WO2014012937A2 - Procédé de fabrication d'un polymère à base de terpène - Google Patents

Procédé de fabrication d'un polymère à base de terpène Download PDF

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WO2014012937A2
WO2014012937A2 PCT/EP2013/065024 EP2013065024W WO2014012937A2 WO 2014012937 A2 WO2014012937 A2 WO 2014012937A2 EP 2013065024 W EP2013065024 W EP 2013065024W WO 2014012937 A2 WO2014012937 A2 WO 2014012937A2
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carbon
alkenyl
terpene
diester
carbon double
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PCT/EP2013/065024
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WO2014012937A3 (fr
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Erik Diederik Jurriën VISSER
Martinus Adrianus Gertrudus JANSEN
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Hovis International B.V.
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Publication of WO2014012937A2 publication Critical patent/WO2014012937A2/fr
Publication of WO2014012937A3 publication Critical patent/WO2014012937A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Definitions

  • the present invention relates to a method for the manufacture of a terpene-based polymer. Further, the present invention relates to the manufactured polymer and to a composite material comprising the polymer. Furthermore, the present invention relates to intermediary compounds
  • Green engineering in particular the manufacture of bio-based polymers and composites derived from plants or natural products is a rising industry.
  • Green engineering is the design, commercialization and use of processes and products that are feasible and economical while reducing pollution at the source and minimizing the risk to human health and the environment. More particularly, green engineering focuses on bio-based material resources, availability, sustainability, bio-based polymer formation, extraction and refining technologies, and the need for integrated research in areas such as adhesives, resins, plastics, and composites derived from plant oils, proteins, starches, and natural fibers in terms of structures, properties, manufacturing, and product performance.
  • terpene-based polymers Due to their abundance in nature, terpene-based polymers have found applications as biomedical or liquid crystalline materials and, more importantly, have greatly contributed to the concept of sustainable polymer chemistry. The design and preparation of terpene-based polymers have involved
  • the goal of the present invention is to provide a polymer fulfilling the requirements of green engineering, such as reducing the generation of pollution at the source and minimizing the risk to human health and the environment. More specifically, this goal is achieved by the method for the manufacture of a terpene-based polymer comprising the steps of:
  • step a) polymerizing the product obtained in step a) .
  • step c) polymerizing the product obtained in step a) .
  • step b) reacting the product obtained in step a) with an acid anhydride, or acyl halide.
  • the method for the manufacture a terpene- based polymer can also comprise the steps of:
  • terpene dioxide with a carboxylic acid comprising at least one unsaturated carbon- carbon bond
  • step b) reacting the product obtained in step a) with an acid anhydride, or acyl halide;
  • step b) polymerizing the product obtained in step b) .
  • the method for the according to the present invention presents the advantages to provide method for manufacturing a terpene oxide and/or terpene dioxide based polymer that can be carried out in one pot, without requiring
  • the method according to the present invention has the advantage that no solvent or co-solvent is necessary to carry out steps a) and/or c) of the method.
  • Step c) is a free radical polymerization.
  • An initiator may be added in step c) , or step c) can be carried out under UV-light or by heating.
  • the free radical polymerization can be a cross-linking step in order to obtain a polymer network.
  • step c) may also, depending on the terpene-based oxide and/or terpene based dioxide component, result in a polymer that is a linear polymer.
  • the free radical polymerization comprises an initiation step, a propagation step and a termination step. In the initiation step, a thermal initiator or a photo-initiator can be used. When heating is carried out in step c) , a thermal initiator is advantageously added.
  • the present method provides a method wherein no benzene derivative (such as styrene) is added.
  • the terpene-based polymer according to the present invention is prepared from terpenes oxides and/or terpenes dioxides, as well as a carboxylic acid comprising at least one unsaturated carbon-carbon bond, as starting materials.
  • These starting materials can be of any origin, such as originating from crude oil, as well as from vegetal or animal sources.
  • Terpenes are a large and diverse class of organic compounds, produced by a variety of plants,
  • terpenes can also be produced by some insects (termites, butterflies) which emit terpenes as well.
  • Terpenes are the major components of resin obtained from coniferous trees, and of turpentine produced from resin. In addition to their roles as end-products in many organisms, terpenes are major biosynthetic building blocks within nearly every living creature. When terpenes are modified chemically (such as for example by oxidation), the resulting compounds have the generic name terpenoids.
  • the term terpene can also to include all terpenoids. Terpenoids are also known as isoprenoids.
  • the present invention relates to particular terpenoids, specifically terpene oxide (also designated as monoxide, or epoxide) and/or terpene dioxide (also designated as diepoxide) .
  • Terpenes are derived biosynthetically from units of isoprene, which has the molecular formula C 5 H g .
  • the basic molecular formulae of terpenes are multiples of the (C 5 H g ) n skeleton, wherein n is the number of linked isoprene units.
  • the isoprene units may be linked together "head to tail” to form linear chains or they may be arranged to form rings.
  • terpene oxide is to be understood as a terpenoid, comprising one oxide moiety.
