Classifications

• • 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
  • C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/10—Epoxy resins modified by unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
  • C09J163/10—Epoxy resins modified by unsaturated compounds

Definitions

• the present invention relates to a method for the manufacture of a polymer network. Further, the present invention relates to the manufactured polymer network and to a composite material comprising the polymer network.
• the present invention relates to adhesives and coating materials comprising said polymer network.
• 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
• US 4,074,008 describes epoxy resins polymerizing on exposure to actinic radiation having at least two photopolymerizable groups and at least two 1,2-epoxide groups per molecule in the presence of aromatics, ketone, alcohol, or ether based solvents. Further, in US 4,074,008, the used materials are photopolymeri zed and the remaining epoxide groups are subsequently cross-linked with a curing agent such as an aromatic amine or polythiol at a temperature of 100-200 °C. US 3,936,366 describes compounds having at least three
• 3-sorboyloxy-2-hydroxypropyl groups directly attached to ether oxygen atoms and polymerized by exposure to actinic radiation in the presence of a sensitizer may be obtained by the reaction in organic solvents of sorbic acid with a substance having at least three glycidyl ether groups or of glycidyl sorbate with a substance having at least three phenolic or alcoholic hydroxyl groups. More specifically, the sorbic acid is reacted with epoxy groups. The resulting ester is subjected to actinic radiation to result in polymerization.
• the cross- linking itself is achieved by the reaction of 1,2-epoxide groups with a heat-curing agent.
• linking compound having conjugated carbon-carbon double bonds or a carbon-carbon triple bond as well as a moiety capable of reacting with an epoxy group.
• An example is sorbic acid; with
• the polymerized acrylic portion is covalently linked with the polymer by previously mentioned linking compound.
• SA sorbic acid
• ESA ethyl sorbate
• polymer networks derived from natural sources also designated as bio-based polymer networks.
• the goal of the present invention is to provide a polymer network 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, as well as providing a method that does not present the drawbacks of the prior art. More specifically, this goal is achieved by the method for the manufacture of a sorbic acid-based polymer network
• glycidylether reacts with one or more compounds comprising a sorbic acid-based moiety, such as one compound, two or more compounds, three or more compounds, four or more compounds, five or more compounds, six or more compounds.
• the amount of compounds reacting with the glycidylether depend the amount of glycidyl unit present in the glycidylether. For example, when the glycidylether is a diglycidylether , one compound comprising a sorbic acid-based moiety or two compounds comprising a sorbic acid-based moiety can react with the diglycidylether .
• a glycidylether is a compound comprising an ether functional group -0- and a cyclic ether unit, also
• a monoglycidylether is represented in formula (1) and a diglycidylether is
• R represents an alkyl chain, a cycloalkyl or an aryl. R can be substituted or unsubstituted .
• the compound comprising a sorbic acid-based moiety can be sorbic acid, or a derivate of sorbic acid, such as sorboyl chloride (also designated as sorbic acid chloride) .
• Sorbic acid (also designated as 2 , 4-hexadienoic acid and abbreviated as SA) , is a natural organic compound used as a food preservative. It has the chemical formula C 6 Hs0 2 . Sorbic acid is represented in formula (3) .
• sorboyl halide is sorboyl chloride.
• Sorbic chloride can also be designated as 2 , 4-hexadienoyl chloride, sorbic acid chloride, or sorboyl chloride.
• the compound comprising the sorbic acid-based moiety according to the present invention can also comprise substitutions on said moiety, such as alkyl rests,
• a C 1 -C6 alkyl such as a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl .
• the sorbic acid-based moiety according to the present invention can also be substituted by one or more alcohol functions (also designated by hydroxyl, -OH) or by one or more carboxylic acid functions (-COOH) .
• Muconic acid is an example of a compound comprising a sorbic acid moiety substituted with a carboxylic acid group.
• the sorbic acid- based moiety comprises two double carbon bonds that are conjugated.
• conjugated diene moiety it can also be designated as a conjugated diene moiety.
