WO2017096187A1 - Monomères époxy d'origine biologique, compositions et leurs utilisations - Google Patents

Monomères époxy d'origine biologique, compositions et leurs utilisations Download PDF

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Publication number
WO2017096187A1
WO2017096187A1 PCT/US2016/064655 US2016064655W WO2017096187A1 WO 2017096187 A1 WO2017096187 A1 WO 2017096187A1 US 2016064655 W US2016064655 W US 2016064655W WO 2017096187 A1 WO2017096187 A1 WO 2017096187A1
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epoxy
biobased
fatty acid
epoxy resin
compound
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PCT/US2016/064655
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English (en)
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Xiuzhi Susan Sun
Cong Li
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Kansas State University Research Foundation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups

Definitions

  • the present invention relates to epoxy resins from renewable resources.
  • Epoxy resin is one of the most versatile polymers, accounting globally for approximately 70% of the market of thermosetting polymers (polyurethanes not included). The global market value of epoxy is projected to reach US $25.8 billion by 2018 for a range of applications including epoxy composites and the adhesive market.
  • Bisphenol A diglycidyl ether (DGEBA) is the most popular epoxy monomer derived from the reaction of bisphenol A (BP A) and epichlorohydrin (ECH).
  • BP A bisphenol A
  • EH epichlorohydrin
  • the aromatic ring of BPA renders good thermal resistance and mechanical strength to the epoxy networks.
  • the impacts of BPA on human health e.g., alterations in both the immune and reproductive systems limits the use of DGEBA, especially in food contact materials.
  • the uncertainty in terms of price and availability of petroleum also urges the chemical industry to seek sustainable alternatives to petroleum chemicals.
  • the intrinsic aromatic rings render rigid structures to the epoxy network, significantly improving the mechanical strength and thermal resistance as well as comparative glass transition temperature (Tg) to commercial DGEBA.
  • Tg comparative glass transition temperature
  • the rigid aromatic rings because of the rigid aromatic rings, they restrict the mobility of epoxy chains that make the epoxy monomers highly viscous liquids or a solid at ambient temperature. Even though plant oil-derived epoxies have low viscosities, the poor thermo-mechanical properties limit the application.
  • the present invention is broadly concerned biobased epoxy compounds, precursors, compositions, methods, and articles of manufacture related to the same.
  • an epoxy resin comprising at least one biobased epoxy compound.
  • each of Ra' and Rv are selected from the group consisting of -H, branched and unbranched alkyl groups, fatty acid moieties, substituted or unsubstituted aliphatic cyclic rings, substituted or unsubstituted aromatic moieties, epoxy moieties, and combinations thereof, with the proviso that at least one of Ra' and Rb' each comprise an epoxy moiety.
  • the article comprises a substrate having a surface; and a layer of a biobased adhesive, coating, or film adjacent the substrate surface. This layer is formed from an epoxy resin according to any of the embodiments described herein.
  • the methods generally comprise providing an epoxy resin according to any of the embodiments described herein; applying the epoxy resin to a substrate; and exposing the epoxy resin to activating radiation to yield a cured biobased adhesive, coating, or film on the substrate.
  • Additional methods are described herein, including methods of forming a biobased epoxy precursor compound.
  • the methods generally comprise reacting an alicyclic oxirane compound with a biobased unsaturated fatty acid or a biobased compound comprising an unsaturated fatty acid moiety under conditions to yield a biobased epoxy precursor compound.
  • the precursor compound comprises an ether- ridged cycloaliphatic ring structure:
  • each of R a and Rb are selected from the group consisting of -H, branched and unbranched alkyl groups, branched and unbranched alkenes, unsaturated fatty acid moieties, substituted or unsubstituted aliphatic cyclic rings, substituted or unsubstituted aromatic moieties, and combinations thereof, with the proviso that at least one of R a and Rb each comprise an alkene.
  • FIG. 1 shows the reaction pathway for UA/ECP system. Solid arrows indicate the main reaction pathways; dash arrow indicates the additional reaction pathways;
  • FIG. 2 shows the reaction pathway for UA/MECP system
  • FIG. 3 shows graphs of the time evolution of FTIR spectra for the stoichiometric UA/ECP system (A) and UA/MECP system (B) at 80 °C;
  • FIG. 4 shows graphs of Synchronous (A) and Asynchronous (B) 2D FTIR correlation spectra of UA /ECP system in the region of 1800-700 cm "1 .
  • the unshaded and shaded areas in the contour maps represent positive and negative peaks, respectively;
  • FIG. 5 shows graphs of the 13 C NMR spectra of (A) CUA and (B) MCUA;
  • FIG. 6 illustrates the transition states of cycloaliphatic epoxide isomers.
  • Ri H or CH 3
  • FIG. 7 illustrates the formation of isomers in CUA due to the stereoisomerism of ECP
  • FIG. 8 illustrates the epoxidation of CUA and MCUA into (a) ECUA and (b) EMCUA;
  • FIG. 9 shows graphs of the 13 C MR spectra of (a) ECUA and (b) EMCUA;
  • FIG. 10 is a graph of the complex viscosities (I]*) of various epoxies determined at 25 °C as a function of shear rate;
  • FIG. 11 is a graph of the exothermic behaviors of epoxy monomers containing of 3 wt% photo-initiator (PC-2506) radiated through UV light as a function of time;
  • FIG. 12 shows (a) a photograph of various epoxy resins after UV-curing and (b) a graph comparison of their % transmittance at various wavelengths;
  • FIG. 13 shows graphs of (A) Temperature dependence of storage moduli; and (B) loss factors for P-ESO, P-DGEBA, P-ECUA and P-EMCUA.
  • C Schematic diagram demonstrating the key features of cured epoxy networks.
  • Type I structure ellipse shading
  • type II structure rectangular shading
  • type III structure square shading
  • type IV structure round shading
  • FIG. 14 illustrates the chain propagation mechanisms in the UV-curing process for epoxy monomers containing photo-initiator PC-2506;
  • FIG. 15 illustrates data on the mechanical property evaluation of cured epoxy resins.
  • A Typical strain-stress curves.
  • B Detailed mechanical results regarding elongation at break (%) and tensile strength (MPa);
  • FIG. 16 is a graphical illustration of the comprehensive performance comparison between DGEBA and bio-epoxies according to the invention.
