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WO2012158250A1 - Plastifiants - Google Patents

Plastifiants Download PDF

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Publication number
WO2012158250A1
WO2012158250A1 PCT/US2012/028956 US2012028956W WO2012158250A1 WO 2012158250 A1 WO2012158250 A1 WO 2012158250A1 US 2012028956 W US2012028956 W US 2012028956W WO 2012158250 A1 WO2012158250 A1 WO 2012158250A1
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WIPO (PCT)
Prior art keywords
diels
composition
formula
plasticizer
farnesene
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PCT/US2012/028956
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English (en)
Inventor
Frank X. Woolard
Daniel Batzel
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Amyris Inc
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Amyris Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • This application relates to plasticizers derived from hydrocarbon terpenes.
  • Plasticized polymer compositions may be used in a variety of uses, including automotive components (e.g., interiors), footwear, adhesives, sealants, coated fabrics, wire and cable coatings, foams, gaskets, inks, cosmetics, medical devices, medical bags and tubing, toys, electrical devices, films, wall coverings, floor coverings, appliances, furniture, hoses, concrete, and the like.
  • automotive components e.g., interiors
  • footwear e.g., adhesives, sealants, coated fabrics, wire and cable coatings, foams, gaskets, inks, cosmetics, medical devices, medical bags and tubing, toys, electrical devices, films, wall coverings, floor coverings, appliances, furniture, hoses, concrete, and the like.
  • Plasticizers are used in a variety of compositions, for instance polymer-based compositions (e.g., polyvinylchloride (PVC)) and in concrete compositions.
  • PVC polyvinylchloride
  • phthalate plasticizers include dibutyl phthalate (DBP), dioctyl phthalate (DOP) and diisononyl phthalate (DINP).
  • DBP dibutyl phthalate
  • DOP dioctyl phthalate
  • DINP diisononyl phthalate
  • phthalates can cause health concerns, making phthalates unsuitable for use in some applications, such as plastics used in children's toys and in food containers. It is believed that some of the problems are tied to the aromatic nature of the phthalate esters. Therefore, there has been a move toward replacing aromatic phthalates with saturated analogs thereof, for instance 1,2-, 1,3- or 1 ,4-cyclohexane
  • dicarboxylate esters see, e.g., Brunner et al. US Pat. No. 7,208,545; Kinkade et al. US Pat. No. 7,973,194; Noe et al. US Pat. No. 7,319,161; Mack et al. US Pat. Publ. 2011/0232825; Hogan et al. US Pat. Publ. 2010/0063178, each of which is incorporated herein by reference.
  • DICH 1 ,2-cyclohexane dicarboxylic acid diisononyl ester
  • plasticizers be prepared from raw materials derived from renewable carbon sources rather than from petroleum or other fossil fuels.
  • Hydrocarbon terpenes such as myrcene and the sesquiterpene ⁇ -farnesene can be synthesized via biological routes from renewable carbon sources such as sugars or biomass.
  • myrcene and ⁇ - farnesene can be produced from sugars or biomass in high yield from modified yeast, as described in U.S. Patent Nos. 7,399,323 and 7,659,097, each of which is incorporated herein by reference in its entirety, as if put forth fully below.
  • a plasticizer comprises a Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile, or comprises a derivative of such a Diels-Alder adduct.
  • the Diels-Alder plasticizer adduct is chemically modified, e.g., by oxidizing the adduct, reducing the adduct, and/or by reacting the adduct with one or more reactants.
  • a Diels-Alder adduct or its derivative is hydrogenated.
  • a Diels-Alder adduct is hydrogenated before chemical modification, and in some cases, a Diels-Alder adduct is hydrogenated after chemical modification.
  • the properties of the plasticizers can be tuned depending on the host resin in which they are intended to be used.
  • the plasticizers can be selected to modify any one of or any combination of physical and/or mechanical properties of the host resin, e.g., lower glass transition temperature, lower melt temperature, lower melt viscosity, increase toughness, increase elasticity, increase elongation at break, increase load at break, increase displacement at break, increase strain at break, increase energy to yield point, improve low temperature brittleness properties, and/or modify durometer hardness.
  • the hydrocarbon terpene can be any hydrocarbon terpene capable of undergoing a Diels- Alder reaction with a dienophile.
  • the hydrocarbon terpene is ⁇ - farnesene. In some variations, the hydrocarbon terpene is myrcene. In some variations, the hydrocarbon terpene used to make the Diels- Alder adduct is derived from a simple sugar by a microorganism. In some variations, ⁇ -farnesene that is derived from a simple sugar by a microorganism is used to make the Diels- Alder adduct.
  • the dienophile may be selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, ⁇ - ⁇ -unsaturated aldehydes, dialkyl maleates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, dialkyl azidocarboxylate
  • the dienophile is maleic anhydride. In some variations, the dienophile is a dialkyl maleate. In some variations, the dienophile is a dialkyl fumarate. In some variations, the dienophile is an ⁇ , ⁇ -unsaturated aldehyde.
  • the plasticizers described herein may be designed for use as plasticizers in a wide variety of host polymers.
  • the plasticizers are used in thermoplastics.
  • the plasticizers are used in thermosets.
  • the plasticizers are used in elastomers or rubbers.
  • plasticizers are suitable for use in PVC, chlorinated polyvinylchloride, polycarbonates, polyurethanes, nitrile polymers (such as acrylonitrile butadiene styrene (ABS)), acrylate polymers, styrenic polymers, polyesters (e.g., lactic-acid containing polymers), polyamides, polyimides, polyvinyl acetals, cellulose polymers, starches, polyolefms, natural rubbers, synthetic rubbers, co-polymers of any of the foregoing, polymer blends of any of the foregoing, or in polymer composites of any of the foregoing.
  • nitrile polymers such as acrylonitrile butadiene styrene (ABS)
  • ABS acrylonitrile butadiene styrene
  • ABS acrylonitrile butadiene styrene
  • styrenic polymers polyesters (e.g
  • the plasticizers described herein may be selected to have sufficiently low volatility under processing and use conditions such that they do not exhibit undesirable levels of migration within the host polymer or exude from the host polymer. Volatility may be reduced by selecting higher molecular weight plasticizers, selecting plasticizers with a high degree of compatibility with a host resin, and/or by selecting functional groups on the plasticizer that increase interaction with the host polymer.
  • a plasticizer disclosed herein comprises a Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile in which the aliphatic portion of the Diels- Alder adduct originating from the terpene and/or one or more substituents of the adduct originating from the dienophile have been selected or modified to increase compatibility with the host resin.
  • unsaturated bonds in the aliphatic portion of the Diels-Alder adduct may be oxidized (e.g., epoxidized) or halogenated (e.g., chlorinated).
  • one or more substituents of a Diels-Alder adduct originating from the dienophile may have been selected or chemically modified to include one or more polar groups (e.g., one or more hydroxy, alkoxy, ether, epoxy, carboxy, amino, carbonyl, and/or halogen groups) to increase compatibility with polar host resins.
  • one or more polar groups e.g., one or more hydroxy, alkoxy, ether, epoxy, carboxy, amino, carbonyl, and/or halogen groups
  • a plasticizer is or comprises a compound having formula (F-
  • R and R' each independently represent a C1-C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, or t-butyl.
  • R and R' each independently represent n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n- tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n- eicosyl, or n-tricosyl.
  • R and/or R' comprises one or more heteroatoms, e.g., oxygen, nitrogen, sulfur, phosphorus, or halogen atoms (e.g., chlorine, bromine or iodine).
  • R and R' are each methyl.
  • a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-1).
  • a plasticizer is or comprises a compound having formula (F-
  • R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2- ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tride
  • a plasticizer is or comprises or is derived from a compound having formula (F-4)
  • n l,2,3 or 4.
  • a plasticizer is or comprises a compound having formula (F-
  • R and R' each independently represent a C 1 -C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, or t-butyl.
  • R and R' each independently represent n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n- tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n- eicosyl, or n-tricosyl.
  • R and/or R' comprises one or more heteroatoms, e.g., oxygen, nitrogen, sulfur, phosphorus, or halogen atoms (e.g., chlorine, bromine or iodine).
  • R and R' are each methyl.
  • a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-l A).
  • a plasticizer is or comprises a compound having formula (F-
  • R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, and
  • the Diels-Alder adducts derived from the hydrocarbon terpenes that are useful as plasticizers comprise at least one epoxy group. In some variations, the Diels-Alder adducts comprise two epoxy groups. In some variations, the Diels-Alder adducts comprise more than two epoxy groups.
  • the epoxidized Diels-Alder adducts are adapted for use as monomers or as cross- linking agents, or as curing agents to make an oligomer or polymer that has utility as a plasticizer.
  • at least one epoxy group of a Diels-Alder adduct may be hydrolyzed to make a plasticizer or a plasticizer precursor.
  • a plasticizer is or comprises or is derived from a compound having formula (F-4A)
  • a plasticizer is, comprises or is derived from a compound having formula (H-XIIA)-(H-XIIF) or (H-XIIA')-(H-XIIE'):
  • each of R and R' independently represents H or any C 1 -C30 linear or branched, cyclic or acyclic, substituted or unsubstituted alkyl group, and R and R' may be the same or different.
  • each of R and R' independently represents a C 1 -C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or t-butyl.
  • each of R and R' independently represent n-pentyl, isopentyl, n-hexyl, 2- ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, n-tetradecyl, n- pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl.
  • each of R and R' independently represent
  • each of R and R' is independently methyl.
  • Described herein are polymer compositions comprising a host resin and one or more Diels-Alder plasticizer adducts derived from a hydrocarbon terpene comprising a conjugated diene and a dienophile, wherein the plasticizer has been incorporated into the host resin in an amount effective to reduce the glass transition temperature, increase toughness, increase elasticity, increase elongation at break, and/or improve a low temperature property.
  • a plasticized composition comprises two or more plasticizers, e.g., two or more plasticizers as described herein, or one or more plasticizers as described herein and one or more plasticizers known in the art.
  • a plasticized composition comprises one or more additives selected from the group consisting of anti-blocking agents, antistatic agents, lubricants, anti-fogging agents, heat stabilizers, antioxidants, discoloration inhibitors, flame retardants, oils, waxes, antioxidants, UV stabilizers, colorants or pigments, tackifiers, waxes, flow aids, coupling agents, crosslinking agents, surfactants, compatibilizers, rheology modifiers, adhesion promoters, catalysts, solvents, corrosion inhibitors, anti-wear agents, antioxidants, rust inhibitors, flame retardants, biocides, algicides, fungicides, acid scavengers, radical scavengers, monomer scavengers, water scavengers, inorganic fillers, conductive particles, fibers, and combinations thereof.
  • additives selected from the group consisting of anti-blocking agents, antistatic agents, lubricants, anti-fogging agents, heat stabilizers,
  • a plasticized composition comprises PVC and one or more
  • a plasticized composition comprises polylactic acid and one or more Diels-Alder adducts between a hydrocarbon terpene having a conjugated diene and a dienophile in an amount effective to improve processability, increase toughness, increase flexibility, increase elasticity, reduce rigidity (e.g., increase elongation at break), and/or improve a low temperature property.
  • a plasticized composition comprises an adhesive and one or more Diels-Alder adducts between a hydrocarbon terpene having a conjugated diene and a dienophile in an amount effective to improve processability, increase toughness, increase flexibility, increase elasticity, reduce rigidity (e.g., increase elongation at break), and/or improve a low temperature property.
  • Nonlimiting examples of adhesives in which the plasticizers may be utilized include those based on acrylates, methacrylates, silanes, siloxanes, polyethers, polyesters, polyurethanes, polyureas, polysulfides, silylated polyurethanes, silylated polyureas, silylated polyethers, silylated polysulfides and silyl-terminated acrylates and the like. [0028] Described herein are compositions comprising a plasticizer derived from a Diels-
  • Alder adduct between a hydrocarbon terpene comprising a conjugated diene and a dienophile combined with a host resin wherein the adduct functions to plasticize the host resin and to provide one or more additional functionalities selected from the group consisting of acid scavenging, radical scavenging, thermal stabilization, color stabilization, charge dissipation, fire retardation, corrosion inhibition, flow viscosity improvement, radical scavenging, dye site creating, adhesion promoting, and mold releasing.
  • the Diels- Alder plasticizer adduct is physically blended with a polymer. In some variations, the Diels- Alder adduct is chemically reacted with a polymer. In some variations, a Diels-Alder adduct or its derivative is used as a monomer, cross-linking agent, or reactive diluent to make an oligomer or polymer that is used as a plasticizer.
  • At least about 25%, at least about 30%>, at least about 40%>, at least about 50%>, at least about 60%>, at least about 70%>, at least about 80%>, at least about 90%, or about 100% of the carbon atoms in the Diels-Alder adducts are derived from renewable carbon sources.
  • Described herein are methods of making a plasticized composition comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels- Alder adduct, and combining the adduct with a host polymer to plasticize the host polymer.
  • Described herein are methods of making a plasticized composition comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels- Alder adduct, chemically functionalizing the adduct to form a plasticizer, and combining the plasticizer with the host polymer to plasticize the host polymer, wherein the chemical functionalization of the adduct increases compatibility with the host polymer.
  • the hydrocarbon terpene may be derived from a sugar using a genetically modified organism.
  • the hydrocarbon terpene is ⁇ -farnesene derived from a sugar using a genetically modified organism.
  • a plasticizer comprises ⁇ -farnesene (or a ⁇ -farnesene derivative such as a dimer, trimer or tetramer of ⁇ -farnesene, or a Diels Alder adduct of ⁇ - farnesene and a dieneophile) that has had one, two, three (or four or more, if present) of its double bonds oxidized (e.g., epoxidized) or chlorinated.
  • ⁇ -farnesene or a ⁇ -farnesene derivative such as a dimer, trimer or tetramer of ⁇ -farnesene, or a Diels Alder adduct of ⁇ - farnesene and a dieneophile
  • FIGURE 1 shows weight loss with heat aging for Example 22, Comparative
  • FIGURE 2 shows toughness for Examples 21 and 22, Comparative Examples 4-
  • FIGURE 3 shows Young's modulus for Examples 21 and 22 and Comparative
  • FIGURE 4 shows engineering strain (% elongation) at failure for Examples 21 and 22, Comparative Examples 4-9, and neat PVC, measured according to ASTM D638 using a pull rate of 50mm/min.
  • FIGURE 5 shows displacement at break for Examples 21 and 22, Comparative
  • FIGURE 6 shows load at break for Examples 21 and 22, Comparative Examples
  • FIGURE 7 shows stress at break for Examples 21 and 22, Comparative Examples
  • FIGURE 8 shows energy to yield point for Examples 21 and 22, Comparative
  • FIGURE 9 shows 1H NMR spectrum of (E)-dimethyl 4-(4,8-dimethylnona-3,7- dienyl)cyclohex-4-ene-l,2-dicarboxylate of Example 30.
  • FIGURE 10 shows 1H NMR spectrum of dimethyl 4-(4,8- dimethylnonyl)cyclohexane-l,2-dicarboxylate of Example 31.
  • FIGURE 11 shows 1H NMR spectrum of (4-(4,8-dimethylnonyl)cyclohane- 1 ,2- diyl)dimethanol of Example 32.
  • FIGURE 12A and FIGURE 12B show 13 C NMR spectra of (4-(4,8- dimethylnonyl)cyclohane-l,2-diyl)dimethanol of Example 32.
  • FIGURE 13 shows 1H NMR spectrum of a mixture of (E)-3-(4,8-dimethylnona-
  • FIGURE 14A and 14B show GC/MS spectra of a mixture of (E)-3-(4,8- dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7- dienyl)cyclohex-3-enecarbaldehyde of Example 33.
  • FIGURE 15 shows 1H NMR spectrum of a mixture of (3-(4,8- dimethylnonyl)cyclohexyl)methanol and (4-(4,8-dimethylnonyl)cyclohexyl)methanol of Example 34.
  • FIGURES 16A-16C show 1H NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentaethylene glycol of Example 35.
  • FIGURES 16D-16F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentaethylene glycol of Example 35.
  • FIGURES 17A-17C show 1H NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- decaethylene glycol of Example 36.
  • FIGURES 17D-17F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- decaethylene glycol of Example 36.
  • FIGURES 18A-18C show 1H NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentadecaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentadecaethylene glycol of Example 37.
  • FIGURES 18D-18F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentadecaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentadecaethylene glycol of Example 37.
  • FIGURES 19A-19C show 1H NMR spectra of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-pentaethylene glycol) of Example 38.
  • FIGURES 19D-19F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3,4-bis(methyl-pentaethylene glycol) of Example 38.
  • FIGURES 20A-20C show 1H NMR spectra of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decaethylene glycol) of Example 39.
  • FIGURES 20D-20F show 13 C NMR spectra of a mixture of 1 -(4,8-dimethyl- nonyl)-cyclohexane-3,4-bis(methyl-decaethylene glycol) of Example 39.
  • FIGURES 21 A-21 C show 1H NMR spectra of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decapentaethylene glycol) of Example 40.
  • FIGURES 21D-21F show 13 C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3,4-bis(methyl-decapentaethylene glycol) of Example 40.
  • FIGURE 22 shows correlation of durometer hardness A with Hansen solubility parameters using durometer hardness A values from Table 64 and Hansen solubility parameters from Table 5.
  • FIGURE 23 shows correlation of durometer hardness A with tensile properties for data shown in Table 64.
  • FIGURE 24 shows DMA results for Example 78.
  • plasticizers that comprise or are derived from Diels-Alder adducts between a hydrocarbon terpene comprising a conjugated diene moiety (e.g., myrcene, ⁇ - farnesene, or a-farnesene) and a dienophile, methods of making the plasticizers, and to the use of the plasticizers in a variety of applications.
  • a conjugated diene moiety e.g., myrcene, ⁇ - farnesene, or a-farnesene
  • plasticizers described herein have utility in construction (e.g., resilient flooring, wall coverings, pool liners, coatings, roofing materials, fillers, insulation backings, adhesives, and the like), electrical products (e.g., wire and cable jackets, electrical tapes, electrical boxes, circuit boards, insulating coatings, and the like), consumer goods (e.g., footwear, toys, clothing, luggage, bookbinding, storage containers, disposable cutlery and plates and cups, garden hose), packaging (e.g., films, bottles, containers, sealants, adhesives and the like), automotive (e.g., upholstery, interior trim, floor mats, hoses, sealants, adhesives, body components, coatings and the like), furnishings (e.g., carpet, furniture, upholstery, lightweight furnitures, curtains such as shower curtains, adhesives, sealants and the like), medical applications (e.g., IV bags, tubing, disposable sheets, disposable garments, and the like).
  • electrical products e.g., wire and cable jackets, electrical tapes, electrical boxes,
  • plasticizers comprise a ring structure resulting from a
  • the hydrocarbon terpene and the dienophile may be selected to impart desired properties to the plasticizer (e.g., to increase compatibility with the host resin, modify molecular weight, modify volatility, and/or modify thermal stability).
  • a Diels-Alder adduct may undergo chemical derivatization following the Diels-Alder reaction to form a plasticizer having desirable properties.
  • the plasticizers can be selected to modify any one of or any combination or physical or mechanical properties of the host resin, e.g., lower glass transition temperature, increase toughness, improve low temperature brittleness temperature, increase flexibility, increase processibility, increase elasticity, increase elongation at break, increase load at break, increase displacement at break, increase strain at break, increase energy to yield point, and/or modify a low temperature property.
  • the plasticizers can be designed to be sufficiently compatible with the host resin so that exudation of the plasticizer under use condition is acceptably low.
  • plasticizers described herein may be designed for use as plasticizers in a wide variety of polymers.
  • ⁇ -farnesene-derived plasticizers are suitable for use in PVC, polycarbonates, polyurethanes, nitrile polymers (such as acrylonitrile butadiene styrene (ABS)), acrylate polymers, polystyrenes, polyesters, polyamides, polyimides, polyvinyl acetals, cellulose polymers, polyolefins, natural rubbers, synthetic rubbers, copolymers of any of the foregoing, polymer blends of any of the foregoing, or in polymer composites of any of the foregoing.
  • ABS acrylonitrile butadiene styrene
  • Section A [001] Provided below is Section A), which includes some definitions.
  • Section B) below describes sources of hydrocarbon terpenes comprising a conjugated diene.
  • Section C) includes non- limiting examples of formation of Diels-Alder adducts from which the plasticizers can be derived.
  • Section D) below provides non-limiting examples of dienophiles that can be used in the Diels-Alder reaction to make the plasticizers.
  • Section E) below provides non- limiting examples of hydrocarbon terpenes comprising a conjugated diene that can be used in the Diels- Alder reaction to make the plasticizers.
  • Section F) below provides non-limiting examples of Diels- Alder adducts that can be formed.
  • Section G) below provides non- limiting examples of chemical modifications that can be performed on a Diels-Alder adduct to make a plasticizer having desired properties.
  • Section H) below provides non-limiting examples of farnesene -based Diels-Alder adducts from which plasticizers can be derived.
  • Section J) below provides non-limiting examples of variations of plasticizers that can be derived from the Diels- Alder adducts, selection of plasticizers for certain applications, and non-limiting examples of compositions comprising the plasticizers.
  • Section K) below provides applications for the plasticizers and plasticized compositions described herein. It should be understood that Sections A)-K) are provided for organization purposes only. Any suitable dienophile from Section D) may be reacted with any suitable hydrocarbon terpene from Section E) to form a plasticizer.
  • Terpene as used herein is a compound that is capable of being derived from isopentyl pyrophosphate (IPP) or dimethylallyl pyrophosphate (DMAPP), and the term terpene encompasses hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes and polyterpenes.
  • a hydrocarbon terpene contains only hydrogen and carbon atoms and no heteroatoms such as oxygen, and in some embodiments has the general formula (C5H 8 ) n , where n is 1 or greater.
  • conjugated terpene or “conjugated hydrocarbon terpene” as used herein refers to a hydrocarbon terpene comprising at least one conjugated diene moiety.
  • the conjugated diene moiety of a conjugated terpene may have any stereochemistry ⁇ e.g., cis or trans) and may be part of a longer conjugated segment of a terpene, e.g., the conjugated diene moiety may be part of a conjugated triene moiety, but is not part of an aromatic ring.
  • a conjugated hydrocarbon terpene may contain a conjugated diene at a terminal position (e.g., myrcene, farnesene) or the conjugated diene may be at an internal position (e.g., isodehydrosqualene or isosqualane precursor I or II).
  • a conjugated diene at a terminal position e.g., myrcene, farnesene
  • the conjugated diene may be at an internal position (e.g., isodehydrosqualene or isosqualane precursor I or II).
  • hydrocarbon terpenes as used herein also encompasses monoterpenoids, sesquiterpenoids, diterpenoids, triterpenoids, tetraterpenoids and polyterpenoids that exhibit the same carbon skeleton as the corresponding terpene but have either fewer or additional hydrogen atoms than the corresponding terpene, e.g., terpenoids having 2 fewer, 4 fewer, or 6 fewer hydrogen atoms than the corresponding terpene, or terpenoids having 2 additional, 4 additional or 6 additional hydrogen atoms than the corresponding terpene.
  • conjugated hydrocarbon terpenes include isoprene, myrcene, a-ocimene, ⁇ -ocimene, a-farnesene, ⁇ - farnesene, ⁇ -springene, geranylfarnesene, neophytadiene, cw-phyta- 1,3 -diene, trans-phyta-1,3- diene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.
  • Terpenes or isoprenoid compounds are a large and varied class of organic molecules that can be produced by a wide variety of plants and some insects. Some terpenes or isoprenoid compounds can also be made from organic compounds such as sugars by
  • the conjugated hydrocarbon terpenes as described herein are derived from microorganisms using a renewable carbon source such as a sugar that can be replenished in a matter of months or a few years unlike fossil fuels.
  • Myrcene refers to a compound having the following structure:
  • Ocimene refers to a-ocimene, ⁇ -ocimene or a mixture thereof.
  • a-ocimene refers to a compound having the following formula: or a stereoisomer (e.g., s-cis isomer) thereof.
  • ⁇ -ocimene refers to a compound having the following formula:
  • Frnesene refers to a-farnesene, ⁇ -farnesene or a mixture thereof.
  • a-Farnesene refers to a compound having the following structure:
  • a-farnesene comprises a substantially pure stereoisomer of a-farnesene.
  • a-farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers.
  • the amount of each of the stereoisomers in an ⁇ -farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.% to about 99.5 wt.%, from about 1 wt.% to about 99 wt.%, from about 5 wt.% to about 95 wt.%, from about 10 wt.% to about 90 wt.% or from about 20 wt.%) to about 80 wt.%, based on the total weight of the ⁇ -farnesene mixture of stereoisomers.
  • ⁇ -farnesene refers to a compound having the following structure:
  • ⁇ -farnesene comprises a substantially pure stereoisomer of ⁇ -farnesene.
  • substantially pure ⁇ -farnesene refers to compositions comprising at least 80%>, at least 90%>, at least 95%, at least 97%, at least 98% or at least 99% ⁇ -farnesene by weight, based on total weight of the farnesene.
  • ⁇ -farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers.
  • the amount of each of the stereoisomers in a ⁇ -farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.% to about 99.5 wt.%), from about 1 wt.% to about 99 wt.%, from about 5 wt.% to about 95 wt.%, from about 10 wt.% to about 90 wt.%, or from about 20 wt.% to about 80 wt.%, based on the total weight of the ⁇ -farnesene mixture of stereoisomers.
