Direct alkoxylation of bio-oil

Patent metadata

Field	Value
Publication number	US-11639485-B2
Application number	US-202017097991-A
Country	US
Kind code	B2
Filing date	Nov 13, 2020
Priority date	Jun 11, 2016
Publication date	May 2, 2023
Grant date	May 2, 2023

Abstract

An alkoxylated bio-oil composition is provided. The alkoxylated bio-oil composition may include an alkoxylated bio-oil prepared from an alkoxylation of dewatered bio-oil. A method for preparing an alkoxylated bio-oil composition is provided. A copolymer composition is provided. The copolymer composition may include an alkoxylated bio-oil copolymer unit. A method for preparing a copolymer composition is provided.

First claim

The invention claimed is:

1. A method for preparing an alkoxylated bio-oil composition, the method comprising:
providing a dewatered bio-oil, wherein the dewatered bio-oil is obtained by dewatering a bio-oil, wherein the dewatered bio-oil is obtained from pyrolysis of wood or other lignocellulosic-containing biomass; and
contacting the dewatered bio-oil with an alkoxylation reagent consisting one of: an epoxide and a cyclic carbonate in a presence of a promoter under reaction conditions effective to form an alkoxylated bio-oil having a hydroxyl value of at least 415, wherein the alkoxylated bio-oil is derived from direct alkoxylation of the dewatered bio-oil using the alkoxylation reagent.

2. The method of claim 1 , further comprising dewatering a bio-oil to produce the dewatered by one or more of: distillation, vacuum distillation, azeotropic distillation, evaporation, salting out, freeze drying, adsorption, desiccation, and centrifugation.

3. The method of claim 1 , wherein the alkoxylated bio-oil is reacted with a polymerization precursor mixture under reaction conditions effective to form a copolymer composition, wherein a cross-linking agent comprised in the precursor crosslinks the alkoxylated bio-oil to form the copolymer.

4. The method of claim 1 , the alkoxylation reagent comprising one or more of:
ethylene oxide optionally substituted with one or more of a linear or branched C 1 -C 6 alkyl, a C 3 -C 6 cycloalkyl group, and a C 4 -C 10 aryl or heteroaryl group; ethylene carbonate optionally substituted with one or more of a linear or branched C 1 -C 6 alkyl, a C 3 -C 6 cycloalkyl group, and a C 4 -C 10 aryl or heteroaryl group; and trimethylene carbonate optionally substituted with one or more of a linear or branched C 1 -C 6 alkyl, a C 3 -C 6 cycloalkyl group, and a C 4 -C 10 aryl or heteroaryl group.

5. The method of claim 1 , the reaction conditions comprising one or more of:
the alkoxylation reagent being present in an amount greater than 5 wt % compared to an amount of the dewatered bio-oil;
the presence of a promoter, comprising one of an acid and a base;
the promoter being present in an amount between about 0.005 wt % and 5 wt % compared to an amount of the dewatered bio-oil;
a reaction temperature of between about 80° C. and about 180° C.;
a reaction pressure in pounds per square inch of between about 0 and about 600;
the dewatered bio-oil comprising a pyrolytic bio-oil or a catalytic pyrolytic bio-oil;
less than about 30 wt % water compared to the dewatered bio-oil; and
production of a free alkylene glycol byproduct at less than about 40 wt % compared to the dewatered bio-oil.

6. The method of claim 1 , further comprising:
contacting the dewatered bio-oil with a promoter;
allowing the dewatered bio-oil and the promotor to react for a period of time prior to contacting the dewatered bio-oil with the alkoxylation reagent;
optionally heating the dewatered bio-oil and the promoter, optionally under reduced pressure, for a period of time prior to contacting the dewatered bio-oil with the alkoxylation reagent, the promoter comprising an alkali metal hydroxide; and
optionally condensing a water vapor into a container separate from the dewatered bio-oil and the promoter prior to contacting the dewatered bio-oil with the alkoxylation reagent.

