WO2016172353A1 - Résine époxy dérivée de la vanilline et produits thermodurcissables obtenus à partir de celle-ci - Google Patents

Résine époxy dérivée de la vanilline et produits thermodurcissables obtenus à partir de celle-ci Download PDF

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WO2016172353A1
WO2016172353A1 PCT/US2016/028666 US2016028666W WO2016172353A1 WO 2016172353 A1 WO2016172353 A1 WO 2016172353A1 US 2016028666 W US2016028666 W US 2016028666W WO 2016172353 A1 WO2016172353 A1 WO 2016172353A1
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vanillin
schiff base
formula
compound
epoxy resin
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PCT/US2016/028666
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English (en)
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Dean C. Webster
Alison ROHLY
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Ndsu 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
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines

Definitions

  • This invention relates to the field of functionalized bio-based resins and curable compostions containing bio-based resins.
  • the invention relates to bio-based resins from vanillin.
  • thermosetting polymers and composites have been widely used in modern industry because of their low density, good mechanical properties, low cost, dimensional stability, and so on.
  • Important monomers and oligomers for thermosets include unsaturated polyester, epoxy resin, vinyl ester, phenol-formaldehyde resin, melamine resin, etc.
  • most of these resins have been synthesized using petroleum-based chemicals as the raw materials.
  • the polymer and composites industry is suffering from potential increasing cost and environmental regulations. Therefore, much effort has been devoted lately to develop polymers and composites from bio-renewable raw materials.
  • Vanillin shown below, is a phenolic aldehyde resulting from the depolymerization of lignin.
  • Lignin an abundant aromatic bio-polymer, is a key component of woddy plants and is found in the cell walls of plants that grow on dry land.
  • lignin is sourced from wood products and produced as a by-product from pulping processes which convert wood into wood pulp and extract cellulose.
  • lignin is treated as a waste product in the pulp and paper industries.
  • This invention which relates to bio-based resins from vanillin, answers the need for additional bio-based resins that expand the number and utility of currently known bio-based resins.
  • the invention relates to a vanillin Schiff base com ound of formula (I):
  • R is an optionally substituted, divalent C1-C15 alkyl, an optionally substituted C3-C15 cycloalkyl, or a group selected from :
  • the invention also relates a method of making a vanillin Schiff base compound.
  • the invention also relates to bio-based e oxy resin of formula (II):
  • the invention further relates to a method of preparing a biobased epoxy resin of formula (II).
  • the invention relates to a glycidated vanillin compound of formula
  • the invention relates to curable coating composition
  • a biobased epoxy resin of formula (I I) or a glycidated vanillin compound of formula (I I I) (b) a curing agent, (c) optionally, a solvent, and (d) optionally, an additive.
  • Figure 1 depicts the FTIR spectrum of Schiff base grind products of vanillin and diamines.
  • Figure 2 depicts the 1 H NMR spectrum of Schiff base grind products of vanillin and diamines.
  • Figure 3 depicts the FTIR spectrum of Schiff base products of vanillin and diamines using solvent addition method.
  • Figures 4a, 4b, and 4c depict the 1 H NMR spectrum of Schiff base products of vanillin and diamines using solvent addition method.
  • Figure 5 depicts the FTIR spectrum of vanillin Schiff base and vanillin glycidation products.
  • Figure 6 depicts the 1 H NMR spectrum of vanillin Schiff base and vanillin glycidated products.
  • a novel epoxy resin is synthesized from the reaction between vanillin, derived from natural sources, and diamines to form a Schiff base. See Equation (1).
  • I n Equation (1) two moles of vanillin are reacted with a diamine to form a vanillin Schiff base compound of formula (I).
  • I n one embodiment, the invention relates to a vanillin Schiff base compound of formula (I), where R is as defined below.
  • Equation (1) Vanillin-Schiff Base compound of Formula (I)
  • Any difunctional primary amines may be used in the synthesis of the bisphenol which is the vanillin Schiff base compound of formula (I). Mixtures of diamines may also be used.
  • R may be an optionally substituted, divalent C1-C15 alkyl, an optionally substituted C3-C15 cycloalkyi, or a group selected from :
  • alkyl includes straight and branched alkyl groups.
