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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
  • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
• • 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
  • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
  • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
  • C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
• • 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
  • 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
  • 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
  • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/10—Rigid foams

Definitions

• the present invention relates to a polyurethane and polyisocyanurate rigid foam with improved characteristics comprising at least two polyols including a polyester polyol typically a biosourced polyester polyol.
• Polyurethanes are versatile polymers and are used in various applications such as automotive, furniture, construction, footwear, acoustic and thermal insulation with a global production of 18 Mt in 2016, placing the PU the 6 th place among the polymers based on the annual results of global production.
• PUR rigid polyurethane foams
• the thermal conductivity of PUR or P IR foams varies between 20 mW / (mxK) and 30 mW / (mxK) compared with 29 mW / (mxK) and 40 mW / (mxK) for expanded polystyrene (EPS) or extruded (XPS) or glass wool or 30 mW / (m> ⁇ K) and 50 mW / (mxK) for mineral wools and fibrous insulation (such as wood fibers or flax fibers).
• EPS expanded polystyrene
• XPS extruded
• glass wool 30 mW / (m> ⁇ K)
• 50 mW / (mxK) for mineral wools and fibrous insulation (such as wood fibers or flax fibers).
• PUR foams there is a difference in the composition between PUR foams and polyisocyanurate-polyurethane foams, commonly referred to as polyisocyanurate (PIR) foams.
• PUR rigid foams are based on the reaction between the alcohol functions of the polyols and the polyisocyanates in the presence of a blowing agent.
• the hydroxyl functionality of the polyols used for PUR foams is much greater than 2 to have rigid foams.
• the PIR foams are based on both the alcohol-isocyanate reaction and also on the trimerization of the high-temperature polyisocyanates in the isocyanurate ring also called triisocyanuric rings (scheme 1) in the presence of a specific catalyst.
• the PIR foam formulation is slightly different from PUR foams. Excess isocyanate function is required to obtain trifunctional isocyanurate rings.
• the polyol reacts with the polyisocyanate to form polyurethane. Then, the excess polyisocyanates trimerize in isocyanurate ring at the origin of the high density of crosslinking of the final foam.
• the high density of crosslinking of PIR foams is their main disadvantage because it induces friability to the material.
• a hydroxyl functional polyol of about 2 can be used to make rigid foams.
• the higher friability of PIR foams compared to PUR foams is largely offset by other superior properties vis-à-vis PUR foams, in particular by their thermal resistance.
• the range of thermal stability of the urethane function depends on their chemical environment and varies between 120 ° C and 250 ° C.
• the thermal stability range of the isocyanurate function also depends on the surrounding chemical function, but is estimated between 365 ° C and 500 ° C.
• the better thermal stability of the isocyanurate functions present in the PIR foams is thus at the origin of their better fire resistance compared to the PUR foams. This increased fire resistance combined with good thermal resistance makes them really attractive in the building insulation sector.
• the properties of PIR foams are mainly related to their morphology and internal structure, which has a significant effect on thermal conductivity and mechanical properties. It is well established that the thermal properties of foam materials depend mainly on the closed cell content and the gas they contain (H. Fleurent and S. Thijs, J. Cell Plast., 1995, 31, 580-599 ). It is also well recognized that the mechanical properties of foamed materials are closely dependent on their bulk density. J. Mills has studied closed cell polyethylene and polystyrene foams and has shown that cell-embedded air contributes significantly to the compressive strength of low bulk density foams (NJ Mills, J. Cell). Plast., 2011, 47, 173-197). Nevertheless, the mechanical properties of PIR foams are not very often studied.
• the Applicant has already developed a new PIR foam prepared from biobased products and more particularly a bio-based polyester polyol in the replacement of the petroleum-based polyols used for the foams on the market in their traditional application.
• the object of the present invention is to provide an at least partly biosourced foam having improved reactive, mechanical and physical properties compared with prior foams in terms of cell size, thermal degradation, reactivity, expansion profile. , hardness, compressive strength, bulk density or thermal conductivity.