  • ⁇ -springene or “springene” refers to a compound having the following structure:
  • Neophytadiene refers to a compound having the following structure:
  • Cz5-phyta-l,3-diene refers to a compound having the following structure:
  • Isodehydrosqualene refers to a compound having the following structure:
  • Isosqualane precursor I or "2,6,18,22-tetramethyl-10-methylene-14- vinyltricosa-2,6,11,17,21 -pentaene” refers to a compound having the following structure:
  • 2,6, 10, 14, 17,21 -pentaene refers to a compound having the following structure:
  • Frnesol refers to a compound having the following structure:
  • Neolidol refers to a compound having the following structure:
  • Farnesol or nerolidol may be converted into a-farnesene or ⁇ -farnesene, or a combination thereof by dehydration with a dehydrating agent or an acid catalyst.
  • a dehydrating agent or an acid catalyst Any suitable dehydrating agent or acid catalyst that can convert an alcohol into an alkene may be used.
  • suitable dehydrating agents or acid catalysts include phosphoryl chloride, anhydrous zinc chloride, phosphoric acid, and sulfuric acid.
  • a "polymer” refers to any kind of synthetic or natural oligomer or polymer having two or more repeat units, including thermoplastics, thermosets, elastomers, polymer blends, polymer composites, synthetic rubbers, and natural rubbers.
  • a synthetic oligomer or polymer can be prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term “polymer” embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as “interpolymer.”
  • Interpolymer refers to a polymer prepared by the polymerization of at least two different types of monomers.
  • the generic term “interpolymer” includes the term “copolymer” (which generally refers to a polymer prepared from two different monomers) as well as the term “terpolymer” (which generally refers to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.
  • Hydrocarbyl refers to a group containing one or more carbon atom backbones and hydrogen atoms, and the group may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups known to one of skill in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic, or any combination thereof. Aliphatic segments may be straight or branched. Aliphatic and cycloaliphatic groups may include one or more double and/or triple carbon-carbon bonds.
  • hydrocarbyl groups include alkyl, alkenyl, alkynyl, aryl, cyclalkyl, cycloalkenyl, alkaryl and aralkyl groups.
  • Cycloaliphatic groups may contain both cyclic moieties and noncyclic portions.
  • the hydrocarbyl group is a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted C1-C30 hydrocarbyl group (e.g., C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkynyl, cycloalkyl, aryl, aralkyl and alkaryl).
  • Alkyl refers to a group having the general formula C n H 2n +i derived from a saturated, straight chain or branched aliphatic hydrocarbon, where n is an integer. In certain embodiments, n is from 1 to about 30, from 1 to about 20, or from 1 to about 10.
  • alkyl groups include C1-C10 alkyl groups such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2,-dimethylpropyl, 2-methylpentyl, 3- methylpentyl, 4-methylpentyl, 2-2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-butyl, isobutyl, tert-butyl, isopentyl, n-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n- octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, 2-propylheptyl, and isode
  • An alkyl group may be unsubstituted, or may be substituted.
  • the alkyl group is straight chain having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12 carbons.
  • the alkyl group is branched having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12 carbons.
  • Cycloaliphatic encompasses "cycloalkyl” and "cycloalkenyl.” Cycloaliphatic groups may be monocyclic or polycyclic. A cycloaliphatic group can be unsubstituted or substituted with one or more suitable substituents.
  • Cycloalkyl refers to a saturated carbocyclic mono- or bicyclic (fused or bridged) ring of 3-12 (e.g., 5-12) carbon atoms.
  • Non-limiting examples of cycloalkyl include C3-C8 cycloalkyl groups, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups and saturated cyclic and bicyclic terpenes. Cycloalkyl groups may be unsubstituted or substituted.
  • Cycloalkenyl refers to a non-aromatic carbocyclic mono- or bicyclic ring of 3 to 12 ⁇ e.g., 4 to 8) carbon atoms having one or more double bonds.
  • Non-limiting examples of cycloalkenyl include C 3 -C 8 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and unsaturated cyclic and bicyclic terpenes. Cycloalkenyl groups may be unsubstituted or substituted.
  • Aryl refers to an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removing a hydrogen atom.
  • Non-limiting examples of the aryl group include phenyl, naphthyl, benzyl, or tolanyl group, sexiphenylene, phenanthrenyl, anthracenyl, coronenyl, and tolanylphenyl.
  • An aryl group can be unsubstituted or substituted with one or more suitable substituents.
  • the aryl group can be monocyclic or polycyclic. In some embodiments, the aryl group contains at least 6, 7, 8, 9, or 10 carbon atoms.
  • one or more dashed bonds in a structure independently represents a bond that may or may not be present.
  • the dashed bond in the structure " ⁇ - ⁇ indicates a bond that may be present to result in a double bond, or may not be present to result in a single bond.
  • Isoprenoid and “isoprenoid compound” are used interchangeably herein and refer to a compound derivable from isopentenyl diphosphate.
  • a substituted group or compound refers to a group or compound in which at least one hydrogen atom is replaced with a substituent chemical moiety.
  • a substituent chemical moiety may be any suitable substituent that imparts desired properties to the compound or group.
  • substituents include halo, alkyl, heteroalkyl, alkenyl, alkynyl, aryl, heteroayrl, hydroxyl, alkoxyl, amino, nitro, thiol, thioether, imine, cyano, amido, phosphonato, phosphine, carbosyl, thiocarbonyl, sulfonyl, sulfonamide, carbonyl, formyl, carbonyloxy, oxo, haloalkyl (e.g., trifluoromethyl or trichloromethyl), carbocyclic cycloalkyl (which may be monocyclic, or fused or non- fused polycyclic) such as cyclo
  • a plasticizer as used herein refers to a compound that can be added to a host polymer (thermoplastics, thermosets, or elastomers), polymer blends, polymer composites, synthetic rubbers, natural rubbers, or other resins (individually and collectively referred to "resin” or “resins” herein) to lower glass transition temperature or melt temperature, increase flexibility, increase toughness, increase elasticity, decrease rigidity, improve low temperature physical properties, and/or improve processibility of the host polymer.
  • a host polymer thermoplastics, thermosets, or elastomers
  • polymer blends polymer composites
  • synthetic rubbers synthetic rubbers
  • natural rubbers or other resins
  • a plasticizer may act to modify any one of or any combination of glass transition temperature, melt temperature, tensile properties (e.g., toughness, % elongation at break, load at break, displacement at break, Young's modulus), flexural properties, impact resistance, extrudability, flexibility, processability, workability, stretchability, and improve a low temperature physical property.
  • tensile properties e.g., toughness, % elongation at break, load at break, displacement at break, Young's modulus
  • flexural properties e.g., impact resistance, extrudability, flexibility, processability, workability, stretchability, and improve a low temperature physical property.
  • a plasticizer acts to lower glass transition temperature of the host resin.
  • a plasticizer increases toughness, increases impact resistance, increases % elongation at break, decreases Young's modulus, increases displacement at break, increases load at break, increases processability, increases flexibility, improves a low
  • the conjugated terpenes disclosed herein may be obtained from any suitable source.
  • the conjugated terpene is obtained from naturally occurring plants or marine species.
  • farnesene can be obtained or derived from naturally occurring terpenes that can be produced by a variety of plants, such as Copaifera langsdorfii, conifers, and spurges; or by insects, such as swallowtail butterflies, leaf beetles, termites, or pine sawflies; and marine organisms, such as algae, sponges, corals, mollusks, and fish.
  • Terpene oils can also be obtained from conifers and spurges.
  • Conifers belong to the plant division Pinophya or Coniferae and are generally cone-bearing seed plants with vascular tissue. Conifers may be trees or shrubs. Non-limiting examples of suitable conifers include cedar, cypress, douglas fir, fir, juniper, kauris, larch, pine, redwood, spruce and yew.
  • Spurges also known as Euphorbia, are a diverse worldwide genus of plants belonging to the spurge family (euphorbiaceae).
  • Farnesene is a sesquiterpene, a member of the terpene family, and can be derived or isolated from terpene oils for use as described herein.
  • a conjugated terpene is derived from a fossil fuel (petroleum or coal), for example, by fractional distillation of petroleum or coal tar.
  • a conjugated terpene is made by chemical synthesis.
  • one non- limiting example of suitable chemical synthesis of farnesene includes dehydrating nerolidol with phosphoryl chloride in pyridine as described in the article by Anet E.F.L.J., "Synthesis of ( ⁇ , ⁇ )- ⁇ -, and (Z)- -farnesene, Aust. J. Chem. 23(10), 2101-2108, which is incorporated herein by reference in its entirety.
  • a conjugated terpene is obtained using genetically modified organisms that are grown using renewable carbon sources (e.g., sugar cane).
  • a conjugated terpene is prepared by contacting a cell capable of making a conjugated terpene with a suitable carbon source under conditions suitable for making a conjugated terpene.
  • suitable carbon source e.g., sugar cane.
  • any carbon source that can be converted into one or more isoprenoid compounds can be used herein.
  • the carbon source is a fermentable carbon source (e.g., sugars), a nonfermentable carbon source or a combination thereof.
  • a non- fermentable carbon source is a carbon source that cannot be converted by an organism into ethanol.
  • suitable non-fermentable carbon sources include acetate, glycerol, lactate and ethanol.
  • the sugar can be any sugar known to one of skill in the art.
  • the sugar is a monosaccharide, disaccharide, polysaccharide or a combination thereof.
  • the sugar is a simple sugar (a monosaccharide or a disaccharide).
  • suitable monosaccharides include glucose, galactose, mannose, fructose, ribose and combinations thereof.
  • suitable disaccharides include sucrose, lactose, maltose, trehalose, cellobiose, and combinations thereof.
  • the sugar is sucrose.
  • the carbon source is a polysaccharide.
  • suitable polysaccharides include starch, glycogen, cellulose, chitin, and combinations thereof.
  • the sugar suitable for making a conjugated terpene can be obtained from a variety of crops or sources.
  • suitable crops or sources include sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain sorghum, switchgrass, barley, hemp, kenaf, potato, sweet potato, cassava, sunflower, fruit, molasses, whey, skim milk, corn, stover, grain, wheat, wood, paper, straw, cotton, cellulose waste, and other biomass.
  • suitable crops or sources include sugar cane, sugar beet and corn.
  • the sugar source is cane juice or molasses.
  • a conjugated terpene can be prepared in a facility capable of biological manufacture of isoprenoids.
  • the facility may comprise any structure useful for preparing C 15 isoprenoids (e.g., a-farnesene, ⁇ - farnesene, nerolidol or farnesol) using a microorganism capable of making the C 15 isoprenoids with a suitable carbon source under conditions suitable for making the C 15 isoprenoids.
  • the biological facility comprises a cell culture comprising a desired isoprenoid (e.g.
  • the biological facility comprises a fermentor comprising one or more cells capable of generating a desired isoprenoid. Any fermentor that can provide for cells or bacteria a stable and optimal environment in which they can grow or reproduce may be used herein.
  • the fermentor comprises a culture comprising one or more cells capable of generating a desired isoprenoid (e.g. , a C 10 , a Ci5, a C 20 , or a C 25 isoprenoid).
  • a desired isoprenoid e.g. , a C 10 , a Ci5, a C 20 , or a C 25 isoprenoid.
  • the fermentor comprises a cell culture capable of biologically manufacturing farnesyl pyrophosphate (FPP).
  • the fermentor comprises a cell culture capable of biologically manufacturing isopentenyl diphosphate (IPP).
  • the fermentor comprises a cell culture comprising a desired isoprenoid (e.g.
  • a C 10 , a C 15 , a C 20 , or a C 25 isoprenoid in an amount of at least about 1 wt.%), at least about 5 wt.%, at least about 10 wt.%, at least about 20 wt.%, or at least about 30 wt.%), based on the total weight of the cell culture.
  • the facility may further comprises any structure capable of manufacturing a chemical derivative from the desired isoprenoid (e.g. , a C 10 , a C 15 , a C 20 , or a C 25 isoprenoid).
  • a facility comprises a reactor for dehydrating nerolidol or farnesol to a- farnesene or ⁇ -farnesene or a combination thereof.
  • a facility comprises a reactor for dehydrating linalool to myrcene or ocimene or a combination thereof. Any reactor that can be used to convert an alcohol into an alkene under conditions known to skilled artisans may be used.
  • the reactor comprises a dehydrating catalyst.
  • Described herein are Diels-Alder adducts of conjugated terpenes and a dienophile, and derivatives of such Diels-Alder adducts.
  • Diels-Alder reaction between a conjugated terpene and a dienophile a [2 ⁇ + 4 ⁇ ] cycloaddition reaction between the conjugated diene moiety of the conjugated terpene and the dienophile occurs.
  • the stereochemistry of the resulting compounds can be reliably predicted using orbital symmetry rules.
  • a Diels-Alder reaction between a conjugated terpene and a dienophile is thermally driven, without the need for a catalyst.
  • a Diels- Alder reaction occurs at a temperature in a range from about 50 °C to about 100 °C, or from about 50 °C to about 130 °C.
  • a catalyst is used, e.g., to increase reaction rate, to increase reactivity of weak dienophiles or sterically hindered reactants, or to increase selectivity of certain adducts or isomers.
  • a Lewis acid catalyst may be used in some variations.
  • a Diels-Alder reaction is run without solvent.
  • reaction conditions ⁇ e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere are selected so that formation of dimers, higher oligomers and/or polymers of the conjugated terpene is suppressed or minimized.
  • reaction conditions ⁇ e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere may be selected so that formation of dimers, higher oligomers and/or polymers of the diene is suppressed or minimized.
  • the reaction conditions ⁇ e.g., temperature, catalyst (if present), solvent (if present), reactant purities, reactant concentrations, reaction times, reaction atmosphere and/or reaction pressure are selected to produce a desired adduct or isomer. More detailed descriptions of the Diels-Alder reaction and reaction conditions for the Diels-Alder reaction are disclosed in the book by Fringuelli et al., titled “Z3 ⁇ 4e Diels-Alder Reaction: Selected Practical Methods," 1st edition, John Wiley & Sons, Ltd., New York (2002), which is incorporated by reference herein in its entirety.
  • Non-limiting Diels-Alder reactions using ⁇ - farnesene to produce pheromones are provided in U.S. Patent No. 4,546,110, which is incorporated herein by reference in its entirety.
  • Certain surfactants derived from Diels-Alder reaction between a hydrocarbon terpene comprising a conjugated diene and a dienophile are disclosed in U.S. Provisional Patent Application Serial No. 61/436,165 filed January 25, 2011, U.S. Provisional Patent Application Serial No. US 61/527,041 filed August 24, 2011, U.S. Provisional Patent Application Serial No. 61/543,747 filed October 5, 2011, U.S. Provisional Patent Application Serial No. 61/544,257 filed October 6, 2011, and PCT Application No. PCT/US2012/02245 filed January 24, 2012, each of which is incorporated herein by reference in its entirety as if put forth fully below.
  • Any conjugated terpene described herein or otherwise known may undergo Diels-Alder reaction with a dienophile to provide a Diels-Alder adduct having utility as a plasticizer.
  • conjugated hydrocarbon terpenes that may be used to make the Diels-Alder adducts are provided in Section E below and include myrcene, ocimene, a-farnesene, ⁇ -farnesene, ⁇ -springene, geranylfarnesene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.
  • Some non- limiting examples of Diels-Alder adducts are provided in Section F below.
  • Non- limiting examples of chemical modifications for Diels-Alder adducts are provided in Section G below.
  • the dienophile used herein can be any dienophile that undergoes a Diels-Alder reaction with a diene on the conjugated hydrocarbon terpene to form the corresponding cyclic compound.
  • the dienophile has formula (I), (II) or (III):
  • each of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted C 1 -C30 hydrocarbyl group (e.g., Ci- C 20 alkyl, C 1 -C 20 alkenyl, C 1 -C 20 alkynyl, cycloalkyl, aryl, aralkyl and alkaryl), hydroxyalkyl (e.g., -CH 2 OH), aminoalkyl (e.g., -CH 2 NH 2 ), carboxylalkyl (e.g., -CH 2 C0 2 H), thioalkyl
  • Ci- C 20 alkyl C 1 -C 20 alkenyl, C 1 -C 20 alkynyl, cycloalkyl, aryl, aralkyl and alkaryl
  • hydroxyalkyl
  • each of R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 is independently H, hydrocarbyl, hydroxyalkyl, aminoalkyl, carboxylalkyl, thioalkyl, epoxyalkyl, hydroxyaryl, aminoaryl, carboxylaryl,
  • each of m, n and k is independently an interger from 1 to 20 or from 1 to 12, with the proviso that at least one of R 11 , R 12 , R 13 and R 14 is not H, and the proviso that at least one of R 15 and R 16 is not H, and the proviso that at least one of R 17 and R 18 is not H.
  • a dienophile has formula (Al), (A2), (A3), (A4), (A5),
  • QA 1 may be O, S, or NRA 19 ; each of QA 2 , QA 3 and QA 4 may independently be a halo
  • substituent e.g., chloro or bromo
  • NRA RA or ORA may be a halo substituent (e.g., chloro or bromo), a cyano group or ORA 23 ; and each of RA 1 , RA 2 , RA 3 , RA 4 , RA 5 , RA 6 , RA 7 , RA 8 , RA 9 , RA 10 , RA 11 , RA 12 , RA 13 , RA 14 , RA 15 , RA 16 , RA 17 , RA 18 , RA 19 , RA 20 , RA 21 , RA 22 and RA 23 is independently H, C 1 -C 20 alkyl, C 1 -C 20 alkenyl, C 1 -C 20 alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, OH, NH 2 , sulfonate, sulfmate,
  • the dienophile comprises an unsaturated carbon-carbon bond with one or more electron withdrawing groups attached to a carbon of the unsaturated bond.
  • electron withdrawing groups that may be attached to an unsaturated carbon-carbon bond in a dienophile include: one or more substituted carbonyl groups such as one or more ester groups represented as -COOR, one or more aldehyde groups represented as -CHO, one or more ketone groups represented as -COR, one or more carboxyl groups represented as -COOH, one or more amide groups represented as -CONRR', one or more imide groups represented as -CONRCOR', one or more aryloxycarbonyl groups such as a phenoxycarbonyl group, one or more carbonyloxycarbonyl groups, or a one or more
  • each of R and R' is independently H or any C 1 -C30 aliphatic, aromatic, linear, branched, cyclic or acyclic, substituted or unsubstituted, saturated or unsaturated hydrocarbyl group, and may include one or more heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or chloride.
  • the dienophile comprises a vinyl sulfonate, vinyl sulfmate, or vinyl sulfoxide.
  • the dienophile comprises sulfur dioxide, or a sulfone
  • R and R' may independently be any C 1 -C30 hydrocarbyl group.
  • Suitable dienophiles that can form Diels-Alder adducts with conjugated terpenes (e.g., farnesene or myrcene) include acrolein, acrylic acid, acrylate esters, vinyl ketones, dialkyl maleates, dialkyl fumarates, maleic anhydride, itaconic acid, maleimides, fumaronitrile, malononitrile, acetylene dicarboxylic acids, and acetylene dicarboxylic acid esters.
  • conjugated terpenes e.g., farnesene or myrcene
  • suitable dienophiles include acrolein, acrylic acid, acrylate esters, vinyl ketones, dialkyl maleates, dialkyl fumarates, maleic anhydride, itaconic acid, maleimides, fumaronitrile, malononitrile, acetylene dicarboxylic acids, and acetylene dicarboxylic
  • dienophiles that can react with a conjugated terpene (e.g., farnesene or myrcene) to produce a compound useful as described herein include dienophiles in groups (A)-(Y) below:
  • dialkyl maleates or dialkyl fumarates e.g., linear or branched, cyclic or acyclic, Ci- C30 dialkyl maleates or dialkyl fumarates such as dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, di-n-propyl maleate, di-n-propyl fumarate, di-isopropyl maleate, di- isopropyl fumarate, di-n-butyl maleate, di-n-butyl fumarate, di(isobutyl) maleate, di(isobutyl) fumarate, di-tert-butyl maleate, di-tert butyl fumate, di-n-pentyl maleate, di-n-pentyl fumarate, di(isopentyl) maleate, di(isopentyl) fumarate, di-n-hexyl maleate, di-n-hexyl fuma
  • dialkyl itaconates e.g., linear or branched, cyclic or acyclic, C 1 -C30 dialkyl itaconates such as dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-isopropyl itaconate, di-n- butyl itaconate, di(isobutyl) itaconate, di-tert-butyl itaconate, di-n-pentyl itaconate, di(isopentyl) itaconate, di-n-hexyl itaconate, di(2-ethylhexyl) itaconate, di(isohexyl) itaconate, di-n-heptyl itaconate, di(isoheptyl) itaconate, di-n-octyl itaconate, di(isooctyl) itaconate, di-n-n-n
  • acrylic acid esters e.g., linear or branched, cyclic or acyclic, Ci-C 30 alkyl acrylates, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isohexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, isoheptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, 2-
  • methacrylic acid esters e.g., linear or branched, cyclic or acyclic, Ci-C 30 alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n- pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, 2- ethylhexyl methacrylate, n-heptyl methacrylate, isoheptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl meth
  • cinnamic acid and cinnamic acid esters e.g., linear or branched, cyclic or acyclic, C 1 -C30 alkyl cinnamate, such as methyl cinnamate and ethyl cinnamate;
  • (M) hydroxyalkyl acrylates e.g., 2-hydroxymethyl acrylate and 2-hydroxyethyl acrylate
  • (N) carboxyalkyl acrylates e.g., 2-carboxyethyl acrylate
  • dialkylamino)alkyl acrylates e.g., 2-(diethylamino)ethyl acrylate
  • dialkyl acetylene dicarboxylates e.g., linear or branched, cyclic or acyclic, C 1 -C30 dialkyl acetylene dicarboxylates such as dimethyl acetylene dicarboxylate, diethyl acetylene dicarboxylate, di-n-propyl acetylene dicarboxylate, di(isopropyl) acetylene dicarboxylate, di-n- butyl acetylene dicarboxylate, di(isobutyl) acetylene dicarboxylate, di(tert-butyl) acetylene dicarboxylate, di-n-pentyl acetylene dicarboxylate, di(isopentyl) acetylene dicarboxylate, di-n- hexyl acetylene dicarboxylate, di(2-ethylhexyl) acet,
  • (Q) vinyl ketones e.g., linear or branched, cyclic or acyclic, aliphatic or aromatic, C 1 -C30 vinyl ketones, such as methyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, n-butyl vinyl ketone, isobutyl vinyl ketone, tert-butyl vinyl ketone, n-pentyl vinyl ketone, n-hexyl vinyl ketone, 2-ethylhexyl vinyl ketone, n-heptyl vinyl ketone, n-octyl vinyl ketone, n-nonyl vinyl ketone, n-decyl vinyl ketone, n-undecyl vinyl ketone, n-dodecyl vinyl ketone, n-tridecyl vinyl ketone, n-tetradecyl vinyl ketone, n-penta
  • maleimide and substituted maleimides e.g., linear or branched, cyclic or acyclic, Ci- C30 alkyl N-substituted maleimides, such as N-methylmaleimide, N-ethyl maleimide, N-n- propyl maleimide, N-isopropyl maleimide, N-n-butyl maleimide, N-tert-butyl maleimide, N-n- pentyl maleimide, N-isopentyl maleimide, N-n-hexyl maleimide, N-isohexyl maleimide, N-(2- ethylhexyl) maleimide, N-n-heptyl maleimide, N-n-octyl maleimide, N-n-decyl maleimide, N-n- undecyl maleimide, N-n-dodecyl maleimide, N-n-tridecyl maleimide
  • (S) dialkyl azidocarboxylates e.g. linear or branched, cyclic or acyclic, C 1 -C30 dialkyl azidocarboxylates, such as dimethyl azidocarboxylate, and diethyl azidocarboxylate;
  • the conjugated hydrocarbon terpene used herein can be any conjugated hydrocarbon terpene having a diene group that undergoes a Diels-Alder reaction with a dienophile to form the corresponding cyclic compound.
  • the conjugated hydrocarbon terpene has formula (IV):
  • each of RB 1 , RB 2 , RB 3 and RB 4 is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted Ci-C 30 hydrocarbyl group, with the proviso that at least one of RB 1 , RB 2 , RB 3 and RB 4 is not hydrogen.
  • hydrocarbon terpene is selected to have a stereochemistry amenable to Diels-
  • the conjugated diene is able to adopt an s-cis conformer.
  • the double bonds exist in an s-cis conformation or conformational rotation around the single bond between the double bonds so that an s-cis conformation of the diene is adoptable.
  • the s-trans conformer population is in rapid equilibrium with s-cis conformers. In some cases, steric effects due to substituents on the conjugated diene may impede a Diels- Alder reaction.
  • hydrocarbon terpenes having terminal conjugated diene groups are selected, i.e., hydrocarbon terpenes in which RB 1 , RB 2 , and RB 3 are each H, but RB 4 is not H.
  • RB 1 is H, but RB 2 , RB 3 and RB 4 are not H.
  • RB 1 and RB 2 are H, but RB 3 and RB 4 are not H.
  • the conjugated hydrocarbon terpene has formula (IV) where each of RB 1 , RB 3 and RB 4 is independently H; and RB 2 has formula (V): wherein n is 1, 2, 3 or 4. In some embodiments, the conjugated hydrocarbon terpene has formula (AI):
  • n 1, 2, 3 or 4.
