NL1039738C2 - Method for the manufacture of a terpene-based polymer. - Google Patents
Method for the manufacture of a terpene-based polymer. Download PDFInfo
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- NL1039738C2 NL1039738C2 NL1039738A NL1039738A NL1039738C2 NL 1039738 C2 NL1039738 C2 NL 1039738C2 NL 1039738 A NL1039738 A NL 1039738A NL 1039738 A NL1039738 A NL 1039738A NL 1039738 C2 NL1039738 C2 NL 1039738C2
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- 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
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The present invention relates to a method for the manufacture of a terpene-based polymer comprising the steps of: a) reacting a terpene oxide and/or a terpene dioxide with a carboxylic acid comprising at least one unsaturated carbon-carbon bond; c) polymerizing the compound obtained in step a). Further, the present invention relates to the terpene-based polymer manufactured by the method and uses thereof.
Description
METHOD FOR THE MANUFACTURE OF A TERPENE-BASED POLYMER
The present invention relates to a method for the manufacture of a terpene-based polymer. Further, the present 5 invention relates to the manufactured polymer and to a composite material comprising the polymer. Furthermore, the present invention relates to intermediary compounds manufactured using the present method.
Green engineering, in particular the manufacture of bio-10 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 15 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 20 from plant oils, proteins, starches, and natural fibers in terms of structures, properties, manufacturing, and product performance.
Polymers based on terpenes are an example of Green Engineering. Terpenes are a large class of diverse 25 biological compounds derived from isoprene. 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 30 preparation of terpene-based polymers have involved different chemical strategies and a wide variety of polymerization techniques, making use of the chemical 1039738 2 functionalities in terpene molecules, e.g. (conjugated) double bonds, hydroxyl and carboxyl groups.
Accordingly, there is a need in the prior art to provide, at an industrial level, polymer derived from 5 natural sources, also designated as bio-based polymer (these polymers may be cross-linked polymers, also designated as polymer network, or linear polymers). Specifically, there is a need in the prior art for providing stable polymer from natural sources in order to be used in industrial processes 10 for the fabrication of adhesives, resins, plastics, and composites, coatings. The goal of the present invention, amongst other goals, is to provide a polymer fulfilling the requirements of green engineering, such as reducing the generation of pollution at the source and minimizing the 15 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: a) reacting a terpene oxide and/or a terpene dioxide with a carboxylic acid comprising at 20 least one unsaturated carbon-carbon bond; c) polymerizing the product obtained in step a).
This goal is also achieved by the method for the manufacture of a terpene-based polymer wherein after step a) and before step c) the method comprises: 25 b) reacting the product obtained in step a) with an acid anhydride, or acyl halide.
Accordingly, the method for the manufacture a terpene-based polymer can also comprise the steps of: a) polymerizing, or reacting, a terpene oxide 30 and/or a terpene dioxide with a carboxylic acid comprising at least one unsaturated carbon-carbon bond; 3 b) reacting the product obtained in step a) with an acid anhydride, or acyl halide; c) polymerizing the product obtained in step b).
5 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 purification and may provide additional properties, such as 10 anti-microbial properties. Further, 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.
Advantageously, step c) is a free radical 15 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. Alternatively, step c) may also, depending on the terpene-based oxide and/or 20 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 25 step c), a thermal initiator is advantageously added.
Furthermore, 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 30 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 4 animal sources. Terpenes are a large and diverse class of organic compounds, produced by a variety of plants, particularly conifers. Some terpenes can also be produced by some insects (termites, butterflies) which emit terpenes as 5 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 10 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 15 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 C5H8. The basic molecular formulae of terpenes are multiples of the (C5H8)n 20 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.
The term "terpene oxide" is to be understood as a terpenoid, comprising one oxide moiety. The term "terpene 25 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 30 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 5 or oxirane, such as in chloromethyloxirane. As a functional group, epoxides feature the epoxy prefix, such as in the compound 1,2-epoxycycloheptane, which can also be called cycloheptene epoxide, or simply cycloheptene oxide.
5 According to the present invention, 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 CioHie, such as geraniol, limonene and terpineol) , 10 sesquiterpenes (three isoprene units and are derived from the molecular formula C15H24, such as farnesenes, farnesol) , diterpenes (four isoprene units and have the molecular formula C20H32, such as the compounds derivating from geranylgeranyl pyrophosphate: cafestol, kahweol, cembrene 15 and taxadiene. Diterpenes also form the basis for biologically important compounds such as retinol, retinal, and phytol. They are known to be antimicrobial and antiinflammatory) , sesterterpenes (terpenes having 25 carbons and five isoprene units, are rare relative to the other 20 sizes, such as geranylfarnesol), triterpenes (six isoprene units and are derived from the molecular formula C30H48, such as squalene, and the squalene-derived compounds such as lanosterol or cycloartenol, the structural precursors to all the steroids), sesquarterpenes (seven isoprene units and are 25 derived from the molecular formula C35H56, such ferrugicadiol and tetraprenylcurcumene), tetraterpenes (eight isoprene units and are derived from the molecular formula C40H64, such as lycopene, gamma-carotene, alpha-carotene and beta-carotene) , and the polyterpenes (long chains of many 30 isoprene units, such as the natural rubber consisting of polyisoprene in which the double bonds are cis.
According to the present invention, the terpene oxide and/or dioxide is advantageously selected from the group 6 monoterpenes, terpinenes and phellandrenes. Monoterpenes are a class of terpenes that consist of two isoprene units and have the molecular formula Ci0H16. Monoterpenes may be linear (acyclic) or contain rings.
5 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. α-Terpinene has been isolated from cardamom and marjoram oils, and from 10 other natural sources. β-Terpinene has no known natural source, but has been prepared synthetically from sabinene. γ-Terpinene and δ-terpinene (also known as terpinolene) are natural and have been isolated from a variety of plant sources. Phellandrene is the name for a pair of organic 15 compounds that have a similar molecular structure and similar chemical properties. α-Phellandrene and β-phellandrene are cyclic monoterpenes and are double-bond isomers. In α-phellandrene, both double bonds are endocyclic and in β-phellandrene, one of them is exocyclic.
20 α-Phellandrene was named after Eucalyptus phellandra, now called Eucalyptus radiata, from which it can be isolated. It is also a constituent of the essential oil of Eucalyptus dives. β-Phellandrene can be isolated from the oil of water fennel and Canada balsam oil.
25 According to the present invention, the terpene oxide and/or the terpene dioxide are an epoxyterpene or a diepoxyterpene. In the context of the present invention, an epoxyterpene comprises one epoxide functional group and a diepoxyterpene comprises two epoxide functional groups.
30 According to the present invention, the terpene oxide is selected from the group α-pinene oxide, cis-limonene oxide, trans-limonene oxide, and a mixture thereof.
