EP2499171A1 - Polymers derived from plant oil - Google Patents

Abstract

Polymers and copolymers are formed from vinylether monomers having fatty acid ester pendent groups derived from plant oils, such as soybean oil.

Description

Polymers Derived from Plant Oil Background

Plant oil-based materials have many applications. For example, they are in use as lubricants, cosmetics, plastics, composites and drying agents. Commercial and industrial interest in plant oil-based materials is high due to the fact that plant oils are renewable resources and typically biodegradable. Soybean oil is the most widely used vegetable oil for non-food applications due to its low cost and availability.

Cycloaliphatic epoxides, which are popular in cationic photopolymerization due to their faster reactivity, tend to produce high Tg crosslinked networks that can be brittle. As a result, vegetable oil-based epoxides are sometimes used to impart flexibility and toughness. Wan Rosli et al., Eur. Polym. J. 2003, 39, (3), 593-600. Epoxidized soybean oil (ESO) has been extensively used in cationic photopolymerization to produce surface coatings and polymer composites. However a major disadvantage of ESO relative to more conventional epoxy resins such as bisphenol-A-based epoxy resins is the relatively low reactivity resulting from disubsitution of the epoxy groups. Zou et al., Macromol. Chem. Phys. 2005, 206, (9), 967-975.

Summary of the Invention

The present invention provides vinylether monomers, as well as polymers and copolymers of vinylether monomers, wherein the vinylether monomers include fatty acid ester pendent groups derived from plant oils, such as soybean oil. Also included in the invention are methods for making the monomers and polymers, and methods of using them to produce lubricating liquids such as lubricants, oils, and gels, as well as coatings, films, composite materials, and the like.

In one aspect, the invention provides a polymer formed from vinyl ether monomers derived from plant oil and having the structure:

wherein R is a C8-C21 aliphatic group. The polymer of the invention thus preferably includes a repeating unit having the general structure:

wherein R is a C8-C21 aliphatic group derived from a plant oil. The plant oil is preferably a vegetable or nut oil, more preferably a soybean oil. In one embodiment, the polymer is the product of a living carbocationic polymerization reaction, optionally a living carbocationic polymerization reaction that occurs in the absence of a Lewis base. Optionally, and in another embodiment, the polymer has a polydispersity index of less than 1.5. The polymer can include a plurality of monomers, such that for each of the plurality of monomers, R is independently a C8-C21 aliphatic group derived from a plant oil.

Chemical derivatives of the polymer, including but not limited to an epoxy- functional polymer, an acrylate-functional polymer and a polyol polymer, are also encompassed by the invention. An epoxy-functional polymer includes, as an R group, at least one C8-C21 aliphatic group derived from a plant oil that has been functionalized to include at least one epoxide group; an acrylate functional polymer includes, as an R group, at least one C8-C21 aliphatic group derived from a plant oil that has been functionalized to include at least one acrylate-functional group; and a polyol polymer includes, as an R group, at least one C8-C21 aliphatic group derived from a plant oil that has been functionalized to include at least one alcohol group.

The invention further includes copolymers of the vinyl ether plant oil fatty acid ester monomers described herein, such as a copolymer with a vinylether polyethylene glycol monomer.

In another aspect, the invention provides a method for making a polymer of the invention that includes contacting vinyl ether plant oil fatty acid ester monomers with an organic initiator molecule and a Lewis acid under reaction conditions to allow

polymerization of the monomer. The polymerization reaction is optionally performed in the absence of a Lewis base. In another aspect, the invention provides a method for making a polymer from plant oil that includes polymerizing vinylether plant oil fatty acid ester monomers to yield a polymer having a polydispersity index of less than 2.0, preferably less than 1.5, more preferably less than 1.2. Optionally, the methods include extracting the plant oil from a plant or plant part to obtain the oil. The method optionally further includes cleaving triglycerides found in the plant oil to yield the monomers comprising vinylethers of plant oil fatty acid esters. Cleavage can be accomplished using base-catalyzed transesterification.

In a further aspect, the invention provides a method for producing a polymer that includes contacting vinylether plant oil fatty acid ester monomers with an initiator to form a reaction mixture; contacting the reaction mixture with a co-initiator, e.g., a Lewis acid, to initiate a polymerization reaction under conditions and for a time to allow polymerization to proceed; and terminating the polymerization reaction yield the polymer. In another aspect, the invention provides a method for producing a copolymer that includes contacting vinylether plant oil fatty acid ester monomers with at least one additional vinylether monomer and an initiator to form a reaction mixture; contacting the reaction mixture with a co-initiator, e.g., a Lewis acid, to initiate a polymerization reaction under conditions and for a time to allow polymerization to proceed; and terminating the polymerization reaction yield the copolymer. Optionally, the additional vinylether monomer is a vinylether polyethyleneglycol (VEPEG) monomer or a 3,6,9,12- tetraoxatetradec-l-ene (VEDEE) monomer. Polymerization can take place at a temperature less than 10°C; preferably less than 5°C, more preferably at about 0°C. The plant oil monomers are preferably vegetable oil or nut oil monomers, more preferably soybean oil monomers. In a preferred embodiment, the first initiator includes 1- isobutoxyethyl acetate and the co-initiator includes ethyl aluminum sesquichloride.

Also included in the invention is a polymer or copolymer produced by a method described herein, as well a composition that includes the polymer or copolymer. The composition can be an uncured composition or a cured composition; it can be an oil, a lubricant, a coating, a gel, a film or a composite, without limitation. Also included in the invention is an article, surface or substrate that includes a polymer or copolymer, cured or uncured, as described herein, such as, without limitation, a coated article, surface or substrate, or an article formed from a composite.

Brief Description of the Drawings

Figure 1 shows (A), an exemplary monomeric vinyl ether of a fatty acid ester; (B) an exemplary polymer of a vinyl ether of soybean oil fatty acid ester; (C) an exemplary polymer of vinyl ether of soybean oil fatty acid esters (polyVESFA); and (D) an exemplary epoxidized polymer of vinyl ether of soybean oil fatty acid esters (E- polyVESFA).

Figure 2 is a schematic showing the difference in molecular architecture between soybean oil and polyVESFA.

Figure 3 shows an exemplary synthesis of vinyl ether of soybean oil fatty acid esters (VESFA).

Figure 4 shows an exemplary synthesis of the polymer of the vinyl ether of soybean oil fatty acid esters (polyVESFA) using carbocationic polymerization.

Figure 5 shows an exemplary synthesis of epoxidized polyVESFA (E- poly VESFA) from the polymer of the vinyl ether of soybean oil fatty acid esters

(polyVESFA). Figure 6 shows a plot of number-average molecular weight (Mn) as a function of monomer conversion for the polymerization of vinyl ether of soybean oil fatty acid esters (VESFA).

Figure 7 shows an 1H NMR spectra of the polymer of the vinyl ether of soybean oil fatty acid esters (poly VESFA) and epoxidized poly VESFA (E-poly VESFA).

Figure 8A shows real time infrared (RTIR) spectroscopy results for various coatings and Figure 8B shows differential scanning calorimeter equipped with a photocalorimetric accessory (photo-DSC) results for various coatings.

Figure 9 shows a storage modulus as a function of temperature for various coatings cured with 1 pass (Figure 9 A) and 2 passes (Figure 9B) under the UV lamp using a belt speed of 24 ft/min.

Figure 10 shows a synthetic scheme for synthesis of a copolymer of VESFA and a polyethylene glycol-functional vinylether monomer.

Figure 11 shows a synthetic scheme for synthesis of a hydrophilic vinyl ether monomer, 3,6,9,12-tetraoxatetradec- 1 -ene.

Figure 12 shows a synthetic scheme for production of cured poly VESFA films using an auto-oxidation process.

Figure 13 shows a synthetic scheme for production of cured poly VESFA films using a vulcanization process.

Figure 14 shows a synthetic scheme for production of cured E-poly VESFA films using an amine curing agent.

Figure 15 shows a synthetic scheme for production of cured E-poly VESFA radiation-curable coatings using an ultraviolet (UV) light initiated cationic

polymerization process.

Figure 16 shows a synthetic scheme for production of acrylated materials using poly VESFA and E-poly VESFA.

Figure 17 shows a synthetic scheme for production of polyols using poly VESFA and E- VESFA copolymers. Detailed Description of Illustrative Embodiments The present invention provides vinylether monomers, as well as polymers and copolymers of vinylether monomers, wherein the vinylether monomers include fatty acid ester pendent groups derived from plant oils, such as soybean oil. Also included in the invention are methods for making the monomers and polymers, and methods of using them to produce lubricating liquids such as lubricants, oils, and gels, as well as coatings, films, composite materials, and the like. Articles, coatings, films, composites, oils, gels and lubricants that include monomers or polymers of the invention, cured or uncured, as well as methods for making and using them, also provided by the invention.

An illustrative embodiment of the plant oil polymer of the invention is referred to herein as a polymev of a vinyl ether of soybean oil fatty acid esters (polyVESFA), although it should be understood that the polymer of the invention is not limited to a polymer produced from soybean oil. The various methods and uses described herein, therefore, although described for convenience with reference to an embodiment of the polymer derived from soybean oil, apply generally to embodiments derived from any suitable plant oil. Thus, in one embodiment, the exemplary polyVESFA is synthesized from monomers derived from the transesterification of soybean oil (the exemplary plant oil) with ethylene glycol monovinylether. These exemplary monomers are referred to herein as vinyl ethers of soybean oil fatty acid esters (VESFA). Because soybean oil contains five different fatty acids (stearic acid, oleic acid, linoleic acid, palmitic and linolenic acid) the vinylether monomers produced by transesterification of soybean oil include a mixture of vinylethers of stearic acid, oleic acid, linoleic acid, palmitic acid and linolenic acid esters. The resulting polymer, polyVESFA, is heterogeneous in the sense that it contains monomers derived from all five fatty acids. PolyVESFA can be produced, for example, using carbocationic polymerization.

