• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present invention relates to a method for manufacturing an ablative resin comprising a pre-polymerization step in which an innovative aldehyde compound is used.
    公开号:FR3031977A1
    申请号:FR1500127
    申请日:2015-01-22
    公开日:2016-07-29
    发明作者:Gabriel M Foyer；Guirao Claire F Negrell；Sylvain Y Caillol；Ghislain C David；Nadia Rodriguez
    申请人:Centre National de la Recherche Scientifique CNRS；Herakles SA；
    IPC主号:
    专利说明:

    [0001] BACKGROUND OF THE INVENTION The invention relates to a novel process for producing a phenolic resin. It is known to make propellant nozzles from phenolic resin resole type, for example from ablative resin such as Ablaphene RS101 resin. The phenolic resins used for this application must have excellent properties of thermal stability and charcoal. Phenolic resins such as Ablaphene RS101 resin are synthesized from formaldehyde and phenol. It is known that formaldehyde is very reactive towards phenol. The phenolic resins synthesized from these two compounds have high aromatic densities and high crosslinking densities, which give the resins the desired thermal stability and charring properties.
    [0002] However, formaldehyde and phenol are compounds classified as Carcinogenic Reprotoxic Mutagenic (CMR) Category 1B and 2 respectively. Due to its toxicity, formaldehyde is a chemical compound whose use becomes strictly regulated by the CMR legislation.
    [0003] In addition, formaldehyde is a chemical compound derived from exhaustible fossil resources. Several projects to synthesize phenolic resins from aldehyde compounds from renewable resources and without formaldehyde have been conducted. Formaldehyde is then substituted with aldehyde compounds such as glyoxal [E.C. Ramires, J.D. Megiatto, C. Gardrat, A. Castellan, E. Frollini, Biobased composites from glyoxalphenolic resins and sisal fibers, Bioresour. Technol., 101 (2010) 19982006.] or furfural [L.H. Brown, Resin-forming reactions of furfural and phenol, J. Ind. Eng. Chem., 44 (1952) 2673-2675.] For example. These compounds are less reactive than formaldehyde and can lead to the production of phenolic resins having properties of thermal stability and insufficient charcoal for the production of aeronautical parts such as propellant nozzles. In addition, these compounds, although less toxic than formaldehyde, are nevertheless classified CMR 2.
    [0004] There is therefore a need for a new route for synthesizing phenolic resins to overcome the use of formaldehyde or other CMR -defined compounds. There is also a need for a new synthesis route for phenolic resins having thermal stability and charcoal properties suitable for producing aeronautical parts such as thruster nozzles. OBJECT AND SUMMARY OF THE INVENTION For this purpose, the invention provides, in a first aspect, a method for producing a phenolic resin comprising the following step: a) prepolymerization of an aromatic aldehyde compound with a phenol compound to obtain the phenolic resin, the aromatic aldehyde compound having either of the following formulas A or B: n3 AB where n1 is an integer from 0 to 4 and when n1 is greater than or 2, the substituents R 1 are the same or different, n 2 is an integer from 0 to 5 and when n 2 is greater than 3 or equal to 2, the substituents R 2 are the same or different and n 3 is an integer of 1 and 6, and wherein the substituents R 1 and R 2 are independently selected from: -OH, -COOH, -COH, -O-Alk groups wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, the hydrocarbon chains comprising between 1 and 20 carbon atoms, saturated or unsaturated, substituted or unsubstituted, interrupted or not by one or more heteroatoms, and optionally having one or more carbonyl or carboxylic acid functions, saturated or unsaturated carbocyclic or heterocyclic groups; or aromatic, monocyclic or polycyclic, substituted or unsubstituted, and optionally having one or more carbonyl or carboxylic acid functions, substituted or unsubstituted aryl groups and optionally having one or more carbonyl or carboxylic acid functions, R2 may further designate a radical of formula A1 in formula A above or a radical of formula B1 in formula B above and R1 may further denote a radical of formula A2 in formula A above, formulas Al, A2 and B1 being the following: ## STR2 ## in the formulas Al, A2 and B1, R1, R2, n1, n2 and n3 are as defined above. By phenolic compound is meant an organic molecule comprising at least one benzene ring to which is attached at least one hydroxyl group (-OH). During the prepolymerization step, the phenol compound is added to the aromatic aldehyde compound to form adducts which will be condensed to obtain the phenolic resin. Step a) results in a phenolic resin which constitutes a prepolymer insofar as it has reactive groups allowing it to participate in a subsequent crosslinking reaction. The invention advantageously makes it possible to dispense with the use of formaldehyde for the manufacture of phenolic resins by proposing a new method for obtaining phenolic resins from aromatic aldehyde compounds that are innovative for this application. As will be detailed below, the aromatic aldehyde