• the present invention relates to a rigid foam or composition for obtaining a rigid polyurethane foam and / or polyisocyanurate, said foam or composition comprising polyols selected from polyol polyesters and polyol polyethers; said polyols comprising:
• polyester polyol A in mass relative to the total mass of the polyols
• polyol B selected from polyester polyol B and polyol polyether B.
• the polyester polyol A is of the general formula Rx-Ry-Z-Ry '-Rx' in which Z is a C3-C8 alcohol sugar selected from glycerol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol, Ry and Ry 'are diesters of formula -OOC-C n -COO- with n between 2 and 34, and Rx and Rx' are monoalcohols, which are identical or different in C2 to C12.
• the mass ratio of polyester polyol A to polyol B is between 5/95 and 50/50.
• the polyester polyol A is obtained by:
• the diacids Y and Y ' are independently selected from butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, , undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid and mixtures thereof.
• the X and X 'diols are independently selected from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and the like. 1,1,10-Decanediol, 1,12-dodecanediol and mixtures thereof.
• the rigid foam or composition making it possible to obtain a rigid foam as described above has a cell size with a minimum diameter in the transverse direction of between 50 and 350 ⁇ m and / or an apparent density. between 22 to 60 kg / m 3 and / or a measurement of the lower thermal conductivity coefficient of between 18 and 30 mW / (m> ⁇ K). and / or said foam or the composition making it possible to obtain such a foam comprises 5 to 49% of a polyester polyol A in mass relative to the total mass of polyol.
• the polyester polyol A has a molecular mass of between 350 g / mol and 2000 g / mol and / or a hydroxyl number of 300 to 900 mg KOH / g and / or a viscosity at 25 ° C. inclusive of 4000 to 25000 mPa.
• the foam has a size of cells with a minimum diameter in the transverse direction of between 50 and 350 ⁇ m and / or a bulk density of between 22 and 60 kg / m 3 .
• said foam comprises at least one reaction catalyst, at least one blowing agent, a stabilizer, at least one polyisocyanate having a functionality of at least 2, optionally a flame retardant.
• the foam is a polyisocyanate foam and comprises:
• 0.1 to 13 parts preferably from 0.5 to 12 parts, even more preferably between 1 and 1 parts of at least one catalyst, preferably at least two catalysts, typically an amine catalyst and a potassium carboxylate,
• the foam is a polyurethane foam and comprises:
• At least one catalyst typically an amine catalyst
• 0.5 to 15 parts of at least one swelling agent typically 0.5 to 12 parts, preferably 0.6 to 10 parts, more preferably 0.7 to 9 parts of a chemical blowing agent such as water and / or 0 to 60 parts, preferably 0.5 to 30 parts, even more preferably 1 to 25 parts of a physical blowing agent,
• a stabilizer such as a polyether-polysiloxane copolymer
• the polyol B has a hydroxyl number of between 80 and 800 mg KOH / g and / or a functionality greater than or equal to 2, and / or a molar mass (Mn) of between 50 and 4000 g / mol and / or an acid number of less than 10 mg KOH / g and / or a viscosity of less than 50,000 mPa.s at 25 ° C.
• Mn molar mass
• the constituents of the rigid foam or composition making it possible to obtain a rigid foam are chosen as follows:
• the at least one polyisocyanate is chosen from toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate and their mixture; and or
• the at least one catalyst is chosen from at least one tertiary amine, at least one potassium carboxylate and at least one triazine and their mixture; preferably the at least one catalyst being selected from N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, 1,3,5-tris (3- [dimethylamino] propyl) hexahydro-s-triazine, 2-ethylhexanoate potassium and their mixture; and or "Pau least one blowing agent is selected from chemical blowing agents selected from skin, formic acid, phthalic anhydride and acetic acid and / or physical blowing agents selected from pentane, isomers of pentane, hydrocarbons , hydrofluorocarbons, hydrochlorofluoroolefins, hydrofluoroolefins, ethers and mixtures thereof; and or
• At least one stabilizer is chosen from silicone glycol copolymers, non-hydrolyzable silicone glycol copolymer, polyalkylene siloxane copolymer, polyoxyalkylene methylsiloxane copolymer, polyetherpolysiloxane copolymer, polydimethylsiloxane polyether copolymer, polyether siloxane, a polyether-polysiloxane copolymer, a polyoxyalkylene polysiloxane copolymer with block or mixtures thereof; and or
• At least one flame retardant is selected from Tris (1-chloro-2-propyl) phosphate, triethylene phosphate, triaryl phosphate esters, ammonium polyphosphate, red phosphorus, trishalogenyl, and mixtures thereof.
