CA3009898A1

CA3009898A1 - Methods for converting glycerol to allyl compounds

Info

Publication number: CA3009898A1
Application number: CA3009898A
Authority: CA
Inventors: Aman Ullah; Yanet Rodriguez Herrero
Original assignee: University of Alberta
Current assignee: University of Alberta
Priority date: 2018-06-28
Filing date: 2018-06-28
Publication date: 2019-12-28

Abstract

The present disclosure is directed towards methods of converting glycerol to an allyl compound, involving deoxydehydrating glycerol with formic acid and heat to form allyl alcohol;
and esterifying the allyl alcohol with formic acid and heat to form allyl formate. In some instances, the heat is generated by a microwave. In further instances, the methods involve polymerizing the allyl alcohol or allyl formate to form poly(allyl alcohol) or poly(allyl formate).

Description

METHODS FOR CONVERTING GLYCEROL TO ALLYL COMPOUNDS
FIELD
[0001] The present disclosure relates generally to conversions of oleo-chemical byproducts.
More particularly, the present disclosure relates to methods for converting glycerol to allyl compounds.
BACKGROUND

[0002] About 10-11% (w/w) glycerol is generated as a main by-product of the biodiesel and oleochemical industries. It is estimated that the world biodiesel market will reach 37 billion gallons by 2016 [Yang F, Hanna MA, Sun R. Biotechnology for Biofuels, 2012.
5(1): p.13], leading to approximately 4 billion gallons of crude glycerol production [Hiremath A, Kannabiran M, Rangaswamy V. New Biotechnology, 2011. 28(1): p. 19-23]. According to estimates, about 2.8 million tonnes of crude glycerol is also produced in Alberta annually.
This crude glycerol is expensive to purify and becomes economically unviable to be used in food, pharmaceutical, or cosmetics industries, where pure glycerol is needed. In recent years, with a rapid expansion in biodiesel production, the biodiesel industry is facing a dilemma of how to meet an ever-growing biofuel demand, and manage excessive crude glycerol so that it does not pose a threat to the environment. Therefore, several approaches to utilize/dispose crude glycerol have been investigated, including compositing [Sadano Y, Toshimitsu R, Kohda J, Nakano Y, Yano T.
Journal of Material Cycles and Waste Management, 2010. 12(4): p. 308-313], animal feed [Nitayavardhana S, Khanal SK. Bioresource Technology,2011. 102(10): p.5808-5814], combustion [Coronado CR, Carvalho JA, Quispe CA, Sotomonte CR. 63(1): p.97-104], thermochemical [Luo X, Hu S, Zhang X, Li Y. Bioresource Technology, 2013. 139:
p.323-329;
Maglinao RL, He BB. Industrial & Engineering Chemistry Research, 2011. 50(10):
p.6028-6033], and biological/microbial conversions [Yazdani SS, Gonzalez R. Current Opinion in Biotechnology, 2007. 18(3): p.213-219; Xu J, Zhao X, Wang W, Du W, Liu D.
Biochemical Engineering Journal, 2012. 65: p.30-36]. Nevertheless, due to the high amount of impurities, direct utilization of the glycerol is not a viable option and a majority of current conversion approaches lead to either low conversion yields, high amount of co-products during conversion, and high energy consumption, which hampers the large scale viability of such processes. Therefore, the selective conversion of this bio-resource into high value products remains a challenge, and the development of new rapid, efficient and economically viable methodologies is desirable.

[0003] Therefore, the transformation of glycerol into valuable compounds has been investigated. Glycerol has been used in the production of hydrogen [Buffoni IN, Pompeo F, Santori GF, Nichio NN. Catalysis Communications, 2009. 10(13): p.1656-1660;
Sabourin-Provost G, Hallenbeck PC. Bioresource Technology,2009. 100(14): p.3513-3517], dihydroxyacetone [Painter RM, Pearson DM, Waymouth RM. Angewandte Chemie International Edition,2010. 49(49): p.9456-9459], propanediols [Gandarias I, Arias P, Requies J, Guemez M, Fierro J. Applied Catalysis B: Environmenta1,2010. 97(1): p.248-256; Guo L, Zhou J, Mao J, Guo X, Zhang S. Applied Catalysis A: Genera1,2009. 367(1): p.93-98], acrolein [Ning L, Ding Y, Chen W, et al. Chinese Journal of Catalysis,2008. 29(3):
p.212-214; Ulgen A, Hoelderich WE. Applied Catalysis A: Genera1,2011. 400(1-2): p.34-38; Alhanash A, Kozhevnikova EF, Kozhevnikov IV. Applied Catalysis A: Genera1,2010. 378(1):
p.11-18], glycerides [Xu J, Zhao X, Wang W, Du W, Liu D. Biochemical Engineering Journa1,2012. 65:
p.30-36], epichlorohydrin [Dibenedetto A, Angelini A, Aresta M, Ethiraj J, Fragale C, Nocito F.
Tetrahedron,2011. 67(6): p.1308-1313; Santacesaria E, Tesser R, Di Serio M, Casale L, Verde D. Industrial & Engineering Chemistry Research,2009. 49(3): p.964-970.], allyl alcohol [Kamm 0, Marvel C. Org.Syn,1921. 1: p.15-17; Arceo E, Marsden P, Bergman RG, Ellman JA.
Chemical Communications, 2009. (23): p. 3357-3359], acrylic acid [Li X, Zhang Y. ACS
Catalysis,2016. 1(6): p.143-150; Omata K, Matsumoto K, Murayama T, Ueda W.
Catalysis Today,2016. 259, Part 1: p.205-212.; Liu L, Wang B, Du Y, Zhong Z, Borgna A.
Applied Catalysis B: Environmenta1,2015. 174-175: p.1-12; Possato LG, Cassinelli WH, Garetto T, Pulcinelli SH, Santilli CV, Martins L. Applied Catalysis A: Genera1,2015. 492:
p.243-251; Shen L, Yin H, Wang A, Lu X, Zhang C. Chemical Engineering Journa1,2014. 244: p.168-177], lactic acid [Yin H, Zhang C, Yin H, Gao D, Shen L, Wang A. Chemical Engineering Journa1,2016.
288: p.332-343; Ftouni J, Villandier N, Auneau F, Besson M, Djakovitch L, Pinel C. Catalysis Today,2015. 257, Part 2: p.267-273], acrylonitrile [Calvino-Casilda V, Guerrero-Perez MO, Batiares MA. Applied Catalysis B: Environmenta1,2010. 95(3-4): p.192-196], and glycerol carbonate [Dibenedetto A, Angelini A, Aresta M, Ethiraj J, Fragale C, Nocito F.
Tetrahedron,2011. 67(6): p.1308-1313]. The transformation of glycerol requires in general use of solid catalysts including heteropolyacids [Martinuzzi I, Azizi Y, Zahraa 0, Leclerc J.
Chemical Engineering Science,2015. 134: p.663-670; Martin A, Armbruster U, Atia H.

