Functionalized polycaryophyllenes and applications thereof

Abstract

Functionalized polycaryophyllenes are described herein. Such functionalized polycaryophyllenes can serve as additives in various compositions or can be employed as reactants to provide polymeric species having a variety of structures.

Description

[0001] FUNCTIONALIZED POLYCARYOPHYLLENES AND APPLICATIONS THEREOF STATEMENT OF GOVERNMENT RIGHTS This invention was made with government support under Grant No. DE-EE0008504 awarded by the Department of Energy and Grant No. N00014-22-S-B001 awarded by the Office of Naval Research. The government has certain rights in the invention. RELATED APPLICATION DATA The present application claims priority pursuant to Article 8 of the Patent Cooperation Treaty to United States Provisional Patent Application Serial Number 63 / 571,217 filed March 28, 2024 which is incorporated herein by reference in its entirety. FIELD The present application relates to polycaryophyllenes and, in particular, to functionalized polycaryophyllenes. BACKGROUND ^-caryophyllene is a naturally occurring sesquiterpene that is typically produced in the synthesis of clove oil. Of the 190 million metric tons of clove oil produced annually, about 19 million metric tons of caryophyllene are obtained as byproduct. Accordingly, the cost of caryophyllene is low. Moreover, ^-caryophyllene exhibits negligible toxicity. These aspects make caryophyllene an attractive renewable source for the production of various polymers. Polycarophyllenes, for example, have been employed in thermoset and plasticizer applications. However, wide application of polycaryophyllenes has been hampered by limited pathways for further functionalization of these polymers and oligomers. SUMMARY In view of the foregoing, functionalized polycaryophyllenes are described herein. Such functionalized polycaryophyllenes can serve as additives in various compositions or can be employed as cross-linking agents and / or reactants to provide polymeric species having a variety of architectures. In some embodiments, the functionalized polycaryophyllenes described herein can be employed as binders for solid-state propellants. In such embodiments, the functionalized polycaryophyllenes can replace hydroxy-terminated polybutadiene in solid state propellant compositions. In some embodiments, a functionalized polycaryophyllene or oligocaryophyllene is of (I) 500 while p and q independently range from 1 to 20. In another aspect, a functionalized polycaryophyllene or oligocaryophyllene is of Formula (II): 500 while In another aspect, a functionalized polycaryophyllene or oligocaryophyllene is of Formula (III):

[0002] III) where , p, q, y p y g . , g 1 to 500 while p, q, and y independently range from 1 to 20. In another aspect, methods of making functionalized polycaryophyllenes or oligocaryophyllenes are described herein. In some embodiments, a method comprises providing a mixture of β-caryophyllene monomer and a transition metal catalyst, and conducting ring opening metathesis polymerization of the β-caryophyllene monomer in the presence of acetoxy- alkenylene monomer to provide acetoxy-terminated polycaryophyllene or acetoxy-terminated oligocaryophyllene of Formula (I) above. In some embodiments, the acetate end groups can be subsequently deprotected to provide hydroxy-terminated polycaryophyllene or hydroxy- terminated oligocaryophyllene of Formula (II). In another aspect, a method comprises providing a mixture of β-caryophyllene monomer and a transition metal catalyst, and conducting ring opening metathesis polymerization of the β- caryophyllene monomer in the presence of alkenylene-diol monomer to provide hydroxy- terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene of Formula (II) or Formula (III). As described above, the functionalized polycaryophyllenes react with other species in the production of various thermoplastics and thermosets. For example, functionalized polycaryophyllenes described herein can be reacted with isocyanates for the production of thermoplastic polyureathanes or thermoset polyurethanes. Functionalized polycaryophyllenes can also be cured with polythiol compositions in the production of thermosets. Additionally, the functionalized polycaryophyllenes can undergo condensation reactions in the formation of polyester compositions. In another aspect, methods of polymer reprocessing are described herein. In some embodiments, a method of polymer reprocessing comprises providing a reaction mixture comprising a transition metal catalyst and a polyurethane including one or more polycaryophyllene or oligoaryophyllene segments, and depolymerizing the polyurethane via chain scission at the one or more polycaryophyllene or oligoaryophyllene segments, wherein the chain scission is initiated from pendant vinylidene groups and / or from terminal vinyl groups of the polyurethane. The polycaryophyllene or oligoaryophyllene segments of the polyurethane can be derived from Formulas (II) and (III). Moreover, the polyurethane undergoing reprocessing can be a thermoplastic or thermoset. In another aspect, composite compositions are described herein. A composite, in some embodiments, comprises a propellant or explosive dispersed in a polymeric matrix, the polymeric matrix comprising hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene. The hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene can be of Formula (II) or Formula (III), in some embodiments. Additionally, the hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene, in some embodiments, can have an enthalpy of combustion greater than 100,000 kJ / mol, such as 100,000-500,000 kJ / mol. In another aspect, functionalized polycaryophyllenes can be of Formula (IV): n, p, and q are independently integers. Functionalized polycaryophyllenes can be of Formula (V):