7
According to the present invention, the terpene oxide can be α-pinene oxide, also designated as α-pinene epoxide, which is represented in formula (1): tQ· 5 (1)
Advantageously, the terpene oxide can be a limonene oxide. The limonene oxide is a compound with the formula (2) : 10 \ (2)
Which isomers are given in formulae (2a), (2b), (2c) and (2d): -Xj V? VJ V?
As. .¾ jC jC
(2a) (2b) (2c) (2d) 15 8 wherein (la) is the (+)-cis-limonene oxide, (lb) is the (+)-trans-limonene oxide, (lc) is the (-)-cis-limonene oxide and (Id) (-)-trans-limonene oxide. The (*) indicates the chiral carbon (determining the stereoisomers (+) or (-), 5 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 10 means "on the same side" and trans means "on the other side" or "across". In the context of the present invention, when the methyl group is on the same side than the hydrogen, it is to be understood cis-limonene oxide. According to the present invention, the limonene oxide can be the cis isomer, 15 the trans isomer or a mixture thereof.
According to the present invention, the terpene dioxide can be limonene dioxide. Limonene dioxide is a compound of the formula (3): CT \ 20 (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 25 (such as -F, -Cl, -Br, -I), a hydroxyl (-0H).
In the context of the present invention, linear polymers can be obtained with carrying out step a) and a free radical polymerization in step c) with the pinene-based 30 oxide represented in formula (1). Polymer networks can be 9 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.
5 Advantageously, the unsaturated hydroxy-ester 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.
Specifically, an unsaturated carboxylic acid is a 10 compound comprising at least one carboxylic function (-COOH) and at least one double C-C bond (designated as unsaturated carbon-carbon bond). A double C-C bond is also designated as a sp2-sp2 carbon-carbon bond (C=C) . In the context of the present invention, the carboxylic acid with at least one 15 unsaturated carbon-carbon bond can comprise one carboxylic function, two carboxylic functions, three carboxylic functions, four carboxylic functions. In the present invention, examples of suitable carboxylic acid with an unsaturated carbon-carbon are acrylic acids, methacrylic 20 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 unsaturated hydroxy-ester in step a) of the method of the present invention. In the context of the present invention, 25 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 30 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 10 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 5 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 molecules react with one carboxylic acid.
10 In the context of the present invention, an unsaturated hydroxy-ester prepared in step a) is a compound that comprises a hydroxyl function (-OH), an ester function (-C00-) and a vinyl unsaturation. An unsaturated hydroxy-ester is prepared in step a) by reacting each epoxy function of 15 the terpene oxide (or dioxide) with a carboxylic function.
According to the present invention, the carboxylic acid comprising at least one unsaturated carbon-carbon bond is selected from the group acrylic acid, methacrylic acid, sorbic acid.
20 Acrylic acid (also designated as prop-2-enoic acid and abbreviated AA) is an organic compound with the formula CH2=CHC02H. It is the simplest unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid terminus. Methacrylic acid, (also designates 25 as 2-methylpropenoic acid and abbreviated MAA), is an organic compound with the chemical formula CH2=C (CH3) C02H. 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 30 compound used as a food preservative. It has the chemical formula C6H802.
The unsaturated carboxylic acids according to the present invention can also be substituted by alkyl rests, 11 advantageously a Ci-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 5 alcohol functions (also designated by hydroxyl, -OH).
In the context of the present invention, 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 10 carboxylic acid, the formula of the anhydride being (RC(0))20. In the present invention, 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 15 from linear acid anhydride comprising at most 4 carbon atoms, more advantageously 3 carbon atoms, most advantageously 2 carbon atoms, on each side of the anhydride function. Examples of such anhydrides are propionic anhydride, acetic anhydride (also designated as(CH3CO) 20)), 20 or formic anhydride formic anhydride (also designated as C2H203 or (H (C=0)-) 20) ) . Advantageously the anhydrides can contain a double bond. Examples of such anhydrides are acrylic anhydride and methacrylic anhydride.
In the context of the present invention, an acyl halide 25 (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). The general formula for such an acyl halide can be written RCOX, where R may be, for example, an alkyl group, CO is the 30 carbonyl group, and X represents the halide, such as chloride. R may be an alkyl group comprising at most three carbon atoms. R may also be an alkenyl comprising a carbon-carbon double bond. Acyl chlorides are accordingly 12 advantageously used in the method according to the present invention. More advantageously, the acyl chloride is chosen from the group acryloyl chloride, methacryloyl chloride, acetyl chloride.
5 In the context of the present invention, 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 10 the resin materials can be prepared in one reactor (singlepot reactions). The method according to the present invention provides products with high yields so that additional purification steps may not be necessary.
Advantageously, step a) of the method according to the 15 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 byproducts due to heat are produced, or that no premature polymerization occurs.
20 Preferably, 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 25 carboxylic acids, such as quaternary ammonium salts (e.g.
benzyltriethyl ammonium chloride, abbreviated as TEBAC), or triphenyl phosphine.
In the context of the present invention, the viscosity of the reaction products is sufficiently low that moulds can 30 be easily filled prior to the curing process. In addition, 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 13 to carry out step b) can be used in the method of the present invention.
Accordingly, in the present invention, step a) and/or b) of the method comprise a step wherein the viscosity is 5 controlled. The viscosity is advantageously controlled before or during any of the steps of the present invention. Advantageously, 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 10 invention is regulated by: - varying the ratio of starting materials in step a); and/or - 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, 15 before carrying out step c).
Accordingly, in the context of the present invention, 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. Specifically in step 20 c), a (cross-linking) polymerization step is carried out in which the product obtained in the preceding step is polymerized. Advantageously, a further step carried out before step c) can be carried out in order to control the viscosity of the formation of the polymer.
25 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 30 (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 14 initiators. Inhibitors can accordingly be added to stabilize the reaction product after step a) or b) to prevent polymerization. Any inhibitor that is suitable to stabilize said reaction product can be used in the method of the 5 present invention. An example is hydroquinone.
According to the present invention, step a) is carried out at a temperature of at most lOCfC. Step a) can also be carried out at a higher temperature, provided no decomposition, or degradation, of the resulting product 10 occurs, and/or provided that no premature polymerization occurs.
According to the present invention, step b) is carried out at a temperature in the range 10 to 60‘C, preferably 20 to 50°C. Advantageously, step b) is carried out at a 15 temperature of at least 10“C, more advantageously at least 20°C, even more advantageously at least 30'C, most advantageously at least 40°C. Preferably, step b) is carried out at a temperature of at most 60'C, more preferably a temperature of at most 50°C. Advantageously, step b) is 20 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 25 out in step b) is exothermic (i.e. with acyl halides).