The polymer of the invention can be derivatized. For example, the polymer can be subjected to epoxidation and optionally subjected to epoxy-amine curing, epoxy- anyhydride curing, cationic photocuring, and/or converted to a polyol or component for use in polyurethane; it can function as an elastomeric alcohol. The polymer can be made acrylate-functional, sulfonated to form an ionomer, vulcanized, subjected to a Diels- Alder reaction to form a film, cured to a film with a thiol using thio-ene chemistry, cured with a peroxide, or it can be air-dried under conditions to initiate crosslinking or exposed to radiation, preferably UV radiation.

Plant oils that can be used to form the monomers and polymers of the invention include vegetable oils, such soybean oil, linseed oil, rung oil, oiticica oil, perilla oil, safflower oil and castor oil; oil from trees or wood pulp such as tall oil, or nut-based oils such as cashew oil. The vegetable oils include at least one triglyceride and contain fatty acids such as at least one of oleic acid, stearic acid, linoleic acid, linolenic acid, palmitic acid, lauric acid, myristic acid, arachidic acid, and palmitioleic acid.

Vinyl ether monomers provided by the invention include vinyl ethers of plant oil fatty acids, more particularly, vinylethers of soybean oil fatty acids VESFA). A preferred monomer has the structure CEb^CH-OR, where R contains an aliphatic group and an ester group derived from a renewable resource such as a plant oil, preferably vegetable oil. Preferred polymers, co-polymers, and polymeric materials are those derived from a preferred monomer.

A particularly preferred monomer (see, e.g., Fig. 1 A) is derived from a plant oil and has the structure:

wherein R is a C8-C21 aliphatic group, preferably a C8-C21 alkyl group or a C8- C21 alkenyl group, more preferably a linear C8-C21 alkyl group or a linear C8-C21 alkenyl group. The aliphatic group preferably includes a linear chain of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 carbon atoms, and preferably contains 0

(saturated), 1 (monounsaturated), 2 or 3 double bonds. Preferably, the monomer is derived from a vegetable or a nut oil; more preferably, it is a derivative of one of the plant fatty acids found in soybeans: stearic acid, oleic acid, palmitic, linoleic acid or linolenic acid.

In one embodiment, monomers are synthesized using base-catalyzed

transesterification of a plant oil, such as soybean oil, with ethylene glycol vinyl ether. The base can be potassium hydroxide, sodium hydroxide, or any convenient base.

Ethylene glycol vinyl ether is a relatively inexpensive chemical, and the resulting monomer is isolated in high purity. In another embodiment, the monomer is synthesized using acid-catalyzed transesterification. More generally, any convenient

transesterification method can be used to generate the vinyl ether plant oil fatty acid ester monomers of the invention.

Vinyl ethers synthesized from fatty alcohols have been reported by others (see additional references, supra). Fatty alcohols are typically produced from hydrogenation of fatty acids. The conversion of the fatty alcohols to the vinyl ether was done using vinylation with acetylene, and the process involved several steps. One advantage of the present invention is that the vinyl ether is produced directly from the plant oil, preferably vegetable oil, by a single-step simple transesterification similar to the process used to produce biodiesel (i.e. methyl esters of vegetable oil fatty acids). The resulting monomer is much easier and less expensive to make. Additionally, the vinyl ether monomers produced by the present invention includes an ester functionality.

A polymer of the invention is formed from one or more of the monomers of the invention, and optionally includes other monomers, preferably other monovinylidene monomers. A preferred polymer (see, e.g., Fig. IB) contains a repeating unit:

wherein R is as defined above for the monomer, e.g., a C8-C21 aliphatic group derived from a plant oil, and is optionally activated or functionalized at the site of one or more double bonds, e.g., by epoxidation, acrylation, or by the incorporation of alcohol groups. The polymer preferably contains a plurality of different monomers, such that R encompasses a plurality of aliphatic groups R_n where n = 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, which aliphatic groups are optionally activated. For example, when the polymer is derived from an oil such as soybean oil that contains five fatty acids, the polymer may contain monomers having five different aliphatic groups:

See, for example, Fig. 1C wherein m, n, p, q and r vary with the relative amount of each monomer, and R = stearate, R₂ = oleate, R₃ = linoleate, R4 = linoleate and R₅ = linolenate. It should be understood that the five monomers are typically evenly dispersed throughout the polymer, according to their abundance. An exemplary composition of soybean oil is about 11% palmitic acid, about 4% stearic acid, about 23% oleic acid, about 54% linoleic acid, and about 7% linolenic acid.

As used herein, the term "aliphatic group" means a saturated or unsaturated linear (i.e., straight chain), cyclic, or branched hydrocarbon group. This term is used to encompass alkyl (e.g., -CH₃) (or alkylene if within a chain such as ~CH₂ --), alkenyl (or alkenylene if within a chain), and alkynyl (or alkynylene if within a chain) groups, for example. The term "alkyl group" means a saturated linear or branched hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like. The term "alkenyl group" means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon double bonds, such as a vinyl group. The term "alkynyl group" means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon triple bonds. The term "aromatic group" or "aryl group" means a mono- or polynuclear aromatic hydrocarbon group. These hydrocarbon groups may be substituted with heteroatoms, which can be in the form of functional groups. The term "heteroatom" means an element other than carbon (e.g., nitrogen, oxygen, sulfur, chlorine, etc.).

In other embodiments of the polymer of the invention, the R group(s) can be activated at the site of one or more double bonds, e.g., by epoxidation, acrylation, or by the incorporation of alcohol groups, as described in more detail elsewhere herein.

Briefly, incorporation of acrylate groups or alcohol groups typically first involves the generation of an epoxide intermediate. The double bonds can be derivatized using epoxidation, Diels-Alder chemistry, or thiol-ene chemistry. Derivatives such as epoxy- functional, acrylate-functional and alcohol-functional (polyol) polymers are likewise included in the invention.

Monomers produced from oil in accordance with the method of the invention contain an ester group. Advantageously, these monomers can be polymerized in a controlled fashion without destroying the ester functionality. In a preferred embodiment, the method of polymerizing monomers of the invention utilizes living carbocationic polymerization (also known as controlled/living cationic polymerization). Typically, living carbocationic polymerization utilizes an initiating system that includes an organic initiator molecule, a Lewis acid (i.e., a co-initiator), and a Lewis base, and results in controlled addition of monomers to the growing chain until all monomers are consumed. Side reactions, such as chain transfer and chain termination, are kept to a minimum. Living cationic polymerization of alkyl vinyl ethers is described, for example, in US Pat. No. 5,196,491. Advantageously, the use of living carbocationic polymerization allows the viscosity of the liquid to be controlled. The concentration of the initiator affects the molecular weight of the resulting polymer; the lower the initiator concentration, i.e., the higher the [Monomer]: [Initiator] ratio, the higher the molecular weight of the resulting polymer.

Polymerization of vinyl ethers typically requires the inclusion of a Lewis base, such as ethylacetate, methylchloroacetate or methyldichloroacetate, to prevent uncontrolled polymerization. A Lewis base is typically included to mediate the polymerization reaction through coordination with the carbocation, thereby lowering its reactivity such that it undergoes propagation reactions but not chain termination or chain transfer reactions. However, it has been surprisingly discovered that the inclusion of a Lewis base during polymerization of the monomers of the invention is not required and, in fact, may slow down polymerization to the point that it does not occur. Without wishing to be bound by theory, it is thought that the monomer itself provides the carbonyl or ester group needed to mediate the polymerization reaction; in other words, it is self- mediated. Thus, the polymerization method of the invention, when based on living cationic polymerization, preferably omits a Lewis base, although a Lewis base may optionally be included in the reaction mixture. Optionally, when the Lewis base is omitted, the amount of the Lewis acid is increased. The amount of Lewis acid used, which is also referred to herein as a "co-initiator," affects the polydispersity in the mixture, and can be adjusted so that it is high enough to produce polymerization, but not so high as to produce an undesirably broad molecular weight dispersion. Polydispersity indices (PDI) of under 1.3, more particularly about 1.1 or 1.2, can be achieved using the polymerization method of the present invention. In one embodiment of the

polymerization method, monomers derived from plant oils, preferably vegetable oils, more preferably vinylether esters of soybean fatty acids, are contacted with a carbonyl- containing initiator compound and a Lewis acid co-initiator in a reaction mixture under conditions sufficient to generate a carbocation which initiates polymerization of the monomers. Exemplary Lewis acids include ΕίυΑΙΟι^ used in the examples below, as well as BC1₃, BF₃, A1C1₃, SnC , TiCLj, SbF₅, SeCl₃, ZnCl₂, FeCl₃ and VC1₄.

An exemplary method for making a polymer from vegetable oil such as soybean oils thus involves polymerizing monomers comprising vinylether esters of vegetable oil fatty acids to yield a polymer. The method optionally includes cleaving the triglycerides present in the vegetable oil, preferably in a base-catalyzed transesterification process, to yield the monomers. In a particularly preferred embodiment of the method of making the polymer, the polymerizing step comprises living carbocationic polymerization, wherein the monomers are contacted with an organic initiator molecule and a Lewis acid co- initiator under reaction conditions to allow polymerization of the monomer. As noted elsewhere herein, surprisingly, the polymerization reaction can be performed in the absence of a Lewis base. The method further optionally includes extracting the vegetable oil from the a plant or plant part. It is to be understood that a polymer produced by any method described herein is also provided by the invention.

