US20190194378A1 - Flexible or semi-flexible foam comprising a polyester polyol - Google Patents

Flexible or semi-flexible foam comprising a polyester polyol Download PDF

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Publication number
US20190194378A1
US20190194378A1 US16/327,555 US201716327555A US2019194378A1 US 20190194378 A1 US20190194378 A1 US 20190194378A1 US 201716327555 A US201716327555 A US 201716327555A US 2019194378 A1 US2019194378 A1 US 2019194378A1
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flexible
semi
foam
polyol
glycerol
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Inventor
Pierre Etienne Bindschedler
Alexandru SARBU
Stephanie LAURICHESSE
Remi Perrin
Pierre FURTWENGLER
Luc AVÉROUS
Andreas Redl
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Tereos Starch and Sweeteners Belgium
Centre National de la Recherche Scientifique CNRS
Universite de Strasbourg
Soprema SAS
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Tereos Starch and Sweeteners Belgium
Centre National de la Recherche Scientifique CNRS
Universite de Strasbourg
Soprema SAS
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Assigned to SOCIÉTÉ SOPREMA SAS, UNIVERSITÉ DE STRASBOURG, CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, TEREOS STARCH & SWEETENERS BELGIUM reassignment SOCIÉTÉ SOPREMA SAS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: REDL, ANDREAS, SARBU, Alexandru, LAURICHESSE, STEPHANIE, PERRIN, REMI, BINDSCHEDLER, PIERRE ETIENNE, FURTWENGLER, Pierre, AVÉROUS, Luc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/40—Succinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/44—Adipic acid esters
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether 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
    • C08G18/70—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
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J9/125—Water, e.g. hydrated salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C08G2101/0008—
    • 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
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/0016—Foam properties semi-rigid
    • 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
    • C08G2110/0025—Foam properties rigid
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls

Definitions

  • the present invention relates to a flexible or semi-flexible polyurethane foam comprising a polyester polyol which can be of bio-sourced origin.
  • PUs Polyurethanes
  • Scheme 1 Polyurethanes
  • PUs are polyvalent polymers obtained by the reaction between a polyol and a polyisocyanate (Scheme 1, a).
  • Scheme 1 Polyisocyanate
  • PUs are used in automobiles, furniture, construction, footwear, acoustic and thermal insulation. With global production of 18 Mt in 2016, PUs rank 6 th in terms of annual global polymer production.
  • Flexible foams represent the largest PU market with more than 1600 kt produced in Europe in 2011.
  • PU foams are made from polyols, polyisocyanates, swelling agents, surfactants, and various catalysts to obtain a chemically crosslinked cellular material.
  • Two types of swelling agents are used in the synthesis of PU foams: chemical swelling agents and physical swelling agents.
  • Chemical swelling agents are compounds that react chemically in the foaming process to release gases. Water reacts with the isocyanate function to form urea and releases one mole of CO 2 per mole of water (Scheme 1, b).
  • Physical swelling agents are compounds having a low boiling point; isopentane derivatives, which evaporate during the exothermic foaming process may be mentioned as physical swelling agents.
  • flexible and semi-flexible PU foams are obtained from polyols presenting a low hydroxyl content (OHV ⁇ 100 mg KOH/g) and high average molecular weight (Mn) value (3000 g/mol). ⁇ Mn ⁇ 6,000 g/mol), in order to increase the flexibility and reduce the crosslinking of the material.
  • Semi-flexible foam boards are a very important part of PU foams. They are an interesting solution to the problems of our modern societies such as noise pollution, moreover, their open-cell structure is permeable to moisture. Permeable materials are in high demand in the insulation industry to prevent moisture build-up and mold growth. These materials generally have low bulk density, low thermal conductivity and, therefore, are inexpensive materials. This means that boards of semi-flexible foams are versatile insulation materials: acoustically and thermally.
  • Flexible and semi-flexible PU foams come from the phase separation of rigid and flexible domains.
  • Flexible domains are extensible chains, mainly provided by the polyols, which provide the elasticity of the material.
  • the hard segments are described as a rigid structure that is physically cross-linked by polyol or by using an excess of polyisocyanate.
  • the excess of polyisocyanate leads to an increase in the biurea bond (Scheme 1, d), the allophanate bond (Scheme 1, c) or the isocyanurate bond (Scheme 1, e).
  • the hard segment is also obtained from a chain extender and an isocyanate. Another way to improve the rigidity of the hard segments is to increase the low interchain forces in the rigid domain by introducing polar groups such as urea. The presence of urea leads to the increase of the amount of hydrogen bonds and the softening temperature.
  • Sorbitol is one of those elements of interest that was cited as one of the top 12 value-added chemicals from biomass by the US Department of Energy in 2004 and more recently in a list updated by Bozell J J et al. in 2010 (J. J. Bozell, G. R. Petersen, Technology Development for the Production of Bio - sourced Products from Biorefinery Carbohydrates - US Department of Energy's “Top 10” revisited, Green Chem. 12 (2010) 539).
  • Sorbitol has a high functionality. It is a crystalline sugar alcohol bearing two primary hydroxyl groups and four secondary hydroxyl groups, which is convenient for chemical modification and its use in polyurethane chemistry. It is important to control the modification of sorbitol to polyol.
  • the polyol functionality, the OH number and the viscosity of the polyol have a strong impact on the formation of the PU network, the density and the morphology of the PU foam. Beyond the open or closed nature of the PU foam cells, the size, shape and spatial distribution of these cells also have an effect on the physical properties of the foam. Thus, the thermal and mechanical properties of PU foams depend closely on the morphology of the foam.
  • the inventors have developed a novel bio-sourced polyurethane foam having good mechanical characteristics and in particular anisotropic mechanical characteristics according to the direction of solicitation of the foam, compared with the petrol-derived PU foam obtained from a classic petrol-sourced polyether polyol.
  • the inventors have established a comparative study and demonstrated correlations between the formulation of the foam, the characteristic foaming times (kinetics) and the mechanical properties of the bio-sourced PU foams.
  • the invention relates to a flexible or semi-flexible foam or a composition for obtaining a flexible or semi-flexible foam comprising a polyester polyol or a polymer comprising a polyester polyol, said polyester polyol being obtained by a first polycondensation (a) of a C3 to C8 sugar alcohol Z and two identical or different C4 to C36 diacids Y and Y′ and a second polycondensation (b) of the product obtained in (a) with two identical or different C2 to C12 X and X′ diols.
  • the invention also relates to a flexible or semi-flexible foam or a composition for obtaining a flexible or semi-flexible foam comprising a polyester polyol or a polymer comprising a polyester polyol, said polyester polyol is of general formula Rx-Ry-Z—Ry′-Rx′ in which
  • foam as used, for example, in the terms “polyurethane foam” or “polyisocyanurate foam” is meant a compound of three-dimensional expanded type alveolar structure. Said foam may be rigid or flexible, with open or closed cells.
  • flexible or semi-flexible or semi-rigid foam means a foam that returns to its initial shape (about 2-60 s) after a deformation in compression of 50%. Generally, such foams have a mixed structure composed of open and closed cells. Their properties are between those of flexible and rigid foams.