According to the present invention, 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 temperatures, provided no degradation of the products 30 occurs. Advantageously, the temperature is in the range 20 to 100°C, more advantageously in the range 20 to 60°C. Advantageously, step c) is carried out at a temperature of at least 10°C, more advantageously at least 20°C.
15
Accordingly, step c) is a curing step, advantageously, the curing temperature is at room temperature. Advantageously, the curing is carried out at a first temperature during a pre-determined period of time and the temperature is then 5 increased (post-curing).
Advantageously in the present invention, in any of the steps a), b) and c), no additional solvent is required in the method. In some cases, when carrying out step b) with certain acid anhydride, some solvent may be used. Such 10 solvents may be diethyl ether, dichloromethane or chloroform. This is to be understood that no difficult removal of excess solvent is needed at any steps of the method according to the present invention. A further advantage is that no solvent that is toxic for the 15 environment is involved in steps a) and/or c) of the method according to the present invention. Furthermore, no difficult separation of the solvent from the final products is necessary.
In the context of the present invention, the product 20 obtained in step a) or b) can also be designated as a resin.
Advantageously, step c) is carried out in the presence of an initiator. The polymerization initiator can be selected from the conventional thermal initiators for free-radical polymerization. They include in particular organic 25 peroxy compounds, such as peroxides, peroxycarbonates and peresters. Combinations of peroxy compounds can also be used. Typical examples of the suitable peroxy initiators are C6-C2o acyl peroxides such as decanoyl peroxide, benzoyl peroxide, octanoyl peroxide, stearyl peroxide, 3,5,5-30 trimethyl hexanoyl peroxide, per-esters of C2-C18 acids and C1-C5 alkyl groups, such as t-butylperbenzoate, t-butylperacetate, t-butyl-perpivalate, t-butylperisobutyrate and t-butyl-peroxylaurate, and hydroperoxides and 16 dihydrocarbyl (C3-C10) peroxides, such as diisopropylbenzene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide or combinations thereof.
Radical initiators different from peroxy compounds are not 5 excluded. A suitable example of such a compound is α,α'-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).
Typical examples of suitable photoinitiators are alpha 10 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).Typically 1-4 wt% of photoinitiator is used.
15 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 reactive vinyl group and form homogeneous mixtures with the previously described bio-based resins obtained after steps 20 a) and b). The reactive diluents are preferably be biobased, but it may also be not bio-based such as diglycidyl ethers, acrylates, styrene. Examples of bio-based reactive diluents are terpenes, such as myrcene, pinene, limonene. Other additives can also be used, such as chain transfer 25 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.
30 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 17 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 5 polymer according to the present invention. Specifically, 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, 10 quartz. Further, 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.
Accordingly, another aspect of the present invention 15 relates to the terpene-based polymer material is used in adhesives or a coating materials. 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 20 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 25 surface properties of the substrate, such as appearance, adhesion, wettability, corrosion resistance, wear resistance, and scratch resistance. In other cases, in particular in printing processes and semiconductor device fabrication (where the substrate is a wafer), the coating 30 forms an essential part of the finished product.
Still another aspect of the present invention relates to the compounds manufactures in step a) of the method according to the present invention, in particular the 18 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): 5 (I) 10 (II) wherein Ri is an alkenyl comprising at least one carbon-carbon double bond. In the context of the present invention, if the alkenyl comprises two carbon-carbon double bonds, it can also be designated by an alken-dien-yl. One example can 15 be when Ri comprising a moiety of 2 carbon-carbon double bonds in conjugation.
Advantageously, either for compound (I) or compound (II), Ri comprises one, two, three, four, five or six carbon-carbon double bond. The alkenyl can be an alkenyl comprising 20 at least two carbons. Preferably, the alkenyl comprises two, three, four, five, six, seven, eight, nine or ten carbons.
Preferably, the group -OCO-Ri is chosen from the group a substituted or unsubstituted acrylate, a substituted or unsubstituted methacrylate and a substituted or 25 unsubstituted sorbate. The substitution can be a -OH, a 19 halogen or an alkyl. Accordingly, the compounds prepared in step a) and represented by formulae (I) and (II) according to the present invention are unsaturated hydroxy-esters. The formulae of said unsaturated hydroxy-esters when the 5 unsaturated ester is acrylate, methacrylate and sorbate are given in the following formulae.
Acrylate (wherein Ri is -CH=CH2) : 0 da) 10 \ (Ha)
Methacrylate (wherein Ri is -C (CH3) =CH2) : (lb) 15 20 ° ' (Hb)
Sorbate (wherein Ri is -CH=CH-CH=CH-CH3) : x
O
(Ic)
(IIO
5 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 chemical formula (III), (IV), (V) and (VI): ch3 21 /ί. ^CH2
Ri (HI) o ch3 o ch2
OH
(IV) 5 ^°Y*1 ch3 HO. Js. 0
0 XT T)H
/L .CH2
Ri (V) ch3 rw .°. | .A. ,Α. o xr ΌΗ o ch2
OH
10 (VI) 22 wherein Ri is an alkenyl comprising at least one carbon-carbon double bond. Both Ri can be the same or different. Advantageously, both Ri are substituted or unsubstituted carboxylic acids selected from acrylic acid, methacrylic 5 acid and sorbic acid. Accordingly, 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 10 and sorbate are given in the following formulae.
Acrylate (wherein Ri is -CH=CH2) : o CH3 JL .CH2 (Ilia) o ch3 o ch2 OH (IVa) ch3 ho.I.Λ. o
O TT ‘OH
JL .CH2 15 O (Va) ch3 23 ο ch2 OH (Vla)
Methacrylate (wherein wherein Ri is -C(CH3) =CH2) : 0 ch3 \ ^/ch2 (mb) ^A0H 0 oh3 o ch2 OH (IVb) /n/°v\ ch3 HO. 0
0 ^0^ X)H
^/CHz 5 (Vb) ch3 24 o ch2 OH (VIb)
Sorbate (wherein Ri is -CH=CH-CH=CH-CH3) : r~Ys · o (IIIc) /o
^ P
ï I
° 0z (IVc)
X
O Vi (vc) fl I 1 (Vic) ° r 5
Furthermore, the present invention relates to the compounds according to formulae (VII) and (VIII), which are obtainable by the reaction of step a) in which a-pinene 10 oxide is reacted with a carboxylic acid comprising at least one unsaturated carbon-carbon bond: 25 <γυ°η° (VII) ^°γΡι ° (VIII) wherein Ri is an alkenyl comprising at least one carbon-carbon double bond.