  • FIG. 17 illustrates the (a) Synthetic pathway of MCCA (typical chemical structure is shown); and (b) Synthetic pathway of EMCCA (typical chemical structure is shown) and structural features of EMCCA;
  • FIG. 18 illustrates the synthesis of MCCA and EMCCA. Only typical chemical structures are shown due to the isomers in reagent and product;
  • FIG. 20 shows the (a) Kinetics of the variations of the epoxy ring (stretching C-O-C of epoxy group centered at 811 cm "1 ) for Amberlyst-15a -A-(MCUA(10g)-ECP(2.5g)-Amberlyst- 15(1.2g) at 25°C), Amberlyst-15b -0-(MCUA(10g)-ECP(2.5g)-Amberlyst-15(1.2g) at 60°C) and Amberlyst-15c -•-(MCUA(10g)-ECP(2.5g)-Amberlyst-15(1.6g) at 60°C).
  • FIG. 21 shows the 3 ⁇ 4- MR spectra of EMCUA and EMCCA. (typical chemical structures are shown). The NMR spectra of EMCUA presented here are for comparison purpose with EMCCA;
  • FIG. 22 shows a photograph of a cured epoxy resin and graph illustrating the transparency values of UV-cured EMCCA film in the light wavelength range of 300-700 nm;
  • FIG. 23 shows comparisons of (a) viscosities, (b) mechanical properties, (c) dynamic mechanical properties, and (d) creep behaviors of EMCUA and EMCCA.
  • Type I structure ellipse shading
  • type II structure rectangular shading
  • type III structure square shading
  • type IV structure round shading
  • FIG. 24 is a table of performance comparison of EMCCA with other typical counterparts containing fatty acid as building blocks
  • FIG. 27 shows photographs of MECP+Amberlyst-15(10wt%) after being heated at 60°Cfor 12h (left panel); and ECP+Amberlyst-15 (10wt%) after being heated at 60°Cfor 12h (right panel); and
  • FIG. 28 illustrates the reaction scheme to depict the acid-catalyzed epoxide ring-opening reaction.
  • the present invention is concerned with renewable epoxy resins, precursors thereof, cured epoxy compositions, and methods related to the same.
  • the materials are biobased and derived from plant-based materials.
  • the inventive compositions can also be used to prepare coatings or films suitable for a variety of uses described herein.
  • the precursor compounds comprise a novel ether-bridged cycloaliphatic ring structure:
  • each of Ra and Rb are selected from the group consisting of -H, branched and unbranched alkyl groups, branched and unbranched alkenes, unsaturated fatty acid moieties, substituted or unsubstituted aliphatic cyclic rings, substituted or unsubstituted aromatic moieties, combinations thereof, and the like, with the proviso that at least one of R a and Rb each contain an alkene (e.g., vinyl moieties, unsaturated fatty acid moieties).
  • at least one Rb is an unsaturated fatty acid moiety. More preferably, the unsaturated fatty acid moiety is a linear moiety that comprises an alkene-terminated aliphatic chain.
  • the resulting epoxidized compounds will also comprise this novel ether-bridged cycloaliphatic ring structure above, except that Ra' and Rb' are used to denote the epoxidized moieties, and at least one of R a ' and Rb' are each moieties comprising at least one epoxy group. Further any unsaturated groups would also be epoxidized in the epoxy resin (e.g., such as the terminal alkene of a fatty acid chain).
  • epoxy precursor compounds are prepared by reacting an alicyclic oxirane compound (aka cycloaliphatic epoxide) with an unsaturated fatty acid or compound comprising an unsaturated fatty acid moiety to yield a precursor compound comprising the ether-bridged cycloaliphatic ring structure above.
  • this reaction is carried out under conditions to facilitate competitive nucleophilic attack of the acid anion on the oxonium ion.
  • the reaction is carried out at temperatures ranging from about room temperature (e.g., about 20°C to about 25°C) up to elevated temperatures of about 160°C.
  • the reaction time can range from about 30 minutes to about 72 hours.
  • this reaction can be carried out without the use of a catalyst or solvents.
  • a heterogeneous catalyst can be used to facilitate the reaction.
  • exemplary catalysts include reusable ion exchange resins, and preferably strongly acidic cation exchange resins suitable for non-aqueous catalysis, such as AMBERLYST® 15 (strongly acid macro reticular polystyrene based ion exchange resin with strongly acidic sulfonic group).
  • Exemplary alicyclic oxirane compounds for use as the starting materials include cyclic epoxides with at least one unsaturated substitution, such as l,2-epoxy-4-vinylcyclohexane (also known as 4-ethenyl-7-oxabicyclo[4.1.0]heptanes (“ECP"), EP-101, or 4-vinyl-l-cyclohexene 1, 2-epoxide), 3,4-epoxy-l-cyclohexene, and substituted forms thereof.
  • ECP 4-ethenyl-7-oxabicyclo[4.1.0]heptanes
  • MECP 4-vinyl-l-cyclohexene 1, 2-epoxide
  • substituted forms thereof such as limonene 1, 2-epoxide (MECP)
  • these linear precursor compounds can be further reacted with ECP to yield precursor compounds with the ether-bridged cycloaliphatic ring structure.
  • Linear precursor compounds can also be used in the epoxy resin
  • Exemplary fatty acids for use as the starting materials include medium chain unsaturated fatty acids.
  • the fatty acids have an aliphatic chain length of from about 3 to about 24 carbons.
  • the fatty acids include a terminal alkene.
  • Suitable fatty acids include 10-undecenoic acid, 8-nonenoic acid, 7-octenoic acid, and the like.
  • epoxy precursor compounds according to embodiments of the invention include branched monomers:
  • Precursor compositions can further include additional linear precursor monomers, such as:
  • n 1 to 21 (preferably 1 to 10), and any one of the cycloaliphatic rings in the foregoing structures may be substituted or unsubstituted.
  • these biobased epoxy precursor compounds can be epoxidized using any suitable reagent for epoxidation of alkenes, such as a peracid or a peroxy acid.
  • suitable reagents include meta-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, and the like.
  • n 1 to 21 (preferably 1 to 10), and any one of the cycloaliphatic rings in the foregoing structures may be substituted or unsubstituted.
  • the properties of the epoxy composition can be adjusted by varying the relative amounts of branched and linear epoxy monomers.