  • the conjugated hydrocarbon terpene is myrcene which has formula (AI) where n is 1. In some embodiments, the conjugated hydrocarbon terpene is ⁇ - farnesene which has formula (AI) where n is 2. In certain embodiments, the conjugated hydrocarbon terpene is ⁇ -springene which has formula (AI) where n is 3. In some embodiments, the conjugated hydrocarbon terpene is geranylfarnesene which has formula (AI) where n is 4.
  • the conjugated hydrocarbon terpene has formula (IV) where each of RB 3 and RB 4 is H; RB 2 is methyl; and RB 1 has formula (VI):
  • the dashed bond in formula (VI) represents a bond that may be present to result in a double bond, or may not be present to result in a single bond.
  • the conjugated hydrocarbon terpene has formula (All):
  • m 1, 2, 3 or 4.
  • the conjugated hydrocarbon terpene is ⁇ -ocimene which has formula (All) where m is 1. In some embodiments, the conjugated hydrocarbon terpene is a-farnesene which has formula (All) where m is 2.
  • the conjugated hydrocarbon terpene that can react with a dienophile disclosed herein is isodehydrosqualene.
  • the conjugated hydrocarbon terpene is isosqualane precursor I.
  • the hydrocarbon terpene is isosqualane precursor II.
  • Diels-Alder adducts can be prepared by reacting a dienophile disclosed herein with one or more conjugated hydrocarbon terpene under Diels-Alder reaction condition with or without the presence of a catalyst.
  • the hydrocarbon terpene and a dienophile in a Diels-Alder reaction may each demonstrate stereoisomerism.
  • Stereoisomerism of the reactants is preserved in the Diels-Alder adduct, and the relative orientation of the substituents on the reactants is preserved in the Diels-Alder adduct.
  • fumaric acid and fumaric acid esters for example, fumaric acid and fumaric acid esters
  • the carboxylate groups in the Diels-Alder adduct have a 1 ,2-anti- (also referred to as trans-) orientation relative to each other.
  • the carboxylate groups (or anhydride) of maleic anhydride, maleic acid, and maleic acid esters (maleates) have a cis- orientation, so that the carboxylate groups in the Diels- Alder adduct have a ⁇ ,2-syn- (also referred to as cis-) orientation relative to each other.
  • a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (I) to provide the Diels-Alder adduct having formula (VIIA) or (VIIB) or a mixture thereof:
  • RB 1 , RB 2 , RB 3 , RB 4 , R 11 , R 12 , R 13 and R 14 are as defined herein.
  • the Diels-Alder adduct of formula (VIIA) and (VIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIA') and (VIIB') respectively:
  • RB 1 , RB 2 , RB 3 , RB 4 , R 11 , R 12 , R 13 and R 14 are as defined herein.
  • a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (II) to provide the Diels-Alder adduct having formula (VIIIA) or (VIIIB) or a mixture thereof:
  • the Diels-Alder adduct of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB"), respectively.
  • the Diels-Alder adduct of formula (VIIIA) and (VIIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIIA') and (VIIIB') respectively:
  • the Diels-Alder adduct of formula (VIIIA) and (VIIIB) or of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB”), respectively:
  • a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (III) to provide the Diels-Alder adduct having formula (IXA) or (IXB) or a mixture thereof:
  • RB 1 , RB 2 , RB 3 , RB 4 , R 17 and R 18 are as defined herein.
  • RB 2 has formula (X): wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.
  • RB 2 having formula (X) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XI): wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.
  • RB 2 having formula (X) in the adducts disclosed herein can be epoxidized by any epoxidation reaction known to a skilled artisan to form the corresponding epoxy group having formula (XII): wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4. [00134] In certain embodiments, each of RB 3 and RB 4 of the adduct of formula (VIIA),
  • m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4.
  • RB 1 having formula (XIII) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XIV): wherein m is 1, 2, 3 or 4.
  • m is 1.
  • m is 2.
  • m is 3.
  • m is 4.
  • the Diels-Alder adduct between a conjugated hydrocarbon terpene and a dienophile is represented by formula (Bl):
  • RB 1 , RB 2 , RB 3 and RB 4 represent the substituents of the conjugated diene of the conjugated terpene and may each independently be H or a C 1 -C30 saturated or unsaturated, cyclic or acyclic, hydrocarbyl group, with the proviso that one of RB 1 , RB 2 , RB 3 and RB 4 is not hydrogen.
  • QB 1 and QB 2 represent the residue of the dienophile directly following the Diels-Alder reaction.
  • QB 1 and QB 2 represent the residue following Diels-Alder reaction that has undergone subsequent chemical modification.
  • a 6-membered ring adduct is formed by the Diels-Alder reaction.
  • the Diels-Alder adduct formed comprises a 5-membered ring so that QB 1 and QB 2 are the same.
  • Each of the dashed bonds in formula (Bl) independently represents a bond that may be present to result in a double bond, or may not be present to result in a single bond.
  • the Diels-Alder adduct is derived form a dienophile containing a double bond and therefore, the bond between QB 1 and QB 2 is single and the bond between RB 2 and RB 3 is double.
  • the Diels-Alder adduct is derived form a dienophile containing a triple bond, and therefore, the bond between QB 1 and QB 2 is double and the bond between RB 2 and RB 3 is double. In some embodiments, the Diels-Alder adduct is derived form a dienophile containing a double bond and is hydrogenated to saturate the double bond between RB 2 and RB 3 to form a single bond.
  • the Diels-Alder adduct is hydrogenated to saturate all or some of the unsaturated bonds in the ring and/or in one or more of the RB 1 , RB 2 , RB 3 , RB 4 , QB 1 and QB 2 groups.
  • a cyclohexenyl ring may be oxidized to form a cyclohex-dienyl ring.
  • a cyclohexenyl or a cyclohex-dienyl ring may be oxidized so that the ring is aromatic.
  • the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (AI) and a dienophile disclosed herein and the adduct has
  • the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 2.
  • the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 1.
  • the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (All) and a dienophile disclosed herein and the adduct has
  • the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 2.
  • the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 1.
  • Table 1 shows RB 1 , RB 2 , RB 3 and RB 4 for exemplary conjugated terpenes, where dashed lines indicate unsaturated olefmic bonds originating from the conjugated terpene that may in some embodiments be completely or partially hydrogenated prior to or subsequent to the Diels-Alder reaction.
  • Table 2 shows QB 1 and QB 2 for some exemplary dienophiles.
  • isomers may be formed in which RB 1 is reversed with RB 4 , RB 2 is reversed with RB 3 , and/or QB 1 is reversed with QB 2 .
  • the Diels-Alder adduct having formula (Bl) may include any combination of RB 1 , RB 2 , RB 3 and RB 4 shown in Table 1 with any combination of QB 1 and QB 2 shown in Table 2.
  • RB 1 , RB 2 , RB 3 and RB 4 are as defined herein, and RB 1' , RB 2' , RB 3' , and RB 4' are defined as RB 1 , RB 2 , RB 3 and RB 4 .
  • a plasticizer is or comprises a compound having formula (F-
  • R and R' each independently represent a C 1 -C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, or t-butyl.
  • R and R' each independently represent n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n- tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n- eicosyl, or n-tricosyl.
  • R and/or R' comprises one or more heteroatoms, e.g., oxygen, nitrogen, sulfur, phosphorus, or halogen atoms (e.g., chlorine, bromine or iodine). In one embodiment, R and R' are each methyl.
  • a ⁇ ,2-syn orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-IA) is preferred.
  • a 1 ,2-anti orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-l A) is preferred.
  • a plasticizer is or comprises a compound having formula (F-
  • R represents H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group.
  • R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n- undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, n-tetradecy
  • a plasticizer is or comprises or is derived from a compound having formula (F-4) or formula (F-4A):
  • a Diels-Alder adduct is formed in which two conjugated terpene molecules react with a single dienophile (e.g. , a dienophile comprising an acetylenic moiety).
  • a single dienophile e.g. , a dienophile comprising an acetylenic moiety.
  • Some non-limiting examples are shown as entries 1 1 , 12, 13, 14, 16 and 17 in Table 2. It should be noted that the two conjugated terpenes that react with a single dienophile may be the same or different.
  • conjugated terpenes may react with a single dienophile: 2 myrcene; 2 a-farnesene; 2 ⁇ -farnesene; 1 a-farnesene and 1 ⁇ - farnesene; 1 myrcene and 1 ⁇ -farnesene, 1 myrcene and 1 ⁇ -farnesene.
  • a Diels- Alder adduct is formed in which one conjugated terpene molecule (e.g., myrcene, a- farnesene, or ⁇ -farnesene) and one substituted or unsubstituted conjugated diene molecules (e.g. , 1 ,3 -butadiene) is reacted with a single dienophile (e.g., a dienophile comprising an acetylenic moiety).
  • a single dienophile e.g., a dienophile comprising an acetylenic moiety
  • oligomers e.g., dimers and trimers
  • Diels-Alder adducts between oligomers e.g., dimers and trimers
  • oligomers e.g., dimers and trimers
  • ⁇ -farnesene can be dimerized (e.g., to form isodehydrosqualene, isosqualane precursor I or isosqualane precursor II), trimerized, or oligomerized as described in U.S. Patent Application No. 13/1 12,991 (U.S. Patent Publ. 201 1/0287988) filed May 20, 201 1 , and U.S. Patent Application No. 12/552278, filed Sept.
  • dimers, trimers and oligomers so formed may contain a conjugated diene, which can undergo Diels- Alder reaction with a dienophile.
  • a Diels-Alder adduct between one or more conjugated terpenes and a dienophile as described herein may be chemically modified following the Diels- Alder reaction.
  • the chemical modifications may be selected to tune the applicability to the modified Diels-Alder reaction for use as plasticizers.
  • any one of or any suitable combination of the following chemical modifications in any suitable order may be made to a Diels-Alder adduct: i) an alkoxycarbonyl group may be reduced to a hydroxymethyl or methyl group; ii) one or more ester groups may be hydrolyzed to a carboxylic acid or a salt thereof; iii) one or more carboxyl groups may be decarboxylated to a hydrogen; iv) an anhydride group may be opened to yield the dicarboxylic acid compound or a salt thereof; v) one or more ester groups on a Diels-Alder adduct may undergo transesterification with an alcohol (e.g.
  • a methyl ester may undergo transesterification with a Cg or longer primary alcohol); vi) a formyl group may be reduced to a methyloyl group; vii) a hydroxyl substituent may be alkoxylated to form an alkoxylated substituent (e.g., ethoxylated or propoxylated); viii) one or more double bonds originating from the conjugated terpene can be oxidized (e.g., epoxidized); ix) one or more double bonds originating from the conjugated terpene may be halogenated; x) a hydroxyl or ester group may undergo a
  • condensation reaction xi) a hydroxyl group or amide group may undergo a condensation reaction; xii) a hydroxyl group or ester group may be sulfated; xiii) an amine group may be converted to an ammonium ion or an N-oxide; and xiv) a reverse Diels-Alder reaction may occur to yield desired products.
  • a Diels-Alder adduct between a conjugated terpene and a dienophile as described herein is hydrogenated so as to completely or partially hydrogenate aliphatic portions of the Diels-Alder adduct.
  • Such hydrogenated Diels-Alder adducts (and derivatives thereof) may in certain circumstances exhibit improved thermo-oxidative stability in use.
  • the ring formed in the Diels-Alder adduct is oxidized.
  • a cyclohexenyl ring may be oxidized to a cyclohexadienyl ring or to an aromatic 6- membered ring, or a cyclohexadienyl ring may be oxidized to an aromatic 6-membered ring.
  • At least one carbon-carbon double bond remains in the aliphatic tail originating from the conjugated terpene in the Diels-Alder adduct.
  • the unsaturated tail provides a reactive site that may have a variety of functions.
  • the unsaturated tail may be oxidized as described in more detail herein, may provide scavenging functionality, may provide a site oligomerization or polymerization, and/or may provide a site for cross- linking into a matrix.
  • Diels-Alder adducts between conjugated terpenes and dienophiles Diels-Alder adducts between conjugated terpenes and dienophiles.
  • one or more carbon-carbon double bonds of a conjugated terpene Diels- Alder adduct as described herein is oxidized (e.g., epoxidized).
  • oxidized (e.g., epoxidized) hydrocarbon terpene derivatives may be useful in a variety of applications.
  • oxidized farnesene derivatives may exhibit increased compatibility or solubility with relatively polar polymers or solvents.
  • an epoxidized farnesene derivative may be useful as a reactive diluent in a resin and/or as a cross-linking agent. Any suitable oxidation technique known to oxidize carbon-carbon double bonds may be used.
  • any suitable oxidant such as peroxides, peracetic acid, meta chloroperoxybenzoic acid, enzymes, or peroxide complexes such as urea-peroxide complexes (e.g., Novozyme-435TM urea- peroxide complex) may be used.
  • the oxidation (e.g. , epoxidation) conditions are adjusted to oxidize only one carbon-carbon double bond, e.g. , one carbon-carbon double bond that originated in the conjugated terpene starting material.
  • the oxidation (e.g. , epoxidation) conditions are adjusted to oxidize two carbon-carbon double bonds, e.g.
  • oxidation (e.g., epoxidation) conditions are adjusted to oxidize three or more carbon-carbon double bonds, e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material.
  • oxidation (e.g., epoxidation) conditions are adjusted to oxidize substantially all carbon-carbon double bonds originating in the conjugated terpene starting material.
  • a molar ratio of oxidantxonjugated terpene may be lowered (e.g.
  • Hydroxy versions of epoxidized hydrocarbon terpene Diels-Alder adducts may be prepared using any known technique that allows for reaction of epoxy groups to form hydroxyl groups.
  • an epoxy group can be reduced to form a single hydroxy group, or an epoxy group can be hydro lyzed to form two hydroxy groups.
  • the hydroxyl groups may be subsequently acetylated to form a compound that may have use as described herein.
  • a plasticizer comprises ⁇ -farnesene (or a ⁇ -farnesene derivative such as a dimer, trimer or tetramer of ⁇ -farnesene, or a Diels Alder adduct of ⁇ - farnesene and a dieneophile) that has had one, two, three (or four or more, if present) of its double bonds oxidized (e.g., epoxidized) or chlorinated.
  • Hydroxy versions of epoxidized b- farnesene, or dimers, trimers or tetramers of ⁇ -farnesene may be prepared using any known technique that allows for reaction of epoxy groups to form hydroxyl groups.
  • an epoxy group can be reduced to form a single hydroxy group, or an epoxy group can be hydrolyzed to form two hydroxy groups.
  • the hydroxyl groups may be subsequently acetylated to form a compound that may have use as described herein.
  • the alcohols and polyols (e.g., diols) disclosed herein have utility as plasticizers.
  • one or more carbon-carbon double bonds of a conjugated terpene Diels- Alder adduct as described herein is halogenated, e.g., with chlorine where one chlorine atom is added to each double bond using a reagent such as HCl, or where two chlorine atoms are added to each double bond using a reagent such as chlorine gas.
  • a reagent such as HCl
  • chlorine gas such as chlorine gas
  • chloride containing hydrocarbon conjugated terpene derivatives may for example exhibit increased compatibility or solubility with relatively polar polymers or solvents.
  • the reaction conditions are adjusted such only one carbon-carbon double bond is chlorinated, e.g., one carbon-carbon double bond that originated in the conjugated terpene starting material.
  • reaction conditions are adjusted so that two carbon-carbon double bonds are halogenated ⁇ e.g., chlorinated), e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material.
  • reaction conditions are adjusted such that three or more carbon-carbon double bonds are halogenated ⁇ e.g., chlorinated), e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material.
  • substantially all carbon-carbon double bonds originating from the conjugated terpene are halogenated ⁇ e.g., chlorinated).
  • Diels-Alder adducts made using ⁇ -farnesene or a-farnesene as the conjugated hydrocarbon terpene. It should be understood that analogs of these examples of Diels-Alder adducts are contemplated in which conjugated terpenes other than a-farnesene or ⁇ -farnesene are used.
  • a Diels-Alder adduct is formed between ⁇ -farnesene and acrylic acid, s 0 r an acrylate ester, s where R is as described below.
  • a plasticizer, or a monomer, cross-linking agent or reactive diluent for use in making oligomers or polymers that have utility as plasticizers may be derived from a Diels-Alder adduct between ⁇ - farnesene and acrylic acid or an acrylate ester.
  • Diels-Alder adducts formed between ⁇ - farnesene and an acrylate ester can be represented by formula (H-IA), (H-IB), and/or an isomer thereof, or a mixture thereof:
  • R 1 may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g., C1-C30 hydrocarbyl. In some embodiments, R 1 is an aliphatic C1-C30 substituent.
  • R 1 is a linear saturated or unsaturated Ci- C30 hydrocarbyl group (e.g., Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , C 14 , C 15 , C 16 , Cn, Ci8, Ci9, C 2 o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., d, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , Ci8, Ci9, C 2 o or C21-C30 hydrocarbyl).
  • Ci Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8
  • R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2- ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, eth
  • R 1 is an aromatic substituent.
  • R 1 may comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride.
  • R 1 may comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydroxyl group.
  • R 1 is a polyol substituent, e.g., including 2, 3 or 4 hydroxyl groups.
  • R 1 is a saturated or unsaturated C8-C30 fatty acid or a saturated or unsaturated C8-C30 fatty alcohol, e.g., R 1 is cetyl, oleyl or stearyl.
  • R 1 is a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • R 1 is selected to increase the compatibility of the Diels-
  • R 1 may be selected to be a relatively short linear or branched aliphatic hydrocarbon chain (e.g., a linear or branched C1-C4 hydrocarbyl), and/or R 1 may be substituted with or include one or more polar moieties (e.g., R 1 may be a C1-C30 aliphatic hydrocarbon that includes one or more hydroxy, carboxy, amino, epoxy, or chloro substituents, or R 1 may include a carbonyl group or an ether group).
  • the host polymer is relatively polar (e.g., PVC)
  • R 1 may be selected to be a relatively short linear or branched aliphatic hydrocarbon chain (e.g., a linear or branched C1-C4 hydrocarbyl), and/or R 1 may be substituted with or include one or more polar moieties (e.g., R 1 may be a C1-C30 aliphatic hydrocarbon that includes one or more hydroxy, carboxy, amino, epoxy, or
  • R 1 comprises one or more hydroxyl groups such that the adduct is a primary alcohol, an amino group, a primary alcohol including an alkoxylate chain, an alkyl-capped alkoxylate, an amide, an ethanolamide, or one or more glucose groups.
  • a Diels-Alder adduct between ⁇ -farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IA) and (HIB) in any relative amount may be used, e.g., a mixture comprising a ratio of formula (H-IA): formula (H- IB) of about 0.1 :99.9, 1 :99, 5 :95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95 :5, 99: 1 , or 99.9:0.1 by weight, by mole, or by volume.
  • the ratio of formula (H-IA): formula (H-IB) is from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5 :95 to about 95 :5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.
  • a Diels-Alder adduct between ⁇ -farnesene and acrylic acid or an acrylate ester is hydrogenated, prior to use, to form a compound having formula (H-IC), or (H-ID) or an isomer thereof, or a combination thereof:
  • R 2 may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g. , Ci-C 30 .
  • R 2 is an aliphatic Ci-C 3 o substituent.
  • R 2 is a linear saturated or unsaturated Ci-C 3 o hydrocarbyl group (e.g., d, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , Ci8, Ci9, C 2 o or C 2 i-C 3 o hydrocarbyl), or a branched saturated or unsaturated Ci-C 3 o hydrocarbyl group (e.g., Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C9, C10, Cn, Ci 2 , Ci 3 , Ci 4 , C15, Ci 6 , C 17 , C 18 , C19, C 2 o or C 2 i-C 3 o hydrocarbyl).
  • Ci Ci, C 2 , C 3 , C 4 , C 5
  • R 2 is methyl, ethyl, n-propyl, isopropyl, n- butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3- ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, eth
  • R 2 is an aromatic group.
  • R 2 may comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride.
  • R 2 may comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydroxyl group.
  • R 2 is a saturated or unsaturated C 8 -C30 fatty acid or a saturated or unsaturated C 8 -C30 fatty alcohol, e.g., R 2 is cetyl, oleyl or stearyl.
  • R 2 is a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • R 2 includes a polyol substituent, e.g., including 2, 3, or 4 hydroxy groups.
  • R 2 is selected to increase the compatibility of the Diels-
  • Alder adduct with a host polymer may be selected so that the adduct is a primary alcohol, an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, or a glucoside.
  • compounds of formula (H-IC) may be derived from compounds of formula (H-IA), and compounds of formula (H-ID) may be derived from compounds of formula (H-IB) by hydrogenation.
  • hydrogenation occurs so that R 2 is the same as R 1 .
  • some degree of hydrogenation occurs in the R 1 group so that R 2 is not the same as R 1 .
  • compounds of formulae (H- IC) and (H-ID) are derived using additional chemical modification of a hydrogenated Diels- Alder adduct between ⁇ -farnesene and acrylic acid or an acrylate ester, so that R 2 is not the same as R 1 .
  • a mixture of compounds of formulae (H-IC) and (H-ID) in any relative amounts may be used in the applications described herein, e.g. , a mixture comprising a ratio of formula (H-IC): formula (H-ID) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume.
  • the ratio of formula (H-IC): formula (H-ID) is from about 0.1 : 99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.
  • a possible Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester may have formula (H-IE), formula (H-IF), or an isomer thereof, or a mixture thereof:
  • R 1 is as described in relation to formula (H-IA) and (H-IB).
  • a Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IE) and (H-IF) in any relative amount, e.g., a mixture comprising a ratio of formula (H-IE): formula (H-IF) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1 , or 99.9:0.1 by weight, by mole, or by volume.
  • the ratio of formula (H-IE): formula (H-IF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • Compounds of formulae (H-IG) and (H-IH) may be obtained by hydrogenating formulae (H-IE) and (H-IF) or by any suitable route.
  • R 2 is as described in relation to formulae (H-IC) and (H-ID).
  • IC IC
  • H-ID H-IE
  • H-IF H-IG
  • H-IH may be used in any application utilizing esters.
  • a compound having formula (H-IA), (H-IB), (H-IC), (H-ID), (H-IE), (H-IF), (H-IG) and (H-IH) or a derivative thereof may have use as a plasticizer, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.
  • R 3 and R 3 are each independently H or a straight or branched chain, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted substituents or hydrocarbyl, e.g. Ci- C30. In some embodiments, R 3 and R 3 are the same. In other embodiments, R 3 and R 3 are different.
  • each of R 3 and R 3 is independently a linear saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , Ci 4 , Ci5, Ci6, C 17 , Ci8, Ci9, C20 or C 2 i-C 3 o hydrocarbyl ), or a branched saturated or unsaturated Ci-C 30 hydrocarbyl group (e.g., d, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , C 14 , C 15 , Ci 6 , C 17 , Ci 8 , Ci 9 , C 2 o or C 2 i-C 30 hydrocarbyl).
  • a linear saturated or unsaturated C1-C30 hydrocarbyl group
  • each of R 3 and R 3 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2- propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, 2- prop
  • each of R 3 and R 3 is independently an aromatic group.
  • each of R 3 and R 3 may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride.
  • each of R 3 and R 3 may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, a polyalkoxylate, a hydroxyl group, an amine, an amide, or one or more glucose groups.
  • each of R 3 and R 3 may independently include a polyol substituent, e.g., each of R 3 and R 3 may independently include 2, 3 or 4 hydroxy groups.
  • each of R 3 and R 3 is independently a saturated or unsaturated C 8 -C 3 o fatty acid or a saturated or unsaturated C 8 -C 30 fatty alcohol, e.g., each of R 3 and R 3 may independently be cetyl, oleyl or stearyl.
  • each of R 3 and R 3 is independently a Ci-C 3 o aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • carboxylate substituents on the adduct have a 1 ,2- syn- orientation relative to each other originating from the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile. If a 1,2-anti- orientation of the carboxylate substituents relative to each other on the adduct is desired, a dialkyl fumarate may be used as a dienophile instead of a dialkyl maleate.
  • each of R 3 and R 3 is independently selected to increase compatibility a host polymer to be modified.
  • each of R 3 and R 3 may independently be selected to be a relatively short linear or branched aliphatic hydrocarbyl (e.g., a linear or branched C1-C4 hydrocarbyl group), or each of R 3 and R 3 may independently be substituted with or include one or more polar moieties (e.g., each of R 3 and R 3 is independently Ci-C 3 o aliphatic hydrocarbyl that includes one or more hydroxy, carboxy, amino, epoxy, or chloro substituents, each of R 3 and R 3 may independently include a carbonyl group, or each of R 3 and R 3 may independently include an ether).
  • R 3 and R 3 may be selected so that the adduct comprises a primary alcohol (a monoalcohol or a diol), an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, or a glucoside.
  • a primary alcohol a monoalcohol or a diol
  • an amine an alkoxylated alcohol
  • an alkyl-capped alkoxylate a carboxylic acid
  • an amide an ethanolamide
  • glucoside a glucoside
  • a compound having formula (H-IIA) is obtained by derivatizing a Diels-Alder adduct between ⁇ -farnesene and a dienophile.
  • a compound having formula (H-IIA) may be obtained by making a Diels-Alder adduct between ⁇ - farnesene and maleic anhydride, hydrolysis of the farnesene-maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques.
  • each of R 4 and R 4 is independently H or a straight or branched chain, cyclic or acyclic, saturated or unsaturated, substituted or unsubsubstituted substituents, e.g. Ci-C 30 .
  • R 4 and R 4 are the same. In other embodiments, R 4 and R 4 are different.