Polymerization yields linear polymers which include branches derived from the various fatty acids found in the oil. The polymers produced using the polymerization method are also included in the invention. When living carbocationic polymerization is used, the resulting polymer advantageously has a narrower molecular weight distribution compared with other polymerization methods, making the polymers especially suitable for commercial and industrial applications. The molecular weight distribution (MWD, also known as the polydispersity index, PDI) for the polymer resulting from this polymerization reaction is typically less than 2 and can be less than 1.8, less than 1.5, and is preferably less than 1.3. Thus, in one embodiment, the polymer of the invention, which is optionally activated at the site of one or more double bonds, e.g., by

epoxidation, acrylation, or by the inclusion of alcohol groups; optionally has a PDI of less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less thanl.5, less than 1.4, less than 1.3, less than 1.2, or less than 1.1. Additionally, the molecular weight of the polymers produced can be controlled by adjusting the nature or amount of the reactants or changing the reaction conditions. More particularly, the molecular weight of the polymer or copolymer can be controlled by controlling the relative amounts or concentrations of initiator, co-initiator, and monomer(s), and the time allowed for polymerization. For example, the [monomer]: [initiator] ratio can be between

[10,000] :[1] to [25]:[1], with ranges bounded on the upper and lower ends by a

[monomer] of any integer between 100 andl0,000. One example of a range of

[monomer]: [initiator] ratios is [5000:1] to [100:1]. As a further example, the

[monomer] : [co-initiator] ratio can be between [2] : [ 1 ] to [200] : [ 1 ] , with ranges bounded on the upper and lower ends by a [monomer] of any integer between 1 and 200. One example of a range of [monomer]: [co-initiator] ratios is [4:1] to [20:1]. Generally, increasing the amount of Lewis acid (co-initiator) will result in an increase in the polymerization rate.

In another embodiment, the polymer of the invention contains the repeating unit shown in the structure above, as well as a single initiator fragment linked to the beginning of the polymer chain (e.g., at the left side of the structure above; see also Fig. ID showing an initiator fragment.

In any embodiment, the polymer can be derivatized, for example epoxidized or acrylated, as described in more detail elsewhere herein.

Importantly, polyVESFA contains significantly more fatty ester branches per molecule than soybean oil (Fig. 2). Depending on the initiator to monomer ratio used for the polymerization of VESFA, each molecule of polyVESFA can possess from 10s to 100s to 1,000s of fatty ester branches as compared to just three for soybean oil. This can be used to great advantage for many applications such as coatings, composites and lubricants. Since each branch in the molecule can result in a crosslink for a cured material, properties that increase with increasing crosslink density, such as modulus, hardness, chemical resistance, corrosion resistance, stain resistance, etc., are expected to be higher for materials based on polyVESFA as compared to analogous materials based on soybean oil. In addition, the higher molecular weight and higher number of fatty ester branches associated with polyVESFA are expected to reduce shrinkage upon cure which ultimately enhances adhesion in coatings and mechanical properties in composites.

Advantageously, polyVESFA, like soybean oil, is a biodegradable liquid, but unlike soybean oil, it can be engineered by controlling chain length, degree of cross-linkmg etc., to have properties, such as viscosity, that are tailored to the particular application, significantly increasing its industrial utility.

The polymer of the invention, for example polyVESFA, can be incorporated into a liquid formulation such as a lubricant, gel or an oil. The liquid may be substantially free of cross-linking. In another embodiment, the polymer can be cured and incorporated into surface treatments, coatings, films, and the like. Cross-linking and further treatment of the polymer to form a coating, film or other surface treatment can be achieved using any convenient method, for example, by air-drying or auto-oxidation (using, e.g., a cobalt, zirconium or zinc catalyst); by sulfur vulcanization (using, for example, sulfur and zinc oxide), via a Diels- Alder reaction followed by air drying, by peroxide curing, acrylate-based curing, or via thiolene formation and radiation curing.

In yet another embodiment, the polymer of the invention can be incorporated into a composite material, such as a fiber-reinforced composite.

The polymers of the invention include homopolymers, heteropolymers and copolymers, including block co-polymers, whether cross-linked or non-cross-linked, that incorporate or contain a vegetable oil or other plant oil monomer or polymer as described herein. Plant oil monomers of the invention can be copolymerized with other vinyl ether monomers to create new polymers with fatty acid ester branches. Accordingly, the invention provides copolymers of plant vinyl ether monomers, such as VESFA, with other vinylether monomers. Copolymerization offers tremendous potential for tailoring polymer properties for a given application and is used extensively in the polymer industry. One example of a useful copolymer is a copolymer containing vinylether monomers as described herein and polyethylene glycol (PEG) vinyl ether monomers. The resulting co-polymer is amphiphilic, further expanding its industrial utility. Other examples of useful copolymers are those containing vinylether monomers as described herein, and 3,6,9,12-tetraoxatetradec-l-ene (VEDEE), or copolymers formed from copolymerization of the vinylether monomers of the invention with styrene monomers. The copolymer of the invention is not limited by the vinyl ether monomer that can be copolymerized with the monomers of the invention; examples of other monomers that can be copolymerized with the vinylether monomers described herein can be found in Aosbima et al, Chem Rev 2009, 109, 5245-5287.

The monomer or polymer of the invention can be derivatized. For example, the invention includes monomers or polymers that have been activated by epoxidation, as well as acrylate-functional and polyol functional polymers synthesized using an epoxy- functional intermediate. Thus, the monomer or polymer can be chemically treated, altered or derivatized for further use according to the desired application, for example by epoxidation, acrylation, and other chemical reactions to produce epoxidized derivatives, acrylates, polyols and the like. Treatment may or may not involve polymer cross-linking. In one embodiment, the polymer is epoxidized at the sites of the double bonds on the aliphatic groups. For example, a soybean oil polymer, polyVESFA, is optionally epoxidized to yield epoxidized polyVESFA (E-polyVESFA; see Fig. ID).

Epoxidized polymers of the invention (also referred to herein as epoxy- functional or epoxide-functional), such as E-polyVESFA, are well-suited for use to produce curable coating compositions. The epoxidized coating composition can be cured using radiation e.g., UV-curing (e.g., via cationic photopolymerization), using an amine curing agent, using an anhydride-functional curing agent and optionally a tertiary amine catalyst, or any suitable curing agent or method. Surface coatings can be readily generated from E- polyVESFA. Compared to analogous coatings based on commercially available epoxidized soybean oil (ESO), coatings based on E-polyVESFA display many advantageous characteristics, including unexpectedly fast cure rates which are not presently fully understood, and higher modulus in the rubbery plateau region. Without wishing to be bound by theory, it is believed that the higher rubbery plateau modulus can be attributed, at least in part, to the tertiary carbon atoms present in the polymer backbone which serve as additional crosslinks in the cured crosslinked network.

In another embodiment, the invention provides an acrylate-functional polymer. For example, an epoxidized vinyl ether fatty acid ester polymer, such as E-polyVESFA, can be reacted with acrylic acid to yield an acrylate-functional polymer; see Example VIII. The acrylated polymer can be cured, for example using radiation (e.g., UV), peroxide or a thermal curing process.

In yet another embodiment, the invention provides a polyol polymer. For example, an epoxidized vinyl ether fatty acid ester polymer, such as E-polyVESFA, can be subjected to a ring-opening reaction to produce a polyol, which finds use in the preparation of, for example, polyurethanes, alkyd resins, and the like.

Vegetable oil-based materials are currently commercially available for a large number on non-food applications, such as lubricants, hydraulic fluids, coatings, drying agents, plastics, composites, insulators, soaps, candles, cosmetics, etc. Essentially, and importantly, the plant oil-derived polymers of the invention, such as polymers derived from soybean oil, can be used for any application which currently utilizes soybean oil. In this regard, see Meier et al, Chem Soc. Rev., 2007, 36, 1788-1802, which reviews the utilization of plant oil as raw material for monomers and polymers, particularly as replacements for petrochemicals currently in use. Due to the renewable aspect of vegetable oil derivatives, many industries are trying to use more chemicals from renewable sources. The polymers of the invention can be used in any and all of these applications. Also included are liquids and solids, including articles of manufacture of any type, that contain monomers or polymers as described herein, including lubricating and hydraulic fluids, gels, plastics, composites, elastomers, polyurethanes, additives, adhesives and the like.

EXAMPLES

The present invention is illustrated by the following examples. It is to be understood that the particular examples, materials, amounts, and procedures are to be interpreted broadly in accordance with the scope and spirit of the invention as set forth herein.

Example I.

Synthesis and Characterization of a Novel Epoxy-Functional Polymer from Soybean Oil

A novel monomer was synthesized using base catalyzed transesterification of soybean oil with ethylene glycol vinyl ether (also referred to as 2-(vinyloxy)ethanol). Ethylene glycol vinyl ether is a relatively inexpensive chemical and the resulting monomer, which will be referred to as the "vinylether of soybean oil fatty acids

(VESFA)," was able to be isolated in high purity.

A novel polyvinylether polymer containing fatty acid ester pendent groups derived from soybean oil was also synthesized. This novel polymer is referred to as the "polymer of the vinyl ether of soybean oil fatty acid esters (polyVESFA). Using a carbocationic polymerization system with tailored reactivity, VESFA was successfully polymerized to polyVESFA homopolymer.

This example also describes epoxidation of polyVESFA to produce epoxidized polyVESFA (E-poly VESFA) and the generation of surface coatings from E-poly VESFA. Additional examples describing synthesis of a monomer (Example II), polymer (Example III), epoxidized polymer (Example VI) and surface coating using the epoxidized polymer (Example VII). Experimental

Materials. Reagent grade ethylene glycol monovinylether (TCI America, >95%) and soybean oil (Cargill Inc.) were used as supplied. 1-isobutoxyethyl acetate was prepared according to the procedure described by Aoshima and Higashimura

(Macromolecules 1989, 22(3): 1009-13). The polymerization solvent, toluene (Sigma- Aldrich, 99.8%), was distilled over calcium hydride prior to use. Et^AlC^s (25 wt. % in toluene) and 3-chloroperoxybenzoic acid (77 % pure) were purchased from Sigma- Aldrich and used as received. UVR 6000 and UVI 6974 were purchased from Dow Chemical and used as received.

Synthesis of the vinyl ether of soybean fatty acid esters (VESFA). 7.5 gm of ethylene glycol monovinylether, 7.5 gm of soybean oil, and 0.21 gm of anhydrous potassium hydroxide were combined in a 100 ml, round-bottom flask and stirred at 70 °C for 3 hours. The excess ethylene glycol monovinylether was removed by rotary evaporation of the reaction mixture at 56 °C for 10 minutes at 5 milibar pressure. The crude product was cooled to 16 °C to remove the byproduct glycerol and subsequently diluted with n-hexane. The solution was washed with deionized water and dried with anhydrous magnesium sulfate. The product monomer was recovered by rotary evaporation and drying under vacuum overnight.