  • terpene dioxide is to be understood as a terpenoid, comprising two oxide moieties.
  • An oxide moiety in the context of the present invention, is a chemical function selected from the group hydroxy (-OH) , carboxylic acid (-COOH) , aldehyde (- CHO) and epoxide.
  • An epoxide is a cyclic ether with three ring atoms. This ring approximately defines an equilateral triangle, which makes it highly strained. The strained ring makes epoxides more reactive than other ethers.
  • Simple epoxides are named from the parent compound ethylene oxide or oxirane, such as in chloromethyloxirane .
  • epoxides feature the epoxy prefix, such as in the compound 1 , 2-epoxycycloheptane, which can also be called cycloheptene epoxide, or simply cycloheptene oxide.
  • the terpene oxide and/or terpene dioxide are terpenoids.
  • the terpene moiety can be any of terpenes chosen from monoterpenes, (two isoprene units and are derived from the molecular formula C 10 H 16 , such as geraniol, limonene and terpineol),
  • sesquiterpenes three isoprene units and are derived from the molecular formula Ci 5 H 2 4, such as farnesenes, farnesol), diterpenes (four isoprene units and have the molecular formula C2 0 H 3 2, such as the compounds derivating from
  • geranylgeranyl pyrophosphate cafestol, kahweol, cembrene and taxadiene. Diterpenes also form the basis for
  • retinol biologically important compounds
  • sesterterpenes terpenes having 25 carbons and five isoprene units, are rare relative to the other sizes, such as geranylfarnesol
  • triterpenes six isoprene units and are derived from the molecular formula C 3 oH 48 , such as squalene, and the squalene-derived compounds such as lanosterol or cycloartol , the structural precursors to all the steroids
  • sesquarterpenes sesquarterpenes (seven isoprene units and are derived from the molecular formula C 35 H 56 , such ferrugicadiol and tetraprenylcurcumene )
  • tetraterpenes eight isoprene units and are derived from the molecular formula C 40 H 64 , such as lycopene, gam
  • isoprene units such as the natural rubber consisting of polyisoprene in which the double bonds are cis.
  • the terpene oxide and/or dioxide is advantageously selected from the group monoterpenes, terpinenes and phellandrenes .
  • Monoterpenes are a class of terpenes that consist of two isoprene units and have the molecular formula CioH 16 .
  • Monoterpenes may be linear (acyclic) or contain rings.
  • the terpinenes are a group of isomeric hydrocarbons that are classified as terpenes. They each have the same molecular formula and carbon framework, but they differ in the position of carbon-carbon double bonds.
  • -Terpinene has been isolated from cardamom and marjoram oils, and from other natural sources.
  • ⁇ -Terpinene has no known natural source, but has been prepared synthetically from sabinene.
  • ⁇ -Terpinene and ⁇ -terpinene also known as terpinolene
  • Phellandrene is the name for a pair of organic compounds that have a similar molecular structure and similar chemical properties.
  • -Phellandrene and ⁇ - phellandrene are cyclic monoterpenes and are double-bond isomers. In -phellandrene, both double bonds are endocyclic and in ⁇ -phellandrene, one of them is exocyclic.
  • a-Phellandrene was named after Eucalyptus phellandra, now called Eucalyptus radiata, from which it can be
  • ⁇ -Phellandrene can be isolated from the oil of water fennel and Canada balsam oil.
  • the terpene oxide and/or the terpene dioxide are an epoxyterpene or a
  • an epoxyterpene comprises one epoxide functional group and a diepoxyterpene comprises two epoxide functional groups.
  • the terpene oxide is selected from the group -pinene oxide, cis-limonene oxide, trans-limonene oxide, and a mixture thereof.
  • the terpene oxide can be a-pinene oxide, also designated as a-pinene epoxide, which is re mula (1) :
  • the terpene oxide can be a limonene oxide.
  • the limonene oxide is a compound with the formula (2) :
  • (+) -trans-limonene oxide, (lc) is the (-) -cis-limonene oxide and (Id) (-) -trans-limonene oxide.
  • the (*) indicates the chiral carbon (determining the stereoisomers ( + ) or (-) , also designated as (D) or (L) depending on the chirality of the molecule) and the arrow on compound (la) represents the methyl group in cis or trans position with respect to the adjacent carbon of the epoxy-group containing a hydrogen (marked -H, on the representation of compound (la)) .
  • Cis means "on the same side” and trans means “on the other side” or "across”.
  • the limonene oxide can be the cis isomer, the trans isomer or a mixture thereof.
  • the terpene dioxide can be limonene dioxide.
  • Limonene dioxide is a compound of the formula ( 3 ) :
  • the limonene dioxide used in the method according to the present invention can be any ( stereo ) isomer of the limonene dioxide, or any mixture of more than one isomers. It can also be substituted at any position by an alkyl, a halogen (such as -F, -CI, -Br, -I), a hydroxyl (-OH) .
  • polymers can be obtained with carrying out step a) and a free radical polymerization in step c) with the pinene-based oxide represented in formula (1) .
