Thermoplastic polymers synthesized from depolymerized lignin via free radical polymerization

Patent metadata

Field	Value
Publication number	US-12134673-B2
Application number	US-202418413501-A
Country	US
Kind code	B2
Filing date	Jan 16, 2024
Priority date	Feb 1, 2019
Publication date	Nov 5, 2024
Grant date	Nov 5, 2024

Abstract

One aspect of the present application relates to a method of synthesizing a thermoplastic polymer. This method includes providing a depolymerized lignin product comprising monomers and oligomers and producing lignin (meth)acrylate monomers and oligomers from the depolymerized lignin product. A thermoplastic lignin (meth)acrylate polymer is then formed by free radical polymerization of the lignin (meth)acrylate monomers and oligomers. The present application also relates to a branched chain thermoplastic lignin (meth)acrylate polymer which includes a chain transfer agent. The thermoplastic lignin based polymers of the present application can be used to prepare carbon fibers, and engineering thermoplastics. Mixtures of lignin (meth)acrylate monomers and oligomers are also disclosed.

First claim

What is claimed:

1. A method of forming carbon fibers, said method comprising:
providing a depolymerized lignin product comprising monomers and oligomers;
producing lignin (meth)acrylate monomers and oligomers from the depolymerized lignin product;
forming a thermoplastic lignin (meth)acrylate polymer by free radical polymerization of the lignin (meth)acrylate monomers and oligomers;
producing a carbon fiber precursor by subjecting the thermoplastic lignin (meth)acrylate polymer to a thermal treatment; and
extruding the thermally treated carbon fiber precursor to form carbon fibers.

2. The method of claim 1 , wherein said producing a carbon fiber precursor comprises:
heating the lignin (meth)acrylate polymer at a temperature of 100 to 230° C.

3. The method of claim 1 , wherein said extruding is carried out at a temperature of 100 to 230° C.

4. The method of claim 1 further comprising:
oxidizing and carbonizing the carbon fibers.

5. The method of claim 1 , wherein said providing a depolymerized lignin product comprises:
processing lignin by a method selected from the group consisting of fast pyrolyzing, solvolysis processing, hydrothermal liquefaction, kraft cooking, soda pulping, hydrolysis, super critical hydrolysis, organosolv processing, and sulfite cooking, to produce the depolymerized lignin product comprising monomers and oligomers.

6. The method of claim 1 , wherein said provided depolymerized lignin product is dissolved in a solvent.

7. The method of claim 6 , wherein said solvent is selected from the group consisting of methylene chloride, toluene, dioxane, THF, chloroform, cyclohexane, dimethyl sulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol, n-pentanol, chlorobenzene, diethylether, tert-butanol, 1,2,-dichloroethylene, diisopropylether, ethanol, ethylacetate, ethylmethylketone, heptane, hexane, isopropylalcohol, isoamylalcohol, methanol, pentane, n-propylalcohol, pentachloroethane, 1,1,2,2,-tetrachloroethane, 1,1,1,-trichloroethane, tetrachloroethylene, tetrachloromethane, trichloroethylene, water, xylene, benzene, nitromethane, glycerol, and mixtures thereof.

8. The method of claim 1 , wherein said producing lignin (meth)acrylate monomers and oligomers is carried out by reacting the depolymerized lignin product with a compound having a (meth)acryloyl group.

9. The method of claim 8 , wherein lignin acrylate monomers and oligomers are produced by reacting the depolymerized lignin product with a compound having an acryloyl group.

10. The method of claim 1 further comprising:
transforming alcohol groups in the lignin (meth)acrylate monomers and oligomers into acetate groups prior to said forming a lignin (meth)acrylate polymer.

11. The method of claim 10 , wherein said transforming is carried out by reacting the lignin (meth)acrylate monomers and oligomers under esterification conditions with an acetyl chloride, acetic acid, or an acetyl ester, prior to said forming a lignin (meth)acrylate polymer.

12. The method of claim 1 , wherein the lignin acrylate oligomers have a number average acrylic content of 1.001 to N acrylic units per oligomer, wherein N is the number average content of alcohol, ester, and phenolic groups in the mixture of the depolymerized lignin monomers and oligomers.

13. The method of claim 1 , wherein the lignin methacrylate oligomers have a methacrylic content of 1 to N methacrylic units per oligomer, wherein N is the number average content of alcohol, ester, and phenolic groups in the mixture of the depolymerized lignin monomers and oligomers.

14. The method of claim 1 , wherein the free radical polymerization is a RAFT process.

15. The method of claim 1 , wherein the free radical polymerization is an ATRP process.

Assignees

• Univ Iowa State Res Found Inc

Inventors

• Cochran Eric W
• Bai Xianglan
• Qu Wangda
• Huang Yuerui
• Luo Yixin

Classifications

• D01F11/122

  Oxygen, oxygen-generating compounds (anode oxidising D01F11/16) · CPC title

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title

• D01F11/125

  Carbon · CPC title

• C08J2397/02

  Lignocellulosic material, e.g. wood, straw or bagasse · CPC title