  • cycloalkyi refers to cyclic alkyl groups having three to ten, preferably three to seven carbon atoms. Suitable cycloalkyls include, but are not limited to cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • substituents for optional substitution include, but are not limited to, halo substituents, e.g., F; CI; Br; or I; a hydroxyl group; a C1-C6 alkoxy group, e.g., -OCH3, -OCH2CH3, or -OCH(CH 3 )2; a C C 6 haloalkyl group, e.g., -CF 3 , -CH 2 CF 3 , or -CHCI 2 ; C C 6 alkylthio; -N0 2 ; -CN; a sulfate group; a C1-C12 alkyl group, and the like.
  • halo substituents e.g., F; CI; Br; or I
  • a hydroxyl group e.g., a C1-C6 alkoxy group, e.g., -OCH3, -OCH2CH3, or -OCH(CH 3 )2
  • the divalent group R is a C 2 -Ci 0 alkyl, a C 4 -C 8 alkyl, ethyl, pentyl, or hexyl.
  • biobased diamines can be used, such as Priamine resins from Croda USA, New Castle, DE, which are believed to be fatty dimer diamines.
  • the diamine is ethylenediamine, 2-methylpentane-l,5-diamine, benzene-l,4-diamine, PACM (bis(para-aminocyclohexyl)methane), or methylene dianiline.
  • a vanillin Schiff base compound of the invention may be prepared using techniques known in the art for preparing Schiff base compounds. As shown in the Examples below, a vanillin Schiff base compound may be prepared by grinding vanillin with a diamine, reacting vanillin and a diamine in a melt, or reacting vanillin and a diamine in the presence of a solvent, preferably in solution. Solvents which dissolve both the vanillin and the diamine are generally preferred. Such solvents include for example, methanol, ethanol, propanol, chloroform, dichloromethane, acetic acid, diethyl ether, tetrahydrofuran, and water.
  • the invention also relates to a method of making a vanillin Schiff base compound of formula (I) by reacting vanillin with a diamine compound having the formula H 2 N-R-NH 2 under sufficient reaction conditions to produce a vanillin Schiff base compound of formula (I).
  • a vanillin Schiff base compound of formula (I) may be reacted with epichlorohydrin to form a biobased epoxy resin of formula (I I) of the invention, where R is as defined above. This glycidation reaction is shown in Equation (2). An excess of epichlorohydrin is used in order to exhaustively react the phenolic hydroxyl groups.
  • Equation (2) Vanillin Schiff Base Glycidation
  • the invention relates to a method of preparing a biobased epoxy resin of formula (II) by reacting a vanillin Schiff base compound of formula (I) with
  • epichlorohydrin For example, excess epichlorohydrin may be added to the Schiff Base compound of formula (I), e.g, in a 10 : 1 molar equivalent ratio, with an effective amount, e.g. 0.1 equivalents, of a catalyst, such as benzyltriethylammonium chloride (TEBAC).
  • a catalyst such as benzyltriethylammonium chloride (TEBAC).
  • TEBAC benzyltriethylammonium chloride
  • the reaction may then be heated, for example to approximately 80 °C, and stirred, for example, for about 1 hour.
  • the solution may then be allowed to cool to room temperature.
  • a 5 mol/L solution of sodium hydroxide, for example, and another 0.1 equivalents of a phase transfer catalyst, such as TEBAC, may then be slowly added to the solution, for example, for over 2 hours, while stirring.
  • the invention relates to another biobased resin, a glycidated vanillin compound of formula (III).
  • Vanillin may be glycidated via a glycidation reaction with epichlorohydrin. This is shown in Equation (3).
  • a further embodiment of the invention relates to a method of preparing a glycidated vanillin compound of formula (III) by reacting vanillin with epichlorohydrin.
  • the epichlorohydrin may be added to vanillin in a 10 : 1 molar equivalent ratio with 0.1 equivalents of a catalyst, such as benzyltriethylammonium chloride (TEBAC).
  • a catalyst such as benzyltriethylammonium chloride (TEBAC).
  • TEBAC benzyltriethylammonium chloride
  • the reaction may then be heated, for example to approximately 80 °C and stirred, for example, for 1 hour.