  • the resin is liquid under ambient conditions and can be mixed with additives, catalysts, initiators, preservatives, thickeners, plasticizers, and the like, without the need for a solvent system.
  • a solvent system may be desired and can optionally be included.
  • epoxy resins according to the invention consist essentially or even consist of one or more epoxy compounds listed above, and are substantially solvent-free.
  • substantially free means that the composition contains less than about 1% by weight, and preferably less than about 0.1% by weight of that particular ingredient, based upon the total weight of the composition taken as 100% by weight.
  • the epoxy resin has a low viscosity of less than 5 Pa s, preferably less than 4 Pa s, and more preferably from about 1 Pa s to about 3 Pa s.
  • the epoxy composition can be used in various applications, including any applications suitable for conventional epoxy compounds, for example as adhesives, films for flexible electronic devices (e.g., solar cell, semiconductor, organic light-emitting diode and display), reusable tapes, sticky notes, medical and pharmaceutical devices (e.g., electrodes, skin wound care, medical tapes, band-aids, etc.), and screen protectors for electronic displays (e.g., computers, tablets, phones, televisions, etc.).
  • flexible electronic devices e.g., solar cell, semiconductor, organic light-emitting diode and display
  • reusable tapes e.g., sticky notes
  • medical and pharmaceutical devices e.g., electrodes, skin wound care, medical tapes, band-aids, etc.
  • screen protectors for electronic displays e.g., computers, tablets, phones, television
  • the epoxy compounds can be cured to create adhesives, films, coatings, elastomers, sealants, foams, composites, and the like.
  • the composition can be applied to various substrates, or molded into a desired shape before curing.
  • the resultant epoxy resin can be cured using heat, radiation (e.g., UV or vis light), or under ambient conditions with the aid of a curing agent.
  • curing in the context of epoxies refers to polymerization of the epoxy monomers and subsequent crosslinking between polymer chains to create the cured epoxy network.
  • the catalyst also functions as a crosslinking agent and participates in crosslinking. In other embodiments, the catalyst does not participate in crosslinking and does not function as a crosslinking agent. Regardless, in either embodiment, the composition is preferably substantially free of additional or any crosslinking agents.
  • a catalyst crosslinking agent when present, it is preferably the only crosslinking agent present in the composition, and no additional crosslinking agents are present. Where the catalyst does not function as a crosslinking agent, the composition is substantially free of any crosslinking agents at all.
  • exemplary "added" crosslinking agents that are preferably excluded in certain embodiments include aminoplasts/melamines, vinyl ethers, glycourils, multifunctional epoxies (unless also biobased), anhydrides, silanes, peroxides, thiadiazoles, and the like.
  • the resultant epoxy resin is UV curable, preferably with the aid of a cationic photoinitiator.
  • the epoxy composition comprises one or more of the above epoxy compounds homogenously mixed with any suitable epoxy photoinitiator and optional solvent system.
  • Suitable photoinitiators include low dose cationic photoinitiators, such as iodonium antimonate salts (e.g., PC-2506; Polyset company, Mechanicville, NY), radical photoinitiators, such as alpha hydroxyketones (e.g., DAROCUR® 1173; BASF resins, Wyandotte, MI), and the like.
  • the resin preferably comprises from about 1% to about 10% by weight photoinitiator, more preferably from about 3% to about 7% by weight, and even more preferably from about 3% to about 5% by weight photoinitiator, based upon the total weight of the resin taken as 100% by weight.
  • the epoxy resins can also be thermally cured if desired.
  • a layer of the epoxy resin is formed on a substrate surface.
  • the composition layer can be formed by brushing, rolling, spin-coating, pouring, and/or spraying the composition onto the substrate surface.
  • Suitable substrates include virtually any solid surface, such as glass, paper, plastic, metal, silicon wafers, electronic displays, marbles, coated woods, composites, and combinations thereof. It will be appreciated that the thickness of the cured layer will depend upon the desired end-used of the composition.
  • the cured layer preferably has a substantially uniform thickness across its surface area. Exposure to the UV radiation causes the cationic polymerization and self-crosslinking of the epoxy compounds. In some embodiments, the exposing process may be repeated multiple times until the desired level of curing is achieved.
  • the total UV dose used for radiation will depend upon the end use (e.g., PSA vs. coating), as well as the thickness of the composition layer (to achieve complete through curing).
  • the total radiation dose will generally range from about 1 to about 5 J/cm 2 , more preferably from about 1 to about 3 J/cm 2 , and even more preferably from about 1 to about 2 J/cm 2 .
  • epoxies prepared according to embodiments of the invention have fast cure times (with UV cure times of less than 20 seconds).
  • the cured biobased epoxy compositions are characterized by a number of additional beneficial features.
  • the cured biobased epoxy compositions possess a high tensile strength of at least about 40 MPa and up to about 65 MPa, depending upon the particular epoxy precursor compounds selected for the composition.
  • the cured biobased epoxy also has a high glass transition temperature of from about 130 to about 160°C.
  • the cured biobased epoxy also has high transparency in the visible region. More specifically, a 150- ⁇ layer of the cured composition will have a % light transmittance of at least about 80% at a wavelength of between 300-325 nm.
  • the composition is preferably substantially free of any pigments, dyes, chromophores, and/or other light attenuating moieties.
  • the cured biobased epoxy is characterized by a biobased content of at least 50 wt %, preferably at least 75 wt%, and more preferably from about 80 to about 90 wt%, based upon the total composition taken as 100% by weight.
  • epoxy resins according to the invention are substantially free of any hardeners, extenders, and the like.
  • the cured composition will also preferably be substantially insoluble in organic solvents, including chloroform, methane chloride, tetrahydrofuran, ethyl acetate, methyl acetate, acetone, ethyl ether, dimethylformamide and hexane.
  • organic solvents including chloroform, methane chloride, tetrahydrofuran, ethyl acetate, methyl acetate, acetone, ethyl ether, dimethylformamide and hexane.
  • the cured composition will also preferably be resistant to moisture and dissolution in water.
  • the phrase "and/or," when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed.
  • the composition can contain or exclude A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
  • biobased refers to renewable resources, particularly from plants, and excludes materials prepared or derived from petroleum or other non-renewable resources. Plant-based materials are particularly preferred biobased materials for use in the invention.