compound used in step a) may advantageously have low toxicity and be produced from renewable resources. As mentioned above, it is possible to cross-link various phenolic resins obtained by carrying out step a) in order to obtain a product having a high molecular weight. Thus, the invention also relates to a process for producing a crosslinked phenolic resin comprising a step b) during which a heat treatment is carried out so as to crosslink phenolic resins obtained by carrying out a process as described above. high in order to obtain the crosslinked phenolic resin. Advantageously, the aromatic aldehyde compound used in step a) may be polyfunctional and, for example, be an aromatic polyaldehyde compound (i.e. an aromatic aldehyde compound having several aldehyde functions). The polyfunctional and aromatic character of such an aromatic aldehyde compound advantageously makes it possible to obtain, after step b) of crosslinking, a resin having a high crosslinking density as well as a high aromatic density. Thus, the use of such an aromatic aldehyde compound advantageously makes it possible to obtain, after step b), a crosslinked phenolic resin whose application properties and properties of thermal stability and charcoal are similar to, or even greater than, those of Ablaphene resin RS101. In the case where R 2 denotes a radical of formula Al in formula A above, it is to be understood that compound A has the following formula: ## STR2 ## wherein n is an integer from 2 to 6 and n is z is an integer between 0 and 6-n4 with n2 = n2 - (n4 - 1) and with R1, R2 and n1 as defined above. It will be advantageous to use in step a) such an aromatic polyaldehyde compound as it will make it possible to obtain phenolic resins with high degrees of crosslinking and high aromatic densities after step b). This will give the formed resins excellent thermal stability and charring properties. In addition, because of its higher molecular weight, such an aromatic polyaldehyde compound will have a greatly reduced volatility and toxicity compared to formaldehyde.
    [0005] In the case where R2 denotes a radical of formula B1 in formula B above, it is to be understood that compound B has the following formula: where n5 is an integer between 2 and 6 and n " 2 is an integer between 0 and 6-n5 with n "2 = n2 - (n5 - 1) and with R2 and n3 as defined above. It will be advantageous to use in step a) such an aromatic polyaldehyde compound since it will make it possible to obtain phenolic resins with high crosslinking densities and high aromatic densities after step b). This will give the formed resins excellent thermal stability and charring properties. In addition, because of its higher molecular weight, such an aromatic polyaldehyde compound will have greatly reduced volatility and toxicity compared with formaldehyde. In the case where R 1 denotes a radical of formula A2 in formula A above, it should be understood that compound A has the following formula: n6 where n6 is an integer between 2 and 5 and is an integer between 0 and 5-n6 with = n1 - (n6 - 1) and with R1, R2 and n2 as defined above.
    [0006] In an exemplary embodiment, the aromatic aldehyde compound employed in step a) may have formula A and the process may further comprise, prior to step a), a step of manufacturing said aromatic aldehyde compound by aromatic nucleophilic substitution reaction between a compound having the formula A3 and a compound having the formula A4 where X is a leaving group, the formulas A3 and A4 being the following: OH 0 A3 (R1) ro A4 3031977 7 In the formulas A3 and A4, R1, R2, n1 and n2 are as defined above. The leaving group X may for example be a halogen atom or a nitro -NO 2 group, the leaving group being preferably a halogen atom. Alternatively, the aromatic aldehyde compound used in step a) may have the formula B and the method may further comprise before step a) the following two steps: 1) a nucleophilic substitution reaction between a compound of formula A3 and a compound of formula B2 to obtain a compound of formula B3, where Z is a protecting group for obtaining an aldehyde function after deprotection and Y is a leaving group, and 2) a reaction of deprotection of the compound of formula B3 in order to obtain the aromatic aldehyde compound of formula B, the formulas A3, B2, B3 being the following: ## STR2 ## In the formulas A3, B2 and B3, R2, n2 and n3 are as defined above. The leaving group Y may for example be a halogen atom. The group Z may for example be an acetal group, in this case the compound B3 has the following formula: ## STR1 ## R4 and R5 are optionally substituted C1-C8 hydrocarbon chains. Alternatively, the Z moiety may be an imine function.
    [0007] Preferably, the substituents R 1 and R 2 may be independently selected from: -OH, -O-Alk where Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, preferably -0Me, and COOH, R2 may further denote a radical of formula A1 in formula A above or a radical of formula B1 in formula B above and R1 may further denote a radical of formula A2 in Formula A above, in formulas Al, A2 and B1, R1 and R2 are as defined above in this paragraph. In formulas Al, A2 and B1, n1, n2 and n3 are as defined above.