10 Advantageously, either for compound (VII) or compound (VIII), Ri comprises one, two, three, four, five or six carbon-carbon double bond. The alkenyl can be an alkenyl comprising at least two carbons. Preferably, the alkenyl comprises two, three, four, five, six, seven, eight, nine or 15 ten carbons.
Preferably, the group -OCO-Ri is chosen from the group a substituted or unsubstituted acrylate, a substituted or unsubstituted methacrylate and a substituted or unsubstituted sorbate. The substitution can be a -OH, a 20 halogen or an alkyl.
Acrylate (wherein Ri is -CH=CH2) : 0 / \ (Vila) 0 26 / \ (Villa)
Methacrylate (wherein Ri is -C (CH3) =CH2) : fCV° (Viib) 5 ° / \ (VUIb)
Sorbate (wherein Ri is -CH=CH-CH=CH-CH3) : fCY°H 0 10 (Vile) /Α-Λ-ΟΗ ° / \ (VIIIc) 27
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. In step b) the free hydroxyl group (-0H) of the 5 compounds described above is reacted with an acid anhydride or an acyl halide such as defined above to give an unsaturated ester. Accordingly, in the formulae (I) to (VIII), the -OH group is esterified to form a second ester functional group of the type -0-(C=0)-R2 wherein R2 is an 10 alkyl, or an alkenyl comprising at least one unsaturated carbon-carbon bond. R2 depends on the acid anhydride or the acyl halide used. In the context of the present invention, Ri and R2 may be different or may be the same. R2 maybe an alkenyl such as defined here above, for example obtained via 15 the reaction of a compound with formulae (I) to (VIII) with an acryloyl chloride, or a (meth)acrylic anhydride, or a sorboyl chloride. R2 may be a linear alkyl, obtained via the reaction of a terpene based compound represented by formulae (I) to (VIII) with acetic anhydride. If R2 is an alkenyl 20 comprising at least one unsaturated carbon-carbon bond, R2 allows decreasing the viscosity of the product before carrying out step c). It simultaneously provides more cross-linking in step c) of the method according to the present invention. If R2 is an alkyl, it allows decreasing the 25 viscosity of the product before carrying out step c). In the context of the present invention, an unsaturated carbon-carbon bond can also be designated by a carbon-carbon double bond.
Accordingly, the compounds obtainable after step b) of 30 the method according to the present invention are diesters and a schematic representation is given in formulae (I-diester) to (VIII-diester), wherein Ri and R2 are the same or different groups and wherein Ri is an alkenyl comprising at 28 least one unsaturated carbon-carbon bond and R2 is an alkyl, or an alkenyl comprising at least one unsaturated carbon-carbon bond.
As described above, R2 is given by the acid anhydride or 5 acyl halide reacted in step b) represented by the formulae (4) and (5), respectively.
o o R2 o r2 (4)
O
R/\x K2 Λ (5) 10 wherein Ri and R2 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.
When step b) is carried out with compounds (I) and (4) 15 or (5), the resulting product has the formula: °y-
0^\R
ϋ K1 (I-diester)
When step b) is carried out with compounds (II) and (4) or (5), the resulting product has the formula: 29 °^R’ ° K2 (Il-diester)
When step b) is carried out with compounds (III) and (4) or (5), the resulting product has the formula: °yR! °^R2 ch3 o/CH2 oAr
Ki R/^0
Kl ° (III-diester) 5 When step b) is carried out with compounds (IV) and (4) or (5), the resulting product has the formula: 30 \^R2 °VR’ r^/'0 ch3
I I
o/CH2 «A* r2 ° (IV-diester)
When step b) is carried out with compounds (V) and (4) or (5), the resulting product has the formula: 5 \^R’ °V/R2 ch3
/CHZ
0 0 Xr2
R'^^O
Kl ° (V-diester)
When step b) is carried out with compounds (VI) and (4) or (5), the resulting product has the formula: 31 °^R’ V/R’ (^l·0 ch3 //CHz ^\ 0 0 \2 r2 0 (VI-diester)
When step b) is carried out with compounds (VII) and (4) or (5), the resulting product has the formula:
o-X.R
5 OK! (VII-diester)
When step b) is carried out with compounds (VIII) and (4) or (5), the resulting product has the formula: /^v° 32 °yRl
O^R
υ K2 (VlII-diester) A specific example of a α-pinene oxide-based compound 5 obtainable after steps a) and b) can be: AV· , xt — .' ™ acrylic acid .. jl yyV0H (Villa) νλ, acryloyl chloride Ψ 0 Γ^'Ί—0 1} di-ester
Accordingly, this aspect of the present invention relates to compounds (I-diester) to (VIII-diester) described above, wherein Ri and R2 are the same or different groups. If 10 they are the same, they comprise at least one carbon-carbon double bond. In the context of the present invention, "at least one" is to be understood as one, two, three, four, 33 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. In the context of the present invention, a carbon-carbon double bond can also be designated as an 5 unsaturated carbon-carbon bond. Accordingly, in the context of the present invention, R2 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 10 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.
The present invention is further illustrated, without being limited to, the present Examples and Figures.
34
Figures
Figure 1. 1H-NMR spectrum of a mixture of cis/trans LO
(as received) in CDCI3.
5 Figure 2. 1H-NMR spectrum of LOAA in CDCI3.
Figure 3. 1H-NMR spectrum of LDO (as received) in CDCI3.
10 Figure 4a. Magnification of 1H-NMR spectrum of SA (as received) in CDCI3; peak positions corresponding to proton (b) at 5.76 and 5.80 ppm.
15 Figure 4b. Magnification (5.4-7.6 ppm region) of 1H-NMR
spectrum from LDOSAl_l in CDCI3; Peak positions corresponding to proton (b) at 5.70, 5.74, 5.79 and 5.83 ppm.
20 Figure 5. IR spectrum of uncured LD0SA1_1 resin
Figure 6. IR spectrum of LD0SA1_1 after curing.
Figure 7a. IR spectra of LDOSAl_l_AAnh with 5 wt% 25 AFR40+0.5wt%TBPB at t=0.5 min (blue) and t= 44 min (green) at a temperature of 105 °C with application of a nitrogen flow.
Figure 7b. Intensity of the C=C stretching bands of the 30 SA moiety between 1575-1655 cm-1 as a function of time.
35
Figure 7c. Intensity of the trans C=H- wag band from the SA moiety between 945-1055 cm'1.
Figure 8. TGA curves of uncured (red) and cured (green) 5 LD0SA1_1 resin. The LD0SA1_1 resin was cured at 70-90 °C using 3 wt% MEK.
Figure 9. TGA curves of cured LDOSAl_l/myrcene=95/05
(blue) and LDOSAl_l/myrcene=90/10 (red). The 10 samples were cured at 90 °C using 3 wt% MEKP
as initiator.