[0003] alo, , , , , , , , , , , e, NHS-ester, sulfate, phosphate, dithiobenzoate, and thiazolidine-2-thione, and wherein n, p, q, and y are independently integers. Functionalized polycaryophyllenes can also be of the Formula (VI): q are independently integers. These functionalized polycaryophyllenes can be reacted with various species to provide various polymeric architectures. These and other embodiments are further described in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS FIG.1 is a1H NMR (benzene-d6, 25 °C) spectrum of acetoxy-terminated polycaryophyllene. FIG.2 is a13C{1H} NMR (benzene-d6, 25 °C) spectrum of acetoxy-terminated polycaryophyllene. FIG.3 is an annotated1H-1H COSY NMR (benzene-d6, 25 °C) spectrum of acetoxy-terminated polycaryophyllene. FIG.4 is an annotated HSQC NMR (benzene-d6, 25 °C) spectrum of acetoxy-terminated polycaryophyllene. FIG.5 is an annotated HMBC NMR (benzene-d6, 25 °C) spectrum of acetoxy-terminated polycaryophyllene. FIG.6 is an annotated APT NMR (benzene-d6, 25 °C) spectrum of acetoxy-terminated polycaryophyllene. FIG.7 is an ATR-IR spectrum of acetoxy-terminated polycaryophyllene. FIG.8 is a1H NMR (benzene-d6, 25 °C) spectrum of HTPCR(1) (Mn= 4.820 kg / mol, Đ = 1.5). FIG.9 is an annotated1H-1H COSY NMR (benzene-d6, 25 °C) spectrum of HTPCR(1) (Mn = 4.820 kg / mol, Đ = 1.5). FIG.10 is a13C{1H} NMR (benzene-d6, 25 °C) spectrum of HTPCR(1) (Mn= 4.820 kg / mol, Đ = 1.5). FIG.11 is an annotated ATR-IR spectrum of HTPCR(1) (Mn = 4.820 kg / mol, Đ = 1.5). FIG.12 is a GPC chromatogram of HTPCR(1) (Mn= 4.820 kg / mol, Đ = 1.5). FIG.13 is an annotated MALDI-TOF spectrum of HTPCR(1) (Mn = 4.820 kg / mol, Đ = 1.5). FIG.14 is a1H NMR (benzene-d6, 25 °C) spectrum of HTPCR(6,8) (Mn = 2.770 kg / mol, Đ = 1.2). FIG.15 is a13C{1H} NMR (benzene-d6, 25 °C) spectrum of HTPCR(6,8) (Mn = 2.770 kg / mol, Đ = 1.2). FIG.16 is an annotated ATR-IR spectrum of HTPCR(6,8) (Mn= 2.770 kg / mol, Đ = 1.2). FIG.17 is a GPC Chromatogram of HTPCR(6,8) (Mn= 2.770 kg / mol, Đ = 1.2). FIG.18 is an annotated MALDI-TOF spectrum of HTPCR(6,8) (Mn = 2.770 kg / mol, Đ = 1.2). FIG.19 provides DSC results for HTPCR(1) and HTPCR(6,8). FIG.20 provides TGA results for HTPCR(1) and HTPCR(6,8). FIG.21 illustrates thermoplastic synthesis from reaction of hydroxyl-terminated polycaryophyllene with isocyanate according to some embodiments. FIG.22 is a1H NMR (benzene-d6, 25 °C) spectrum of HTPCR-TDI elastomer. FIG.23 is a13C{1H} NMR (benzene-d6, 25 °C) spectrum of HTPCR-TDI elastomer. FIG.24 is an Annotated1H1H COSY NMR (benzene-d6, 25 °C) spectrum of HTPCR-TDI elastomer. FIG.25 is a GPC chromatogram of HTPCR-TDI elastomer (Mn= 14.480 kg / mol, Đ = 2.2). FIG.26 is an annotated ATR-IR spectrum of HTPCR-TDI adhesive (top) and HTPCR-TDI elastomer (bottom). FIG.27 is an annotated ATR-IR spectrum of HTPCR-polyHDI adhesive (top) and HTPCR- polyHDI elastomer (bottom). FIG.28 provides TGA data for HTPCR-TDI and HTPCR-polyHDI variants. FIG.29 provides DSC spectra for HTPCR-TDI (top) and HTPCR-polyHDI (bottom) elastomers. FIG.30 provides DSC spectra for HTPCR-TDI (top) and HTPCR-polyHDI (bottom) adhesives. FIG.31 provides and annotated temperature-sweep DMA plot of HTPCR-TDI. FIG.32 provides an annotated temperature-sweep DMA plot of HTPCR-polyHDI. FIG.33 provides an annotated temperature-sweep DMA plot of HTPB-polyHDI. FIG.34 provides stress-strain curves obtained from the tensile testing of HTPCR-TDI and HTPCR-polyHDI PUs. FIG.35 provides ballistic TGA of polyurethanes described herein. FIG.36 illustrates depolymerization of HTPCR-TDI monitored by13C NMR (C6D6, 25 °C) according to methods described herein. DETAILED DESCRIPTION Embodiments described herein can be understood more readily by reference to the following detailed description and examples and their previous and following descriptions. Elements, apparatus and methods described herein, however, are not limited to the specific embodiments presented in the detailed description and examples. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations will be readily apparent to those of skill in the art without departing from the spirit and scope of the invention. EXAMPLE 1 – S nth i f t x -t rmin t d l r h ll n nd b nt d r t tion Scheme 1. General scheme for the polymerization of ^-caryophyllene in the presence of cis-2- acetoxy-2-butene. Specific reaction conditions are listed in Table 1. Table 1. ROMP of ^-caryophyllene with varied [Monomer]0:[CTA]0, with CTA = cis-1,4- diacetoxy-2-butene and Monomer = ^-caryophyllene.aEntry [Monomer] [Monomer]0:[CTA]0Conv. Mn(kg / mol) Mn(GPC) Đ (%)b(theoretical)c(kg / mol)d1 1.5 M 100 >99 20.4 15.7 1.3 2 1.5 M 50 >99 10.2 10.4 1.3 3 1.5 M 25 >99 5.1 6.6 1.3 4 1.5 M 15 >99 2.6 2.3 1.1 5 1.75 M 25 >99 5.1 7.8 1.3aPolymerizations were conducted on a 1-gram scale at 50 °C for 24 hours, under an inert atmosphere in toluene. Catalyst loading