  • the solution may then be allowed to cool to room temperature.
  • a 5 mol/L solution of sodium hydroxide, for example, and another 0.1 equivalents of a phase transfer catalyst, such as TEBAC, may then be slowly added to the solution, for example, for over 2 hours, while stirring.
  • Catalysts that may be use to prepare the biobased epoxy resin of formula (II) and the glycidated vanillin compound of formula (III) include, but are not limited to,
  • methyltributylammonium chloride tetrabutylammonium chloride, tetramethylammonium chloride, dodecyltrimethylammonium chloride, methyltriethylammonium chloride,
  • cetyltrimethylammonium chloride dibenzyldimethylammonium chloride
  • benzyldimethylhexadecylammonium chloride benzyldimethyltetradecylammonium chloride, hexadecyltributylphosphonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltributylammonium bromide, benzalkonium bromide, cetyltrimethylammonium bromide, didecyldimethylammonium bromide, dodecyltrimethylammonium bromide, tetraoctylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium nitrate, tetrabutylammonium fluoride, tetrabutylammonium hydrogen sulfate, tetramethylammonium hydroxide, tetraethylammonium hydrox
  • the biobased epoxy resins of the invention can be cured using typical curing agents used for petrochemical epoxy resins. These include amines, anhydrides, and phenolic resins, and other such curing agents known in the art.
  • typical curing agents used for petrochemical epoxy resins include amines, anhydrides, and phenolic resins, and other such curing agents known in the art.
  • An example of crosslinking biobased epoxy resins of formula (I I) with a diamine curing agent, (H 2 N-R'-NH 2 , such as those listed below), to form thermosets according to the invention is shown in Equation (4).
  • Equation (5) shows the crosslinking reaction of a glycidated vanillin compound of formula I II) with a diamine.
  • the biobased epoxy resins of this invention are useful in various coating compostions such as coatings, composites, and adhesives. Accordingly, the invention also relates to curable coating compositions comprising (a) a biobased epoxy resin of formula (II) or a glycidated vanillin compound of formula (III), (b) a curing agent, (c) optionally, a solvent, and (d) optionally, an additive.
  • a curable coating composition of the invention therefore, may be a solvent-free coating composition or may optionally contain a solvent such as, for example, acetone, THF, methyl ethyl ketone (MEK), xylene, etc.
  • the curable coating composition of the invention may be a solution in such a solvent or mixture of solvents.
  • Suitable amine curing agents are those which are soluble or at least dispersible in a coating composition of the invention.
  • Amine curing agents known in the art include, for example, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine, etc., as well as 2,2,4- and/or 2,4,4-trimethylhexamethylenediamine; 1,2- and 1,3-diaminopropane; 2,2- dimethylpropylenediamine; 1,4-diaminobutane; 1,6-hexanediamine; 1,7-diaminoheptane; 1,8- diaminooctane; 1,9-diaminononane; 1,12-diaminododecane; 4-azaheptamethylenediamine; N,N"-bis(3-aminopropyl)butane-l,4-diamine; l-ethyl-l,3-propanediamine; 2,2(4),4-
  • cycloaliphatic amine curing agents include, but are not limited to, 1,2- and 1,3-diaminocyclohexane; l,4-diamino-2,5-diethylcyclohexane; 1,4- diamino-3,6-diethylcyclohexane; l,2-diamino-4-ethylcyclohexane; l,4-diamino-2,5-diethylcyclo- hexane; l,2-diamino-4-cyclohexylcyclohexane; isophorone-diamine; norbornanediamine; 4,4'- diaminodicyclohexylmethane; 4,4'-diaminodicyclohexylethane; 4,4
  • araliphatic amines in particular those amines in which the amino groups are present on the aliphatic radical, include, for example, m- and p-xylylenediamine and its hydrogenation products as well as diamide diphenylmethane; diamide diphenylsulfonic acid (amine adduct); 4,4"-methylenedianiline; 2,4-bis (p-aminobenzyl)aniline; diethyltoluenediamine; and m- phenylene diamine.
  • the amine curing agents may be used alone or as mixtures.