Figure 10. TGA curve of a cured LOAA resin (green) and LD0AA1_1 resin (blue). The samples were cured 15 at 90 °C using 3 wt% MEKP as initiator.
Figure 11. Stress-strain curves during compression of LD0SA1_1 after a) 0 weeks in water b) 4 weeks 20 in water and LDOSAl_l/myrcene=90/10 c) 0 weeks in water d) 4 weeks in water.
Examples 25 Starting materials - Limonene dioxide (LDO) and sorbic acid (SA)
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 30 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 36 is obtained commercially from citrus fruits through two primary methods: centrifugal separation or steam distillation.
Sorbic acid, or 2,4-hexadienoic acid, is a natural organic 5 compound used as a food preservative. It is a colorless solid that is slightly soluble in water and sublimes readily. It was first isolated from the unripe berries of Rowan (Sorbus aucuparia), hence its name. Sorbic acid and its salts, such as sodium sorbate, potassium sorbate, and 10 calcium sorbate, are antimicrobial agents often used as preservatives in food and drinks to prevent the growth of mold, yeast, and fungi. In general 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 15 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 20 be produces from oil-based feedstock, production from biobased feedstock is feasible. One of the starting materials to prepare sorbic acid is crotonaldehyde. This is a chemical compound with the formula CH3CH=CHCHO. The compound is usually sold as a mixture of the E- and Z- isomers, which 25 differ with respect to the relative position of the methyl and formyl groups. The E-isomer is more common. 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 30 the production of sorbic acid is ketene. Another option to produces sorbic acid is by reaction of acetone with crotonic acid.
37
Example 1
Step A synthesis of resins: reaction of a terpene oxide or dioxide with a carboxylic acid or acid chloride 5 Step B acetylation: reaction of resin as obtained by step a) with an anhydride to reduce the number of free hydroxyl groups .
1) a) LDO + SA: LDOSA 1_1 10 2) b) LD0SA1_1+ AAnh: LDOSA_AAnh 3) a) LDO + AA: LDOAA 1_1
4) a) LO + SA: LOSA
5) a) LO + AA: LOAA
6) b) LOAA + AAnh: LOAA_AAnh 15 1) a) LDO + SA: LD0SA1_1 (glass reactor) 96.3 g (0.86 moles) SA, 2.44 g TEBAC (1.25 mol% based on LDO) and 143 mg hydroquinone (0.06 wt% based on weight LDO + 20 SA) were added to a 300 ml double wall glass reactor, equipped with motorized stirrer and nitrogen inlet. The reactor was heated to 80 °C whereas the powder mixture (SA + TEBAC + hydroquinone) was homogenized by stirring at 250 rpm. After approximately 15 min stirring at 80 °C, 144.4 g 25 (0.86 moles) LDO was slowly added. The temperature was subsequently increased to 91 °C. At TR = 91 °C, tR = 0. The reaction mixture became transparent after approximately tR = 0.5 h. After tR = 8 h, the reaction was cooled down to room temperature. A transparent yellow/orange viscous liquid 30 (237.2 g yield) was obtained.
2) b) LDOSA + AAnh: LDOSAl_l_AAnh (glass reactor) 38 100 g (0.36 moles) LDOSA was added to a 1 liter double wall glass reactor equipped with motorized stirrer and nitrogen inlet. The LDOSA resin was heated to 70 °C and subsequently 45.5 g acetic anhydride (125 mol% based on 5 LDOSA) was slowly added at a stirring rate of 250 rpm. The reaction temperature was subsequently cooled to 40 °C. As soon as TR = 40 °C, tR = 0 and 1.99 g Mg (0104)2 (2.5 mol% based on LDOSA) was added over 1 hours in portions of approximately 0.5 g. The flakes of Mg(0104)2 dissolved 10 slowly. After tR = 6 h, the reaction was cooled down to room temperature.
Acetic acid excess removal 200 ml dichloromethane was added to the reactor to 15 dissolve the LDOSA_AAnh resin. Subsequently, a saturated
NaHC03 solution was slowly added to the reaction mixture under stirring (350 rpm) until no longer development of CO2 occurred. The stirring was stopped and the two phase mixture was added to a separation funnel and allowed to 20 phase separate. The dichloromethane layer was removed and washed once again with pure water. The washed dichloromethane layer was subsequently dried of anhydrous magnesium sulfate and filtrated. The clear yellow colored dichloromethane layer was concentrated using a rotary 25 evaporator. A clear yellow oil was obtained.
3) a) LDO + AA: LDOAA (glass reactor) 30 160.3 g LDO (0.95 moles) + 68.8 g AA (0.95 moles) was added to a 1 liter double wall glass reactor, equipped with motorized stirrer and nitrogen inlet. The stirring rate was set at 250 rpm whereas the temperature of the reactor was 39 kept at 20 °C. A powder mixture of 2.17 g TEBAC and 135 mg hydroquinone was added in portions during a period of 30 min. The temperature was then increased to 60 °C in 2 hours. After 2 hours at 60 °C, the temperature was increased to 80 5 °C in 2 hours. The reaction was kept for 30 min at 80 °C and then cooled to room temperature.
4) a) LO + SA: LOSA (heating block) 10 7.03 g (0.046 moles) LO, 4.64 g (0.041 moles) SA, 156 mg TEBAC (1.5 mol% based on LO) and 5 mg hydroquinone (0.04 wt% based on weight LO + SA) were added to a 20 ml glass vial containing a stirring magnet. The vial was capped with a Teflon coated rubber and placed in a heating block at 85 °C.
15 The stirring rate was 500 ppm. After 6.75 h, the reaction was stopped. A transparent yellow viscous liquid was obtained.
5) a) LO + AA: LOAA (glass reactor) 20 80.1 g (0.53 moles) LO, 1.11 g TPP (0.8 mol% based on LO) and 47 mg hydroquinone (0.04 wt% based on weight LO+AA) were added to a 300 ml double wall glass reactor, equipped with motorized stirrer and nitrogen inlet. The reactor was heated 25 to 50 °C whereas the mixture (LO + TPP + hydroquinone) was homogenized by stirring at 250 rpm. After approximately 15 min stirring at 50 °C, 37.9 g (0.53 moles) AA was slowly added to the reaction mixture. The temperature was subsequently increased to 91 °C. At T = 91 °C, tR = 0. The 30 reaction was stopped after tR = 8 h. A transparent yellow low viscous liquid (116.4 g yield) was obtained.
40 6) b) LOAA + AAnh: LOAA_AAnh (glass reactor) 29.31 g (0.1293 moles) LOAA, 580 mg Mg(Cl04)2, (2 mol* based on LO) and 16.6 g (0.1616 moles) acetic anhydride 5 (AAnh) were added to a 300 ml glass reactor equipped motorized stirrer and with nitrogen inlet. The stirring rate was set at 250 rpm and the temperature was subsequently increased to 40 °C. At T = 40 °, tR = 0. The flakes of Mg(C104)2 slowly dissolved. At tR = 6 h, 10 the reaction was stopped.
