WO2011143379A2 - Poly(dihydroferulic acid) a biorenewable polyethylene terephthalate mimic derived from lignin and acetic acid - Google Patents

Abstract

A novel biorenewable thermoplastic, poIy(dihyroferulic acid) (PHFA), is an effective polyethylene terephthalate (PET) mimic. The PHFA can be prepared by the homocondensation of acetyldihyroferulic acid, which, ultimately, can be synthesized from vanillin isolated from lignin or other biorenewable sources.

Description

DESCRIPTION

POLY(DIHYDROFERULIC ACID) A BIORENEWABLE POLYETHYLENE TEREPHTHALATE MIMIC DERIVED FROM LIGNIN AND ACETIC ACID

CROSS-REFERENCE TO RELATED APPLICATION The present application claims the benefit of U.S. Provisional Application Serial No. 61/334,342, filed May 13, 2010, which is hereby incorporated by reference herein in its entirety, including any figures, tables, or drawings.

The subject invention was made with government support under the National Science Foundation, Contract No. 0848236. The government has certain rights to this invention.

BACKGROUND OF INVENTION

The development of new polymeric materials from renewable resources is gaining considerable attention. Biorenewabihty is directed toward a sustainable raw material supply where the raw material is renewed from plants or other biological matter, generally through agricultural. Biorenewable polymers are pursued as environmentally friendly replacements for commodity plastics from petrochemical starting materials. The goal is to use low cost ready available starting materials from biorenewable resources such that biorenewable polymers can be competitive with current commercial plastics in the marketplace.

Rather than creating a biorenewable polymer directly from a crop with the limitations imposed by nature with respect to processing and properties, a practical goal is to develop polymers from monomers derived from biorenewable sources that are chemically identical to or a mimic of those derived from petroleum sources. In this manner the market for the biorenewable polymer need not be generated as materials with the properties to be provided by the new polymers are presently commodities. Additionally, polymerization techniques and processing technologies that are developed along with the monomers for the biorenewable polymers can be designed in light of the methods currently used to produce the commodity polymers.

In general, thermoplastics constitute more than 65% of all global polymer demand and have the possibility to be recycled by melt-processing. Thermoplastic biorenewable polymers are potentially recyclable, which is advantageous for consumer packaging and other high volume needs. A commercially important thermoplastic or its mimic that is prepared by a step-growth process is a particularly practical target for biorenewable monomers.

Step-growth produced polyethylene terephthalate (PET) is the third most common synthetic polymer and accounts for about 20% of world polymer production. This aromatic/aliphatic polyester has very useful thermal properties that are not displayed in an all-aliphatic commodity thermoplastic. PET displays a glass transition temperature (T_g) of 67 °C and a melting temperature (T_m) of 265 °C. The key aromatic monomer for preparation of PET, terephthalic acid, is derived from petroleum and its complementary monomer, ethylene glycol, is derived from petroleum or natural gas.

The design of a sustainable PET mimic requires an aromatic monomer. To this end, an attractive biorenewable source for the aromatic monomer is lignin. Lignin is found in all vascular plants and is the second most abundant naturally-occurring organic polymer, making up approximately 30% of wood. The extraction of lignin from wood is carried out in large scale in the paper pulping industry, and as such, constitutes an attractive source for a PET mimic.

BRIEF SUMMARY

An embodiment of the invention is directed to a biorenewable thermoplastic homopolymer comprising poly(dihyroferulic acid), which is a PET mimic. The poly(dihyroferulic acid) can have at least one acetoxy end group. In other embodiments of the invention an aromatic/aliphatic polymer of the structure:

wherein R¹, R², R³, R⁴ are independently H or OR where R is Q to C₆ alkyl can be produced and can have an acetoxy end-group. Some of these polymers can be prepared from monomers that can be derived from biorenewable resources.