Synthesis of polyVESFA. VESFA was polymerized using a carbocationic polymerization process. The characteristics of the polymerization of VESFA monomer was determined by monitoring polymer yield and polymer molecular weight as a function of polymerization time. Prior to use, VESFA was dried with magnesium sulfate. The reaction was carried out in a dry 250 ml two neck round bottom flask partially immerged into heptanes bath at 0 °C inside a dry box. In the reaction vessel, 9.1 mg of initiator (1- isobutoxyethyl acetate) and 4 gm of VESFA monomer ([M]₀:[I]₀ = 200:1) were dissolved in 20 gm of toluene and solutions chilled to 0 °C. The polymerization was started by the addition of 1.25 ml of ethylaluminum sesquichloride solution (25 wt. % in toluene) ([Μ]₀:[ Et1.5AlCl1.5jo - 200:40) to the reaction mixture. Polymers were obtained after withdrawing known weight of aliquot at different time of intervals and terminated with chilled methanol. Each polymer was isolated and washed with methanol using

centrifugation. Polymer yield was determined gravimetrically after drying the purified polymer at 40 °C under vacuum overnight. Polymer molecular weight was characterized using a high-throughput Symyx Rapid Gel Permeation Chromatography equipped with an evaporative light scattering detector (PL-ELS 1000) and polystyrene standards.

A plot of number average molecular weight obtained from gel permeation chromatograph (GPC) analysis as a function of VESFA monomer conversion yielded a straight line with a slope of 72.7, a Y-axis intercept of 3511, and correlation coefficient of 0.99. The data used to generate the plot is shown below:

the polydispersity index Synthesis of E-polyVESFA. 4 gm of poly VESFA was dissolved in 80 ml of methylene chloride in a two-neck, round-bottom flask. Next, 4.73 gm of 3- chloroperoxybenzoic acid was added under vigorous stirring and the reaction allowed to occur over a 4 hour period at room temperature. The epoxidized polymer was isolated by precipitation into methanol and drying overnight under vacuum.

Preparation of surface coatings. E-poly VESFA was mixed with a reactive diluent

(UVPv 6000) and a photoinitiator (UVI 6974) at different ratios (Table 1) to produce a series of homogeneous coating solutions. The coatings were cast over Teflon® coated glass slides using a draw down bar (BYK Gardner) to produce approximately 200 μπι wet films that were subsequently cured by passing them through a F 300 UVA lamp (Fusion UV Systems, UVA light intensity ~ 1420 mW/cm as measured by UV Power Puck II^® from EIT Inc) equipped with a conveyer belt set at a belt speed of 24 feet/min. Coating samples were prepared using a single pass (IP) under the lamp and two passes (2P) under the lamp. Dynamic mechanical thermal analysis was conducted on coating free films using a TA800 from TA Instruments.

Table 1. Coatings formulations.

The kinetics of photopolymerization was investigated using a Q1000 differential scanning calorimeter equipped with a photocalorimetric accessory (photo DSC).

Experiments were performed at a UV light intensity of 50 mW/cm and a temperature of 30 °C. Samples were equilibrated for 1 minute and exposed to UV light for 7 minutes followed by a temperature ramp from 0 °C to 200 °C at a ramp rate of 10 °C/min.

Real time infrared spectroscopy (RTIR) experiments were carried out using a Nicolet Magna-IR 850 spectrometer Series II fitted with a 100 W DC UVA mercury vapor lamp from LESCO Super Spot MK II. Samples were spin coated and exposed to UVA light for 3 minutes followed by 2 minutes of dark cure. FTIR spectra were taken at a rate of 1 spectrum/s with a resolution of 4 cm^"1. Conversion of epoxy groups was monitored after integrating the base line in between 800 cm^"1 to 860 cm^"1.

Results and Discussion. Figs. 3, 4, and 5 display the synthetic schemes for producing VESFA, poly VESFA, and E-poly VESFA, respectively. Both poly VESFA and E-poly VESFA were viscous liquids at room temperature. The living nature of the carbocationic polymerization of VESFA was demonstrated by the linear relationship between number- average molecular weight (Mn) determined using gel permeation chromatograph (GPC) and VESFA conversion, as shown in Fig. 6. Additionally, the narrow molecular weight distribution (<1.4) indicated fast and efficient initiation.

The successful polymerization of poly VESFA was confirmed by the absence any peaks associated with methylene protons attached to the vinylether double bond at 6.4 ppm (Fig. 7). It should be noted that polymerization occurred exclusively through the vinylether groups. No vinyl groups in the fatty acid ester side chains were consumed during the polymerization. The synthesis of E-poly VESFA from poly VESFA was also confirmed using 1H NMR. As shown in Fig. 7, the shift of the methine proton at 5.3 ppm in poly VESFA to 2.9 ppm in E-poly VESFA was due to successful epoxidation of the double bonds in fatty acid ester side chains.

Results obtained from RTIR spectroscopy analysis (Fig. 8A) showed that the rate of epoxy consumption with E-poly VESFA was much higher than with ESO. A faster reaction rate with E-polyVESFA was also illustrated using photo-DSC (Fig. 8B).

DMTA analysis showed (Fig. 9A and 9B) that use of E-poly VESFA provided significantly higher storage modulus for the rubbery plateau region than could be obtained with commercially available ESO. The higher modulus of the rubbery plateau region can be attributed to the higher crosslink density associated with the polymeric nature of E-poly VESFA. For E-poly VESFA, each tertiary carbon in the polymer backbone serves as a crosslink in the cured film. Thus, for a given extent of epoxy conversion during cure, films based on E-poly VESFA will necessarily possess a higher crosslink density compared to analogous films based on ESO.

Conclusion

A novel monomer, VESFA, was synthesized by base-catalyzed transesterification of soybean oil with ethylene glycol monovinylether. PolyVESFA containing fatty acid ester pendent groups was synthesized using living carbocationic polymerization. It was found that the polymerization process occurred selectively through the vinyl groups of VESFA enabling the double bonds in the fatty acid esters to remain intact. PolyVESFA was successfully epoxidized to E-poly VESFA, which was subsequently used to produce UV-curable coating compositions. Compared to analogous coatings based on

commercially available ESO, coatings based on E-poly VESFA displayed much faster cure rates and higher modulus in the rubbery plateau region. At present, the higher cure rate associated with use of E-poly VESFA is not fully understood. The higher rubbery plateau modulus can be attributed, at least in part, to the tertiary carbon atoms present in the polymer backbone which serve as additional crosslinks in the cured crosslinked network.

Example II.

Synthesis of Vinyl Ether of Soybean Oil Fatty Acid Esters (VESFA) One example of a synthesis of a monomeric VESFA is described in Example I.

Another exemplary synthesis of the monomer, also using the same general synthetic scheme shown in Fig. 3, is as follows: 20 g of soybean oil, 20 g of ethylene glycol monovinylether, and 0.56 g of anhydrous potassium hydroxide were added to a two-neck, 100 ml, round-bottom flask and stirred at 70 °C for 3 hours under a blanket of nitrogen. The reaction mixture was cooled to room temperature and diluted with 120 ml of n- hexane. The organic layer was separated from the aqueous layer and washed once with 35 ml of aqueous acid (pH 4) and multiple times with deionized (DI) water until the wash water was neutral as indicated by litmus paper. The hexane layer was then dried with magnesium sulfate. The product was recovered by rotary evaporation of n-hexane and dried under vacuum overnight. Proton NMR was used to confirm the production of

VESFA: 1H NMR: 6.45 ppm (q, 1H, OCH=C), 4.0 - 4.2 ppm (m, 2H, C=CH₂), 4.25 ppm (t, 2H, COOCH₂C ), 3.82 ppm (t, 2H, OCH₂C ), 5.3 ppm (m, 3.3H, CH=CH), 2.3 ppm (t, 2H, OCOCH₂), 0.8 ppm (m, 3H, C¾C), 1.55 ppm (m, 2H, COCH₂CH₂C). Example III.

Polymerization of Soybean Oil-Derived Vinylether Monomers One example of a synthesis of the homopolymer of VESFA (polyVESFA) is described in Example I.

Another exemplary synthesis of the homopolymer of VESFA, using the same general carbocationic polymerization scheme shown in Fig. 4 and producing a polymer referred to herein as polyVESFA- 1, is as follows: Prior to use, VESFA was dried with magnesium sulfate. The dried VESFA was polymerized at 0 °C within a glove box in a three-neck, round-bottom flask baked at 200 °C prior to use. 23.4 mg of initiator (1- isobutoxyethyl acetate) and 256 g of VESFA monomer ([M]₀:[I]₀ = 5000:1) were dissolved in 1600 ml of dry toluene and chilled to 0 °C. The polymerization was initiated by the addition of 36.05 ml of ethylaluminum sesquichloride solution (25 wt. % in toluene) ([M]₀:[Co-initiator]₀ = 200:18). The reaction was terminated after 17 hours by the addition of 1600 ml of chilled methanol which caused the polymer to precipitate. The polymer was isolated and washed multiple times with methanol using centrifugation. The purified polymer was collected as a viscous liquid after centrifuging at 4500 rpm at 21 °C for 10 minutes and drying under vacuum overnight. This synthesis resulted in a low polydispersity index (PDI) polyVESFA, as shown below.