Purification: removal of acetic acid A saturated solution of NaHCC>3 in water was prepared.
15 The prepared LOAA_AAnh mixture was dissolved in 200 ml dichloromethane and extracted with the saturated NaHCC^ solution in a separation funnel. When the CO2 development became less, the aqueous layer was removed from the dichloromethane layer. The dichloromethane 20 layer was put back into the separation funnel and subsequently washed again with a new portion of NaHC03 solution. The washing procedure was repeated until the CO2 development ceased. The dichloromethane layer was collected and dried over anhydrous magnesium sulfate.
25 The dichloromethane layer was subsequently filtrated and concentrated using a rotary evaporator.
41
Analysis of the resins according step a) by 1H-NMR
1) LOAA 1H-NMR
2) LDOSA 1H-NMR
5 Analysis of LOAA resin by 1H-NMR spectroscopy
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 10 expected product LOAA are schematically depicted in table la and lb, respectively. The 1H-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 1H-NMR spectra. Two 15 isomers are formed which differ from each other by the position of the ester group and adjacent hydroxyl group.
This can be concluded from the presence of two peaks (al) and (a2) (triplets) at 4.14 and 4.91 ppm in the 1H-NMR spectrum of LOSA resin (see figure 2). The original peaks 20 corresponding to proton (a) at approximately 3 ppm (see figure 1) are almost not present anymore in the 1H-NMR spectrum of LOAA. These peaks are now shifted downfield to 4.14 and 4.91 ppm due to the presence of electron withdrawing ester groups and hydroxyl groups adjacent to 25 proton (a).
The doublet corresponding to proton (c) of the starting compound AA (see table 2a) is located at 5.82/5.84 ppm.
After the formation of the hydroxyl ester with LO, proton (b) gives two doublets with positions at 5.76/5.79 ppm and 30 5.84/5.87 ppm. The presence of these two doublets shows that two isomers are present which is in agreement with the presence of two peaks originating from protons (al) and (a2) .
42
Table la. Chemical structures of LO and AA H Cis/trans
H LO
π H
(a) (d)
Η O
(0
H
(b)
Table lb. Chemical structures of product LOAA resin Ö
LOAA 1 H
(al) LOAA 2
(a2) I
5 1H-NMR analysis of LDOSA resin
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 10 in table 2a. When cis/trans LDO reacts with 2 moles SA, 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, 43 although the chemical shift might change a bit due to difference in chemical structure.
Table 2a. Chemical structures of LDO and SA
lX^(p2) h,c xr ch , „ (pD LD° ö
XX I SA
(d) (b) 5
Table 2b. Different possible isomers of LD0SA1_2 _ f —oh o ?h3 _O (c) (e) o ho—0~^^^^ch3 LD0SA1_2 1 II H (b) (d) 0_<u (d) (b) _
f -OH O
9 ?H3 _II (c) (e) °~Λ^ί?^^\0Η3 LD0SA1_2 2 H;C/V/V/ I » (b) (d) (d) (b) CH2
OH
ch3 9 II (C) (e) ch3 ^^^ch3 I i X_oh (W (d> ο LD0SA1_2 3
(e) (c) I
yv i1-O-CH2 H3C"^ (d) (b) Ö 0 π W (e) 0 CH3 Nsi^Ns^iNsCH3 II I JL ___oh (b) (d) (e) (0 \\_0_LD0SA1_2 4
(d) (b) OH
OH
44
The 1H-NMR spectrum of cis/trans LDO is shown in figure 3. The peaks around 2.5 and 3 ppm originate from protons (pi) and (p2) which are part of the monosubstituted (pi) and 5 disubstituted (p2) epoxy rings.
It was observed that a reaction of 1 mole LDO with 2 mole SA resulted in a wax-like product. 1H-NMR spectroscopy showed that a significant fraction of unreacted SA was still present. Therefore the ratio SA/LDO was reduced to 1/1.
10
Figure 4a shows the 5.6-5.9 ppm region of the 1H-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 1H-NMR spectrum corresponding 15 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. Also some underlying smaller peaks appear to be present. Hence, LDOSAl_l consists of multiple compounds having SA esters bonds. Proton (c) of pure unreacted SA 20 gives a multiplet between 7.3 - 7.4 ppm. Since no peaks are observed in this specific region in the 1H-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. Furthermore, multiple peaks are present between 3-4 ppm.
25 These peaks may be result of protons next to an ether linkage which are usually located between 3 and 4 ppm.
45
Example 2: Control of viscosity 1) Reducing the number of free hydroxyl groups by esterification with acetic anhydride (acetylation) 5
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 10 combination with fillers (like woodchips, cork, sand) or fibers (glass, carbon, flax, etc).
2) Addition of reactive diluents: myrcene, styrene, acrylics, glycidyl ethers.
15 the viscosity of the LDOSA resin (but also of the 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 20 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.
25 3) Reducing the ratio SA/LDO from 1/1 to 0.75/1: Another way to decrease the viscosity is by increasing the molar ratio of LDO/SA. When a ratio of LDO:SA=l:l is used, a highly viscous resin at room temperature is 30 obtained. A molar ratio of LDO:SA=1:0.75 results in a decreased viscosity at room temperature. This resin shows good curing behaviour. When the ratio LDO:SA= 1:0.625 is used the cured LDOSA1_0.625 resin is rubber 46 like at 90 °C and a solid material at room temperature. This solid material easily breaks. Accordingly, the method according to the present invention allows tuning the rate of the polymer network produced.
5 47
Example 3: Step C Free-radical polymerization: curing of resins obtained via step a) and additionally b) 1) Example: curing of LDOSAl_l/myrcene=90/10 with thermal 5 initiator + Co-accelerator 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.
10 Subsequently, 32.25 g LD0SA1_1 resin (90 wt%) was mixed with 3.58 g myrcene (10 wt%), containing 0.1 wt% Co(II). Subsequently, 0.73 g cumene hydroperoxide (CHP) (2 wt% based on total weight LD0SA1_1/myrcene mixture) was added to the LD0SA1_1/myrcene mixture and mixed.
15
The mold was filled at room temperature and subsequently placed in an oven at 40 °C. A N2 flow was purged through the oven. After 2h at 40 °C, the material was almost hard. After 3 h at 40 °C, the sample was hard and the temperature was 20 increased to 90 °C. After 1 h at 90 °C, the oven was put under vacuum and the samples were kept in the oven overnight and removed the next morning.