• the invention further relates to a rigid foam board or block comprising a rigid foam as described above.
• the invention also relates to a thermal or cryogenic insulation method or a method of filling, sealing, sealing or improving the floatation of an object or a building by depositing or introducing blocks. or rigid foam panels according to the invention or by in situ projection of a rigid foam or a composition for obtaining a rigid foam as described above.
• the invention relates to a rigid foam or composition for obtaining a rigid foam comprising polyols including a polyester polyol A, said foam having:
• said foam or composition for obtaining such a foam comprises 5 to 50% typically 5 to 49% of a polyester polyol A in mass relative to the total mass of polyol, preferably of polyol polyester and / or polyol polyether,
• polyester polyol A being obtained by a first polycondensation (a) of a C3 to C8 alcohol sugar Z and of two identical or different C4 to C36 diacids Y and Y 'and of a second polycondensation (b) of the product obtained in (a) with two identical or different C2 and C12 diols X and X ', or
• polyester polyol A being of the general formula Rx-Ry-Z-Ry '-Rx' wherein Z is a C3-C8 alcohol sugar, Ry and Ry 'are diesters of the formula -OOC-C n -COO- with n between 2 and 34, and Rx and Rx 'are monoalcohols, identical or different C2 to C12.
• the polyester polyol A is of the general formula Rx-Ry-Z-Ry '-Rx' in which Z is a C3-C8 alcohol sugar, Ry and Ry 'are diesters of formula -OOC- C n -COO- with n between 2 and 34, and Rx and Rx 'are monoalcohols, identical or different C2 to C12.
• the polyester polyol A is obtained by a first polycondensation (a) of a C 3 to C 8 alcoholic sugar Z and of two diacids Y and Y ' identical or different C4 to C36 and a second polycondensation (b) of the product obtained in (a) with two diol X and X 'identical or different C2 to C12.
• foam as used, for example, in the terms “polyurethane foam” or “polyisocyanurate foam” is intended to mean a compound of cellular structure of three-dimensional expanded type. Said foam may be rigid or flexible, with open or closed cells.
• rigid foam is meant a foam having a good compressive strength and whose internal structure is irreversibly damaged during compression deformation of between 5 and 50%. Generally such foams have glass transition temperatures (T g) above 70 ° C often close to 200 ° C.
• rigid foams means a foam generally having a high level of closed cells, typically foams having a closed cell level of greater than 80%, or even greater than 85% or 90% (for example from 80 to 100%). The calculation of the closed cell rate is known to those skilled in the art typically according to the standards EN ISO4590 (October 2016) and ASTM D-6226 (January 2015).
• Polyurethane is used for foams whose formulations are predominantly based on polyurethane or polyisocyanurate (P IR) for foams whose formulations are predominantly based on polyisocyanurate.
• the invention relates to a rigid foam or composition for obtaining a rigid polyurethane foam and / or polyisocyanurate.
• the invention relates to a rigid foam or composition for obtaining a rigid polyurethane foam.
• the invention relates to a rigid foam or composition for obtaining a rigid polyisocyanurate foam.
• the invention relates to a rigid foam or composition for obtaining a rigid polyurethane foam and polyisocyanurate.
• closed cell foam is meant a foam whose honeycomb structure has walls between each cell constituting a set of joined and separate cells for the imprisonment of an expansion gas.
• a foam is termed closed-cell foam when it has a maximum of 10% open cells.
• closed cell foams are mostly rigid foams.
• open-cell foam is meant a foam whose honeycomb structure consists of a continuous open-cell foam matrix between the cells which does not allow the imprisonment of an expansion gas. Such a foam allows the creation of percolation paths within its alveolar matrix. Typically, open cell foams are predominantly soft or semi-rigid foams.
