Classifications

• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/302—Water
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
  • C08G65/3314—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic
  • C08G65/3315—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic
  • C08G65/3317—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic phenolic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/141—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/08—Polyurethanes from polyethers
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/005—< 50kg/m3
• • 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
  • C08G2190/00—Compositions for sealing or packing joints
• • 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
  • C08G2330/00—Thermal insulation material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
  • C08J2375/08—Polyurethanes from polyethers

Definitions

• the present disclosure relates to the field of alkoxylated polyphenols, in particular alkoxylated lignins. More specifically, the present invention relates to a process for the manufacture in a single step, in a single pot (“one-pot reaction” in English) and under mild conditions of a mixture of alkoxylated polyphenols. These alkoxylated polyphenols can then be used directly to make different polyurethane materials, especially to make polyurethane foams.
• PRIOR ART [0002] The search for biosourced products that can replace products of petroleum origin constitutes a future strategy for reducing our dependence on fossil resources.
• Polyurethanes constitute an important family of polymers, very demanding of compounds of biosourced origin.
• the building industry sector is looking for biosourced and sustainable materials, particularly in the field of foams that can be used for thermal and/or acoustic insulation in buildings.
• the uses of polyurethanes in this sector are essentially in the form of rigid polyurethane (PUR) and polyisocyanurate (PIR) foams.
• PUR rigid polyurethane
• PIR polyisocyanurate
• Polyurethane materials rigid and flexible foams, elastomers, adhesives, etc.
• a polyol must have specific properties to be used in the manufacture of polyurethane materials.
• a polyol intended for the manufacture of a foam preferably has a viscosity at 25° C. of between 0.5 Pa.s and 100 Pa.s and a hydroxyl number of between 100 mg(KOH).g -1 and 700 mg(KOH).g -1 .
• a polyol having such a viscosity is liquid and mixes easily with the polyisocyanate compound and any additives during the conventional manufacture of a polyurethane foam at room temperature.
• the range of hydroxyl index indicated above makes it possible to obtain a cross-linked three-dimensional network giving the foam, inter alia, its properties of dimensional stability and its resistance to compression.
• lignins and tannins have therefore been studied to improve/modify their properties, in particular their viscosity and their hydroxyl index.
• One of these chemical modifications is etherification. It makes it possible to replace the phenolic group OH of these polyphenols by alkylation. Etherification can be carried out according to two principles: the opening of epoxide cycles or the reaction with cyclic carbonates.
• WO 2018/065728 describes a process for manufacturing alkoxylated polyphenols in two steps, based on the principle of opening the epoxide cycle.
• This process uses an agent alkoxylate chosen from propylene oxide, ethylene oxide, butylene oxide and mixtures thereof.
• alkoxyling agents are particularly dangerous to handle because they are toxic, carcinogenic and highly flammable, even explosive.
• These alkoxylating agents also require the etherification step to be carried out at high pressure because they have a boiling point lower than the temperature at which the reaction is carried out.
• a step for eliminating residual alkoxyling agents is also necessary because, for safety reasons, the product formed from alkoxylated polyphenols must not contain these dangerous products. There is therefore a need to replace these alkoxylating agents and to simplify the implementation of the modified polyphenols.
• US 2019/0144674 describes a process for the manufacture of alkoxylated polyphenols comprising the following two steps: a) dispersion of lignin in a solvent to obtain a dispersion of lignin, b) bringing the dispersion of lignin into contact with a cyclic carbonate such as ethylene carbonate to obtain a dispersion of alkoxylated lignin.
• the solvent used in this process is a compound comprising alcohol functions and having a boiling point of between 120°C and 300°C.
• This compound can, for example, be ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, dimethoxyethane or their mixtures.
• This process requires a step c) of removing the solvent included in the dispersion of alkoxylated lignin in order to obtain an alkoxylated lignin having the viscosity suitable for the manufacture of foam.
• a viscosity adapter compound can also be added to the dispersion of alkoxylated lignin obtained by this process. Such an adapter is necessary to manufacture a polyurethane foam with the solid alkoxylated lignin of Example 1.
• Application WO2019/099405 also describes a process for manufacturing alkoxylated polyphenols. This process also requires a step of removing the solvent, by distillation, to obtain an alkoxylated lignin having the viscosity suitable for the manufacture of foam. The manufacture of polyurethane foam by the alkoxylated lignins obtained by these processes is therefore not simple. [0008] There is therefore a need for a process for manufacturing alkoxylated polyphenols which: - does not use propylene, ethylene and butylene oxides, and - produces alkoxylated polyphenols having physico-chemical properties (composition chemical, viscosity, hydroxyl number, etc.
• the present invention relates to a process for manufacturing a mixture of alkoxylated polyphenols comprising the following step: (a) bringing into contact at least one polyphenol and one cyclic carbonate ester in the presence of a solvent , characterized in that the solvent has a molar mass of between 150 g.mol -1 and 600 g.mol -1 , in particular between 175 g.mol -1 and 600 g.mol -1 , in particular between 175 g.mol -1 -1 and 500 g.mol -1 , most particularly between 200 g.mol -1 and 400 g.mol -1 and is chosen from a polyether, a polyester comprising OH groups at the end of the chain and their mixture, in particular a polyether, and the cyclic carbonate ester:polyphenol mass ratio is between 0.3:1 and 5:1, in particular between 0.5:1 and 3:1, especially between 0.6:1 and 1.5 :1.