  • plant-based material refers to ingredients that are derived from plants, whether through chemical or biological processes. In other words, the compositions are preferably substantially free of non-plant-based materials, including petroleum-based compounds or synthetic polymers and/or elastomers, such as petrol-based acrylates, acrylics, silicones, synthetic rubbers (e.g., isoprenes, isobutylenes, ethylene propylene diene monomer, urethanes, butadienes), polypropylenes, and the like.
  • the compositions comprise greater than 50% by weight plant-based materials, preferably greater than about 75% by weight plant-based materials, and even more preferably greater than about 90% by weight plant-based materials, based upon the total weight of the solids in the composition taken as 100% by weight. In other embodiments, the compositions comprise greater than about 95% by weight plant-based materials, preferably greater than about 97% by weight plant-based materials, and even more preferably greater than about 99% plant-based materials, based upon the total weight of solids in the composition taken as 100% by weight.
  • the present description also uses numerical ranges to quantify certain parameters relating to various embodiments of the invention. It should be understood that when numerical ranges are provided, such ranges are to be construed as providing literal support for claim limitations that only recite the lower value of the range as well as claim limitations that only recite the upper value of the range. For example, a disclosed numerical range of about 10 to about 100 provides literal support for a claim reciting "greater than about 10" (with no upper bounds) and a claim reciting "less than about 100" (with no lower bounds).
  • Bioepoxy derived from 10-undecenoic acid for high performance UV-curable resins was used the building block for a biobased epoxy precursor.
  • a one-step solvent-free chemical pathway was proposed to synthesize the bioepoxy precursor by utilizing a UA nucleophilic attack upon a cycloaliphatic oxide (4-ethenyl-7-oxabicyclo[4.1.0]heptanes, ECP), as depicted in FIG. 1.
  • a hydroxyl group was formed during the formation of alkene-terminated epoxy precursor.
  • the hydroxyl group together with the UA nucleophilic group attacked the oxonium ion to obtain a novel ether-bridged cyclohexyl structure with more stiff chain segments and cross-linking sites:
  • the epoxy ring of cycloaliphatic oxide is prone to be protonated, resulting in the formation of oxonium ion intermediate.
  • This intermediate has a fused six- and three- membered ring with high strain. Nucleophiles, such as fatty acid anion, can attack the three-membered ring, realizing an effective connection of fatty acid chain and cycloaliphatic ring.
  • 10-undecenoic acid (UA) and 4-ethenyl-7-oxabicyclo[4.1.OJheptanes (ECP) were used as the building blocks for a bioepoxy with a flexible aliphatic chain and a stiff ether-bridged cyclohexyl structure (FIG. 1).
  • a 13 C MR spectrum was obtained to further reveal the structural features of CUA (FIG. 5 A).
  • the chemical shifts around 173 ppm were attributed to the carboxyl carbons.
  • the characteristic peaks of carbon atoms on double bonds were identified at 138-142 ppm and 111- 115 ppm.
  • the chemical shifts at 72-75 ppm and 67-70 ppm were attributed to the ester carbons (C12, 12') and hydroxyl carbons (C19 1 , C25), respectively.
  • the chemical shifts at 51-53 ppm were attributed to the two ring-bridging ether carbons (CI 9, C20), showing the existence of a branched structure in the CUA system.
  • the corresponding molar ratio of double bonds I and II was estimated to be 1 :0.8, based on the area ratio of the integrated peaks around 142 ppm (C15, C15 * and C26) and 139 ppm (C2, C2'). If the CUA system contains totally branched structures, the corresponding molar ratio between double bonds I and II should be higher than 1 :0.5. Therefore, the resulting molar ratio of 1 :0.8 indicated that in addition to the branched structures, a linear structure also existed:
  • CUA appears to be a multicomponent system containing both branched and linear monomers with an estimated molar ratio of 1 :3, based on the molar ratio of double bonds I and II discussed above.
  • UA-ECP The stereo specific reactions of UA-ECP can be illustrated by the transition state model proposed by John C. Leffingwell, etc., as shown in FIG. 6.
  • transition state model proposed by John C. Leffingwell, etc.
  • nucleophilic reagent attacks upon the positive charge part of the carbon atom from the bottom direction (FIG. 6a), and a cis- substituted structure formed.
  • nucleophilic reagent attacks upon the positive charge part of the carbon atom from the top direction (FIG. 6b), and a trans-substituted structure formed.
  • ECP used in this work is a mixture of isomers, based on the transition states, the cis-ECP would be attacked by UA anion from the bottom direction, resulting in a cis-isomer, and correspondingly, the trans-isomers were derived from the trans-ECP.
  • the NFH group would act as a second nucleophile involving the CNA against UA anion, which led to more complicated isomers with branched structures (see FIG. 7).
  • FIG. 3B shows the time evolution of FTIR spectra for the UA/MECP system (stoichiometric coefficient equal to one) at a reaction temperature of 80 °C. Similar to the UA/ECP system, the bands centered at 2678 cm “1 (stretching O-H of carboxylic acid dimer) decreased and the bands centered at 3454 cm “1 (stretching O-H of hydroxyl group) increased, as reaction time increased. This result confirmed the nucleophilic attack of UA upon the epoxide ring of MECP and formation of hydroxyl groups. However, different from UA/ECP system, the epoxy groups centered at 840 cm "1 are still notable after 48 hours reaction, indicating that MECP had not been fully consumed during the reaction.
  • the chemical structure of MECP is very similar to that of ECP, except that the individual hydrogen atoms on the cycloaliphatic ring and the double bond are respectively substituted by methyl groups.
  • This minor structure change resulted in different FTIR results, indicating distinct reaction pathways in UA/MECP and UA/ECP systems.
  • the chemical shifts derived from carboxyl carbon and double bond carbons of MCUA are similar to those in the CUA 13 C NMR spectrum (FIG. 5B).
  • the observed chemical shifts around 50 ppm in CUA were attributed to the two ring-bridging ether carbons disappeared in MCUA, indicating the lack of ether-bridged cyclohexyl structure in MCUA system (i.e.
  • the 10-undecenoic acid anion was more capable of realizing the nucleophilic attack upon the oxonium ion due to the electronic effect.
  • the hydroxyl group could not achieve a further nucleophilic attack upon cycloaliphatic epoxide, resulting only in a linear-structured alkene monomer as in the reaction pathway shown in FIG. 2.