    [0008] Preferably, n1 may be between 0 and 2 and n2 may be between 0 and 3 for formula A. In this embodiment, n1 may preferably be 0. Preferably, n2 may be between 0 and 3 and n3 can be between 1 and 3 for formula B.
    [0009] Preferably, the compound of formula A3 used to manufacture the aromatic aldehyde compound may be chosen from: single phenols, polyphenolic compounds, for example diphenol compounds, hydroxybenzoic aldehydes, hydroxybenzoic acids, hydroxybenzyl alcohols, hydroxycinnamyl alcohols, hydro-polymeric acids, phenylpropenes, coumarins, naphthoquinones, stilbenoids, flavonoids, iso-flavonoids, anthocyanins, lignans, lignins, condensed tannins, hydrolyzable tannins, tannins depolymerized and resole and novolak resins.
    [0010] In a particularly preferred manner, the compound of formula A3 used to manufacture the aromatic aldehyde compound may be chosen from: simple phenols, for example phenol, resorcinol or phloroglucinol, and hydroxybenzoic aldehydes, for example para-hydroxybenzaldehyde, vanillin or syringaldehyde. For example, the compound of formula A3 used to manufacture the aromatic aldehyde compound may be chosen from: phenol, pyrocatechol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, guaiacol, syringol, bisphenol phenol A, bis-phenol S, para-hydroxybenzaldehyde, vanillin, syringaldehyde, dehydrodivanillin, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, vanillyl alcohol, syringyl alcohol, paracoumaryl alcohol, coniferyl alcohol, sinapyl alcohol, ferulic acid, parahydroxybenzoc acid, gallic acid, paracoumaric acid, eugenol, isoeugenol, cardanols, cardols, acids catacin, umbelliferone, juglone, trans-resveratrol, kaempferol, daidzein, delphinidol, enterodiol, lignins, procyanidins, gallotannins, condensed tannins, resole and novolak resins. Such examples of compounds A3 may be produced from renewable resources and may advantageously be used within the scope of the invention. In an exemplary embodiment, the phenolic compound may be chosen from: simple phenols and polyphenol compounds, for example diphenol compounds, phenols and polyphenol compounds which may optionally be substituted by alkoxyl groups, for example. The phenol compound may, for example, be chosen from: phenol, pyrocatechol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, guaiacol, syringol, bis-phenol A, bis-phenol S, Para-hydroxybenzaldehyde, vanillin, syringaldehyde, dehydrodivanillin, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, vanillyl alcohol, syringic alcohol, paracoumaryl alcohol, coniferyl alcohol, sinapyl alcohol, ferulic acid, parahydroxybenzoic acid, gallic acid, paracoumaric acid, eugenol, isoeugenol, cardanols, cardols, anacardial acids, catechin, umbelliferone, juglone, trans-resveratrol, kaempferol, daidzein, delphinidol, enterodiol, lignins, procyanidines, gallotannins, condensed tannins, resole and novolak resins. Such examples of phenolic compounds may be produced from renewable resources and may advantageously be used within the scope of the invention. In an exemplary embodiment, an aromatic aldehyde compound of formula A5 or A6 may be used during step a), the formulas A5 and A6 being as follows: ## STR2 ## where R1 and n1 are as defined higher and Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms. In an exemplary embodiment, an aromatic aldehyde compound of formula B4 or B5 may be used during step a), the formulas B4 and B5 being as follows: ## STR2 ## where n3 is such that as defined above and Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms. The invention also relates to a method of manufacturing a thruster nozzle in which the nozzle is manufactured from a phenolic resin obtained by using a method as described above or from a resin crosslinked phenol obtained by carrying out a process as described above. BRIEF DESCRIPTION OF THE DRAWINGS Other features and advantages of the invention will become apparent from the following description with reference to the accompanying drawings, in which: FIGS. 1 and 2 show thermogravimetric analysis results comparing the properties of resins obtained by a process according to the invention and the resin Ablaphene RS 101.