was 0.2 mol% of (1,3-Bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium) (G2).bConversions were determined by relative integration of olefinic protons using1H NMR spectroscopy.cTheoretical Mnwas calculated with respect to ratio of monomer to CTA at full conversion.dGPC data were obtained with THF as the eluent. The values reported are relative to polystyrene standards. Representative ROMP of ^-caryophyllene in the presence of cis-1,4-diacetoxy-2-butene: In an inert atmosphere, a 50 mL round-bottom flask was charged with a PTFE coated magnetic stir bar and ^-caryophyllene (90.0 g, 0.440 mol). Grubbs II catalyst (0.748 g, 0.880 mmol) was dissolved in toluene (220 mL) and the solution was added to the round bottom flask. While the mixture stirred, cis-1,4-diacetoxy-2-butene was added dropwise (9.36 mL, 58.7 mmol). The round bottom flask was sealed with a rubber septum and heated to 50 °C for 24 hours. Conversion was determined by1H NMR spectroscopy of a reaction aliquot. The reaction was terminated by the addition of ethyl vinyl ether. The mixture was stirred for 20 minutes, after which the polymer was precipitated by addition into anhydrous methanol. The supernatant was removed, and the polymer was washed with anhydrous methanol two additional times. The resulting polymer was dried under vacuum for an excess of 24 hours and 74.0 g were isolated in 92.5% yield. Representative spectroscopic data for acetoxy-terminated polycaryophyllene: 1H NMR (500 MHz, benzene-d6,25 °C): δ 5.55 (m, 3H); 5.44 (m, 3H); 5.32 (m, 9H); 5.27 (m, 4H); 4.92 (m, 34H); 4.63 (m, 6H); 2.48 (m, 16H); 2.29 (m, 35H); 2.15 (m, 39H); 2.03 (m, 47H); 1.91 (m, 9H); 1.82 (m, 16H); 1.76 (app. s, 15H); 1.72 (app. s, 11H); 1.65-1.49 (m, 105 H). Acetate end groups: CH2: 4.63, CH3: obs.2.30.13C NMR (126 MHz, benzene-d6,25 °C): δ 170.14; 152.70; 152.64; 152.57; 152.42; 142.66; 141.99; 135.91; 135.56; 135.50; 130.54; 130.04; 128.35; 125.06; 124.68; 124.61; 119.80; 119.27; 65.07; 61.22; 60.88; 49.73; 49.39; 48.89; 48.75; 46.86; 42.21; 42.09; 40.03; 39.92; 38.63; 38.28; 35.55; 35.24; 35.16; 34.30; 33.92; 33.83; 31.62; 31.46; 31.14; 30.28; 30.10; 29.54; 27.19; 27.11; 26.40; 23.73; 23.53; 22.62; 22.52; 20.64; 16.37; 16.25; 15.88. Acetate end groups: C=O: 170.84, CH2: 65.07 CH3: 20.26.1H-1H COSY,1H-13C HSQC,1H-13C HMBC, and13C APT NMR experiments were used to establish the identity of the chain end -CH2-OAc resonance. ATR-IR: (cm-1, assignment):1741 cm-1, - C=O, 1640 cm-1, -C=C- and -C=CH2. Spectra are provided in FIGS.1-7. Representative Deprotection of Polymer Acetate End Groups: OH Scheme 2. Deprotection of acetoxy-terminated poly-^-caryophyllene to hydroxy-terminated poly-^-caryophyllene [HTPCR(1)]. Polycaryophyllene (74.0 g) was dissolved in THF in a round-bottom flask and cooled to 0 °C. A 25 wt% solution of sodium methoxide in methanol (10.0 mL) was prepared and added dropwise to the reaction mixture. The reaction was stirred for 24 hours at 23 °C. The reaction mixture was precipitated into acidic methanol by dropwise addition using a dropping funnel. The supernatant was decanted, and the resulting polymer was washed two additional times with anhydrous methanol. The polymer was dried for a minimum of 24 hours under vacuum and 41.7 g of the product were isolated in a 57.2% yield. Representative Spectroscopic Data (Mn= 4.820 kg / mol, Đ = 1.5):1H NMR (400 MHz, benzene-d6, 25 °C): δ 5.54 ppm (app s, 2H); 5.39 (t, 2H); 5.32 (m, 20H); 5.27 (m, 4 H); 4.00 (m, 4H); 2.45 (m, 28H); 2.26 (m, 58H); 2.14 (m, 64H); 2.01 (m, 84H); 1.81 (m, 29H); 1.75 (s, 6H); 1.64 (m, 144H), 1.49 (s, 8H); 1.10 (m, 88H); 1.05 (72H); 1.02 (app s, 10H).1H-1H COSY NMR was used to establish the identity of the chain end -CH2-OH resonance.13C{1H} NMR (101 MHz, benzene-d6, 25 °C): δ 152.67; 152.60; 152.39; 138.44; 135.88; 135.47; 125.23; 124.65; 124.09, 107.44; 59.39; 48.81; 42.07; 40.18; 39.99; 38.60; 35.52; 35.21; 33.91; 31.63; 31.52; 31.28; 30.24; 30.07; 29.87; 27.10; 23.87; 23.76; 22.62; 16.35; 16.13. ATR-IR: (cm-1, assignment): 3319 cm-1, -OH, 1640 cm-1, -C=C- and -C=CH2. Molecular weight and dispersity were determined by GPC. Quantitation of OH functional groups was conducted by MALDI-TOF analysis. Spectra are provided in FIGS.8-13. Thermal and rheological properties of the HTPCR(1) sample are provided in Table 2. Table 2. Tabulated Thermal and Rheological Data for HTPCR(1) Prepared on Multigram Scale. HTPCR(1) EXAMPLE 2 – Synthesis of hydroxy-terminated polycaryophyllene (Chain Transfer Agent = cis- 2-butene-diol). OH through the ROMP of ^-caryophyllene in the presence of cis-2-butene-1,4-diol. Specific reaction conditions are presented in Table 3. Representative ROMP of ^-caryophyllene in the presence of cis-2-butene-diol: To a 50 mL round-bottom flask, ^-caryophyllene (1.00 g, 4.89 mmol) was added. To the round bottom was added 1.63 mL of a 3 mM solution of Grubbs II catalyst