  • Non-rigid foams of polyurethane or polyisocyanurate are referred to as flexible or semi-flexible polyurethane or polyisocyanurate foams.
  • closed cell foam means a foam of which the alveolar structure comprises walls between each cell that form a set of attached and separate cells allowing for the imprisonment of an expansion gas.
  • a foam is qualified as a closed cell foam when it has a maximum of 10% of open cells.
  • closed cell foams are mostly rigid foams.
  • open cell foams means a foam whose alveolar structure is formed of a continuous cell matrix with an open wall between the cells which do not allow for the imprisonment of an expansion gas. Such a foam allows for the creation of percolation paths within the cell matrix thereof.
  • open cell foams are mostly flexible foams.
  • polyester polyol refers to molecules that comprise hydroxyl groups (diols or sugar alcohols) bonded together by ester bonds.
  • the molecules X, Y, Z, Y′ and X′ are bonded together by ester bonds.
  • the diols X and X′ and the sugar alcohol Z are bonded to the two diacids Y and Y′ by ester bonds each formed between an acid function of Y or of Y′ and a primary hydroxyl function of Z, X or X′.
  • the polyester polyol is of neutral pH, typically, when it is obtained by two successive polycondensations followed by a step of neutralisation (for example with potash or with sodium hydroxide).
  • the polyester polyol according to the invention advantageously has the general chemical formula C a H b O c having 22 ⁇ a ⁇ 42, 38 ⁇ b ⁇ 78, 14 ⁇ c ⁇ 22.
  • the polyester polyol according to the invention has a molecular weight of between 350 g/mol and 2000 g/mol, preferably between 420 g/mol and 1800 g/mol and more preferably between 450 and 1700 g/mol.
  • the molar weight of the polyester polyol can be determined by various methods such as size exclusion chromatography.
  • the polyester polyol has a hydroxyl number of 300 to 900 mg KOH/g.
  • the hydroxyl number (IOH) can be calculated with the following formula:
  • IOH functionality of polyester polyol ⁇ 56109.37/Molar mass of polyester polyol.
  • the hydroxyl number corresponds to the number of mg of KOH necessary to deprotonate all the hydroxyl groups present in one gram of polyol.
  • the hydroxyl number can be determined by reverse assay using potassium hydroxide, for example according to ASTM 4274-99 in which the colorimetric titration is replaced by a pH-metric titration.
  • sugar alcohol or “polyol” means a hydrogenated form of monosaccharide of which the carbonyl group (aldehyde or ketone) has been reduced to a primary or secondary hydroxyl.
  • sugar alcohol is chosen from glycerol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol.
  • the polyester polyol means a carbon chain comprising two acid groups.
  • the polyester polyol comprises two molecules Y and Y′ of diacid. These molecules can be identical or different in C4 to C36, preferably C4 to C24.
  • the two molecules of diacid are independently chosen from butanedioic acid (Succinic acid), pentanedioic acid (Glutaric acid), hexanedioic acid (Adipic acid), heptanedioic acid (Pimelic acid), octanedioic acid (Suberic acid), nonanedioic acid (Azelaic acid), decanedioic acid (Sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid (Brassylic acid), tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, fatty acid dimers having up to 36 carbons (C36) or mixture thereof.
  • Y and Y′ are diacids in C5 to C16 or C6 to C12.
  • the preferred molecules of diacid are independently chosen from
  • the polyester polyol means a carbon chain comprising two alcohol functions.
  • the polyester polyol comprises two molecules X and X′ of diols which are identical or different.
  • the molecules of diol are independently chosen from 1,2 ethanediol, 1,3 propanediol, 1,4-butanediol, 1,6 hexanediol, 1,8 octanediol, 1,10 decanediol, 1,12 dodecanediol and mixtures thereof.
  • the polyester polyol according to the invention is chosen from bis(1,2 ethanediol)-sorbitol diadipate, bis(1,3 propanediol)-sorbitol diadipate, bis(1,4-butanediol)-sorbitol diadipate, bis(1,4-butanediol)-sorbitol diadipate modified with glycerol, bis(1,6 hexanediol)-sorbitol diadipate, bis(1,8 octanediol)-sorbitol diadipate, bis(1,10 decanediol)-sorbitol diadipate, bis(1,12 dodecanediol)-sorbitol diadipate, bis(1,4 butanediol)-sorbitol disuccinate and sorbitol-diadipate-sorbitol.
  • said polyester polyol is chosen from bis(1,8 octanediol)-sorbitol diadipate, bis(1,10 decanediol)-sorbitol diadipate and bis(1,4-butanediol)-sorbitol diadipate.
  • the invention also relates to a flexible or semi-flexible foam or a composition for obtaining a flexible or semi-flexible foam comprising a polyester polyol obtained by a process comprising the following steps:
  • the diols X and X′ and the sugar alcohol Z are at a molar ratio (X+X′)/Z of between 1 and 3, preferably between 1.5 and 2.5, more preferably between 1.8 and 2.2.
  • the diacids Y and Y′ and the sugar alcohol are at a molar ratio (Y+Y′)/Z of between 1 and 3, preferably between 1.5 and 2.5, even more preferably between 1.8 and 2.2.
  • the diols X and X′ and the diacids Y and Y′ are at a molar ratio (X+X′)/(Y+Y′) of between 0.5 and 2, preferably between 0.7 and 1.5, even more preferably between 0.8 and 1.2.
  • the polycondensation step comprises a first polycondensation (a) of the sugar alcohol Z and diacids Y and Y′ and a second polycondensation (b) of the product obtained in (a) with the diols X and X′.
  • This polycondensation in two stages makes it possible to obtain the polyester polyol with this symmetric structure.
  • the diacids Y and Y′ are identical and/or the diols X and X′ are identical.
  • the sugar alcohol Z is mixed with the diacid molecule(s) Y and Y′ and then incubated for more than one hour, more preferably between 2 and 5 hours, even more preferentially between 2.5 and 4 hours, typically for 3 hours.
  • the diol molecule(s) X and X′ are added in a second step to the mixture and then incubated for more than 4 hours, preferably between 5 and 10 hours, typically between 5.5 and 7 hours.
  • the polycondensation step is carried out under vacuum.
  • the diacid molecules Y and Y′ react with the primary alcohols of sugar alcohol molecules Z and diols X and X′.
  • the water molecules resulting from the reaction are recovered in view of being eliminated.
  • the invention further relates to a flexible or semi-flexible foam comprising a polymer comprising the polyester polyol according to the invention, typically, said polymer is a polyurethane and/or a polyisocyanurate.
  • the polymer according to the invention has a molar mass greater than 1.7 ⁇ 10 6 g/mol.
  • the polymer is a crosslinked polymer.
  • polyurethane is meant a polymer comprising urethane functions, that is in other words, a urethane polymer.
  • polymers result essentially from the reaction of polyols, in particular the polyester polyols of the invention with polyisocyanates.