    [0011] EXAMPLES Example 1: Grafting of aromatic aldehyde functions (synthesis of 4-phenoxybenzaldehyde and application of the latter in phenolic resin synthesis without formaldehyde) Phenol (5 g, 1 eq., 53 mmol), 4-fluorobenzaldehyde (5) 4 g, 0.82 eq., 43.5 mmol), the potassium carbonate (14.68 g, 2 eq., 106 mmol) and 50 mL of N, N-dimethylformamide are placed in a 100 mL flask. equipped with a refrigerant with magnetic stirring and argon atmosphere. The flask is immersed in an oil bath thermostated at 110 ° C. for 15 hours. At the end of the 15 hours of reaction, a NMR analysis of the crude reaction product indicates that the conversion of 4-fluorobenzaldehyde to 4-phenoxybenzaldehyde is complete. The reaction medium is filtered on filter paper, the filtrate is recovered and then distilled under reduced pressure in order to remove the DMF. The product is purified by liquid-liquid extraction with AcOEt / H2O. The organic phases are recovered and washed three times with a solution of sodium hydroxide concentrated to 1 mol / l. These washes are intended to remove the residual phenol and DMF. The organic phases are recovered, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 4.93 g of product 4-phenoxybenzaldehyde is recovered. The product analyzed by 1F and 13C NMR is pure. Appearance: colorless oil. Mass yield = 57%.
    [0012] This reaction is summarized by the synthesis scheme below. OH K2CO3 (2 eq.) DMF, 110 ° C, 15h 1 eq. 0.82 eq. phenol 4-fluorobenzaldehyde 4-phenoxybenzaldehyde A phenolic resin was then synthesized without formaldehyde from 4-phenoxybenzaldehyde according to the operating procedure detailed below. 4-Phenoxybenzaldehyde (6.32 g, 1.5 eq., 31.9 mmol), phenol (2 g, 1 eq, 21.3 mmol) and 50% aqueous sodium hydroxide The mass (0.41 g, 0.5 eq, 10.3 mmol) is placed in a 50 mL flask equipped with a magnetic stirring condenser. The flask is immersed in an oil bath thermostated at 130 ° C for 20 minutes. At the end of this reaction, the mixture is in the form of resitol, homogeneous and viscous. It is recovered, placed in an aluminum cup and cooked in an oven, under atmospheric pressure, according to a cooking program consisting of a temperature rise of 40 ° C. to 180 ° C. at a rate of 3 ° C. h and an isotherm of 24h at 180 ° C. The resite material obtained at the end of this cooking is black, rigid and totally insoluble in acetone.
    [0013] These reactions are summarized by the synthesis scheme below. HO NaOH (0.5 eq.) Resitol 130 ° C, 20 min 1.5 eq. 1 eq. Example 2: Grafting of aromatic aldehyde functions (vanillin-benzaldehyde synthesis and application of the latter in phenolic resin synthesis without formaldehyde) Vanillin (1.62 g, 1 equiv., 10.6 mmol) 4-fluorobenzaldehyde (2.63 g, 2 eq., 21.2 mmol), potassium carbonate (2.94 g, 2 eq., 21.2 mmol) and 10 mL of N, N-dimethylformamide. are placed in a 50 mL flask equipped with a magnetic stirring condenser and argon atmosphere. The flask is immersed in an oil bath thermostated at 110 ° C. for 42 hours. The vanillin used may, for example, be obtained by a bio-sourced synthetic route as described in the article: M.B. Hocking, Vanillin: Synthetic flavoring from sulfite liquor, J. Chem. Educ., 74 (1997) 1055-1059. At the end of the 42 hours of reaction, the conversion of vanillin to vanillin-benzaldehyde, determined by 1 H NMR analysis of the crude reaction product, is complete. The reaction medium is filtered on filter paper, the filtrate is recovered and then distilled under reduced pressure in order to remove the DMF. The product is purified by liquid-liquid extraction with AcOEt / H20 and then washed three times with a brine solution in order to remove the residual DMF. The organic phases are recovered, dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The vanillin-benzaldehyde product is separated from the excess of 4-fluorobenzaldehyde reagent by separation chromatography on silica with the eluent: 90% cyclohexane / 10% AcOEt. 2.04g of product is recovered. The 1H and 13C NMR analyzes indicate that the product is pure. Appearance: white powder. Mass yield = 75%.