  • CUA and MCUA were further epoxidized using m-chloroperoxybenzoic acid (m-CPB A), resulting in bio-epoxy monomers, termed ECUA and EMCUA, as shown in FIG. 8. 13 C MR spectra were collected to identify the chemical structures of ECUA and EMCUA (FIG. 9):
  • Low viscosity of epoxy resin is preferred in the UV-curing process to achieve good flowability and faster wetting on the substrate.
  • addition of diluents can reduce viscosity, from an eco-friendly viewpoint synthesis of epoxy resin with low viscosity is preferable.
  • the viscosities of epoxy monomers diglycidyl ether of bisphenol-A (DGEBA), ECUA, and EMCUA, as a function of shear rate were evaluated (FIG. 10). Compared with DGEBA, the complex viscosities of ECUA and EMCUA were considerably lower and, consequently, more desirable for UV-curing.
  • the viscosity of EMCUA was lower than ECUA when shear rate was above 20 rad/s, which was attributed to the higher amount of linear structures in the EMCUA monomer compared to ECUA.
  • Epoxidized soybean oil (ESO) possessed the slowest curing speed and lowest exothermic enthalpy.
  • the bulky fatty acid ester chains hindered the propagation of epoxides during the ESO curing.
  • Table 1 Exotherm parameters of epoxy monomers in the UV-curing process.
  • UV-cured films is crucial for exterior coating applications.
  • the built-in hydroxyl groups in bio-epoxy synthesized here not only accelerated the curing speed, but also suppressed the "orange skin” effect on the cured film surface (FIG. 12a).
  • An "orange skin” mark was found on the surface of P-DGEBA film (marked by circle), while smooth surfaces were achieved for the P-ECUA and P-EMCUA systems.
  • the origin of surface drawbacks such as "orange skin” is complicated. One possible reason is the internal stresses generated during the polymerization.
  • the networks of P-DGEBA and P-ESO are created by two types of crosslink structures: chain segments derived from the ring-opening of oxiranes (type I, circled by ellipse shadow), and chain segments derived from the DGEBA backbone or ESO fatty acid section (type II, circled by rectangle shadow) (FIG. 13C). Due to the presence of hydroxyl groups, the connection of hydroxyl and epoxides resulted in a third type of crosslink (type III, circled by square shadow) in P-ECUA and P-EMCUA. The ether-bridged cyclohexyl structure formed in preparation of CUA lead to a fourth type crosslink (type IV, circled by round shadow) in P-ECUA.
  • P-ECUA Compared with P-DGEBA, P-ECUA demonstrates superior mechanical properties with higher tensile strength and elongation at break (FIG. 15), which is ascribed to its unique network structure.
  • the network of P-ECUA is constructed by four types of crosslink structures: the inherent crosslink structure (type IV), the subsequently formed crosslink structures (types I and III) with a rigid skeleton and high crosslink density, and the crosslink structure (type II) derived from the flexible undecenoic acid chain and conferring a certain toughness.
  • the tensile strength of P-EMCUA is lower than that of P-DGEBA: however, this strength is still acceptable in non- structural applications.
  • P-EMCUA exhibits an interesting ductile feature.
  • the inset in FIG. 15A shows that the P-EMCUA film was integral without cracking and the nail was firmly stuck after penetrating the film.
  • the methyl group on the cycloaliphatic ring hindered the nucleophilic attack of the hydroxyl group and the formation of the secondary ester crosslink structure (type IV). Consequently, the resulting network constructed by EMCUA has lower crosslink density and longer chain segments compared with ECU A, leading to more extensible and ductile networks.
  • FIG. 16 A comprehensive performance comparison of epoxy resins is shown in FIG. 16. Relative to commercial DGEBA, the UV-cured epoxy resins derived from 10-undecenoic acid showed outstanding performance across a range of properties. P-ECUA with well-balanced features of processability, appearance, renewability, heat resistance, and mechanical properties is a promising renewable alternative to some bisphenol A-based epoxies.
  • EEO epoxidized soybean oil
  • VIKOFLEX® 7170 epoxidized soybean oil
  • PC-2506 cationic initiator
  • UA-ECP Epoxy Precursor CUA UA (100.0 g) and ECP (67.4 g) were charged into a 250 mL round-bottomed flask equipped with a reflux condenser, and the mixture was stirred with a magnetic bar at 80 °C for 48 h and transferred to a 2000 mL separating funnel. 400 mL hexane and 800 mL sodium carbonate solution (10 wt %) were then added to separate the residual UA from the product. Hexane solvent was then removed and collected through high vacuum rotary evaporation at 60 °C, and a colorless CUA liquid with a yield rate of 82 % (relative to pure ECP) was obtained.
  • Cationic photo-initiator (PC-2506, 3wt%) was added into DGEBA, ESO, ECUA and EMCUA, respectively.
  • the mixture was mixed homogenously with the aid of a Vortex mixer and sonicator, then coated onto a 15.24 cm x25.4cm glass plate with a film casting knife (model 4302, BYK-Gardner USA) set at 160 ⁇ wet thickness.
  • the resin containing photo-initiator was cured with a Fusion 300S UV system (300 W/inch power, D bulb, UVA radiation dose 1.7-1.8J/cm 2 ) equipped with a LC6B benchtop conveyor at conveyor speed of 213 cm/min.
  • the corresponding cured resins were named as uv-DGEBA, uv-ESO, uv-ECUA and uv- EMCUA, respectively.
  • FTIR Fourier transform infrared
  • the contents of epoxy precursors CUA and MCUA were determined by gas chromatography (GC) using a Shimadzu GC-2010 plus GC system (Shimadzu, Columbia, MD) equipped with a flame ionization detector (FID). Helium was used as the carrier gas at a flow rate of 1.5 ml/min.
  • the injector and column temperatures were ramped from 80 °C to 300 °C at 7 °C/min with the detector temperature held at 380 °C.
  • Rheological behaviors were measured using a Bohlin CVOR150 rheometer (Malvern Instruments, Southborough, MA) with a parallel plate (PP20, 20-mm plate diameter and 500- ⁇ gap).
  • Frequency sweep was conducted at 25 °C with a strain of 0.5 % and an angular frequency range of 0.1-30 rad/s.
  • the photocalorimetric measurements of resins were performed with a TA Q200 DSC coupled to a photocalorimeter accessory (PCA, OmniCure S2000, TA instruments) equipped with a high-pressure 200-W mercury lamp.