• the properties of the mixture of alkoxylated polyphenols produced by the method of the invention in particular a hydroxyl number of between 100 mg (KOH).g -1 and 1000 mg (KOH).g -1 and a viscosity at 25°C between 0.5 Pa.s and 100 Pa.s, allow its use to manufacture different types of polyurethane materials, in particular polyurethane foams.
• the mixture of alkoxylated polyphenols can therefore be used to manufacture polyurethane materials without the addition of a viscosity adapter compound or in other words without the addition of a viscosity modifying agent.
• the mixture of alkoxylated polyphenols produced by the process of the invention is also devoid of reagents of the propylene, ethylene and butylene oxide type. More generally, it comprises a low content of residual reagents.
• the mixture of alkoxylated polyphenols can therefore be used to manufacture polyurethane materials without an intermediate step of purification of said mixture being necessary.
• the method of the invention does not require a step for purifying the mixture of alkoxylated polyphenols or for adding a viscosity adapter compound to the mixture of alkoxylated polyphenols so that said mixture can be used to make polyurethane materials, especially polyurethane foam.
• the present invention also relates to a mixture of alkoxylated polyphenols obtainable by the manufacturing process as defined above.
• Another object of the present invention consists in the use of a mixture of alkoxylated polyphenols capable of being obtained by the manufacturing process according to the invention as defined above or of the mixture of alkoxylated polyphenols according to the invention as defined above for produce polyurethane and/or polyisocyanurate material of various types, including for example sealant, adhesive, wood binder, cast elastomer, flexible or semi-flexible molded part, rigid structural composite, polyurethane foam, binder, semi-flexible foam, pipe insulation, cavity sealant, or microcellular foam.
• Another object of the present invention consists of a process for manufacturing a polyurethane foam in which the mixture of alkoxylated polyphenols produced during step (a) of the manufacturing process according to the invention as defined below above or the mixture of alkoxylated polyphenols according to the invention as defined above is brought into contact with a polyisocyanate compound.
• the mixture of alkoxylated polyphenols produced according to the method of the present invention or object of the present invention also has the advantage of being very reactive.
• the quantity of catalyst which can be implemented in the process for manufacturing a polyurethane foam of the invention can advantageously be at least 60% less than the quantity of catalyst implemented in a conventional process for manufacturing polyurethane foam.
• the characteristic times for forming a foam from the mixture of alkoxylated polyphenols, in particular the yarn times and tack-free times, are less than the characteristic times for forming a conventional foam.
• the polyurethane foam obtained by the method of manufacturing a polyurethane foam of the invention has properties of the same order of magnitude as the properties of a conventional polyurethane foam. It can therefore be used advantageously in an acoustic and/or thermal insulation product.
• the method that is the subject of the present invention therefore makes it possible to effectively valorize polyphenols derived from renewable sources such as lignin and tannins.
• Another object of the present invention consists of a polyurethane foam obtainable by the process for manufacturing a polyurethane foam according to the invention as defined above.
• Another object of the present invention consists of an acoustic and/or thermal insulation product comprising a foam according to the invention as defined above.
• Another object of the present invention consists of a kit for manufacturing a polyurethane foam comprising: - a mixture of alkoxylated polyphenols obtainable by the method according to the invention as defined above or a mixture alkoxylated polyphenols according to the invention as defined above, and - a polyisocyanate compound.
• a process for the manufacture of a mixture of alkoxylated polyphenols comprising the following step: (a) bringing into contact at least one polyphenol and one ester of cyclic carbonate in presence of a solvent, characterized in that the solvent has a molar mass of between 150 g.mol -1 and 600 g.mol -1 , in particular between 175 g.mol -1 and 600 g.mol -1, in particular between 175 g.mol -1 and 500 g.mol -1 , more particularly between 200 g.mol -1 and 400 g.mol -1 and is chosen from a polyether, a polyester comprising OH groups at the end of the chain and their mixture, in particular a polyether, and the cyclic carbonate ester:polyphenol mass ratio is between 0.3:1 and 5:1, in particular between 0.5:1 and 3:1, most particularly between 0.6: 1 and 1.5:1.
• the polyphenol used in the process according to the invention can be chosen from a lignin, a condensed tannin, a hydrolyzable tannin and their mixtures, in particular is a lignin.
• Lignin is a biopolymer that binds cellulose and hemicellulose together to help provide structural rigidity to plants and also acts as a protective barrier against fungi.
• the lignin used in the method of the invention can be derived from softwoods, hardwoods, annual plants, agricultural plants or mixtures thereof. Typically the lignin can be derived from hardwoods, in particular beech.
• the lignin can also be chosen from a kraft lignin (also called “kraft process lignin” is a lignin obtained by the kraft papermaking process), a lignosulphonate (lignin obtained by the sulphite pulping process), a soda lignin (also called “soda process lignin” is a lignin obtained by the process which uses sodium hydroxide and anthraquinone to depolymerize lignins), a lignin obtained from a solvent pulping process, a lignin derived from a biorefinery process, pyrolytic lignin (lignin obtained by the pyrolysis process), steam explosion lignin (lignin obtained by the use of high pressure steam), organosolv lignin and mixtures thereof, particular be chosen from an organosolv lignin, a kraft lignin, a soda lignin and mixtures thereof.