European Journal of Lipid Science and Technology,2012. 114(1): p.10-23; Erfle S, Armbruster U, Bentrup U, Martin A, Bruckner A. Applied Catalysis A: Genera1,2011. 391(1-2): p.102-109], metal oxides [Braga TP, Essayem N, Valentini A. RSC Advances,2015. 5(113):
p.93394-93402; Chai S, Tao L, Yan B, Vedrine JC, Xu B. RSC Advances,2014. 4(9): p.4619-4630] and zeolites [Possato LG, Cassinelli WH, Garetto T, Pulcinelli SH, Santilli CV, Martins L. Applied Catalysis A: Genera1,2015. 492: p.243-251; dos Santos MB, Andrade HMC, Mascarenhas AJS. Microporous and Mesoporous Materials,2016. 223: p.105-113; Nafe G, Lopez-Martinez M-, Dyballa M, et al. Journal of Catalysis,2015. 329: p.413-424; Carrico CS, Cruz FT, dos Santos MB, et al. Journal of Catalysis,2016. 334: p.34-41] at high temperature. Coke deposition [Cheng CK, Foo SY, Adesina AA. Catalysis Today,2011. 164(1): p.268-274] is reported as a cause for catalyst deactivation and low selectivity and conversion. Allyl alcohol (AA) is an important building block for the production of glycidyl ethers [LIU
H, ZHANG Z, ZOU
J. Industrial Catalysis,2003. 12: p.006], esters [Mitsunobu 0, Yamada M.
Bulletin of the Chemical Society of Japan,1967. 40(10): p.2380-2382], amines [Kinoshita H, Shinokubo H, Oshima K. Organic Letters,2004. 6(22): p.4085-4088], poly (ally' alcohol) [Volodina V, Tarasov A, Spasskii S. Russian Chemical Reviews,1970. 39(2): p.140; Laible R. Chemical Reviews,1958. 58(5): p.807-843], and a variety of polymerizable esters like diallyl phthalate [Guo S. In: ACS Publications; 2000]. The low polymerization reactivity of AA
has found limited commercial use in polymers.
SUMMARY

[0004] In an aspect of the present disclosure, there is provided a method of converting glycerol to an allyl compound, comprising deoxydehydrating glycerol with formic acid and heat to form allyl alcohol; and esterifying the allyl alcohol with formic acid and heat to form allyl formate.

[0005] In an embodiment of the present disclosure, there is provided a method wherein the heat is generated by a microwave.

[0006] In another embodiment, there is provided a method wherein deoxydehydrating the glycerol with the formic acid and heat to form the allyl alcohol comprises heating the glycerol and the formic acid to about 195 C, and then heating the glycerol and the formic acid to about 240 C.

[0007] In another embodiment, there is provided a method further comprising isolating the allyl alcohol while heating the glycerol and the formic acid to about 240 C.

[0008] In another embodiment, there is provided a method further comprising cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid.

[0009] In another embodiment, there is provided a method wherein heating the glycerol and the formic acid to about 195 C, then heating the glycerol and the formic acid to about 240 C, and cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid is repeated three times.

[0010] In another embodiment, there is provided a method wherein esterifying the allyl alcohol with formic acid and heat to form allyl formate comprises heating the allyl alcohol and formic acid at about 60 C.

[0011] In another embodiment, there is provided a method, wherein the glycerol has a % purity of about 82-100%.

[0012] In another embodiment, there is provided a method wherein the ally' alcohol formed has a purity of ?. 90%.

[0013] In another embodiment, there is provided a method wherein the ally' alcohol formed has a purity of about 95%.

[0014] In another embodiment, there is provided a method wherein the allyl formate formed has a purity of 85 %.

[0015] In another embodiment, there is provided a method wherein the allyl formate formed has a purity of about 90%.

[0016] In another embodiment, there is provided a method further comprising polymerizing the ally' formate using a radical initiator and heat to form poly(ally1 formate).

[0017] In another embodiment, there is provided a method wherein the heat is generated by a microwave.

[0018] In another embodiment, there is provided a method wherein the poly(ally1 formate) has a molecular weight of at least 1000 g/mol.

[0019] In another embodiment, there is provided a method wherein the poly(ally1 formate) has a molecular weight of at least 1150 g/mol.

[0020] In another embodiment, there is provided a method wherein the radical initiator is a,ar-azoisobutyronitrile, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, or benzoyl peroxide.

[0021] In another aspect of the present disclosure, there is provided a use of the ally!
formate formed from the method as described herein as a solvent in spray lacquers, enamels, varnishes, or latex paints.

[0022] In another aspect, there is provided a use of the allyl formate formed from the method as described herein as an ingredient in paint thinners, paint strippers, varnish removers, or herbicides.

[0023] In another aspect, there is provided a use of the allyl formate formed from the method as described herein as a co-monomer with maleic anhydride, vinyl stearate, and vinyl triethoxysilane to prepare protective coatings for glass.

[0024] In another aspect of the present disclosure, there is provided a use of the poly(ally1 formate) formed from the method as described herein as a reactive plasticizer. In an .. embodiment, the poly(ally1 formate) is used as reactive plasticizer in thermoplastics processing.

[0025] In another aspect of the present disclosure, there is provided a method of converting glycerol to an allyl compound, comprising deoxydehydrating glycerol with formic acid by microwave-assisted distillation to form allyl alcohol; and esterifying the allyl alcohol with formic acid by microwave-assisted reflux to form allyl formate.

[0026] In another embodiment of the present disclosure, there is provided a method wherein deoxydehydrating the glycerol with the formic acid by microwave-assisted distillation to form the allyl alcohol comprises distilling the glycerol and the formic acid at about 195 C, and then distilling the glycerol and the formic acid up to about 240 C.

[0027] In another embodiment, there is provided a method further comprising isolating the allyl alcohol while distilling the glycerol and the formic acid up to about 240 C.

[0028] In another embodiment, there is provided a method further comprising cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid.

[0029] In another embodiment, there is provided a method wherein distilling the glycerol and the formic acid at about 195 C, then distilling the glycerol and the formic acid up to about 240 C, and cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid is repeated three times.