  • Polymer networks can be obtained with the limonene oxide and/or limonene dioxide (represented by formulae (2) and (3), respectively) after carrying out step a) and a free radical polymerization in step c) according to the present invention.
  • step a) obtainable in step a) , as an intermediary compound of the method according to the present invention, results in a monomer, an oligomer or a resin comprising vinyl group.
  • an unsaturated carboxylic acid is a compound comprising at least one carboxylic function (-COOH) and at least one double C-C bond (designated as unsaturated carbon-carbon bond) .
  • the carboxylic acid with at least one unsaturated carbon-carbon bond can comprise one carboxylic function, two carboxylic functions, three carboxylic
  • examples of suitable carboxylic acid with an unsaturated carbon-carbon are acrylic acids, methacrylic acids, sorbic acids, unsaturated fatty acids, such as carboxylic acids having at least one unsaturated double bond, that are suitable for the preparation of an
  • step a) of the method of the present invention if an allyl group is obtained in the compound prepared in step a) of the method, said double bond is not reactive in free radical polymerizations since the free radical is stabilized by resonance.
  • a possibility is a conjugated double bond such as conjugated carboxylic acid, such as sorbic acid, or conjugated fatty acids ( i . e . calendic acid, eleostearic acid, and catalpic acid) .
  • the carboxylic acid as defined in the present invention can also comprise two carboxylic groups, such as itaconic acid, maleic acid, citraconic acid, fumaric acid, mesaconic acid.
  • Terpene oxides and/or terpene dioxides that react in step a) with a carboxylic acid comprising at least one unsaturated carbon-carbon bond and comprising two carboxylic acid functions (i.e. itaconic acid, maleic acid, citraconic acid, fumaric acid, mesaconic acid) , react in a ratio terpene oxide (and/or terpene dioxide ): carboxylic acid of 2:1. It means that two terpene oxide and/or dioxide
  • an unsaturated hydroxy-ester prepared in step a) is a compound that
  • step a) comprises a hydroxyl function (-OH) , an ester function (- COO-) and a vinyl unsaturation .
  • An unsaturated hydroxy-ester is prepared in step a) by reacting each epoxy function of the terpene oxide (or dioxide) with a carboxylic function.
  • the carboxylic acid comprising at least one unsaturated carbon-carbon bond is selected from the group acrylic acid, methacrylic acid, sorbic acid.
  • Acrylic acid also designated as prop-2-enoic acid and abbreviated AA
  • Sorbic acid an aliphatic carboxylic acid in which two double carbon bonds are conjugated (also designated as 2,4- hexadienoic acid and abbreviated SA) , is a natural organic compound used as a food preservative. It has the chemical formula C6H S C>2.
  • the unsaturated carboxylic acids according to the present invention can also be substituted by alkyl rests, advantageously a C 1 -C6 alkyl, such as a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl .
  • alkyl rests advantageously a C 1 -C6 alkyl, such as a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl .
  • the unsaturated carboxylic acids according to the present invention can also be substituted by one or more alcohol functions (also designated by hydroxyl, -OH) .
  • the acid anhydride is an organic compound that has two acyl groups bound to the same oxygen atom.
  • Acid anhydrides can be linear or cyclic.
  • the acyl groups are derived from the same
  • the acid anhydride is advantageously selected from the group acetic anhydride, formic anhydride and maleic anhydride.
  • the preferred anhydrides in the method of the present invention are chosen from linear acid anhydride comprising at most 4 carbon atoms, more advantageously 3 carbon atoms, most
  • anhydride acetic anhydride (also designated as (CH 3 CO) 2 0) )
  • the anhydrides can contain a double bond. Examples of such anhydrides are acrylic anhydride and methacrylic anhydride.
  • an acyl halide (also known as an acid halide) is a chemical compound containing a -COX functional group, which consists of a carbonyl group singly bonded to a halogen atom (X) .
  • RCOX The general formula for such an acyl halide can be written RCOX, where R may be, for example, an alkyl group, CO is the carbonyl group, and X represents the halide, such as
  • R may be an alkyl group comprising at most three carbon atoms.
  • R may also be an alkenyl comprising a carbon- carbon double bond.
  • the acyl chloride is chosen from the group acryloyl chloride, methacryloyl chloride, acetyl chloride.
  • method steps a) and/or c) are preferably be performed without using additional solvents.
  • Solvents are often not bio-based. If a solvent is used, it is recommended to use a bio-based solvent.
  • the synthesis methods are chosen in such a way that the resin materials can be prepared in one reactor (single- pot reactions) . The method according to the present
  • step a) of the method according to the present invention is carried out at a temperature below 100 ° C.
  • Step a) can also be done at temperatures higher than 100 ° C, as long as no decomposition occurs, or that no by- products due to heat are produced, or that no premature polymerization occurs.
  • step a) is carried out at a temperature providing a reaction mixture that is suitable for carrying out the method according to the present invention.
  • Catalysts may be used in step a) .
  • Said catalysts are any catalysts suitable for the reaction of epoxy resins with carboxylic acids, such as quaternary ammonium salts (e.g. benzyltriethyl ammonium chloride, abbreviated as TEBAC) , or triphenyl phosphine.