An embodiment of the invention is directed to a method of preparing poly(dihyroferulic acid) where acetyldihyroferulic acid and a catalyst are combined and the acetyldihyroferulic acid polymerized to poly(dihyroferulic acid) with the liberation of acetic acid. The acetyldihyroferulic acid can be derived from a biorenewable source, for example lignin. In another embodiment of the invention, the polymerization of a monomer of the structure:

where R¹, R², R³, R⁴ are independently H or OR where R is Ci to C₆ alkyl can be combined with a catalyst and polymerized to any polymer of the structure:

wherein R¹ , R², R³, R⁴ are independently H or OR where R is C_\ to C₆ alkyl with the liberation of acetic acid. For these polymerizations, the catalyst comprises an oxide, alkoxide or acetate of Sb, Ti, Ge, Fig, Si, Zr, Al, or Zn, such as Zn(OAc)₂. The polymerization can be carried out under vacuum and can be carried out at a temperature of 200 to 300 °C.

BRIEF DESCRIPTION OF DRAWINGS

Figure 1 shows a synthetic scheme for the preparation of poly(dihydroferulic acid), PFIFA, from biorenewable feedstocks in accordance with an embodiment of the invention.

Figure 2 is a Ή NMR spectrum of acetylferulic acid.

Figure 3 is a ^ljC NMR spectrum of acetylferulic acid.

Figure 4 is a Ή NMR spectrum of acetyldihydroferulic acid.

Figure 5 is a C NMR spectrum of acetyldihydroferulic acid.

Figure 6 is a Ή NMR spectrum of PHFA according to an embodiment of the invention with peak assignment indicated that was used for end-group analysis for the determination of the degree of polymerization.

Figure 7 is a ^ljC NMR spectrum of PHFA according to an embodiment of the invention.

Figure 8 is a DSC thermogram of PHFA in accordance with an embodiment of the invention. Figure 9 is a TGA plot for PHFA in accordance with an embodiment of the invention.

DETAILED DISCLOSURE

Embodiments of the invention are directed to a novel biorenewable polymer, po 1 y ( d i hydro fcrul ic acid) (PHFA), and a method for its preparation by the step-growth polycondensation of a biorenewable monomer, acetyldihydroferulic acid. The preparation of the biorenewable polymer begins with the aromatic aldehyde, vanillin, which can be extracted from lignin at up to about 5% by mass of the lignin. As shown in Figure 1 , vanillin is condensed with acetic anhydride in the presence of a base, a Perkin reaction, to yield acetylferulic acid. Acetic anhydride can be prepared commercially from biorenewable sources. Acetylferulic acid is subsequently reduced with H₂ to acetyldihydroferulic acid. Polytransesterification of the acetyldihydroferulic acid results in the desired PHFA with the liberation of acetic acid, which can be recycled for the preparation of acetic anhydride if desired. As the PHFA results from the self condensation of acetyldihydroferulic acid, no molecular weight limitations due to a stoichiometric imbalance of reactive functionality is possible. The net transformation from vanillin to PHFA has the potential for the very efficient use of the renewable resources. In another embodiment dihyroferulic acid can be polymerized to PHFA.

The PHFA is biorenewable and is potentially recyclable. PHFA is a polyethylene terephthalate (PET) mimic, displaying a T_m of 234 °C and a T_g of 73 °C. Hence, the thermal processing and recycling of PHFA and PET, T_m = 265 °C and T_s = 67 °C, is inherently similar, and for many applications the thermal properties of PHFA are arguably an improvement over those of PET. Devices, such as plastic water bottles, which are commonly made of PET, have uses confined by the thermal properties of the amorphous phase reflected in the 7'_g, and can be formed from PHFA with no compromise. Since most PET devices are rarely subjected to extremely high temperatures during routine use, the lower T_m of PHFA implies that it can be readily substituted and allow a facile processability with lower energy consumption. PHFA also has a cooling-cycle crystallization temperature that is 17 °C higher (207 °C) than that of PET (190 °C), suggesting a faster rate of crystallization which is conducive to greater throughput of PHFA devices during extrusion, spinning, or molding processes than is possible for PET that has a lamentably slow crystallization rate. Additionally, PHFA typically exhibits a peak decomposition temperature near 462 °C (50% mass loss under nitrogen, as measured by thermal gravimetric analysis), which is comparable to that of PET (470 °C).