• Kraft lignin is obtained in Kraft pulp mills as a co-product of pulp.
• kraft lignin it is possible to use, inter alia, Inndulin AT® marketed by the company Ingevity, Amallin® marketed by the company West Fraser, BioChoice® marketed by the company Domtar, the kraft lignin marketed by the company Fibria, or else the lignin Lineo® marketed by Stora Enso.
• Lignosulphonate differs structurally from kraft lignin by the addition of sulphonic functions which are generally salified, which gives it better solubility in water.
• Organosolv lignin is obtained by chemical attack on ligneous plants, such as cereal or wood straw, by means of various solvents, such as ethanol, acetone, formic acid and/or l acetic acid, sometimes in the presence of an acid catalyst.
• various sources of organosolv lignin there is Biolignin® marketed by the company CIMV, lignin organosolv marketed by the company Fibria® and the organosolv lignin produced by the Fabiola® process.
• the lignin is an organosolv beech wood lignin, a kraft lignin or a soda lignin, more particularly an organosolv beech wood lignin produced by the Fabiola® process.
• "molar mass designates the number-average molar mass.
• the solvent used in the process of the invention has a molar mass of between 150 g.mol - 1 and 600 g.mol -1 , in particular between 175 g.mol -1 and 600 g.mol -1 , in particular between 175 g.mol -1 and 500 g.mol -1 , most particularly between 200 g.mol - 1 and 400 g.mol -1
• the solvent has a molar mass of less than 150 g.mol -1 , in particular less than 175 g.mol -1 , then the the hydroxyl index of the mixture of alkoxylated polyphenols is too high for said mixture to be able to be used for the manufacture of polyurethane materials, in particular rigid polyurethane foams, having satisfactory properties.
• the solvent has a molar mass greater than 600 g.mol -1 then the index hy droxyl of the mixture of alkoxylated polyphenols is too low for said mixture to be able to be used for the manufacture of polyurethane materials, in particular rigid polyurethane foams, having satisfactory properties. In fact, these materials are insufficiently crosslinked and therefore too soft. In addition, the viscosity of the mixture of alkoxylated polyphenols is so high that it cannot be used for the manufacture of polyurethane materials, in particular polyurethane foams, without using a viscosity modifying agent.
• polyether denotes a polymer whose macromolecular skeleton contains repeating units containing an ether group.
• the macromolecular chains of the polyethers useful in the present invention (advantageously) have hydroxyl functions (-OH) as end groups.
• the polyethers can be aliphatic or aromatic, more preferably the polyethers useful in the present invention are aliphatic.
• the polyether can be chosen from poly(oxyalkylene glycol) such as polybutylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, block, alternating or random copolymers obtained from these monomers and mixtures thereof, in particular is a poly(oxyalkylene glycol), more particularly is polyethylene glycol.
• poly(oxyalkylene glycol) such as polybutylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, block, alternating or random copolymers obtained from these monomers and mixtures thereof, in particular is a poly(oxyalkylene glycol), more particularly is polyethylene glycol.
• poly(oxyalkylene glycol) such as polybutylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, block, alternating or random copolymers obtained from these monomers and mixtures thereof, in particular is a poly(oxyalkylene glycol), more particularly is polyethylene glycol.
• the polyphenol:solvent mass ratio is between 0.1:1 and 1:1, in particular is between 0.2:1 and 0.5:1, more particularly is between 0.25:1 and 0.35:1.
• the cyclic carbonate ester:polyphenol mass ratio is between 0.6:1 and 1.5:1, and the polyphenol:solvent mass ratio is between 0.25:1 and 0. ,35:1.
• the cyclic carbonate ester useful in the present invention as an alkoxylating agent can be chosen from butylene carbonate, ethylene carbonate, propylene carbonate, glycerol carbonate and their mixtures, in particular ethylene carbonate and propylene carbonate and their mixture, most particularly is ethylene carbonate.
• a catalyst can be implemented in step (a). This makes it possible to accelerate the kinetics of the reactions implemented in step (a). The use of a catalyst is particularly suitable when the lignin is not basic enough for the mixture of alkoxylated polyphenols to be able to be manufactured by the method of the present invention.
• the process for manufacturing a mixture of alkoxylated polyphenols comprises the following step: (a) bringing into contact at least one polyphenol, a cyclic carbonate ester, a catalyst in presence of a solvent, characterized in that the solvent has a molar mass of between 150 g.mol -1 and 600 g.mol -1 , in particular between 175 g.mol -1 and 600 g.mol -1, in particular between 175 g.mol -1 and 500 g.mol -1 , more particularly between 200 g.mol -1 and 400 g.mol -1 and is chosen from a polyether, a polyester comprising OH groups at the end of the chain and their mixture, in particular a polyether, and the cyclic carbonate ester:polyphenol mass ratio is between 0.3:1 and 5:1, in particular between 0.5:1 and 3:1, most particularly between 0.6: 1 and 1.5:1.