  • quaternary ammonium salts e.g. benzyltriethyl ammonium chloride, abbreviated as TEBAC
  • triphenyl phosphine triphenyl phosphine.
  • the viscosity of the reaction products is sufficiently low that moulds can be easily filled prior to the curing process.
  • reinforcing materials such as glass fiber mats can be easily impregnated with the resin after step a) or b) .
  • Some catalyst can also be used in step b) . Any catalyst suitable to carry out step b) can be used in the method of the present invention.
  • step a) and/or b) of the method comprise a step wherein the viscosity is controlled.
  • the viscosity is advantageously controlled before or during any of the steps of the present invention.
  • the viscosity is controlled during step a) and/or step b) and before step c) .
  • the viscosity of the resins obtained by the method according to the present invention is regulated by:
  • step b) by modification of the product (resin) by reaction with an acid anhydride or an acyl halide (step b) ) ; and/ or - by the use of an additive, such as a reactive diluents, before carrying out step c) .
  • an additive such as a reactive diluents
  • a the viscosity is a pre-determined viscosity that is suitable to carry out step a) and/or step b) and/or step c) until the desired level of reaction is reached.
  • step c) a (cross-linking) polymerization step is carried out in which the product obtained in the preceding step is
  • step c) a further step carried out before step c) can be carried out in order to control the viscosity of the formation of the polymer.
  • the obtained resin materials obtained after step a) or b) have reactive vinyl groups so that curing via a free radical polymerization process is possible. Free radicals are obtained in order to carry out step c) , via thermal or UV initiation using suitable peroxides.
  • the obtained resins (after step a) or step b) ) when not stabilized by a suitable inhibitor, under certain conditions like: elevated temperature, exposure to atmospheric air or exposure to UV irradiation, can polymerize spontaneously without the use of initiators. Inhibitors can accordingly be added to stabilize the reaction product after step a) or b) to prevent
  • Any inhibitor that is suitable to stabilize said reaction product can be used in the method of the present invention.
  • An example is hydroquinone .
  • step a) is carried out at a temperature of at most 100 ° C.
  • Step a) can also be carried out at a higher temperature, provided no
  • step b) is carried out at a temperature in the range 10 to 60 ° C, preferably 20 to 50 ° C.
  • step b) is carried out at a temperature of at least 10 ° C, more advantageously at least 20 ° C, even more advantageously at least 30 ° C, most
  • step b) is carried out at a temperature of at most 60 ° C, more preferably a temperature of at most 50 ° C.
  • step b) is carried out at room temperature.
  • Step b) can also be carried out at a temperature higher than 60 ° C, if step b) is carried out with the use of a catalyst allowing it, or with no catalyst.
  • Step b) can also be carried out at a temperature between 0 and 10 ° C, if the reactivity of the reaction carried out in step b) is exothermic (i.e. with acyl halides) .
  • step c) is carried out at a temperature of at most 110 ° C, preferably at most 108 ° C. Step c) can also be carried out at higher
  • the temperature is in the range 20 to 100 ° C, more advantageously in the range 20 to 60 ° C.
  • step c) is carried out at a temperature of at least 10 ° C, more advantageously at least 20 ° C.
  • step c) is a curing step, advantageously, the curing temperature is at room temperature.
  • the curing is carried out at a first temperature during a pre-determined period of time and the temperature is then increased (post-curing) .
  • step b) in any of the steps a) , b) and c) , no additional solvent is required in the method.
  • some solvent may be used.
  • Such solvents may be diethyl ether, dichloromethane or
  • the product obtained in step a) or b) can also be designated as a resin.
  • step c) is carried out in the presence of an initiator.
  • the polymerization initiator can be any polymerization initiator.
  • the conventional thermal initiators for free- radical polymerization include in particular organic peroxy compounds, such as peroxides, peroxycarbonates and peresters. Combinations of peroxy compounds can also be used.
  • Typical examples of the suitable peroxy initiators are C 6 -C 2 o acyl peroxides such as decanoyl peroxide, benzoyl peroxide, octanoyl peroxide, stearyl peroxide, 3,5,5- trimethyl hexanoyl peroxide, per-esters of C2-C18 acids and C 1 -C5 alkyl groups, such as t-butylperbenzoate, t- butylperacetate, t-butyl-perpivalate, t-butylperisobutyrate and t-butyl-peroxylaurate, and hydroperoxides and
  • dihydrocarbyl (C3-C 1 0) peroxides such as diisopropylbenzene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide or combinations thereof.
  • Radical initiators different from peroxy compounds are not excluded.
  • a suitable example of such a compound is , '- azobisobutyronitrile .
  • the amount of radical initiator is suitably from 0.01 to 4 wt, based on the weight of the product obtained after step a) .
  • Suitable photoinitiators are alpha hydroxyketones such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-Hydroxy-2-methyl-l-phenyl-propan-l-one .
  • Another group is the bis-acyl phosphine oxides (bis- ( 2 , 4 , 6-trimethylbenzoyl ) - phenylphosphine oxide ).