  • Suitable amine-epoxide adduct curing agents include, for example, reaction products of diamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, m- xylylenediamine and/or bis(aminomethyl)cyclohexane with terminal epoxides, such as the polyglycidyl ethers of the polyhydric phenols listed above.
  • Polyamide resins can also serve as curing agents for the resins.
  • Suitable polyamide reins include those prepared through the reaction product of multifunctional amines with diacids. Dimer fatty acids are the most commonly used diacids for the synthesis of polyamide resins.
  • a preferred amine curing agent used with the coating compositions of the invention is PACM (bis(para-aminocyclohexyl)methane).
  • Epoxy-amine reactions may also be used to cure the coating compositions of the invention.
  • Epoxy-amine reactions may be catalyzed by, for example, by water, alcohols, tertiary amines, and weak acids, such as phenols.
  • any acid anhydride such as those used in coatings applications, may be used to prepare an epoxy-anhydride coating composition.
  • acid anhydrides which may be used include, but are not limited to, succinic anhydride, maleic anhydride, 4-Methyl-l,2-cyclohexanedicarboxylic anhydride (MCHDA), dodecynyl succinic anhydride, phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride (Me-THPA), methyl hexahydrophthalic anhydride (Me-HHPA), trialkyl tetrahydrophthalic anhydride (TATHPA), trimellitic anhydride, chlorendic anhydride, nadic methyl anhydride (methylbicyclo[2.2.1]hept-5-ene-2,3-
  • tertiary amine catalysts known in the art may be used in the coating compositions of the invention.
  • Tertiary amine catalysts include at least one tertiary nitrogen atom in a ring system.
  • tertiary amine catalysts include, but are not limited to, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4- diazabicyclo[2.2.2]octane (DABCO), 4-(dimethylamino)pyridine (DMAP), 7-methyl-1.5.7- triazabicyclo[4.4.0]dec-5-ene (MTBD), quinuclidine, pyrrocoline, and similar materials.
  • DBU l,8-diazabicyclo[5.4.0]undec-7-ene
  • DABCO 1,4- diazabicyclo[2.2.2]octane
  • DMAP 4-(dimethylamino)pyridine
  • MTBD 7-methyl-1.5.7- triazabicyclo[4.4.0]dec-5-ene
  • quinuclidine pyrrocoline, and similar materials.
  • the invention also relates to the use of a coating composition which may be coated onto a substrate
  • the substrate can be any common substrate such as paper, polyester films such as polyethylene and polypropylene, metals such as aluminum and steel, glass, urethane elastomers, primed (painted) substrates, and the like.
  • the coating composition of the invention may be cured at room temperature (ambient cure) or at elevated temperatures (thermal cure), or may be cured photochemically.
  • a coating composition of the invention may further contain coating additives.
  • coating additives include, but are not limited to, one or more leveling, rheology, and flow control agents such as silicones, fluorocarbons, or cellulosics; extenders; reactive coalescing aids such as those described in U.S. Pat. No.
  • plasticizers plasticizers; flatting agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; colorants; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; anti- flooding and anti-floating agents; biocides, fungicides and mildewcides; corrosion inhibitors; thickening agents; or coalescing agents.
  • UV absorbers ultraviolet (UV) absorbers
  • UV light stabilizers tinting pigments
  • colorants defoaming and antifoaming agents
  • anti-settling, anti-sag and bodying agents anti-skinning agents
  • anti- flooding and anti-floating agents biocides, fungicides and mildewcides
  • corrosion inhibitors thickening agents; or coalescing agents.
  • specific examples of such additives can be found in Raw Materials Index, published by the National Paint & Coatings Association, 1500 Rhode Island Avenue, N.W
  • Vanillin, ethylenediamine, and p-phenylenediamine were purchased from Sigma Aldrich (99%) and used as is.
  • Priamine 1071, 1073, and 1074 were obtained from Croda.
  • PACM was received from Air Products.
  • Dytek A was obtained from I nvista.
  • Methanol and epichlorohydrin were purchased from VWR.
  • FTI R measurements were done by a Bruker Optics Vertex 70 FTIR spectrometer. Spectra acquisitions were based on 32 scans with data spacing of 4.0 cm 1 in the range of 4000-500 cm 1 .