7. An alkoxylated bio-oil composition comprising:
an alkoxylated bio-oil having a hydroxyl value of at least 415, the alkoxylated bio-oil derived from direct alkoxylation of a dewatered bio-oil using an alkoxylation reagent consisting one of: an epoxide and a cyclic carbonate in a presence of a promoter, the dewatered bio-oil is obtained by dewatering a bio-oil, wherein the bio-oil is obtained from the pyrolysis of wood or other lignocellulosic-containing biomass; and
an amount of a free alkylene glycol of less than about 40 wt % compared to an amount of the alkoxylated bio-oil.

8. The alkoxylated bio-oil composition of claim 7 , the alkoxylated bio-oil characterized by one or more of:
comprising at least one polyalkylene glycol unit covalently bound to one or more of an acid, an alcohol, and a phenol functionality originated in the dewatered bio-oil;
the dewatered bio-oil comprising a pyrolytic bio-oil or a catalytic pyrolytic bio-oil; and
in comparison to the dewatered bio-oil, by one or more of: a reduced viscosity, an increased molecular weight, a lower gel permeation chromatography retention time, and a reduced hydroxyl value.

9. The method of claim 1 , wherein the alkoxylated bio-oil characterized by one or more of:
comprising at least one polyalkylene glycol unit covalently bound to one or more of an acid, an alcohol, and a phenol functionality originated in the dewatered bio-oil; and
in comparison to the dewatered bio-oil, by one or more of: a reduced viscosity, an increased molecular weight, a lower gel permeation chromatography retention time.

10. The method of claim 1 , wherein the dewatered bio-oil comprising water in less than about 3 wt % compared to the amount of dewatered bio-oil.

11. The method of claim 1 , the alkoxylated bio-oil produced from the dewatered bio-oil, the dewatered bio-oil comprising water of less than about 30 wt %.

12. The method of claim 1 , wherein the alkoxylated bio-oil has a hydroxyl value from 415 to 584.

13. The method of claim 3 , wherein the crosslinking reagent comprising one of:
at least two isocyanate groups;
at least two carboxylic acid derivative groups;
one or more of: a carboxylic acid, an ester, a acyl halide, a cyclic anhydride, and an anhydride; and
a phenol compound substituted at an aryl carbon with at least one —CR′R 2 OH, wherein: le is H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 CH 3 , C 6 H 5 , CHO, CHO, CH 2 CHO, CH 2 CH 2 CHO, CH 2 CH 2 CH 2 CHO, C(O)CH 3 , or CH 2 C(O)CH 3 ; and R 2 is H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 CH 3 , C 6 H 5 , CHO, CHO, CH 2 CHO, CH 2 CH 2 CHO, CH 2 CH 2 CH 2 CHO, C(O)CH 3 , or CH 2 C(O)CH 3 .

14. The method of claim 3 , the polymerization precursor comprising one of:
one or more of: toluene diisocyanate, methylene diphenyl diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane;
(ii) one or more of: a petroleum polyol, a bio-based polyester polyol, a foam forming surfactant, a trialkylamine, a polyalkylamino alkyl ether, an alkanol amine, a promoter, an antioxidant, a flame-retardant, an ultraviolet light stabilizer, a pigment, a dye, and a plasticizer;
(iii) one or more of: formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal, benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone, 2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione;
(iv) a phenol compound, a urea or a substituted urea, and one or more of: formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal, benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone, 2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione;
(v) a urea or substituted urea and one or more of: formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal, benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone, 2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione; and
(vi) a phenol-formaldehyde resin.

15. The method of claim 3 , wherein the forming of the copolymer further comprising contacting a viscosity-reducing modifier to one or more of the alkoxylated bio-oil and the polymeriz

Assignees

• Battelle Memorial Institute

Inventors

• Cafmeyer Jeffrey T
• Garbark Daniel
• Perry Mark J

Classifications

• C08G2101/00

  Manufacture of cellular products · CPC title

• C11C3/006 Primary

  by oxidation · CPC title

• C08G18/4891

  modified with higher fatty oils or their acids or by resin acids · CPC title

• C08G18/6677

  having at least three hydroxy groups · CPC title

• C08G2110/0033

  having integral skins · CPC title