• the foam according to the invention has a size of cells with a minimum diameter in the transverse direction of between 50 and 390 mh, preferably between 60 and 385 mh, 70 and 380 mh, 75 and 375 mh, 80 and 350 mih. , or 90 and 325 mhc
• Minimum diameter in the transverse direction or minimum diameter in the longitudinal direction means the value Ü F mm below the minimum ferret diameter measured transversely or longitudinally to the expansion of the foam, ie the diameter minimum of a cell in the given direction.
• Maximum diameter in the transverse direction or “Maximum diameter in the longitudinal direction” means the maximum value D F max below the maximum diameter of Feret measured in the direction transverse or longitudinal to the expansion of the foam, that is the maximum diameter of a cell in the given direction.
• the diameter of the cells is measured by scanning electron microscopy (SEM), with a SEM from Jeol JSM-IT100, by the observation of cubic foam cut with a microtome blade and analyzed according to two characteristic orientations: parallel and perpendicular to the rising direction of the foam, using the ImageJ software (open source treatment program).
• SEM scanning electron microscopy
• Jeol JSM-IT100 a SEM from Jeol JSM-IT100
• n is the number of cells measured for a given sample.
• transverse direction to the expansion is meant the section of the foam perpendicular to the main direction of volume increase of the reaction mixture and / or parallel to the deposition surface of the reaction mixture.
• longitudinal expansion direction is meant the section of the foam parallel to the main direction of volume increase of the reaction mixture and / or perpendicular to the deposition surface of the reaction mixture.
• the foam according to the invention has a bulk density of between 20 to 80 kg / m 3 , preferably 22 to 60 kg / m 3 , even more preferably 25 to 50 kg / m 3, typically 27 to 40 kg. / m 3 .
• the bulk density of the foam is measured by a Foamat FPM 150 (Messtechnik GmbH) equipped with cylindrical containers 180 mm high and 150 mm in diameter, an ultrasonic probe LR 2-40 PFT / a thermocouple type K , and a FPM 150 pressure sensor according to the supplier's instructions.
• the apparent density is determined according to EN 1602 (September 2013).
• the foam has a cell size with a minimum diameter in the transverse direction between 40 and 400 ⁇ m and a bulk density of between 20 to 80 kg / m 3 , or a cell size with a minimum diameter in the direction transverse between 40 and 400 ⁇ m and a bulk density of between 22 to 60 kg / m 3 or a cell size with a minimum diameter in the transverse direction between 40 and 400 ⁇ m and a bulk density between 25 to 50 kg / m 3 , or a cell size with a minimum diameter in the transverse direction between 50 and 350 ⁇ m and a bulk density of between 20 to 80 kg / m 3 , or, a cell size with a minimum diameter in the transverse direction between 50 and 350 ⁇ m and a bulk density of between 22 to 60 kg / m 3 or, a cell size with a minimum diameter in the transverse direction between 50 and 350 mhi and a bulk density between 25 to 50 kg / m 3 or a cell size with a minimum diameter in the transverse direction
• the foam according to the invention has a measurement of the thermal conductivity coefficient of less than 30 mW / (m> ⁇ K), preferably between 18 and 30 mW / (mxK), even more preferably between 28 and 20 mW / (MXK).
• thermal conductivity is meant the measurement of the physical quantity characterizing the energy transfer (quantity of heat) passing through the material per unit area under a given temperature gradient.
• the measurement of the thermal conductivity coefficient corresponds to a quantification of the thermal conductivity and can be measured by a flux meter such as a HFM 436/3 marketed by the company Netzsch following the protocol recommended by the standard EN 12667 (July 2001).
• the foam according to the invention has a measurement of the coefficient of thermal conductivity of less than 30 mW / (m ⁇ K), and / or a size of cells with a minimum diameter in the transverse direction of between 40 and 400 ⁇ m, preferably the foam according to the invention.