• the catalyst may, for example, be a basic compound chosen from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkali metal carbonates.
• the catalyst can be chosen from sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, lithium hydroxide, calcium hydroxide, calcium carbonate, calcium hydrogen carbonate and mixtures thereof, more particularly is potassium carbonate.
• the catalyst:cyclic carbonate ester molar ratio can be between 0.001:1 and 0.5:1, in particular between 0.025:1 and 0.3:1, most particularly between 0.05:1 and 0.2:1.
• Step (a) can be carried out at a temperature between 80° C.
• Step (a) can be carried out at a pressure below 1.5 bar, in particular carried out at atmospheric pressure.
• Step (a) can be carried out under an inert atmosphere, in particular under a flow of inert gas.
• the inert atmosphere makes it possible to avoid parasitic reactions such as oxidation and the flow of inert gas makes it possible to carry away the gaseous products formed during step a) such as CO 2 .
• Any inert gas such as argon, nitrogen or mixtures thereof can be used.
• step (a) can therefore be carried out under mild operating conditions.
• step (a) of the process of the invention can be followed by conventional methods of chemical analysis, such as, for example, NMR.
• step (a) comprises the following sub-steps: (a1) mixing in a reactor the at least one polyphenol and the solvent to obtain a mixture, (a2) adding to the mixture the cyclic carbonate ester, and (a3) optionally adding the catalyst to the mixture obtained in step (a2), and (a4) mixing the mixture obtained in step (a2) or in step (a3) to make the mixture of alkoxylated polyphenols.
• the sub-steps (a1), (a2) and (a3) can be carried out at ambient temperature.
• Step (a4) can be carried out under the inert atmosphere described above and/or in the temperature range described above.
• the polyphenol is a lignin
• the cyclic carbonate ester is ethylene carbonate
• the solvent is a polyethylene glycol with a molar mass of between 200 g.mol -1 and 400 g. mol -1
• the catalyst is potassium carbonate.
• the cyclic carbonate ester:polyphenol mass ratio is between 0.6:1 and 1.5:1
• the polyphenol:solvent mass ratio can be between 0.25:1 and 0.35:1
• the catalyst:cyclic carbonate ester molar ratio is between 0.05:1 and 0.2:1.
• the polyphenol is a lignin
• the cyclic carbonate ester is ethylene carbonate
• the solvent is a polyethylene glycol with a molar mass of between 200 g.mol -1 and 400 g.mol -1
• the catalyst is potassium carbonate
• - the cyclic carbonate ester:polyphenol mass ratio is between 0.6:1 and 1.5:1
• - the polyphenol:solvent mass ratio can be between 0.25:1 and 0.35:1
• - the catalyst:cyclic carbonate ester molar ratio is between 0.05:1 and 0.2:1.
• the mixture of alkoxylated polyphenols produced by the process of the invention has a hydroxyl number of between 100 mg (KOH).g -1 and 1000 mg (KOH).g -1 and a viscosity, at 25° C., between 0.5 Pa.s and 100 Pa.s.
• hydroxyl index designates the quantity of potassium hydroxide in milligrams necessary to neutralize the acetic acid absorbed during the acetylation of one gram of alkoxylated polyphenols containing free hydroxyl groups.
• the mixture of alkoxylated polyphenols may have an index between 150 mg(KOH).g -1 and 800 mg(KOH).g -1 , more particularly between 200 mg(KOH).g -1 and 650 mg(KOH) .g -1 .
• the process of the invention makes it possible to obtain a mixture of alkoxylated polyphenols whose hydroxyl number is included in a wider range than the ranges usually reported for lignin-based polyols prepared by oxypropylation.
• this makes it possible to use the mixture of alkoxylated polyphenols for a wide range of applications, such as rigid or flexible polyurethane foams, or polyisocyanurate foams.
• the hydroxyl number range of the mixture of alkoxylated polyphenols produced by the method of the invention is suitable for the synthesis of polyurethane materials, in particular polyurethane foam.
• the range of hydroxyl index sought by a rigid polyurethane foam manufacturer extends from 100 mg(KOH).g ⁇ 1 to 700 mg(KOH).g ⁇ 1 .
• the range of hydroxyl index enabling a cross-linked three-dimensional network to be obtained is between 300 mg(KOH).g -1 and 700 mg(KOH).g - 1 whereas for a PIR-type foam, the hydroxyl index range must be between 100 mg(KOH).g -1 and 500 mg(KOH).g -1 .
• the mixture of alkoxylated polyphenols having a high hydroxyl number, ie up to 1000 mg (KOH).g -1 can, for its part, be used in a mixture with a polyol to manufacture, for example, coatings or varnishes in polyurethane.
• the mixture of alkoxylated polyphenols having a viscosity at 25°C between 0.5 Pa.s and 100 Pa.s is liquid and mixes easily with the polyisocyanate compound and any additives during the conventional manufacture of a polyurethane foam with Room temperature.
• viscosity designates the Brookfield viscosity and/or the viscosity measured by a cone-plane viscometer of the mixture of alkoxylated polyphenols at 25°C.
• the mixture of alkoxylated polyphenols may have a viscosity of between 1.5 Pa.s and 10 Pa.s, most particularly between 2 Pa.s and 8 Pa.s.