• the compound comprising the conjugated diene moiety can also be muconic acid.
• the reaction products of a glycidylether and the one or more compounds comprising a sorbic acid-based moiety depend on the ratio of both reactants. This reaction results in the formation of a hydroxy-ester. The resulting products
• the ratio (equivalents) of glycidylether to the compound comprising a sorbic acid-based moiety can be 1:1-2. Said ratio can take any values in that range, such as 1:1.1, 1:1.2, 1:1.3,
• polyglycidylether (comprising 3 or more glycidylether units) can react with more than two sorbic acid molecules.
• R represents a linear alkyl, a cycloalkyl or an aryl .
• the linear alkyl is a C 1 -C 1 2 alkyl. More advantageously, R is chosen from the group comprising methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, and n-hexyl .
• the linear alkyl can be unsubstituted or substituted by an alkyl, an aryl, a functional group chosen from the group alcohol (- OH) , ketone (-CO-) , halogen, a thiol (-SH) .
• the cycloalkyl is chosen from the group cyclohexyl,
• the cycloalkyl may or may not be substituted by an alkyl, an aryl, a functional group chosen from the group alcohol (-OH) , ketone (-CO-) , halogen, a thiol (-SH) .
• the aryl is chosen from the group a phenyl, a benzyl, a naphtyl .
• the aryl may or may not be substituted by an alkyl, an aryl, a functional group chosen from the group alcohol (-OH) , ketone (-CO-) , halogen, a thiol (-SH) .
• step a) the glycidylether and the one or more compounds comprising a sorbic acid-based moiety react together and can subsequently polymerize.
• the products obtained in the method of the present invention can also be designated as a resin.
• the resin materials obtained in step a) have reactive conjugated carbon-carbon double bond so that curing via a free radical polymerization process is possible. Free radicals are obtained in order to carry out the polymerization, via thermal or UV initiation using suitable peroxides.
• the resins obtained after step a) can either be stabilized with a suitable inhibitor or be polymerized (without initiators and inhibitors) under suitable conditions like: elevated
• step c) is a polymerization step, namely a cross-linking step.
• the cross-linking is achieved by free radical polymerization.
• step c) is advantageously a free radical polymerization.
• the free radical polymerization comprises an initiation step, a propagation step and a termination step.
• the sorbic acid-based moiety only is responsible for the cross-linking. Accordingly, in the method of the present invention, the cross-linking is not achieved by a polycarboxylic acid anhydride or a heat curing agent.
• the method of the present invention provides a polymer network that is easier to handle and for this reason, the polymer network obtainable by the method according to the present invention also provides the possibility of modifying its physical properties with the presence of additives, for example, is applicable for all aspects and embodiments of the present invention.
• compositions obtained by the method of the present invention are compositions obtained by the method of the present invention.
• the sorbic acid moiety is polymerized to result in a cross-linked network.
• step b) reacting the product obtained in step a) with an acid anhydride or an acyl halide.
• the method for the manufacture of a sorbic acid-based polymer network can be described as comprising:
• step b) reacting the product obtained in step a) with an acid anhydride or an acyl halide; and c) polymerizing the product obtained in the preceding step into a polymer network.
• the acid anhydride is an organic compound that has two acyl groups bound to the same oxygen atom.
• the acyl groups are derived from the same carboxylic acid, the formula of the anhydride being (R'C(0)) 2 0, wherein R'can be an alkyl or an alkenyl .
• R' may be, for
• an alkyl group of any length but preferably an alkyl group comprising at most 6 carbon atoms, more
• R' can also be an alkenyl comprising at least one carbon-carbon double bond, such as one, two or three carbon-carbon double bond.
• Symmetrical acid anhydrides of this type are named by replacing the word acid in the name of the parent carboxylic acid by the word anhydride. Thus, (CH 3 CO)20 is called acetic anhydride.
• Symmetrical, mixed (or unsymmetrical ) acid anhydrides, or cyclic anhydride are examples of the anhydrides used in step b) .