  • each of R 4 and R 4 is independently a linear saturated or unsaturated C 1 -C30 hydrocarbyl group (e.g., d, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , Cig, Cig, C 2 o or C 2 i-C 3 o hydrocarbyl), or a branched saturated or unsaturated Ci-C 3 o hydrocarbyl group ⁇ e.g., Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 2 o or C 2 i-C 3 o hydrocarbyl).
  • each of R 4 and R 4 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, methyl
  • R 4 and R 4 comprises an aromatic group (e.g., one or both of R 4 and R 4 may comprise a phenyl group or one or both of R 4 and R 4 ' may be a benzyl group).
  • each of R 4 and R 4' may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride.
  • each of R 4 and R 4 may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, a polyalkoxylate, a hydroxyl group, an amide group, an amine group, or one or more glucose groups.
  • each of R 4 and R 4' may independently include a polyol substituent, e.g., each of R 4 and R 4 may
  • each of R 4 and/or R 4 is independently a saturated or unsaturated C 8 -C 30 fatty acid or a saturated or unsaturated C 8 -C 30 fatty alcohol, e.g., each of R 4 and R 4 may independently be cetyl, oleyl or stearyl.
  • each of R 4 and R 4 is independently a Ci-C 3 o aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • Compounds having formula (H-IIB) can be obtained by a variety of methods using Diels- Alder reactions.
  • compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIA).
  • R 3 and R 3 are not affected by the hydrogenation so that R 4 is the same as R 3 and R 4 is the same asR 3 .
  • R 3 and R 3 are at least partially hydrogenated so that R 4 and R 4 are not the same as R 3 and R 3' .
  • compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIB) with further chemical modification, e.g.
  • compounds having formula (H-IIB) are obtained by making a Diels- Alder adduct between ⁇ - farnesene and maleic anhydride, hydrogenating the adduct, and hydrolysis of the hydrogenated farnesene -maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques.
  • (H-IIB) is derived by hydrogenating (H-IIA) made using a maleate dienophile
  • the carboxylate groups on (H-IIB) have a 1 ,2-syn- orientation relative to each other originating from cis- orientation of the carboxylate substituents on the maleate dienophile
  • (H-IIB) is derived by hydrogenating (H-IIA) made by using a fumarate dienophile
  • the carboxylate groups on (H-IIB) have a 1 ,2-anti orientation relative to each other originating from the trans- orientation of the carboxylate substituents on the fumarate dienophile.
  • each of R 4 and R 4 is independently selected to increase compatibility with a host polymer to be modified.
  • the host resin is a relatively polar substance
  • each of R 4 and R 4 may independently be selected to be a relatively short linear or branched aliphatic hydrocarbyl chain (e.g., a linear or branched C 1 -C4 hydrocarbyl), or each of R 4 and R 4' may independently be substituted with or include one or more polar moieties (e.g., each of R 4 and R 4 may independently be a C 1 -C30 aliphatic hydrocarbyl that includes one or more hydroxy, carboxy, amino, epoxy, or chloro substituents, each of R 4 and R 4 may
  • R 4 and R 4 may independently include an ether group).
  • one or both of R 4 and R 4 may be selected so that the adduct comprises a primary alcohol, an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, a glucoside, or a glucamide.
  • H-IIA where R 3 and R 3 are as described in relation to formula (H-IIA).
  • the carboxylate substituents on the adduct (H-IIC) have a 1 ,2-syn- orientation relative to each other originating from the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile. If a 1,2-anti- orientation of the carboxylate substituents on the adduct is desired, a dialkyl fumarate may be used as a dienophile instead of a dialkyl maleate.
  • Compounds having formula (H-IID) may be made by hydrogenating compounds of formula (H-IIC), or by any suitable reduction reaction:
  • maleic anhydride Dienophiles [00180] In some embodiments, maleic anhydride is used as a dienophile in a Diels- Alder reaction with farnesene. A reaction product with ⁇ -farnesene is shown as compound (H-IIIA):
  • Compound (H-IIIA) can be hydrogenated to form Compound (H-IIIB).
  • Compound (H-IIIC) can be hydrogenated to form Compound (H-IIID).
  • the anhydride compounds (H-IIIA), (H-IIIB), (H-IIIC) and (H-IIID) may be used as plasticizers.
  • the anhydride compounds disclosed herein may be used as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.
  • the anhydride compounds are treated with one or more polyols such as diols and triols as comonomers to make polyesters that may have utility as plasticizers.
  • Compounds (H-IVA), (H-IVB), (H-IVC) and (H-IVD) can be made by any suitable method.
  • a Diels- Alder adduct between ⁇ -farnesene and maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g., using lithium aluminum hydride) to form Compound (H-IVA).
  • Compound (H-IVB) may be made by hydrogenating Compound (H-IVA), or alternatively by reducing Compound (H- IIIB) using known techniques.
  • a Diels- Alder adduct between a- farnesene and maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g., using lithium aluminum hydride) to form Compound (H-IVC).
  • Compound (H-IVD) may be made by hydrogenating Compound (H-IVC), or alternatively by reducing a compound having formula (H-IIID) using known techniques.
  • the diols of formulae (H-IVA), (H-IVB), (H-IVC) and (H-IVD) may be used in place of any diol.
  • the diol of formula (H-IVA), (H-IVB), (H-IVC) or (H-IVD) or a derivative thereof may be used to make an ester or a diester as a plasticizer.
  • the diols disclosed herein may be use as monomers or comonomers, cross- linking agents, or reactive diluents for making oligomers or polymers that may have utility as plasticizers.
  • Nonlimiting examples of polymers that may employ diols disclosed herein include polyesters, co-polyesters, polyurethanes, and polycarbonates.
  • the diols disclosed herein may be alkoxylated to make a plasticizer.
  • R 5 and R 5 may independently be H, a C1-C30 saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubsubstituted aromatic group.
  • each of R 5 and R 5 may independently be a linear saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C9, C 10 , C11, C12, Ci3, CM, Ci5, Ci6, Ci7, C 18 , Ci9, C 2 o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., C C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C u , C 12 , C 13 , CM, Ci5, Ci6, C 17 , Ci8, Ci9, C 2 o or C21-C30 hydrocarbyl).
  • C1-C30 hydrocarbyl group e.g., Ci, C 2 , C 3 , C 4 , C 5
  • each of R 5 and R 5 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n- pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, methyl
  • each of R 5 and R 5 is independently aromatic, or alkylaromatic. In some embodiments, each of R 5 and R 5 ' is benzyl. In some embodiments, each of R 5 and R 5 may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R 5 and R 5 may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydro xyl group. In some embodiments, each of R 5 and R 5 is independently a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • Compounds of formula (H-VA) may be obtained as a Diels- Alder reaction product between ⁇ -farnesene and a maleimide.
  • Compounds of formula (H-VC) may be obtained as a Diels- Alder adduct between a-farnesene and a maleimide.
  • the Diels-Alder adduct may be subsequently chemically modified to incorporate a desired functionality into the adduct.
  • a compound having formula (H-VB) may be derived by hydrogenating a compound having formula (H-VA).
  • a compound having formula (H-VD) may be derived by hydrogenating a compound having formula (H-VC).
  • a compound having formula (H-VB) is obtained by hydrogenating a compound having formula (H-VA), with additional chemical modification.
  • a compound having formula (H-VD) is obtained by hydrogenating a compound having formula (H-VC), with additional chemical modification.
  • the maleimide compounds of formulae (H-VA), (H-VB), (H-VC) and (H-VD) may be used in any application utilizing a maleimide.
  • the maleimide compounds disclosed herein may be used as plasticizers, or as monomers or comonomers, cross- linking agents, or reactive diluents for making oligomers or polymers that may have utility as plasticizers.
  • fumaronitrile, CN ? undergoes a Diels-Alder reaction with ⁇ -farnesene or a-farnesene.
  • the reaction product between ⁇ -farnesene and fumaronitrile is Compound (H-VIA) and the proposed reaction product between a-farnesene and fumaronitrile is Compound (H-VIB):
  • the cyano groups in the Diels-Alder adducts have a trans- orientation relative to each other originating from the trans orientation of the fumaronitrile.
  • compounds having formula (H-VIA) and (H-VIB) or derivatives thereof may be used as plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.
  • compounds (H-VIA) and (H-VIB) are hydrogenated.
  • the nitrile groups on compounds (H-VIA) and (H-VIB) may undergo hydrolysis under acid or base to form the dicarboxamide or dicarboxylic acid using known techniques.
  • compounds having structure (H-VIC) or (H-VID) may be derived from compound (H-VIA) using hydrolysis:
  • an unsaturated aldehyde is used as a dienophile in a Diels-
  • R may be H, a linear or branched hydrocarbyl group or a halo substituent.
  • C1-C30 alkyl In some embodim C1-C30 alkyl .
  • unsaturated aldehydes include acrolein, , and crotonaldehyde, O .
  • the reaction product between ⁇ - farnesene and acrolein may be Compound (H-VIIA) or (H-VIIB) or a mixture thereof in which Compound (H-VIIA) and Compound (H-VIIB) are present in any relative amounts, e.g., a mixture comprising a ratio of Compound (H-VIIA): Compound (H-VIIB) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume.
  • the ratio of Compound (H- VIIA):Compound (H-VIIB) is from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a ratio of Compound (H-VIIC) Compound (H-VIID) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight
  • the ratio of Compound (H-VIIC) :Compound (H- VIID) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • reaction products between ⁇ -farnesene and crotonaldehyde are illustrated by Compounds (H-VIIE) and (H-VIIF), where the reaction product may be (H-VIIE), (H-VIIF), or a mixture thereof in which Compounds (H-VIIE) and (H-VIIF) are present in any relative amounts, e.g., a ratio of Compounds (H-VIIE): Compounds (H-VIIF) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume.
  • a ratio of Compounds (H-VIIE): Compounds (H-VIIF) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50
  • the ratio of Compound (H- VIIE):Compound (H-VIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • the ratio of Compound (H-VIIG) Compound (H-VIIH) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • H-VIID H-VIIE
  • H-VIIF H-VIIG
  • H-VIIH or derivatives thereof
  • compounds having formula (H-VIIA), (H-VIIB), (H-VIIC), (H-VIID), (H-VIIE), (H-VIIF), (H- VIIG), or (H-VIIH) may be hydrogenated, and alcohols derived from the aldehydes, e.g., as shown in Examples 3, 4, and 11 herein. As described herein and as illustrated in the Examples, the alcohols may be ethoxylated. The ethoxylated alcohols may have utility as platicizers in certain applications.
  • itaconic anhydride itaconic acid
  • dialkyl itaconate is used as a dienophile in a Diels- Alder reaction with ⁇ - farnesene or a-farnesene, where R is any suitable hydrocarbyl group, e.g., a C 1 -C30 hydrocarbyl group.
  • R is any suitable hydrocarbyl group, e.g., a C 1 -C30 hydrocarbyl group.
  • dialkyl itaconates that may be used include dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-sec-butyl itaconate, di-tert-butyl itaconate,
  • reaction product between ⁇ -farnesene and itaconic acid or a dialkyl itaconate is illustrated by formulae (H-VIIIA) and (H-VIIIB) where R is H or any suitable hydrocarbyl group, e.g., a C 1 -C30 hydrocarbyl group , where the reaction product may have formula (H- VIIIA) or (H-VIIIB), or a mixture thereof in which formula (H-VIIIA) and formula (H-VIIIB) are present in any relative amounts, e.g., a ratio of formula (H-VIIIA): formula (H-VIIIB) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume.
  • R is H or any suitable hydrocarbyl group, e.g
  • the ratio of formula (H- VIIIA): formula (H-VIIIB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • the ratio of Compound (H-VIIIE): Compound (H-VIIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a-farnesene may undergo Diels- Alder reaction with itaconic anhydride, itaconic acid or a dialkyl itaconate.
  • itaconic anhydride for example, possible reaction products between a-farnesene and itaconic anhydride are shown as Compounds (H-VIIIJ) and (H-VIIIK),
  • the reaction product may be Compound (H-VIIIJ) or (H-VIIIK) or a mixture thereof, where Compounds (H-VIIIJ) and (H-VIIIK) are present in any relative amounts, e.g., a ratio
  • Compound (H-VIIIJ) Compound (H-VIIIK) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99: 1, or 99.9:0.1 by weight, by mole, or by volume.
  • the ratio of Compound (H-VIIIJ): Compound (H-VIIIK) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • Compounds (H-VIIIL) and (H-VIIIM) may be obtained by hydrogenating Compounds (H-VIIIJ) and (H-VIIIK) respectively, or by any suitable route.
  • the anhydride compounds disclosed herein can be used as monomers or co- monomers, cross-linking agents, or reactive diluents to make oligomers or polymers that have utility as plasticizers.
  • the anhydride compositions may be used in any oligomerization or polymerization reaction that utilizes anhydride monomers to make plasticizers.
  • R or R may be selected to increase compatibility of the plasticizer with a host polymer to be modified.
  • the anhydride functionality may be opened up using known techniques to form a diacid, which may be used as is as a plasticizer, or further reacted to form a plasticizer as described herein.
  • acetylene dicarboxylic acid , or acetylene
  • R can be any suitable hydrocarbyl group (e.g., Ci-C 30 hydrocarbyl), is used as a dienophile in a Diels-Alder reaction with farnesene.
  • a reaction product between ⁇ -farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXA) and (H-IXB), where the reaction product may be represented by Compound (H-IXA) or (H-IXB), or a mixture thereof, in which Compound (H- IXA) and Compound (H-IXB) are present in any relative amounts, e.g., a ratio of Compound (H- IXA):Compound (H-IXB) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5 :95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95 :5, 99: 1 , 99.9:0.1 , 99.99:0.01 , 99.999:0.001 by weight, by mole, or by volume.
  • the ratio of Compound (H- IXA):Compound (H-IXB) is from about 0.001 :99.999 to about 99.999:0.001 , from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5 :95 to about 95 :5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a reaction product between a-farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXC) and (H-IXD), where the reaction product may be represented by Compound (H-IXC) or (H-IXD), or a mixture thereof, in which Compound (H- IXC) and Compound (H-IXD) are present in any relative amounts, e.g., a ratio of Compound (H- IXC):Compound (H-IXD) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume.
  • the ratio of Compound (H- IXC):Compound (H-IXD) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a reaction product between ⁇ -farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXE) and (H-IXF),where the reaction product may be represented by formula (H-IXE) or (H-IXF), or a mixture thereof, in which formula (H-IXE) and formula (H-IXF) are present in any relative amounts, e.g., a ratio of formula (H-IXE): formula (H-IXF) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1 , 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume.
  • the ratio of formula (H-IXE) the ratio of formula (H
  • each of R 6 and R 6 is independently H, a C 1 -C 30 saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group.
  • each of R 6 and R 6 may independently be a linear saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C9, C 10 , C11, C12, Ci3, CM, Ci5, Ci6, Ci7, C 18 , Ci9, C 2 o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C 12 , C 13 , C M , Ci 5 , Ci 6 , C 17 , Ci 8 , Ci 9 , C 2 o or C 21 -C30 hydrocarbyl).
  • C1-C30 hydrocarbyl group e.g., Ci, C 2 , C 3
  • each of R 5 and R 5 is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n- pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylunde
  • each of R 6 and R 6 is independently aromatic (e.g., one or both of R 6 and R 6 may be phenyl or benzyl groups).
  • each of R 6 and R 6 may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen, or chloride.
  • each of R 6 and R 6 may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy, or a hydroxyl group.
  • each of R 6 and R 6 is independently a Ci-C 30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.
  • a reaction product between a-farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXG) and (H-IXH), where the reaction product may be represented by formula (H-IXG) or (H-IXH) or a mixture thereof, in which formula (H-IXG) and formula (H-IXH) are present in any relative amounts, e.g., a ratio of formula (H- IXG):formula (H-IXH) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume.
  • the ratio of formula (H-IXG): formula (H-IXH) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • R 6 and R 6 are as described in relation to formulae (H-IXE) and (H-IXF).
  • Compounds (H-IXA), (H-IXB), (H-IXC) and (H-IXD) and compounds of formulae (H-IXE), (H-IXF), (H-IXG), and (H-IXH) may be used in any application that utilizes an unsaturated carboxylic acid or unsaturated carboxylic acid ester.
  • Compounds (H-IXA) and (H-IXC), and Compounds of formulae (H-IXE) and (H-IXG) may be reacted with another conjugated terpene or conjugated diene.
  • Compounds (H-IXA), (H-IXB), (H-IXC) and (H-IXD) and Compounds of formulae (H-IXE), (H-IXF), (H-IXG) and (H-IXH) and derivatives thereof may have utility as plasticizers and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.
  • compound (H-IXB) or (H-IXD) or compounds having formulae (H-IXF) or (H-IXH) may be used in applications utilizing benzoate plasticizers.
  • an acetylene diamide or dicyanoacetylene is used as a dienophile with farnesene in a Diels-Alder reaction.
  • a reaction product between an acetylene diamide and ⁇ -farnesene is represented by formulae (H-XA) and (H-XB), where the reaction product may have formula (H-XA) or (H-XB), or a mixture thereof , in which formulae (H-XA) and (H-XB) may be present in any relative amounts, a ratio of formula (H-XA): formula (H-XB) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.00
  • the ratio of formula (H-XA): formula (H-XB) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a reaction product between an acetylene diamide and a-farnesene is represented by formulae (H-XC) and H- (XD), where the reaction product may be formula (H-XC) or (H- XD), or a mixture thereof, in which formulae (H-XC) and (H-XD) may be present in any relative amounts, e.g., a ratio of formula (H-XC): formula (H-XD) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume.
  • the ratio of formula (H-XC): formula (H-XD) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a ratio of Compound (H-XE): Compound (H-XF) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :
  • the ratio of Compound (H-XE): Compound (H-XF) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • a reaction product between dicyanoacetylene and a-farnesene is shown as
  • a ratio of Compound (H-XG): Compound (H-XH) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1
  • the ratio of Compound (H-XG):Compound (H-XH) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • dicyanoacetylene is derived from acetylene dicarboxylic acid, following by treatment with ammoniolysis, followed by dehydration with P2O5 or the like. In some embodiments, dicyanoacetylene is derived from acetylene diamide, followed by dehydration with P2O5 or the like. In some embodiments, a Diels- Alder adduct between ⁇ - farnesene and acetylene dicarboxylic acid or acetylene diamide is dehydrated to make
  • (H-XE), (H-XF), (H-XG) and (H-XH) may be used in any application that utilizes an unsaturated diamide or saturated dicyanoacetylene.
  • compounds of formula (H-XA) and (H-XC), and Compounds (H-XE) and (H-XG) may be reacted with another conjugated terpene or conjugated diene ⁇ e.g., 1,3-butadiene or a substituted 1,3 -butadiene).
  • H-XA Compounds of formula (H-XA), (H-XB), (H-XC) and (H-XD), and Compounds (H-XE), (H- XF), (H-XG) and (H-XH) and derivatives thereof may have utility as plasticizers and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.
  • H-XI Quinone Dienophiles
  • a benzoquinone or a naphthoquinone is used as a dienophile.
  • Compound (H-XIA), (H-XIB) or (H-XIC) may be made as a Diels- Alder adduct between ⁇ -farnesene and 1,4-benzoquinone.
  • Compounds (H-XIA), (H-XIB) and (H-XIC) may be hydrogenated to form compounds (H-XID), (H-XIE) and (H-XIF) respectively.
  • H-XIA Only one of Compounds (H-XIA), (H-XIB) and (H-XIC) is produced during a Diels-Alder reaction.
  • the reaction conditions may be slowed or otherwise controlled to produce only Compound (H-XIA).
  • the reaction conditions may favor formation of a mixture of Compounds (H-XIB) and (H-XIC) in which Compounds (H-XIB) and (H-XIC) are present in any relative amounts, e.g., a ratio of Compound (H-XIB): Compound (H-XIC) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume.
  • a ratio of Compound (H-XIB): Compound (H-XIC) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:
  • the ratio of Compound (H-XIB) Compound (H-XIC) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.
  • all three of compounds (H-XIA), (H- XIB) and (H-XIC) are present.
  • Compound (H-XIA) may be oxidized to form a benzoquinone having structure ( ⁇ - ⁇ '):
  • Compounds (H-XIB) and/or (H-XIC) may be oxidized to form a benzoquinone having structures ( ⁇ - ⁇ ') and (H-XIC), respectively:
  • H-XIB Compounds (H-XIB) and/or (H-XIC) may be oxidized to form an anthraquinone having structures (H-XIB”) and (H-XIC”) respectively:
  • ⁇ -Farnesene may also react with 1 ,4-benzoquinone or 1 ,2-benzoquinone in a
  • H-XIS may be completely or partially hydrogenated prior to use.
  • Compounds of formulae (H- XIA)-(H-XIS) may be used in any application that utilizes ketones or quinones.
  • Compounds (H-XIA)-(H-XIS) and derivatives thereof may have utility as plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.
  • one or more unsaturated bonds of a conjugated hydrocarbon terpene may be oxidized (e.g., epoxidized).
  • oxidized e.g., epoxidized
  • mono-epoxides, di- epoxides, tri-epoxides, and tetra-epoxides derived from ⁇ -farnesene are Compounds (15a), (15b), (16), (17) and (18) as shown below:
  • one or more unsaturated bonds originating from the conjugated terpene in a Diels-Alder adduct is oxidized (e.g., epoxidized).
  • epoxidized Diels-Alder adduct having any of structures (H-XIIA)-(H-XIIF) may be formed.
  • one or more remaining double bonds of adducts (H-XIIA)-(H-XIIE) may be hydrogenated to the corresponding Compounds (H-XIIA')-(H-XIIE') as shown below:
  • each of R and R' independently represents H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted alkyl group, and R and R' may be the same or different.
  • each of R and R' independently represents a C1-C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or t-butyl.
  • each of R and R' independently represent n-pentyl, isopentyl, n-hexyl, 2- ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, n-tetradecyl, n- pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl.
  • each of R and R' independently represent
  • each of R and R' is independently methyl.
  • any suitable Diels-Alder adduct described herein may be oxidized in a similar fashion.
  • Epoxidized Diels-Alder adducts or derivatives thereof may have utility as plasticizers, or as monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers that have utility as plasticizers.
  • the epoxidized Diels-Alder adducts disclosed herein can be used to prepare epoxy containing plasticizers or various epoxidized or epoxy-modified plasticizers.
  • one or more unsaturated bonds ⁇ e.g. , in the aliphatic tail originating from the conjugated hydrocarbon terpene) may be halogenated ⁇ e.g., chlorinated).
  • Halogenated Diels-Alder adducts or derivatives thereof may have utility as plasticizers, or monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers that have utility as plasticizers.
  • a 1 ,2-syn orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-1A) is preferred.
  • a 1 ,2-anti orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-l A) is preferred.
  • Plasticizers described herein can be used to make a variety of plasticized compositions.
  • Plasticized compositions comprise one or more plasticizers described herein and a host resin (which may comprise a homopolymer, an interpolymer, or a polymer blend, and may be a thermoplastic, thermoset, elastomer or rubber).
  • host resin which may comprise a homopolymer, an interpolymer, or a polymer blend, and may be a thermoplastic, thermoset, elastomer or rubber.
  • plasticized compositions may comprise one or more secondary plasticizers and/or one or more additives.
  • a plasticizer as described herein can be combined with a host polymer
  • thermoplastics thermosets, elastomers or rubbers
  • polymer blends polymer composites, synthetic rubbers, natural rubbers, or other resins (individually and collectively referred to "resin” or “resins” herein) to lower rigidity, decrease brittleness (e.g., at low temperature), increase flexibility, increase toughness and/or improve processibility of the host polymer.
  • a plasticizer may act to modify any one of or any combination of glass transition temperature, melt viscosity, tensile properties (e.g., toughness, % elongation at break, load at break, displacement at break, Young's modulus), flexural properties, hardness, impact resistance, extrudability, flexibility, processability, workability, stretchability and/or a physical property at low temperature.
  • tensile properties e.g., toughness, % elongation at break, load at break, displacement at break, Young's modulus
  • flexural properties e.g., hardness, impact resistance, extrudability, flexibility, processability, workability, stretchability and/or a physical property at low temperature.
  • a plasticizer acts to lower glass transition temperature of the host resin.
  • a plasticizer decreases melt viscosity.
  • a plasticizer increases toughness, increases impact resistance, increases % elongation at break, decreases Young's modulus (stiffness), increases displacement at break, increases load at break, increases processability, increases flexibility, improves a low temperature property, or any combination of two or more of the foregoing.
  • a plasticizer as described herein is incorporated into a host polymer at a level as to antiplasticize the polymer, thereby increasing glass transition temperature, increasing rigidity, and/or decreasing flexibility of the host polymer.
  • Polymer compositions are disclosed herein that comprise one or more plasticizers described herein in a host resin, wherein the plasticizer is present in an effective amount to modify one or more of the glass transition temperature, melt viscosity, hardness, impact resistance, low temperature brittleness, elasticity, toughness, elongation at break, displacement at break, load at break, energy to yield, impact resistance, flexibility, flexural strength, processability, or stretchability.
  • the plasticizers described herein may be selected to have sufficiently low volatility under processing and use conditions such that they do not exhibit undesirable levels of migration within the host polymer or exude from the host polymer. Volatility may be reduced by selecting higher molecular weight plasticizers, selecting plasticizers with a high degree of compatibility with a host resin, and/or by selecting functional groups on the plasticizer that increase interaction with the host polymer.