• the method of the invention also makes it possible to obtain a mixture of alkoxylated polyphenols whose viscosity is suitable for the synthesis of polyurethane materials, in particular polyurethane foam.
• the mixture of polyphenols is liquid at 25° C.
• the inventors are of the opinion that the combined use of the cyclic carbonate ester and of the solvent with a molar mass greater than 150 g/mol, in particular of ethylene carbonate and polyethylene glycol comprising a molar mass of between 200 g/mol and 400 g/mol, implemented in the method of the invention, allows the manufacture of mixtures of alkoxylated polyphenols with varied properties. More particularly, by increasing or decreasing the molar mass of the solvent, it is easy to adapt the hydroxyl index and the viscosity of said mixture according to its subsequent use.
• the particular conditions implemented in the method according to the present invention make it possible to obtain, at the end of step a), a product of viscosity and of hydroxyl index compatible with a use in the manufacture of polyurethane materials. Unlike the processes of the prior art, it is not necessary to purify, in particular by distillation, the product obtained at the end of step a).
• the cyclic carbonate ester:polyphenol mass ratio is between 0.3:1 and 5:1, in particular between 0.5:1 and 3:1, most particularly between 0.6 :1 and 1.5:1.
• the cyclic carbonate ester content used is therefore low. However, the cyclic carbonate ester may not have fully reacted.
• the mixture of alkoxylated polyphenols obtained according to the process which is the subject of the present invention may comprise cyclic carbonate ester which has not reacted, in other words residual cyclic carbonate ester.
• these residual cyclic carbonate ester contents are very low.
• the content of residual cyclic carbonate ester in the mixture can be between 1% and 5%, in particular between 2.5% and 4.5% relative to the mass of the mixture of alkoxylated polyphenols.
• These residual cyclic carbonate ester contents being very low, it is not necessary to purify the mixture of alkoxylated polyphenols to remove the residual cyclic carbonate ester before using said mixture of alkoxylated polyphenols.
• the method according to the invention does not comprise, after step (a), a step for purifying the mixture of alkoxylated polyphenols and/or a step for adding a viscosity-adaptor compound for the mixture of alkoxylated polyphenols, in particular for the step of purifying the mixture of alkoxylated polyphenols.
• purification step designates any step conventionally used by those skilled in the art to completely or partially eliminate the solvent and/or the residual cyclic carbonate ester from the mixture of alkoxylated polyphenols, such as for example a step of distillation or evaporation under vacuum.
• the reactivity of the mixture of alkoxylated polyphenols obtained by the process which is the subject of the present invention is very high. This makes it possible to advantageously reduce the quantity of catalyst required to manufacture a polyurethane material by at least 60%, or even up to 95%.
• the mixture of alkoxylated polyphenols produced by the method of the invention therefore has properties (chemical composition, viscosity, hydroxyl number, reactivity, etc.) such that it is suitable for use directly in the manufacture of polyurethane materials. , in particular polyurethane foam.
• the present invention also relates to a mixture of alkoxylated polyphenols capable of being obtained by the method according to the invention as defined above.
• the inventors are of the opinion that, during step (a) of the process of the invention, the polyphenol can react with the cyclic carbonate ester and/or with the solvent according to the various following reactions (for reasons of clarity but in a non-limiting manner, the polyphenol is lignin, the cyclic carbonate ester is ethylene carbonate and the
• solvent is polyethylene glycol (PEG) in the following reactions:
• PEG polyethylene glycol
• the inventors are also of the opinion that the reactivity of the solvent, in particular polyethylene glycol, with the cyclic carbonate ester is low so that the solvent does not hinder the reaction of the cyclic carbonate ester with the polyphenol.
• the mixture of alkoxylated polyphenols, object of the present invention has a hydroxyl number of between 100 mg (KOH).g -1 and 1000 mg (KOH).g -1 and a viscosity, at 25°C, between 0.5 Pa.s and 100 Pa.s.
• the mixture of alkoxylated polyphenols may have an index between 150 mg(KOH).g -1 and 800 mg (KOH).g -1 , more particularly between 200 mg (KOH).g -1 and 650 mg (KOH).g ⁇ 1 , even more particularly between 300 mg(KOH).g ⁇ 1 and 500 mg(KOH).g ⁇ 1 .
• the viscosity of the mixture of alkoxylated polyphenols can be between 1.5 Pa.s and 10 Pa.s, very particularly between 2 Pa.s and 8 Pa.s, in particular between 2.5 Pa.s and 8.5 Pa.s.
• the mixture of alkoxylated polyphenols has a hydroxyl number of between 150 mg(KOH).g -1 and 600 mg(KOH).g -1 and a viscosity of between 2.5 Pa. s and 10 Pa.s.
• the mixture of alkoxylated polyphenols has a hydroxyl number of between 300 mg(KOH).g -1 and 500 mg(KOH).g -1 and a viscosity of between 2.5 Pa.
• the mixture of alkoxylated polyphenols of the present invention advantageously has properties (chemical composition, viscosity, hydroxyl number, reactivity) such that it is particularly suitable for use directly in the manufacture of materials in polyurethane, particularly in the manufacture of polyurethane foam.