  • bis-acyl phosphine oxides bis- ( 2 , 4 , 6-trimethylbenzoyl ) - phenylphosphine oxide
  • Typically 1-4 wt% of photoinitiator is used.
  • Reactive diluents can also be used at any stage prior to step c) of the present method. Diluents are described as monomers with low viscosity which have more than one
  • the reactive diluents are preferably be bio- based, but it may also be not bio-based such as diglycidyl ethers, acrylates, styrene.
  • bio-based reactive diluents are terpenes, such as myrcene, pinene, limonene.
  • Other additives can also be used, such as chain transfer agents, dyes, fillers, flame retarding compounds, nucleating agents.
  • Other (partly) bio-based materials containing reactive vinyl groups can be added as well.
  • An example is commercially available acrylated soybean oil.
  • Another aspect of the present invention relates to the terpene-based polymer obtainable by the method according to the present invention. All the definitions, advantages and preferences described above for the method according to the present invention are applicable to all the aspects of the present invention.
  • Yet another aspect of the present invention relates to a composite polymer material comprising the terpene-based polymer according to the present invention.
  • the terpene-based polymer network manufactured according to the method of the present invention can be part of a coating composition and/or composite polymer material such as glass fiber, wood flour, cork, stone, sand, basalt, flax and jute, quartz.
  • the terpene-based polymers according to the present invention can be used for its binding properties, alone or in a composition such as in glues, e.g. for glues between metals, wood based materials, glass or plastics.
  • Adhesives are materials that adheres items together. Adhesives cure (harden) by either evaporating a solvent or by chemical reactions that occur between two or more constituents. Adhesives are advantageous for joining thin or dissimilar materials, as well as in applications where a vibration-damping joint is needed.
  • Coating materials are covering materials that are applied to the surface of an object, usually referred to as the substrate. In many cases coatings are applied to improve surface properties of the substrate, such as appearance, adhesion, wettability, corrosion resistance, wear
  • the coating forms an essential part of the finished product.
  • step a) of the method according to the present invention relates to the compounds manufactures in step a) of the method according to the present invention, in particular the compounds fabricated from a limonene oxide and acrylic acid, or limonene oxide and methacrylic acid, or limonene oxide and sorbic acid. Accordingly, the present invention relates to the compounds according to formulae (I) and (II) :
  • Ri is an alkenyl comprising at least one carbon- carbon double bond.
  • the alkenyl comprises two carbon-carbon double bonds, it can also be designated by an alken-dien-yl.
  • R x comprising a moiety of 2 carbon-carbon double bonds in conjugation.
  • Ri comprises one, two, three, four, five or six carbon- carbon double bond.
  • the alkenyl can be an alkenyl comprising at least two carbons.
  • the alkenyl comprises two, three, four, five, six, seven, eight, nine or ten carbons.
  • the group -OCO-Ri is chosen from the group a substituted or unsubst ituted acrylate, a substituted or unsubst ituted methacrylate and a substituted or
  • the compounds prepared in step a) and represented by formulae (I) and (II) according to the present invention are unsaturated hydroxy-esters.
  • unsaturated ester is acrylate, methacrylate and sorbate are given in the following formulae.
  • Another aspect of the present invention relates to the products obtainable by the reaction of limonene dioxide and a carboxylic acid comprising at least one unsaturated carbon-carbon bond. Particularly, these compounds have the chemi I) :
  • Ri is an alkenyl comprising at least one carbon- carbon double bond.
  • Both Ri can be the same or different.
  • both Ri are substituted or unsubstituted carboxylic acids selected from acrylic acid, methacrylic acid and sorbic acid.
  • the compounds prepared in step a) and represented by formulae (III), (IV), (V) and (VI) according to the present invention are unsaturated hydroxy-esters .
  • the formulae of said unsaturated hydroxy- esters when the unsaturated ester is acrylate, methacrylate and sorbate are given in the following formulae.
  • the present invention relates to the compounds according to formulae (VII) and (VIII), which are obtainable by the reaction of step a) in which -pinene oxide is reacted with a carboxylic acid comprising at least one unsaturated carbon-carbon bond:
  • Ri is an alkenyl comprising at least one carbon- carbon double bond.
  • Ri comprises one, two, three, four, five or six carbon-carbon double bond.
  • the alkenyl can be an alkenyl comprising at least two carbons.
  • the alkenyl comprises two, three, four, five, six, seven, eight, nine or ten carbons .
  • the group -OCO-Ri is chosen from the group a substituted or unsubst ituted acrylate, a substituted or unsubst ituted methacrylate and a substituted or
  • the substitution can be a -OH, a halogen or an alkyl .
  • step b) Another aspect of the present invention relates to the compounds obtained after step b) , wherein the product obtained in step a) is reacted with an acid anhydride or an acyl halide.
  • step b) the free hydroxyl group (-OH) of the compounds described above is reacted with an acid anhydride or an acyl halide such as defined above to give an
  • ⁇ 1 ⁇ 2 depends on the acid anhydride or the acyl halide used.
  • R x and R 2 may be different or may be the same.
