# US 8,569,425 B2 · Modified phenolic resins > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,569,425 B2 - Document ID: US8569425B2 - Status: Granted - Kind: B2 - Application number: 13/165,267 - Filed: 2011-06-21 - Published: 2011-11-10 - Granted: 2013-10-29 - Earliest claimed: 2008-12-19 - Assignees: HüTtenes-Albertus Chemische Werke Gesellschaft Mit BeschräNkter Haftung - Applicants: David Strunk; Gerard Ladegourdie; Frank Lenzen - Inventors: David Strunk; Gerard Ladegourdie; Frank Lenzen - Web page: https://patentgrep.com/patent/US8569425B2 ## CPC - C08G 8/28: Chemically modified polycondensates - B22C 1/2253: {with phenols} - B22C 1/2273: {Polyurethanes; Polyisocyanates} - C08G 18/289: {containing silicon} - C08G 18/542: {with phenols} - C08L 61/14: Modified phenol-aldehyde condensates - C09D 161/14: Modified phenol-aldehyde condensates - C09J 161/14: Modified phenol-aldehyde condensates - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - B22C: FOUNDRY MOULDING (moulding refractory materials in general B28B) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) ## Abstract The present invention relates to modified phenolic resins which contain silicic acid ester units. The modified phenolic resins may, for example, be used as components of a foundry binder system. The invention also relates to a method for producing such modified phenolic resins and to two-component binder systems which contain these modified phenolic resins. The invention furthermore relates to methods for producing foundry molds and foundry cores which contain the modified phenolic resins, and to the foundry molds and foundry cores themselves. ## Claims ### Claim 1 A foundry mold hardened in the cold-box method or polyurethane no-bake method or a hardened foundry core, comprising a molding material and a hardened binder, the binder comprising phenolic resin units which are substituted and/or linked by esters of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, wherein the phenolic resin is a high a o,o′-resol, wherein said binder, prior to hardening, forms a solution with a solvent comprising tetraethyl silicate. ### Claim 2 A modified phenolic resin, comprising phenolic resin units which are substituted and/or linked by esters of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, wherein the phenolic resin is a high o,o′-resol, and/or which can be produced by reacting free hydroxyl groups of a high o,o′-resol phenolic resin with one or more esters of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, wherein said modified phenolic resin forms a solution with a solvent comprising tetraethyl silicate. ### Claim 3 (depends on 2) The modified phenolic resin as claimed in claim 2, comprising phenolic resin units which are linked by esters of orthosilicic acid in which 1 or 2 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, wherein individual or a plurality of esters of orthosilicic acid in which 1 or 2 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues and are linked to exactly two phenolic resin units. ### Claim 4 (depends on 2) The modified phenolic resin as claimed in claim 2, which can be produced by a method in which free hydroxyl groups of a phenolic resin are reacted with diethoxydimethylsilane so that the modified phenolic resin is obtained. ### Claim 5 (depends on 2) The modified phenolic resin as claimed in claim 2, which can be produced by a method in which free hydroxyl groups of a high o,o′-resol are reacted with a dialkyldialkoxysilane so that the modified phenolic resin is obtained. ### Claim 6 (depends on 2) The modified phenolic resin as claimed in claim 2, which can be produced by a method in which free hydroxyl groups of a phenol-formaldehyde high-o,o′-resol are reacted with a dialkyldialkoxysilane so that the modified phenolic resin is obtained. ### Claim 7 (depends on 2) The modified phenolic resin as claimed in claim 2, wherein said modified phenolic resin is produced by a process comprising: i. preparing a reaction mixture comprising or consisting of a high o,o′-resol, at least one alkyl ester of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, and an acid having a pKa≦5, wherein the ratio of the amount of silicon to the weight of basic resin used lies in the range of from 0.5 to 20.0 mol of Si per kg of resin, ii. reacting the mixture at a temperature in the range of from 20 to 120° C., with