    [0014] This reaction is summarized by the synthesis scheme below. K2CO3 (2 eq.) DMF, 110 ° C, 42h OH F 1 eq. 2 eq. vanillin 4-fluorobenzaldehyde vanillin-benzaldehyde A phenolic resin was then synthesized without formaldehyde from vanillin-benzaldehyde according to the operating protocol detailed below. Vanillin-benzaldehyde (1.4 g, 0.75 eq., 5.5 mmol), phenol (0.686 g, 1 eq., 7.3 mmol) and 50% aqueous sodium hydroxide solution (0.1 g, 0.3 eq, 2.5 mmol) are placed in a 50 mL flask equipped with a magnetic stirring condenser. The flask is immersed in an oil bath thermostated at 130 ° C for 20 minutes. At the end of this reaction, the mixture is in the form of resitol, homogeneous and viscous. It is recovered, placed in an aluminum cup and oven-cooked under atmospheric pressure, according to a cooking program consisting of a temperature rise of 40 ° C. to 180 ° C. at a rate of 5 ° C. h and an isotherm of 24h at 180 ° C. The resite material obtained at the end of this cooking is black, rigid and totally insoluble in acetone. These reactions are summarized by the synthesis scheme below.
    [0015] HO NaOH (0.3 eq) Resitol 130 ° C, 20 min 0.75 eq. 1 eq. Example 3 grafting of aliphatic aldehyde functional groups for the preparation of phenolic resins without formaldehyde In this example, 2-phenoxymethyl-1,3-dioxolane was first synthesized according to the operating protocol described below. Phenol (3 g, 1 eq., 31.9 mmol), potassium carbonate (8.81 g, 2 eq., 63.8 mmol), 2-bromomethyl-1,3-dioxolane (10.65 g), g, 2 eq., 46.1 mmol) and butyronitrile (30 mL) are placed in a 100 mL flask equipped with a condenser and magnetically stirred. The medium is refluxed with butyronitrile at 115 ° C. After reacting for 58 hours, the conversion of the phenol to 2- (phenoxymethyl) -1,3-dioxolane, determined by 1 H NMR analysis of the crude reaction product, is complete. The reaction medium is filtered on filter paper and the product is purified by liquid-liquid extraction with AcOEt / H20. The organic phases are recovered, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residual dioxolane reagent present in the product is distilled under secondary vacuum (T = 100 ° C., P = 2.10-2 mbar). 4.12 g of 2- (phenoxymethyl) -1,3-dioxolane is obtained. The product characterized by 1H NMR and 13C is pure. Appearance: colorless liquid. Mass yield = 72%. This reaction is summarized by the synthesis scheme below.
    [0016] 5 K2CO3 (2 eq.), 58h / - 0N./ 0 HO Br 2 eq. 1 eq. 2-bromomethyl-1,3-dioxolane phenol butyronitrile, reflux (115 ° C) 0 2- (phenoxynethyl) -1,3-dioxolane From 2- (phenoxymethyl) -1,3-dioxolane, 2-phenoxyacetaldehyde was then synthesized by carrying out the operating procedure described below. The compound 2- (phenoxymethyl) -1,3-dioxolane (0.756 g, 1 eq., 4.2 mmol) and the solvent mixture consisting of 32 mL of 1 mol / L HCl solution (7.6 eq. 32 mmol) and 32 ml of 1,4-dioxane are placed in a 250 ml flask with magnetic stirring and equipped with a refrigerant.
    [0017] The flask is placed in an oil bath thermostated at 80 ° C. for 5 hours. At the end of this reaction, the pH of the reaction medium is neutralized with a saturated solution of NaHCO 3, the dioxane solvent is evaporated off under reduced pressure and the product is purified by liquid-liquid extraction with AcOEt / H 2 O. The organic phases are recovered, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The product is isolated pure by separation chromatography with a mixture of eluent AcOEt / Cyclohexane: 20/80. 0.35 g of 2-phenoxyacetaldehyde product is obtained. The product characterized by 11-I and 13C NMR is pure. Appearance: colorless oil. Mass yield = 62%.
    [0018] This deprotection reaction of 2- (phenoxymethyl) -1,3-dioxolane to 2-phenoxyacetaldehyde is summarized by the synthesis scheme below.
    [0019] 3031977 16 O.
    [0020] 0 O-HCl (1M) / 1,4-Dioxane OH HO 80 ° C, 5h 2- (phenoxynethyl) -1,3-dioxolane 2-phenoxyacetaldehyde ethylene glycol A phenolic resin was then synthesized without formaldehyde from 2- phenoxyacetaldehyde according to the operating protocol detailed below.