  • These polymers are generally obtained from formulations having an index from 100 to 150, preferably from 105 to 130 corresponding to a NCO/OH ratio of between 1 and 1.5, preferably between 1.05 and 1.3.
  • polyisocyanurate is meant the polymers resulting from the reaction of polyols, in particular the polyester polyol of the invention and polyisocyanates, which contain, in addition to urethane linkages, other types of functional groups, in particular rings. triisocyanuric compounds formed by the trimerization of polyisocyanates.
  • These polymers normally also called modified polyurethanes, are generally obtained from formulations having an index of 10 to 500, preferably between 115 and 460, even more preferably between 150-450, or an NCO/OH ratio of between 1.1 and 5.0 preferably between 1.15 and 4.6, preferably between 1.5 and 4.5.
  • said polymer is a mixture of polyurethane and polyisocyanurate. Such a mixture is observed for example when said polymer comprises major urethane functions and a minor portion of polyisocyanates trimerized to triisocyanuric rings.
  • said polymer is a mixture of polyurethane and polyisocyanurate and has an index greater than 100 or less than or equal to 150, corresponding to an NCO/OH ratio greater than 1 or less than or equal to 1.5.
  • NCO/OH ratio means, in terms of this invention, the ratio between the number of NCO functions of the polyisocyanate and the number of OH functions of the sugar alcohol of the diol and of any other component comprising OH groups (water, solvents).
  • the NCO/OH ratio is calculated with the following formula:
  • the term “urea bond” or “urea function” means a disubstituted urea linkage which is the product of the reaction between a primary amine function and an isocyanate function of a polyisocyanate.
  • the amine functions are formed in situ by the reaction of a water molecule with an isocyanate function carried by a polyisocyanate.
  • the foam according to the invention or the composition for obtaining such a foam comprising the polyester polyol according to the invention or the polymer according to the invention, further comprises, at least one reaction catalyst, at least one swelling agent, a stabilizer, at least one polyisocyanate having a functionality of at least 2, optionally at least one co-polyol and additives.
  • co-polyol is meant a compound carrying two or more hydroxyl functions (diol type) (polyol) added to the composition comprising the polyester polyol in order to adjust the properties thereof such as the functionality or the viscosity, to create crosslinking nodes or chain extension.
  • the co-polyols may be C2 to C8, preferably C2 to C7, advantageously C3 to C6.
  • the copolyols may advantageously be chosen from ethylene glycol, glycerol, 1,4-butanediol, butane-1,3-diol, 1,3-propanediol and propane-1,2-diol.
  • the preferred co-polyols are glycerol, 1,4-butanediol, 1,3 propanediol and sorbitol.
  • the co-polyol(s) is/are added in a polyol polyester/co-polyol (s) ratio of 70/30 to 99/1, preferably 75/25 to 95/5, even more preferably between 80/20 a,d 92/8, typically between 82/8 and 90/10, for example 85/15.
  • the composition comprises two co-polyols, typically a co-polyol C2 and a co-polyol C3 or a co-polyol C2 and a co-polyol C4 or a co-polyol C2 and a co-polyol C5 or a co-polyol C2 and a co-polyol C6 or a co-polyol C3 and a co-polyol C4 or a co-polyol C3 and a co-polyol C5 or a co-polyol C3 and a co-polyol C6 or a co-polyol C4 and a co-polyol C5 or a co-polyol C4 and a co-polyol C6 or a C5 or a co-polyol C4 and a co-polyol C6 or a C5 co-polyol and a co-pol
  • the composition comprises at least one C2 co-polyol, typically two co-polyols, typically ethylene glycol and glycerol, ethylene glycol and 1,4-butanediol, ethylene glycol and erythritol, ethylene glycol and xylitol, ethylene glycol and araditol, ethylene glycol and ribitol, ethylene glycol and dulcitol, ethylene glycol and mannitol or ethylene glycol and volemitol.
  • the preferred mixture of co-polyols is glycerol and ethylene glycol.
  • the composition comprises two co-polyols, typically erythritol and sorbitol, xylitol and sorbitol, araditol and sorbitol, ribitol and sorbitol, dulcitol and sorbitol, mannitol and sorbitol or volemitol and sorbitol.
  • co-polyols typically erythritol and sorbitol, xylitol and sorbitol, araditol and sorbitol, ribitol and sorbitol, dulcitol and sorbitol, mannitol and sorbitol or volemitol and sorbitol.
  • the composition comprises two co-polyols typically in a ratio between 95/05 to 50/50, preferably 90/10 to 55/45, preferentially 87/13 to 60/40, more preferably 85/15 to 62/38, still more preferably 80/20 to 65/35.
  • a C3/C6 or C3/C5 or C4/C6 or C5/C6 ratio between 95/05 to 50/50, preferably 90/10 to 55/45, preferentially 87/13 to 60/40, more preferentially 85/15 to 62/38, even more preferably 80/20 to 65/35.
  • the preferred ratio is 66/33, a particularly advantageous ratio in the context of the mixture of glycerol/sorbitol co-polyols, in particular for a final polyol polyester/glycerol/sorbitol 85/10/5 mixture.
  • polyisocyanate means any chemical compound comprising at least two separate isocyanate chemical functions (NCO), in other words, that have “a functionality at least equal to 2”. When the polyisocyanate has a functionality of 2, this is referred to as diisocyanate.
  • functionality means, in terms of this invention, the total number of reactive isocyanate functions per molecule of isocyanate.
  • the functionality of a product is evaluated via the titration of the NCO function by a method of return dosage of the excess dibultylamine by the chloridric acid.
  • said polyisocyanate has a functionality between 2 and 5, preferably between 2.5 and 3.5 even more preferably between 2.7 and 3.3.
  • said polyisocyanate is chosen from aromatic, aliphatic, cycloaliphatic polyisocyanates and mixtures thereof. Mention can be made for example of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, cis/trans of cyclohexane diisocyanate hexamethylene diisocyanate, m- and p-tetramethylxylylene-diisocyanate, m-xylylene, p-xylylene diisocyanate, naphthalene-m, m-diisocyanate, 1,3,5-hexamethyl mesitylene triisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4′-diphenyl-methane,
  • the polyisocyanate is chosen from toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (or 4,4′-diisocyanate of diphenylmethylene or 4,4′-MDI), polymethylene polyphenylene polyisocyanate (polymeric MDI, pMDI) and mixtures thereof.
  • TDI toluene diisocyanate
  • 4,4′-diphenylmethane diisocyanate or 4,4′-diisocyanate of diphenylmethylene or 4,4′-MDI
  • polymethylene polyphenylene polyisocyanate polymeric MDI, pMDI
  • reaction catalyst means a compound that introduced in a small quantity accelerates the kinetics of the formation of the urethane bond (—NH—CO—O—) by reaction between the polyester polyol of the invention and a polyisocyanate or activates the reaction between a polyisocyanate and water or activate the trimerisation of the isocyanates.