dissolved in toluene. The mixture was stirred for 5 minutes with a PTFE-covered magnetic stir bar. To the stirring mixture, cis-2-butene-1,4-diol (0.41 microliters, 0.0050 mmol) was added dropwise. The reaction was sealed in an inert atmosphere and then stirred at 40 °C overnight. It was quenched with ethyl vinyl ether and the product precipitated by dropwise addition of MeOH. The resulting polymer was dried under vacuum for a minimum of 24 hours to remove residual solvent, resulting in a 64% yield.1H NMR (500 MHz, tetrachloroethane-d2, 25 °C): NMR characterization matched that of the polymer synthesized through the deprotection of acetoxy end groups. Table 3. ROMP of β-caryophyllene with varied [Monomer]0:[CTA]0 where CTA = cis-2-butene- 1,4-diol.aEntr [m n m r] nv (%)cM M Đ n toluene. Catalyst loading was 0.1 mol % of G2.bPolymerization conducted with 0.05 mol % G2.cConversion was determined by relative integration of olefinic protons using1H NMR spectroscopy.dTheoretical Mnwas calculated with respect to ratio of monomer to CTA at full conversion.eGPC data was obtained with THF as the eluent. The values reported are relative to polystyrene standards.fContained 2.5% aldehyde chain ends from isomerization. EXAMPLE 3 – Synthesis of hydroxy-terminated polycaryophyllene [HTPCR(6,8)] (Chain Transfer Agent = cis-7-hexadec-6-ene-1,16-diol). Table 4. Representative ROMP of ^-caryophyllene in the presence cis-7-hexadec-6-ene-1,16-diol: In a 100 mL round bottom flask, cis-7-hexadec-6-ene-1,16-diol (1.00 g, 3.58 mmol) and ^-caryophyllene (10.0 g, 48.9 mmol) were dissolved in 15.3 mL of toluene. A solution of G2 (40 mg, 0.0471 mmol) dissolved in 1 mL of toluene was added to the round bottom flask and stirred for 12 hours at 50 °C. Full conversion was determined by1H NMR spectroscopy. The reaction was cooled to room temperature and then quenched with the addition of ethyl vinyl ether (2.00 mL). The mixture was stirred for 20 minutes, after which the product was precipitated by addition of 200 mL of methanol. The supernatant was decanted, and the resulting polymer was washed two more times with methanol. The polymer was dried for a minimum of 24 hours. The product was isolated (7.40 g) in 67.2% yield. Table 4. ROMP of ^-caryophyllene at various ratios of [Monomer]0:[CTA]0where CTA = cis- 7-hexadec-6-ene-1,16-diol.aEntry [monomer]0conv. MnMnMnĐaP e in toluene. Catalyst loading was 0.2 mol % of G2.bConversion was determined by relative integration of olefinic protons using1H NMR spectroscopy.cTheoretical Mnwas calculated with respect to ratio of monomer to CTA at full conversion.dDetermined by end-group analysis.eGPC data was obtained with THF as the eluent. The values reported are relative to polystyrene standards. Representative Spectroscopic Data for HTPCR(6,8) (Mn = 2.770 kg / mol, Đ = 1.2):1H NMR (400 MHz, benzene-d6, 25 °C): δ 5.53 (m, 2H); 5.32 (m, 12H); 4.91 (m, 24H); 3.36 (app t, 4H); 2.48 (m, 14H); 2.26 (m, 25H); 2.14 (m, 25H); 2.01 (m, 42H); 1.81 (t, 14H); 1.75 (s, 8H); 1.64 (s, 36H); 1.59 (m, 34H); 1.39 (m, 16H); 1.25 (m, 12H); 1.10 (s, 40H); 1.05 (s, 30H); 1.00 (s, 3H); 0.92 (s, 3H).13C{1H} NMR (101 MHz, benzene-d6, 25 °C): δ 152.67, 152.61, 152.39, 151.50, 135.89, 135.51, 135.47, 135.23, 134.68, 132.26, 130.52, 128.30, 128.06, 127.82, 125.44, 125.32, 125.18, 125.11, 125.04, 124.85, 124.66, 124.62, 107.41, 62.75, 62.72, 53.75, 51.89, 49.67, 48.83, 48.76, 46.77, 42.98, 42.16, 42.09, 40.80, 40.69, 40.32, 40.04, 39.98, 39.87, 38.71, 38.65, 38.61, 37.92, 35.91, 35.53, 35.21, 35.10, 33.93, 33.90, 33.87, 33.11, 32.86, 31.62, 31.57, 31.11, 30.42, 30.37, 30.24, 30.10, 30.07, 29.80, 29.72, 29.60, 29.10, 29.00, 28.87, 28.84, 28.48, 28.40, 27.15, 27.10, 26.37, 26.23, 26.16, 25.91, 22.61, 16.24. ATR-IR: (cm-1, assignment): 3315 cm-1, -OH, 1640 cm-1, -C=C- and -C=CH2. Quantitation of OH functional groups was conducted by MALDI-TOF analysis. Spectra are provided in FIGS.14-18. Table 5 provides thermal and rheological data for HTPCR(6,8) prepared on multigram scale. Table 5 HTPCR(68) Differential scanning calorimetry was conducted to identify the glass transition temperatures (Tg) for HTPCR(1) and HTPCR(6,8). As presented in FIG.19, the Tgof HTPCR(1) was -33.5oC, and the Tgof HTPCR(6,8) was -47.7oC. TGA analysis was also conducted as provided in FIG.20. EXAMPLE 4 – Thermoplastic Synthesis with functionalized polycaryophyllenes Scheme 5 provided in FIG.21 illustrates thermoplastic synthesis from reaction of hydroxyl- terminated polycaryophyllene with isocyanate according to some embodiments. As provided in Scheme 5, two differing isocyanates were employed, toluene diisocyanate (TDI) and poly(hexamethylene diisocyanate) (HDI), to provide HTPCR-TDI and HPCR-polyHDI urethanes, respectively. General Cast-Cure Procedure for Adhesives. 