Yet another exemplary synthesis of polyVESFA, producing a polymer referred to herein as polyVESFA-2, and also using the same general carbocationic polymerization scheme shown in Fig. 4, is as follows: Prior to use, VESFA was dried with magnesium sulfate. The dried VESFA was polymerized at 0 °C within a glove box in a three-neck, round-bottom flask baked at 200 °C prior to use. 9.7 mg of initiator (1-isobutoxyethyl acetate) and 105.9 g of VESFA monomer ([M]:[I] = 5000:1) were dissolved in 643.7 ml of dry toluene and chilled to 0 °C. The polymerization was initiated by the addition of 36.5 ml of ethylaluminum sesquichloride solution (25 wt. % in toluene). ([M]₀:[Co- initiator]o = 200:44). The reaction was terminated after 17 hours by the addition of 643 ml of methanol which caused the polymer to precipitate. The polymer was isolated and washed multiple times with methanol using centrifugation. The purified polymer was collected as a viscous liquid after centrifuging at 4500 rpm at 21 °C for 10 minutes and drying under vacuum overnight. The chemical structure of polyVESFA was confirmed using proton NMR: 1H NMR: 4.1 - 4.2 ppm (m, COOCH₂C), 3.4 - 3.8 ppm (m, OCH₂C, OCHC ), 5.2 - 5.4 ppm (m, CH=CH), 2.2 - 2.3 ppm (m, OCOC¾), 0.8 ppm (m, C¾C), 1.45 - 1.7 ppm (m, COCH₂C¾C).

The thermal properties of the polymer were determined using differential scanning calorimetry (Q1000 from TA Instruments) by first heating the sample from -120 °C to 70 °C at a heating rate of 10 °C/minute (1^st heat), cooling from 70 °C to -120 °C at a cooling rate of 10 °C/minute (cooling), and reheating from -120 °C to 120 °C at a heating rate 10 °C/minute (2^nd heat). The thermogram obtained from the 2^nd heat showed a glass transition at -98.7 °C and a very weak, diffuse melting transition with an enthalpy of melting of 8.43 J/gm and a peak maximum at -27.6 °C. The rheological characteristics of the polymer produced were compared to that of soybean oil using an ARES Rheometer from TA Instruments. The shear rate was varied from 0.1 radians/sec. to 500 radians/sec. while temperature was held constant at 25 °C. Over this shear rate range, the soybean oil showed a constant shear viscosity of 45 centipoise, while the polyVESFA displayed a constant shear viscosity of 2,971 centipoise. Over a shear rate range of 500 radians/sec. to 1,000 radians/sec, the viscosity of the soybean oil remained constant at 45 centipoise while the viscosity of the polyVESFA dropped dramatically illustrating the

pseudoplasticity typically seen with polymers that possess a molecular weight above the minimum required for polymer chain entanglement.

The characteristics of the polymerization of VESFA monomer was determined by monitoring polymer yield and polymer molecular weight as a function of polymerization time. The reaction was carried out in a dry 250 ml two-neck, round-bottom flask partially submerged in a heptane bath at 0 °C inside a dry box. In the reaction vessel, 14.3 mg of initiator (1-isobutoxyethyl acetate) and 6.25 gm of VESFA monomer ([M]₀:[I]o ⁼ 200:1) were dissolved in 32.06 gm of toluene and the solution chilled to 0 °C. The polymerization was started by the addition of 882 μΐ of ethylaluminum sesquichloride solution (25 wt. % in toluene) ([M]o:[Co-initiator]₀ = 200:18) to the reaction mixture. Aliquots of the reaction mixture were removed from the vessel at various time intervals and terminated with chilled methanol. Polymers from each aliquot were isolated and washed with methanol using centrifugation. Polymer yield was determined

gravimetrically after drying the purified polymer at 40 °C under vacuum overnight.

Polymer molecular weight was characterized using a high-throughput Symyx Rapid Gel Permeation Chromatography equipped with an evaporative light scattering detector (PL- ELS 1000) and polystyrene standards.

A plot of number average molecular weight obtained from gel permeation chromatograph (GPC) analysis as a function of VESFA monomer conversion yielded a straight line that passed through the origin with a slope of 504 and correlation coefficient of 0.977. The data used to generate the plot is shown below:

*PDI is the polydispersity index

Another example of the living carbocationic polymerization of VESFA monomer is as follows: A total of eight polymerizations were carried out inside a dry box at 0 °C using dry test tubes as polymerization vessels. In each test tube, 1.6 mg of initiator (1- isobutoxyethyl acetate) and 0.7 gm of VESFA monomer ([M]:[I] = 200:1) were dissolved in 3.68 gm of toluene and solutions chilled to 0 °C. Each polymerization was started by the addition of 241 μΐ of ethylaluminum sesquichloride (Et^s AlCl ) solution (25 wt. % in toluene) to the reaction mixture. After a predetermined time interval, 20 ml of methanol was added to the polymerization mixture to terminate the polymerization. Each polymer was isolated and washed with methanol using centrifugation. Polymer yield was determined gravimetrically after drying the purified polymer at 40 °C under vacuum overnight. Polymer molecular weight was characterized using a high-throughput Symyx Rapid Gel Permeation Chromatography equipped with an evaporative light scattering detector (PL-ELS 1000) and polystyrene standards. A plot of number average molecular weight obtained from gel permeation chromatograph (GPC) analysis as a function of VESFA monomer conversion yielded a straight line that passed through the origin with a slope of 347 and correlation coefficient of 0.978. The data used to generate the plot is shown below:

PDI is the polydispersity index

The linear relationship between monomer conversion and number-average molecular obtained from the experiment showed that the polymerization was a "living" polymerization. A "living" polymerization is polymerization that occurs without termination or chain transfer reactions resulting in the ability to produce polymers with controlled molecular weight and polymers and potentially copolymers with well-defined molecular architectures such as block copolymers, star polymers, and graft copolymers.

Example IV.

Copolymers of VESFA and Other Vinylether Monomers

Copolymers of VESFA with a polyethylene glycol-functional vinylether monomer were also produced. The synthetic scheme is shown in Fig. 10.

A polyethylene glycol-functional monovinylether monomer (VEPEG) was synthesized by end-capping a commercially available polyethylene glycol

monovinylether (R500 from Clariant) as follows: 20 gm of iodoethane and 8.08 gm of potassium hydroxide were added to a 500 ml, round-bottom flask and stirred at 300 rpm at 40 °C. Then, 58.8 gm of R500 was added drop-wise to the reaction mixture. After the addition was complete, the temperature was raised to 64 °C and stirring continued for 12 hours under a blanket of nitrogen. R500 possesses a hydroxy group at one end which will terminate a carbocationic polymerization, thus reaction with iodoethane was used to convert the hydroxyl group to an ethoxy group (-O-CH₂CH₃). The reaction mixture was cooled to room temperature and then diluted with 300 ml of methylene chloride. The organic layer was filtered as a clear liquid and washed three times with 300 ml of DI water. The organic layer was then dried with anhydrous magnesium sulfate and the product monomer was recovered by rotary evaporation of volatiles. Successful synthesis of VEPEG was confirmed by proton NMR spectra analysis: 1H NMR: 6.4 ppm (q, 1H, OCH=C), 3.9 - 4.13 ppm (dd, 2H, C=CH₂), 3.4 - 3.8 ppm (m, 48H, OCH₂CH₂0, OCH₂CH₃), 1.2 ppm (t, 3H, CH₃CH₂).

VESFA and VEPEG were copolymerized at 0° C within a glove box in a test tube dried at 250 °C under vacuum just before use. 1 g of VEPEG, 0.61 g of VESFA, and 2.77 mg of initiator (1 -isobutoxyethyl acetate) were dissolved in 8.43 g of dry toluene and chilled to 0 °C. The polymerization was initiated with the addition of 0.417 ml of ethyl aluminum sesquichloride (25 wt. % in toluene). After 12 hours, the reaction was terminated with addition of 20 ml of methanol. The copolymer was recovered by rotatory evaporation of all the volatiles and drying under vacuum overnight. GPC using polystyrene standards showed that the polymer produced possessed a number average molecular weight of 14,350 g/mol.

A copolymer of VESFA and 3,6,9, 12-tetraoxatetradec-l-ene (VEDEE) was also synthesized. VEDEE was produced using the synthetic scheme shown in Fig. 11.

In the first step, 16.5 gm of diethyleneglycol monoethylether (DEE) (99% purity from Aldrich), 8 gm of sodium hydroxide, 60 ml of tetrahydrofuran, and 40 ml of DI water were combined in a 500 ml, 3-neck, round-bottom flask using constant stirring to produce a homogeneous solution. The mixture was cooled to 0 °C and then 25.7 gm of p- toluenesulfonyl chloride (Aldrich, 99% purity) in 50 ml of tetrahydrofuran (THF) was added to the reaction mixture drop- wise using an addition funnel and the reaction was continued for 2 hours at 0 °C. The reaction mixture was then poured into 100 ml of ice cold water and the product extracted with methylene chloride. The organic layer was washed with DI water and dried with anhydrous magnesium sulfate. The product (Ts- DEE) was recovered after rotary evaporation of all the volatiles and dried under vacuum overnight. In the second step, 1.5 gm of sodium hydride (Aldrich 95 % purity) and 75 ml of THF were dissolved in a 500 ml, 3 -neck, round-bottom flask equipped with a nitrogen blanket. The solution was cooled at 0 °C and a solution of 4.77 gm of ethylene glycol mono vinyl ether (TCI America, 95 % purity) in 30 ml THF was added drop wise. Next, a solution of 15 gm of Ts-DEVE in 45 ml THF was added to the reaction mixture and the temperature was raised to 60 °C. After 24 hours, the reaction mixture was cooled to room temperature and diluted with 150 ml of diethyl ether. The organic layer was washed three times with 75 ml of DI water and dried with anhydrous magnesium sulfate. The product monomer, VEDEE, was collected after rotary evaporation of all volatiles and dried under vacuum overnight. Successful synthesis of VEDEE was confirmed by proton NMR: 6.4 ppm (q, 1H, OCH=C), 4. 0 - 4.2 ppm (m, 2H, C=C¾), 3.4 - 3.8 ppm (m, 14H,

OCH₂CH₂0, OCH₂C), 1.2 ppm (t, 3H, CH₃C).