• the invention also relates to the use of the mixture of alkoxylated polyphenols capable of being obtained by the manufacturing process according to the invention as defined above or of the mixture of alkoxylated polyphenols according to the invention such as defined above to produce polyurethane and/or polyisocyanurate material of various types, such as sealant, adhesive, wood binder, cast elastomer, flexible or semi-flexible molded part, rigid structural composite, polyurethane foam, binder, semi-flexible foam, pipe insulation, cavity sealing module, or microcellular foam.
• sealant such as sealant, adhesive, wood binder, cast elastomer, flexible or semi-flexible molded part, rigid structural composite, polyurethane foam, binder, semi-flexible foam, pipe insulation, cavity sealing module, or microcellular foam.
• the invention also relates to a process for manufacturing a polyurethane foam in which the mixture of alkoxylated polyphenols produced during step (a) of the manufacturing process according to the invention as defined above or the mixture of alkoxylated polyphenols according to the invention as defined above is brought into contact with a polyisocyanate compound.
• a polyurethane foam as used, for example, in the expression “polyurethane foam”, denotes a compound with a three-dimensional alveolar structure of the expanded type. Said foam can be rigid or flexible, with open or closed cells.
• PUR rigid polyurethane
• closed-cell foam designates a foam whose alveolar structure comprises walls between each cell constituting a set of joined and separate cells allowing the imprisonment of an expansion gas.
• a foam is qualified as closed cell foam when it has a maximum of 10% open cells.
• closed cell foams are mostly rigid foams.
• open cell foam means a foam whose alveolar structure consists of a continuous alveolar matrix with open walls between the cells not allowing the imprisonment of an expansion gas . Such a foam allows the creation of percolation paths within its alveolar matrix.
• open cell foams are mostly soft foams.
• the polyisocyanate compound can be chosen from m-phenylene diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, hexamethylene 1,6-diisocyanate, 1,4-diisocyanate -tetramethylene diisocyanate, cyclohexane 1,4-diisocyanate, hexahydrotoluene diisocyanate, naphthylene 1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, 4,4′-diisocyanate diphenylmethane, 4 ,4′-biphenylene, 3,3′-dimethoxy-4,4′-biphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, 3,4′-diisocyanate, 3′-dimethyldipheny
• the polymeric diphenylmethane diisocyanate is advantageously suitable for the production of a polyurethane foam.
• the mass ratio mixture of alkoxylated polyphenols:polyisocyanate compound can be between 1:100 and 45:100, in particular between 3:100 and 40:100, very particularly between 5:100 and 35:100.
• the mixture of alkoxylated polyphenols can be used alone in the process for manufacturing a polyurethane foam according to the invention.
• the mixture of alkoxylated polyphenols can be used in a mixture with another type of polyol, for example with a polyol conventionally used for the manufacture of polyurethane foam of petrochemical origin chosen from alkoxylated glycerol, alkoxylated sorbitol, alkoxylated diethyl triamine, alkoxylated sucrose and mixtures thereof.
• a polyol conventionally used for the manufacture of polyurethane foam of petrochemical origin chosen from alkoxylated glycerol, alkoxylated sorbitol, alkoxylated diethyl triamine, alkoxylated sucrose and mixtures thereof.
• the mixture of alkoxylated polyphenols is used in a mixture with another type of polyol, for example with a polyol conventionally used for the manufacture of polyurethane foam of petrochemical origin chosen from among alkoxylated glycerol, alkoxylated sorbitol, alkoxylated diethyl triamine, alkoxylated sucrose and mixtures thereof.
• a polyol conventionally used for the manufacture of polyurethane foam of petrochemical origin chosen from among alkoxylated glycerol, alkoxylated sorbitol, alkoxylated diethyl triamine, alkoxylated sucrose and mixtures thereof.
• the polyol:polyisocyanate compound mass ratio can be between 40:100 and 75:100, in particular between 45:100 and 70:100, very particularly be from 50:100 to 66:100.
• the term “polyols” designates the mixture of alkoxylated polyphenols and the other type of polyol.
• a catalyst can be used to accelerate the kinetics of the reaction between the mixture of alkoxylated polyphenols and the polyisocyanate compound during the contacting step of the process for manufacturing a polyurethane foam.
• the contacting step of the process for manufacturing a polyurethane foam is carried out in the presence of a catalyst.
• the amount of catalyst used in the process for manufacturing a polyurethane foam of the invention depends on the compounds used in said process. A person skilled in the art will know how to adapt this quantity.
• the quantity of catalyst used in the process of the invention can advantageously be at least 60% and up to 95% lower than the quantity of catalyst used in a conventional process for manufacturing polyurethane foam.
• the catalyst can be chosen from tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, pentamethyl-diethylenetriamine and homologs, 1,4- diazabicyclo(2.2.2)octane, N-methyl-N'-dimethyl-aminoethylpiperazine, bis- (dimethylaminoalkyl)piperazines, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N- diethyl-benzylamine, bis-(N ,N-diethylaminoethyl) adipate, N,N,N',N-tetramethyl-1,3-butanediannine, N,N-dimethyl-1,3-phenylethylamine, 1,2-
• an additive known to those skilled in the art can be added during the contacting step.