In one embodiment of the invention, the polymerization method for formation of PHFA involves melting acetyldihydroferulic acid in the presence of a catalyst. The catalyst can be any that can be used for the polymerization to PET such as Sb₂0₃. Additionally other oxides, alkoxides or acetates of Sb, Ti, Ge, Hg, Si, Zr, Al, or Zn can be used, for example Zn(OAc)₂-2H₂0. Polycondensation can be carried out at temperatures as low as about 200 to 220 °C but can be carried out at higher temperatures in excess of 220 °C but below about 370 °C, for example 280 to 300 °C. The polymerization can be carried out under a dynamic vacuum to effectively remove acetic acid and drive the polymerization. Traditional "solid stating" and either standard or flow induced "crystallizing" steps that are used for the preparation of PET can be included for the processing of PHFA.

The method employed to provide the biorenewable acetyldihydroferulic acid can provide other aromatic/aliphatic polyesters from a phenyl substituted 3-(4- acetoxyphenyl)propanoic acid. For example, syringaldehyde, which can also be isolated from lignin, can be converted into 3-(4-acetoxy-3,5-dimethoxyphenyl)acrylic acid, reduced to 3-(4-acetoxy-3,5-dimethoxyphenyl)propanoic acid and self-condensed to a poly(3-(4- hydroxy-3,5-dimethoxyphenyl)propanoic acid) in an analogous manner to that for the preparation of PHFA. Hence, any monomer of the structure:

w here R¹, R², R³, R⁴ are independently H or OR where R is Ci to C₆ alkyl can be employed to prepare an aromatic/aliphatic polyester of the structure:

where R¹, R², R³, R⁴ are independently H or OR where R is C to C₆ alkyl, according to an embodiment of the invention. The aromatic/aliphatic polyester can have acetoxy terminal units. METHODS AND MATERIALS

Unless otherwise noted, all solvents were sparged with nitrogen, dried over molecular sieves using an MBraun Solvent Purification System, dispensed into oven-dried Straus flasks, and degassed by stirring under reduced pressure for 20 minutes. Toluene for polymerization reactions was distilled from sodium/benzophenone under a nitrogen atmosphere and stored in an oven-dried Straus flask until used. All other chemicals and solvents were used as received.

Proton nuclear magnetic resonance (1H NMR) spectra were recorded using a Varian Mercury 300 MHz spectrometer. Chemical shifts are reported in parts per million (ppm) downfield relative to tetramethylsilane (TMS, 0.0 ppm) or residual proton in the specified solvent. Coupling constants (J) are reported in Hertz (Hz). Multiplicities are reported using the following abbreviations: s, singlet; d, doublet; t, triplet; q, quartet; quin, quintuplet; m, multiplet; br, broad.

Differential scanning chromatographs were obtained with a DSC Q1000 from TA instruments. About 5-10 mg of each sample were massed and added to a sealed pan that went through a heat/cool/heat cycle at 10°C/min. Reported data are from the second full cycle. The temperature range depends on the experiment, but was limited to 300°C by the instrument.

Thermogravimetric analyses were measured under nitrogen with a TGA Q5000 from TA Instruments. About 5-10 mg of each sample was heated at 50°C/min from 25-600°C.

Viscosity measurements were performed at 35°C in a 1 :2 mixture of phenol: 1 ,1 , 2,2 tetrachloroethane with a CANNON -Ubbelohde type 150 viscometer. -(4-acetoxy-3-methoxyphenyl)acrylic acid (acetylferulic acid)

In a round bottomed flask, 30.04 g of vanillin (0.197 mol) and 26.0 g of sodium acetate (0.317 mol) were dissolved in 200 mL of acetic anhydride (2.12 mol). About 1 mL of pyridine was added to the flask and the mixture was heated to reflux. After 24h, the brown solution was poured over about 500 g of crushed ice and the solution was stirred until the appearance of a yellow-brown solid. The flask was left overnight in the freezer and a dark yellow solid was obtained by filtration. The crude solid was recrystallized from acetic acid/water to give 32.3 g of a yellow beige solid in a 69% yield.