[0030] In another embodiment, there is provided a method wherein esterifying the allyl alcohol with formic acid by microwave-assisted reflux to form allyl formate comprises distilling .. the allyl alcohol and formic acid at about 60 C.

[0031] In another embodiment, there is provided a method wherein the glycerol has a % purity of about 82-100%.

[0032] In another embodiment, there is provided a method wherein the allyl alcohol formed has a purity of 90%.

[0033] In another embodiment, there is provided a method wherein the allyl alcohol formed has a purity of about 95%.

[0034] In another embodiment, there is provided a method wherein the ally, formate formed has a purity of 85%.

[0035] In another embodiment, there is provided a method wherein the ally! formate formed has a purity of about 90%.

[0036] In another embodiment, there is provided a method further comprising polymerizing the allyl formate using a radical initiator and microwave-assisted heating to form poly(allylformate).

[0037] In another embodiment, there is provided a method wherein the poly(ally1 formate) has a molecular weight of at least 1000 g/mol.

[0038] In another embodiment, there is provided a method wherein the poly(ally1 formate) has a molecular weight of at least 1150 g/mol.

[0039] In another embodiment, there is provided a method wherein the radical initiator is a,a'-azoisobutyronitrile, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, or benzoyl peroxide.

[0040] In another aspect of the present disclosure, there is provided a use of the allyl formate formed from the method as described herein as a solvent in spray lacquers, enamels, varnishes, or latex paints.

[0041] In another aspect, there is provided a use of the ally' formate formed from the method as described herein as a co-monomer with maleic anhydride, vinyl stearate, and vinyl triethoxysilane to prepare protective coatings for glass.

[0042] In another aspect, there is provided a use of the allyl formate formed from the method as described herein as an ingredient in paint thinners, paint strippers, varnish removers, or herbicides.

[0043] In another aspect of the present disclosure, there is provided a use of the .. poly(ally1 formate) formed from the method as described herein as a reactive plasticizer. In an embodiment, the poly(ally1 formate) is used as reactive plasticizer in thermoplastics processing.

[0044] In another aspect of the present disclosure, there is provided a method of converting glycerol to an ally' polymer, comprising deoxydehydrating glycerol with formic acid and heat to form allyl alcohol; and polymerizing the ally' alcohol using a radical initiator and heat to form poly(ally1 alcohol).

[0045] In another embodiment of the present disclosure, there is provided a method wherein, wherein the heat is generated by a microwave.

[0046] In another embodiment, there is provided a method wherein deoxydehydrating the glycerol with the formic acid and heat to form the allyl alcohol comprises heating the glycerol and the formic acid to about 195 C, and then heating the glycerol and the formic acid to about 240 C.

[0047] In another embodiment, there is provided a method further comprising isolating the allyl alcohol while heating the glycerol and the formic acid to about 240 C.

[0048] In another embodiment, there is provided a method further comprising cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid.

[0049] In another embodiment, there is provided a method wherein heating the glycerol and the formic acid to about 195 C, then heating the glycerol and the formic acid to about 240 C, and cooling the glycerol and formic acid to between about 95 - 100 C, and then adding more of the formic acid is repeated three times.

[0050] In another embodiment, there is provided a method wherein the glycerol has a % purity of about 82-100%.

[0051] In another embodiment, there is provided a method wherein the allyl alcohol formed has a purity of 90%.

[0052] In another embodiment, there is provided a method wherein the allyl alcohol formed has a purity of about 95%.

[0053] In another embodiment, there is provided a method wherein the poly(ally1 formate) has a molecular weight of at least 2400 g/mol.

[0054] In another embodiment, there is provided a method wherein the poly(ally1 formate) has a molecular weight of at least 2530 g/mol.
BRIEF DESCRIPTION OF THE FIGURES

[0055] Embodiments of the present disclosure will now be described, by way of example only, with reference to the attached Figures.

[0056] FIG. 1 depicts a sand bath (left) and microwave OEM Discovery (right) setup for preparation and purification of AA, wherein a round bottom flask was connected to a two-way adapter to connect a condenser and a receiving flask; temperature in the reaction mixture was measured by an immersed thermometer; flask was placed in a sand bath and covered with aluminum foil paper to preserve the heat; the round bottom flask was connected to a three-way adapter connected to addition funnel and a condenser; and, the condenser was connected to a vacuum adapter to connect the receiving flask.

[0057] FIG. 2 depicts FT-IR spectra monitoring for deoxydehydration of glycerol to ally!
alcohol assisted by formic acid I-every 5 minutes, and II-intensity of alkoxy band 1110 cm-1.

[0058] FIG. 3 depicts FT-IR spectra of AA (standard) and distilled collected during microwave-assisted distillation.

[0059] FIG. 4 depicts 1H-NMR spectra of crude distilled of AA and purified AA after K2CO3 treatment.

[0060] FIG. 5 depicts a FT-IR spectral comparison of AA (top) and AF
(bottom).

[0061] FIG. 6 depicts FT-IR spectra monitoring of the intensity of band 1273 during esterification of allyl alcohol and formic acid to allyl formate under conventional heating at 100 C.

[0062] FIG. 7 depicts a 1H-NMR spectral comparison of AA and allyl formate in c16-acetone.

[0063] FIG. 8 depicts PAA after drying, Table 2, entry 2, 3, and 4 from left to right (a, b, and c), respectively, wherein the PAA were light yellow to dark orange depending on reaction conditions.

[0064] FIG. 9 depicts GPO traces of polymers (Table 2, entry 1-6).

[0065] FIG. 10 depicts a FT-IR spectral comparison of PAA (bottom) under different conditions and AA. (CH) conventional heating (second from bottom), (MW) microwave.

[0066] FIG. 11 depicts 1H-NMR spectra of selected polymers in CD3OD
(Table 2, entry 1-2; AA-bottom, CH-1 top).

[0067] FIG. 12 depicts a TGA and DTG spectral comparison of polymers (Table 2, entry 2-5).

[0068] FIG. 13 depicts DSC thermograms of polymers (Table 2, entry 2-5; MW-2 top, MW-5 bottom, MW-3 second from bottom).

[0069] FIG. 14 depicts polyallylformate (PAF) after drying, wherein the PAF had a light yellow color.

[0070] FIG. 15 depicts GPO spectrum of polymer (Table 3, entry 2).

[0071] FIG. 16 depicts FT-IR spectra of polymers (Table 3, entry 2;
AA bottom, PAF
top).