4.000 grams (0.833 mmol) of HTPCR(1) was added to a vial in a glove box. DBTDL (25 μL, 0.0416 mmol, 0.05 equiv.) was then added to the vial with a syringe.0.833 mmol (1 equiv.) of di- or triisocyanate and 3 mL of toluene was added to a separate vial. The toluene solution was poured into the polyol vial, and the vial was capped and quickly agitated until dissolution of the components. The resulting homogeneous solution was poured into a 2.5 inch diameter aluminum pan and added to an oven at 110 °C to cure for 24 hours. After 24 hours, the solidified contents were removed pans using a spatula and collected in respective vials. The polyurethanes were then characterized by ATR-IR, lap shear testing, DSC, and TGA. HTPCR-TDI was also analyzed by NMR and GPC due to its solubility in organic solvents. A gelation test was conducted on adhesive-like HTPCR-polyHDI in order to estimate the degree of crosslinking. NMR and GPC Spectroscopic Data for HTPCR-TDI Thermoplastics. HTPCR-TDI was characterized by1H,13C{1H}, and1H-1H COSY NMR. The data are reported as follows:1H NMR (400 MHz, benzene-d6, 25 °C): δ 8.09 (br s, 4H); 7.54 (br s, 4H); 7.36 (s, 1H); 6.96 (s, 1H); 6.89 (br s, 3H); 6.79 (br s, 2H); 6.09 (br s, 2H); 6.01 (app. m, 1H); 5.57 (br s, 12H); 5.35 (m, 48 H); 4.98 (m, 102H); 4.72 (m, 12H); 3.36 (m, 2H); 2.50 (m, 50H); 2.31-2.02 (m, 372 H); 1.84 (t, 58H); 1.77 (s, 43H); 1.65 (m, 300H); 1.30 (m, 26H); 1.08 (m, 355H).13C{1H} NMR (101 MHz, benzene-d6, 25 °C): δ 152.67, 135.92, 135.51, 128.30, 128.06, 127.82, 125.04, 124.67, 107.45, 49.67, 48.82, 42.10, 40.01, 38.62, 35.53, 35.21, 33.93, 31.63, 31.14, 30.08, 27.12, 23.76, 22.62, 16.26.1H-1H COSY NMR was used to establish correlations between chain end groups and carbamate-adjacent groups. Molecular weight and dispersity were determined by GPC. Assignment of the integration of the1H NMR spectrum of HTPCR-TDI was based on the obtained molecular weight of the PU by GPC (14.480 kg / mol) as well as the molecular weight of HTPCR(1) obtained by GPC (4820 kg / mol) and1H NMR spectroscopy. Based on the molecular weights of the polyol and PU, there are three HTPCR(1) units and either two or three TDI units in the PU chain for a total molecular formula of C1044H1704N4O7(14.400 kg / mol, two TDI units) or C1053H1710N6O9 (14.574 kg / mol, three TDI units), in excellent agreement with the GPC results. Three HTPCR units give rise to 12 protons associated with the methylenes adjacent to the urethane oxygens or terminal oxygens at 4.70 ppm, setting a starting point for assignment of integrations of the1H NMR spectrum. Relevant spectra are provided in FIGS.22-25. Adhesive HTPCR-TDI was also characterized by NMR spectroscopy as well as GPC and was found to have identical spectroscopic signatures to that of the elastomer material. ATR-IR Data for HTPCR-TDI and HTPCR-polyHDI Variants. The purity of the cures and the formation of urethane linkages in the thermoplastics and thermosets synthesized was established by ATR-IR. The spectroscopic data are reported as follows: ATR-IR of HTPCR-TDI: (cm-1, assignment): 3310 cm-1, -NH- and terminal -OH, 1733 cm-1, - C=O, 1640 cm-1, -C=C- and -C=CH2. ATR-IR of HTPCR-polyHDI: (cm-1, assignment): 3310 cm-1, -NH- and terminal -OH, 1733 cm-1, -C=O, 1640 cm-1, -C=C- and -C=CH2. Annotated ATR-IR spectra of HTPCR-TDI adhesive (top) and HTPCR-TDI elastomer (bottom) is provided in FIG.26. Annotated ATR-IR spectra of HTPCR-polyHDI adhesive (top) and HTPCR-polyHDI elastomer (bottom) is provided in FIG.27. FIG.28 provides TGA data for HTPCR-TDI and HTPCR-polyHDI variants. DSC Data for HTPCR-TDI and HTPCR-polyHDI. DSC was employed to confirm either thermoplastic behavior for HTPCR-TDI or thermosetting behavior for HTPCR-polyHDI elastomers. DSC data were recorded on a TA Instruments Q20 scanning calorimeter equipped with a RCS40 cooling system using 3-6 mg of material in crimp-sealed TA standard aluminum pans. The pans were referenced to a duplicate empty aluminum pan. For determination of melting and crystallization temperatures, the temperature was cycled in the following sequence: isothermal 25 °C for 5 minutes, ramp 10 °C / min to 250 °C, isothermal 250 °C for 5 minutes, ramp 10 °C / min to -40 °C, isothermal -40 °C for 5 minutes, ramp 10 °C / min to 250 °C, isothermal 250 °C for 5 minutes, ramp 10 °C / min to - 40 °C, isothermal -40 °C for 5 minutes, ramp 10 °C / min to 25 °C. For determination of glass transition temperatures of polyols, the temperature was cycled in the following sequence: Isothermal 25.00 °C for 5 minutes, ramp 5 °C / min to -100.00 °C, isothermal -100.00 °C for 5 min, ramp 5 °C / min to 25.00 °C, isothermal 25.00 °C for 5 min, ramp 5 °C / min to -100.00 °C, isothermal -100.00 °C for 5 min, ramp 5 °C / min to 25.00 °C. Data were analyzed using Universal Analysis software. For HTPCR-TDI, a melting event was identified at 223 °C, indicative of thermoplastic behavior. For HTPCR-polyHDI, no melting or crystallization events were found in the