  • the UV wavelength was adjusted to 320-500 nm using a cut-off filter, and a light intensity of 100 mW/cm 2 was used.
  • Approximately 10 mg of each resin was accurately weighed in an open aluminum pan, and an empty aluminum pan was used as reference.
  • the sample was equilibrated at 25 °C for 0.5 min without UV, then UV-irradiated for 20 min under a nitrogen atmosphere.
  • Light transmittances were measured by UV spectrometer (Hewlett-Packard 8453) with 0.16 mm thickness for specimens.
  • Dynamic mechanical analysis (DMA) was performed with a DMA (Q800 New Castle, DE) using a tension mode. A 5 ⁇ amplitude was applied to guarantee the measurement was within the linear viscoelastic region. Samples were heated from - 50 °C to 270 °C using a heating rate of 3 °C/min and frequency of lHz.
  • Tensile strength and elongation at break were measured according to ASTM D882-12 using a tensile tester (TT-1100, Chemlnstruments, Fairfield, OH) with a specimen dimension of 40 ⁇ 8 x 0.16 mm and a grip separation rate of 2.54 cm min "1 . Five specimens were tested for each sample to obtain an average.
  • TT-1100 Chemlnstruments, Fairfield, OH
  • a unique bio-alkene with ether-bridged cyclohexyl structures and built-in hydroxyl groups was obtained through a one-step solvent-free nucleophilic substitution reaction.
  • the ether-bridged cycloaliphatic rings provided stiffer chain segments and cross-link sites, while the long aliphatic chains derived from UA provided flexibility.
  • As an ideal structure for an epoxy precursor it achieved a good balance between stiffness and flexibility.
  • the built-in hydroxyl group offered higher UV-curing reactivity and the possibility for further modification.
  • the resulting bio-epoxy resin ECUA exhibited higher T g of 142 °C compared to reported values, and good potential in heat resistance suggesting the poor heat resistance of plant oil-based epoxy can be overcome provided the appropriate structure is generated.
  • ECUA Compared with commercial epoxy DGEBA, ECUA demonstrated superior performance across a range of properties including lower viscosity, higher reactivity, better appearance and more robust mechanical properties.
  • Example 1 described a high-performance bio-based epoxy ECUA via the CNA (competitive nucleophilic attack) strategy utilizing 10-undecenoic acid (UA) and 4-ethenyl-7- oxabicyclo[4.1.0]heptanes (ECP) as building blocks.
  • the major contribution of the CNA is to generate a branched structure in the ECUA system that demonstrated high glass transition and high mechanical strength.
  • MECP limonene oxide
  • MECP limonene oxide
  • the epoxy (EMCUA) derived from UA and MECP showed lower glass transition and lower mechanical strength compared to the epoxy (ECUA) derived from UA and ECP, because there is no branched structure in the EMCUA system.
  • the corresponding epoxy EMCCA can be cross-linked in seconds via UV-radiation to achieve a highly transparent colorless film (transmittance -90%) with bio-content of about 80 wt% and tensile strength of abou
  • the work herein shows a promising candidate for bio-based epoxies and provides a direction to design high bio-content epoxies with desirable properties (e.g., low viscosity, high strength, thermal resistance, and transparency) via a rational combination of plant oil and terpene derived building blocks.
  • FIG. 17(a) The specific procedure for MCCA synthesis is described in FIG. 18.
  • MCUA was prepared following the same methods as described in Example 1 above.
  • the synthetic pathway of MCCA (FIG. 17(a)) shows the reaction characteristics, in which the oxirane ring on ECP was activated by the Amberlyst-15 (SN1 route, FIG. 18) and then the hydroxyl group on MCUA attacked upon the positive charge part of the carbon atom on the oxirane ring (SN2 route, FIG. 18) to accomplish the graft of ECP onto MCUA.
  • the ring opening between ECPs was effectively avoided via the selective catalysis of Amberlyst-15 (see FIG. 19).
  • the MCCA system is a combination of MCCA and MCUA monomers, and the chemical structural features were revealed by 1 H- MR spectra (FIG. 20(d).
  • the stereoisomerism of cycloaliphatic rings led to the stereospecific reactions of nucleophile upon oxonium, which caused the complication of the nucleophilic attack and the existence of isomers in the product, as discussed in Example 1.
  • FIG. 20(b) only typical chemical structures are demonstrated in FIG. 20(b).
  • the graft of ECP ring onto MCUA can be distinguished via the comparison of 3 ⁇ 4-3 ⁇ 4 COSY spectra of MCUA and MCCA (FIG. 20(c) and (d)).
  • This peak can be attributed to the coupling of protons connected by hydroxyl or ether group with the vicinity protons on ECP or limonene oxide ring.
  • Epoxidation of MCCA was conducted using m-chloroperoxybenzoic acid (m-CPB A) at room temperature (FIG. 17(b) and related 1H-NMR and mass spectra are presented in FIG. 21).
  • the resultant product EMCCA is a clear liquid and can be easily cured via ultraviolet radiation to achieve a colorless, highly transparent film (FIG. 22).
  • the grafting of ECP on the MCUA resulted in a slight increase in viscosity (FIG. 23(a)). Even though, the viscosity of EMCCA (2.7 Pa s at 25°C) is about 50% lower than the commercial DGEGA (5.3 Pa s at 25°C).
  • the UV-cured film from this newly developed epoxy monomer demonstrated an impressive mechanical enhancement: tensile strength was doubled with a value higher than 60 MPa (FIG. 23(b)) via a few seconds of UV radiation, without the aid of hardeners and further heating treatment. Remarkable increase in thermal resistance (e.g., Tg shifting from 50 °C of the UV-cured EMCUA to 90 °C of the UV-cured EMCCA) was also observed (FIG. 23(c)). These significant improvements are attributed to the unique chemical structure of EMCCA. As FIG.
  • EMCCA 17(b) shows, 10-undecenoic acid segment composed the flexible moiety of EMCCA, which is built up by an aliphatic chain with 11 carbon atoms, sharing the transfer of applied stress and external deformation.
  • the rigid moiety of EMCCA is composed of cycloaliphatic rings from citrus oil and ECP, in which the rings are bridged by ether group.
  • the hydroxyl group attached to the cycloaliphatic ring is also capable of taking part in the ring-opening reaction of oxiranes, contributing to the cross-linking sites in the network formation process.