VESFA and VEDEE were copolymerized at 0° C within a glove box in a test tube dried at 200 °C under vacuum just before use. . A series of copolymers were synthesized by varying the initial concentration of monomer to co-initiator (i.e. Lewis acid) ratio. The table below describes the amount of raw materials use to synthesize the copolymers. VESFA, VEDEE, and initiator (1-isobutoxy ethyl acetate) were dissolved in dry toluene and chilled to 0 °C. Each polymerization was initiated with the addition of ethyl aluminum sesquichloride (25 wt. % in toluene). After 17 hours, the reactions were terminated with the addition of 3 mis of methanol. 5 ml of methylene chloride was added to the terminated solutions and the organic layers were washed with 3 ml of deionized water three times to remove the initiator and co-initiator residues. The polymers were recovered by rotary evaporation of all the volatiles and drying under vacuum overnight. Successful polymerization was demonstrated using proton NMR by observing the absence of protons associated with the vinyl ether units of the monomers. GPC using polystyrene standards showed that copolymers 1, 2, and 3 possessed number average molecular weight of 15210, 13800, and 12880 g/mol respectively. ([Μι]ο:[Μ₂]₀:[Γ|ο: (MO wt, (M₂) wt., wt., mg (EtLsAlClLs) wt., gm

[ EtLsAlClLslo) gm gm volume, ml

Copolymer 1 0.51 0.51 3.2 0.48 5

(74: 126:1:44)

Copolymer 2 0.50 0.50 0.31 0.19 5.10 (74:126:1:18)

Copolymer3 0.51 0.51 3.2 0.096 5.28 (74: 126:1:9)

Example V. Cured Films of PolyVESFA

Cured films of polyVESFA were prepared using an auto-oxidation process. The synthetic scheme used to produce the cured films is shown in Figure 12.

An example of a cured film produced with this method is as follows: 2 g of polyVESFA was dissolved in 0.5 g toluene in a 20 ml vial equipped with an overhead stirrer. 16.6 mg of 12% cobalt octoate in mineral spirit, 55.6 mg of 18% zirconium octoate in mineral spirit, and 75 mg of 8% zinc nuxtra in mineral spirit was added to the solution and the solution stirred at 5000 rpm for 10 minutes. The liquid solution was cast over a clean aluminum panel using a draw down bar (BYK Gardner) to produce approximately a 200 micron thick film which was cured by allow the film to stand at room temperature for 2 days and then heating at 40 °C for 3 days. The thermal properties of the cured film were determined using differential scanning calorimetry (Q1000 from TA Instruments) by first heating the sample from 25 °C to 100 °C at a heating rate of 10 °C/minute (1^st heat), cooling from 100 °C to -120 °C at a cooling rate of 10 °C/minute (cooling), and reheating from -120 °C to 100 °C at a heating rate 10 °C/minute (2^nd heat). The thermogram obtained from the 2^nd heat showed a glass transition at -27.2 °C.

In another experiment, a series of cured films produced with this method is as follows: polyVESFA, 12% cobalt octoate in mineral spirit, 18% zirconium octoate in mineral spirit, and 8% zinc nuxtra in mineral spirit were mixed together using a FlackTek mixer at 3500 rpm for 3 minutes. The table below describes the compositions of the coatings produced. The air drying behavior of liquid coatings was characterized using a BK 3-Speed Drying Recorder (MICKLE Laboratory Engineering Co. Ltd., United Kingdom). A needle carrier holding 6 hemispherical ended needles travels across the length of six 305 25 mm glass strips with time. A weight of 5 gm is attached to each hemispherical needle to study the through drying property of coating. Each liquid coating mixture was casted over glass strips using a 25 mm cube film applicator to produce wet films about 75 microns in thickness. The coating drying time was evaluated as open time, dust free time and tack free time for 48 hours time period.

The table below lists drying time for films produced by air oxidative curing.

The rate of crosslinked network formation was characterized by a dynamic time sweep test using the ARES Rheometer. Each liquid mixture was placed in between the two parallel plates and heated for 63 minutes at a constant frequency of 10 rad/s, strain rate of 0.3 %, and temperature of 120 °C. For the coating based on PolyVESFA-1, storage modulus increased from 1.8 KPa to 46.1 KPa while the storage modulus of the reference coating based on soybean oil showed no increase in modulus at 120 °C over this time period. In addition to curing using an auto-oxidation process, curing was also

accomplished using a vulcanization process as shown in Figure 13.

One example of a cured film produced with this process is as follows: In an 8 ml glass vial, 5 g polyVESFA, 0.3 g zinc oxide, and 0.025 g stearic acid were added and stirred with an overhead stirrer at 9000 rpm for 2 minutes. Next, 0.175 g sulfur and 0.025 g tetramethylthiuram disulfide were added and the mixture stirred at 18000 rpm for 4 minutes with constant cooling by partial immersion in a water bath. The rate of development of the crosslinked network due to sulfur vulcanization reaction of C=C double bonds in fatty acid ester chains was characterized by dynamic temperature ramp test using ARES Rheometer (TA Instruments). The liquid dispersion was placed in between two parallel plates and heated at a constant temperature of 140 °C. The storage modulus was measured with time at a constant frequency of 10 radian/s and a strain of 0.3 %. Over the period of 22 minutes, storage modulus increased from about 1 Pa to 0.19 MPa and then remained relatively constant with time over a total time period of 100 minutes.

Another example of a cured film produced with this process is as follows: The table below describes the compositions of three liquid coatings produced from

polyVESFA- 1, polyVESFA-2, and soybean oil. Generally, in a 20 ml glass vial, polyVESFA, zinc oxide, and stearic acid were added and stirred with an overhead stirrer at 15,000 rpm for 2 minutes. Next, sulfur and tetramethylthiuram disulfide were added and the mixture stirred at 15000 rpm for 4 minutes with constant cooling by partial immersion in a water bath. The rate of development of crosslinked network due to sulfur vulcanization reaction of C=C double bonds in fatty acid ester chains was characterized by dynamic temperature ramp test using ARES Rheometer (TA Instruments). The liquid dispersion was placed in between two parallel plates and heated at a constant temperature of 140 °C. The storage modulus was measured with time at a constant frequency of 10 radian/s and a strain of 0.3 %. Over the period of 22 minutes, the storage modulus of Formulation-2 increased from about 1 Pa to 0.19 MPa and then remained relatively constant with time over a total time period of 65 minutes. For Formulation- 1, the storage modulus increased from about 1 Pa to 0.27 MPa over a time period of 22 minutes and then remained relatively constant with time over a total time period of 54 minutes. In contrast, the reference formulation based on soybean oil showed a storage modulus value of 1.82 Pa after 4.56 h under the same curing condition.

Example VI. Epoxy-functional polyVESFA

For many material applications, soybean oil is subjected to a chemical conversion and used as one component of a formulated material. For example, epoxidized soybean oil (ESO) is a commercial product produced by epoxidation of the double bonds of soybean oil. ESO has found application as a component of epoxy-based coatings and composites. ESO has been further chemically modified to produce other reactive soybean-oil based materials such as soybean oil-based polyols, which are typically used to produce polyurethanes, and soybean oil-based acrylates, which are typically used in radiation-curable coatings.

An example of the synthesis of E-polyVESFA is as follows (see also Example I): 4 g of polyVESFA-2 was dissolved in 80 ml of methylene chloride in a round bottom flask and 4.73 g of 3-chloroperoxybenzoic acid added with vigorous stirring. The reaction was continued for 4 hours at room temperature at a stirrer speed of 650 rpm. After the reaction was complete, the polymer was precipitated into methanol, isolated by centrifugation, and dried under vacuum overnight. Successful synthesis of E- polyVESFA-2 was confirmed using proton NMR by observing the disappearance of peaks associated with CH=CH groups in the fatty acid ester chain of polyVESFA at 5.3 ppm (m) and the corresponding appearance of peaks at 2.8 - 3.1 ppm (m) associated with the glycidyl groups in E-polyVESFA-2. The thermal properties of the polymer were determined using differential scanning calorimetry by first heating the sample from -120 °C to 70 °C at a heating rate of 10 °C/minute (1^st heat), cooling from 70 °C to - 120 °C at a cooling rate of 10 °C/minute (cooling), and reheating from - 120 °C to 120 °C at a heating rate 10 °C/minute (2^nd heat). The thermogram obtained from the 2^nd heat showed a glass transition at -58.0 °C and a very weak, diffuse melting transition with an enthalpy of melting of 5.97 J/gm and a peak maximum at -21.7 °C.

Example VII. Cured Films from Epoxy-functional polyVESFA

From the E-polyVESFA-2 (Example VI), cured films were prepared by crosslinking using an amine curing agent as shown in Figure 14.

An example of the production of an amine-cured film produced from E- polyVESFA-2 is as follows: 3 g of E-polyVESFA-2 (epoxy equivalent weight = 290 g/eq) and 0.421 g triethylene tertamine (technical grade 60% purity, used as received from Sigma Aldrich, amine hydrogen equivalent weight of 24.372 g/eq) were mixed with a FlackTek mixer using 3500 rpm for 3 minutes. The clear mixture was coated over a Teflon® coated glass panel. The wet film thickness was approximately 1 mm and the film cured in a forced air oven at 120 °C for 36 hours. A reference coating based on epoxidized soybean oil (Vikoflex-7170 from Arkema, epoxy equivalent weight = 233 g/eq) was produced by mixing 3 gm of the epoxidized soybean oil (ESO) with 0.524 g of triethylene tertamine using the FlackTek mixer. The coating mixture was cast over a Teflon® coated glass panel. The wet film thickness was approximately 1 mm and the film cured in a forced air oven at 120 °C for 99 hours. A cure time exceeding 36 hours was used for the reference coating because the coating was still in liquid form after 36 hours at 120 °C. Free films were characterized using an ARES Rheometer (TA

Instruments). Cured films were placed in between two parallel plates and the storage modulus measured by ramping the temperature from - 90 °C to 120 °C at ramp rate of 5 °C/min with a constant frequency of 10 rad/s and a strain rate of 0.3 %. From the experiment, the film based on E-polyVESFA-2 gave a glass transition temperature (Tg) of 15.2 °C and a rubbery plateau modulus (at 70 °C) of 27.7 MPa. The reference coating based on ESO showed a Tg and rubbery plateau modulus (at 70 °C) of - 5.3 °C and 11.6 MPa, respectively. These results indicate a higher crosslink density was achieved with use of E-polyVESFA-2 as compared to ESO. In addition, the rate of crosslinked network formation was characterized by a dynamic time sweep using the ARES Rheometer. Each liquid mixture was placed in between the two parallel plates and heated for 20 hours at a constant frequency of 2 rad/s, strain rate of 0.1 %, and temperature of 120 °C. For the coating based on E-polyVESFA-2, storage modulus increased from 17 Pa to 778 KPa over the period of 5 hours while the storage modulus of the reference coating based on ESO showed no increase in modulus until 16 hours at 120 °C. After 20 hours, the reference coating reached a storage modulus of 4.63 KPa, while the experimental coating based on E-polyVESFA-2 reached this storage modulus after just 49 minutes at 120 °C. These results indicate that E-polyVESFA develops a crosslinked network much faster than the analogous material based on ESO.