Ή NMR (DMSO) (Figure 2): δ 12.35 (br s, 1H, COOH), 7.56 (d, J = 1 5.9 Hz, 111. Ar-CH) , 7.46 (d, J = 1.7 Hz, 1H, Ax—H ), 7.24 (del J = 8.2 Hz, 1.7 Hz, 1H, Ar-H), 7.09 (d, J = 8.2 Hz, 1 H, Ar-H). 6.56 (d, J = 15.9 Hz, 1H, CHCOOH), 3.8 (s, 3H, OCH₃), 2.24 (s, 3Η. C¾).

C NMR (DMSO) (Figure 3): δ 168.4, 1 67.6. 151.1 , 143.4, 140.8, 138.3, 123.2, 121.3, 1 19.5, 1 1 1.8, 56.0, 20.4. -(4-acetoxy-3-niethoxyphenyl)propanoic acid (acetyldihydroferulic acid)

A 15.0 g (0.064 mol) portion of acetylferulic acid was dissolved in 230 mL of a 1 5 :8 by volume mixture of tetrahydrofurammethanol. The solution and 1.5 g of 10% palladium on charcoal was placed in a Parr pressure reactor. The reaction mixture was stirred at room temperature under 60 psi of hydrogen for 5 hours. The resulting black suspension was filtered through celite to remove the palladium on charcoal. The resulting clear brown solution was dried over magnesium sulfate and concentrated in vacuo. The solid was then dissolved in tetrahydrofuran and precipitated by addition to hexanes giving 12.8 g of an off- white product in 85% yield.

lR NMR (DMSO) Figure 4): δ 12.15 (br s, 1Η, COOH), 6.98 (s, 1 Η, Ar-H), 6.93 (d, J = 7.9 Hz, 1H, Ar-H), 6.76 (d, J = 7.9 Hz, 1H, Ar-H), 3.72 (s, 3Η, OCH₃), 2.79 (t, J = 8.0 Hz, 2H, Ar-CH₂), 2.53 (t, J= 8.0 Hz, 2H, C¾COOH), 2.20 (s, 3H, CH₃).

¹³C NMR (DMSO) (Figure 5): δ 174.1 , 168.9, 150.8, 140.1 , 137.8, 122.7, 120.3, 1 13.1, 55.9, 35.5, 30.5, 20.7. Polymers

A series of polymerization of acetyldihydroferulic acid were carried out as summarized in the following tables where Table 1 gives the polymerization conditions and polymer size and viscosity and Table 2 gives the thermal properties of the polymers. Polymer Molecular Weight Analysis

Viscosity analysis

Intrinsic viscosity measurements were performed with a Ubbelohde viscometer. 15 ml, of clean 1 : 2 mixture of phenol: 1, 1, 2, 2- tetrachloroethane were poured in the viscometer and allow to thermally equilibrate for 2h. Exactly 1 mL of about 8 g/L solution of polymer was added for each measurement until the final volume is 20 mL in the viscometer giving a final concentration of about 2 g/L.

[η] = lim --^ with η =

c to

c * 0

¾L = /(c)

c

From a Kramer plot and extrapolating to infinitely dilute solution (c -> 0), the intrinsic viscosity is obtained. The value is then related to the Mark-Houwink constant for PET in the same solvent and temperature.

[η] = 1.09 x 10^"2 _V° ⁸⁴

End group analysis

End group analysis was used to determine the degree of polymerization of the polymer. In an NMR analysis, the chemical environment for the end group is different from that of the repeat unit in the middle of the polymer chain. For PHFA, as shown in Figure 6, the end groups are carboxylic acid and acetyl groups, which bears a methyl group that has a chemical shift of about 2.4 ppm. Four aliphatic hydrogens, associated with each repeat unit of the chain, resonate near 2.9 to 3.1 ppm. By measuring the integration of the methyl group hydrogens 7_eiUi by ¹H NMR and that of the methylene hydrogens (/,,) present in each repeat unit, the number of repeat units (the degree of polymerization, DP) and by the repeating unit's molecular weight, RU, the number average molecular weight of the polymer chain is determined using the following equation.