• the acid anhydride is preferably selected from the group propionic anhydride, acetic anhydride, formic anhydride, acrylic anhydride, methacrylic anhydride, cinnamic anhydride.
• the cyclic anhydrides are preferably selected from the group maleic anhydride, phthalic anhydride, itaconic anhydride, citraconic anhydride, succinic 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) .
• X halogen atom
• R'COX where R' may be, for example, an alkyl group of any length, but preferably an alkyl group comprising at most 6 carbon atoms, more preferably at most 4 carbon atoms, even more preferably at most 3 carbon atoms, most preferably at most 2 carbon atoms.
• R' can also be an alkenyl comprising at least one carbon-carbon double bond, such as one, two or three carbon-carbon double bond.
• CO is the carbonyl group
• X represents the halide, such as chloride.
• the acyl chloride is chosen from the group acryloyl chloride, methacryloyl chloride, acetyl chloride.
• the effect of step b) is predominantly to reduce the viscosity of the product and/or additionally to increase the number of reactive functional groups to increase the cross ⁇ link density of the polymer network.
• 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 a) varying the ratio of glycidylether to compound comprising a sorbic acid-based moiety
• step b) by modification of the product (resin) by reaction with an acid anhydride or an acyl halide (step b) ) ; and/ or
• step c) i.e. during or after step a), during or after step b) .
• a predetermined viscosity is a 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
• a further step carried out before step c) can be carried out to control the viscosity of the resin to be a liquid prior to carry out step c.
• the viscosity of the product obtained in the steps preceding step c) is in a liquid form at the moment of polymerization in step c) .
• step b) when step b) is carried out, no polymerization occurs in step a) .
• the method steps are preferably 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
• the method according to the present invention provides products with high yields so that additional purification steps are not necessary.
• step a) and b) are carried out at a temperature suitable to carry out the reactions as well as providing a reaction mixture that has a controlled viscosity.
• step a) of the method according to the present invention is carried out at a temperature below 100 ° C.
• step b) of the method according to the present invention is carried out at a temperature in the range 10 ° C to 60 ° C.
• Step b) can also be carried out at higher temperature than 60 ° C (i.e. 80 ° C-90 ° C) if the catalyst used in step b) allows it, or if no catalyst is used.
• Step b) can also be carried out at a temperature between 0 ° C and 20 ° C, if the reactivity of the reaction carried out in step b) is exothermic (i.e. with acyl halides, reactions are performed at 0 ° C at first and when the acyl halide is added, the reaction is carried out at room temperature) .
• step b) is advantageously so that the viscosity of the products is sufficiently low to provide a good mixing in the machinery or apparatus in which the method of the present invention is carried out.
• step a) and/or b) of the method comprise a step wherein the viscosity is controlled.
• Step b) has the effect of controlling, or if necessary decreasing, the viscosity of the resin obtained in step a)
• the viscosity of the reaction products is sufficiently low so that moulds or reactors can be easily filled prior to the curing
• reinforcing materials such as glass fiber mats can be easily impregnated with the resin after step a) or step b) .
• step a) is carried out at a temperature of at most 100 ° C at the moment of mixing the reactant participating in the reaction of step a) .
• the temperature is at most 91 ° C, more
• the temperature is in the range 85-91 ° C.
• the temperature can also be raised of about 2-10% (preferably 5- 8%) of the reaction temperature, at the end of step a), i.e. once the glycidylether and the sorbic acid-based moiety have reacted .
• 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
• 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.
• the polymerization is step c) , that is a free radical polymerization (i.e. curing) can be done thermally (addition of thermally decomposable initiators) or by UV-irradiation (addition of photo initiators).
• step c) is carried out at a temperature of at most 150 ° C, preferably at most at 140 ° C.
• the temperature is in the range 10 to 150 ° C, 10 to 140 ° C, 10 to 100 ° C, more advantageously in the range 10 to 90 ° C.
• the polymerization is carried out at a temperature of at least 10 ° C, more advantageously at least 20 ° C.