  • a plasticizer may be either a liquid or a solid at ambient temperature.
  • the plasticizer exhibits sufficient thermal stability at temperatures at which the resin will be processed, including temperatures used for melt-mixing, extrusion, injection molding, compression molding calendaring, laminating, blown film processing, and the like.
  • the plasticizer exhibits sufficiently low volatility at typical resin processing temperatures so as to allow melt mixing, extrusion, injection molding, compression molding, calendaring, laminating, blown film processing, and the like.
  • a plasticizer used to plasticize PVC may exhibit sufficient thermal stability and sufficiently low volatility to allow polymer processing at temperatures in a range from 150°C-210°C.
  • a plasticizer is solid at ambient temperature, in some variations, the plasticizer has a softening temperature that allows melt mixing with the polymer to be plasticized, e.g., if used to plasticize PVC, a solid plasticizer may have a softening temperature appropriate for melt mixing at temperatures in a range from 150°C-210°C.
  • Diels-Alder plasticizer adducts and farnesene derivative plasticizers as described herein may be designed using known principles to increase thermal stability while maintaining a desired degree of compatibility with the host polymer.
  • Diels-Alder derivatives having functionality known to exhibit improved thermal stability may be selected, such as imides.
  • Such thermally stable molecules may be functionalized or derivatized using known methods to improve compatibility with host resins.
  • Non- limiting examples of Diels-Alder adducts that are imides have formula (H-VA)-(H-VD).
  • Diels-Alder imide adducts having formula (H-VA), (H-VB), (H-VC), or (H-VD) with R5 or R5' as benzyl are used as plasticizers, e.g., plasticizers exhibiting enhanced thermal stability in some applications.
  • Diels-Alder imide adducts having formula (H-VA) or (H-VC) with unsaturated bonds may be chlorinated or oxidized (e.g., to form epoxides) as described herein to improve compatibility with a host polymer.
  • a plasticizer may be incorporated into the resin and interact with the resin in any suitable manner to impart the desired physical or mechanical properties to the plasticized resin.
  • the plasticizer is at least partially miscible in the host resin.
  • a portion of the plasticizer is compatible with the resin.
  • the plasticized resin is not completely homogeneous in composition, such that domains rich in resin or domains rich in plasticizer are formed.
  • the plasticized resin shows evidence of phase separation between the resin and the plasticizer.
  • the amount of plasticizer used in a polymer composition to impart the desired physical or mechanical properties to the plasticized resin may be affected by a number of factors, including the compatibility between the resin and the plasticizer, the effectiveness of the plasticizer, migration of the plasticizer within the host resin, bleeding or leaching of the plasticizer out of the host resin, the intended use for the plasticized resin, processing conditions, and any applicable industry standards.
  • a plasticizer disclosed herein is added to a resin in an amount sufficient to impart desired physical or mechanical properties to the plasticized resin.
  • plasticizer is used to impart desired physical or mechanical properties to the plasticized resin, where wt% is based on the total weight of the plasticized resin.
  • the amount of plasticizer in a plasticized resin is about 50wt% or less, about 45wt%, or less, about 40 wt% or less, about 30wt% or less, about 35wt% or less, about 30wt% or less, about 25wt% or less, about 20wt% or less, about 15wt% or less, about 10wt% or less, or about 5 wt% or less, based on total weight of the plasticized resin.
  • an effective amount of plasticizer is from greater than 0 to about 60 wt%, from greater than 0 to about 50 wt%, from greater than 0 to about 40 wt%, from greater than 0 to about 30 wt%, from greater than 0 to about 20 wt%, from greater than 0 to about 15 wt%, from greater than 0 to about 10 wt%, from greater than 0 to about 5 wt%, from about 1 to about 40 wt%, from about 1 to about 30 wt%, from about 1 to about 20 wt%, from about 5 to about 40 wt%, from about 5 to about 30 wt%, from about 5 to about 20 wt%, about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 w
  • the host polymer resin can be any type of polymer in which plasticization is desired to improve one or more physical or mechanical parameters (e.g., decrease glass transition temperature, decrease rigidity, increase flexibility, decrease melt viscosity, toughen, improve low temperature properties, and the like).
  • plasticization e.g., decrease glass transition temperature, decrease rigidity, increase flexibility, decrease melt viscosity, toughen, improve low temperature properties, and the like.
  • the host resin is a polyvinylchloride, a chlorinated polyvinylchloride, a polycarbonate, a polyurethane, a nitrile polymer (such as acrylonitrile butadiene styrene (ABS)), an acrylate polymer (e.g., a polymethacrylate), a polystyrene, a polyester, a polyamide, a polyimide, a polyvinyl acetal, a cellulose polymer, a polyolefm, a phenolic resin, a starch, a natural rubber, a synthetic rubber, an interpolymer of any of the foregoing, a polymer blend of any of the foregoing, or a polymer composite of any of the foregoing.
  • ABS acrylonitrile butadiene styrene
  • polymer compositions comprise one or more additives in addition to one or more plasticizers described herein, e.g., an antioxidant, a flame retardant, a processing aid, an inorganic filler, or a colorant.
  • additives e.g., an antioxidant, a flame retardant, a processing aid, an inorganic filler, or a colorant.
  • the polymer to be plasticized can be a vinyl polymer or copolymer, a non- vinyl polymer or copolymer, or a combination thereof.
  • vinyl polymers and copolymers are disclosed in Malcolm P. Stevens, "Polymer Chemistry, an
  • PVC polystyrene resin
  • any suitable grade of PVC can be used, to be selected by intended application.
  • a rigid grade or a flexible grade of PVC may be used.
  • a flexible grade of PVC is used.
  • a grade of PVC suitable for making bottles is used.
  • a grade of PVC suitable for making thin films is used.
  • a grade of PVC suitable for making blown films is used.
  • a grade of PVC suitable for extrusion is used.
  • a grade of PVC suitable for coating wire is used.
  • a host resin comprises a chlorinated PVC (CPVC).
  • CPVC chlorinated PVC
  • solubility parameters e.g., Hansen solubility parameters
  • PVC may be plasticized using one or more plasticizers described herein to decrease rigidity, increase flexibility, improve processibility, increase toughness, improve low
  • the host resin comprises a polyolefm.
  • polyolefms that may be plasticized with plasticizers described herein include polyethylene, polypropylene, an ethylene/a-olefm interpolymer, a copolymer of ethylene and propylene, a copolymer of ethylene and vinyl acetate (EVA), a polyfarnesene, a polyfarnesane, an interpolymer of farnesene such as a copolymer of farnesene and a styrene), or hydrogenated versions farnesene interpolymers.
  • EVA ethylene and vinyl acetate
  • a polyfarnesene a polyfarnesane
  • an interpolymer of farnesene such as a copolymer of farnesene and a styrene
  • hydrogenated versions farnesene interpolymers Nonlimiting examples of farnesene interpolymers are disclosed in U.S. Pat. Publ.
  • the host resin comprises a styrenic polymer.
  • solubility parameters e.g., Hansen solubility parameters
  • the host resin comprises a styrenic polymer.
  • styrenic polymers that may be plasticized with plasticizers described herein include polystyrene, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene),
  • solubility parameters may be useful in determining a suitable plasticizer for a given styrenic host resin.
  • the host resin comprises a polyester or a copolymer comprising a polyester.
  • a polyester that may be plasticized with one or more plasticizers described herein may be aromatic, aliphatic, or aliphatic-aromatic interpolymers.
  • a linear saturated aromatic polyester such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) is plasticized with one or more plasticizers described herein.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • an aliphatic-aromatic terpolyester e.g., poly(butylene terephthalate-co- succinate-co-adipate
  • plasticizers described herein is plasticized with one or more plasticizers described herein.
  • an aliphatic polyester or copolyester such as a lactic-acid based polyester, a polycaprolactone, a polyesteramide, or a polyhydroxyalkanoate (e.g., poly(hydroxybutyrate-co- hydroxyvalerate) may be plasticized with one or more plasticizers described herein.
  • the polymer is a biodegradable polyester such as poly(lactic acid) or an interpolymer of lactic acid, a polycaprolactone, a polyesteramide, a
  • Non-limiting examples of aliphatic lactic acid-based polyesters that may be plasticized with plasticizers described herein include poly(lactic acid) (PLA); interpolymers between lactic acid and an aliphatic
  • polyesters comprising polyfunctional polysaccharides and a lactic acid repeat unit; aliphatic polyesters comprising an aliphatic polyvalent carboxylic acid unit, an aliphatic polyvalent alcohol unit, and a lactic acid unit; and mixtures or blends of the foregoing.
  • polyesters that may be plasticized with certain plasticizers described herein are described in U.S. Patent No. 6,544,607, which is incorporated herein by reference.
  • Lactic acid used in poly(lactic acid) and interpolymers of lactic acid can be produced in any manner known in the art, e.g., by chemical synthesis, or by fermentation of a sugar source from lactobaciUus, and the term lactic acid encompasses both D-lactic acid and L- lactic acid.
  • Poly(lactic acid) or interpolymers of lactic acid can be made using enantiomeric monomers D-lactic acid and/or L-lactic acid by known methods.
  • Poly(lactic acid) may be poly(L-lactic acid) (solely composed of L-lactic acid), poly(D-lactic acid) (solely composed of D-lactic acid), poly(DL-lactic acid), composed of both D-lactic acid and L-lactic acid in varying proportions, e.g., a molar ratio of D-Lactic acid:L-Lactic acid of about 100:1, 50:1, 10:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:10, 1:50, or 1:100.
  • Properties of PLA and interpolymers of lactic acid are affected by relative amounts of the D- and L- forms.
  • poly(L-lactic acid) may exhibit a higher degree of crystallinity than copolymers of L-lactic acid and D-lactic acid, or copolymers of L-lactic acid with other non-lactic acid monomers.
  • one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid and another aliphatic hydroxycarboyxlic acid, such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5- hydroxyvaleric acid, 6-hydroxycaproic acid, and the like.
  • Any relative proportions of lactic acid and another aliphatic hydroxycarboxylic acid may be used in the plasticized interpolymers, e.g., lactic acid: aliphatic hydroxycarboxylic acid molar ratio of about 1:10, 1:5, 1:2, 1:1, 2:1, 5:1 or 10:1.
  • one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid and a saccharide, such as cellulose, cellulose acetate, cellulose nitrate, methyl cellulose, ethyl cellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, cupro-ammonoium rayon, cuprofan, bemberg, hemicellulose, starch, acropectin, dextrin, dextran, glycogen, pectin, chitin, chitonsan, gum Arabic, cyamoposis gum , locust bean gum, acacia gum, and mixtures or blends thereof, or derivatives thereof.
  • lactic acid saccharide molar ratio of about 1:10, 1:5, 1:2, 1:1, 2:1, 5:1 or 10:1.
  • one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid, an aliphatic polyvalent carboxylic acid (e.g., oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, and anhydrides thereof), and an aliphatic polyvalent alcohol (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1 ,4-butanediol, 3-methyl-l,5-pentanediol, 1,6-hexandediol, 1 ,0-nonanediol, neopentyl glycol, tetramethylene glycol, 1 ,4-cyclohex
  • Any relative proportions of lactic acid, aliphatic polyvalent carboxylic acid, and aliphatic polyvalent alcohol may be used, e.g., molar ratio of lactic acid:acid:alcohol of about 1:1:1,2:1:1, 3:1:1,4:1:1,5:1:1, 10:1:1, 1:2:2, 1:3:3, 1:4:4, 1:5:5, 1:10:10:, 10:2:1,5:2:1,2:2:1, 10:1:2,5:1:2, 2:1:2.
  • Any suitable plasticizer may be selected to plasticize a polyester such as a lactic- acid based polyester as described above.
  • alcohols e.g., monoalcohols, diols or other polyols
  • esters e.g., monoesters or diesters
  • one or more solubility parameters e.g., Hansen solubility parameters
  • PLA or interpolymers of lactic acid may be plasticized using one or more plasticizers described herein to decrease rigidity and increase flexibility.
  • plasticized PLA or interpolymers of lactic acid may be sufficiently plasticized to attain a flexibility making it suitable for use in applications traditionally using polyethylene, polypropylene, soft polyvinyl chlorides, and the like.
  • a variety of useful articles may be formed from plasticized polyesters (e.g., lactic acid based polyesters such as PLA) as described herein, e.g., trays, cups, plates, bottles, films, cutlery, toys, storage containers, tools, and the like.
  • plasticized polyesters e.g., lactic acid based polyesters such as PLA
  • Any suitable test method may be used to evaluate plasticization effects of a plasticizer in a host resin.
  • a plasticizer' s effect on ease of processibility of the host resin in a melt compounder or extruder may be evaluated.
  • change in glass transition temperature or melt temperature may be used to evaluate plasticization.
  • change in melt viscosity may be used to evaluate plasticization.
  • DMA (dynamic mechanical analysis) testing may be used to measure plasticization.
  • tensile properties of plasticized samples may be measured. Any suitable tensile measurements may be made.
  • tensile measurements may be carried out according to ASTM D638 "Standard Test Method for Tensile Properties of Plastics” or ASTM D412 “Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers— Tension,” each published by ASTM International, and each of which is incorporated herein by reference in its entirety.
  • ASTM D638-10 involves inserting a test sample having a specified dog-bone shape into a tensile testing machine that applies a uniaxial load to the sample along the axis of the sample by fixing one end of the sample and pulling on the opposite end along the sample axis or by pulling on both ends of the sample in opposite directions along the sample axis at the specified rate.
  • Stress as the applied force per unit area is measured as a function of strain (% elongation) to generate a stress-strain curve.
  • Many parameters can be derived from stress-strain curves.
  • elastic or Young's modulus, % elongation at break or strain at break, displacement at break, ultimate tensile strength (stress at break), and toughness can be derived from stress-strain curves. Toughness is calculated as the area under the stress-strain curves, up to point of fracture. Young's modulus (or modulus of elasticity) is calculated as the slope of the early (low strain) portion of the measured stress-strain curves. Elasticity represents the property of complete and immediate recovery of displacement of a sample caused by loading of that sample, upon release of the load.
  • a plasticized composition as described herein may provide a % elongation at break that is about 20% or greater, about 50% or greater, about 100% or greater, about 150%) or greater, about 200% or greater, about 250%) or greater, about 300%) or greater, or about 350% or greater.
  • a plasticized PVC composition may provide a % elongation at break that is at least about 20-100%, (e.g., at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%), at least about 90%>, at least about 100%), at least about 150%), at least about 200%), at least about 250%), at least about 300%), at least about 350%), or even greater)
  • a plasticized composition as described herein e.g., a plasticized
  • PVC composition may provide a toughness of about 25 MPa or greater, or about 30 MPa or greater.
  • Thermal stability and volatility as to weight loss may be measured by heating aging the samples in an oven using any defined protocol and weighing samples before and after exposure to applicable thermal aging protocols.
  • a plasticized sample loses no more than about 15 wt%, no more than about 12 wt%, no more than about 10 wt%, no more than about 8 wt%, or no more than about 5 wt% after thermal aging at 100°C for a week.
  • a plasticized sample loses no more than about 2 wt%, or no more than about 1.5 wt%, or no more than about 1 wt% after thermal aging at 70°C for 170 hours.
  • Thermal stability as to color of a plasticized sample may be evaluated by reflectance using any suitable reference standard, and using the CIE (International Commission on Illumination) coordinates L*, a*, and b*.
  • a* represents a value between red and green (with negative values indicating green and positive values indicating red)
  • b* represents a value between yellow and blue (with negative values indicating blue and positive values indicating yellow). See, e.g., Commission Internationale de L'Eclairage at www.cie.co.at.
  • the observer may be positioned at 10°, and the illuminant may be a CIE standard D65 illuminant to simulant standard daylight illumination.
  • An Color-Eye® 7000A spectrophotometer (available from XRite Corp., Grand Rapids, MI) or similar apparatus may be used to evaluate color of the samples relative to the standard.
  • the coordinates L*, a*, and b* can be measured for each sample.
  • the difference between each of the coordinates L*, a* and b* of a sample and that of the reference can be calculated, and a color parameter
  • Impact strength is a measure of a polymer's ability to absorb impact without cracking or breaking. Toughness contributes to increased impact strength. Toughness contributes to increased impact strength. Toughness contributes to increased impact strength. Toughness contributes to increased impact strength. Toughness can be measured as a function of temperature, as certain polymers decrease in impact strength at low temperatures. There are a variety of methods known in the art to measure impact strength. Generally, an arm held at a defined height and having a defined potential energy is released to impact the sample. The amount of energy that is absorbed by the sample without failing determines impact strength. Samples may be notched or unnotched. In some variations, Izod impact strength is measured, in which a cantilevered, notched sample is mounted, and a pendulum arm is raised to a variable height and dropped to impact the sample.
  • Brittle polymers cannot deform much without cracking or breaking. In some cases, brittle polymers exhibit high tensile strength but low toughness. In some variations, a plasticizer as described herein decreases brittleness, i.e., increases amount of deformation that the polymer can withstand without cracking or breaking.
  • Low temperature brittleness testing may be used to evaluate the effect of a plasticizer on low temperature mechanical properties of a composition.
  • One example of a low temperature brittleness test that may be used to evaluate plasticizers is ASTM D746-07
  • a plasticizer' s effect on hardness may be evaluated using any suitable test method.
  • durometer hardness may be measured.
  • One nonlimiting example of a hardness measurement that can be made to evaluate a plasticizer's effect on a host resin's hardness is ASTM D2240-05 "Standard Test Method for Rubber Property— Durometer
  • a plasticizer and an amount of plasticizer may be selected to tune the durometer hardness of a plasticized composition.
  • a plasticizer and an amount of plasticizer may be selected to achieve a durometer hardness A of about 80, about 85, or about 90.
  • a 5D Hansen solubility parameter of a plasticizer candidate may be correlated with durometer hardness A, as shown in FIGURE 22.
  • the properties of a Diels-Alder plasticizer adduct between a conjugated terpene and a dienophile may be tuned, adjusted or modified to accomplish effective compatibility with a host resin and compatibility with processing of the host resin so as to result in effective plasticization with the host resin, while limiting undesired effects such as migration, bleeding out of the host resin, or thermal degradation.
  • the plasticizers described herein have a structure X H C T -
  • a D A-Y DP in which X H C T represents one or more tails originating from one or more conjugated hydrocarbon terpenes reacted with a dienophile, Y DP represents one or more heads (which may be originating from one or more dienophiles, and A D A comprises one or more cyclic groups (e.g., a 6-membered ring) resulting from the Diels-Alder reaction between the dienophile and the one or more conjugated hydrocarbon terpenes.
  • X H C T represents one or more tails originating from one or more conjugated hydrocarbon terpenes reacted with a dienophile
  • Y DP represents one or more heads (which may be originating from one or more dienophiles
  • a D A comprises one or more cyclic groups (e.g., a 6-membered ring) resulting from the Diels-Alder reaction between the dienophile and the one or more conjugated hydrocarbon terpene
  • a Diels-Alder plasticizer may have a single tail and a single head in certain embodiments.
  • a plasticizer may have a single tail and two heads so as to have structure .
  • a plasticizer has two tails and a single head. For example, two conjugated hydrocarbon terpenes (which may be the same or different) undergo a Diels-Alder reaction with one dienophile so that the plasticizers may have a structure
  • X H C TI refers to a first conjugated terpene and A D
  • a I refers to a cyclic group resulting from the Diels- Alder reaction between the first conjugated terpene and the dienophile
  • X HCT 2 refers to a second conjugated terpene
  • a DA 2 refers to a cyclic group resulting from the Diels- Alder reaction between the second conjugated terpene and the dienophile.
  • a plasticizer having two tails and a single head has a structure , which may result from a Diels-Alder reaction with a hydrocarbon terpene having an internal conjugated diene (e.g., isodehydrosqualene, isosqualane precursor I, or isosqualane precursor II) that reacts with a dienophile.
  • a Diels-Alder plasticizer has two tails and two
  • such a plasticizer may have structure x or x
  • X HCT and/or Y DP may be selected or chemically modified to make the Diels-Alder adduct suitable for use in certain plasticizer applications.
  • XHCT is a C10-C30 (e.g., C10-C15, or C10-C20, C10-C25, or C10-C30) hydrocarbon tail comprising one or more methyl branches having formula (X), (XI), (XIII), or (XIV) as shown herein.
  • X HCT comprises no heteroatoms.
  • X HCT comprises oxygen atoms, e.g., having formula (XII) or an oxidized version thereof.
  • Y DP may contain heteroatoms such as O, S, P or N. Y DP may be neutral or charged.
  • hydrophobicity of X HCT may be tuned or modified in a variety of ways.
  • X HCT in general includes methyl substituents originating from the conjugated terpene.
  • X HCT is an unsaturated hydrocarbon chain
  • X HCT is a saturated hydrocarbon chain
  • X HCT includes one or more nonionic oxygen groups (e.g., epoxy, hydroxy); in some embodiments X HCT includes one or more halogen atoms. Hydrophobicity of X HCT may be decreased by using a shorter chain conjugated terpene and/or oxidizing or halogenating one or more of the unsaturated carbon carbon bonds of X HCT -
  • Hydrophilicity of Y DP may be tuned or modified in a variety of ways.
  • a dienophile may be selected to vary the number of polar substituents on the Diels- Alder plasticizer adduct.
  • a dienophile may be selected that results in only one polar substituent to the cyclic group formed by the Diels-Alder reaction.
  • a dienophile may be selected that results in more than one (e.g., two) polar substituents to the cyclic group formed by the Diels-Alder reaction, e.g., a dienophile that is an anhydride, a diacid, a diester, or a di-cyano may be selected.
  • a Diels- Alder adduct is alkoxylated (any number of ethylene oxide or propylene oxide segments are incorporated into the adduct) to tune hydrophilicity.
  • X H C T and/or Y DP may be selected or chemically modified to accomplish any one of or any combination of the following: i) modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule; ii) improve compatibility with a desired host polymer; iii) provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; iv) undergo a reverse Diels-Alder reaction to produce desired species; v) inhibit chemical reaction with other components that may be present in a composition; vi) increase thermal stability; vii) increase light stability; viii) modify molecular weight; ix) modify volatility; x) modify viscosity, crystallinity, or volatility at processing temperatures and/or at use temperatures; xi) modify migration or leaching behavior in operation; xii) enable the plasticizer to be suitable for use in food grade applications; xiii) enable the plasticizer to be suitable for use
  • a plasticizer has structure (Bl), where one of or both of RB 2 and RB 3 represent tails originating from one or more hydrocarbon terpenes, and QB 1 and QB 2 represent one or two heads originating from one or more dienophiles.
  • a Diels-Alder plasticizer molecule has structure (Bl) with a single tail originating from a hydrocarbon terpene and a single head originating from the dienophile.
  • Non-limiting examples of combinations of RB 1 , RB 2 , RB 3 and RB 4 are provided in Table 1 herein, and non-limiting examples of Diels- Alder adducts are provided in Table 2 herein.
  • each of RB 1 , RB 3 , RB 4 and RJ 1 are H.
  • a Diels-Alder plasticizer molecule has structure (Bl) with a single tail and two heads.
  • a plasticizer molecule may be represented by formula (J2).
  • RB 1 , RB 3 and RB 4 are as described in connection with formula (Bl) herein
  • X H CT RB 2 which represents the tail originating from the hydrocarbon terpene
  • YDPI and YDP2 represent the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction.
  • Non-limiting examples of combinations of RB 1 , RB 2 , RB 3 and RB 4 are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein.
  • each of RB 1 , RB 3 , RB 4 are H.
  • a plasticizer molecule has structure (Bl) and comprises two tails and a single head.
  • such a plasticizer has structure (J3a), (J3b), or comprises a mixture of structures (J3a) and (J3b), or has structure (J4):
  • RJ 2 is H or a C 1 -C30 hydrocarbyl group, and Y DP represents the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction.
  • Non-limiting examples of combinations of RB 1 , RB 2 , RB 3 and RB 4 are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein.
  • each of RB 1 , RB 3 and RJ 1 are H.
  • a Diels-Alder plasticizer molecule has structure (Bl) with two tails and two heads.
  • a plasticizer molecule may be represented by formula (J5):
  • RB 1 , RB 3 and RB 4 are as described in connection with formula (Bl) herein
  • X H C T RB 2 which represents the tail originating from the hydrocarbon terpene
  • Y DPI and Y DP2 represent the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction.
  • Non-limiting examples of combinations of RB 1 , RB 2 , RB 3 and RB 4 are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein.
  • each of RB 1 , RB 3 , and RB 4 are H.
  • a plasticizer molecule has formula (Bl) with two tails and two heads has formula (J6):
  • Non-limiting examples of combinations of RB 1 , RB 2 , RB 3 and RB 4 are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein.
  • each of RB 1 and RB 3 are H.
  • plasticized thermoplastics have greater strain at break than unplasticized thermoplastics do when subjected to sufficient stress.
  • plasticizers serve various functional roles when compounded with thermoplastics, thermosets, elastomers or rubbers including making them more flexible, durable, tough, extrudable and/or moldable.
  • plasticizers when selected for such functional roles they are incorporated with the host polymer at levels anywhere from about 5 phr (parts per hundred parts resin) to about 120 phr either depending upon the mechanical or geometric properties needed of the finished article or composition or depending upon the properties needed for their fabrication.
  • a plasticizer' s ability to modify the stress-strain properties of a thermoplastic is generally related to the mutual solubility of the plasticizer and thermoplastic where, in general, the greater the mutual solubility then the more effective the modification.