• this additive can be chosen from a surfactant, a flame retardant, a swelling agent, an antioxidant, a mold release agent, an anti-hydrolysis agent, a biocide, an anti-UV agent and mixtures thereof, in particular chosen from a surfactant, a flame retardant, a blowing agent and mixtures thereof, more particularly being a mixture of surfactant and blowing agent.
• flame retardant agent also called flame retardant agent
• the flame retardant can, for example, be antimony, graphite, a silicate, boron, a nitrogenous, halogenated or phosphorus compound such as tris (1-chloro-2-propyl) phosphate (TCPP), triethylene phosphate (TEP), a triaryl phosphate ester, an ammonium polyphosphate, red phosphorus, trishalogenaryl or mixtures thereof.
• blowing agent designates a compound inducing by a chemical and/or physical action an expansion of a composition during a foaming step.
• the chemical blowing agent is selected from water, formic acid, phthalic anhydride and acetic acid.
• the physical blowing agent can be chosen from pentane and pentane isomers, hydrocarbons, hydrofluorocarbons, hydrochlorofluoroolefins, hydrofluoroolefins (HFOs), ethers and mixtures thereof. Mention may be made of methylal as an example of an ether-type blowing agent.
• a preferred chemical and physical blowing agent mixture is, for example, a mixture of water/pentane isomer or formic acid/pentane isomer or water/hydrofluoroolefins or pentane isomer/methylal/water or alternatively water/ methylal.
• surfactant denotes an agent allowing the physical stability of the polymer matrix during the progress of the reactions, in particular by anti-coalescent stabilization during the polymerization.
• the surfactant is chosen from any of the silicone glycol copolymers (for example Dabco® DC198 or DC193 marketed by Air Products), a non-hydrolysable silicone glycol copolymer (for example DC5000 from Air Products), a polyalkylene siloxane copolymer (for example Niax* L-6164 from Momentive), a polyoxyalkylene methylsiloxane copolymer (for example Niax* L-5348 from Momentive), a polyetherpolysiloxane copolymer (for example Tegostab® B8870 or Tegostab® B1048 from Evonik), a polydimethylsiloxane polyether copolymer (for example for example Tegostab® B8526 from Evonik), a polyethersiloxane (for example Tegostab® B8951 from Evonik), a modified polyether-polysiloxane copolymer (for example Tegostab® B8871 from Evonik), a
• the antioxidant can be an agent for neutralizing the ends of chains at the origin of the depolymerization and/or an agent for neutralizing the ends of comonomer chains capable of stopping the propagation of depolymerization.
• the mold release agent can be talc, a paraffin solution, silicone or mixtures thereof.
• the anti-UV agent can be titanium oxide, triazine, benzotriazole or mixtures thereof.
• the additive is a mixture of modified polyether-polysiloxane copolymer surfactant, tris (1-chloro-2-propyl) phosphate (TCPP), triethylene phosphate (TEP), a phosphate ester triaryl, an ammonium polyphosphate and red phosphorus.
• the present invention relates to a polyurethane foam which can be obtained by the process for manufacturing a polyurethane foam according to the invention as defined above.
• the polyurethane foam made from polyphenols derived from renewable sources such as lignin or tannins by the process of the invention has properties, in particular density, thermal conductivity and fire resistance, of the same order of magnitude as a conventional polyurethane foam made with products of petroleum origin.
• an acoustic and/or thermal insulation product comprising a foam according to the invention as defined above.
• the acoustic and/or thermal insulation product can for example be in the form of a panel or a block of foam.
• panel means an object having approximately a rectangular parallelepiped shape having relatively smooth surfaces and the following dimensions of 0.1 m2 to 50 m2 of surface area for a thickness of 10 mm to 1000 mm, preferably, from 0 .2 m2 to 20 m2 of surface for a thickness of 15 mm to 500 mm; even more preferentially, from 0.3 m2 to 15 m2 of surface area for a thickness of 17 mm to 400 mm typically, from 0.35 m2 to 7 m2 of surface area for a thickness of 20 mm to 250 mm. Examples of dimensions are typically, an area of 600 mm * 600 mm or 1200 mm * 600 mm for a thickness of 20 mm to 250 mm.
• block is meant a structure of any geometric shape, cubic parallelepiped, star or cylindrical, with or without recess(es), with a volume of between 1 cm3 to 100 m3, preferably 10 cm3 to 70 m3, even more preferably 100 cm3 to 50 m3 typically 0.5 m3 to 35 m3, typically 1 m3 to 30 m3.
• a kit for manufacturing a polyurethane foam comprising: - a mixture of alkoxylated polyphenols obtainable by the process according to the invention as defined above or a mixture of alkoxylated polyphenols according to the invention as defined above, and, - a polyisocyanate compound.
• the polyisocyanate compound is as described below in connection with the process for manufacturing a polyurethane foam according to the invention. More particularly, the polyisocyanate compound of the manufacturing kit can be chosen from toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, hexamethylene 1,6-diisocyanate, 4,4′- diphenylmethane diisocyanate, a polymethylene polyphenylisocyanate, polymeric diphenylmethane diisocyanate, isophorone diisocyanate and mixtures thereof, in particular from diphenylmethane 4,4′-diisocyanate, polymeric diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6- toluene diisocyanate and mixtures thereof.
• the cream time corresponds to the beginning of the formation of bubbles causing a change in color of the mixture which becomes creamy.