    [0021] 2-Phenoxyacetaldehyde (2 g, 1.5 eq, 14.7 mmol), phenol (0.922 g, 1 eq, 9.8 mmol) and 50% aqueous sodium hydroxide ( 0.15 g, 0.4 eq., 3.6 mmol) are placed in a 50 ml flask equipped with a magnetic stirring condenser. The flask is immersed in an oil bath thermostated at 130 ° C for 10 minutes. At the end of this reaction, the mixture is in the form of resitol, homogeneous and viscous. It is recovered, placed in an aluminum cup and cooked in an oven, under atmospheric pressure, according to a cooking program consisting of a temperature rise of 40 ° C to 180 ° C at a rate of 3 ° C / h and an isotherm of 24h at 180 ° C. The resulting material obtained at the end of this cooking is black and rigid. This reaction is summarized by the synthesis scheme below. O HO NaOH (0.4 eq.) Resitol 130 ° C, 10 min 1.5 eq. 1 eq. Example 4 Grafting Aliphatic Aldehyde Functions for the Preparation of Formaldehyde-Free Phenolic Resins In this example, vanillin-methoxyethane was first synthesized according to the operating procedure described below.
    [0022] Vanillin (11.25 g, 1 eq., 74 mmol), potassium carbonate (40.9 g, 4 eq., 296 mmol), 2-bromo-1,1-dimethoxyethane (25.9 mmol), g, 2 eq., 147.9 mmol) and butyronitrile (240 mL) are placed in a 500 mL flask equipped with a condenser and with magnetic stirring. The medium is refluxed with butyronitrile at 115 ° C. After four days of reaction, the conversion of vanillin to vanillin-dimethoxyethane, determined by 1 H NMR analysis of the crude reaction product, is complete. The reaction medium is filtered on filter paper and the product is purified by liquid-liquid extraction with AcOEt / H20. The organic phases are recovered, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residual acetal reagent present in the product is distilled under secondary vacuum (T = 100 ° C., P = 2.10-2 mbar). 16.74 g of vanillin-dimethoxyethane product is obtained. The product characterized by 1H and 13C NMR is pure. Appearance: yellow oil. Mass yield = 94%.
    [0023] This reaction is summarized by the synthesis scheme below. Br / butyronitrile, reflux (115 ° C), K 2 CO 3 (4 eq), vanillin-dimethoxyethane OH 1 eq. 2 eq. vanillin 2-bromo-1,1-dimethoxyethane From vanillin-dimethoxyethane, vanillin-acetaldehyde was then synthesized by carrying out the operating procedure described below. The vanillin-dimethoxyethane compound (1 g, 1 eq., 4.2 mmol) and the solvent mixture consisting of 16 mL of 1 mol / L solution (3.8 eq., 16 mmol) and 16 mL of tetrahydrofuran are placed in a 100 ml flask with magnetic stirring and equipped with a condenser. The flask is placed in an oil bath thermostated at 60 ° C for 22 hours. At the end of this reaction, the pH of the reaction medium is neutralized with a saturated solution of NaHCO 3, the THF solvent is evaporated off under reduced pressure and the product is purified by liquid-liquid extraction with AcOEt / H 2 O. The organic phases are recovered, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 0.75 g of vanillin-acetaldehyde product is obtained. The product characterized by 11-I and 13C NMR is pure. Appearance: white powder. Mass yield = 90%. This reaction is summarized by the synthetic figure below. o + 2 60 ° C, 22h O Co HCl (1M) / THF 5 vanillin-dimethoxyethane vanillin-acetaldehyde methanol A phenolic resin was then synthesized without formaldehyde from vanillin-acetaldehyde according to the operating procedure detailed below. Vanillin-acetaldehyde (2 g, 0.75 eq, 10.3 mmol), phenol (1.29 g, 1 eq, 13.7 mmol) and 50% aqueous sodium hydroxide Mass (0.16 g, 0.3 eq., 4 mmol) are placed in a 50 mL flask equipped with a magnetic stirring condenser. The flask is immersed in an oil bath thermostated at 130 ° C for 5 minutes. At the end of this reaction, the mixture is in the form of resitol, homogeneous and viscous. It is recovered, placed in an aluminum cup and cooked in an oven, under atmospheric pressure, according to a cooking program consisting of a temperature rise of 40 ° C to 180 ° C at a rate of 3 ° C / h and an isotherm of 24h at 180 ° C. The resulting material obtained at the end of this cooking is black, rigid and totally insoluble in acetone. This reaction is summarized by the synthetic figure below.
