EP2499171A1 - Polymères issus d'une huile végétale - Google Patents

Polymères issus d'une huile végétale

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Publication number
EP2499171A1
EP2499171A1 EP10830812A EP10830812A EP2499171A1 EP 2499171 A1 EP2499171 A1 EP 2499171A1 EP 10830812 A EP10830812 A EP 10830812A EP 10830812 A EP10830812 A EP 10830812A EP 2499171 A1 EP2499171 A1 EP 2499171A1
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EP
European Patent Office
Prior art keywords
polymer
plant oil
monomer
monomers
oil
Prior art date
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Withdrawn
Application number
EP10830812A
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German (de)
English (en)
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EP2499171A4 (fr
Inventor
Bret Ja Chisholm
Samim Alam
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North Dakota State University Research Foundation
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North Dakota State University Research Foundation
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Publication of EP2499171A1 publication Critical patent/EP2499171A1/fr
Publication of EP2499171A4 publication Critical patent/EP2499171A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F116/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/06—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/08—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/10—Acylation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/14—Unsaturated oxiranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups

Definitions

  • 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.
  • 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.
  • the invention provides a polymer formed from vinyl ether monomers derived from plant oil and having the structure:
  • the polymer of the invention thus preferably includes a repeating unit having the general structure:
  • 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.
  • 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.
  • 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;
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • a co-initiator e.g., a Lewis acid
  • 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.
  • a co-initiator e.g., a Lewis acid
  • 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.
  • the first initiator includes 1- isobutoxyethyl acetate and the co-initiator includes ethyl aluminum sesquichloride.
  • 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.
  • 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.
  • FIG 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.
  • FIG. 5 shows an exemplary synthesis of epoxidized polyVESFA (E- poly VESFA) from the polymer of the vinyl ether of soybean oil fatty acid esters
  • FIG. 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.
  • RTIR real time infrared
  • photo-DSC photocalorimetric accessory
  • 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
  • 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.
  • 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.
  • polyVESFA polymev of a vinyl ether of soybean oil fatty acid esters
  • the polymer of the invention is not limited to a polymer produced from soybean oil.
  • the exemplary polyVESFA is synthesized from monomers derived from the transesterification of soybean oil (the exemplary plant oil) with ethylene glycol monovinylether.
  • vinyl ethers of soybean oil fatty acid esters are referred to herein as vinyl ethers of soybean oil fatty acid esters (VESFA).
  • 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.
  • 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:
  • 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
  • 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.
  • monomers are synthesized using base-catalyzed
  • 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.
  • 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:
  • 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 may contain monomers having five different aliphatic groups:
  • 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.
  • 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., -CH 3 ) (or alkylene if within a chain such as ⁇ CH 2 --), alkenyl (or alkenylene if within a chain), and alkynyl (or alkynylene if within a chain) groups, for example.
  • alkyl e.g., -CH 3
  • alkenyl or alkenylene if within a chain
  • alkynyl or alkynylene if within a chain
  • 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.
  • alkenyl group means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon double bonds, such as a vinyl group.
  • alkynyl group means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon triple bonds.
  • 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.
  • heteroatom means an element other than carbon (e.g., nitrogen, oxygen, sulfur, chlorine, etc.).
  • 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.
  • 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.
  • these monomers can be polymerized in a controlled fashion without destroying the ester functionality.
  • the method of polymerizing monomers of the invention utilizes living carbocationic polymerization (also known as controlled/living cationic polymerization).
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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 ⁇ used in the examples below, as well as BC1 3 , BF 3 , A1C1 3 , SnC , TiCLj, SbF 5 , SeCl 3 , ZnCl 2 , FeCl 3 and VC1 4 .
  • 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.
  • 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.
  • 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.
  • 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.
  • the polymer of the invention which is optionally activated at the site of one or more double bonds, e.g., by
  • 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
  • [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].
  • increasing the amount of Lewis acid (co-initiator) will result in an increase in the polymerization rate.
  • 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.
  • the polymer can be derivatized, for example epoxidized or acrylated, as described in more detail elsewhere herein.
  • polyVESFA contains significantly more fatty ester branches per molecule than soybean oil (Fig. 2).
  • 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.
  • 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.