^ /

DP =— x—^s- and M„ = RU x DP

' end Table 1 Polymerization results and characterization of poly(dihydroferulic acid), PHFA.

melt vacuum stirring yield

Entry T_v (°C) catalyst"

time (h) time (h) stops (h) [u]^b DP^d M <

(%)

acetyl dihydroferulic acid -> PHFA

1 '200 - 220 None 2 2 1.5 83 31 12,900 27 4,800

2 200 - 220 Sb₂0₃ 2 2 0.5 67 29 12,000 23 4,100

3 200 - 220 Zn(OAc)₂ 2 2 0.5 82 27 1 1,000 38 6,800

4 200 - 220 Zn(OAc)₂ 2 6 0.5 91 36 15,500 50 8,900

5 220 - 250 Zn(OAc)₂ 2 6 0.5 68 35 14,800 100 17,800

6 200 - 220 Zn(OAc)₂ 2 0.17 - 75 17 6,300 17 3,000 dihydroferulic acid -> PHFA

7 200 - 220 Sb₂0₃ 5 6 ~5 n.d. n.d. 3.5^e 630^{e a}Catalyst loading = 1 mol%. Intrinsic viscosity measured with an Ubbelohde viscometer in a

1 :2 solution of phenol/ 1 , 1 ,2,2-tetrachloroethane at 35°C. intrinsic viscosity (niL/g) calculated with [η]= 1.09 x 10^"2 _v ^0,84. ^dDegree of Polymerization measured by Ή NMR end group analysis. ^eGPC analysis.

Table 2 Differential Scanning Calorimetry (DSC), as shown in Figure 8, and

Thermogravimetric Analysis (TGA), as shown in Figure 9, data for PHFA from Table 1, entries \-6.^a

major T_m minor T_m AH melt comp.

Entry 7g (°C)

(°C) (°C) r_c (°c)^a AH cryst T 50% de

(J/g) (J/g) ^a (°C)^b

1 74.0 242.6 228.9 47.7 207.1 51.0 471

2 73.4 234.4 216.9 43.5 193.4 48.1 462

3 73.3 234.1 220.4 39.8 195.8 44.9 461

4 66.9 231.2 215.2 43.2 189.3 46.9 464

5 66.6 216.3 27.9 162.2 26.8 456

6 65.1 240.3 219.6 51.4 203.2 54.6 452

"Crystallization was observed on the cooling scan, but not the heating scan. The temperature at which 50% mass loss is observed. TGA was performed under nitrogen.

Poly(3-(4-hydroxy-3-methoxyphen I)propanoic acid) (poly(dihyroferulic acid), PHFA)

Table 1, Entry 1. 1.61 g (6.8 mmol) of acetyldihydro lerulic acid were melted under nitrogen for 2h and vacuum was applied for 2h leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid/dichloromethane and precipitated with methanol. 1.0 g of off-white product was obtained by filtration in 83% yield.

1H NMR (CF3COOD/CDCI3): δ 6.92 (m, 3H, Ar-H), 3.84 (s, 311. OC//3), 3.1 1 (m, 2H, C¾), 3.00 (m, 2H, CH₂).

^{I 3}C NMR (DMSO): δ 176.1 , 150.9, 140.6, 138.3, 123.2, 121.8, 1 13.9, 56.6, 36.2, 31.2.

Table 1, Entry 2. 1 .61 g (6.8 mmol) of acetyldihydroferulic acid and 0.021 g (0.072 mmol) of antimony trioxide (1 mol%) were melted under nitrogen for 2h and vacuum was applied for 2h leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid/dichloromethane and precipitated with methanol. 0.8 g of off-white product was obtained by filtration in 67% yield.