    [0024] HO NaOH (0.3 eq.) M. Resitol 130 ° C, 5 min O 0.75 eq. 1 eq. Vanillin-acetaldehyde phenol resin Example 5 Analysis of the thermal stability and charcoal properties of the obtained crosslinked phenolic resins The coke rate measurements of the synthesized resins were carried out by thermogravimetric analysis (TGA) on a Q50 apparatus sold by the company TA Instrument . A 30 mg monolithic sample of resitance is placed on a platinum boat and then heated under a stream of nitrogen (60 mL / min) according to the following program: Linear rise from 20 ° C to 160 ° C at the speed of 10 ° C / min 10 hour isothermal at 160 ° C (mid) Linear rise from 160 ° C to 900 ° C at a rate of 10 ° C / min Isotherm of one hour at 900 ° C (mf) The coke rate is calculated according to the following equation in which the quantities mi and mf correspond to the masses of the sample at the end of the isotherms at 160 ° C. and 900 ° C., respectively: Coke rate = mf / mi The figure 1 shows the results obtained by ATG for the resins synthesized in Examples 1 (4-phenoxybenzaldehyde / phenol) and 2 (vanillin-benzaldehyde / phenol) in comparison with the results obtained for Ablaphene RS101. FIG. 2 represents the results obtained by ATG for the resins synthesized in Examples 3 (2-phenoxyacetaldehyde / phenol resistor) and 4 (vanillin-acetaldehyde / phenol) in comparison with the results obtained for Ablaphene RS101.
    [0025] The coke levels as well as the degradation temperatures at 10% by mass (Td10%) of the resins tested are reported in Tables 1 and 2 below.
    [0026] Vanillin-4-Ablaphene Resistance RS101 Benzaldehyde / Phenol Phenoxybenzaldehyde / Phenol Td10 ° / 0 440 ° C 375 ° C 370 ° C Coke 68% 56% 63% Table 1 Resistance Vanillin-2-Ablaphene Acetaldehyde / Phenol Phenoxyacetaldehyde / These results show that the resins produced by the process according to the invention can exhibit properties of thermal stability and thermal stability. similar charcoal, even superior to those of the reference Ablaphene RS101 resin. This process thus provides access to phenolic resins which can advantageously substitute conventional formophenolic resins for the preparation of aeronautical parts such as propellant nozzles. In addition, these results show that the use of a polyfunctional aromatic aldehyde compound (vanillin-acetaldehyde or vanillin-benzaldehyde) advantageously makes it possible to obtain improved thermal stability and charcoal properties compared to the use of monofunctional aromatic aldehyde compounds (2-phenoxyacetaldehyde and 4-phenoxybenzaldehyde). The phrase "comprising / containing / comprising one" must be understood as "comprising / containing / comprising at least one". The expression "understood between ... and ..." or "from ... to ..." must be understood as including boundaries.
    权利要求:
    Claims (11)
    [0001]
    REVENDICATIONS1. A process for producing a phenolic resin comprising the following step: a) prepolymerizing an aromatic aldehyde compound with a phenolic compound to obtain the phenolic resin, wherein the aromatic aldehyde compound exhibiting one or other of the following formulas A or B: where n1 is an integer between 0 and 4 and when n1 is greater than or equal to 2, the substituents R1 are identical or different, n2 is an integer between 0 and 5 and when n2 is greater than or equal to 2, the substituents R2 are identical or different and n3 is an integer between 1 and 6, and in which the substituents R1 and R2 are chosen independently of one another from: -OH, -COOH, -COH, the -O-Alk groups where Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, the hydrocarbon chains comprising between 1 and 20 carbon atoms, saturated or unsaturated, substituted or no n substituted, interrupted or not by one or more heteroatoms, and optionally having one or more carbonyl or carboxylic acid functions, saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic groups, substituted or unsubstituted, and optionally having one or more carbonyl or carboxylic acid functions, substituted or unsubstituted aryl groups and optionally having one or more carbonyl or carboxylic acid functions, R2 may also denote a radical of formula Al in formula A above or a radical of formula B1 in formula B above and R 1 may further denote a radical of formula A2 in formula A above, the formulas Al, A2 and B1 being the following: o (R1) 111 (R2) 1-12 O n3 A2 Al in the formulas Al, A2 and B1, R1, R2, n1, n2 and n3 are as defined above. 10
    [0002]
    2. Method according to claim 1, characterized in that the aromatic aldehyde compound used in step a) has the formula A and in that the process further comprises, before step a) a step of manufacture of said aromatic aldehyde compound by aromatic nucleophilic substitution reaction between a compound having the formula A3 and a compound having the formula A4 where X is a leaving group, the formulas A3 and A4 being the following: OH (R1) n1 A3 A4
    [0003]
    3. Process according to claim 1, characterized in that the aromatic aldehyde compound used in step a) has the formula B and in that the process further comprises before step a). the two following steps: 1) a nucleophilic substitution reaction between a compound of formula A3 and a compound of formula B2 to obtain a compound of formula B3, where Z is a protecting group for obtaining an aldehyde function after deprotection and Y is a leaving group, and 2) a deprotection reaction of the compound of formula B3 to obtain the aromatic aldehyde compound of formula B, the formulas A3, B2, B3 being as follows: OH YO n3 n3 A3 B2
    [0004]
    4. Process according to any one of Claims 1 to 3, characterized in that the substituents R1 and R2 are chosen independently of one another from: -OH, the groups -O-Alk where Alk denotes a chain substituted or unsubstituted alkyl of 1 to 4 carbon atoms, preferably -OMe, and COOH, R2 may further denote a radical of formula A1 in formula A above or a radical of formula B1 in formula B below. And wherein R 1 may further denote a radical of formula A2 in formula A above, in formulas A1, A2 and B1, R1 and R2 are as defined above in this claim.