  • a DSC Q1000 from TA I nstruments (New Castle, DE) with an auto sampler was used for differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) glass transition temperature (T g ) and Ts%, determination. Samples were subjected to a heat-cool-heat cycle from -90 to +100°C by ramping at 10 °C/min for both heating and cooling cycles. The second heating cycle was used to characterize the samples.
  • Mass spectra were run using electrospray ionization (ESI) using a Waters SYNAPT G2-Si in positive ion mode.
  • ESI electrospray ionization
  • Fig. 1 depicts the FTIR spectrum of the Schiff Base grind products of vanillin and diamines.
  • the 1 H NMR spectra of these Schiff Base grind products, Fig. 2 indicates significant amount of unreacted aldehyde, which correlates to incomplete Schiff base formation.
  • Vanillin was heated to 85 °C to ensure the vanillin melted. Diamine was slowly added to the melted vanillin and stirred with a stir bar. The materials were highly exothermic and reacted instantaneously. The product was not characterized, as the material was difficult to recover. Diamines used were Priamine 1071 (aliphatic dimer diamine), PACM (bis(para- aminocyclohexyl)methane), Dytek A (2-methylpentamethylenediamine), and ED
  • Vanillin was solubilized in methanol (50% methanol by weight) at room temperature. Once vanillin was fully dissolved, diamine was slowly added to the solution and stirred. The reaction appeared to occur instantaneously (bright color change observed). However, the solution was stirred overnight at room temperature to ensure complete reaction. The methanol was removed using a rotary evaporator and the remaining product was placed under vacuum overnight to ensure complete removal of methanol and water. Diamines used were Priamine 1071 (aliphatic dimer diamine), PACM (bis(para-aminocyclohexyl)methane), Dytek A (2-methylpentamethylenediamine), and PD (p-phenylenediamine).
  • the vanillin Schiff base compounds prepared by solvent addition were characterized by FTIR as shown in Fig. 3.
  • the imines were present at 1650 wavenumbers in the FTIR spectrum, indicating Schiff base formation.
  • the vanilin p-phenylenediamine Schiff base product (Van-PD) was difficult to detect (the concentration was too small), however, mass spectrometry confirms the Van-PD product formation. Table 1 shows all mass spectrometry data.
  • the Priamine has an approximate molecular weight of 620 g/mol. However, the exact molecular weight was unknown, and, therefore, the Vanillin-Priamine Schiff base product (Van- Priamine) cannot be confirmed from mass spectrometry. However, the remaining Schiff base products were all confirmed from mass spectrometry at less than 5 ppm.
  • Figs. 4a Van-Priamine
  • 4b Van-PACM
  • 4c Van-Dytek A
  • Figs. 4a Van-Priamine
  • 4b Van-PACM
  • 4c Van-Dytek A
  • the X H NMR is not available.
  • the remaining Schiff base products were all confirmed from 1 H NMR based on the disappearance of the aldehyde peak and the formation of the imine peak (peak a).
  • Vanillin, epichlorohydrin, and a phase transfer catalyst TEBAC were added to a round bottom flask. The mixture was heated to 80 °C for an hour. After an hour, the temperature was turned off and allowed to cool to room temperature. An aqueous sodium hydroxide solution was slowly added over 30 minutes, and the solution was stirred overnight. The next day, the product was washed with ethyl acetate, deionized water, and finally a brine solution. Solvent was removed by rotary evaporator and the product was then dried under vacuum overnight to ensure complete removal of solvent. The glycidylated vanillin product will be referred to as Van-EPC.
  • Fig. 5 shows the FTIR spectra of the vanillin Schiff base and vanillin glycidation products.
  • the oxirane groups were present within the FTI R spectra of the glycidylated products between 800-900 wavenumbers.
  • Fig. 6 shows the 1 H N MR spectra of the glycidation products.
  • the 1 H NMR peaks indicate aldehyde reformation with the glycidylated vanillin Schiff base products. This is most likely a result of the hydrolysis of the imine upon an aqueous sodium hydroxide addition during the glycidation procedure. Imine peaks were also noticeable on the glycidylated vanillin Schiff base products, indicating only partial hydrolysis of the imine.