  • There are a variety of energetic methods known in the art for compounding plasticizers and thermoplastics In most embodiments some combination of mechanical and thermal energy is employed in the compounding process. In some variations, plasticized films may be solvent cast. In general, the greater the molar volume of the plasticizer, the greater energy employed for plasticizers having similar solubility parameters.
  • plasticizer characteristics that can affect diffusion include polarity of the plasticizer, polarity of the resin, plasticizer interaction with or compatibility with the resin, plasticizer molecular weight, and viscosity of the resin and/or plasticizer under use conditions.
  • a plasticizer for a target resin is selected based on one or more measured or calculated solubility parameters of plasticizer and of the target resin.
  • a plasticizer for use in PVC may be selected to have solubility parameters close to that of PVC.
  • a solubility parameter is empirical, calculated or semi-empirical numerical value that indicates relative solvency of a host resin for a plasticizer. Any suitable solubility parameter or combination of parameters can be used to evaluate and quantify intermolecular interactions between the plasticizer and the host resin to estimate or predict efficacy as a plasticizer.
  • Nonlimiting examples of intermolecular interactions that can be evaluated to incorporate into a solubility parameter include dispersion (van der Waals forces, related to polarizable electrons), dipole moment, hydrogen bonding, and orientation effects.
  • Any scheme or algorithm known in the art to calculate or measure solubility of a plasticizer candidate molecule in a host resin can be used to arrive at a solubility parameter.
  • Hildebrand solubility parameters, Hansen solubility parameters, UNIFAC semi-empirical calculations, or a combination thereof can be used to estimate solubility parameters for a plasticizer/host resin combination.
  • quantum mechanical chemical calculations e.g., COSMO-RS® software, available from COSMOlogic® GmbH & Co. KG are used to calculate solubility parameters.
  • Hildebrand solubility parameters do not take account for hydrogen bonding, and are more useful for nonpolar systems than for polar systems.
  • Hansen solubility parameters include three different parameters: 5D (dispersion), ⁇ (dipole moment), and ⁇ (hydrogen bonding) and are useful for polar systems as well as nonpolar systems.
  • a smaller value for R a indicates a greater "likeness" or compatibility between a plasticizer candidate and a host resin.
  • the solubility of a host resin in a variety of candidate plasticizers can be visualized as a sphere, in which R a is the radius of the sphere, and the center of the sphere is located at the point (5D host , 6Phost, 6H ost).
  • R 0 represents a maximum distance for an acceptably compatible interaction between a plasticizer and a host resin
  • a RED value approximately equal to or less than 1 for a particular plasticizer/host resin combination indicates that combination is compatible, which will result in effective plasticization.
  • plasticizer/host resin combination indicates an incompatible combination, such that the plasticizer is unlikely to be sufficiently compatible with the host resin to provide effective plasticization.
  • the parameters 5D, ⁇ , ⁇ for the host resin and the plasticizers can be calculated, measured or estimated in any suitable manner or retrieved from existing databases.
  • Hansen solubility parameters for a substance are determined from empirical solubility data for that substance in about 20 to 30 known solvents.
  • One software package that uses Hansen Solubility parameters to evaluate suitability of particular plasticizers for a desired application is HSPiP, available at www.hansen-solubility.com.
  • the HSPiP package has the capability to read a data table containing chemical name and structure encoded as a SMILES string, and to automatically calculate the HSP of the chemical using the so-called Y-MB fragment-based method.
  • Hansen solubility Parameters A User's Handbook, CRC Press, Boca Raton, FL, 1999, Hansen, C M., Hansen Solubility Parameters: A User's Handbook, Second Ed., CRC Press, Boca Raton, FL, 2007, or Hansen Solubility Parameters in Practice, eBook/software, 1st Ed.2008, 2nd Ed. 2009, with Prof. Stephen Abbott and Dr. Hiroshi Yamamoto available from www.hansen-solubility.com, each of which is incorporated herein by reference in its entirety.
  • a set of solvents is selected to sufficiently characterize solubility or swellability of a substance in a host resin of choice. In some cases, Hansen solubility parameters for a substance are determined by mathematical modeling of the substance.
  • mathematical modeling comprises mathematically dividing the substance into functional groups to facilitate modeling (group contribution methods).
  • Y-MB Yamamoto molecular breaking model
  • Stefanis-Panayiotou 2008 model
  • Hansen Solubility Parameters in Practice eBook/software, 1st Ed.2008, 2nd Ed. 2009, with Prof. Stephen Abbott and Dr. Hiroshi Yamamoto available from www.hansen-solubility.com.
  • the RED for a plasticizer/host resin combination calculated using Hansen solubility parameters is about 1 or less, about 0.95 or less, about 0.9 or less, about 0.85 or less, about 0.8 or less, about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.55 or less, or about 0.5 or less.
  • conjugated terpene and dienophile may be used to make plasticizers suitable for certain applications.
  • the conjugated terpene used to make the Diels- Alder plasticizers described herein is ⁇ -farnesene.
  • the conjugated terpene is a-farnesene.
  • the dienophile is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, dialkyl maleates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, dialkyl maleates
  • monoester or diester Diels-Alder adducts as described herein have utility as plasticizers.
  • Monoesters and diesters have relatively high dipole moments, causing intermolecular forces to be increased, which may decrease vapor pressure, decrease volatility, and/or increase flash point. These properties may make an ester containing Diels- Alder adduct described herein advantageous for a variety of plasticizer applications.
  • the polarity of the ester-containing Diels-Alder adduct may increase their compatibility with other polar molecules.
  • Monoester, diester-containing Diels-Alder adducts may exhibit relative stability against oxidative and thermal breakdown, but have high biodegradability.
  • ester-containing Diels-Alder adducts that are hygroscopic are not used in applications in which the presence of moisture is deleterious.
  • a conjugated terpene e.g., myrcene, ⁇ -farnesene or a- farnesene
  • the adduct undergoes a Diels-Alder reaction with acrylic acid
  • the adduct is hydrogenated to form a saturated adduct
  • the saturated adduct is esterified with a polyol (e.g., pentaerythritol, neopentyl glycol, and the like) to obtain a high boiling point ester that exhibits increased polarity, increased molecular volume, increased molecular weight, and decreased tendency to leach out, migrate out, be extracted out, and the like from a polymer host matrix.
  • a polyol e.g., pentaerythritol, neopentyl glycol
  • a monoester or diester-containing Diels-Alder adduct is used in place of all or a portion of a vegetable oil or petroleum-derived monoester, diester (e.g. , an adipate), phthalate, benzoate, dimerate, or trimellitate plasticizer.
  • the conjugated terpene and/or alkyl substituent on the ester moiety or moieties that are used to make an ester-containing Diels-Alder adduct are selected to adjust solubility and molar volume of a plasticizer candidate in a desired host polymeric matrix.
  • longer aliphatic chains may be selected to increase molar volume while exhibiting compatibility with nonpolar host resins (e.g., hydrocarbon polymers such as polyolefms), and shorter chains may be selected to decrease molar volume and increase compatibility with more polar host resins.
  • Increased branching in chains may be selected to increase solubility, decrease waxiness, or modify molecular volume.
  • Diester or mono-ester containing Diels-Alder adducts may be used in place of adipate diesters in some embodiments.
  • diester or monoester containing Diels-Alder adducts are used in combination with a polyalphaolefm (PAO).
  • PAO polyalphaolefm
  • diester or monoester containing Diels-Alder adducts are used in combination with PAOs or mineral oils in compressor oils, gear oils, transmission oils, crankcase oils, or hydraulic fluids.
  • diester or monoester containing Diels-Alder adducts are used as base stock where biodegradability is desired or high temperature low sludge formation is critical (e.g., lubricants for textile machines or ovens).
  • Non-limiting examples of ester-containing plasticizer candidates are provided in the Examples.
  • One non-limiting example of a preparation of Diels-Alder adduct between ⁇ - farnesene and 1 ,4-benzoquinone is provided in the Examples.
  • a plasticizer disclosed herein comprises a Diels-Alder adduct that has been hydrogenated so as to saturate the aliphatic portion of the Diels-Alder adduct originating from the conjugated terpene (e.g., farnesene).
  • a hydrogenated Diels- Alder adducts (and derivatives thereof) may in certain circumstances exhibit improved thermo- oxidative stability in use.
  • a hydrogenated Diels- Alder adduct undergoes post-hydrogenation reaction, e.g., to modify one or more substituents originating in the dienophile. For example, one or more a carboxylic acid ester moieties remaining in the hydrogenated Diels- Alder adduct may undergo transesterification, reduction, hydrolysis, and the like.
  • a compound having utility as a plasticizer is, comprises, or is derived from a Diels- Alder adduct between a conjugated terpene and acrylic acid or an acrylate ester.
  • Diels- Alder adducts formed when the hydrocarbon terpene is farnesene are given by formulae (H-IA), (H-IB), (H-IC), (H-ID), (H-IE), (H-IF), (H-IG) and (H-IH) as shown in Section H above.
  • plasticizers have formulae (H-IC) and/or (H-ID).
  • plasticizers have formulae (H-IG) and/or (H-IH).
  • H-IG Diels-Alder adduct produces more than one isomer
  • any one of the isomers may be present without significant amounts of other isomers may be used as a plasticizer, or any mixture of the isomers may be used, with the isomers present in any relative amounts.
  • any mixture comprising a ratio of 1,3- isomer: 1,4-isomer of about 0.1 :99.9, 5:95, 1 :99, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 may be used as a plasticizer.
  • a compound having utility as a plasticizer is, comprises, or is derived from a Diels-Alder adduct between a conjugated terpene and a dialkyl maleate or a dialkyl fumarate.
  • Diels-Alder adducts produced when the hydrocarbon terpene is farnesene are given by formula (H-IIA), (H-IIB), (H-IIC) and (H-IID) as shown in Section H above.
  • plasticizers have formula (H-IIB).
  • plasticizers have formula (H- IID).
  • a plasticizer is, comprises, or is derived from a compound having formula (H-XIIA), ( ⁇ - ⁇ '), (H-XIIB), ( ⁇ - ⁇ '), (H-XIIC), (H-XIIC), (H-XIID), (H-XIID'), (H-XIIE), ( ⁇ - ⁇ '), or (H-XIIF).
  • a plasticizer is, comprises, or is derived from a compound having formula ( ⁇ - ⁇ '), ( ⁇ - ⁇ '), (H-XIIC), (H-XIID'), (H-XIIE '), or (H-XIIF).
  • a plasticizer is or comprises one of or a mixture of
  • compound (J-3a) and/or (J-3b) may be useful as plasticizers in relatively low polarity host resins, e.g., in polyolefins, polystyrenes, synthetic rubbers, natural rubbers, or in copolymers thereof, or in polymer blends thereof, or in polymer composites thereof.
  • a plasticizer is or comprises compound (J-5):
  • a plasticizer is or comprises compound (J- 11):
  • a plasticizer is or comprises one of or a mixture of compounds (J- 13a) and (J-13b), where a ratio of 13a: 13b is about 0.1 :99.9, 5 :95, 1 :99, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95 :5, 99: 1 , or 99.9:0.1 :
  • a plasticizer is, comprises, or is derived from a Diels-
  • a plasticizer is, comprises, or is derived from a compound having formula (H-IIIA), (H-IIIB), (H- IIIC), or (H-IIID) as shown in Section H above.
  • a plasticizer is, comprises, or is derived from a compound having formula (H-IIIB) or (H-IIID) as shown in Section H above.
  • a Diels-Alder adduct that has utility as a plasticizer can be obtained by reacting a conjugated hydrocarbon terpene (e.g., ⁇ -farnesene , a-farnesene, or myrcene) with any suitable dienophile that can be converted to an alcohol or diol.
  • a conjugated hydrocarbon terpene e.g., ⁇ -farnesene , a-farnesene, or myrcene
  • any suitable dienophile that can be converted to an alcohol or diol.
  • any substituted or unsubstituted ⁇ , ⁇ -unsaturated aldehyde such as:
  • R 1 , R 2 , and R 3 is independently, H, Ci-Ci 0 alkyl, C 3 -C 6 cycloalkyl, aryl, substituted aryl, and the like; or the dienophile may be an acrylate or substituted acrylate such as:
  • R 1 is H or Ci-Cg alkyl
  • R 2 , R 3 , and R 4 are, each independently, H, Ci-Cio alkyl, C 3 - C 6 cycloalkyl, aryl, substituted aryl, and the like.
  • allylic alcohols may be used as a dienophile in a Diels-Alder reaction with a conjugated terpene such as ⁇ -farnesene or a-farnesene.
  • methyl vinyl ketones may be used in a Diels-Alder reaction with a conjugated terpene such as ⁇ -farnesene or a-farnesene.
  • the compounds and plasticizers can be made by Diels-Alder addition of a dienophile to the diene functionality of the conjugated terpene (e.g., ⁇ -farnesene).
  • suitable dienophiles that can be used to produce substituted aldehydes (e.g., 4,8-dimethyl-3,7-nonadienyl-substituted) include: substituted ⁇ , ⁇ -unsaturated aldehydes such as: wherein R 1 , R 2 , and R 3 are, each independently, H, Ci-Cio alkyl, C 3 -C 6 cycloalkyl, aryl, substituted aryl, and the like; and acrylates or substituted acrylates such as: wherein R 1 is H or Ci-Cg alkyl, and R 2 , R 3 , and R 4 are, each independently, H, Ci-Cio alkyl, C 3 - C 6
  • Substituted aldehydes resulting from a Diels-Alder reaction can be reduced to form a substituted alcohol as described above. Any suitable reducing methods and conditions may be used.
  • the unsaturated aldehyde e.g., 4,8-dimethyl-3,7-nonadienyl- substituted aldehyde
  • an unsaturated alcohol e.g., 4,8-dimethyl-3,7-nonadienyl- substituted alcohol
  • the saturated alcohol e.g., 4,8- dimethylnonyl-substituted alcohol.
  • One non- limiting example of such a method is shown in the Examples.
  • the unsaturated aldehyde resulting from the Diels- Alder reaction is reduced to a saturated alcohol (e.g., 4,8-dimethylnonyl-substituted alcohol) in a single step, without forming an unsaturated alcohol intermediate.
  • a saturated alcohol e.g., 4,8-dimethylnonyl-substituted alcohol
  • a catalyst such as a ruthenium catalyst over carbon or a palladium catalyst over carbon can be used to reduce the 4,8-dimethyl-3,7- nonadienyl-substituted aldehyde directly to a 4,8-dimethylnonyl-substituted alcohol.
  • An alcohol made by any of the methods described above can be further alkoxylated by any method now known or later side chain.
  • Any of the mono-alcohols or diols described herein may be reacted with an alkylene oxide (e.g., ethylene oxide as shown in the Examples, or propylene oxide, or both ethylene oxide and propylene oxide) under standard industrial alkoxylation conditions (e.g. sodium hydride, potassium tert-butoxide, or any base having pK>about 16 or 17).
  • the reaction conditions e.g. time, temperature, pK, concentrations of reagents, solvents
  • the ratio of ethoxyl to propoxyl repeat units can be controlled by adjusting the ratio of ethylene oxide to propylene oxide during the alkoxylation reaction.
  • plasticizers described herein comprise or are derived from alcohol (J-4-I):
  • J-4-I represents any one of, or any combination of the two isomers J-4-IA and J-4-IB shown below:
  • alcohol J-4-1 includes both isomers, J-4-IA and J-4-IB.
  • alcohol J-4-1 includes isomer J-4-IA, with only trace amounts or no detectable amount of isomer J-4-IB.
  • alcohol J-4-1 includes isomer J-4-IB, with only trace amounts or no detectable amount of isomer J-4-IA.
  • alcohol J-4-1 includes about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J-4-IA.
  • Alcohol J-4-1 may include any ratio of isomer J-4-IA to isomer J-4-IB.
  • alcohol J-4-1 includes a ratio of isomer J-4-IA to isomer J-4-IB of about 0.001 : 1, 0.005: 1, 0.01 : 1, 0.05:1, 0.1 : 1, 0.5: 1, 1 : 1, 3: 1, 3.2: 1, 3.4: 1, 3.6: 1, 3.8: 1, 4: 1, 4.2: 1, 4.4: 1, 4.6:, 4.8: 1, 5: 1, 10: 1, 50: 1, 100: 1, 500: 1, or 1000: 1 .
  • compound J-4-II functions as a plasticizer:
  • Compound J-4-II represents any one of or any combination of the two isomers J-4-IIA and J-4-IIB as shown below:
  • compound J-4-II includes both isomers, J-4-IIA and J-4-IIB.
  • compound J-4-II includes isomer J-4-IIA, with only trace amounts or no detectable amount of isomer J-4-IIB. In some variations, compound J-4-II includes isomer J-4- IIB, with only trace amounts or no detectable amount of isomer J-4-IIA. In some variations, compound J -4-II includes 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J -4-IIA. Compound J -4-II may include any ratio of isomer J -4-IIA to isomer J -4-IIB.
  • compound J -4-II includes a ratio of isomer J -4-IIA to isomer J -4-IIB of about 0.001 : 1, 0.005: 1, 0.01 : 1, 0.05: 1, 0.1 : 1, 0.5: 1, 1 : 1, 3: 1, 3.2: 1, 3.4: 1, 3.6:1, 3.8: 1, 4: 1, 4.2: 1, 4.4:1, 4.6:, 4.8: 1, 5: 1, 10: 1, 50: 1, 100: 1, 500: 1, or 1000: 1.
  • plasticizers contain alkoxy repeat units that are different than ethoxyl repeat units.
  • some plasticizers include propoxyl repeat units in the hydrophilic end, rather than ethoxyl repeat units.
  • Some plasticizers include both ethyoxyl and propoxyl repeat units.
  • plasticizers are derived from alcohols described herein (e.g., J -4-1 J -
  • m is in the range 1 to 30. In some variations, m is in the range 5 to 25. In some variations of the plasticizers, m is in the range 6 to 20. In some variations, m is in the range 6 to 12. In some variations, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, m is 9.
  • plasticizers contain both ethoxy and propoxy repeat units, and have structures analogous to compound J -4-II, J -4-VI, J -4-VIIIA, J -4-VIIIB and J -4-X, with the following structure substituted for the ethoxy repeat units:
  • the ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units.
  • the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions.
  • p and q are independently in the range 1 to 30.
  • p and q are independently in the range 1 to 30.
  • p and q are independently in the range 5 to 25. In some variations p and q are independently in the range 6 to 12. In some variations, p and q are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, the sum (p+q) is in the range 1 to 30, or 6 to 20, or 5 to 25, or 6 to 12. In some variations, the sum (p+q) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.
  • compound J-4-III as shown below functions as a plasticizer:
  • compound J-4-III includes the 1,3- isomer with only trace amounts or no detectable amount of the 1,4- isomer.
  • compound J -4-III includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer.
  • compound J -4-III includes a ratio of the 1,3- isomer to the 1,4- isomer of about 0.001 : 1, 0.005: 1, 0.01 : 1, 0.05:1, 0.1 : 1, 0.5: 1, 1 : 1, 3: 1, 3.2:1, 3.4: 1, 3.6: 1, 3.8: 1, 4:1, 4.2: 1, 4.4: 1, 4.6:, 4.8: 1, 5: 1, 10: 1, 50: 1, 100: 1, 500:1, or 1000:1.
  • compound J -4-IV as shown below functions as a plasticizer:
  • the ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units.
  • the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions.
  • compound J-4-IV includes the 1,3- isomer with only trace amounts or no detectable amount of the 1 ,4- isomer.
  • compound J -4-IV includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer.
  • compound J -4-IV includes a ratio of the 1,3- isomer to the 1,4- isomer of about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.
  • Isomers J-4-VA and J-4-VB can be present in any relative amount, e.g., alcohol J-4-V may consist of isomer J -4-VA with no detectable amount of isomer J-4-VB, or may consist of isomer J-4-VB with no detectable amount of isomer J-4-VA, or a ratio of isomer J -4-VA: J-4-VB may be about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.
  • alcohol J -4-V can be formed by carrying out a Diels-Alder reaction of ⁇ -farnesene with acrolein in the presence of a methyl magnesium halide (e.g. methyl magnesium bromide) or the like.
  • a methyl magnesium halide e.g. methyl magnesium bromide
  • the alcohol J-4-V may be used as is in a formulation in some embodiments, or in other
  • the alcohol may be subsequently alkoxylated to form a plasticizer.
  • alcohol J-4-V can be ethoxylated to form plasticizer J-4-VI:
  • Isomers J-4-VIA and J-4-VIB can be present in any relative amount, e.g. plasticizer J-4-VI may consist of isomer J-4- VI A with no detectable amount of isomer J-4- VIB, or may consist of isomer J-4-VIB with no detectable amount of isomer J-4-VIA, or a ratio of isomer J-4-VIA: J-4- VIB maybe about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.
  • plasticizer J-4-VI may consist of isomer J-4- VI A with no detectable amount of isomer J-4- VIB, or may consist of isomer J-4-VIB with no detectable amount of isomer J-4-VIA, or a
  • the alcohols J-4-VIIA and J-4-VIIB may be used in a formulation as is in some embodiments, or in other embodiments, may be subsequently treated with an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to form a mixture of plasticizers J-4-VIIIA and J-4-VIIIB (where ethoxylation is shown as a model alkoxylation):
  • an alkylene oxide e.g., ethylene oxide and/or propylene oxide
  • plasticizers J-4-VIIIA and J-4-VIIIB are independently in the range of 1 to 30, or 5 to 25, 6 to 20, or 6 to 12. That is, y and y' can each independently be 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, or 30.
  • plasticizers comprise or are derived from diol J-4-IX:
  • the diol J-4-IX is used as is in a formulation, and in other embodiments, the diol may be treated with an alkylene oxide (e.g. , ethylene oxide and/or propylene oxide) to form a plasticizer having formula J-4-X (where ethoxylation is shown as a model alkoxylation):
  • an alkylene oxide e.g. , ethylene oxide and/or propylene oxide
  • n is in the range 1 to 30. In some variations, n is in the range 5 to 25. In some variations of the plasticizers, n is in the range 6 to 20. In some variations n is in the range 6 to 12. In some variations, n is 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, n is about 9.
  • plasticizers J-4-VI, J-4-VIIIA, J-4-VIIIB, and J-4-X are contemplated, in which a different alkoxyl repeat unit is substituted in place of some of or all of the ethoxyl repeat units.
  • the alcohols J-4-V, J-4-VIIA, J-4-VIIB, and J-4-IX can be propoxylated instead of ethoxylated, or propoxylated and ethoxylated instead of ethoxylated.
  • a Diels- Alder adduct comprising one or more alcohol substituents is reacted with a fatty acid, succinic acid, or the like to make a plasticizer.
  • a Diels- Alder adduct comprising one or more carboxylic acid substituents is reacted with an isosorbide or a fatty alcohol to make a plasticizer.
  • a plasticizer derived from ⁇ -farnesene and isosorbide is shown in the Examples.
  • a plasticizer is or comprises one or more of compounds (J-
  • a plasticizer is or comprises compound (J- 19):
  • a plasticizer comprises a dimer of ⁇ -farnesene (e.g., a cyclic or linear dimer as described in U.S. Pat. No. 7,691,792, which is incorporated by reference herein in its entirety) that has had one or more, or essentially all, of the carbon-carbon double bonds oxidized (e.g., epoxidized).
  • a ⁇ -farnesene derived plasticizer comprises one of or a mixture of two or more of compounds (J-21), (J-22), (J-23), and (J-24):
  • plasticizers may be made from conjugated hydrocarbon terpenes that are not farnesene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a plasticizer is myrcene.
  • the conjugated terpene used to make a Diels-Alder adduct useful as a plasticizer is not myrcene or farnesene, and may for example be any of the C 10 -C30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.
  • the Diels-Alder adducts disclosed herein comprising one or more functional groups, such as one or more anhydride groups or two or more epoxy groups, may be used as comonomers for making oligomers or polymers by addition polymerization or for making oligomers or polymers by condensation polymerization (e.g., oligomers of polyesters or polyamides).
  • the oligomers or polymers thus formed may be useful as plasticizers that exhibit limited or no leaching out, migration, or extraction.
  • the oligomers or polymers may be designed to be compatible with a desired host matrix by the use of Hansen solubility parameters as discussed herein.
  • a Diels-Alder adduct between ⁇ -farnesene and a dienophile is a monomer that undergoes co-polymerization with one or more co-monomers to make an oligomer or polymer having utility as a plasticizer.
  • the nature of the polymerization reaction and type and relative amounts of one or more co-monomers may be selected to tune one or more physical properties of the resulting oligomer or polymer. For example, polymerization conditions favorable to the formation of block copolymers may be selected in one instance, and polymerization conditions favorable to the formation of random copolymers may be selected in another instance.
  • a conjugated terpene Diels-Alder adduct replaces an acid anhydride, a carboxylic acid, an amine, and/or a polyol in a polymerization reaction, e.g., in a condensation polymerization reaction.
  • a ⁇ -farnesene Diels-Alder adduct can replace an acid anhydride, a carboxylic acid and/or a polyol to make a polyester, or a ⁇ - farnesene Diels-Alder adduct can replace an acid anhydride, a carboxylic acid, or an amine to make a polyamide.
  • a Diels-Alder adduct that includes an anhydride moiety is used as a monomer that undergoes a condensation reaction with a polyol to make an unsaturated polyester resin, or an alkyd resin.
  • unsaturated polyester resins or alkyd resins are useful as coatings.
