# US 10,246,544 B2 · Method for producing an ablative resin > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,246,544 B2 - Document ID: US10246544B2 - Status: Granted - Kind: B2 - Application number: 15/545,457 - Filed: 2016-01-20 - Published: 2018-01-11 - Granted: 2019-04-02 - Earliest claimed: 2015-01-22 - Assignees: Arianegroup SAS; Centre National De La Recherche Scientifique - Applicants: Centre National De La Recherche Scientifique; Arianegroup SAS - Inventors: Gabriel M. Foyer; Ghislain C. David; Sylvain Y. Caillol; Nadia Rodriguez - Web page: https://patentgrep.com/patent/US10246544B2 ## CPC - C08G 8/04: of aldehydes - B64D 33/04: of exhaust outlets or jet pipes - C08G 65/38: derived from phenols - F02K 1/00: Plants characterised by the form or arrangement of the jet pipe or nozzle; Jet pipes or nozzles peculiar thereto (rocket nozzles F02K9/97) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - B64D: EQUIPMENT FOR FITTING IN OR TO AIRCRAFT; FLIGHT SUITS; PARACHUTES; ARRANGEMENT OR MOUNTING OF POWER PLANTS OR PROPULSION TRANSMISSIONS IN AIRCRAFT - F02K: JET-PROPULSION PLANTS (features of jet-propulsion plants common to gas-turbine plants, air intakes or fuel supply control of air-breathing jet-propulsion plants F02C7/00, F02C9/00) ## Abstract A method for producing an ablative resin by carrying out a reduction reaction for the reduction of a compound of formula A, followed by a polymerization reaction, formula A being the following: ## Claims ### Claim 1 A method for producing a propulsion nozzle, wherein the nozzle is produced from a phenolic resin obtained by carrying out a production method comprising the following steps: a) reduction of a compound of formula A in order to obtain a hydroxybenzyl alcohol of formula B, formulae A and B being the following: wherein: n1 is an integer between 1 and 4 and when n1 is greater than or equal to 2, the substituents R1 are identical or different, R1 is chosen from: —COOH, —CHO, the groups —O-Alk wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, substituted or unsubstituted, monocyclic or polycyclic, unsaturated or aromatic carbocyclic or heterocyclic groups having or not having one or more carbonyl or carboxylic acid functions, and substituted or unsubstituted aryl groups having or not having one or more carbonyl or carboxylic acid functions, and R2 denotes H or OH, and b) polymerization reaction using the hydroxybenzyl alcohol of formula B obtained during step a) in order to obtain the phenolic resin. ### Claim 2 (depends on 1) The method as claimed in claim 1, wherein there is homopolymerization of the hydroxybenzyl alcohol of formula B during step b). ### Claim 3 (depends on 1) The method as claimed in claim 1, wherein there is reaction of the hydroxybenzyl alcohol of formula B with an aldehyde other than formaldehyde during step b). ### Claim 4 (depends on 3) The method as claimed in claim 3, wherein the aldehyde is chosen from benzaldehyde, terephthalaldehyde and trimesaldehyde or has one of the following two formulae C or D: in formulae C and D, n3 is an integer between 0 and 4 and when n3 is greater than or equal to 2, the substituents R3 are identical or different, n4 is an integer between 0 and 5 and when n4 is greater than or equal to 2, the substituents R4 are identical or different and n5 is an integer between 1 and 6, the substituents R3 and R4 being chosen independently from one another from: —OH, —COOH, —CHO, the groups —O-Alk wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, saturated or unsaturated, substituted or unsubstituted hydrocarbon-based chains comprising between 1 and 20 carbon atoms, interrupted or not with one or more heteroatoms, and having or not having one or more carbonyl or carboxylic acid functions, substituted or unsubstituted, monocyclic or polycyclic, saturated, unsaturated or aromatic carbocyclic or heterocyclic groups having or not having one or more carbonyl or carboxylic acid functions, and substituted or unsubstituted aryl groups having or not having one or more carbonyl or carboxylic acid functions, R4 also denoting or not denoting a radical of formula C1 in formula C above or a radical of formula D1 in