide, benzoyl peroxide, unsaturated alcohols, hydroxyethyl methacrylate, 2-butene-1,4-diol, unsaturated anhydrides, maleic anhydride, saturated epoxides, glycidyl methacrylate, irradiation and combinations of these.

22. The method of claim 1 , wherein the poly hydroxy-carboxylic acid is blended with a second polymer either when the poly hydroxy-carboxylic acid is transferred to the thin film polymerization/devolatilization device or after the thin film polymerization/devolatilization device.

23. The method of claim 22 , wherein the second polymer is selected from the group consisting of polyglycols, polyvinyl acetate, polyolefins, styrenic resins, polyacetals, poly(meth)acrylates, polycarbonate, polybutylene succinate, polyesters, polyurethanes, natural rubber, polybutadiene, neoprene, silicone, other poly hydroxy carboxylic acids, and combinations of these.

24. The method of claim 1 , comprising combining the poly hydroxy-carboxylic acid with fillers.

25. The method of claim 24 , wherein the filler is selected from the group consisting of silicates, layered silicates, polymer and organically modified layered silicate, synthetic mica, carbon, carbon fibers, glass fibers, boric acid, talc, montmorillonite, clay, starch, corn starch, wheat starch, cellulose fibers, paper, rayon, non-woven fibers, wood flours, whiskers of potassium titanate, whiskers of aluminum borate, 4,4′-thiodiphenol, glycerol and mixtures of these.

26. The method of claim 1 , further comprising combining the poly hydroxyl-carboxylic acid with a dye or pigment.

27. The method of claim 26 , wherein the dye is selected from the group consisting of blue 3, blue 356, brown 1, orange 29, violet 26, violet 93, yellow 42, yellow 54, yellow 82 and combinations of these.

28. The method of claim 1 , further comprising combining the poly hydroxy-carboxylic acid with a fragrance.

29. The method of claim 28 , wherein the fragrance is selected from the group consisting of wood, evergreen, redwood, peppermint, cherry, strawberry, peach, lime, spearmint, cinnamon, anise, basil, bergamot, black pepper, camphor, chamomile, citronella, eucalyptus , pine, fir, geranium, ginger, grapefruit, jasmine, juniper berry, lavender, lemon, mandarin, marjoram, musk, myrrh, orange, patchouli, rose, rosemary, sage, sandalwood, tea tree, thyme, wintergreen, ylang ylang, vanilla, new car or mixtures of these fragrances.

30. The method of claim 28 , wherein t

Assignees

• Xyleco Inc

Inventors

• Medoff Marshall
• Masterman Thomas Craig
• Paradis Robert

Classifications

• C08G63/06

  derived from hydroxycarboxylic acids · CPC title

• C08K5/0016

  Plasticisers · CPC title

• C08K5/0008

  Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59 · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08K2201/007

  Fragrance additive · CPC title