  • reaction catalysts are chosen from tertiary amines (such as dimethylcyclohexane), derivatives of tin (such as tin dibutyldilaurate), ammonium salts (such as methanaminium N,N,N-trimethyl of 2,2-dimethylpropanoate), carboxylates of alkali metals (such as potassium 2-ethylhexanoate or potassium octoate) amine ethers (such as bis(2-dimethylaminoethyle) ether), and triazines (such as 1,3,5-Tris(3-(dimethylamino)propyl))hexahydro-1,3,5-triazine).
  • tertiary amines such as dimethylcyclohexane
  • derivatives of tin such as tin dibutyldilaurate
  • ammonium salts such as methanaminium N,N,N-trimethyl of 2,2-dimethylpropanoate
  • a composition intended for obtaining a foam comprises said polyester polyol according to the invention or said polymer according to the invention, at least one reaction catalyst, at least one polyisocyanate having a functionality at least equal to 2, at least one swelling agent, a stabilizer and optionally a flame retardant or at least one co-polyol.
  • the preferred polyester polyol is a neutral pH polyester polyol and/or comprises sorbitol as sugar-alcohol Z.
  • the polyester polyol preferred is bis (1,2-ethanediol)-sorbitol-diadipate, bis (1,6-hexanediol) sorbitol-diadipate or bis (1,4-butanediol)-sorbitol-diadipate, more preferably, bis (1,4-butanediol)-sorbitol. diadipate, or bis (1,6 hexanediol)-sorbitol-diadipate.
  • a foam typically comprises, after polymerization, a polymer according to the invention, in particular a crosslinked polymer, at least one reaction catalyst, at least one swelling agent, at least one stabilizer, and optionally at least one co-polyol.
  • swelling agent or “expansion agent” is meant a compound inducing by a chemical and/or physical action an expansion of a composition during a foaming step.
  • the chemical swelling agent is chosen from water, formic acid, phthalic anhydride and acetic acid
  • the physical swelling agent is chosen from pentane and pentane isomers, hydrocarbons and hydrofluorocarbons, hydrochlorofluoroolefins, hydrofluoroolefins (HFOs), ethers and their mixtures thereof.
  • Methylal may be mentioned as an example of an ether-type swelling agent.
  • a preferred chemical and physical swelling agent mixture is for example a water/pentane isomers mixture or water/methylal or water/hydrofluoroolefins.
  • the stabilizers are chosen from any of the silicone glycol copolymers (for example Dabco DC198 or DC193 sold by Air Products), non-hydrolyzable silicone glycol copolymer (for example DC5000 from Air Products), polyalkylene siloxane copolymer (for example Niax L 6164 from Momentive), polyoxyalkylene methylsiloxane copolymer (for example Niax L-5348 from Momentive), polyetherpolysiloxane copolymer (for example Tegostab B8870 or Tegostab B1048 from Evonik), polydimethylsiloxane polyether copolymer (for example Tegostab B8526 from Evonik), polyethersiloxane (for example Tegostab B8951 from silicone glycol copolymers (for example Dabco DC198 or DC193 sold by Air Products), non-hydrolyzable silicone glycol copolymer (for example DC5000 from Air Products), polyalkylene siloxane copolymer (for example
  • additives agents such as antioxidants (neutralisation agents of chain ends at the origin of the depolymerisation or co-monomer chains capable of stopping the propagation of depolymerisation), demoulding agents (talc, paraffin solution, silicone), anti-hydrolysis agents, biocides, anti-UV agents (titanium oxide, triazine, benzotriazole) and/or flame retardants (antimony, phosphorus, boron, nitrogen compounds).
  • flame retardant means a compound that has the property of reducing or preventing the combustion or the heating of the materials that it impregnates or covers, referred to as flame or fire retardant. Mention can be made for example to graphite, silicates, boron, halogenated or phosphorous derivatives such as Tris (1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP), triaryl phosphate esters, ammonium polyphosphate, red phosphorous, trishalogenaryl, and mixtures thereof.
  • TCPP Tris (1-chloro-2-propyl) phosphate
  • TEP triethyl phosphate
  • triaryl phosphate esters triaryl phosphate esters
  • ammonium polyphosphate red phosphorous, trishalogenaryl, and mixtures thereof.
  • composition according to the invention for obtaining a flexible or semi-flexible or flexible open-cell foam is typically formulated with an index of 90 to 150, preferably 105 to 120, typically 115, or an NCO/OH ratio. from 0.90 to 1.5, preferably from 1.05 to 1, 20, typically 1.15.
  • such a composition comprises
  • a flexible or semi-flexible open-cell polyurethane foam comprises, for example, 100 parts of a polyester polyol, 160 parts of a polyisocyanate, 2 parts of an amine catalyst such as dimethylcyclohexyleamine, 2 parts of a swelling agent such as water and 13 parts of a swelling agent such as isopentane derivatives, 2.5 parts of a stabilizer such as a polyether-polysiloxane copolymer and 10 parts of a flame retardant.
  • a second example of open-cell flexible or semi-flexible polyurethane foam is a foam comprising 85 parts of a polyester polyol and 15 parts of a co-polyol, 330 parts of a polyisocyanate, 2 parts of amine catalyst such as dimethylcyclohexyleamine, 9 parts of a swelling agent such as water, 2.5 parts of a stabilizer such as a polyether-polysiloxane copolymer and 10 parts of a flame retardant.
  • the invention also relates to a panel or a block of flexible or semi-flexible foam comprising the flexible or semi-flexible foam of the invention, typically for thermal or acoustic insulation, namely thermal or acoustic insulation of buildings or cryogenic insulation of refrigerators, cold chamber, or for empty space filling or buoyancy help such as in buoyancy aids (belts or vests . . . ) or water sports, for the damping of shocks and vibrations (for example, shoes, carpets or mattresses, foams for packaging or padding hard structures in order to improve the comfort, typically roof lining, seating (seats, chairs . . . ), soles, areas for gripping for example the wheels of cars, . . . ), for filtration.
  • thermal or acoustic insulation namely thermal or acoustic insulation of buildings or cryogenic insulation of refrigerators, cold chamber, or for empty space filling or buoyancy help
  • buoyancy aids belts or vests . . .
  • water sports for the
  • panel having approximately a rectangular parallelepiped shape having relatively smooth surfaces and the following dimensions from 0.3 to 50 m 2 of surface for a thickness of 10 to 1000 mm, preferably from 0.5 to 20 m 2 of surface for a thickness of 15 to 500 mm; even more preferably, from 0.8 to 15 m 2 of surface for a thickness 17 to 400 mm typically, from 1 to 7 m 2 of surface for a thickness of 20 to 250 mm Examples of dimensions are typically, a surface of 600*600 mm or 1200*600 mm for a thickness of 20 to 250 mm.
  • block is meant a structure of any geometrical shape, cubic, parallelepiped, star-shaped or cylindrical, with or without recess(es), of a volume of between 1 cm 3 and 100 m 3 , preferably 10 cm 3 to 70 m 3 , even more preferentially 100 cm 3 to 50 m 3 typically 0.5 to 35 m 3 , typically 1 to 30 m 3 .
  • the invention also relates to a method for obtaining a panel or a block of flexible or semi-flexible foam block according to the invention, namely by molding.