temperature window, consistent with thermosetting behavior. FIG.29 provides DSC spectra for HTPCR-TDI and HTPCR-polyHDI elastomers. FIG.30 provides DSC spectra for HTPCR-TDI (top) and HTPCR-polyHDI (bottom) adhesives used to determine glass transition temperatures. DMA Data for HTPCR-TDI and HTPCR-polyHDI Elastomers. The glass transition temperatures for HTPCR-TDI and HTPCR-polyHDI were identified by temperature-sweep DMA of the dogbones in tension mode, using the tan(δ) plot using parameters. DMA data were recorded on a TA Instruments Discovery HR-2 rheometer equipped with a thin film-fiber accessory in tension mode. Temperature sweeps were conducted from -25 to 50 °C at a ramp rate of 3 °C / min with a minimum axial force of 1 N, sensitivity of 0.1 N, axial displacement of 25 μm and frequency of 1.0 Hz. Runs were analyzed using TRIOS software. FIG.31 provides and annotated temperature-sweep DMA plot of HTPCR-TDI. FIG.32 provides an annotated temperature-sweep DMA plot of HTPCR-polyHDI. Lap Shear Testing of HTPCR-TDI and HTPCR-polyHDI Adhesives. The lap shear strength of the adhesives was tested by curing the PU adhesive formulations between two aluminum plates Two aluminum lap shear plates were roughened with 80 grit sandpaper. In a 20 mL scintillation vial in the glove box was added 0.25 g of HTPCR(1) (0.3125 mmol) and 2 mg (0.0156 mmol, 0.05 equiv.) of DBTDL. In a separate vial was added 1 equiv. of TDI or 0.67 equiv. of polyHDI and 1 mL of toluene. The polyisocyanate solutions were added to the polyol solutions, after which the contents were spread onto a ca.20 x 20 mm section of each aluminum grip. Duplicates of each formulation were prepared. The grips were adhered to each other by weighting with a 30 g steel weight, after which the sealed grips were cured in an oven at 110 °C for 24 hours. The resulting thickness of the adhesives between the plates was 0.10-0.14 mm. The plates were positioned on the tensile tester equipped with a 250 lbf force transducer, after which the position was adjusted 1.5 mm / min until the load was 400 N, sampling at 500 samples per second. The maximum load was then obtained from the load vs. position traces.Table 6. Tabulated Maximum Load Data for HTPCR-based PU Adhesives Synthesized.Max load length width area Max Load (N) (mm) (mm) (mm2) (kPa) Tensile Testing of HTPCR-TDI and HTPCR-polyHDI Elastomers. The elongation at break, load at break, and Young’s Moduli of the polyurethane cures were determined by tensile testing. Both the thermoplastic and thermoset data were obtained in duplicate. Tensile and lap shear testing was conducted on an ADMET MTEST Quattro Materials Testing System with an Interface SM-250250 lbf force transducer. Materials were suspended for testing using either dual pneumatic grips or lap shear testing pins. The position was adjusted at a rate of 1.000 inch per minute until the load was 4.800 lb, or the sample load dropped 10% (indicating breakage). The sampling rate was 127 samples / second. Dogbones and adhered aluminum plates were prepared in duplicate and the elongation at break, load at break, Young’s Moduli, or shear strength averaged. FIG.34 provides stress-strain curves obtained from the tensile testing of HTPCR-TDI and HTPCR-polyHDI PUs. Table 7 provides thermal properties of the PUs, while FIG.35 provides ballistic TGA of the PUs. Table 7. Thermal Properties HTPCR-TDI HTPCR-TDI HTPCR-polyHDI HTPCR-polyHDI (adhesive) (elastomer) (adhesive) (elastomer) °b c b c y . . EXAMPLE 5 – Polyurethane Reprocessing Polyurethanes synthesized and characterized in Example 4 were subjected to reprocessing according to methods described herein. Metathesis degradative pathways for HTPCR-based PUs presented herein were attempted with the same ADMET catalyst employed in the HTPCR synthesis. Accordingly, homogeneous solutions of HTPCR(1) and HTPCR-TDI in THF were stirred with 1 weight % of G2 at ambient or elevated temperature for 48 hours, with periodic monitoring by GPC (Table 6). As provided in Table 6, entries 1 and 2, minimal to no decomposition or change in dispersity was observed in the HTPCR(1) polyol at either ambient or elevated temperatures. However, at 48 hours of reaction at 50 °C, the molecular weight of the polymer increased from the 24-hour time point, indicating the presence of repolymerization mechanisms. Such repolymerization can necessarily inhibit depolymerization pathways at elevated temperature. HTPCR-TDI, on the other hand, displayed an approximately 60% decrease in Mn after 24 hours at ambient temperature. Additional decreases in molecular weight over prolonged reaction times were minimal, see for example, Table 8, entry 3. Increasing the temperature to 50 °C led to a similar molecular weight distribution as obtained from the ambient reaction conditions (Table 8, entry 4). As further evidence of depolymerization, the dispersities of the soluble