  • the branched structure imparts EMCCA a higher potential in the enhancement of epoxy resin.
  • the network of UV-cured EMCUA is created by three type crosslinked structures: chain segments derived from the ring-opening of oxiranes (type I, highlighted by ellipse shadow); chain segments derived from the EMCUA backbone (type II, highlighted by rectangle shadow); and chain segments derived from the connection of hydroxyl and epoxides (type III, highlighted by square shadow).
  • chain segments derived from the ring-opening of oxiranes type I, highlighted by ellipse shadow
  • chain segments derived from the EMCUA backbone type II, highlighted by rectangle shadow
  • chain segments derived from the connection of hydroxyl and epoxides type III, highlighted by square shadow.
  • the intrinsic ether-bridged cyclohexyl in the EMCCA network leads to the fourth type of crosslinking (type IV, highlighted by round shadow in FIG. 23(e)).
  • This crosslink is composed of two rigid ether-bridged cyclohexyl rings, which remarkably increase the chain stiffness and sustaine the stress applied to the network, and that contributes to the high tensile strength compared to the EMCUA network (increased from 32 MPa to 64 MPa, FIG. 23(b)). Creep curves further confirms the distinct network structures of UV-cured EMCUA and EMCCA. As FIG. 23(d) shows, EMCCA network shows a sharper slope in the initial stage of the creep curve. Since initial slope is related to the elastic response of polymers, for EMCCA network, the sharper slope meant a faster elastic response to stress and shorter average molecular chains between cross-links compared to that of EMCUA network. Higher amount of cross-links in EMCCA network effectively sustains the applied stress and retards the network deformation, and in the recovery stage (95 min -155 min), contrary to the slow recovery process of EMCUA network, an instant restoration is accomplished.
  • EMCCA Since fatty acid was used as the building block of EMCCA, two conventional epoxy monomers are shown in FIG. 24 for the performance comparison.
  • EMCCA (FIG. 24, #3) demonstrated superior properties over other monomers in terms of viscosity, heat resistance and tensile strength.
  • monomer #1 in FIG. 24 the lack of rigid structures limited its improvement in heat resistance and mechanical strength.
  • the rigid sucrose moiety was introduced into monomer #2 in Table 1, the reinforcement is limited because of the lower reactivity of internal oxiranes occurring in the network-curing process (FIG. 25). More rational design was achieved for EMCCA (FIG. 24, #3) through the introduction of rigid moiety (cycloaliphatic rings) and terminal oxiranes (higher reactivity).
  • EMCCA Compared to the counterparts, EMCCA demonstrates lower viscosity, higher thermal resistance and tensile strength even without the aid of a hardener. Considering most hardeners are petrochemicals, this hardener-free epoxy resin obviously increased the bio-based content. EMCCA combined the advantages of building blocks derived from terpene (rigid structure) and plant oil (low viscosity) resources. As FIG. 26 shows, the various building block members in terpene and plant oil families provide a variety of possible combinations of these two family members for the design of high bio-content epoxies as demonstrated in this work. Promising epoxy candidates can be expected via selecting appropriate members and combining them through rational chemical strategies, a.
  • Monomer 1 was cured with an equivalent of hardener; monomer 2 was cured with 0.4 equivalent of hardener; EMCCA (monomer 3) was cured without hardener and was cured with 0.4 equivalent of hardener for the comparison with monomer 2.
  • b. viscosity was determined at room temperature.
  • a combination of plant oil and terpene- derivatives for the epoxy design appear to be an attractive direction to overcome the traditional deficiencies of bio-based epoxies (e.g., high viscosity, or low mechanical strength, or relatively low bio- content), and, hence, to further advance the sustainable development of bio-based epoxy materials.
  • bio-based epoxies e.g., high viscosity, or low mechanical strength, or relatively low bio- content
  • 10-undecenoic acid (UA, 98%), 4-ethenyl-7-oxabicyclo[4.1.0]heptanes (ECP, 98%), (+)-limonene 1,2-epoxide (MECP, 98%), 4-methyl hexahydrophthalic anhydride (98%) and 4(5)-methylimidazole (98%) were purchased from Sigma-Aldrich (USA).
  • Amberlyst-15 dry hydrogen form (particle size ⁇ 300 ⁇ , capacity 4.7meq/g by dry weight) was obtained from Dow Chemical Company.
  • M-chloroperoxybenzoic acid (m-CPBA, 70-75%) was purchased from Acros Organics.
  • Cationic initiator (PC-2506,[4-(2-hydroxyl-l-tetradecyloxy)-phenyl], phenyliodonium hexafluorantimonate) was kindly provided by Polyset Inc.
  • Epoxy Precursor CUA UA (100.0 g) and ECP (67.4 g) were charged into a 250 mL round-bottomed flask equipped with a reflux condenser, and the mixture was stirred with a magnetic bar at 80 °C for 48 h and transferred to a 2000 mL separating funnel. 400 mL hexane and 800 mL sodium carbonate solution (10 wt %) were then added to separate the residual UA from the product. Hexane solvent was then removed and collected through high vacuum rotary evaporation at 60 °C, and a colorless CUA liquid with a yield rate of 82 % (relative to pure ECP) was obtained.
  • Epoxy EMCUA The synthesis and purification procedures of EMCUA were the same as that of ECUA, and a clear and colorless liquid with a yield rate of 91% (relative to the MCUA) was obtained.
  • the mixture was mixed homogenously with the aid of a Vortex mixer and sonicator, then coated onto a 6 inch x 10 inch glass plate with a film casting knife (model 4302, BYK-Gardner USA) set at 160 ⁇ wet thickness.
  • the resin containing photo-initiator was cured with a Fusion 300S UV system (300 W/inch power, D bulb, UVA radiation dose 1.7-1.8J/cm 2 ) equipped with a LC6B bench top conveyor at conveyor speed of 213 cm/min.
  • the corresponding cured film was named as uv-EMCCA.
  • the UV cured film from EMCUA was name as uv-EMCUA.
  • FTIR Fourier transform infrared
  • Spectra acquisitions were based on 32 scans with data spacing of 2.0 cm "1 .
  • 3 ⁇ 4 MR were performed using a Bruker 300 MHz spectrometer at room temperature.
  • 3 ⁇ 4-3 ⁇ 4 COSY spectra were obtained with 128 increments and four scans for each increment.