  • R 2 maybe an alkenyl such as defined here above, for example obtained via the reaction of a compound with formulae (I) to (VIII) with an acryloyl chloride, or a (meth) acrylic anhydride, or a sorboyl chloride.
  • R 2 may be a linear alkyl, obtained via the reaction of a terpene based compound represented by formulae (I) to (VIII) with acetic anhydride. If R 2 is an alkenyl comprising at least one unsaturated carbon-carbon bond, R 2 allows decreasing the viscosity of the product before
  • step c) It simultaneously provides more cross- linking in step c) of the method according to the present invention.
  • R 2 is an alkyl, it allows decreasing the viscosity of the product before carrying out step c) .
  • an unsaturated carbon- carbon bond can also be designated by a carbon-carbon double bond .
  • the compounds obtainable after step b) of the method according to the present invention are diesters and a schematic representation is given in formulae (I- diester) to (VI I I-diester ) , wherein Ri and R 2 are the same or different groups and wherein Ri is an alkenyl comprising at least one unsaturated carbon-carbon bond and R 2 is an alkyl, or an alkenyl comprising at least one unsaturated carbon- carbon bond.
  • R 2 is given by the acid anhydride or acyl halide reacted in step b) represented by the formulae (4) and (5), respectively.
  • Ri and ⁇ 1 ⁇ 2 are the same or different groups and wherein Ri is an alkenyl comprising at least one carbon- carbon double and R2 is an alkyl, or an alkenyl comprising at least one carbon-carbon double bond.
  • step b) is carried out with compounds (I) and (4) or (5 t has the formula:
  • step b) When step b) is carried out with compounds (II) and (4) or (5), the resulting product has the formula:
  • step b) is carried out with compounds (III) and (4) o has the formula:
  • step b) When step b) is carried out with compounds (IV) and (4) or (5), the resulting product has the formula:
  • step b) When step b) is carried out with compounds (V) and (4) or (5), the resulting product has the formula:
  • step b) When step b) is carried out with compounds (VI) and (4) or (5), the resulting product has the formula:
  • step b) When step b) is carried out with compounds (VII) and (4) or 5), the resulting product has the formula:
  • step b) When step b) is carried out with compounds (VIII) and (4) or (5), the resulting product has the formula:
  • a specific example of a -pinene oxide-based compound obtainable after steps a) and b) can be:
  • this aspect of the present invention relates to compounds (I-diester) to (VI I I-diester ) described above, wherein R x and R 2 are the same or different groups. If they are the same, they comprise at least one carbon-carbon double bond.
  • “at least one” is to be understood as one, two, three, four, five, six.
  • “At least one” can also to be understood as at least two, at least three, at least four, at least five, at least six, or more.
  • a carbon-carbon double bond can also be designated as an unsaturated carbon-carbon bond.
  • R 2 is an alkyl, or an alkenyl comprising at least one unsaturated carbon-carbon bond.
  • All the compounds described here above are terpene- based compounds. Said compounds are intermediary compounds of the method of the present invention. They are obtainable by step a) and additionally step b) of the method according to the present invention.
  • Figure 2 1 H-NMR spectrum of LOAA in CDCI 3 .
  • Figure 3 1 H-NMR spectrum of LDO (as received) in
  • FIG. 8 TGA curves of uncured (red) and cured (green) LD0SA1_1 resin.
  • the LD0SA1_1 resin was cured at 70-90 °C using 3 wt% MEK.
  • LD0AA1_1 resin blue
  • the samples were cured at 90 °C using 3 wt% MEKP as initiator.
  • Limonene dioxide is obtained by epoxidation of limonene.
  • Limonene takes its names from the lemon, as the rind of the lemon, like other citrus fruits, contains considerable amounts of this compound, which contributes to their odor. Limonene is a colorless liquid hydrocarbon classified as a cyclic terpene. Limonene occurs naturally as the (R) - enantiomer, but racemizes to dipentene at 300 °C. D-Limonene is obtained commercially from citrus fruits through two primary methods: centrifugal separation or steam
  • Sorbic acid or 2 , 4-hexadienoic acid
  • Sorbic acid and its salts such as sodium sorbate, potassium sorbate, and calcium sorbate
  • Sorbic acid and its salts are antimicrobial agents often used as preservatives in food and drinks to prevent the growth of mold, yeast, and fungi.
  • the salts are preferred over the acid form because they are more soluble in water, but it is the acid form that is active.
  • the optimal pH for the antimicrobial activity is below pH 6.5.
  • Sorbates are generally used at concentrations of 0.025% to 0.10 %. The commercial route to synthesize sorbic acid is from
  • crotonaldehyde and ketene As estimated 30,000 tons are produces annually. Although sorbic acid may presently only be produces from oil-based feedstock, production from bio- based feedstock is feasible.
  • crotonaldehyde As an unsaturated aldehyde, crotonaldehyde is a very versatile intermediate in organic synthesis. It occurs in a variety of foodstuffs, e.g. soybean oils.
  • the other raw material for the production of sorbic acid is ketene. Another option to produces sorbic acid is by reaction of acetone with crotonic acid .