material also increased significantly from that of the parent HTPCR-TDI thermoplastic elastomer. No depolymerization was observed in the control experiments where metal catalyst was omitted. Table 8. Mn, Dispersity, and Yield Data for the Metathesis Depolymerization of HTPCR-based Polyol, Thermoplastic, and Thermoset Polymers.aEntry Polymer Time (hr) Temp. MnĐ Percent (°C) (kg / mol) Solubilizeda aConditions: 200 mg polymer, 1 wt % G2, 5 mL THF, inert atmosphere.bDetermined from isolation of insoluble material post-reaction. Metathesis degradative methods were also applied to thermoset polyurethane. HTPCR- polyHDI thermoset was comminuted and suspended in a solution of 1 weight % G2 in THF. The heterogeneous mixture was stirred at ambient temperature or 50 °C for 48 hours with periodic monitoring by GPC. Swelling and gelation of the mixture preceded dissolution of the thermoset fragments under ambient conditions. An aliquot of the solubilized thermoset polymer was taken and analyzed by GPC. This analysis provided a Mn of 10.0 kg / mol with broad dispersity (Đ = 5.3) after 24 hours (Table 8, entry 5). Significant decreases in Mnand improvement in dispersity were not observed over an additional 48 hour reaction period. At the conclusion of the reaction period, the soluble material was separated from the insoluble solids by filtration. The solids were dried and weighed, resulting in 5% recovery of initially insoluble thermoset. Increases in reaction temperature were also investigated. A reaction temperature of 50oC resulted in a significant truncation of polymer chain length, as indicated by the Mn of 3.3 kg / mol obtained after 24 hours. While this result was promising, a concomitant decrease in percent depolymerization was also observed (Table 8, entry 6). The Mnof the solubilized material increased from 24 hours to 48 hours concurrent with a significant erosion in dispersity (Đ = 7.1). As with the polyol depolymerization above, these results indicate interference by competing repolymerization mechanisms. In view of the foregoing results, the dominant mechanism of depolymerization was investigated. Metathesis reactions were monitored by1H and13C NMR spectroscopies. For the depolymerization of the thermoplastic, a homogeneous solution of HTPCR-TDI and 3 weight % G2 was prepared in benzene-d6. Higher catalyst loading was used along with sonication, and the bath remained at ambient temperatures, given the competing repolymerization mechanisms at elevated temperatures discussed above. No small molecule ring closing metathesis products were detected, nor was ethylene produced as a byproduct, as evidenced by the NMR monitoring. The spectra remained largely static, except for the appearance of new olefinic signals identified at 108.3 and 125.3 ppm by13C NMR. These signals were assigned to terminal vinyl groups in the polycaryophyllene fragment (FIG. 36). The stereochemical information from the olefinic signal at 125.3 ppm was lost, supporting the assignment as signals belonging to terminal olefins. Complete analysis of potential reaction products indicated these signals are consistent with the production of linear chain end vinyl groups. Signals congruent with the in-growth of propenyl carbamate chain termination from the other end of the cleaved polymer fragment were also registered. Consumption of vinylated TDI fragments during the reaction was evidenced by signal located at 131.3 ppm, which decreased over a period of 12 hours. Such consumption indicates participation of end vinyl groups in depolymerization. Similar phenomena were observed from the in situ NMR monitoring of the depolymerization of thermoset HTPCR-polyHDI under the same conditions as the NMR-scale depolymerization of HTPCR-TDI. The same metathesis depolymerization pathway was identified for the deconstruction of a PU thermoset made from the condensation of HTPCR(6,8) with polyHDI. Based on this experimental evidence, the depolymerization is hypothesized to occur through several potential cross-metathesis pathways outlined in Scheme 6. initiated from pendent vinylidene groups. B. Model for chain scission initiated by cross- metathesis from residual terminal vinyl groups. The depolymerization can be initiated from either the metathesis-active vinylidenes or from the 0.5% of free terminal vinyl groups. Products resulting from the depolymerization of thermoplastic and thermoset PUs, including short chain vinyl-terminated polycaryophyllenes and vinylated carbamates, can be repolymerized with other reactants for the production of new materials. EXAMPLE 6 – Enthalpy of Combustion Fuel value (kJ / g) ΔH (kJ / mol) ΔH / monomer Various embodiments of the invention have been described in fulfillment of the various objects of the invention. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations thereof will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.