  • 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.
  • polyVESFA like soybean oil
  • polyVESFA 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.
  • 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.
  • air-drying or auto-oxidation using, e.g., a cobalt, zirconium or zinc catalyst
  • sulfur vulcanization using, for example, sulfur and zinc oxide
  • Diels- Alder reaction followed by air drying, by peroxide curing, acrylate-based curing, or via thiolene formation and radiation curing.
  • the polymer of the invention can be incorporated into a composite material, such as a fiber-reinforced composite.
  • a useful copolymer is a copolymer containing vinylether monomers as described herein and polyethylene glycol (PEG) vinyl ether monomers.
  • PEG polyethylene glycol
  • 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.
  • 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.
  • 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.
  • the polymer is epoxidized at the sites of the double bonds on the aliphatic groups.
  • a soybean oil polymer, polyVESFA is optionally epoxidized to yield epoxidized polyVESFA (E-polyVESFA; see Fig. ID).
  • Epoxidized polymers of the invention 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.
  • 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.
  • the invention provides an acrylate-functional polymer.
  • an epoxidized vinyl ether fatty acid ester polymer such as E-polyVESFA
  • 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.
  • the invention provides a polyol polymer.
  • an epoxidized vinyl ether fatty acid ester polymer such as E-polyVESFA
  • 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.
  • 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.
  • 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.
  • 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
  • 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).
  • 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.
  • 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.
  • UVPv 6000 UVPv 6000
  • UVI 6974 photoinitiator
  • Table 1 Table 1
  • the coatings were cast over Teflon® coated glass slides using a draw down bar (BYK Gardner) to produce approximately 200 ⁇ 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.
  • the kinetics of photopolymerization was investigated using a Q1000 differential scanning calorimeter equipped with a photocalorimetric accessory (photo DSC).
  • RTIR Real time infrared spectroscopy
  • 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.
  • Mn number- average molecular weight
  • GPC gel permeation chromatograph
  • ⁇ 1.4 narrow molecular weight distribution
  • 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.
  • E-poly VESFA each tertiary carbon in the polymer backbone serves as a crosslink in the cured film.
  • films based on E-poly VESFA will necessarily possess a higher crosslink density compared to analogous films based on ESO.
  • VESFA 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
  • VESFA Vinyl Ether of Soybean Oil Fatty Acid Esters
  • Another exemplary synthesis of the monomer 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
  • initiator 1- isobutoxyethyl acetate
  • PDI polydispersity index
  • 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
  • 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.
  • 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.
  • Et ⁇ s AlCl ethylaluminum sesquichloride
  • PDI is the polydispersity index
  • 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.
  • 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
  • R500 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-CH 2 CH 3 ).
  • 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.
  • VEDEE 3,6,9, 12-tetraoxatetradec-l-ene
  • 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).
  • Copolymer 1 0.51 0.51 3.2 0.48 5
  • Copolymer 2 0.50 0.50 0.31 0.19 5.10 (74:126:1:18)
  • 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.
  • a draw down bar BYK Gardner
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • soybean oil is subjected to a chemical conversion and used as one component of a formulated material.
  • ESO epoxidized 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.
  • E-polyVESFA 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.
  • 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.
  • triethylene tertamine triethylene tertamine
  • 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.
  • 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.
  • UV ultraviolet light
  • 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/cm 2 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 ⁇ response.
  • 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.
  • 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.
  • 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.
  • acrylated polyVESFA 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.
  • 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/cm 2 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 ⁇ response was 29.9 °C.
  • A-polyVESFA-1 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.
  • the following table lists the amount of raw materials used to synthesize A-polyVESFA-1 and acrylated soybean oil.
  • 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.
  • 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.
  • 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.

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Abstract

L'invention porte sur des polymères et des copolymères qui sont formés à partir de monomères éthers vinyliques ayant des groupes pendants ester d'acide gras issus d'huiles végétales, telles que l'huile de soja.
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US9631040B2 (en) 2012-05-18 2017-04-25 Ndsu Research Foundation Functionalized amphiphilic plant-based polymers
US9834626B2 (en) 2013-01-15 2017-12-05 Ndsu Research Foundation Plant oil-based materials
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US10315985B2 (en) 2014-08-08 2019-06-11 Ndsu Research Foundation Bio-based acrylic monomers
WO2019076709A1 (fr) 2017-10-19 2019-04-25 Basf Se Nouveaux composés benzonaphtathiophènes substitués pour éléments électroniques organiques
KR102367372B1 (ko) 2018-03-07 2022-02-25 주식회사 클랩 상부-게이트, 하부-컨택 유기 전계효과 트랜지스터 제조를 위한 패터닝 방법
JP2021530577A (ja) * 2018-06-26 2021-11-11 クラップ カンパニー リミテッドClap Co., Ltd. 誘電体としてのビニルエーテル系高分子

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