[0072] FIG. 17 depicts 1H-NMR spectra of selected polymers in CD3OD
(Table 3, entry 2; AA bottom).

[0073] FIG. 18 depicts TGA and DTG spectra comparison of polymers (Table 3, entry 2).

[0074] FIG. 19 depicts DSC thermograms of polymers (Table 3, entry 2).
DETAILED DESCRIPTION

[0075] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0076] As used in the specification and claims, the singular forms "a", "an" and "the"
include plural references unless the context clearly dictates otherwise.

[0077] The term "comprising" as used herein will be understood to mean that the list following is non-exhaustive and may or may not include any other additional suitable items, for example one or more further feature(s), component(s) and/or ingredient(s) as appropriate.

[0078] The term "deoxydehydration" or "deoxydehydrating" as used herein refers to a chemical reaction wherein two adjacent hydroxyl groups in a compound are removed to form an alkene.

[0079] The term "esterification" or "esterifying" as used herein refers to a chemical reaction between a carboxylic acid and an alcohol to form an ester.

[0080] As used herein, "glycerol" refers to a compound having the chemical formula HOCH2CH(OH)CH2OH. In an example, as described herein, the term "glycerol" also refers to substituted glycerols.

[0081] As used herein, "allyl alcohol" refers to a compound having the chemical formula CH2CHCH2OH, and the structural formula CH2=CHCH2OH.

[0082] As used herein, "allyl formate" refers to a compound having the chemical formula CH2CHCH20C(0)H, and the structural formula CH2=CHCH20C(0)H.

[0083] As used herein, "microwave-assisted distillation" or "microwave-assisted reflux"
or "microwave-assisted heating" refers to a distillation or reflux or heating wherein a microwave is used as a heat source. Further, as used herein, "reflux" refers to a distillation involving the condensation of vapours, and the return of the condensed vapours to the system from which it was distilled.

[0084] As used herein, the term "polymer" means a molecule of high relative molecular mass, the structure of which essentially comprises multiple repetition of units derived from molecules of low relative molecular mass. The term "oligomer" refers to a molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of units derived from molecules of low relative molecular mass. A
molecule can be regarded as having a high relative molecular mass if the addition or removal of one or a few of the units has a negligible effect on the molecular properties. A molecule can be regarded as having an intermediate relative molecular mass if it has molecular properties which do vary significantly with the removal of one or a few of the units. (See IUPAC
Recommendations 1996 in (1996) Pure and Applied Chemistry 68: 2287-2311.). Thus, as used herein, the term "poly(ally1 alcohol)" refers to a polymer or oligomer comprising repetitions of units derived from ally! alcohol. Further, as used herein, the term "poly(ally1 formate)" refers to a polymer or oligomer comprising repetitions of units derived from allyl formate.

[0085] In an aspect of the present disclosure, there is provided methods for converting glycerol to allyl compounds. In an example, there is a method of converting glycerol to an allyl compound, comprising deoxydehydrating glycerol with formic acid and heat to form allyl alcohol; and esterifying the allyl alcohol with formic acid and heat to form allyl formate. In another example, there is a method of converting glycerol to an allyl polymer, comprising deoxydehydrating glycerol with formic acid and heat to form allyl alcohol; and polymerizing the allyl alcohol using a radical initiator and heat to form poly(ally1 alcohol).
In some examples, there is a method wherein the heat is generated by a microwave. In another example, there is a method of converting glycerol to an allyl compound, comprising deoxydehydrating glycerol with formic acid by microwave-assisted distillation to form allyl alcohol; and esterifying the allyl alcohol with formic acid by microwave-assisted reflux to form allyl formate.

[0086] Microwave-assisted heating, or microwave (MW) efficiency is based on a heating of materials by microwave dielectric heating effects. This phenomenon is considered dependent on an ability of a specific material (e.g., catalyst, solvent, or reagent) to adsorb microwave energy and convert it into heat. A key parameter is considered a 'loss factor' or 'loss tangent' (tans), which is a quotient between a dielectric loss (6") accounting for efficiency in converting electromagnetic radiation into heat, and a dielectric constant (E') that describes molecular polarization by an electric field. High tan8 values are indicative of high microwave absorption and rapid heating. It is considered that the resultant rapid and efficient conversions might be due to change in activation energy and pre-exponential factor of polar species under microwave irradiation.

[0087] In examples of the method described herein, there is an observed increased rate of converting glycerol to an allyl compound when using microwave-assisted heating relative to conventional heating methods, such as heating with a heating mantel and sand bath.
In other examples of the method described herein, the rate of converting glycerol to an allyl compound requires less than one hour to reach completion when using microwave-assisted heating, relative to several hours to reach completion when using conventional heating methods.

[0088] In other examples, there is a method wherein deoxydehydrating the glycerol with the formic acid and heat to form the ally' alcohol comprises heating the glycerol and the formic acid to about 195 C, and then heating the glycerol and the formic acid to about 240 'C.

[0089] In other examples, there is a method further comprising isolating the allyl alcohol while heating the glycerol and the formic acid to about 240 C.

[0090] In other examples, there is a method further comprising cooling the glycerol and the formic acid to between about 950 - 100 C, and then adding more of the formic acid.

[0091] In other examples, there is a method wherein heating the glycerol and the formic acid to about 195 C, then heating the glycerol and the formic acid to about 240 C, and cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid is repeated three times.

[0092] In other examples, there is a method esterifying the allyl alcohol with formic acid and heat to form ally' formate comprises heating the allyl alcohol and formic acid at about 60 C.

[0093] In other examples, there is a method wherein the glycerol has a % purity of about 82-100%. In other examples, there is a method wherein the allyl alcohol formed has a purity of .?. 90%, or about 95%. In other examples, there is a method wherein the allyl formate formed has a purity of 85 %, or about 90%.

[0094] In other examples, there is a method further comprising polymerizing the ally' formate using a radical initiator and heat to form poly(ally1 formate). In some examples, the heat is generated by a microwave.

[0095] In other examples, there is a method wherein the poly(ally1 formate) has a molecular weight of at least 1000 g/mol, or of at least 1150 g/mol.

[0096] In other examples, there is a method wherein the radical initiator is a,a'-azoisobutyronitrile, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, or benzoyl peroxide.

[0097] In yet other examples, there is a method wherein deoxydehydrating the glycerol with the formic acid by microwave-assisted distillation to form the allyl alcohol comprises distilling the glycerol and the formic acid at about 195 C, and then distilling the glycerol and the formic acid up to about 240 C.