  • Step A synthesis of resins reaction of a terpene oxide or dioxide with a carboxylic acid or acid chloride
  • Step B acetylation: reaction of resin as obtained by step a) with an anhydride to reduce the number of free hydroxyl groups .
  • dichloromethane layer was subsequently dried of anhydrous magnesium sulfate and filtrated.
  • the clear yellow colored dichloromethane layer was concentrated using a rotary evaporator. A clear yellow oil was obtained.
  • a saturated solution of NaHCC>3 in water was prepared.
  • the prepared LOAA_AAnh mixture was dissolved in 200 ml dichloromethane and extracted with the saturated NaHCC>3 solution in a separation funnel.
  • Limonene oxide (mixture of cis/trans) has one disubstituted epoxy group and hence can only form a LOAA mono-ester.
  • the chemical structures of starting materials AA, LO and the expected product LOAA are schematically depicted in table la and lb, respectively.
  • the 1 H-NMR spectra of starting material cis/trans LO and the obtained LOAA resin are shown in figures 1 and 2, respectively.
  • the letters of the protons correspond with the letters in the 1 H-NMR spectra.
  • Two isomers are formed which differ from each other by the position of the ester group and adjacent hydroxyl group.
  • Limonene dioxide has two epoxy groups so that theoretically two SA molecules can react with each LDO molecule.
  • the chemical structures of LDO and SA are schematically depicted in table 2a.
  • the chemical structures of LDOSA as schematically depicted in table 2b are expected.
  • the letters refer to different protons in the structures of LDOSA. Note that the same letters are used for starting compounds and final products, although the chemical shift might change a bit due to difference in chemical structure.
  • FIG. 4a shows the 5.6-5.9 ppm region of the H-NMR spectrum of unreacted SA The doublet at 5.76/5.80 ppm originates from proton b of unreacted SA.
  • Figure 4b shows the 5.4-7.6 ppm region of the 1 H-NMR spectrum corresponding to LD0SA1_1 which shows that the peaks corresponding to proton (b) (see table 2b) are located at 5.70, 5.74, 5.79 and 5.83 ppm.
  • LD0SA1_1 consists of multiple compounds having SA esters bonds. Proton (c) of pure unreacted SA gives a multiplet between 7.3 - 7.4 ppm. Since no peaks are observed in this specific region in the 1 H-NMR spectrum of LD0SA1_1 (see figure 4b), it can be concluded that no free SA monomer is present after the synthesis of LD0SA1_1.
  • peaks are present between 3 - 4 ppm. These peaks may be result of protons next to an ether linkage which are usually located between 3 and 4 ppm.
  • the LDOSA (1:1 ratio) resins show a high viscosity at room temperature. Modification of the LDOSA resin by acetylation decreases the viscosity to a level at which the resin can be easily processed as a matrix in combination with fillers (like woodchips, cork, sand) or fibers (glass, carbon, flax, etc) .
  • LDOSA_AAnh resin can be reduced by reactive diluents such as myrcene. Addition of 10 wt% myrcene to LDOSA resin reduces the viscosity at room temperature enough to make the LDOS/myrcene mixture useful or mould filling. The myrcene mixes homogeneously with LDOSA resin after a short period of stirring and participates in the polymer network during curing.
  • a master solution containing 0.1 wt% Co was prepared by dissolution of 18.4 mg Cobalt (II) 2-ethylhexanoate solution (65 wt% in mineral spirits) in 12.019 g myrcene.
  • CHP cumene hydroperoxide
  • LD0SA1_1 were mixed. This mixture was heated to 70 °C. A small amount of this LD0SA1_1 / Irgacure ® mixture was placed over the whole length of a square sized preheated glass substrate. A coating of 20 um was made by doctor blading. The glass substrate with the LD0SA1_1 resin coated on it was subsequently irradiated with an UV lamp for 300 seconds. The LD0SA1_1 coating formed a hard layer on top of the glass substrate.
  • TBPB peroxybenzoate
  • norm sand was added.
  • the norm sand was homogeneously mixed with the LD0SA1_1/TBPB mixture by a mechanical stirrer.
  • the mixture was subsequently placed in an oven at 100 °C + 800 mbar to reduce entrapped air inside the resin/sand mixture and to lower the viscosity of the LD0SA1_1 resin.
  • the LD0SA1_1 resin/sand mixture was mixed again shortly with a spoon and poured into a pre-heated silicon mold containing cylindrical spaces with a length of approximately 30 mm and a diameter of approximately 28 mm.
  • the resin/sand mixture was pressed on top with a cylinder of the same surface dimensions.
  • the silicon mold was placed back into the oven.
  • the temperature of the oven was set at 120 °C and a vacuum of 600-700 mbar was applied for a period of approximately 4 hours.
  • the pressure was then further reduced to high vacuum ( ⁇ 10 mbar) and the mold was kept in the oven at 120 °C for one more hour.
  • IR spectra of LD0SA1_1 before and after curing are shown in figures 5 and 6, respectively.