  • the invention relates to a method for thermal, phonic or cryogenic insulation, namely for buildings, fluid transport pipes or a method of filling (cracks or free space), sealing (structures, cracks, etc.).), waterproofing or improving the floatation (typically buoyancy aids or water sports) or damping shock and vibration or filtration by depositing or introducing blocks or panels of flexible or semi-flexible foam according to the invention or by the projection of a flexible or semi-flexible foam or a composition for obtaining a flexible or semi-flexible foam according to the invention.
  • a composition for obtaining a flexible polyurethane foam typically has an index of 100 to 120 and comprises, for example,
  • a flexible polyurethane foam composition comprises, for example, 100 parts of the polyester polyol according to the invention; 5 parts of swelling agent such as water; 50 parts of polyisocyanate such as toluene diisocyanate; 1 part of stabilizer such as Tegostab BF 2370; 0.2 parts of catalyst such as tin dibutyldilaurate.
  • the invention also relates to an insulation panel such as a sound or acoustic insulation panel, a mattress, a seat, a seat, an armchair or a sofa such as a car seat or furniture comprising said flexible or semi-flexible foam of the invention.
  • an insulation panel such as a sound or acoustic insulation panel, a mattress, a seat, a seat, an armchair or a sofa such as a car seat or furniture comprising said flexible or semi-flexible foam of the invention.
  • the invention also relates to a process for obtaining a flexible or semi-flexible foam typically of polyurethane and/or polyisocyanurate comprising:
  • a step of obtaining a polyester polyol according to the invention or of a polymer according to the invention a step of adding at least one polyisocyanate, at least one reaction catalyst, at least one swelling agent and a stabilizer, and a polymerization step.
  • the invention also relates to the use of a foam according to the invention in thermal and acoustic insulation or in the filling of space in the building or in the mechanical industry.
  • a foam according to the invention in thermal and acoustic insulation or in the filling of space in the building or in the mechanical industry.
  • FIG. 1 Foaming profile: evolution of the temperature (a), maximum height (b) and the foaming rate (c) with respect to the time of the foaming step
  • FIG. 2 a. FTIR spectra of formulated foams, b. FTIR spectra zoomed on the absorption zone of isocyanurates
  • FIG. 3 a. ATG curves of PU foams, under dry air, b. Derivative from ATG curves for PU foams, under dry air
  • FIG. 4 SEM image of PU foams in the transverse (T) and longitudinal (L) directions in the rising direction of the foam
  • FIG. 5 a) Module of conservation, modulus of loss and evolution of Tan ⁇ of REF, and b) Evolution of Tan ⁇ of REF and the bio-sourced foams
  • FIG. 6 Strain curves of REF and B100-2 bio-sourced foam, in —a) longitudinal direction, —b) transverse direction
  • FIG. 7 Deformation-stress curves of bio-sourced PU foams, in —a) longitudinal direction, —b) transverse direction
  • Sorbitol was supplied by the company TEREOS (MERITOL®, 98%, water content ⁇ 0.5%, reducing sugar content ⁇ 0.1%).
  • 1,4-Butanediol (BDO, 99%) was obtained from SIGMA ALDRICH.
  • Adipic acid (AA) (99%) was obtained from ACROS ORGANICS.
  • Polyol polyether is an oxypropylated polyol of the company Huntsman (Daltolac® R570), with an average functionality of 3.0 and an OH value of 570 mg KOH/g.
  • the polyisocyanate is 4,4′-methylenebis (diphenyl isocyanate) (MDI) polymer BORSODCHEM (ONGRONAT 2500).
  • N N-dimethylcyclohexylamine
  • KB potassium 2-ethylhexanoate
  • the flame retardant is SHEKOY Tris (1-chloro-2-propyl) (TCPP) phosphate
  • the surfactant was polydimethylsiloxane (B84501) obtained from EVONIK and glycerol (gly) (99.5%) was obtained from FISHER SCIENTIFIC.
  • INVENTEC isopentane was used as a physical swelling agent.
  • the sorbitol-based polyester polyol was synthesized by a two-step bulk polycondensation from sorbitol, 1,4-butanediol and adipic acid.
  • One molar equivalent of sorbitol and two molar equivalents of adipic acid were charged into a 600 ml Parr thermoregulated reactor (Model No. 4568) equipped with a heating mantle, a mechanical stirrer with a U-shaped blade, a thermocouple, a Dean Stark having an output at the top of the capacitor to be able to link a vacuum pump and a low output to recover the condensate, an inlet and an outlet of inert gas.
  • the medium was heated at 150° C.
  • BASAB viscous yellow polyol
  • PU foams were prepared with an isocyanate/hydroxyl (NCO/OH) molar ratio of 1.15.
  • NCO/OH isocyanate/hydroxyl
  • all the reactive hydroxyl groups are taken into account, that is to say the polyols, the water and the possible solvents associated with the different catalysts.
  • a premix containing polyol(s), catalysts, surfactant (polydimethylsiloxane, B84501), flame retardant (TCPP) and the swelling agent (s) is prepared.
  • the swelling agents were chosen between isopentane (physical swelling agent) and water (chemical swelling agent). The total ratio of swelling agent remains constant in all formulations.
  • the number of TCPP and surfactant parts is constant and equal to 10 parts for TCPP and 2.5 parts of surfactants.
  • the total amount of polyol never exceeds 100 parts.
  • the mixture is stirred mechanically until a fine white emulsion is obtained with total incorporation of the swelling agent.
  • the temperature of the mixture is controlled and adjusted to 20° C.
  • the temperature of the polyisocyanate is also controlled and an adequate amount thereof is added rapidly to the emulsion.
  • the whole reaction mixture is vigorously stirred for 5 s and then foamed freely in a 250 ml disposable beaker at room temperature (controlled at 20° C.) to monitor the kinetics of the foam or in the FOAMAT device.
  • the foam samples were stored for three days at room temperature for complete maturation of the foam.
  • Thermogravimetric (TGA) analyzes were performed using a TA Hi-Res TGA Q5000 instrument in reconstituted air (flow rate 25 mL/min). 1-3 mg samples were heated from room temperature to 700° C. (10° C./min). The main characteristic degradation temperatures are those at most of the derivative of the weight loss curve (DTG) (Tdeg, max).
  • TTG weight loss curve
  • Infrared spectroscopy was performed with a NICOLET 380 Fourier transform infrared spectrometer used in reflection mode equipped with an ATR diamond module (ATR-FTIR). An atmospheric background was collected before the analysis of the sample (64 scans, 4 ⁇ 1 cm resolution). All spectra were normalized to a stretch peak of the C—H bond at 2950 cm ⁇ 1 .
  • Dynamic mechanical analysis (DMA) was performed on TRITEC 2000 (Triton) compressive devices. The samples were analyzed at a constant frequency of 1 Hz for a temperature range of 30 to 270° C. with a heating rate of 2° C./min and a constant static resistance of 0.5 N. Samples were 7.5 ⁇ 7.5 ⁇ 7.5 mm 3 .