• the polymerization can be preferably carried out at room temperature, i.e. at atmospheric pressure at
• step c) is a curing step
• the curing temperature is at room
• 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) and step c) may be carried out at the same temperature.
• steps a) and/or c) no additional solvent is required in the method. This is to be understood that no 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 environment is involved in step a) and/or step c) of the method according to the present invention. Furthermore, no difficult separation of the solvent from the final products is necessary.
• the polymerization in step c) is carried out in the presence of an initiator.
• polymerization initiator can be selected from the
• peroxy compounds such as peroxides, peroxycarbonates and peresters. Combinations of peroxy compounds can also be used.
• suitable peroxy initiators are C6-C20 acyl peroxides such as decanoyl peroxide, benzoyl peroxide, octanoyl peroxide, stearyl peroxide, 3 , 5 , 5-trimethyl hexanoyl peroxide, per- esters of C 2 -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 10 ) peroxides such as diisopropylbenzene hydroperoxide, di-t-butyl peroxide, cumyl hydroperoxide, dicumyl peroxide or combinations thereof.
• Radical initiators different from peroxy compounds are not excluded.
• a suitable example of such a compound is , '- azobisisobutyronitrile .
• the amount of radical initiator is suitably from 0.01 to 3% wt, based on the weight of the product obtained after steps a) or b) . Further, an
• accelerator may be added.
• Examples are cobalt naphthenate, cobalt octoate, cobalt acetate, cobalt neodecanoate , cobalt (II) 2-ethylhexanoate .
• Typical concentrations are 5- 100 ppm (0.0005-0.01 wt% based on the weight of resin), although higher Co-concentrations are not excluded.
• a reactive diluent can also be added before step c) of the present method. Accordingly, in the method according to the present invention, a reactive diluent can be added to the product obtained in step a) or in step b) , before carrying out step c) .
• Reactive diluents are monomers with low viscosity which have at least one reactive vinyl group and form homogeneous mixtures with the previously described bio-based resins obtained after steps a) and b) .
• Examples of reactive diluents are methyl methacrylate, styrene, methyl acrylate.
• the reactive diluents are advantageously bio- based.
• bio-based reactive diluents examples include myrcene (tested) , limonene, pinene (alpha, beta) .
• 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 sorbic acid-based polymer network 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 sorbic acid- based polymer network according to the present invention. Specifically, the sorbic acid-based polymer network
• the sorbic acid-based polymer network 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, glass, wood based materials or plastics.
• Adhesives are materials that fix 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.
• Still another aspect of the present invention relates to the compounds manufactured in step a) of the method according to the present invention.
• Yet another aspect of the present invention relates to the compounds manufactured after carrying out the two first steps of the method of the present invention, steps a) and b) .
• 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) to (X) .
• R' is given by the acid anhydride or acyl halide reacted in step b) represented by the formulae (A) and (B) , respectively.
• R' is an alkyl, or an alkenyl having one or more carbon-carbon double bond, preferably comprising at most six carbon atoms, more preferably comprising at most four carbon atoms, even more preferably comprising at most three carbon atoms, most preferably comprising at most two carbon atoms.
• R' is preferably a short alkyl chain: CH 3 or CH 2 CH 3 such as when step b) is carried out with formic anhydride, or acetic anhydride.
• a carbon-carbon double bond can also be designated by an unsaturated carbon-carbon bond.
• step b) When step b) is carried out with compounds (4) and (A) or (B) , the resulting product has the formula:
• step b) When step b) is carried out with compounds (5) and (A) or (B) , the resulting product has the formula:
• step b) When step b) is carried out with compounds (6) and (A) the resulting product has the formula:
• step b) When step b) is carried out with compounds (6) and (B) the resulting products have the formulae:
• step b) When step b) is carried out with compounds (7) and (A), the resulting product has the formula:
• step b) When step b) is carried out with compounds (7) and (B) , the resulting products have the formulae:
• step b) is carried out with compounds (8) and (A) or (B
• step b) When step b) is carried out with compounds (9) and (A) or (B) , the resulting product has the formula:
• this aspect of the present invention relates to compounds comprising two ester (-COO-) groups (diesters), three ester groups (triesters), four esters groups ( tetraesters ) .