E-polyVESFA was investigated for use in radiation-curable coatings using a ultraviolet light (UV) initiated cationic polymerization process as shown in Example I and further, as shown in Figure 15.

A series of radiation cured coatings were prepared by mixing E-polyVESFA-2, 3- methyloxetan-3-yl)methanol (Oxetane 101 from Dow Chemical), and 50 wt. % triarylsulfonium hexafluoroantimonate salt in propylene carbonate (UVI 6974 photoimtiator from Dow Chemical) together using a FlackTek mixer at 3500 rpm for 3 minutes. An analogous series of reference coatings was produced by replacing E- polyVESFA-2 with commercially available ESO (Vikoflex-7170 from Arkema). The table below describes the compositions of the coatings produced. Each liquid coating mixture was casted over Teflon® coated glass using a square draw down bar (BYK Gardner) to produce wet films about 200 microns in thickness. The films were cured by passing coated substrates once or twice under a F300 UVA lamp from Fusion UV Systems (UVA light intensity ~ 1420 mW/cm² as measured by UV Power Puck^® II from EIT Inc.) equipped with a bench top conveyor belt set at a belt speed of 24 feet/min. Free films were characterized using dynamic mechanical thermal analysis (Q800 from TA Instruments).The experiment was carried out from -90 °C to 140 °C using a heating rate of 5 °C/min., frequency of 1 Hz, and strain amplitude of 0.02%. The T_g was obtained from the peak maximum in the tan δ response.

The table below lists T_g and storage modulus of the rubbery plateau region (at 70 °C) for films produced using one and two passes under the UVA lamp.

* Coating was still in the liquid state

In order to characterize cure kinetics of the UV curable materials described above, a photo DSC experiment was performed using a Q 1000 differential scanning calorimeter (TA Instruments) equipped with a photocalorimetric accessory (PC A). The experiment was carried out at a UV light intensity of 50 mW/cm² and a temperature of 30 °C.

Samples were equilibrated for 1 minute before exposure to UV light for 7 minutes followed by a temperature ramp from 0 °C to 200 °C at a rate of 10 °C/min under nitrogen to determine the residual heat associated with thermal cure of residual

(unreacted functional groups). The % of total conversion was calculated by the following formula: Hphotopolymerization

% of Total Conversion = X 100

AHphotopolymerization AHResudual Heat

The following table lists the time period associated with the peak maximum of the reaction exotherm (i.e. time to peak maximum) and the percent of conversion obtained by UV light exposure for both the control and experimental coatings. From the table below, it can be seen that the coatings based on E-polyVESFA-2 possess faster cure rates as indicated by the shorter time period associated with peak of the reaction exotherm and higher extent of conversion after a 2 minute UV exposure.

In addition to photo-DSC, a real-time FTIR (RTIR) instrument was used to characterize cure kinetics. The RTIR experiments were carried out using a Nicolet Magna-IR 850 spectrometer Series II. The light source was a LESCO Super Spot MK II 100W DC UVA mercury vapor short lamp. Samples were spin-coated onto a KBR plate at 4000 rpm for 20 seconds and exposed to UV light for 3 minutes followed by a dark cure of 2 minutes. FTIR Spectra were taken at 1 spectrum/s with a resolution of 4 cm . The experiment was carried out in air at 25 °C and the UV light intensity was 34 mW/cm as measured by UV Power Puck II from EIT Inc. The consumption of epoxy groups was determined by monitoring the peak area in between 800 cm^"1 and 860 cm^"1. For Control- 1, Control-2, Exp-1, and Exp-2, the percent of epoxide conversion after 2 minutes of UV light exposure were 9.7, 17.9, 78.5, and 88.4, respectively. With 3 minutes of light exposure, Control- 1, Control-2, Exp-1, and Exp-2, reached epoxide conversions of 15.8 %, 25.9 %, 86.1 % and 91.8 %, respectively. This data further illustrates the surprising result that coatings based on E-polyVESFA provide much faster cationic photocure than analogous coatings based on ESO.

Example VIII. Acrylated Derivatives

Acrylate-functional materials can be prepared by reaction of epoxidized polyVESFA with acrylic acid and the acrylate-functional materials used to prepare coatings produced using a radiation-cure process (Khot et al., J Polym. Set, Part A: Polym. Chem., 82, 703-723 (2001)). The properties of UV-cured coatings based on acrylate-functional polyPVESFA can be compared to analogous coating based on acrylate-functional soybean oil.

Acrylated materials for use in applications such as radiation-curable coatings can be produced from E-polyVESFA and VESFA copolymers precursors by epoxide ring- opening with acrylic acid as shown in Figure 16.

An example of the synthesis of acrylated polyVESFA is as follows: In a 40 ml vial, 1.41 gm of epoxidized polyVESFA-2, 1.7 mg hydroquinone, and 8.6 mg potassium acetate were dissolved in 7.93 ml of toluene. The rapidly stirring solution was heated to 110 °C and 0.316 gm of acrylic acid was added drop wise over the period of 30 minutes. After 42 hours of reaction, the temperature was cooled to room temperature and the toluene was removed by rotary evaporation. The crude product was diluted with methylene chloride and washed with deionized water. The organic layer was dried with anhydrous magnesium sulfate. The pure polymer was isolated by rotary evaporation of methylene chloride and drying under vacuum overnight. Successful synthesis of acrylated polyVESFA was confirmed using proton NMR by observing the disappearance of peaks associated with the glycidyl groups in the fatty acid ester chains of E-poly VESFA at 2.8 - 3.1 ppm (m) and the corresponding appearance of new peaks at 4.2 - 4.3 ppm (m, CHOCO) and 3.7 - 3.8 ppm (m, CHOH) associated with ring-opening of the epoxide groups with acrylic acid. The incorporation of acrylate groups into polyVESFA was also demonstrated by the appearance of new peaks at 5.8 ppm, 6.4 ppm (m, C^CHb), and 6.1 ppm (m, C=CH) associated with the vinyl groups of acrylic acid esters.

An example of the production of a cured film produced from acrylated

polyVESFA is as follows: 47 mg of Irgacure 184 photoinitiator from Ciba was dissolved in 0.178 gm of 1,6-hexanediol diacrylate. Next, 1 gm of acrylated polyVESFA-2 was added to the mixture resulting in a homogeneous solution. The solution was applied over a Teflon® coated glass panel using a drawdown bar (BYK Gardner) to produce a 200 micron thick wet film and the mixture cured by passing the coated panel through a F300 UVA lamp from Fusion UV Systems (UVA light intensity ~ 1420 mW/cm² as measured by UV Power Puck^® II from EIT Inc) equipped with a bench top conveyor belt running at a belt speed of 24 feet/min. A free film of the coating was characterized using dynamic mechanical thermal analysis (Q800 from TA Instruments). The experiment was carried out from -90 °C to 150 °C using a heating rate of 3 °C/min., frequency of 1 Hz, and strain amplitude of 0.03%. The T_g obtained from the peak maximum in the tan δ response was 29.9 °C.

An example of the synthesis of acrylated polyVESFA (A-polyVESFA-1) is as follows: In a 250 ml two-neck round-bottom flask, epoxidized polyVESFA- 1, hydroquinone, and potassium acetate were dissolved in toluene. The rapidly stirring solution was heated to 110 °C and acrylic acid was added drop wise over the period of 30 minutes. After 42 hours of reaction, the temperature was cooled to room temperature. The crude product was diluted with methylene chloride and washed with deionized water. The organic layer was dried with anhydrous magnesium sulfate. The pure polymer was isolated by rotary evaporation of solvents and drying under vacuum overnight. A reference material, acrylated soybean oil was produced from epoxidized soybean oil (Vikoflex-7170 from Arkema, epoxy equivalent weight = 233 g/eq). The following table lists the amount of raw materials used to synthesize A-polyVESFA-1 and acrylated soybean oil. Formulation Hydroqu Potassium Toluene Acrylic E- ESO inone acetate (gm) acid (gm) polyVESF (gm)

(mg) (mg) A-l (gm)

Experimental 12.9 62.5 49.7 2.46 10.09 —

Reference 130.4 652 492.6 30.38 — 100

A series of radiation cured coatings were prepared by mixing A-polyVESFA-1, Irgacure 184 photoinitiator from Ciba, and 1,6-hexanediol diacrylate together using a FlackTek mixer at 3500 rpm for 3 minutes. An analogous series of reference coatings was produced by replacing A-polyVESFA-1 with synthesized A-soybean oil. The table below describes the compositions of the coatings produced.

In order to characterize cure kinetics of the UV curable materials described above, a photo DSC experiment was performed using a Q 1000 differential scanning calorimeter (TA Instruments) equipped with a photocalorimetric accessory (PCA). The experiment was carried out at a UV light intensity of 50 mW/cm² and a temperature of 30 °C. Samples were equilibrated for 1 minute before exposure to UV light for 30 seconds. The following table lists the time period associated with the peak maximum of the reaction exotherm (i.e. time to peak maximum) obtained by UV light exposure for both the reference and experimental coatings. From the table below, it can be seen that the coatings based on A-polyVESFA-1 possessed faster cure rates as indicated by the shorter time period associated with peak of the reaction exotherm.