2) Curing of LDOSAl_l coating with ÜV initiator 25 3.0 g LD0SA1_1 and 62 mg Irgacure® 184(2 wt% based on 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 30 substrate. A coating of 20 ym 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 48 LD0SA1_1 coating formed a hard layer on top of the glass substrate.
3) Composite preparation: LD0SA1_1 resin with norm sand as 5 filling material LD0SA1_1 : norm sand = 12.5 wt% : 87.5 wt% 66.2 g LD0SA1_1 (12.5 wt% of total weight) was weighed in a 10 glass beaker to which 1.66 g of initiator tert-butyl peroxybenzoate (TBPB) (2.5 wt% of weight LDOSAl_l resin) was added. The initiator and resin were homogeneously mixed. Subsequently, 463.7 g (87.5 wt% of total weight) norm sand was added. The norm sand was homogeneously mixed with the 15 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 LDOSAl_l resin. After 20 min, the LD0SA1_1 resin/sand mixture was mixed again shortly with a 20 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. To improve the packing in the mold, the resin/sand mixture was pressed on top with a cylinder of the same surface dimensions.. The silicon mold 25 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. The 30 temperature was then reduced to 100 °C and the mold was left overnight in the oven under vacuum. The samples were removed next day and the top surface of each sample was flattened by cutting with a water saw.
49 90 wt% LD0SA1_1 + 10wt% myrcene : norm sand = 12.5 wt% : 87.5 wt% 5 72.2 g LD0SA1_1 resin (90 wt% of total monomer mixture) and 8.02 g myrcene (10 wt% of weight LD0SA1_1/myrcene mixture) were weighed a glass beaker. Subsequently, 2.41 g MEKP solution was added (3 wt% of weight LDOSAl_l/myrcene mixture) and homogeneously mixed with the LD0SA1_1/myrcene 10 mixture. The addition of myrcene decreased the viscosity of the LD0SA1_1 resin. Subsequently, 560.3 g (87.5 wt% of total weight) norm sand was added. The norm sand was homogeneously mixed with the LDOSAl_l/initiator mixture by a mechanical stirrer. The mixture was subsequently poured into a pre-15 heated silicon mold containing cylindrical spaces with a length of approximately 30 mm and a diameter of approximately 28 mm. To improve the packing in the mold, the resin/sand mixture was pressed on top with a cylinder of the same surface dimensions. The oven was set at 70 °C at which 20 the silicon mold was placed into the oven. A vacuum of 700 mbar was applied. After 2 hours curing, the temperature was increased to 90 °C and the vacuum was released; a nitrogen flow was purged through the oven instead. After 5 hours of curing, a vacuum was applied and the samples were allowed to 25 cure for approximately 48 hours. The samples were then removed from the oven and the top surface of each sample was flattened by cutting with a water saw.
4) Composite preparation: LD0SA1_1 resin with glass fiber 30
An isotropic glass fiber mat of approximately (1 x b) 27 x 21 cm (1 glass mat weighs about 25-27 g) was placed in a 50 silicon mold. Subsequently, the glass fiber mat was impregnated with LDOSAl_l/myrcene = 90/10 resin using a roller that is used for hand lay-up applications. After complete impregnation, a second glass fiber mat was placed 5 on top and subsequently impregnated with the resin. This was repeated for the third and fourth glass fiber mat layer.
The upper impregnated glass fiber mat was covered with a silicon sheet on top of which a metal plate (1 x b = 27 x 21 cm) was placed. The whole mold was placed in a press at 10 approximately 0.05 bar pressure to remove excess of resin which came out of the mold. The mold was subsequently placed in an oven at 90 °C. On top of the metal plate, a weight of 10 kg was placed. A vacuum of 800 mbar was applied. After 3 hours, the vacuum was set at < 10 mbar. The plate was left 15 in the oven for 72 hours. For preparation of the glass reinforced plate, a total of 104 g glass fiber and 140.7 g LD0SA1_1 resin was initially used. A specific fraction of resin came out of the mold when the mold was placed in the press. The final plate after curing weighed 198 g. Assuming 20 that the amount of glass fiber did not change (104 g), then the weight fraction glass fiber is 52.5 wt% and the residual fraction of cured LD0SA1_1 resin is 47.5 wt% (94 g).
25 51
Example 4: Analysis of the resins before and after curing ( curing according to step C) IR spectra of LD0SA1_1 before and after curing 5
The 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 10 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. Also the C-0 stretching band at 1242 cm"1 shows that an ester is present. A sharp absorption 15 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 confirmed with certainty. The C=C stretching bands at 1644 and 1617 cm"1 are clearly present in LD0SA1_1 which implies 20 that LDOSAl_l theoretically can cross-link via free-radical polymerization.
52
Table 3. IR absorption bands for uncured LD0SA1_1 resin IR absorption bands LDOSA Wavenumber, cm'1 OH stretching and hydrogen bonded OH 3200-3600 stretching C=0 stretching, SA ester 1703 C=C symmetric stretching SA 1644 C=C antisymmetric stretching SA 1617 trans-trans C-0 stretching, SA ester 1243 and 1186 most likely C-0 stretching, tertiary alcohol or C-0 stretching, secondary alcohol or C-O-C antisymmetric stretching or C-O stretching, SA ester 1136
Trans =C-H wag from SA ester 997 C-O-C symmetric stretching 869? C-O-C symmetric stretching
Or In-phase C-C-0 stretch from secondary/tertiary alcohol 800? 5
Figure 6 shows the IR spectrum of a LD0SA1_1 resin that was cured at 90 °C using 3 wt% MEKP. It can be seen that the bands corresponding to the C=C stretching band around 1645 and 1617 cm"1 have almost disappeared after curing. The clear 10 C=0 stretching bond at 1721 cm"1 show that ester bonds are still present.
Curing of LDOSAl_l_AAnh monitored by FTIR.
The curing kinetics of LDOSAl_l_AAnh was studied with IR spectroscopy. The sample was heated on a golden gate at T = 105 °C under inert nitrogen atmosphere. Figure 7a shows the 15 53 IR spectra at t = 0.5 min (blue) and t = 44 min (green), respectively. The intensity of the C=C stretching bands and trans C=H wag as a function of polymerization time is shown in figures 7b and 7c, respectively. It can be seen that the 5 intensity of both absorption bands decreases as a function of curing time. This implies that the double bonds of the SA moiety react during the curing step.
10 Thermal Gravimetric Analysis (TGA) of resins before and after curing
To analyze the influence of curing on the thermal stability, TGA measurements were performed. The TGA curves of uncured 15 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 20 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 25 polymerization occurred and that no significant fraction of low molecular weight material is left.