  • the quasi-static compression tests were carried out with an INSTRON dynamometer (E1000, USA), equipped with a load sensor of 1 KN, at room temperature and at a constant strain rate of 2.5 mm/min.
  • the cubic samples used for the compression tests have dimensions of 25*25*25 mm 3 . Samples were tested in the longitudinal direction (corresponding to foam expansion during the process) and in the transverse direction. Young's modulus was defined as the slope of the stress-strain curves in the elastic region and the elasticity rate as the first maximum of the stress curve.
  • Thermal conductivity was measured from the heat flux.
  • the device consists of a heating element with two thermocouples to obtain the temperature on the front and rear surfaces.
  • the device is also equipped with two sensors dedicated to the measurement of heating time and cycle time.
  • the heating and cycle times are used to correct the maximum conduction heat flux, which is necessary for the calculation of the thermal conductivity coefficient, by the Fourier law, used in steady-state thermal conduction. Plates of different materials with dimensions of 300*400*3 mm 3 were used for the determination of the thermal conductivity coefficient.
  • the temperature of the foams, the heights and the rate of expansion, the density and the pressure of the foam were recorded using a FOAMAT FPM 150 (Messtechnik GmbH) equipped with cylindrical containers of 180 mm height and 150 mm diameter, an ultrasonic probe LR 2-40 PFT recording the height of the foam, a NiCr/Ni type K thermocouple and a FPM 150 pressure sensor. The data was recorded and analyzed with specific software.
  • the open cell count is determined using a Quantachrome Instruments Ultrapyc 1200e based on the technique of gas expansion (Boyle's Law). Cubic samples of foams (approximately 2.5 cm ⁇ 2.5 cm ⁇ 2.5 cm) are cut for a first measurement. Then, the cubic sample was cut into eight equivalent pieces and the measurement was repeated. This second measure makes it possible to correct the level of the closed cells from the damaged cells because of the cutting of the sample. Measurements were made according to EN ISO4590 and ASTM 6226.
  • Foam cell morphology was observed on a HITACHI TM-1000 Field Emission Scanning Electron Microscope (SEM).
  • SEM Field Emission Scanning Electron Microscope
  • a petrol-sourced foam (hereinafter REF) is used as a reference.
  • Formulations B85-2, B85-4, B100-2 and B100-4 are bio-sourced foams to be evaluated.
  • the characteristics of the formulations as well as the kinetics of the foams obtained are presented in Table 2.
  • the reference foam (REF) has the fastest kinetics with a cream time of 10 s, while all bio-sourced foams are up to 15 s.
  • a 15 s cream time is an acceptable time for the formulation of such foams especially for foam panels continuously produced for the insulation of buildings.
  • the tack-free time is a surface indication of the formation of the PU network, but is not indicative of the end of the foaming process.
  • the polymerization stage of REF ends at the surface in 66 s, the other bio-sourced foams have times greater than 100 s.
  • the tack-free time offset indicates a lower end-of-foaming reactivity.
  • the entire polyurethane network is reached at longer times than for petrol-sourced foams. This can be particularly advantageous in the case of production of foam blocks by molding.
  • the measurements made by FOAMAT indicate that the reference foam REF reaches its highest expansion speed of 5 mm/s ( FIG. 1 , c) by 40 s, and by 70 s reaches its maximum height of 160 mm ( FIG. 1 , b).
  • This expansion rate is a direct consequence of the exothermic polyaddition between the isocyanate and hydroxyl functions exhibiting a reaction enthalpy of 100.32 kJ/mol ( M. lonescu, polyol chemistry and polyol technology, Rapra Technology , Shawbury, Shrewsbury, Shropshire, United Kingdom, 2005), the internal temperature of REF is stabilized only after 210 s at 170° C., indicating the complete polymerization time of the PU network.
  • Foam B100-2 is the bio-sourced equivalent of REF and the FOAMAT measurement ( FIG. 1 ) clearly indicates the effect of the polyol change from a petrol-sourced polyether to a bio-sourced polyester on the foaming temperature, the speed of expansion as well as the evolution of the foam height.
  • the expansion rate is five times lower than that of REF.
  • the attained foam temperature during the foaming step for B100-2 is lower than for REF.
  • the decrease in these two measures is indicative of a lower reactivity of the polyester (BASAB bio-sourced) compared with that of the polyether (petrol-sourced). This lower reactivity is explained by the lower accessibility of the secondary hydroxyl groups and the lower reactivity of the terminal hydroxyl groups of the bio-sourced polyester compared to the reference polyether.
  • the temperature curve B100-2 ( FIG. 1 , a) shows a delay of nearly 60 s compared to REF, corresponding to the time required for the system to reach the reaction temperature. This difference between B100-2 and REF is a direct consequence of the foaming speed. A similar profile is also observed on all the temperature curves of bio-sourced foams. This slower foaming rate does not represent a limit at the industrial level since it may vary depending on the catalyst used and may represent an advantage in molding processes to allow complete filling of the mold before polymerization of the foam.
  • the B100-4 foam was formulated with a higher water content than the B100-2 and REF mixtures.
  • B100-4 shows shorter string and tack-free times of 10 s and 5 s respectively compared to B100-2 (Table 2).
  • the formulation B100-4 is advantageous in that it has foaming characteristics close to the petrol-sourced reference formulation (REF). Nevertheless, the formulation B100-2 remains of interest in that it allows a sufficiently long working time and suitable for production in molding for example of foam blocks.
  • compositions based on bio-sourced products having a good reactivity and therefore a foam kinetics completely comparable to that of petrol-based compositions in terms of temperature and rate of expansion can be obtained according to the invention.
  • compositions comprising only BASAB (B100-2 and B100-4) as a polyol or comprising a BASAB mixture, glycerol and sorbitol in a BASAB/glycerol/sorbitol ratio of 85/10/5 (B85-2 and B85-4) have been prepared.
  • compositions B85-2 and B100-2 are distinguished from each other solely by the presence or absence of these small polyols. It is the same for the compositions B85-4 and B100-4.
  • comparing the expansion rates of the B85-2 and B100-2 foams shown in FIG. 1 clearly shows the high reactivity of the BASAB-short diols mixture, compared to BASAB alone. Indeed, the expansion speed of the B100-2 foam never exceeds 2 mm/s, while that of B85-2 exceeds 3 mm/s.
  • the effects of this high reactivity are also visible on the foaming temperature of B100-2, shown in FIG. 1 a , which is 40° C. lower than that of B85-2.
  • the resulting expansion of the foam is affected by the lowest temperature ( FIG.
  • the B85-2 foam height is twice as high as the B100-2 foam height, while they both have the same amount of swelling agents.
  • the BASAB glycerol and sorbitol mixture in a 85/10/5 BASAB/glycerol/sorbitol ratio shows a clear effect on the profile of the foaming kinetics of the formula and therefore on the height. as well as the final density of the foam.
  • Compositions B85-2 and B85-4 both contain a BASAB mixture, glycerol and sorbitol, the B85-4 composition being distinguished by a high-water content.