  • Table 3 shows the IR absorption bonds for uncured LD0SA1_1.
  • the uncured LD0SA1_1 resin shows a strong absorption band at 1703 cm -1 which originates from the carbonyl ester group.
  • the presence of this band at 1694 cm -1 shows that reaction between the carboxylic acid group from SA and the epoxide group of LDO has occurred.
  • the C-0 stretching band at 1242 cm -1 shows that an ester is present.
  • a sharp absorption band is observed at 1136 cm -1 . This band can originate from hydroxyl groups, C-0 esters, or C-O-C ethers. So, possibly ether bonds have been formed although this cannot be
  • TGA Thermal Gravimetric Analysis
  • the TGA curves of uncured LD0SA1_1 resin and cured LD0SA1_1 resin are shown in figure 8.
  • the curing conditions for the LD0SA1_1 resin are shown in table 4. From figure 8, it can be seen that the uncured LD0SA1_1 resin is stable up to approximately 108 °C (weight loss ⁇ 1 %) . Above this temperature, the sample weight decreases rapidly. Hence, curing is preferably done at temperature below 108 °C to prevent evaporation of LD0SA1_1.
  • the cured LD0SA1_1 resin is stable up to a temperature of approximately 193 °C (weight loss ⁇ 1 %) .
  • the improved thermal stability of the LD0SA1_1 after curing shows that polymerization occurred and that no significant fraction of low molecular weight material is left.
  • Figure 10 shows the TGA curves of LOAA and LD0AA1_1 after curing. It can be seen that the weight loss of the cured LOAA resin is ⁇ 1 wt% up to 213 °C. The cured LD0AA1_1 resin is less stable at higher temperatures ( ⁇ 1 wt% up to 149 °C) .
  • the cylinders consisting of LDOSA resin with additionally myrcene (no fillers or additives) were placed in a distilled water bath at room temperature. The samples were measured with a Zwick tensile tester after different residence times in the water. The compression strain rate was set at 2 mm/min. The compressive modulus was determined, as well as the compressive yield strength (maximum in the stress strain curve after which plastic deformation occurs) and the ultimate compressive strength if applicable.
  • Figure lla-d shows typical compressive stress-strain curves for different cured resins.
  • Figure 11a and lib show the stress-strain curve for cured LD0SA1_1 after 0 weeks (not being put in water) and after 4 weeks in water.
  • the stress- strain curve of LD0SA1_1 (0 weeks) shows glassy behavior.
  • the material suddenly breaks which results in the formation of a conical shape.
  • approximately 0.9 wt% water was taken up by the cured LD0SA1_1 sample.
  • the water uptake seems to have a plasticizing effect on the sample as can be seen from figure lib.
  • the material becomes a bit more ductile. After reaching the yield stress, the material does no longer break at once, but small pieces gradually leap away from the edge of the cylinder so that the compressive stress is maintained more or less constant.
  • LD0SA1_1 /myrcene 90 / 10 cylinders as a function of storage time in water.
  • dumbbell shaped tensile bars were prepared which were subsequently cured in the oven. The tests were performed on a Zwick tensile tester using a tensile strain rate of 2 mm/min. The results from the tensile tests are shown in table 9.
  • a glass fiber reinforced plate was prepared from

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Abstract

La présente invention concerne un procédé de fabrication d'un polymère à base de terpène qui comporte les étapes consistant à : a) faire réagir un oxyde de terpène et/ou un dioxyde de terpène avec un acide carboxylique qui comprend au moins une liaison carbone-carbone insaturée ; b) polymériser le composé obtenu à l'étape a). En outre, la présente invention concerne le polymère à base de terpène obtenu au moyen de ce procédé et ses utilisations.
PCT/EP2013/065024 2012-07-17 2013-07-16 Procédé de fabrication d'un polymère à base de terpène WO2014012937A2 (fr)

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NL1039738A NL1039738C2 (en) 2012-07-17 2012-07-17 Method for the manufacture of a terpene-based polymer.

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Cited By (2)

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CN104877076A (zh) * 2015-05-19 2015-09-02 广西众昌树脂有限公司 无色萜烯树脂的制备方法
EP3680263A1 (fr) 2019-01-14 2020-07-15 Basf Se (méth)acrylates à base de limonène pour l'impression 3d

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US4524157A (en) * 1981-07-01 1985-06-18 Union Carbide Corporation Adducts and polymer-polyols useful in the preparation of improved plastics, including polyurethane foams, elastomers and the like
WO2011104704A2 (fr) * 2010-02-24 2011-09-01 Corona Dent. Ltd. Restaurations dentaires de longue durée et leurs procédés de préparation

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104877076A (zh) * 2015-05-19 2015-09-02 广西众昌树脂有限公司 无色萜烯树脂的制备方法
EP3680263A1 (fr) 2019-01-14 2020-07-15 Basf Se (méth)acrylates à base de limonène pour l'impression 3d
WO2020148189A1 (fr) 2019-01-14 2020-07-23 Basf Se (méth)acrylates à base de limonène destinés à être utilisés dans une impression 3d

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