formula D above and R3 also denoting or not denoting a radical of formula C2 in formula C above, formulae C1, C2 and D1 being the following: ### Claim 5 (depends on 1) The method as claimed in claim 1, wherein there is, during step b), reaction of the hydroxybenzyl alcohol of formula B with a phenolic compound other than said hydroxybenzyl alcohol. ### Claim 6 (depends on 1) The method as claimed in claim 1, wherein R2 denotes —OH and wherein the compound of formula A is formed, before step a), by a Kolbe-Schmitt carboxylation reaction using a compound of formula A1, the formula A1 being the following: in the formula A1, R1 and n1 are as defined above. ### Claim 7 (depends on 6) The method as claimed in claim 6, wherein the compound of formula A1 is chosen from: simple phenols, polyphenolic compounds, for example diphenolic compounds, hydroxybenzoic aldehydes, hydroxybenzoic acids, hydroxybenzyl alcohols, hydroxycinnamyl alcohols, hydroxycinnamic acids, phenylpropenes, coumarins, naphthoquinones, stilbenoids, flavonoids, isoflavonoids, anthocyans, lignans, lignins, condensed tannins, hydrolyzable tannins, depolymerized tannins, and resol and novolac resins. ### Claim 8 (depends on 1) The method as claimed in claim 1, wherein R2 denotes —H and wherein the compound of formula A is formed, before step a), by a reaction for formylation of a compound of formula A1 or by a reaction for oxidation of a compound of formula A2, the formulae A1 and A2 being the following: in the formula A2, X is a group forming —CHO after an oxidation reaction and, in the formulae A1 and A2, R1 and n1 are as defined above. ### Claim 9 (depends on 8) The method as claimed in claim 8, wherein the compound of formula A1 or A2 is chosen from: simple phenols, polyphenolic compounds, hydroxybenzoic aldehydes, hydroxybenzoic acids, hydroxybenzyl alcohols, hydroxycinnamyl alcohols, hydroxybenzoic acids, hydroxybenzyl alcohols, hydroxycinnamyl alcohols, hydroxycinnamic acids, phenylpropenes, coumarins, naphthoquinones, stilbenoids, flavonoids, isoflavonoids, anthocyans, lignans, lignins, condensed tannins, hydrolysable tannis, depolymerized tannis, and resol and novolac resins. ### Claim 10 (depends on 1) The method as claimed in claim 1, wherein R1 is chosen from: —O-Alk wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, —CHO, —COOH, and substituted or unsubstituted aryl groups having or not having one or more carbonyl or carboxylic acid functions. ### Claim 11 (depends on 10) The method as claimed in claim 10, wherein R1 is —O-Alk wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms. ### Claim 12 (depends on 1) The method as claimed in claim 1, wherein n1 is between 1 and 3. ### Claim 13 (depends on 1) The method as claimed in claim 1, further comprising forming a fibrous preform of the propulsion nozzle and impregnating the fibrous preform with the phenolic resin. ### Claim 14 (depends on 13) The method as claimed in claim 13, wherein the fibrous preform comprises carbon fibers, silica fibers, glass fibers or fibers of a ceramic material. ### Claim 15 A method for producing a phenolic resin comprising the following steps: reduction of a compound of formula A in order to obtain a hydroxybenzyl alcohol of formula B, formulae A and B being the following: wherein: n1 is an integer between 0 and 4 and when m is greater than or equal to 2, the substituents R1 are identical or different, R1 is chosen from: —OH, —COOH, —CHO, the groups —O-Alk wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, saturated or unsaturated, substituted or unsubstituted hydrocarbon-based chains comprising between 1 and 20 carbon atoms, interrupted or not with one or more heteroatoms, and having or not having one or more carbonyl or carboxylic acid functions, substituted or unsubstituted, monocyclic or polycyclic, saturated, unsaturated or aromatic carbocyclic or heterocyclic groups having or not having one or more carbonyl or carboxylic acid functions, and substituted or unsubstituted aryl groups having or not having one or more carbonyl or carboxylic acid functions, and R2 denotes —H or —OH, and polymerization reaction between the hydroxybenzyl alcohol and aldehyde