[0098] In yet other examples, there is a method further comprising isolating the ally' alcohol while distilling the glycerol and the formic acid up to about 240 C.

[0099] In yet other examples, there is a method further comprising cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid.

[00100] In yet other examples, there is a method wherein distilling the glycerol and the formic acid at about 195 C, then distilling the glycerol and the formic acid up to about 240 C, and cooling the glycerol and the formic acid to between about 95 - 100 C, and then adding more of the formic acid is repeated three times.

[00101] In yet other examples, there is a method wherein esterifying the allyl alcohol with formic acid by microwave-assisted reflux to form allyl formate comprises distilling the allyl alcohol and formic acid at about 60 C.

[00102] In yet other examples, there is a method wherein the glycerol has a % purity of about 82-100%. In yet other examples, there is a method wherein the allyl alcohol formed has a purity of 90%, or of about 95%. In yet other examples, there is a method wherein the allyl formate formed has a purity of 85, or of about 90%.

[00103] In yet other examples, there is a method further comprising polymerizing the allyl formate using a radical initiator and microwave-assisted heating to form poly(allylformate).

[00104] In yet other examples, there is a method wherein the poly(ally1 formate) has a molecular weight of at least 1000 g/mol, or of at least 1150 g/mol.

[00105] In yet other examples, there is a method wherein the radical initiator is a,a1-azoisobutyronitrile, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, or benzoyl peroxide.

[00106] In yet another example, there is a method wherein the poly(ally1 formate) has a molecular weight of at least 2400 g/mol, or of at least 2530 g/mol.

[00107] In some examples of the method described herein, the glycerol is optionally substituted.

[00108] In other examples, there is a method wherein the heat is generated from a conventional heating source, such as but not limited to a heating mantle and a sand bath. In some examples, wherein the heat is generated from a conventional heating source, deoxydehydrating the glycerol with the formic acid and heat to form the allyl alcohol comprises heating the glycerol and the formic acid to about 210 C. In some examples, wherein the heat is generated from a conventional heating source, esterifying the allyl alcohol with the formic acid and heat to form the ally! formate comprises heating the allyl alcohol and the formic acid to about 60 C.

[00109] In another example, there is a use of the allyl formate formed from the method as described herein as a solvent in spray lacquers, enamels, varnishes, or latex paints. In another example, there is a use of the allyl formate formed from the method as described herein as an ingredient in paint thinners, paint strippers, varnish removers, or herbicides. In another example, there is a use of the ally! formate formed from the method as described herein as a co-monomer with maleic anhydride, vinyl stearate, and vinyl triethoxysilane to prepare protective coatings for glass. In another example, there is a use of the poly(ally1 formate) formed from the method as described herein as a reactive plasticizer.
In some examples, the poly(ally1 formate) is used as reactive plasticizer in thermoplastics processing.

[00110] The high reactivity of allyl alcohol makes it useful in the synthesis of pesticides, plastics, and intermediates. Allyl alcohol reacts with organic acids or acid anhydrides at moderate temperatures to produce esters. This high reactivity favors the synthesis of unsaturated polyesters with terminal allyl groups. Allyl alcohol reacts with unsaturated fatty acids to give drying oils. It can be copolymerized with styrene in the presence of oxygen for faster drying oils with excellent durability. It can be grafted to polyimides to improve heat and solvent resistance. The reaction of methyl glucoside polyethers with allyl alcohol, followed by bromination and addition of isocyanates, provides flame resistant polyurethane foams. Mono-or poly-functional allylic monomers also may be added as regulators or modifiers of vinyl polymerization for controlling molecular weight and polymer properties. The ally' resins have found extensive applications in electronic, electrical engineering, and biomaterials because of their physical and electrical properties. Further, co-polymerized allyl alcohol can be used as an intermediate in the production of flame-resistant materials that can be incorporated into plastics, resins, and fibers.

[00111] To gain a better understanding of the invention described herein, the following examples are set forth. It should be understood that these examples are for illustrative purposes only. Therefore, they should not limit the scope of this invention in anyway.

[00112] EXAMPLES

[00113] Example 1 ¨ Allyl monomers and polymers from glycerol

[00114] As by-products of deoxydehydration (DODH) of glycerol, formic acid, water, carbon dioxide, and allyl formate (AF) are produced. AF being a minor by-product in the DODH
process, previous research has focused on reducing or removing the AF, however it has been found, as described herein, that AF can be rapidly produced as a major product through easy esterification of AA with formic acid under microwave heating at low temperatures (60 C), and can be easily separated from an aqueous solution. Generally, conversion of glycerol to AA has been carried out at high temperatures by using conventional heating over extended periods of time. Overall, microwave-assisted pyrolysis of glycerol to syngas, esterification of glycerol to polysaccharides, as well as oxidation of glycerol to glycolic acid and oxalic acid have been reported under microwave activation. Recently, the direct conversion of glycerol to acrylonitrile at 100 C under microwave activation, where acrolein was the main product, has also been reported.

[00115] The intrinsic characteristics of glycerol, such as its low vapour pressure, high boiling point, high dielectric constant and polarity value make it a suitable solvent for microwave (MW) irradiation. Therefore, it was found, as described herein, that glycerol could be rapidly converted into AA and AF.

[00116] AF has several potential applications, such as it can be used as a solvent in spray lacquers, enamels, varnishes, and latex paints, and as an ingredient in paint thinners .. and strippers, varnish removers, and herbicides. It is used in liquid soaps, cosmetics, industrial and household cleaners, and dry-cleaning compounds. Further, polymerization of allyl esters under microwave conditions were investigated. Gels at relatively high conversion were obtained, which could be used as reactive plasticizers to improve the thermoplastics processing.

[00117] As described herein, the conversion of glycerol to allyl alcohol (AA), with an optional use of microwaves, and further esterification of AA to allyl formate was investigated.
The conversion of glycerol to AA using formic acid (FA) was studied in a OEM
discover microwave reactor using open and closed vessel conditions, as well as conventional heating.
Optimization of the reaction was carried out using statistical methods.
Intermediate and final products were characterized using proton nuclear magnetic resonance (1H-NMR), gas chromatography (GC) and Fourier transform infrared spectroscopy (FTIR). Rapid conversion of glycerol to AA was observed under microwave irradiation in the presence of FA. Particularly, addition of FA to preheated glycerol resulted in conversion into AA at lower temperatures and shorter time with higher purity as compared to conventional heating. This supported that glycerol could be rapidly converted to AA at lower temperatures using microwave irradiation.