1H NMR (CF3COOD/CDCI3): δ 6.88 (m, 3H, Ar-H), 3.80 (s, 3H, OCH3), 3.07 (m, 2H, C¾), 2.96 (m, 2H, CH₂).

¹³C NMR (CF3COOD/CDCI3): δ 175.5, 150.4, 140.1 , 137.8, 122.6, 120.0, 113.4, 56.1, 35.8, 30.7.

Table 1, Entry 3. 1.63 g (6.8 mmol) of acetyldihydroferulic acid and 0.018 g (0.082 mmol) of zinc diacetate dihydrate (1 mol%) were melted under nitrogen for 2h and vacuum was applied for 2h leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid/dichloromethane and precipitated with methanol. 1.0 g of off-white product was obtained by filtration in 82% yield.

1H NMR (CF₃COOD/CDCI3): 6.92 (m, 3H, Ar-H), 3.84 (s, 3Η, OCH₃), 3.11 (m, 2Η, CH₂), 3.00 (m, 2Η, CH₂).

¹³C NMR (CF₃COOD/CDCI₃): 175.4, 150.4, 140.0, 137.8, 122.6, 121.7, 1 13.3, 56.0, 35.7, 30.7.

Table 1, Entry 4. 1.63 g (6.8 mmol) of acetyldihydroferulic acid and 0.018 g (0.082 mmol) of zinc diacetate dihydrate (1 mol%) were melted under nitrogen for 2h and vacuum was applied for 6h leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid/dichloromethane and precipitated with methanol. 1.1 g of off-white product was obtained by filtration in 91% yield. 1H NMR (CF₃COOD/CDCI3) (Figure 6): δ 6.90 (m, 3H, Ar-H), 3.83 (s, 3Η, OCH₃), 3.10 (m, 2Η, CH₂), 2.99 (m, 2Η, CH₂).

¹³C NMR (CF₃COOD/CDCI₃) (Figure 7): δ 175.5, 150.4, 140.0, 137.7, 122.6, 121.1 , 1 13.3, 56.0, 35.7, 30.7.

Table 1, Entry 5. 1.61 g (6.8 mmol) of accty ldihydro ferulic acid and 0.017 g (0.077 mmol) of zinc diacetate dihydrate (1 mol%) were melted under nitrogen at 220-250°C for 2h and vacuum was applied for 6h leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid/dichloromethane and precipitated with methanol. 0.82 g of off-white product was obtained by filtration in 68% yield.

Ή NMR (CF3COOD/CDCI3): δ 6.88 (m, 3Η, Ar-H), 3.80 (s, 3Η. OCH3), 3.07 (m, 2Η, CH₂), 2.96 (m, 2Η, CH₂).

¹³C NMR (CF3COOD/CDCI3): δ 175.0, 150.4, 139.8, 137.7, 122.5, 121.0, 1 13.1 , 56.0, 35.7, 30.7.

Table 1, Entry 6. 1.61 g (6.8 mmol) of acetyldihydrofcrulic acid and 0.017 g (0.077 mmol) of zinc diacetate dihydrate (1 mol%) were melted under nitrogen for 2h and vacuum was applied for 10 min, leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid/dichloromethane and precipitated with methanol. 0.90 g of off-white product was obtained by filtration in 75% yield.

Ή NMR (CF3COOD/CDCI3): δ 6.88 (m, 3Η, Ar-H), 3.80 (s, 3Η, OC//3), 3.07 (m, 2Η, CH₂), 2.96 (m, 2Η, C¾).

¹³C NMR (CF3COOD/CDCI3): δ 176.0, 150.5, 140.4, 138.0, 122.8, 121.6, 1 13.7, 56.2, 35.9, 30.9.

3-(4-hydroxy-3-methoxyphenyl)propanoic acid (dihyroferulic acid)

A solution was prepared from 8.0 g (0.034 mol) of acetyldihydroferulic acid and 4.7 g

(0.1 18 mol) of sodium hydroxide in 100 mL of water and refluxed for 5h. After cooling to room temperature, the aqueous solution was acidified with hydrochloric acid and extracted with dichloromethane. The organic layer was washed with brine and dried over magnesium sulfate. The evaporation of the solvent left a yellow crude product that was dissolved in dichloromethane and precipitated in hexanes to yield 5.5 g of an off- white powder in 83% yield.