  • the positive-ion electro-spray ionization time-of-flight (ESI-TOF) mass spectra were acquired by injecting the sample (solubilized in acetonitrile) into the ESI-TOF mass spectrometer (Q-Tof-2TM, Micromass Ltd.).
  • the sample was equilibrated at 25 °C for 0.5 min without UV, then UV-irradiated for 20 min under a nitrogen atmosphere. Light transmittances were measured by UV spectrometer (Hewlett-Packard 8453) with 0.16 mm thickness for specimens. Dynamic mechanical analysis (DMA) was performed with a DMA (Q800 New Castle, DE) using a tension mode. A 5 ⁇ amplitude was applied to guarantee the measurement was within the linear viscoelastic region. Samples were heated from 0 °C to 120 °C using a heating rate of 3 °C/min and frequency of lHz. Creep behavior measurements was also carried out on DMA (Q800 New Castle, DE).
  • DMA Dynamic mechanical analysis
  • the attack takes place preferentially from the backside (like in an SN2 reaction) because the carbon-oxygen bond is still to some degree in place, and the oxygen blocks attack from the front side.
  • the epoxy ring of ECP was first protonated (SN1 route) by the Amberlyst- 15. Then the hydroxyl group on MCUA attacked the electrophilic carbonon epoxy ring to realize a ring opening (SN2 route), and a graft of ECP on MCUA was achieved.
  • MECP is a "greener" building block compared to ECP because of the fully bio-based component from citrus oil.
  • solid catalyst Amberlyst-15 is dissolvable in MECP, and consequently the product cannot be separated from the catalyst easily through a simple filtration. Distinct from the case in MECP, Amberlyst-15 is insoluble in ECP (FIG. 27 (b)) and can be easily removed from the system; thereby ECP was selected as the cycloaliphatic ring for grafting onto MCUA in this work, under the following reaction conditions.
  • EMCUA and EMCCA electrospray ionization (ESI) mass spectra (positive-ion mode) of EMCUA and EMCCA were determined.
  • the ion peak at m/z 391.2 is speculated to be the ion that lost one oxygen atom from [EMCUA+ CH3CN] + .
  • Cationic photo-initiator (PC-2506, 3wt%) was added into EMCCA.
  • the mixture was mixed homogenously with the aid of a Vortex mixer and sonicator, then coated onto a 6 inch x 10 inch glass plate with a film casting knife (model 4302, BYK- Gardner USA) set at 160 ⁇ wet thickness.
  • the resin containing photo-initiator was cured with a Fusion 300S UV system (300 W/inch power, D bulb, UVA radiation dose 1.7-1.8J/cm 2 ) equipped with a LC6B bench top conveyor at conveyor speed of 213 cm/min.
  • the corresponding cured film was named as uv-EMCCA.
  • the UV cured film from EMCUA was name as uv-EMCUA.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)

Abstract

L'invention concerne un composé époxy d'origine biologique, des précurseurs, des compositions, des procédés et des articles de fabrication associés à celui-ci. Le composé époxy d'origine biologique comprend une structure cyclique cycloaliphatique à pont éther : où, chacun parmi Ra' et Rb' est choisi dans le groupe constitué par -H, des groupes alkyle ramifiés et non ramifiés, des fragments d'acide gras, des cycles aliphatiques substitués ou non substitués, des fragments aromatiques substitués ou non substitués, des fragments époxy et des combinaisons correspondantes, à condition qu'au moins l'un parmi Ra' et Rb' comprenne un fragment époxy.
PCT/US2016/064655 2015-12-04 2016-12-02 Monomères époxy d'origine biologique, compositions et leurs utilisations WO2017096187A1 (fr)

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US10556919B2 (en) 2017-12-04 2020-02-11 International Business Machines Corporation Limonene-based, non-halogenated flame retardants for polymeric applications
CN111117162A (zh) * 2019-12-30 2020-05-08 长春工业大学 基于白藜芦醇的生物基碳纤维复合材料及其制备方法
CN112457471A (zh) * 2020-11-28 2021-03-09 江苏泰特尔新材料科技股份有限公司 一种高透光高耐热环氧树脂及其制备方法
WO2021240071A1 (fr) 2020-05-28 2021-12-02 Aalto University Foundation Sr Revêtements de surfaces lignine-particule-époxy à base d'eau, thermodurcis et adhésifs

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US20100105856A1 (en) * 2006-12-07 2010-04-29 Basf Se Epoxy resin compositions and process for preparing them
US20110144272A1 (en) * 2009-12-16 2011-06-16 Hexion Specialty Chemicals, Inc. Compositions useful for preparing composites and composites produced therewith
US20140275343A1 (en) * 2013-03-12 2014-09-18 Dow Global Technologies Llc Epoxy resin adducts and thermosets thereof

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US5741835A (en) * 1995-10-31 1998-04-21 Shell Oil Company Aqueous dispersions of epoxy resins
US20100105856A1 (en) * 2006-12-07 2010-04-29 Basf Se Epoxy resin compositions and process for preparing them
US20110144272A1 (en) * 2009-12-16 2011-06-16 Hexion Specialty Chemicals, Inc. Compositions useful for preparing composites and composites produced therewith
US20140275343A1 (en) * 2013-03-12 2014-09-18 Dow Global Technologies Llc Epoxy resin adducts and thermosets thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10556919B2 (en) 2017-12-04 2020-02-11 International Business Machines Corporation Limonene-based, non-halogenated flame retardants for polymeric applications
US11053264B2 (en) 2017-12-04 2021-07-06 International Business Machines Corporation Limonene-based, non-halogenated flame retardants for polymeric applications
CN111117162A (zh) * 2019-12-30 2020-05-08 长春工业大学 基于白藜芦醇的生物基碳纤维复合材料及其制备方法
WO2021240071A1 (fr) 2020-05-28 2021-12-02 Aalto University Foundation Sr Revêtements de surfaces lignine-particule-époxy à base d'eau, thermodurcis et adhésifs
CN112457471A (zh) * 2020-11-28 2021-03-09 江苏泰特尔新材料科技股份有限公司 一种高透光高耐热环氧树脂及其制备方法
CN112457471B (zh) * 2020-11-28 2022-12-27 江苏泰特尔新材料科技股份有限公司 一种高透光高耐热环氧树脂及其制备方法

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