• R represents a linear alkyl, a cycloalkyl or an aryl (as defined above for compounds (4) to (9) and R' represents preferably an alkyl, or alternatively an alkenyl comprising 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.
• Figure 2a 1 H-NMR spectrum of pure GDGE in CDC1 3 .
• Figure 2b 1 H-NMR spectrum of GDGESA1_1.5 in CDC1 3 .
• Figure 3a 1 H-NMR spectrum of pure RDGE in CDC1 3 .
• Figure 3b 1 H-NMR spectrum of RDGESA1_1.75 in CDC1 3 .
• Figure 4a Stress-strain curve during compression of cured GDGESA1_1.55 resin : 0 weeks in water.
• GDGESA1_1.65/myrcene 85/15: 0 weeks in water .
• GDGESA1_1.65/myrcene 85/15: 4 weeks in water .
• modulus cylinders made of cured GDGESA1_1.5 resin .
• BGE Benzyl glycidyl ether
• protons (e) and (g) give two peaks.
• the position of protons (el, 2) and (f) moves downfield to approximately 4.25 and 4.05 ppm, respectively.
• Glycerol diglycidyl ether has an average of two epoxide groups per molecule. This may result in GDGESA mono-ester and GDGESA di-ester compounds which are schematically represented in table 2.
• SA approximately 1.5 mole SA can react with 1 mole GDGE.
• Figures 2a and 2b show the 1 H- NMR spectra of GDGE and GDGESA1_1.5, respectively. The shift of peaks (el, 2) from 2.6/2.8 ppm to 4.25 ppm in the 1 H-NMR spectrum of GDGESA1_1.5 shows the formation of an ester bond.
• the obtained resin almost exclusively consists of GDESA di-ester since only a small amount of unreacted epoxide is left (see residual peaks denoted with (el, 2*) .
• Proton d that is part of the SA moiety only shows a large doublet at 5.78/5.81 ppm. There are no traces present of free SA for which proton d* should give a doublet at 5.76/5.80 ppm.
• Resorcinol diglycidyl ether has an average of two epoxide groups per molecule.
• RDGESA mono- ester and RDGESA di-ester can be obtained.
• the chemical structures of RDGE and RDGESA are shown in table 3.
• the 1 H- NMR spectrum of RDGE and RDGESA1_1.75 are shown in figure 3a and 3b, respectively.
• GDGE 114 mg hydroquinone (0.05 wt% based on weight GDGE + 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
• the fraction of SA di-ester in the resin can be enlarged by increasing the SA/glycidylether ratio .
• oven is flushed with N 2 prior to curing.
• oven is flushed with N 2 prior to curing.
• the resins shown in table 4b consist of SA mono-esters and SA di-esters. It can be seen that these resins result in solid materials. Increasing the SA/epoxy ratio of the mixture prior to the ring opening reaction results in an increased fraction of SA di-esters in the final resin.
• the cross-link density of the cured resins will increase which transforms the cured material from rubber like into a glassy state at room temperature.
• Viscosity measurements of the polymer network obtained by the method of the present invention have a suitable
• Table 7 shows the curing conditions for GDGES1_1.55 (Bl) which were used for preparation of test cylinders for compression tests. Table 7. Composition and curing conditions used for
• Figures 4a-b and 4c-d show the compressive stress-strain curves of the in table 7 mentioned GDGESA samples after 0 weeks and 4 weeks storage in water, respectively. All GDGESA samples show ductile behavior. The stress increases after reaching the yield stress. The cylinders eventually break with a loud bang. Addition of 15 wt% myrcene lowers the yield strength significantly (figure 4c-d) . The storage of the GDGESA samples in water results in an increase of the maximum compressive strength as can be seen from figures 4a- d.
• Figures 5a and 5b show the compressive yield strength and modulus, respectively as a function of storage time in water for GDGESA1_1.55.

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