Ή NMR (CDC ): δ 6.87 (d, J = 8.0 Hz, I I I, Ar-H), 6.73 (br s, 111. Ar-H), 6.71 (d, J = 8.0 Hz, 1H, Ar-H), 3.88 (s, 3Η, OCH3), 2.90 (t, J = 7.8 Hz, 2H, Ar-CH₂), 2.70 (t, J = 7.8 Hz, 2H, CH2COOH).

¹³C NMR (CDCI₃): δ 179.2, 146.4, 144.1 , 132.0, 120.8, 1 14.4, 1 10.9, 55.8, 36.0, 30.3. -(4-hydroxy-3-methoxyphenyI)propanoic acid) (oligo(dihyroferulic acid))

Table 1, Entry 7. 1.61 g (8.2 mmol) of dihyroferulic acid and 0.0195g (0.067 mmol) of antimony trioxide (1 mol%) were heated under nitrogen for 5h and vacuum was applied for 6h. At the end of the 6h period, the product was still a brown melt in the flask. The product was dissolved in dichloromethane/trifluoroacetic acid and only 0.07g (5%) of product precipitated upon addition of methanol. The methanol was subjected to rotary distillation, leaving 1.5 g of brown, amorphous solid that was analyzed by GPC showing only low molecular weight material.

All patents, patent applications, provisional applications, and publications referred to or cited herein are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.

It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.

Claims

CLAIMS We claim:

1. A biorenewable thermoplastic homopolymer comprising poly(dihyroferulic acid).

2. The biorenewable thermoplastic homopolymer of claim 1 wherein the po 1 y (di h yr feru 1 i c acid) has at least one acetoxy end-group.

3. A method of preparing poly(dihyroferulic acid) comprising:

providing acetyldihyroferulic acid and a catalyst; and

polymerizing the acetyldihyroferulic acid to a poly(dihyroferulic acid) with the liberation of acetic acid.

4. The method of claim 3, wherein the acetyldihyroferulic acid is derived from one or more biorenewable sources.

5. The method of claim 4, wherein the biorenewable source is lignin.

6. The method of claim 3, wherein the catalyst comprises an oxide, alkoxide or acetate of Sb, Ti, Ge, Hg, Si, Zr, Al, or Zn.

7. The method of claim 6, wherein the catalyst is Zn(OAc)₂.

8. The method of claim 3, wherein polymerizing is carried out under vacuum.

9. The method of claim 3, wherein polymerizing is carried out at a temperature of 200 to 300 °C.

10. An aromatic/aliphatic thermoplastic homopolymer comprising a polymer of the structure:

wherein R¹ , R², R³, R⁴ are independently H or OR where R is Q to C₆ alkyl.

1 1. The aromatic/aliphatic thermoplastic homopolymer of claim 10, wherein the polymer is poly(3-(4-hydroxy-3,5-dimethoxyphenyl)propanoic acid).

12. The aromatic/aliphatic thermoplastic homopolymer of claim 10, wherein the polymer has at least one acetoxy end unit.

13. A method of preparing an aromatic/aliphatic thermoplastic homopolymer comprising:

providing a monomer of the structure:

where R', R", R\ R are independently H or OR where R is Ci to C₆ alkyl and a catalyst; and polymerizing the monomer to a polymer of the structure:

where R¹, R², R³, R⁴ are independently H or OR where R is d to C₆ alkyl with the liberation of acetic acid.

14. The method of claim 13, wherein the catalyst comprises an oxide, alkoxide or acetate of Sb, Ti, Ge, Hg, Si, Zr, Al, or Zn.

15. The method of claim 14, wherein the catalyst is Zn(OAc)₂.

16. The method of claim 13, wherein polymerizing is carried out under vacuum.

17. The method of claim 13, wherein polymerizing is carried out at a temperature of 200 to 300 °C.