[00118] Following the deoxydehydration (DODH) of glycerol to allyl alcohol (AA) AA was converted to allyl formate (AF) under solvent free conditions. AA and AF were then rapidly polymerized in a microwave seal-vessel. Products were characterized with IR
spectroscopy, proton nuclear magnetic resonance, differential scanning calorimetry, and thermal analysis.

[00119] Materials and Methods

[00120] Conversion of glycerol

[00121] Typically, glycerol (40 g, 0.43 mol, 82-100% purity) and formic acid (9.8 ml, 0.26 mol 98% purity) were charged into a 50 ml round bottom flask and placed in a microwave vessel. The flask was connected with a condenser set for downward distillation. Temperature .. within the reaction mixture was measured with an infrared temperature sensor. The temperature program involved ramping to 195 C, holding for one minute, ramping to 240 C, and holding 10 minutes. A fraction of the distillate was collected before 195 C. The fraction of distillate collected until 195 C was separated from a fraction of distillate collected between 195 C to 240 C. Once the mixture cooled to a temperature between 95 to 100 C, 7.0 ml (0.18 mol) of formic acid was added. Another distillation was carried out as described above. The reaction mixture was then cooled again, and a third portion of 7.0 ml of formic acid was added, following which a third distillation was carried out as described above. It was found that use of another type of acid, in place of formic acid, produced charring and very low yields.

[00122] The 195-240 C fractions of the distillate were treated with potassium carbonate to salt out AA and to neutralize the formic acid present. The mixture was distilled in the microwave. AA was collected in a fraction of distillate up to 80 C. AA was then converted to AF as follows.

[00123] AA (20 ml, 0.3 mol) and formic acid (11.2 ml, 0.3 mol) were placed in a round bottom flask in the microwave vessel. The vessel was connected to a reflux system. The reaction was run at 60 C for 30 min. Water was added to separate two layers, which were separated with a separatory funnel. The separated AF was used for further polymerization to poly (ally! formate). 1H-NMR was used to calculate yield and purity of each compound, AA
(95% purity) and AF (90% purity).

[00124] Polymerizations

[00125] Polymerization of Allyl Alcohol: AA (4 ml, 0.06 mol) was purged with nitrogen (10 min solution, 10 min headspace) and then tert-butyl hydroperoxide 0.75 ml (0.004 mol) was added. The reaction was carried out in a microwave sealed vessel at 130 C
for 10 min.

[00126] Polymerization of Allyl Formate: AF (4 ml, 0.04 mol) was purged with nitrogen (10 min solution, 10 min headspace) and then tert-butyl hydroperoxide 0.75 ml (0.004 mol) was added. The reaction was microwave sealed vessel at 130 C for 20 min at 100 PSI.

[00127] Characterization

[00128] Infrared spectra were recorded at room temperature in the region of cm-1 at 16 scans and resolution of 4 cm-lwith a Bruker Alpha FTIR
spectrophotometer (Bruker Optics, Esslingen, Germany) equipped with a single-bounce diamond ATR crystal.
FT-IR
samples for allyl alcohol monitoring were collected every minute, and kept cold until analysis the same day of reaction. For allyl formate monitoring, samples were collected every five minutes and analyzed immediately. Gel permeation chromatography of the polymers was carried out on the system equipped with styragel HR1 GPC column and detector (ELSD2000s, Santa Clara, CA, USA). The injected volume of sample was 10 pL with 0.5 mg/mL.
THF was used as eluent at a flow rate of 0.5 mL/min. Differential Scanning Calorimetry (DSC) analysis was performed on calorimetric apparatus (2920 Modulated DSC, TA Instrument, USA) under a stream of nitrogen gas. Pure indium sample was used to calibrate heat flow and temperature of the instrument. All samples were scanned in a temperature range of -50-50 C at a heating rate of 5 C per minute. Thermogravimetric analyses of all polymers were performed on TGA
Q50 (TA Instrument, USA) under a flow of nitrogen gas. Analyses were performed by heating samples in a temperature range of 25-600 C with heating rate of 10 C per minute. Proton nuclear magnetic resonance (1H NMR) samples were recorded on a AgilentNarian Inova three-channel 400 MHz spectrometer. Spectra were recorded in 5 mm NMR tubes. 3-(TrimethylsilyI)-1-propanesulfonic acid sodium salt was used as internal standard for 1H NMR
quantitation.

[00129] Results and Discussion

[00130] Microwave-assisted distillation

[00131] DODH of glycerol was carried out in a microwave-assisted distillation, and in a sand bath for comparison purpose (FIG. 1). At first, the sand bath distillation (210 C, 1819 min) for DODH of glycerol to AA under conventional heating was carried out and required several hours to reach completion (Table 1, entry 1). The reaction was followed by FT-IR
showing amounts of starting material still left during the reaction.

[00132] The microwave-assisted DODH of glycerol was carried out in an open-vessel .. connected to a distillation system (240 C, 54 min) (Table 1, entry 2) with continuous removal of AA from the reaction mixture through distillation. FIG. 2 depicts rapid conversion to AA using direct microwave heating through sequential additions of formic acid.
Intensity of the alkoxy band of allyl alcohol (vc_o= 1110 cm-1) as a function of time increased, and a maximum yield of allyl alcohol occured between 15 and 25 minutes after distillation started.
After a second addition of formic acid was added, only 10 minutes was required for allyl alcohol to start to distill again

[00133] Table 1: Comparison of the energy consumed by sand bath and microwave for the DODH of glycerol.
Energy Heating Glycerol Formic acid Entry Yield (%) tR (min) (KWh) method (mol) (mol) 1 MW 0.4 0.5 61 54 0.342 2 Sand bath 0.4 0.5 45 1819 5.672

[00134] As is apparent from the FT-IR spectra (FIG. 3), the broad peak at 1700 cm-1 is a characteristic band for the 0=0 of formic acid, because fraction 1 has formic acid as a major product. As the temperature increased, this peak was considerable decreased and the alkenyl C=C stretch (fraction 2, 1646 cm-1) was more evident. The 1H-NMR spectra confirmed removal of formic acid collected during the second fraction (FIG. 4), as per the peak at 8.06 in the crude distillate that disappeared after purification with K2CO3.

[00135] Microwave-assisted conversion of AA to AF

[00136] Esterification of AA to AF was carried out using open-vessel microwave under reflux (60 C, 30 min). Water was added to the mixture after reaction and two layers were formed. The top layer was AF and the bottom layer contained unreacted reagents. FT-IR (FIG.
5) analysis confirmed formation of AF with new peaks at 1162, 1273, 1648, and 1717 cm-1.
The peak related to 0-H band (3307 cm') disappeared after the two layers separation.