In addition to photo-DSC, a real-time FTIR (RTIR) instrument was used to characterize cure kinetics. The RTIR experiments were carried out using a Nicolet Magna-IR 850 spectrometer Series II. The light source was a LESCO Super Spot MK II 100W DC UVA mercury vapor short lamp. Samples were spin-coated onto a KBR plate at 4000 rpm for 20 seconds and exposed to UV light for 1 minute. FTIR Spectra were taken at 1 spectrum/s with a resolution of 4 cm^"1. The experiment was carried out in air at 25 °C and the UV light intensity was 34 mW/cm as measured by UV Power Puck II from EIT Inc. The consumption of C=C groups in the acrylate was determined by monitoring the peak area in between 1605 cm^"1 and 1650 cm^"1. For Experimental- 1, Experimental-2, Reference- 1, and Reference-2, the percent of C=C conversion after 5 seconds of UV light exposure were 72.2, 58.5, 65.5, and 34.3, respectively. With 1 minute of light exposure, Experimental- 1, Experimental-2, Reference- 1, and Reference-2, reached C=C conversions of 77.1 %, 63.6 %, 74.9 % and 38.5 %, respectively. This data further illustrates the result that coatings based on A-polyVESFA provide faster free radical photocure than analogous coatings based on A-soybean oil. Example ΓΧ. Polyols

Model polymer networks based on epoxidized polyVESFA can be produced, characterized, and compared to analogous networks derived from epoxidized soybean oil. Both epoxidized polyVESFA and epoxidized soybean oil can be converted to polyol derivatives by ring-opening the epoxide groups with methanol (Zlatanic, et al., J Polym. Set, Part B: Polym. Phys., 42, 809-819 (2003)). The polyols can be used to prepare model polyurethane networks and the properties of the networks prepared from

polyVESFA-based polyols compared to analogous polyols derived from soybean oil.

Polyols are important building-blocks for producing crosslinked materials such as crosslinked polyurethanes. Polyols can be produced from E-polyVESFA and epoxidized VESFA copolymers using a process such as that shown in Figure 17.

Additional References

Eckey et al, J. Am. Oil Chemist's Soc, 32(4):185 (1955)

Teeter et al., J. Am. Oil Chemist's Soc, 40(4):143-156 (1963)

US Pat No. 2,692,256 (Bauer et al, 1951)

Brekke et al, J. Am. Oil Chemist's Soc, 37(11):568-570 (1963)

Dufek et al, J. Am. Oil Chemist's Soc, 37:37-40 (1960)

Teeter et al, Ind. Eng. Chem., 5o(l l):1703-1704 (1958)

Teeter et al, J. Am. Oil Chemist's Soc, 33:399-404 (1956)

Schneider et al., J. Am. Oil Chemist's Soc, 34(5):244-247 (1957)

Gast et al, J. Org. Chem., 42:160-165 (1958)

Gast et al., J. Am. Oil Chemist's Soc, 37:78-80 (1959)

Dufek et al, J. Am. Oil Chemist's Soc, 39:238-241 (1961)

Schneider et al, J. Am. Oil Chemist's Soc, 39:241-244 (1961) The complete disclosures of all patents, patent applications including provisional patent applications, and publications, and electronically available material (e.g., GenBank amino acid and nucleotide sequence submissions) cited herein are incorporated by reference. The foregoing detailed description and examples have been provided for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described; many variations will be apparent to one skilled in the art and are intended to be included within the invention defined by the claims.

Claims

What is claimed is:

1. A polymer of at least one monomer having the structure

wherein R is a C8-C21 aliphatic group derived from a plant oil; and wherein said polymer is the product of a living carbocationic polymerization reaction.

2. The polymer of claim 1 wherein the living carbocationic polymerization occurs in the absence of a Lewis base.

3. The polymer of claim 1 or 2 which has a polydispersity index of less than 1.5.

4. A polymer of at least one monomer having the structure

wherein R is a C8-C21 aliphatic group derived from a plant oil, wherein said polymer has a polydispersity index of less than 1.5.

5. A polymer comprising a repeating unit

wherein R is a C8-C21 aliphatic group derived from a plant oil; and wherein said polymer is the product of a living carbocationic polymerization reaction.

6. The polymer of claim 5 wherein the living carbocationic polymerization occurs in the absence of a Lewis base.

7. The polymer of claim 5 or 6 which has a polydispersity index of less than 1.5.

8. A polymer comprising a repeating unit

wherein R is a C8-C21 aliphatic group derived from a plant oil; and wherein said polymer has a polydispersity index of less than 1.5.

9. The polymer of any of the preceding claims, wherein the polymer comprises a plurality of monomers, and wherein for each of the plurality of monomers, R is independently a C8-C21 aliphatic group derived from a plant oil.

10. A polymer comprising a chemical derivative of the polymer of any of claims 1 to 9.

11. The polymer of claim 10 selected from the group consisting of an epoxy-functional polymer, an acrylate-functional polymer and a polyol.

An epoxy-functional polymer of at least one monomer having the structure

wherein R is a C8-C21 group derived from a plant oil and comprising at least one epoxide group; and wherein said polymer has a polydispersity index of less than 1.5.

An epoxy-functional polymer comprising a repeating unit

wherein R is a C8-C21 group derived from a plant oil and comprising at least one epoxide group; and wherein said polymer has a polydispersity index of less than 1.5.

14. An acrylate-functional polymer of at least one monomer having the structure

wherein R is a C8-C21 group derived from a plant oil and comprising at least one acrylate-functional group; and wherein said polymer has a polydispersity index of less than 1.5.

15. An acrylate-functional polymer comprising a repeating unit

wherein R is a C8-C21 group derived from a plant oil and comprising at least one acrylate-functional group; and wherein said polymer has a polydispersity index of less than 1.5.

16. A polyol polymer of at least one monomer having the structure

wherein R is a C8-C21 group derived from a plant oil and comprising at least one alcohol group; and wherein said polymer has a polydispersity index of less than 1.5.

17. A polyol polymer comprising a repeating unit

wherein R is a C8-C21 group derived from a plant oil and comprising at least one alcohol group; and wherein said polymer has a polydispersity index of less than 1.5.

18. A method for making a polymer comprising:

contacting a monomer having the structure

wherein R is a C8-C21 aliphatic group, with an organic initiator molecule and a Lewis acid under reaction conditions to allow polymerization of the monomer.

19. The method of claim 18 wherein the polymerization reaction is performed in the absence of a Lewis base.

20. The method of claim 18 or 19 wherein the monomers are derived from plant oil.

21. A method for making a polymer from plant oil, the method comprising:

polymerizing monomers comprising vinylethers of plant oil fatty acid esters; to yield a polymer having a polydispersity index of less than 1.5.

22. The method of any of claims 18 to 21 further comprising extracting the plant oil from a plant or plant part.

23. The method of claim 18 to 22 wherein the plant oil comprises triglycerides, and wherein the method further comprises cleaving the triglycerides to yield the monomers comprising vinylethers of plant oil fatty acid esters.

24. The method of claim 23 wherein the cleaving the triglycerides comprises base- catalyzed transesterification.

25. The method of any of claims 16 to 24 wherein the polymerizing step comprises living carbocationic polymerization.

26. The method of claim 25 wherein the monomers are contacted with an organic initiator molecule and a Lewis acid under reaction conditions to allow polymerization of the monomer.

27. The method of claim 26 wherein the polymerization reaction is performed in the absence of a Lewis base.

28. The method of any of claims 20 to 27 wherein the plant oil comprises soybean oil.

29. A polymer produced by the method of any of claims 18 to 28.

30. A composition comprising the polymer of any of claims 1 to 17 or 29.

31. The composition of claim 30 which is an uncured composition. 33. The composition of claim 30 which is a cured composition. 34 The composition of any of claims 30 to 33 selected from the group consisting of an oil, a lubricant, a coating, a gel, a film and a composite.

35. An article comprising the polymer of any of claims 1 to 17 or 29.

36. A co-polymer comprising the polymer of any of claims 1 to 17 or 29.

37. The co-polymer of claim 36 formed from a vinylether polyethylene glycol monomer.

38. The polymer of any of claims 1 to 17 or 29 wherein the plant oil is vegetable oil.

39. The polymer of any of claims 1 to 17 or 29 wherein the plant oil is soybean oil.

40. A method for producing a polymer comprising:

contacting vinylether plant oil fatty acid ester monomers with an initiator to form a reaction mixture;

contacting the reaction mixture with a co-initiator to initiate a polymerization reaction under conditions and for a time to allow polymerization to proceed;

terminating the polymerization reaction yield the polymer.

41. A method for producing a copolymer comprising:

contacting vinylether plant oil fatty acid ester monomers with at least one additional vinylether monomer and an initiator to form a reaction mixture;

contacting the reaction mixture with a co-initiator to initiate a polymerization reaction under conditions and for a time to allow polymerization to proceed;

terminating the polymerization reaction yield the copolymer.

42. The method of claim 41 wherein the additional vinylether monomer is selected from the group consisting of a vinylether polyethyleneglycol (VEPEG) monomer and a 3,6,9, 12-tetraoxatetradec-l-ene (VEDEE) monomer.

43. The method of any of claims 40 to 42 wherein the polymerization reaction takes place at a temperature less than 10°C.

44. The method of claim 43 wherein the polymerization reaction takes place at a temperature less than 5°C.

45. The method of claim 43 wherein the polymerization reaction takes place at a temperature of about 0°C.

46. The method of any of claims 40 to 45 wherein the plant oil monomers are vegetable oil monomers.

47. The method of claim 46 wherein the vegetable oil monomers are soybean oil monomers.

48. The method of any of claims 40 to 47 wherein the first initiator comprises 1- isobutoxyethyl acetate and the co-initiator comprises ethyl aluminum sesquichloride.