    [0005]
    5. Process according to any one of claims 1 to 4, characterized in that n1 is between 0 and 2 and n2 is between 0 and 3 for formula A. 303 19 77 24
    [0006]
    6. Process according to any one of claims 1 to 4, characterized in that n2 is between 0 and 3 and n3 is between 1 and 3 for formula B. 5
    [0007]
    7. Method according to any one of claims 2 to 6, characterized in that the compound of formula A3 used to manufacture the aromatic aldehyde compound is chosen from: simple phenols, polyphenol compounds, hydroxybenzoic aldehydes, acids hydroxybenzoids, hydroxybenzyl alcohols, hydroxycinnamyl alcohols, hydroxycinnamic acids, phenylpropenes, coumarins, naphthoquinones, stilbenoids, flavonoids, iso-flavonoids, anthocyanins, lignans, lignins, condensed tannins, tannins hydrolyzable, depolymerized tannins and resole and novolak resins. 15
    [0008]
    8. Process according to claim 7, characterized in that the compound of formula A3 used to manufacture the aromatic aldehyde compound is chosen from: simple phenols and hydroxybenzoic aldehydes. 20
    [0009]
    9. Process according to any one of claims 7 and 8, characterized in that the compound of formula A3 used to manufacture the aromatic aldehyde compound is chosen from: phenol, pyrocatechol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, guaiacol, syringol, bis-phenol A, bis-phenol S, para-hydroxybenzaldehyde, vanillin, syringaldehyde, dehydrodivanillin, 2-hydroxybenzyl alcohol, alcohol 4- hydroxybenzyl alcohol, vanillic alcohol, syringic alcohol, paracoumaryl alcohol, coniferyl alcohol, sinapyl alcohol, ferulic acid, parahydroxybenzoic acid, gallic acid, paracoumaric acid, eugenol , isoeugenol, cardanols, cardols, anacardial acids, catechin, umbelliferone, juglone, trans-resveratrol, kaempferol, daidzein, delphinidol, enterodiol, lignins, procyanidines, gallotannins, condensed tannins, resole resins and novolaks. 3031977 25
    [0010]
    10. A process for producing a crosslinked phenolic resin comprising a step b) during which a heat treatment is carried out in order to crosslink phenolic resins obtained by carrying out a process according to any one of claims 1 to 9. to obtain the crosslinked phenolic resin.
    [0011]
    11. A method of manufacturing a propellant nozzle in which the nozzle is manufactured from a phenolic resin obtained by carrying out a process according to any one of claims 1 to 9 or from a crosslinked phenolic resin obtained by carrying out a process according to claim 10.
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    同族专利:
    公开号 | 公开日
    FR3031977B1|2018-04-20|
    EP3247636A1|2017-11-29|
    WO2016116697A1|2016-07-28|
    EP3247636B1|2019-06-12|
    US20180022853A1|2018-01-25|
    US10364313B2|2019-07-30|
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    2018-07-27| TQ| Partial transmission of property|Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, FR Effective date: 20180621 Owner name: ARIANEGROUP SAS, FR Effective date: 20180621 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1500127A|FR3031977B1|2015-01-22|2015-01-22|PROCESS FOR PRODUCING AN ABLATIVE RESIN|
    FR1500127|2015-01-22|FR1500127A| FR3031977B1|2015-01-22|2015-01-22|PROCESS FOR PRODUCING AN ABLATIVE RESIN|
    US15/545,494| US10364313B2|2015-01-22|2016-01-20|Method for producing an ablative resin|
    PCT/FR2016/050104| WO2016116697A1|2015-01-22|2016-01-20|Method for producing an ablative resin|
    EP16705566.4A| EP3247636B1|2015-01-22|2016-01-20|Method for producing an ablative resin|
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