  • the glycidylated vanillin product (Van-EPC) indicated aldehyde peaks as would be expected.
  • Epoxy equivalent weight was done on Van-EPC in accordance with ASTM D1652-11.
  • the EEW was 187.26 g/eq, with the theoretical EEW of 208.21 g/eq.
  • Van-EPC Due to the hydrolysis of the glycidylated vanillin Schiff base products, crosslinking was mostly focused on the glycidylated vanillin product (Van-EPC). Van-EPC was crosslinked with various diamines in a 1:0.5, 1:1, and 1:2 epoxy to amine ratio. Van-EPC was melted at 93 °C in a copper heating plate. Diamine was added and quickly vortexed for ⁇ 5-10 seconds and poured into a small aluminum pan as quickly as possible before material cured. The epoxy was cured in a vacuum oven at 100 °C for 2 hours followed by 30 °C overnight. The diamines used were ethylene diamine, DytekA, IPDA, PACM, Jeffamine T403, Jeffamine D230, Priamine 1071, Priamine 1073, and Priamine 1074.

Abstract

L'invention concerne un composé de base de Schiff de vanilline de formule (I) : (I) et un procédé de préparation d'un composé de base de Schiff de vanilline. Les composés de base de Schiff de vanilline peuvent être glycidés pour former une résine époxy d'origine biologique. L'invention concerne également un composé de vanilline glycidé ayant une fonctionnalité époxy. La résine époxy d'origine biologique selon la présente invention et le composé de vanilline glycidé peuvent être utilisés comme produits thermodurcissables dans des compositions de revêtement.
PCT/US2016/028666 2015-04-21 2016-04-21 Résine époxy dérivée de la vanilline et produits thermodurcissables obtenus à partir de celle-ci WO2016172353A1 (fr)

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US10167427B2 (en) 2017-05-02 2019-01-01 International Business Machines Corporation Flame-retardant vanillin-derived cross-linkers
US10214693B2 (en) 2017-05-02 2019-02-26 International Business Machines Corporation Flame-retardant vanillin-derived small molecules
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US10266772B2 (en) 2017-05-02 2019-04-23 International Business Machines Corporation Flame-retardant vanillin-derived monomers
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CN110386907A (zh) * 2019-06-18 2019-10-29 东华大学 一种含亚胺键的环氧树脂单体及其制备方法和应用
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WO2020106815A1 (fr) * 2018-11-21 2020-05-28 The Regents Of The University Of California Résines époxy thermodurcissables dégradables et recyclables
CN111620992A (zh) * 2020-06-24 2020-09-04 江南大学 一种生物基可回收热固性树脂
CN111704711A (zh) * 2019-03-18 2020-09-25 中国科学院宁波材料技术与工程研究所 一种基于缩醛结构的环氧单体及其制备方法与应用
CN112662276A (zh) * 2020-12-23 2021-04-16 华南理工大学 一种生物基防火耐盐水性环氧树脂涂料及其制备方法
WO2021139651A1 (fr) * 2020-01-07 2021-07-15 厦门大学 Résine époxyde de biomasse résistant aux températures élevées, ignifuge, intrinsèque et son procédé de préparation
CN113698575A (zh) * 2021-09-02 2021-11-26 四川大学 一种基于硅氧烷席夫碱结构的高抗冲击可重塑阻燃环氧树脂及制备方法
CN113897026A (zh) * 2021-09-09 2022-01-07 深圳优美创新科技有限公司 生物基树脂基体材料、碳纤维生物基树脂复合材料及其制备方法
CN114573790A (zh) * 2022-03-17 2022-06-03 宁波锋成先进能源材料研究院有限公司 一种生物基可降解环氧树脂、其制备方法和应用
CN114853696A (zh) * 2022-05-19 2022-08-05 厦门大学 一种生物基本征阻燃环氧单体及其制备方法和应用
CN115093544A (zh) * 2022-06-07 2022-09-23 西北师范大学 一种席夫碱结构丁香醛基环氧树脂及其制备方法

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WO2020106815A1 (fr) * 2018-11-21 2020-05-28 The Regents Of The University Of California Résines époxy thermodurcissables dégradables et recyclables
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