Claims

CLAIMS 1. A functionalized polycaryophyllene or oligocaryophyllene of Formula (I): (I)2. The functionalized polycaryophyllene or oligocaryophyllene of claim 1, wherein n ranges from 1 to 500 and p and q independently range from 1 to 20.

3. A functionalized polycaryophyllene or oligocaryophyllene of Formula (II):

4. The functionalized polycaryophyllene or oligocaryophyllene of claim 3, wherein n ranges from 1 to 500 and p and q independently range from 1 to 20.

5. A functionalized polycaryophyllene or oligocaryophyllene of Formula (III):OH II) 6. The functionalized polycaryophyllene or oligocaryophyllene of claim 5, wherein n ranges from 1 to 500 and p, q, and y independently range from 1 to 20.

7. A method of making a functionalized polycaryophyllene or oligocaryophyllene comprising: producing a mixture of β-caryophyllene monomer and a transition metal catalyst, and conducting ring opening metathesis polymerization of the β-caryophyllene monomer in the presence of acetoxy-alkenylene monomer to provide acetoxy-terminated polycaryophyllene or acetoxy-terminated oligocaryophyllene of Formula (I): (I)hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene of Formula (II):(II) wherein n, p, and q are independently integers.

9. A method of making a functionalized polycaryophyllene or oligocaryophyllene comprising: providucing a mixture of β-caryophyllene monomer and a transition metal catalyst, and conducting ring opening metathesis polymerization of the β-caryophyllene monomer in the presence of alkenylene-diol monomer to provide hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene of Formula (II) or Formula (III): ,10. The method of claim 8 or claim 9, wherein the hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene of Formula (II) or Formula (III) has an enthalpy of combustion greater than 100,000 kJ / mol.

11. A polyurethane comprising: one or more segments of polycaryophyllene.

12. The polyurethane of claim 11, wherein the polyurethane is a thermoplastic.

13. The polyurethane of claim 11, wherein the polyurethane is a thermoset.

14. A method of making polyurethane comprising: reacting an isocyanate with a hydroxy-terminated polycaryophyllene or hydroxy- terminated oligocaryophyllene of Formula (II) or Formula (III): ,15. The method of claim 14, wherein the isocyanate is a polyisocyanate.

16. A method of making a polymer comprising: reacting a polythiol with a hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene of Formula (II) or Formula (III): ,17. A method of polymer reprocessing comprising: producing a reaction mixture comprising a transition metal catalyst and a polyurethane including one or more polycaryophyllene or oligoaryophyllene segments; and depolymerizing the polyurethane via chain scission at the one or more polycaryophyllene or oligoaryophyllene segments, wherein the chain scission is initiated from pendant vinylidene groups and / or from terminal vinyl groups of the polyurethane.

18. The method of claim 17, wherein the one or more polycaryophyllene or oligoaryophyllene segments are of the formula / or 19. A composite comprising: a propellant or explosive dispersed in a polymeric matrix, the polymeric matrix comprising hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene.

20. The composite of claim 19, wherein the hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene has an enthalpy of combustion greater than 100,000 kJ / mol.

21. The composite of claim 19, wherein the hydroxy-terminated polycaryophyllene or hydroxy-terminated oligocaryophyllene is of Formula (II) or Formula (III):II), 22. A functionalized polycaryophyllene or oligocaryophyllene of Formula (IV):n, p, and q are independently integers.

23. A functionalized polycaryophyllene or oligocaryophyllene of Formula (V):lo, , , , , , , , , , , e, NHS-ester, sulfate, phosphate, dithiobenzoate, and thiazolidine-2-thione, and wherein n, p, q, and y are independently integers.

24. A functionalized polycaryophyllene or oligocaryophyllene of Formula (VI):q are independently integers.

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