  • one or more fatty acids may be co-reacted with the polyol and the anhydride-containing adduct to make an alkyd resin.
  • the aliphatic tail originating from the hydrocarbon terpene may provide sufficient long chain hydrocarbon functionality to the resulting resin so a fatty acid is not used.
  • the polyol used to make an alkyd resin is glycerine.
  • the Diels-Alder adduct having formula (J-XVA) or (J-
  • n 1, 2, 3 or 4
  • diols can be used to react with a diol to form a polyester or with a diamine to form a polyamide or with a dithiol to form a polythioester.
  • suitable diols include 2,2'-bi-7- naphtol, 1 ,4-dihydroxybenzene, 1,3 dihydroxybenzene, 10,10 bis(4 hydroxyphenyl)anthrone, 4,4'-sulfonyldiphenol, bisphenol, 4,4' (9 fluorenylidene)diphenol, 1,10-decanediol, 1,5- pentanediol, diethylene glycol, 4,4'-(9-fluorenylidene)-bis(2-phenoxyethanol), bis(2
  • hydroxyethyl) terephthalate bis[4 (2-hydroxyethoxy)phenyl] sulfone, hydroquinone-bis (2- hydroxyethyl)ether, and bis(2-hydroxyethyl) piperazine.
  • Non-limiting examples of suitable diamine include diaminoarenes such as 1 ,4-phenylenediamine, 4,4-diaminobenzophenone and 4,4-diaminodiphenyl sulfone, and diaminoalkanes such as 1 ,2-ethanediamine and 1,4- butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino-2(4),8- dimethyldibenzothiophene 5,5-dioxide.
  • diaminoarenes such as 1 ,4-phenylenediamine, 4,4-diaminobenzophenone and 4,4-diaminodiphenyl sulfone
  • diaminoalkanes such as 1 ,2-ethanediamine and 1,4- butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino-2(4),8- dimethyld
  • Non-limiting examples of suitable dithiol include 3,6- dioxa- 1 ,8-octanedithiol, erythro- 1 ,4-dimercapto-2,3-butanediol, ( ⁇ )-threo- 1 ,4-dimercapto-2,3- butanediol, 4,4'-thiobisbenzenethiol, 1 ,4 benzenedithiol, 1,3-benzenedithiol, sulfonyl- bis(benzenethiol), 2,5 dimecapto 1,3,4 thiadiazole, 1 ,2-ethanedithiol, 1 ,3-propanedithiol, 1,4- butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, and 1,6-hexanedithiol.
  • the Diels- Alder adduct having formula (J-XVIA) or (J-
  • n 1, 2, 3 or 4; and R 11 , R 12 , R 13 and R 14 are as defined herein, can be used to react with a diamine to form an epoxy resin.
  • suitable diamine include
  • diaminoarenes such as 1 ,4-phenylenediamine, 4,4-diaminobenzophenone and 4,4- diaminodiphenyl sulfone, and diaminoalkanes such as 1 ,2-ethanediamine and 1,4- butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino-2(4),8- dimethyldibenzothiophene 5,5-dioxide.
  • diaminoarenes such as 1 ,4-phenylenediamine, 4,4-diaminobenzophenone and 4,4- diaminodiphenyl sulfone
  • diaminoalkanes such as 1 ,2-ethanediamine and 1,4- butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino-2(4),8- dimethyldibenzothiophene 5,5-d
  • a polyol formed from a Diels- Alder adduct as described herein may be used as a cross-linker and/or monomer in a polymer resin (e.g., a polyurethane or polyester).
  • a polyol formed from a Diels- Alder adduct may be used in polymer formulations to enhance hardness, mechanical performance, and/or increase solvent resistance.
  • multifunctional plasticizer molecules or multifunctional plasticizers having at least two functions when they are combined with thermoplastics, thermosets, elastomers, or rubbers where one of these functions relates to modifying the mechanical, geometric, and/or fluid flow properties of the host resin or articles made therefrom and where the other one or more functions may fulfill any beneficial purposes, with nonlimiting examples including charge dissipation, antithrombosis, heat stabilization, fire retardation, corrosion inhibition, flow viscosity improvement at relatively low plasticizer levels, radical scavenging, acid scavenging, oxygen scavenging, dye site creating, adhesion promoting, particularly of paints and coatings, blowing (to give foams and popcorns), and mold releasing.
  • Multifunctional plasticizers may be used to eliminate the need for additional additives in some cases, thereby potentially reducing cost and potentially reducing the need for additional blending and/or compatibilization, and potentially simplifying the composition.
  • One advantage of the multifunctional plasticizers is a cost savings relating to the use of fewer molecules in plasticizer- thermoplastic formulations.
  • a multifunctional plasticizer that provides an HC1 acid scavenging benefit is useful during the processing of PVC at elevated temperatures because it prevents degradation and the formation of color bodies during processing.
  • a multifunctional plasticizer that provides dye sites for anionic or cationic dyes for example is useful to the final article or composition because it improves its ability to be colored with dyes without containing pigment additives which often damage the mechanical properties of plasticized thermoplastics.
  • a multifunctional plasticizer that provides an anticorrosion benefit is useful both during and after processing because it keeps the processing equipment corrosion free and provides for corrsion protection to plasticized articles when they contact or contain metal parts such as nails and screws for example.
  • a conjugated terpene e.g., ⁇ -farnesene
  • its oligomers may be advantageous precursors to multifunctional plasticizer molecules due to the ease of derivatization of its double bonds (in the case of farnesene, up to four of its double bonds) can be derivatized, and in some embodiments selectively derivatized, with groupings which give the derivative multiple functions.
  • groupings which give the derivative multiple functions.
  • the diene moiety of farnesene and certain oligomers can undergo Diels-Alder reactions and the trisubstituted double bonds of farnesene can undergo electrophilic and nucleophilic reactions.
  • these groupings may give the derivative (e.g., Diels-Alder adducts) both plasticizing function and one or more aditional functions.
  • the farnesene molecule and its derivatives e.g., Diels-Alder adducts
  • the farnesene molecule and its derivatives can be readily cyclized, bicylized, and tricylized to give useful multifunctional plasticizers.
  • multifunctional plasticizers especially multifunctional plasticizers for PVC, made from farnesene and its derivatives are disclosed in the plasticizer candidates of Table 5.
  • a plasticizer may be altered in a processing step to give multifunctional properties.
  • anhydride grouings at the surface can be solvolyzed after extrusion in an alkaline water-alcohol quench bath to give a charge dissipating plasticized material.
  • such a charge dissipating plasticized material may safely eliminate charge buildup resulting from the streaming of fluids.
  • a plasticizer described herein plasticizes a host polymer and also modifies its gas transport properties towards one or more select gases. For example, if you chlorinate or brominate a plasticizer described herein, the oxygen permeability of the resultant plasticized articles should likely decrease. Certain plasticizers described herein may provide articles having improved permselectivities towards important gas pairs, such as industrial blanketing gas pairs (oxygen/nitrogen), ripening gases (C0 2 /0 2 /ethylene system), and for industrial hydrocarbon separations (CH 4 /H 2 , etc.).
  • a plasticizer candidate as described herein that comprises one or more unsaturated bonds may function both as a plasticizer and as a thermal stabilizers and/or acid scavengers.
  • Examples 72, 73, and 77 provide illustrative, but nonlimiting examples of plasticizers that may function as thermal stabilizers and/or acid scavengers.
  • the compositions disclosed herein may comprise more than one plasticizer.
  • one or more secondary plasticizers are used in addition to a primary plasticizer. Secondary plasticizers may be used to allow use of reduced amounts of a primary plasticizer (e.g., to reduce cost) and/or to adjust viscosity of the composition for improved processing.
  • the plasticizers described herein may be employed as primary and/or secondary plasticizers in a composition. Any plasticizer or combination of plasticizers known to a person of ordinary skill in the art may be used in combination with one or more plasticizers described herein in a plasticized composition.
  • Non-limiting examples of plasticizers that may be used in combination with plasticizers described herein include mineral oils, abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, butyrates, cvoleates, pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromellitates, biphenyl derivatives, stearates, difuran diesters, fluorine-containing plasticizers, hydroxybenzoic acid esters, isocyanate adducts, multi-ring aromatic compounds, natural product derivatives, nitriles, siloxane -based plasticizers, tar-based products, thio
  • the amount of total plasticizer (primary plasticizers plus secondary plasticizers) in the polymer composition can be from greater than 0 to about 90wt%, from greater than 0 to about 80 wt%, from greater than 0 to about 70wt%, from greater than 0 to about 60 wt%, from greater than 0 to about 50 wt%, from greater than 0 to about 40 wt%, from greater than 0 to about 30 wt%, from greater than 0 to about 20 wt%, 0 to about 15 wt.%, from about 0.5 wt.% to about 10 wt.%, or from about 1 wt.% to about 5 wt.% of the total weight of the polymer composition.
  • Some plasticizers have been described in George Wypych,
  • a ratio of primary:secondary plasticizers may be about 100: 1, 50: 1, 40: 1, 30: 1, 20:1 , 10: 1, 5: 1, 2: 1, 1 : 1, 1 :2, 1 :5, 1 : 10, 1 :20, 1 :30, 1 :40, 1 :50, or 1 : 100.
  • compositions disclosed herein comprise at least one additive or modifier (designated as "additive") for the purposes of improving and/or controlling the processibility, appearance, physical, chemical, and/or mechanical properties of the polymer compositions.
  • additive any additive known to a person of ordinary skill in the art may be used in the compositions disclosed herein.
  • Non-limiting examples of suitable additives include anti-blocking agents, antistatic agents, lubricants, anti-fogging agents, heat stabilizers, antioxidants, discoloration inhibitors, flame retardants, oils, waxes, antioxidants, UV stabilizers, colorants or pigments, fillers, tackifiers, waxes, flow aids, coupling agents, crosslinking agents, surfactants (e.g., wetting agents, leveling agents, deaerating agents or defoamers, or dispersants), compatibilizers, rheology modifiers, adhesion promoters, catalysts, solvents, corrosion inhibitors, anti-wear agents, antioxidants, rust inhibitors, flame retardants, biocides, algicides, fungicides, acid scavengers, radical scavengers, monomer scavengers, water scavengers, inorganic fillers (e.g., inorganic salts, clays, silica, alumina, magnesia
  • a plasticized composition may comprise or be formed around an insulating mesh (e.g., fiberglass) or a conductive mesh (e.g., carbon fibers or metal- coated insulating fibers).
  • insulating mesh e.g., fiberglass
  • conductive mesh e.g., carbon fibers or metal- coated insulating fibers.
  • the total amount of the additives can range from about greater than 0 to about
  • the amount of each of the additives can range from about greater than 0 to about 25%, from about 0.001 % to about 20%, from about 0.01 % to about 15%, from about 0.1 % to about 10%, from about 0.1 % to about 5%, or from about 0.1 % to about 2.5% of the total weight of the polymer composition.
  • Nonlimiting examples of anti-blocking agents include silica, calcium carbonate, titania, mica, talc and the like.
  • Nonlimiting examples of lubricants include liquid paraffins, polyolefm waxes, fatty acids (e.g., stearic acid or isostearic acid), fatty acid esters, fatty amides, aliphatic alcohols, polyvalent alcohols, polyglycols, metal soaps (e.g., calcium stearate, zinc stearate and the like).
  • Nonlimiting examples of antistatic agents include fatty acid salts, alcohol sulfuric acid esters, liquid fatty oil sulfuric acid ester salts, aliphatic amines, aliphatic amides sulfuric acid salts, aliphatic alcohol phosphoric acid ester salts, sulfonic acid salts of dibasic fatty acid esters, aliphatic amide sulfonic acid slats, alkylallylsulfonic acid salts, aliphatic amine salts, quaternary ammonium salts, alkylpyridium slats, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, imidazoline derivatives, alkyl amines, and the like.
  • Nonlimiting examples of antifogging agents include glycerin fatty esters (e.g., glycerin monostearate and the like), sorbitan fatty esters (e.g., sorbitan monolaurate, sorbitan monoleate and the like), polyglycerin fatty esters, propylene glycol fatty esters, and combinations thereof.
  • Nonlimiting examples of UV absorbers include benzotriazoles, benzophenones (e.g., 2-hydroxy-4- methoxybenzophenone), salicylic acid derivates (e.g., p-tert-butylphenyl salicylate).
  • Heat stabilizers and light stabilizers may be selected based on the polymer matrix, mechanisms of thermal degradation and light degradation, respectively, and processing and environmental conditions for a particular polymer matrix.
  • thermal degradation may occur by a dehydrochlorination reaction, leading to discoloration and degradation of physical and mechanical properties.
  • a thermal stabilizer may replace labile chlorine atoms in the polymer, interrupt or limit formation of hydrogen chloride, and/or interrupt or limit formation of colored unsaturated compounds.
  • thermal stabilizers for PVC include carboxylic acid metal soaps (e.g., Ba, Ca, Cd, Zn and/or Pb carboxylates), esters or mercaptides of alkyl tin, and epoxy compounds.
  • the plasticized compositions disclosed herein can comprise a wax, such as a petroleum wax, a low molecular weight polyethylene or polypropylene, a synthetic wax, a polyolefm wax, a beeswax, a vegetable wax, a soy wax, a palm wax, a candle wax or an ethylene/a-olefm interpolymer having a melting point of greater than 25 °C.
  • the wax is a low molecular weight polyethylene or polypropylene having a number average molecular weight of about 400 to about 6,000 g/mole.
  • the wax can be present in the range from about 10% to about 50% or 20% to about 40% by weight of the total composition.
  • a plasticized composition comprises one or more plasticizers as described herein and a polyalkylene glycol or a polyalkylene glycol derivative, where the terminal hydroxyl groups of the polyalkylene glycol may be modified by
  • Non-limiting examples of suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof.
  • suitable polyalkylene glycol derivatives include ethers of polyalkylene glycols (e.g., methyl ether of polyisopropylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.), mono- and polycarboxylic esters of polyalkylene glycols, and combinations thereof.
  • a plasticized composition comprises one or more plasticizers described herein and any of the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, and the like) with one or more of a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, and the like).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebac
  • Non-limiting examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2- ethylhexyl diester of linoleic acid dimer, and the like.
  • a plasticized composition disclosed herein may comprise a dispersant that can aid distribution of plasticizer or additives within the host resin during film or article formation (e.g., during melt blending, solvent casting, plastisol formation and the like).
  • a dispersant known by a person of ordinary skill in the art may be used in the plasticized composition.
  • suitable dispersants include succinimides, succinamides, benzylamines, succinate esters, succinate ester-amides, Mannich type dispersants, phosphorus-containing dispersants, boron-containing dispersants and combinations thereof.
  • the amount of the dispersant may vary from about 0.01 to about 10 wt%, from about 0.05 to about 7 wt%, or from about 0.1 to about 4 wt%, based on the total weight of the composition.
  • the plasticized composition disclosed herein may comprise an antioxidant that can reduce or prevent the oxidation of the composition.
  • Any antioxidant known by a person of ordinary skill in the art may be used in the plasticized compositions.
  • suitable antioxidants include amine -based antioxidants (e.g., alkyl diphenylamines, phenyl-a- naphthylamine, alkyl or aralkyl substituted phenyl-a-naphthylamine, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and the like), phenolic antioxidants (e.g., 2-tert- butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-p- cresol, 2,6-di-tert-butylphenol, 4,4'-methylenebis-(2,6-d
  • antioxidants include aromatic or hindered amines such as alkyl diphenylamines, phenyl-a- naphthylamine, alkyl or aralkyl substituted phenyl-a- naphthylamine, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and the like; phenols such as 2,6-di-t-butyl-4-methylphenol; l,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'- hydroxybenzyl)benzene; tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane (e.g., IRGANOXTM 1010, from Ciba Geigy, New York); acryloyl modified phenols; octadecyl- 3,5-di-
  • the amount of the antioxidant in the polymer composition can be from about greater than 0 to about 5 wt.%, from about 0.0001 to about 2.5 wt.%, from about 0.001 wt.% to about 1 wt.%, or from about 0.001 wt.% to about 0.5 wt.% of the total weight of the polymer composition.
  • Some antioxidants have been described in Zweifel Hans et al., Plastics Additives Handbook " Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 1, pages 1-140 (2001), which is incorporated herein by reference.
  • the amount of the antioxidant may vary from about 0.01 to about 10 wt %, from about 0.05 to about 5%, or from about 0.1 to about 3%, based on the total weight of the composition.
  • the plasticized composition disclosed herein may comprise a rust inhibitor that can inhibit the corrosion of ferrous metal surfaces.
  • Any rust inhibitor known by a person of ordinary skill in the art may be used in the compositions.
  • suitable rust inhibitors include monocarboxylic acids (e.g., 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid and the like), polycarboxylic acids (e.g., those produced from tall oil fatty acids, oleic acid, linoleic acid and the like), alkenylsuccinic acids in which the alkenyl group contains 10 or more carbon atoms (e.g., tetrapropenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, and the like); long
  • compositions disclosed herein optionally comprise an
  • UV stabilizer that may prevent or reduce the degradation of the polymer compositions by UV radiations.
  • Any UV stabilizer known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants, metallic salts, zinc compounds and combinations thereof.
  • the amount of the UV stabilizer in the polymer composition can be from about greater than 0 to about 5 wt.%, from about 0.01 wt.% to about 3 wt.%, from about 0.1 wt.% to about 2 wt.%, or from about 0.1 wt.% to about 1 wt.% of the total weight of the polymer composition.
  • compositions disclosed herein optionally comprise a colorant or pigment that can change the look of the polymer compositions to human eyes. Any colorant or pigment known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • Non-limiting examples of suitable colorants or pigments include inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthanthrones, azo and monoazo compounds, arylamides, benzimidazolones, BONA lakes, diketopyrrolo-pyrroles, dioxazines, disazo compounds, diarylide compounds, flavanthrones, indanthrones,
  • inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthanthrones, azo and monoazo compounds, arylamides, benzimidazolones, BONA lakes, diketopyrrolo-pyrroles, dioxazines, disazo compounds, diarylide compounds, flavanthrones, indanthrones,
  • the amount of the colorant or pigment in the polymer composition can be from about greater than 0 to about 10 wt.%, from about 0.1 wt.% to about 5 wt.%, or from about 0.25 wt.% to about 2 wt.% of the total weight of the polymer composition.
  • compositions disclosed herein can comprise an inorganic filler which can be used to adjust, inter alia, volume, weight, costs, and/or technical performance. Any filler known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein.
  • Non-limiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as alumina trihydrate, glass microsphere, ceramic microsphere, thermoplastic microsphere, barite, wood flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates and combinations thereof.
  • the filler is barium sulfate, talc, calcium carbonate, silica, glass, glass fiber, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, glass fiber or a mixture thereof.
  • the amount of the filler in the polymer composition can be from about greater than 0 to about 80 wt.%, from about 0.1 wt.% to about 60 wt.%, from about 0.5 wt.% to about 40 wt.%), from about 1 wt.% to about 30 wt.%, or from about 10 wt.% to about 40 wt.% of the total weight of the polymer composition.
  • a plasticized composition may comprise one or more adhesion promoters. Any adhesion promoter known in the art may be used.
  • one or more silane adhesion promoters may be included in a composition.
  • Nonlimiting examples include epoxysilanes, anhydridosilanes, adducts of silanes with primary aminosilanes, ureidosilanes, aminosilanes, diaminosilanes, and also their analogs in the form of monomer or oligomer and urea-silanes; e.g., Dynasylan AMEO, Dynasylan AMMO, Dynasylan DAMO-T, Dynasylan 1146, Dynasylan 1189, and Silquest A-Link 15.
  • a plasticized composition may comprise one or more compatibilizers.
  • a compatibilizer when added to a blend of immiscible substances, modifies the interface between them and stabilizes the blend. Any compatibilizer known in the art may be used, e.g., graft copolymers or block copolymers.
  • the additives may be in the form of an additive concentrate having more than one additive.
  • the solubilizing of the Diels- Alder adduct disclosed herein or any solid additives in the host resin may be assisted by heating the mixture to a temperature between about 25 and about 200°C, from about 50 and about 150°C or from about 75 and about 125°C.
  • hydrocarbon terpene e.g., ⁇ -farnesene or a-farnesene
  • feed used to make the plasticizers described herein can be derived from renewable carbon sources.
  • any of the plasticizers comprising or derived from the Diels-
  • Alder adducts described herein may be made from conjugated terpenes and/or dienophiles that have been derived from renewable carbon sources.
  • a “renewable carbon” source refers to a carbon source that is made from modern carbon that can be regenerated within a several months, years or decades rather than a carbon source derived from fossil fuels (e.g., petroleum) that takes typically a million years or more to regenerate.
  • the terms “renewable carbon” “biobased carbon” are used interchangeably herein.
  • “Atmospheric carbon” refers to carbon atoms from carbon dioxide molecules that have been free in earth's atmosphere recently, in the most recent few decades.
  • renewable carbon content can be measured using any suitable method.
  • renewable carbon content can be measured according to ASTM D6866-1 1 , "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis," published by ASTM International, which is incorporated herein by reference in its entirety.
  • Some carbon in atmospheric carbon dioxide is the radioactive 14 C isotope, having a half life of about 5730 years. Atmospheric carbon dioxide is utilized by plants to make organic molecules. The atmospheric 14 C becomes part of biologically produced substances.
  • Isotope fractionation occurs during physical processes and chemical reactions, and is accounted for during radiocarbon measurements. Isotope fractionation results in enrichment of one isotope over another isotope. Exemplary processes that can affect isotope fractionation include diffusion (e.g., thermal diffusion), evaporation, and condensation. In some chemical reactions, certain isotopes may exhibit different equilibrium behaviors than others. In some chemical reactions, kinetic effects may affect isotope ratios.
  • isotope fractionation occurs.
  • the relative amounts of different carbon isotopes that are consumed are 12 C> 13 C> 14 C, due to slower processing of heavier isotopes.
  • Plants species exhibit different isotope fractionation due to isotopic discrimination of photosynthetic enzymes and diffusion effects of their stomata. For example C 3 plants exhibit different isotope fractionation than C 4 plants.
  • the international reference standard for isotope fractionation between 13 C and 12 C is PDB (Pee Dee Belemnite standard) or VPDB (Vienna Pee Dee Belemnite standard, replacement for depleted PDB standard).
  • ⁇ C is the relative change of the CI C ratio for a given sample from that of the VPDB standard.
  • Carbon isotopic ratios are reported on a scale defined by adopting a 5 13 C value of +0.00195 for NBS-19 limestone (RM 8544) relative to VPDB.
  • RM 8544 NBS-19 limestone
  • 14 C content of a sample can be measured using any suitable method.
  • 14 C content can be measured using Accelerator Mass Spectrometry (AMS), Isotope Ratio Mass Spectrometry (IRMS), Liquid Scintillation Counting (LSC), or a combination of two or more of the foregoing, using known instruments.
  • Activity refers to the number of decays measured per unit time and per unit mass units. To compare activity of a sample with that of a known reference material, isotope fractionation effects can be normalized.
  • a SN As ⁇ [( 13 C/ 12 C)reference]/[( 13 C/ 12 C)sample] ⁇ 2 .
  • Radiocarbon measurements are performed relative to a standard having known radioactivity.
  • the factor 0.95 is used to correct the value to 1950 because by the late 1950s, 14 C in the atmosphere had artificially risen about 5% above natural values due to testing of thermonuclear weapons.
  • Fraction of modern (fM) refers to a radiocarbon measured compared to modern carbon, referenced to AD 1950. Modern carbon as defined above has .
  • f M is approximately 1.1. Percent modern carbon (pMC) is fM x 100%.
  • the AD 1950 standard had 100 pMC.
  • Fresh plant material may exhibit a pMC value of about 107.5.
  • Biobased carbon content is determined by setting 100% biobased carbon equal to the pMC value of freshly grown plant material (such as corn), and pMC value of zero corresponds to a sample in which all of the carbon is derived from fossil fuel (e.g., petroleum).
  • a sample containing both modern carbon and carbon from fossil fuels will exhibit a biobased carbon content between 0 and 100%.
  • a sample that is more than several years old but containing all biobased carbon (such as wood from a mature tree trunk) will exhibit a pMC value to yield a biobased carbon content > 100%.
  • Renewable carbon content or biobased carbon content as used herein refers to fraction or percent modern carbon determined by measuring 14 C content, e.g., by any of Method A, Method B, or Method C as described in ASTM D6866-1 1 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis.” Counts from 14C in a sample can be compared directly or through secondary standards to SRM 4990C. A measurement of 0% 14 C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based). A measurement of 100% 14 C indicates carbon originating entirely from modern sources. A measurement of >100% 14 C indicates the source of carbon has an age of more than several years.
  • At least about 25%, at least about 30%, at least about 40%, at least about 50%>, at least about 60%>, at least about 70%>, at least about 80%>, at least about 90%>, or about 100% of the carbon atoms in the Diels-Alder adducts or derivatives thereof originate from renewable carbon sources.
  • the Diels-Alder adducts or derivatives have a 5 13 C of from about -11 to about -6 %o, from about -15 to about -10 % 0 , from about -22 to about -15 %o, from about -22 to about -32 %o, from -8 to about -18 %o, from about -14 to about -12 %o, or from about -13 to about -11 % 0 .
  • the Diels- Alder adducts or derivatives have a ⁇ greater than about 0.3, greater than about 0.4, greater than about 0.5, greater than about 0.6, greater than 0.7, greater than about 0.8, greater than about 0.9, or greater than about 1.0.