[00137] Ally' formate was studied under conventional heating to facilitate the sampling of products during reaction. Samples were taken every five minutes and measured immediately. The acyl vibration band of allyl formate (vc_o= 1273 cm-1) and the alkyl band of allyl alcohol were monitored. FIG. 6 shows after 20 minutes of reaction a higher yield of allyl formate and a reduction of intensity of the characteristic band of allyl alcohol (vc_o= 1110 cm1).
As the reaction evolved overtime, the equilibrium of the reaction was displaced to constantly shifting allyl formate to allyl alcohol and vice versa.

[00138] These results were corroborated by 1H-NMR analysis (FIG. 7). The terminal H
(Hf, 8.12) was in the spectrum of the allyl formate.

[00139] Polymerization of AA to poly(allyl) alcohol

[00140] Polymerization of allyl alcohol was performed in a microwave, solvent free, by a radical initiator mechanism. Reactions were carried out at 130 C under nitrogen in a seal tube using as initiator tert-butyl hydroperoxide or benzoyl peroxide.
Polymerization results are collected in Table 2.

[00141]
Table 2: Polymerization of allyl alcohol (AA) initiated by tert-butyl hydroperoxide (tBuO0H) and benzoyl peroxide (BP0) (a) silicon oil and (b) microwave.
Mw i Entry Monomer Initiator M/I Condition Temperature T mi ( C) (me n) (g/mol) la AA tBuO0H 100/6 N2 130 2b AA tBuO0H 100/6 N2 130 10 3b AA tBuO0H 100/6 N2 130 10 4b AA tBuO0H 100/6 N2 130 20 5b 6 b AA tBuO0H 100/6 N2 60,100 30, 15

[00142]
The isolated polymer was analyzed by IR spectroscopy, NMR spectroscopy, TGA, and DSC. The characteristic band in the IR spectra at 1644 cm-1, a sign of unsaturation, generally disappeared but was observed in some polymers indicating some monomer left in after polymerization (FIG. 10). 1H-NMR spectra of the polymers in CD3OD
solution were also obtained and peaks at 1.18, 1.51, 3.36, and 3.54 ppm for methylene and methyl moieties of the main chain, and hydroxyl and methylene moieties of the side chain, respectively were observed (FIG. 11).

[00143]
AA polymerized to give a molecular weight (Mw=2531 g/mol) higher than previously reported [Laible R. Chemical Reviews, 1958. 58(5): p.807-8431. It was found that the yield% increased with reaction time. Degradation and thermal stability behavior of the polymers were studied by TG (thermogravimetric) and DTG (derivative thermogravimetric) (FIG. 12). The major weight loss (%) of all polymers was in the temperature range of 170-230 C. The polymer labeled as entry 5 showed an initial weight lost starting at 170 C, while the polymer of entry 2 started at 230 C, which could be attributed to a difference in the polymer's molecular weights. DTG curves of polymers showed the temperature where maximum weight loss (Tmax) was observed. Polymers underwent different weight loss during the analyses.

[00144] DSC thermograms were also run (FIG. 13). The plots showed the 2nd heating run of the selected polymers. The polymers of entries 2-5 generally showed transition before -20 C, which could be the glass transition. All polymers had a crystallization peak and melting peak between 0-5 C, indicating the polymers crystallized. Polymer (entry 2) with a higher molecular weight underwent a big endothermic change with Tma.=30 C.

[00145] Polymerization of allyl formate to poly (ally! formate)

[00146] Allyl formate was polymerized with tert-butyl hydroperoxide (Table 3). When polymerization of the monomer was undertaken in a sealed-vessel at atmospheric pressure, no conversion occurred (Table 3, entry 1). Once the pressure was 100 PSI, with the same conditions, a yellow viscous solution was obtained (Table 3, entry 2). FT-IR
analysis confirmed the polymerization. A band at C=C (1646 cm-1) disappeared in FT-IR spectra of the polymer, while aC=0 band (1710 cm-1) increased in intensity. 1H-NMR spectra of the polymer in ci6-acetone solution were acquired and peaks at 1.45, 4.13, and 8.14 were observed. The molecular weight (Mw=1198) is the same order of the PAA polymers.

[00147] Table 3: Polymerization of allyl formate (AF) initiated by tert-butyl hydroperoxide on microwave in open vessel connected to reflux system in solvent free.
Mw Reaction Ti Monomer Initiator M/I Condition Pressure Temperature mmen (g/mol) number (PSI) (C) (i) 1 tBuO0H N2 0 130 20 2 tBuO0H N2 100 130 20

[00148] The initial weight loss of the polymer was after 170 C.
Compared with the polymers from the AA monomer, the maximum weight loss temperature of the allyl formate polymer was at a higher temperature (356 C). By 600 C, the polymer had losses of 100% in weight.

[00149] The embodiments described herein are intended to be examples only.
Alterations, modifications and variations can be effected to the particular embodiments by those of skill in the art. The scope of the claims should not be limited by the particular embodiments set forth herein, but should be construed in a manner consistent with the specification as a whole.

[00150] All publications, patents and patent applications mentioned in this Specification are indicative of the level of skill those skilled in the art to which this invention pertains and are herein incorporated by reference to the same extent as if each individual publication patent, or patent application was specifically and individually indicated to be incorporated by reference.

[00151]
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modification as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.

Claims

WHAT IS CLAIMED IS:

1. A method of converting glycerol to an allyl compound, comprising:
a) deoxydehydrating glycerol with formic acid and heat to form allyl alcohol;
and b) esterifying the allyl alcohol with formic acid and heat to form allyl formate.

2. The method of claim 1, wherein the heat is generated by a microwave.

3. The method of claim 1 or 2, wherein deoxydehydrating the glycerol with the formic acid and heat to form the allyl alcohol comprises heating the glycerol and the formic acid to about 195 °C, and then heating the glycerol and the formic acid to about 240 °C.

4. The method of claim 3, further comprising isolating the allyl alcohol while heating the glycerol and the formic acid to about 240 °C.

5. The method of claim 4, further comprising cooling the glycerol and the formic acid to between about 95 ° - 100 °C, and then adding more of the formic acid.

6. The method of claim 5, wherein heating the glycerol and the formic acid to about 195 °C, then heating the glycerol and the formic acid to about 240 °C, and cooling the glycerol and the formic acid to between about 95 ° - 100 °C, and then adding more of the formic acid is repeated three times.