  • the resulting B85-2 and B85-4 foams reach a similar height with respect to the REF foam. Nevertheless, variations in expansion speed and temperature are observed.
  • the reactivity of the bio-sourced polyester polyol differs greatly depending on the foaming temperature and can be adapted using the combined or non-combined effects of swelling agent such as water and short diols such as glycerol and/or sorbitol.
  • Water is a chemical swelling agent and is the simplest way to increase the rate of expansion, but it also results in an increase in the urea bond content in the final foam. As these bonds induce a stiffness of the segments, the increase in their presence should affect the mechanical properties of the foam.
  • the NH groups also show a torsion signal at 1510 cm ⁇ 1 .
  • the broad peak at 2950 cm ⁇ 1 corresponds to the stretching of the CH bond present in the PU backbone and the signal at 1595 cm ⁇ 1 corresponds to at the Ar—H stretch of the phenyl groups of the polyisocyanate (M. Rogulska, AJ Therm. Anal. calorimeter. 114 (2013) 903-916).
  • thermogravimetric analysis TGA was performed on each of the foams and made it possible to obtain ATG and DTG thermograms (see FIG. 3 a ). Weight loss following two-stage thermal degradation is observed for the reference composition. The first weight loss corresponds to the decomposition of the polyether urethanes and polyol, with a maximum of the DTG curve at 250° C. The second weight loss is attributed to cleavage of the carbon-carbon bond with a maximum on the DTG curve at 560° C.
  • the thermal stability of the foams is influenced by several parameters depending on the raw material initially used for the formulation.
  • the decomposition temperature of the urethane group is influenced by its surroundings. It has been reported that the urethane function surrounded by two alkyls has an initial decomposition at 250° C., while surrounded by two aryl groups, it would start at 120° C. (J. Simon, Chromatographia. 25 (1988) 99-106). This decomposition is mainly induced by the thermal reversibility of the urethane function, according to the main decomposition pathways, which are the reverse reaction, the dissociation, the formation of amines and the transcarbamoylation.
  • the analysis of the morphology of the foams was carried out by a SEM analysis and coupled to an evaluation of the anisotropic ratio (R) of the cells of the foam.
  • the SEM images presented in FIG. 4 show microstructures of foam samples in the longitudinal direction (L) and in the transverse direction (T) at the rise of the foam. Different and non-homogeneous structures with open-cell PU foams are obtained except with the reference, which has a homogeneous foam of closed cells.
  • the SEM images provide the overall structure of the foams.
  • B100-4 exhibits extensively elongated cells at the origin of small pipes in the material. While B100-2 corresponding to the formulation with BASAB and a lower water content, is closer to a conventional open cell structure. This difference can be easily explained by the high content of chemical swelling agent (water) in B100-4.
  • the foam samples from a formulation with a mixture of polyols show a cellular structure with an inferion coefficient R compared to B100-2 and B100-4.
  • Their cellular structure is related to a higher crosslinking density during the formation of the PU network in the foaming process.
  • the higher crosslinking density is induced by the addition of polyfunctional glycerol and sorbitol which limit gas expansion and increase the rigidity of the material.
  • variable reactivity of BASAB as a function of the content of expansion agent or of small polyols (C2 to C6) during the foaming process makes it possible to adapt the cellular structure of the foams obtained.
  • the structure of the foam having an impact on its mechanical properties, the BASAB therefore allows the following formulation to obtain foams of various mechanical qualities.
  • BASAB also makes it possible to obtain foams having different structural characteristics from foams comprising products that are petroleum-based in alveolar form.
  • the REF foam shows the lowest thermal conductivity value of 25 mW/m. K because of its high content of closed cells.
  • the level of closed cells is responsible for 60 to 65% of the thermal properties of low density foams (H. Fleurent, J. Cell. Plast. 31 (1995) 580-599).
  • bio-sourced PU foams have a thermal conductivity of between 35 and 51 mW/mK, they have a majority of open cells. Indeed, these values of thermal conductivity are equivalent to those observed for the air (40 mW/(m ⁇ K)) or glass wool (30 to 40 mW/(m ⁇ K)) which are very good thermal insulators.
  • the polyurethanes and the polyurethane-urea have a heat capacity (Cp) within a range of 0.422 to 0.665 cal. g ⁇ 1 ⁇ ° C. ⁇ 1 and 0.389 to 0.513 J ⁇ g ⁇ 1 ⁇ K, respectively (J. E. Mark, ed., Polymer data handbook, 2nd ed., Oxford University Press, Oxford, New York, 2009).
  • Cp heat capacity
  • the low Cp values of the polymers constituting the foams are an explanation for the low thermal conductivity of the material compared with non-polymeric materials such as metal foams.
  • the B85-4 and B85-2 or B100-4 and B100-2 foams show close thermal conductivity to each oter, probably because of their equivalent closed cell rate and similar cell sizes.
  • B100-4 and B100-2 foam systems are lower than B85-4 and B85-2.
  • Bio-sourced foams are generally open systems, so the main difference between B100-4 and B100-2 is their bulk density.
  • the thermal conductivity coefficient of the B100-4 foam is lower due to its low bulk density compared to B100-2.
  • B85-4 and B85-2 have the same bulk density and similar closed cell levels, roughly the same cell sizes; it therefore seems normal that the two foam systems have the same coefficient of thermal conductivity.
  • the prepared bio-sourced foams have characteristics of interest in terms of thermal conductivity and therefore insulating properties comparable to that of petrol-based foams.
  • the best results are obtained for bio-sourced foams with a formulation with high water content and in the absence of co-polyol.
  • the bio-sourced foams have a small percentage of closed cells, especially compared to the petrol-sourced foam used as a reference for the base of the formulations. Nevertheless, a large number of open-cell petrol-based foams are available on the market and do not necessarily have as good thermal conductivity as BASAB-based bio-sourced foams.
  • a Dynamic Mechanical Analysis (DMA) was performed to characterize the viscoelastic properties of the foams as a function of temperature, in particular to define the typical relaxation temperatures of the polyurethane network constituting the foam.
  • the evolution of the conservation module, the loss module and the loss factor (Tan ⁇ ) as a function of the temperature for the reference (REF) is presented in FIG. 5 - a ).
  • the conversion module remains higher in the glassy region, before a sudden drop in the glass transition region.
  • the Tan ⁇ spectrum shows only a peak, which gives a relaxation temperature that can be associated with the glass transition temperature (Tg) of the soft segments of the foams. This temperature is about 200° C. for the PU foam samples.
  • the mechanical properties were evaluated by a 50% compression analysis of the foam samples.
  • the various foams were analyzed on a plate compression bench in order to highlight the difference in compressive strength and resilience of the foams as a function of the orientation of the stress. These properties are evaluated by the measurement of the Young's moduli and conservation of different foam.
  • FIG. 6 compares the mechanical properties in compression of the reference and the bio-sourced foam B100-2, at ambient temperature in the longitudinal and transverse directions.
  • a stress exerted in the longitudinal direction it is observed that the stress increases linearly with the deformation (due to the elastic behavior of the two foams), before reaching the plastic yield point ( FIG. 6 a ).