  • the Diels- Alder derivatives have a fM of about 1.0 to about 1.05, about 1.0 to about 1.1, or about 1.1 to about 1.2. In some variations, the Diels-Alder derivatives have a 5 13 C from about -15 to about -10 %o and a ⁇ greater than about 0.5, greater than about 0.7, or greater than about 1.0. In some variations, the Diels-Alder derivatives have a 5 13 C from about -8 to about -18 %o and a fM greater than about 0.5, greater than about 0.7, or greater than about 1.0.
  • the conjugated hydrocarbon terpene (e.g., myrcene, ⁇ -farnesene, or a-farnesene) is made by genetically modified microorganisms using renewable carbon sources such as a sugar (e.g., sugar cane).
  • a dienophile is at least partially derived from renewable carbon sources.
  • a dienophile may be derived from ethanol derived from plant sources, e.g., a dienophile may be derived from renewable ethylene that is derived from renewable ethanol.
  • one or more chemicals used to modify the Diels-Alder adducts described herein may be at least partially derived from renewable carbon sources.
  • renewable alcohols may be used to derivatize a Diels-Alder adduct as described herein.
  • renewable carbon content of a Diels-Alder adduct or its derivatives may be measured using any suitable method, e.g., using radiocarbon analysis as described herein.
  • the plasticizer may be incorporated into the polymer using any suitable method.
  • the plasticizer may be mechanically mixed with the polymer (e.g., melt blended).
  • the adduct may be co-dissolved with the polymer in a solution, and solvent cast.
  • the adduct may be chemically reacted with the host polymer to incorporate into the matrix, e.g. , by cross-linking,
  • the ingredients for a plasticized composition i.e., one or more plasticizers, the polymer and optional additives
  • suitable blending methods include melt blending, solvent blending, extruding, and the like.
  • the incorporation of the one or more plasticizers and any additives into the host matrix may be accomplished by melt-blending, wherein the ingredients are processed at a temperature higher than a temperature at which the host polymer flows to allow mixing of the plasticizers and any additives therein.
  • melt-blending equipment known in the art may be used, e.g., melt-blend extruders such as single screw extruders and twin screw extruders, Brabender® melt-blend compounders, two roll mills, and the like).
  • the ingredients are melt blended by a method as described by Guerin et al. in U.S. Patent No. 4,152,189.
  • all solvents, if there are any, are removed from the ingredients by heating to an appropriate elevated temperature of about 100 °C to about 200 °C or about 150 °C to about 175 °C at a pressure of about 5 torr (667 Pa) to about 10 torr (1333 Pa).
  • the ingredients are weighed into a vessel in the desired proportions and the foam is formed by heating the contents of the vessel to a molten state while stirring.
  • the ingredients are processed using solvent blending.
  • the ingredients are dissolved in a suitable solvent and the mixture is then mixed or blended. Next, the solvent is removed to form a plasticized film.
  • incorporation of a plasticizer into a host resin may be sensitive to the method of preparation of the plasticized film.
  • a host resin e.g., PVC
  • plasticization examples include type of PVC resin used (e.g., rigid, semi-rigid or flexible PVC), the type of mixing equipment (two roll mill, extruder, melt compounder and the like), whether melt blending or solvent casting is used, the solvent and solution concentration if solvent casting is used, etc.
  • type of PVC resin used e.g., rigid, semi-rigid or flexible PVC
  • type of mixing equipment two roll mill, extruder, melt compounder and the like
  • melt blending or solvent casting is used
  • solvent and solution concentration if solvent casting is used, etc.
  • physical blending devices that can provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing can be used in preparing homogenous blends.
  • Both batch and continuous methods of physical blending can be used.
  • Non- limiting examples of batch methods include those methods using BRABENDER ® mixing equipments (e.g., BRABENDER PREP CENTER ® , available from C. W. Brabender Instruments, Inc., Southhackensack, N.J.) or BANBURY ® internal mixing and roll milling (available from Farrel Company, Ansonia, Conn.) equipment.
  • Non-limiting examples of continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding.
  • the additives can be added into an extruder through a feed hopper or feed throat during the extrusion of the farnesene interpolymer, the optional polymer or the foam.
  • the mixing or blending of polymers by extrusion has been described in C. Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, NY, pages 322-334 (1986), which is incorporated herein by reference.
  • any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the plasticizers and any additives.
  • the blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer ⁇ e.g., Ross double planetary mixers and Collette planetary mixers), a homogenizer ⁇ e.g., Gaulin homogenizers and Rannie homogenizers), a mill ⁇ e.g., colloid mill, ball mill and sand mill) or any other mixing or dispersing equipment known in the art.
  • the plasticizers described herein may be incorporated into a melt-blend using a variety of schemes.
  • the plasticizers are pre-blended with one or more components of the composition (e.g., as a masterbatch).
  • the plasticizers are added directly into a melt blender (e.g., together with the host resin, or through an addition port or an injection port).
  • One or more Diels-Alder adducts disclosed herein and the optional additives may be added to the host resin individually or simultaneously.
  • one or more Diels-Alder adducts disclosed herein and the optional additives are added to the host resin individually in one or more additions and the additions may be in any order.
  • one or more Diels-Alder adduct disclosed herein and the additives are added to the host resin simultaneously, optionally in the form of an additive concentrate.
  • the solubilizing of the Diels-Alder adduct disclosed herein or any solid additives in the host resin may be assisted by heating the mixture to a temperature between about 25 and about 200°C, from about 50 and about 150°C or from about 75 and about 125°C.
  • Plasticized polymer compositions can be formed into a suitable structure for the intended use.
  • the plasticized polymer compositions can be extruded into shapes or beads for application on surfaces, spun into fibers, molded into shaped parts, coated on surfaces, and the like.
  • the compositions can be molded using injection molding, blow molding, compression molding, thermoforming and the like.
  • plasticized compositions may be used in a variety of applications.
  • plasticized compositions employing one or more plasticizers described herein include automotive components (e.g., interiors), footwear, adhesives, sealants, coated fabrics, wire and cable coatings, foams, gaskets, inks, cosmetics, medical devices, medical bags and tubing, toys, electrical devices, films, wall coverings, floor coverings, appliances, furniture, hoses, concrete and the like.
  • automotive components e.g., interiors
  • footwear adhesives, sealants, coated fabrics, wire and cable coatings, foams, gaskets, inks, cosmetics, medical devices, medical bags and tubing, toys, electrical devices, films, wall coverings, floor coverings, appliances, furniture, hoses, concrete and the like.
  • one or more plasticizers described herein is substituted for all or part of an existing vegetable oil or petroleum-derived monoester, diester (e.g., an adipate), phthalate, benzoate, dimerate, or trimellitate plasticizer.
  • a plasticizer described herein e.g., an unsaturated Diels-Alder adduct formed between a conjugated hydrocarbon terpene (e.g., farnesene) and an acrylate ester
  • a plasticizer described herein may be used as a renewable starch bioplastic modifier.
  • the ester function on the Diels-Alder adduct may react with hydroxyl groups in starch, and unsaturated ethylenic bonds on the adduct may react with other unsaturated monomers.
  • biodegradability of the compositions incorporating the adducts may be tested according to country-based regulations, local regulations, and/or standards-based tests, and according to anticipated uses (e.g., regulations for substances to come into contact with food to be ingested, substances to be used in food processing equipment, substances to come into contact with the human body, substances to be ingested, or substances to be implanted in the human body).
  • regulations for substances to come into contact with food to be ingested substances to be used in food processing equipment, substances to come into contact with the human body, substances to be ingested, or substances to be implanted in the human body.
  • a monoester or diester-containing Diels-Alder adduct is used in place of all or a portion of a vegetable oil or petroleum-derived monoester, diester (e.g. , an adipate), phthalate, benzoate, dimerate, or trimellitate plasticizer.
  • plasticizers when incorporated in high levels, typically in the 50-100 phr range (pounds per hundred pounds resin) range, can modify thermoplastics to give fluid compositions known as plastisols which are compositions of sufficiently low viscosity that may be applied to the surfaces of solid or porous articles, such as metals, plastics, and textiles for example, by various coating means including spray, dip, knife over drum and gravure. Said coated articles may sometimes be finished in a subsequent step in order to cure the composition or to remove some or all of the plasticizer.
  • the plasticizers described herein are useful as high solvating plasticizers.
  • a desirable procedure involves forming a resin dispersion (e.g., a vinyl chloride resin) that can be cast in a film or thicker article, and heated to form a homogeneous article of plasticized resin.
  • a resin dispersion e.g., a vinyl chloride resin
  • Such dispersions are suspensions of resin particles (e.g., a vinyl chloride resin) in one or more nonaqueous liquids including the plasticizer which do not dissolve the resin at ordinary temperatures but do at elevated temperatures.
  • the dispersion is often termed as "plastisol,” whereas if the dispersing liquid also contains volatile organic solvents or organic components which evaporate upon heating, the dispersion is often termed as "organosol.”
  • organosols may include other additives, including stabilizers, normally used in vinyl chloride resin compositions.
  • the term "plastisol” as used herein is intended to include both plastisols and organosols. Plastisols can be prepared using any method known in the art. For example, high, low or combination intensity mixers, such as ribbon blenders, conical screw, planetary, Cowles, Morehouse, or any other suitable mixer, may be used.
  • ingredients used in making plastisols include PVC, acrylic or other polymeric resins; primary or secondary plasticizers; fillers; pigments; heat stabilizers; solvents; and other ingredients known in the industry.
  • the plasticizers can be added to the plastisols at a range of from about 1.0 weight % to about 60 weight %, or at a range of from about 5.0 weight % to about 40 weight %, or at a range of from about 10.0 weight % to about 30 weight %, depending on the efficiency of the plasticizer and the desired properties of the final product. Any one of or any combination of the order of ingredients, shaft rpm, mixing times, and temperature may play a role to the producing a plastisol with reproducible quality.
  • plastisol temperature during mixing is maintained at less than 95° F. (35° C), or even less than 80° F. (27° C). In some cases where for instance a higher loading is desired, the maximum temperature may be higher.
  • Air is both incorporated in the mixing process and may also be introduced from the surface of the dry ingredients. If necessary, air can be removed by deaeration under reduced pressure either during or after mixing. Some of the air may be released during storage of a plastisol.
  • the present plasticizers may be incorporated into vinyl chloride resin, with or without other additions, by any suitable process such as, mixing or kneading of the ingredients.
  • the plasticizers described herein may be added at any time and in any convenient manner to the PVC plastisol. If desired, the PVC plastisol and viscosity reducing compounds may be mixed simultaneously, for example, in conventional mixing or blending equipment.
  • the plasticizers described herein can be used in a variety of adhesives to increase the flexibility, decrease rigidity (e.g., increase elongation at break), increase toughness, improve low temperature physical properties, and/or improve processability of the adhesives.
  • Nonlimiting examples of adhesives in which the plasticizers may be utilized include those based on acrylates, methacrylates, silanes, siloxanes, polyethers, polyesters, polyurethanes, polyureas, polysulfides, silylated polyurethanes, silylated polyureas, silylated polyethers, silylated polysulfides and silyl-terminated acrylates and the like. Further nonlimiting examples of adhesives in which the plasticizers may be used are described in U.S. Patent Publ.
  • adhesive compositions may comprise additional components. These may include, among others, the following auxiliaries and additives. Adhesion promoters may be included, examples being epoxysilanes,
  • anhydridosilanes adducts of silanes with primary aminosilanes, ureidosilanes, aminosilanes, diaminosilanes, and also their analogs in the form of monomer or oligomer and urea-silanes; e.g. Dynasylan AMEO, Dynasylan AMMO, Dynasylan DAMO-T, Dynasylan 1146, Dynasylan 1189, Silquest A-Link 15.
  • Water scavengers may be included, e.g.
  • vinyltriethoxysilane vinyltrimethoxysilane, a-functional silanes such as N-(silylmethyl)-0-methyl-carbamates, more particularly N-(methyldimethoxysilylmethyl)-0-methyl-carbamate,
  • (methacryloyloxymethyl)silanes methoxymethylsilanes, N-phenyl-, N-cyclohexyl- and N- alkylsilanes, ortho formic esters, calcium oxide or molecular sieve.
  • Catalysts may be included, examples being metal catalysts in the form of organotin compounds such as dibutyltin dilaurate and dibutyltin diacetylacetonate, organobismuth compounds or bismuth complexes; compounds containing amino groups, examples being l,4-diazabicyclo[2.2.2]octane and 2,2'- dimorpholinodiethyl ether, and also aminosilanes.
  • metal catalysts include titanium, zirconium, bismuth, zinc and lithium catalysts, and also metal carboxylates, it also being possible to use combinations of different metal catalysts and also combinations of aminosilanes and metal catalysts.
  • Light stabilizers and aging inhibitors which act in particular as stabilizers against heat, light and UV radiation. Flame retardants may be included.
  • Biocides such as, for example, algicides, fungicides or fungal growth inhibitor substances, may be included.
  • the adhesive compositions may include fillers, e.g., ground or precipitated calcium carbonates, which optionally are coated with fatty acids or fatty acid mixtures, e.g., stearates, more particularly finely divided, coated calcium carbonate, carbon blacks, especially industrially manufactured carbon blacks, kaolins, aluminium oxides, silicas, highly disperse silica from pyrolysis processes, PVC powders or hollow beads, calcium carbonates, such as precipitated or natural chalks such as Omyacarb® from Omya, Ultra P-Flex® from Specialty Minerals Inc, Socal® U1 S2, Socal® 312, Winnofil® 312 from Solvay, Hakuenka® from Shiraishi, highly disperse silicas from pyrolysis processes, and combinations of these fillers.
  • fillers e.g., ground or precipitated calcium carbonates, which optionally are coated with fatty acids or fatty acid mixtures, e.g., stearates, more particularly fine
  • suitable additives are minerals such as siliceous earth, talc, calcium sulfate (gypsum) in the form of anhydrite, hemihydrate or dihydrate, finely ground quartz, silica gel, precipitated or natural barium sulfate, titanium dioxide, zeolites, leucite, potash feldspar, biotite, the group of soro-, cyclo-, ino-, phyllo- and hecto silicates, the group of low-solubility sulfates such as gypsum, anhydrite or heavy spar, and also calcium minerals such as calcite.
  • Rheology modifiers may be included, such as thickeners, e.g.
  • urea compounds polyamide waxes, bentonites, fumed silica and/or acrylates.
  • Surface-active substances may be included such as, for example, wetting agents, leveling agents, deaerating agents or defoamers, and dispersants.
  • Fibers as for example of polyethylene or polypropylene may be included.
  • Pigments may be included, e.g. titanium dioxide or carbon black. Solvents may be utilized. Any other substances commonly used in moisture-curing compositions may be utilized.
  • the adhesive or sealant comprises 10 to 90% by weight of polymer, 3 to 50%> by weight of plasticizer, 0 to 80%> by weight of fillers, 0 to 20%> by weight of water scavengers and 0.5 to 20%> by weight of rheology modifiers, or an amount of 25 to 40%> by weight of polymer, 5 to 40%> by weight of plasticizers, 30 to 55% by weight of fillers, 1 to 10%> by weight of water scavengers and 1 to 10%> by weight of rheology modifiers.
  • Adhesives may be one component (IK) or two-component (2K) systems. IK systems bind through chemical reactions of the binder with the ambient moisture. 2K systems are additionally set by chemical reactions of the mixed components, with continuous solidification.
  • an adhesive or sealant is a one-component system.
  • compositions so that such components comprise no water or at most traces of water.
  • the moisture curable adhesives may be stored in the absence of moisture, e.g., kept in a suitable pack or facility, such as a drum, a pouch or a cartridge, for example, over a period of several months to a number of years, without suffering change that significantly affects its properties after curing.
  • a suitable pack or facility such as a drum, a pouch or a cartridge, for example, over a period of several months to a number of years, without suffering change that significantly affects its properties after curing.
  • the storage stability or shelf-life is typically determined via measurement of the viscosity, the extrusion quantity or the extrusion force.
  • Plasticized adhesive or sealant compositions described herein may produce material bonds between parts that are to be joined.
  • the functional groups of the polymer comes into contact with moisture.
  • a property of the functional groups is that of undergoing hydrolysis on contact with moisture.
  • the composition finally cures or crosslinks.
  • the water required for the curing reaction may come from the air (atmospheric humidity), or else the composition may be contacted with a water- comprising component, by being brushed with a smoothing agent, for example, or by being sprayed, or else a water-comprising component may be added to the composition at application, in the form, for example, of a water-containing paste which is mixed in, for example, via a static mixer.
  • the composition described cures, as already stated, on contact with moisture. Curing takes place at different rates depending on temperature, nature of contact, amount of moisture, and the presence of any catalysts. Curing by means of atmospheric moisture first forms a skin on the surface of the composition. The so-called skin formation time, accordingly, constitutes a measure of the cure rate.
  • the plasticized composition possesses a high mechanical strength in conjunction with high extensibility, and also has good adhesion properties. This makes it suitable for a multiplicity of applications, more particularly as an elastic adhesive, as an elastic sealant or as an elastic coating. It is especially suitable for applications which require rapid curing and which impose exacting requirements on extensibility at the same time as exacting requirements on the adhesion properties and the strengths.
  • Suitable applications are, for example, the material bonds between parts to be joined made of concrete, mortar, glass, metal, ceramic, plastic and/or wood.
  • the parts to be joined are firstly a surface and secondly a covering in the form of carpet, PVC, laminate, rubber, cork, linoleum, wood, e.g. woodblock flooring, floorboards, boat decks or tiles.
  • the plasticized composition can be used in particular for the manufacture or repair of industrial goods or consumer goods, and also for the sealing or bonding of components in construction or civil engineering, and also, in particular, in the sanitary sector.
  • the parts to be joined may especially be parts in auto, trailer, truck, caravan, train, aircraft, watercraft and railway construction.
  • An adhesive for elastic bonds in this sector is applied with preference in the form of a bead in a substantially round or triangular cross-sectional area.
  • Elastic bonds in vehicle construction are, for example, the adhesive attachment of parts such as plastic covers, trim strips, flanges, bumpers, driver's cabs or other components for installation, to the painted body of a means of transport, or the bonding of glazing into the bodywork.
  • composition described is used as an elastic adhesive or sealant.
  • the composition typically has an elongation at break of at least 50%, and in the form of an elastic sealant it typically has an elongation at break of at least 300%, at room temperature.
  • the composition may have a paste-like consistency with properties of structural viscosity.
  • a paste-like sealant or adhesive of this kind is applied by means of a suitable device to the part to be joined. Suitable methods of application are, for example, application from standard commercial cartridges which are operated manually or by means of compressed air, or from a drum or hobbock by means of a conveying pump or an eccentric screw pump, if desired by means of an application robot.
  • the parts to be joined may where necessary be pretreated before the adhesive or sealant is applied.
  • pretreatments include physical and/or chemical cleaning processes, non- limiting examples being abrading, sandblasting, brushing or the like, or treatment with cleaners or solvents, or the application of an adhesion promoter, an adhesion promoter solution or a primer.
  • the plasticized composition is applied either to one or the other part to be joined, or to both parts to be joined. Thereafter the parts to be bonded are joined, and the adhesive cures through contact with moisture. In each case it is ensured that the joining of the parts takes place within what is referred to as the open time, in order to ensure that the two parts to be joined are reliably bonded to one another.
  • the multifunctional plasticizers may be compounded with the thermoplastic, thermosets, elastomers or rubbers, along with any additional additives, to give useful compositions including
  • plasticization function of a multifunctional plasticizer that it be directed toward affecting the bulk property of the thermoplastic article or composition, it should be recognized that in some application areas it is desirable that the other one or more functions of a multifunctional plasticizer be directed to the surface of the article or composition.
  • a multifunctional plasticizer that also functions as a antithrombolytic is present both in the bulk and entangled with the thermoplastic at the surface of the article or composition.
  • At least three methods for effecting migration of some of the multifunctional plasticizer towards the surface while maintaining a level of plasticizer in the bulk that is satisfactory for good plasticization.
  • One of these methods employs a thermal treatment step.
  • Another method employs contact of the surface of said article with a liquid which promotes migration either by swelling, chemical potential, or diffusion gradient mechanisms.
  • a third method employs the use of small amount of a separate surfactant molecule that when added to the multifunctional plasticizer-thermoplastic composition effects surface migration.
  • a plasticizer described herein (e.g., plasticizers in Table 5) is used to plasticize PVC to make a bottle cap.
  • a plasticizer provided herein may be mixed together in a 1 :4 weight ratio respectively in a blender for a suitable length of time (e.g., about 10 minutes) to give a divided composition.
  • an acid scavenger in a suitable amount e.g., about 1 phr
  • the divided composition may be blended for an additional time period (e.g., about 5 minutes).
  • the resulting composition may be kneaded for a suitable length of time in a suitable mixing apparatus (e.g., about 20 minutes under moderate energy using a Banbury batch mixer at about 200 degree blade temperature) to give a doughy composition.
  • a suitable mixing apparatus e.g., about 20 minutes under moderate energy using a Banbury batch mixer at about 200 degree blade temperature
  • a portion of the composition may be compression molded, e.g., into a 9x9x0.03" rectangular sheet using a Carver Press at a guage pressure of 10 tons and a mold temperature of about 230 degrees.
  • dog bone specimens may be cut from the molded sheet and its tensile properties measured using methods prescribed in ASTM D638.
  • the specimens may give an average elongation at break of about 20%, 30%, 40%>, 50%>, 100%, 150%), 200%), 250%) or 300%>.
  • round coupons may be cut from the sheet with a punch and then pressed into HDPE bottle caps.
  • the resulting lined caps may exhibit good barrier and excellent sealing properties when fitted to bottles.
  • Bottle caps may be prepared with an additional step of incorporating a commercial oxygen scavenger during the mixing step.
  • the resulting lined caps may exhibit excellent barrier and sealing properties.
  • a low-color molded article comprising PVC and a multifunctional plasticizer possessing acid scavenging function may be made by incorporating a plasticizer described herein with alkenyl chemical groupings into PVC by any method known in the art, but withought adding any separate acid scavenger ingredient giving a plasticized sheet or article with very low color.
  • a low-color molded article comprising PVC and a multifunctional plasticizer possessing acid scavenging function may be made by incorporating a plasticizer described herein with epoxy chemical groupings into PVC by any method known in the art, but without adding any separate acid scavenger ingredient giving a plasticized sheet or article with very low color.
  • a plasticizer described herein may be used to make a flexible safety hose having a charge dissipating fluid-contact surface.
  • a plasticizer described herein with an anhydride chemical grouping may be extruded in a continuous process into a hose geometry using any suitable method known in the art.
  • a screw extruder equipped with a tube die head may be used.
  • Tables 5 and the Examples provide non- limiting examples of Diels- Alder adducts that may be used as plasticizers, and test results for select ones of those plasticizers.
  • the Examples provide non-limiting examples of epoxidized farnesenes that may have utility as plasticizers, monomers in making oligomers or polymers, as cross-linking agents, curing agents, as reactive solvents or diluents, and the like.
  • compositions or methods may include numerous compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not include, or are substantially free of, any compounds or steps not enumerated herein. Variations and modifications from the described embodiments exist.
  • ⁇ -farnesene refers to trans- ⁇ -farnesene.
  • ⁇ -farnesene is manufactured using genetically modified organisms by Amyris, Inc., and has been distilled prior to use to result in a purity of >97%, and includes lOOppm 4-tert-butylcatechol (TBC) as stabilizer.
  • TBC 4-tert-butylcatechol
  • Example 1 Preparation of 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid methyl ester (la) and 4-(4,8-Dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid methyl ester (lb).
  • Example 2 Preparation of 4-(4,8-Dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid dodecyl ester (2a) and 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid dodecyl esters (2b).
  • a 5 L three-necked round-bottomed flask equipped with a magnetic stirrer, heating mantle and dean stark trap carrying a reflux condenser was charged with 486 g (1.76 mol) of la, lb, 332 g (1.78 mol) of 1-dodecanol, 0.10 g of /?-toluenesulfonic acid and 200 mL of toluene. The mixture was stirred and heated to refluxing.
  • Example 6 Preparation of 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2- dicarboxylic acid bis-(2-ethylhexyl) ester (6).
  • Example 7 Preparation of 4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid bis- (2-ethylhexyl) es -00448-026]).
  • Example 8 Preparation of 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2- dicarboxylic acid dimethyl ester (8).
  • Example 11 4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid diheptyl ester (compound 11 -00448-031]).
  • Example 12 4-(4,8-Dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid 2-ethylhexyl ester (12a) and 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid 2-ethylhexyl ester (12b).
  • the reaction was analyzed by GCMS after 25 hours, indicating the presence of the following compounds: 5.4 % ethylhexyl acrylate, 6.0 % farnesene, and two peaks corresponding to the 1,3- and 1,4- isomers of (12b and 12a, respectively) representing 29.2 and 58.0 % of the final product mixture. Heating was discontinued and the mixture was subjected to hydrogenation.
  • Example 13 Preparation of 4-(4,8-Dimethylnonyl)cyclohexane carboxylic 2-ethylhexyl ester (13a) and 3-(4,8-Dimethylnonyl)cyclohexane carboxylic acid 2-ethylhexyl ester (13b) [KJF-437-56-01]

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Abstract

La présente invention concerne des plastifiants dérivés de terpènes hydrocarbonés (par exemple, myrcène ou farnésène), des procédés de fabrication des plastifiants, des compositions comprenant les plastifiants, et des applications pour les compositions plastifiées.
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