compound in order to obtain the phenolic resin, the aldehyde compound having one of the following two formulae C or D in formulae C and D, n3 is an integer between 0 and 4 and when n3 is greater than or equal to 2, the substituents R3 are identical or different, n4 is an integer between 0 and 5 and when n4 is greater than or equal to 2, the substituents R4 are identical or different and n5 is an integer between 1 and 6, the substituents R3 and R4 being chosen independently from one another from: —OH, —COOH, —CHO, the groups —O-Alk wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, saturated or unsaturated, substituted or unsubstituted hydrocarbon-based chains comprising between 1 and 20 carbon atoms, interrupted or not with one or more heteroatoms, and having or not having one or more carbonyl or carboxylic acid functions, substituted or unsubstituted, monocyclic or polycyclic, saturated, unsaturated or aromatic carbocyclic or heterocyclic groups having or not having one or more carbonyl or carboxylic acid functions, and substituted or unsubstituted aryl groups having or not having one or more carbonyl or carboxylic acid functions, R4 also denoting or not denoting a radical of formula C1 in formula C above or a radical of formula D1 in formula D above and R3 also denoting or not denoting a radical of formula C2 in formula C above, formulae C1, C2 and D1 being the following: ### Claim 16 (depends on 15) A method for producing a propulsion nozzle, wherein the nozzle is produced from a phenolic resin obtained by carrying out the method of claim 15. ### Claim 17 (depends on 15) The method as claimed in claim 15, wherein the aldehyde is an aromatic polyaldehyde compound. ### Claim 18 A method for producing a propulsion nozzle, wherein the nozzle is produced from a phenolic resin obtained by carrying out a production method comprising the following steps: a) reduction of a compound of formula A in order to obtain a hydroxybenzyl alcohol of formula B, formulae A and B being the following: wherein: 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, R1 is chosen from: —OH, —COOH, —CHO, the groups —O-Alk wherein Alk denotes a substituted or unsubstituted alkyl chain of 1 to 4 carbon atoms, saturated or unsaturated, substituted or unsubstituted hydrocarbon-based chains comprising between 1 and 20 carbon atoms, interrupted or not with one or more heteroatoms, and having or not having one or more carbonyl or carboxylic acid functions, substituted or unsubstituted, monocyclic or polycyclic, saturated, unsaturated or aromatic carbocyclic or heterocyclic groups having or not having one or more carbonyl or carboxylic acid functions, and substituted or unsubstituted aryl groups having or not having one or more carbonyl or carboxylic acid functions, and R2 denotes —H or —OH, and b) polymerization reaction using the hydroxybenzyl alcohol of formula B obtained during step a) in order to obtain the phenolic resin, wherein there is, during step b), reaction of the hydroxybenzyl alcohol of formula B with a phenolic compound other than said hydroxybenzyl alcohol, the phenolic compound which reacts with the hydroxybenzyl alcohol during step b) being chosen from: phenol, pyrocatechol, hydroquinone, phloroglucinol, pyrogallol, guaiacol, syringol, bisphenol A, bis-phenol S, para-hydroxybenzaldehyde, vanillin, syringaldehyde, dehydrodivanillin, vanillyl alcohol, syringyl alcohol, para-coumaryl alcohol, coniferyl alcohol, sinapyl alcohol, ferulic acid, sinapylic acid, para-hydroxybenzoic acid, vanillic acid, syringic acid, gallic acid, para-coumaric acid, eugenol, isoeugenol, cardanols, cardols, anacardic acids, catechin, umbelliferone, juglone, trans-resveratrol, kaempferol, daidzein, delphinidol, enterodiol, lignins, procyanidins, gallotanins, condensed tannins, and resol and novolac resins. ### Claim 19 (depends on 18) The method as claimed in claim 18, wherein the phenolic compound which reacts with the hydroxybenzyl alcohol during step b) is chosen from: phenol, pyrocatechol, hydroguinone, phloroglucinol, bis-phenol A, bis-phenol S, para-hydroxybenzaldehyde, vanillin, resol and novolac resins, procyanidins and condensed tannins.