• the wire time corresponds to the beginning of the formation of a stable network by the intensive reactions of crosslinking and formation of urethanes.
• the tack-free time corresponds to the moment when the outer surface of the foam loses its adhesiveness, - the density according to standard EN 1602 (September 2013), - the thermal conductivity using a heat flow meter ("Heat Flow Meter " according to English terminology) HFM 446 according to standard EN 12939 (March 2001), and - fire resistance according to standard EN 11925-2 (March 2020).
• Examples 1 to 4 Mixture of alkoxylated polyphenols made from an organosolv lignin [0120] Organosolv lignin from beech wood produced by the Fabiola® process (supplied by Fraunhofer CBP (Leuna, Germany)) and poly(ethylene glycol) (denoted PEG, supplied by Acros Organics, CAS No. 25322-68-3) were introduced into a 1L reactor and then mixed. PEGs of different molar masses (g.mol ⁇ 1 ), different lignin contents and different PEG contents were used.
• the lignin/PEG mixture is then stirred using a mechanical stirrer then ethylene carbonate (mass ratio ethylene carbonate:lignin of 1.1:1) and potassium carbonate (K2CO3) (molar ratio K2CO3:ethylene carbonate of 0.1:1) are successively added.
• ethylene carbonate mass ratio ethylene carbonate:lignin of 1.1:1
• K2CO3 potassium carbonate
• the mixture is then placed under a flow of argon and immersed in an oil bath regulated at 130° C. for 4 h to produce a mixture of alkoxylated polyphenols.
• Example 5 Mixture of alkoxylated polyphenols made from a kraft lignin.
• the operating protocol is that of Examples 1 to 4, the differences being that the lignin used is a kraft lignin (Indulin AT®, Ingevity) and a single poly(ethylene glycol) (PEG 300) with a single content is used.
• the lignin and PEG contents (% by mass relative to the total mass of the lignin/PEG mixture), the molar mass of the PEG, the hydroxyl number (IOH) and the viscosity of the mixture of alkoxylated polyphenols produced are indicated. in Table 1 below.
• Example 6 Mixture of alkoxylated polyphenols made from a soda lignin.
• the operating protocol is that of Examples 1 to 4, the differences being that the lignin used is a soda lignin (Protobind 1000, Green Value) and a single poly(ethylene glycol) (PEG 300) with a single content is used.
• the lignin and PEG contents (% by mass relative to the total mass of the lignin/PEG mixture), the molar mass of the PEG, the hydroxyl number (IOH) and the viscosity of the mixture of alkoxylated polyphenols produced are indicated. in Table 1 below. [0128] [Table 1] The mixtures of alkoxylated polyphenols of Examples 1 to 6 have a hydroxyl number between 200 and 800 mg(KOH).g ⁇ 1 and a viscosity between 2 and 10 Pa.s. They are therefore suitable for the manufacture of polyurethane foam.
• Examples 7 to 10 Polyurethane foam
• the mixtures of alkoxylated polyphenols of Examples 1 to 4 are respectively used to manufacture a polyurethane foam according to Examples 7 to 10.
• a mixture of alkoxylated polyphenols is mixed with a polyol conventional (Daltolac® R570), a polyisocyanate compound (Desmodur® 44V70L) in the presence of a catalyst (Polycat® 8) and a mixture of additives (Tegostab® B1048 which is a surfactant, TCPP which is a flame retardant and isopentane which is a blowing agent).
• TCPP flame retardant and isopentane which is a blowing agent
• composition by mass relative to the total mass of polyols (conventional polyol alone or mixed with the mixture of alkoxylated polyphenols) and the properties of the various foams are indicated in Table 2.
• Table 2 shows that the substitution of at least part of the conventional polyol by the mixture of alkoxylated polyphenols makes it possible to reduce the quantity of catalyst by at least 60% and even approximately 95%.
• the characteristic times of formation of the foams according to the invention in particular the yarn times and the tack-free times, are much lower than the characteristic times of formation of the reference foam. This confirms that the mixture of alkoxylated polyphenols object of the present invention is very reactive.
• Table 2 also shows that: - the densities of the foams according to the invention and of the reference foam are of the same order of magnitude - the thermal conductivities of the foams according to the invention and of the reference foam are of the same order of magnitude, and - the fire resistance of the foams according to the invention and of the reference foam comply with standard EN 11925-2.
• the foams according to the invention based on lignin can therefore be used in an insulation product. This makes it possible to valorize the lignin.
• [Claim 2] A method according to claim 1, wherein the polyphenol is selected from lignin, condensed tannin, hydrolyzable tannin and mixtures thereof.
• [Claim 3] A process according to claim 1 or claim 2, wherein the cyclic carbonate ester is selected from butylene carbonate, ethylene carbonate, propylene carbonate, glycerol carbonate and mixtures thereof.
• [Claim 4] Process according to any one of Claims 1 to 3, in which the polyether is chosen from polybutylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, block, alternating or random copolymers obtained from of these monomers and their mixtures.
• step (a) comprises the following sub-steps: (a1) mixing in a reactor the at least one polyphenol and the solvent to obtain a mixture , (a2) adding the cyclic carbonate ester to the mixture, and

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