  • the stress remains almost constant due to the densification of the foam.
  • the behavior of the foam is different ( FIG. 6 b ). Indeed, after an elastic region to the point of plastic flow, the stress continues to increase, which corresponds to the densification of the foam.
  • the B100-2 bio-sourced foam has different mechanical properties, with a Young's modulus and a lower plastic pour point shown in Table 5.
  • the Young modulus and the plastic yield point in the longitudinal direction are respectively 8.5 and 0.31 MPa for the reference and 3 and 0.08 MPa for B100-2 (see Table 5).
  • the same trends are measured in the cross direction for the B100-2 foam compared to the reference (Table 5).
  • These drastic variations in properties come mainly from the morphology of the foams.
  • the closed cell content of these foams decreased from 90 to 10% between the reference and B100-2, respectively (Table 4).
  • the compression of the gas contained in the closed cells of the reference contributes to increasing its mechanical properties with respect to the B100-2 foam (J. D'Souza, et al J. Appl. Polym. Sci. 131 (2014)).
  • the B100-2 foam has a majority of open cells, small cells and a higher bulk density than other bio-sourced foams. In compression, the rapid densification and the good distribution of the load lead to improve the mechanical properties and more particularly the conservation modulus, Young's modulus and the plastic yield point.
  • Formulation B100-4 has water and isopentane as swelling agent. After the foaming process, the high open cell content and the lower density explain the weaker compression properties of the resulting B100-4 foam.
  • the slight improvement in the mechanical properties measured by the conservation modulus or the modulus in the transverse direction (Table 5) of B85-4 compared to the B85-2 sample is also due to the chemical structure of the two materials. Indeed, the B85-4 bio-sourced foam is produced with a higher water content than the B85-2 foam. In addition, it is also important to note that the presence of glycerol and sorbitol in the B85-4 and B85-2 formulations increases the crosslinking density. A similar phenomenon is observed if we compare the mechanical properties of B85-4 and B100-4 foams. Indeed, the B85-4 foam has better mechanical properties than the B100-4 foam.
  • the transverse compression-stress curves of B85-4, B100-4, B85-2 and B100-2 are shown in FIG. 7 , b.
  • the difference in the mechanical properties observed between the different bio-sourced foams follows the same trend as those observed in the longitudinal direction.
  • FIG. 7 , b shows that the stress-strain behavior is very different from that of the longitudinal direction, which shows a clear anisotropic mechanical behavior of bio-sourced foams.
  • a careful examination of the slopes of stress-strain curves in the elastic region indicates that the Young's modulus measured in the transverse direction is 10 times lower than that in the longitudinal direction for B85-4 and B100-4. This ratio is about 14 and 6 for B85-2 and B100-2, respectively. This decrease is less pronounced for elastic stress.
  • the yield stress in the transverse direction is only 3 times lower than that determined in the longitudinal direction.
  • open cell PU foams have been successfully developed from sorbitol-based polyester polyol and have been studied.
  • the swelling agent, polyol or mixture of polyols and co-polyol have been shown to be key parameters for the modulation of kinetics, foaming profile and properties of bio-sourced foams through the range of reactivity offered by BASAB.
  • the use of water as a chemical swelling agent in the formulation of foams has effectively improved the characteristic times (kinetics), the expansion rate and the foaming temperature. It also significantly reduces the foam density from 41 to 25 kg/m 3 with respect to the same foams inflated with a physical expansion agent (isopentane) when only the bio-sourced polyol is used.
  • a range of PU foams with different mechanical properties was then obtained. The mechanical compression tests show that the mechanical properties are very different in the longitudinal and transverse direction.
  • the prepared foams exhibit a significant anisotropy of their mechanical properties.
  • all of the foams exhibit significant changes in Young's modulus, plastic yield point, and stress at the beginning of the densification region. These results are fully consistent with the viscoelastic properties measured by DMA.
  • the glass transition decreases when the bio-sourced polyol is used for the formulation, compared to the petro-sourced reference.
  • the use of chemical and physical swelling agents allows variations in bulk density, closed cell count and foam microstructure.
  • Bio-sourced PUR foams meet the requirements of a wide range of applications from furniture to acoustic and thermal insulation of buildings, as they have a low coefficient of thermal conductivity and a high rate of open cells.
  • PU bio-sourced foams seem particularly suited to the new demand for thermal and acoustic insulation due to their high open cell content and their elastic behavior.
  • the anisotropy of the mechanical properties of such foams can also be used for filling applications of all kinds in the building in particular. Indeed, foams also having a low thermal conductivity can be deformed in the longitudinal direction at the rise of the foam and then return to their original size to fill spaces present in a defective part of the initial insulation of a building.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)
US16/327,555 2016-08-24 2017-08-24 Flexible or semi-flexible foam comprising a polyester polyol Abandoned US20190194378A1 (en)

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FR1601253A FR3055335B1 (fr) 2016-08-24 2016-08-24 Methode de production de polyol polyesters et leur utilisation dans le polyurethane
FR16/01253 2016-08-24
PCT/IB2017/055116 WO2018037376A1 (fr) 2016-08-24 2017-08-24 Mousse souple ou semi flexible comprenant un polyol polyester

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FR3077075B1 (fr) * 2018-01-22 2020-09-18 Tereos Starch & Sweeteners Belgium Mousse rigide avec pouvoir isolant ameliore

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FR3070393B1 (fr) 2019-09-13
BE1024923A1 (nl) 2018-08-10
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CA3036188A1 (fr) 2018-03-01
CA3034942A1 (fr) 2018-03-01
BE1024970A1 (nl) 2018-08-29
FR3055335A1 (fr) 2018-03-02
DK3504180T3 (en) 2022-04-25
ES2911017T3 (es) 2022-05-17
WO2018037376A1 (fr) 2018-03-01
US11180606B2 (en) 2021-11-23
WO2018037373A1 (fr) 2018-03-01
BE1024969A1 (nl) 2018-08-29
CN109843847A (zh) 2019-06-04
FR3055335B1 (fr) 2020-03-27
FR3070392B1 (fr) 2019-09-06
US11180605B2 (en) 2021-11-23
EP3504180A1 (fr) 2019-07-03
BE1024923B1 (nl) 2018-08-22
ES2910828T3 (es) 2022-05-13
CA3034943A1 (fr) 2018-03-01
BR112019003666A2 (pt) 2019-05-21
EP3504181A1 (fr) 2019-07-03
EP3504180B1 (fr) 2022-03-23
BE1024970B1 (nl) 2018-09-04
HUE059317T2 (hu) 2022-11-28
PL3504180T3 (pl) 2022-05-30
BE1024969B1 (nl) 2018-09-04
US20190194380A1 (en) 2019-06-27
FR3070393A1 (fr) 2019-03-01
PT3504180T (pt) 2022-04-13
EP3504179A1 (fr) 2019-07-03
FR3070392A1 (fr) 2019-03-01
WO2018037371A1 (fr) 2018-03-01
EP4067335A1 (fr) 2022-10-05

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