54
Table 4. Curing conditions LD0SA1_1 Curing conditions LDOSAl_l with 3 wt% MEKP
3 h at 70 °C + N2 2.75 h at 90 °C + N2 overnight at 90 °C + vacuum
Figure 9 shows the TGA curves of cured LDOSA/myrcene = 90/10 and LDOSA/myrcene=95/05. These thermosets are stable up to 5 approximately 177 °C (weight loss < 1%). The slight difference in thermal stability compared with LD0SA1_1 resins without myrcene (see figure 8) shows that myrcene is copolymerized with the SA moieties of the LDOSA resin.
Figure 10 shows the TGA curves of LOAA and LD0AA1_1 after 10 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) .
15 DMTA measurements of cured resins
The results from DMTA measurements are summarized in table 5.
Table 5. DMTA measurements of cured resins Cured resin Tg [°C] E' [GPa] E' ' [MPa]
at 25 °C at 25 °C
LOAA nTd nTd nTd los a nTd nTd nTd LD0AA1_1 NTD nTd nTd LD0SA1_1 98 2T7 74 90 wt% LD0SA1_1/ 96 O 47 5 wt% myrcene 90 wt% LD0SA1_1/ 93 ΓΤδ 5Ö 10 wt% myrcene LDOAAl_l_AAnh N/D nTd nTd LDOSAl_l_AAnh NAD nTd nTd 20 55
Example 5: Mechanical testing of cured resins
Compression tests
Several cylinders (1 = 21 mm, d = 23 mm) were made by pouring LD0SA1_1 (additionally with myrcene) in a silicon 5 mold with cylindrical holes. The curing conditions are summarized in table 6.
Table 6. Curing conditions for the preparation of cylinders of LD0SA1_1 and LD0SA1_1/myrcene resins
Resin Initiator Curing conditions 100 wt% LD0SA1_1 3 wt% 2.5 h at 70 °C + 600-700 mbar MEKP 2 h at 90 °C + N2 flow overnight at 90 °C + 0 bar 90 wt% LD0SA1_1 + 3 wt% 1.5 h at 65 °C + 800 mbar 10 wt% myrcene MEKP 3 h at 90 °C + 800 mbar overnight at 90 °C + 0 bar 9 h at 100 °C + 0 mbar 10
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 15 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.
20
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- 56 strain curve of LD0SA1_1 (0 weeks) shows glassy behavior. As soon as plastic deformation occurs (after reaching the yield stress), the material suddenly breaks which results in the formation of a conical shape. After a storage time of 4 5 weeks in water, 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, 10 but small pieces gradually leap away from the edge of the cylinder so that the compressive stress is maintained more or less constant.
The addition of myrcene to LDOSAl_l results in a less 15 brittle behavior as can be seen from figure 11c. The cured LDOSAl_l/myrcene=90/10 resin does not break after reaching its yield strength.
The water uptake after 4 weeks was not measured. However, the increased ductility is shown from the stress-strain 20 curve as shown in figure lid. The material does no longer break. After reaching the yield stress, the stress continuously increases. The cylinder flattens (increase of the strain) and its surface becomes broader (barrelling effect).
25
Table 7 gives an overview of the yield strength and compression modulus of cured LD0SA1_1 and LDOSAl_l/myrcene=90/10 cylinders as a function of storage time in water.
30 57
Table 7. Results obtained from compression tests of cured LD0SA1_1 and LDOSAl_l/myrcene=90/10 cylindrical shaped samples
Number of weeks in water
Sample ~g Π Γ4 Π} name £ ay E ay E ay E ay [GPa] [MPa] [GPa] [MPa] [GPa] [MPa] [GPa] [MPa] ΪΤβ Ϊ4Ϊ 174 128 175 Ϊ28 175 Ϊ24 LD0SA1 1 1.5 133 1.6 137 1.5 136 1.5 127 LD0SA1_1/ ΪΤ4 ÏÖ5 ITT ÏÖÖ Ο ΪΙΪ ΓΤ3 96 myrcene 1.3 100 1.3 111 1.4 103 1.4 99 = 90/10 5
The compression tests were also performed on LDOSA samples that were stored in aliphatic and aromatic media. The results of these compression tests are shown in table 8.
10 From this table, it is observed that LD0SA1_1 resin after curing is resistant to apolar aliphatic and aromatic solvents but not to polar solvents.
58
Table 8. Compression tests on LDOSA samples which were stored in other media than water
Sample Medium Residence Compressive Compressive time strength modulus LD0SA1_1 + Reference 0 weeks 152 1.6 3 wt% MEKP 149 1.5 after Toluene 2 weeks 146 1.6 curing at 4 weeks 147 1.5 90 °C Heptane 2 weeks 150 1.7 4 weeks 146 1.5
Acetone Fell into small pieces after about 1 week: not resistant against acetone Chloroform Fell into small pieces after about 1 week: not resistant against chloroform
Ethanol Fell into small pieces after about 1 week: not resistant against chloroform
Tensile tests 5 1) Pure resins
From several resins, dumbbell shaped tensile bars were prepared which were subsequently cured in the oven. The tests were performed on a Zwick tensile tester using a 10 tensile strain rate of 2 mm/min. The results from the tensile tests are shown in table 9.
Table 9. Tensile properties of cured resins
Tensile modulus Tensile strength [GPa] [MPa] LD0SA1_1 ΓΓβ 27 ' 59 LDOSAl_l/myrcene=90/10 1.6-2.0 23-32 LOAA 2 Ï7 LDOAA 273 14 2) Glass fiber reinforced LDOSAl_l/myrcene=90/10 5 A glass fiber reinforced plate was prepared from LDOSAl_l/myrcene=90/10 (see example 3.4). From this plate, several bars were cut in two different sizes (1 x w = 10 x 20 cm and 12 x 21.5 cm). These bars were used for tensile tests. For the tensile testing, a strain rate of 2 mm/min 10 was used. The results are shown in table 10. The samples show a tensile modulus between 8.5-9.6 GPa and a tensile strength between 116-154 MPa.
Table 10. Results from tensile tests of 15 'LDOSAl_l/myrcene=90/10 reinforced with isotropic glass fiber mats
Sample Tensile Tensile
Number L* W modulus strength [GPa] [MPa]
SÏ 110 10.38 875 III
52 110 12.27 8.6 116 53 110 12.25 8.9 143 54 110 12.22 9.0 148 55 90 10.32 9.6 154 56 90 10.35 9.1 146 L*: distance between the clamps in mm 1039738 20
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| WO2011104704A2 (en) * | 2010-02-24 | 2011-09-01 | Corona Dent. Ltd. | Long lasting dental restorations and methods for preparation thereof |
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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 (en) * | 2010-02-24 | 2011-09-01 | Corona Dent. Ltd. | Long lasting dental restorations and methods for preparation thereof |
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