a reaction time in the range of from 1 minute to 20 hours, iii. neutralizing the reaction mixture reacted according to step ii, iv. distilling off the alcohol formed during the reaction according to step ii and optionally a solvent from the neutralized reaction mixture at reduced pressure. ### Claim 8 (depends on 2) The modified phenolic resin as claimed in claim 2, wherein said modified phenolic resin forms a solution in tetraethyl silicate. ### Claim 9 (depends on 2) A method tor making a product, comprising: providing a modified phenolic resin according to claim 2, wherein the modified phenolic resin comprises phenolic resin units which are substituted and/or linked by esters orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, and/or can be produced by reacting free hydroxyl groups of a phenolic resin with one or more esters or orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues; and wherein the modified phenolic resin is: a binder or a constituent of a binder, a molding material or a constituent of a molding material, an insulator or a constituent of an insulator, or a coating materiel or a constituent of a coating material. ### Claim 10 (depends on 9) The method as claimed in claim 9, wherein the modified phenolic resin comprises phenolic resin units which are linked by esters of orthosilicic acid in which 1 or 2 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues. ### Claim 11 (depends on 10) The method as claimed in claim 10, wherein individual, a plurality of or the majority of the orthosilicic acid ester units in which 1 or 2 residues are replaced by substituted or unsubstituted hydrocarbon residues are linked to exactly two phenolic resin units. ### Claim 12 (depends on 9) The method as claimed in claim 9, wherein the modified phenolic resin is produced by a method in which free hydroxyl groups of a phenolic resin are reacted with a dialkyldialkoxysilane so that the modified phenolic resin is obtained. ### Claim 13 (depends on 12) The method as claimed in claim 12, wherein the dialkyldiakoxysilane comprises diethoxydimethylsilane. ### Claim 14 (depends on 9) The method as claimed in claim 9, wherein the modified phenolic resin is produced by reacting free hydroxyl groups of a high o,o′-resol with a dialkyldialkoxysilane. ### Claim 15 (depends on 9) The method as claimed in claim 9, wherein the modified phenolic resin is produced by reacting free hydroxyl groups of a phenol-formaldehyde high-o,o′-resol with a dialkyldialkoxysilane. ### Claim 16 (depends on 9) The method as claimed in claim 9, wherein, when heated in air to 1000° C. in a muffle furnace to constant mass, the modified phenolic resin gives an SiO2 residue of from 1 percent by weight to 30 percent by weight, expressed in terms of the weight of the mass of modified phenolic resin used. ### Claim 17 (depends on 2) A method for producing a modified phenolic resin as claimed in claim 2, comprising: reacting a phenolic resin with at least one ester of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues. ### Claim 18 (depends on 17) The method as claimed in claim 17, further comprising: i. preparing a reaction mixture comprising or consisting of a high o,o′-resol, at least one alkyl ester of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, and an acid having a pKa≦5, wherein the ratio of the amount of silicon to the weight of basic resin used lies in the range of from 0.5 to 20.0 mol of Si per kg of resin, ii. reacting to the mixture at a temperature in the range of from 20 to 120° C. with a reaction time in the range of from 1 minute to 20 hours, iii. neutralizing the reaction mixture reacted according to step ii, iv. distilling off the alcohol formed during the reaction according to step ii and optionally a solvent from the neutralized reaction mixture at reduced pressure. ### Claim 19 (depends on 17) The method as claimed in claim 17 wherein the phenolic resin comprises a phenol-formaldehyde high-o.o′-resol. ### Claim 20 (depends on 2) A cold-box or polyurethane no-bake method by producing foundry molds and/or cores, comprising: providing a modified phenolic resin according to claim 2 as a binder or a constituent of a binder, wherein the modified phenolic resin comprises phenolic resin units which are substituted and/or linked by esters of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, and/or can be produced by