7. The method of any one of claims 1-6, wherein esterifying the allyl alcohol with formic acid and heat to form allyl formate comprises heating the allyl alcohol and formic acid at about 60 °C.

8. The method of any one of claims 1-7, wherein the glycerol has a % purity of about 82-100%.

9. The method of any one of claims 1-8, wherein the allyl alcohol formed has a purity of 90%.

10. The method of claim 9, wherein the allyl alcohol formed has a purity of about 95%.

11. The method of any one of claims 1-10, wherein the allyl formate formed has a purity of ?. 85 %.

12. The method of claim 11, wherein the allyl formate formed has a purity of about 90%.

13. The method of any one of claims 1-12, further comprising polymerizing the allyl formate using a radical initiator and heat to form poly(allyl formate).

14. The method of claim 13, wherein the heat is generated by a microwave.

15. The method of claim 13 or 14, wherein the poly(allyl formate) has a molecular weight of at least 1000 g/mol.

16. The method of claim 15, wherein the poly(allyl formate) has a molecular weight of at least 1150 g/mol.

17. The method of any one of claims 13 to 16, wherein the radical initiator is a,a'-azoisobutyronitrile, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, or benzoyl peroxide.

18. Use of the allyl formate formed from the method of any one of claims 1-12 as a solvent in spray lacquers, enamels, varnishes, or latex paints.

19. Use of the allyl formate formed from the method of any one of claims 1-12 as an ingredient in paint thinners, paint strippers, varnish removers, or herbicides.

20. Use of the allyl formate formed from the method of any one of claims 1-12 as a co-monomer with maleic anhydride, vinyl stearate, and vinyl triethoxysilane to prepare protective coatings for glass.

21. Use of the poly(allyl formate) formed from the method of any one of claims 13-17 as a reactive plasticizer.

22. The use of claim 21, wherein the poly(allyl formate) is used as reactive plasticizer in thermoplastics processing.

23. A method of converting glycerol to an allyl compound, comprising:
a) deoxydehydrating glycerol with formic acid by microwave-assisted distillation to form allyl alcohol; and b) esterifying the allyl alcohol with formic acid by microwave-assisted reflux to form allyl formate.

24. The method of claim 23, wherein deoxydehydrating the glycerol with the formic acid by microwave-assisted distillation to form the allyl alcohol comprises distilling the glycerol and the formic acid at about 195 °C, and then distilling the glycerol and the formic acid up to about 240 °C.

25. The method of claim 24, further comprising isolating the allyl alcohol while distilling the glycerol and the formic acid up to about 240 °C.

26. The method of claim 25, further comprising cooling the glycerol and the formic acid to between about 95 ° - 100 °C, and then adding more of the formic acid.

27. The method of claim 26, wherein distilling the glycerol and the formic acid at about 195 °C, then distilling the glycerol and the formic acid up to about 240 °C, and cooling the glycerol and the formic acid to between about 95 ° - 100 °C, and then adding more of the formic acid is repeated three times.

28. The method of any one of claims 23-27, wherein esterifying the allyl alcohol with formic acid by microwave-assisted reflux to form allyl formate comprises distilling the allyl alcohol and formic acid at about 60 °C.

29. The method of any one of claims 23-28, wherein the glycerol has a %
purity of about 82-100%.

30. The method of any one of claims 23-29, wherein the allyl alcohol formed has a purity of 2. 90%.

31. The method of claim 30, wherein the allyl alcohol formed has a purity of about 95%.

32. The method of any one of claims 23-31, wherein the allyl formate formed has a purity of ? 85%.

33. The method of claim 32, wherein the allyl formate formed has a purity of about 90%.

34. The method of any one of claims 23-33, further comprising polymerizing the allyl formate using a radical initiator and microwave-assisted heating to form poly(allyl formate).

35. The method of claim 34, wherein the poly(allyl formate) has a molecular weight of at least 1000 g/mol.

36. The method of claim 35, wherein the poly(allyl formate) has a molecular weight of at least 1150 g/mol.

37. The method of any one of claims 34 to 36, wherein the radical initiator is a,a'-azoisobutyronitrile, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, or benzoyl peroxide.

38. Use of the allyl formate formed from the method of any one of claims 23-33 as a solvent in spray lacquers, enamels, varnishes, or latex paints.

39. Use of the allyl formate formed from the method of any one of claims 23-33 as a co-monomer with maleic anhydride, vinyl stearate, and vinyl triethoxysilane to prepare protective coatings for glass.

40. Use of the allyl formate formed from the method of any one of claims 23-33 as an ingredient in paint thinners, paint strippers, varnish removers, or herbicides.

41. Use of the poly(allyl formate) formed from the method of any one of claims 34-37 as a reactive plasticizer.

42. The use of claim 41, wherein the poly(allyl formate) is used as reactive plasticizer in thermoplastics processing.

43. A method of converting glycerol to an allyl polymer, comprising:
a) deoxydehydrating glycerol with formic acid and heat to form allyl alcohol;
and b) polymerizing the allyl alcohol using a radical initiator and heat to form poly(allyl alcohol).

44. The method of claim 43, wherein the heat is generated by a microwave.

45. The method of claim 43 or 44, wherein deoxydehydrating the glycerol with the formic acid and heat to form the allyl alcohol comprises heating the glycerol and the formic acid to about 195 °C, and then heating the glycerol and the formic acid to about 240 °C.

46. The method of claim 45, further comprising isolating the allyl alcohol while heating the glycerol and the formic acid to about 240 °C.

47. The method of claim 46, further comprising cooling the glycerol and the formic acid to between about 95 ° - 100 °C, and then adding more of the formic acid.

48. The method of claim 47, wherein heating the glycerol and the formic acid to about 195 °C, then heating the glycerol and the formic acid to about 240 °C, and cooling the glycerol and formic acid to between about 95 ° - 100 °C, and then adding more of the formic acid is repeated three times.

49. The method of any one of claims 43-48, wherein the glycerol has a %
purity of about 82-100%.

50. The method of any one of claims 43-49, wherein the allyl alcohol formed has a purity of 90%.

51. The method of claim 50, wherein the allyl alcohol formed has a purity of about 95%.

52. The method of any one of claims 43-51, wherein the poly(allyl formate) has a molecular weight of at least 2400 g/mol.

53. The method of claim 52, wherein the poly(allyl formate) has a molecular weight of at least 2530 g/mol.