reacting free hydroxly groups of a phenolic resin with one or more esters of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues wherein the modified phenolic resin comprises high o,o′-resol units. ### Claim 21 (depends on 20) The method as claimed in claim 20, wherein the modified phenolic resin comprises phenolic resin units which are linked by esters of orthosilicic acid in which 1 or 2 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues. ### Claim 22 (depends on 20) The method as claimed in claim 20, wherein the modified phenolic resin is produced by reacting free hyrdoxyl groups of a phenolic resin with a dialkyldialkoxysilane. ### Claim 23 (depends on 20) The method as claimed in claim 20, wherein the modified phenolic resin is produced by reacting free hyrdoxyl groups of a high o,o′-resol with a dialkyldialkoxysilane. ### Claim 24 (depends on 20) The method as claimed in claim 20, wherein the modified phenolic resin is produced by reacting free hydroxyl groups of a phenol-formaldehyde high-o,o′-resol with a dialkyldialkoxysilane. ### Claim 25 (depends on 20) The method as claimed in claim 20, wherein, when heated in air to 1000° C. in a muffle furnace to constant mass, the modified phenolic resin gives an SiO2 residue of from 1 percent by weight to 30 percent by weight, expressed in terms of the weight of the mass of modified phenolic resin used. ### Claim 26 (depends on 2) A method for producing a modified phenolic resin as claimed in claim 2, comprising: reacting a phenolic resin with at least one ester of orthoslicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, wherein the phenolic resin is a high a o,o′-resol. ### Claim 27 The method as claimed in chum 26, further comprising: i. preparing a reaction mixture comprising or consisting of a high o,o′-resol, at least one alkyl ester of orthosilicic acid in which 1, 2 or 3 alcohol residues are replaced by substituted or unsubstituted hydrocarbon residues, and an acid having a pKa≦5, wherein the ratio of the amount of silicon to the weight of basic resin used lies in the range of from 0.5 to 20.0 mol of Si per kg of resin, ii. reacting the mixture at a temperature in the range of from 20 to 120° C. with a reaction time in the range of from 1 minute to 20 hours, iii. neutralizing the reaction mixture reacted according to step ii, iv. distilling off the alcohol formed during the reaction according to step ii and optionally a solvent from the neutralized reaction mixture at reduced pressure. ### Claim 28 (depends on 26) The method as claimed in claim 26, wherein the phenolic resin is a phenol-formaldahyde high o,o′-resol. ### Claim 29 (depends on 2) A method for producing a hardened foundry mold or a hardened foundry core according to the cold-box method, comprising: i. producing a mixture comprising or consisting of a modified phenolic resin as clamed in claim 2, a polyisocyanate and a molding material, ii. molding the mixture to form a foundry mold or a foundry core and iii. hardening the molded mixture. ### Claim 30 (depends on 29) The method as claimed in claim 29, wherein the modified phenolic resin and/or the polyisocyanate are dissolved in a solvent before producing the mixture. ### Claim 31 (depends on 29) The method as claimed in claim 29 wherein the modified phenolic resin and/or the polyisocyanate are dissolved in a solvent comprising tetraethyl ester of orthosilicic acid before producing the mixture. ### Claim 32 (depends on 31) The method as claimed in claim 31, wherein the hardening step comprises use of a catalyst. ### Claim 33 (depends on 32) The method as claimed in claim 32, wherein the catalyst is an amine. ### Claim 34 (depends on 32) The method as claimed in claim 32, wherein the catalyst comprises a catalyst selected from the group consisting of triethylamine, dimethylethylamine and dimethylisopropylamine. ### Claim 35 (depends on 2) A two-component binder system, comprising or consisting of a phenolic resin component and a polyisocyanate component, wherein the polyisocyanate component comprises a polyisocyanate having at least two isocyanate groups per molecule and the phenolic resin component comprises a phenolic resin as claimed in claim 2. ### Claim 36 (depends on 2) A hardened foundry mold or a hardened foundry core, comprising a molding material and a hardened binder, the binder comprising a phenolic resin as claimed in claim 2.