• the invention has a measurement of the thermal conductivity coefficient of less than 30 mW / (mxK), and / or a size of cells with a minimum diameter in the transverse direction of between 50 and 350 mht, typically the foam according to the invention has a measuring the conductivity coefficient less than 30 mW / (m> ⁇ K), and / or a cell size with a minimum diameter in the transverse direction between 60 and 325 ⁇ m, or the foam according to the invention has a measurement of the conductivity coefficient between 18 and 30 mW / (m> ⁇ K), and / or a cell size with a minimum diameter in the transverse direction between 40 and 400 ⁇ m, preferably the foam according to the invention has a measurement of the conductivity coefficient between 18 and 30 mW / (mxK), and / or a cell size with a minimum diameter in the transverse direction between 50 and 350 ⁇ m, typically the foam according to the invention has a measurement of the coefficient of thermal conductivity included between 18 and 30 mW / (
• the foam according to the invention has a measurement of the coefficient of thermal conductivity of between 20 and 28 mW / (m ⁇ K). and / or a size of cells with a minimum diameter in the transverse direction between 50 and 350 ⁇ m, typically the foam according to the invention has a measurement of the coefficient of thermal conductivity of between 20 and 28 mW / (mxK) and / or a cell size with a minimum diameter in the transverse direction between 60 and 325 ⁇ m.
• polyol refers to a molecule having at least 2 hydroxyl groups.
• the polyol may be for example a polyester polyol or a polyether polyol or a sugar alcohol.
• polyester polyol refers to molecules comprising hydroxyl groups linked together by ester bonds.
• the polyol is selected from a polyester polyol or a polyether polyol.
• the foam or the composition of the invention comprises at least two polyols, a so-called polyol polyol A and a polyol said polyol B.
• the foam or composition of the invention comprises a mixture of two polyols, the so-called polyol polyol A and polyol said polyol B.
• the polyol A is selected polyester polyols or polyols polyethers, preferably the polyol A is a polyester polyol A.
• the polyol B is selected polyester polyols B, polyether polyols B or a mixture thereof.
• the polyol B is a polyester polyol B.
• the foam or the composition of the invention comprises at least two polyols (polyesters), a polyester polyol said Polyol polyester A and a polyol said polyol B selected from polyester polyols and polyether polyols B.
• the polyester polyol A may be bio-based in that it is obtained from polyols found naturally in plants or obtained from derivatives derived from biomass.
• the foam or the composition making it possible to obtain such a foam comprises 5 to 49%, 6 to 48% or 7 to 48%, preferably 10 to 45%, 15 to 42%, 17 to 40%, at 37%, 22 to 36% polyester polyol A in mass relative to the total mass of polyol, preferably polyol polyester and / or polyol polyether.
• the other polyols, in particular polyol polyesters and / or polyol polyethers, such as polyol B, contained in the foam may be of petroleum-based origin.
• petroleum-based polyol means a polyether polyol or a polyester polyol whose production process involves at least 20% of reagents derived from fossil resources.
• the X, Y, Z, Y 'and X' molecules are bonded together by ester bonds.
• the diols X and X 'and the alcohol sugar Z are bonded to the two diacids Y and Y' by ester bonds each formed between an acid function of Y or Y 'and a primary hydroxyl function of Z, X or X' .
• the polyester polyol has a low residual acidity, typically when it is obtained by two successive polycondensations followed by a neutralization step (for example with potassium hydroxide or soda).
• the residual acidity should for example be less than 5 mg kOH / g.
• the measurement of this residual acidity is well known the skilled person. It is determined, for example, by colorimetric determination with methylene blue using 0.1 mol / l potassium hydroxide solution in methanol.
• the polyester polyol A according to the invention advantageously has the general chemical formula C a H b O c with 22 ⁇ a ⁇ 42, 38 ⁇ b ⁇ 78, 14 ⁇ c ⁇ 22.
• the polyester polyol A according to the invention has a molecular mass 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 mass of the polyester polyol can be determined by various methods such as size exclusion chromatography.
• the polyester polyol A has a hydroxyl value of 300 to 900 mg
• IOH functionality of polyester polyol x 56109.37 / Molar mass of polyester polyol.
• the polyol A typically the polyester polyol A has a functionality greater than 2, from 2 to 5, preferably from 2.5 to 3.5, even more preferably from 2.7 to 3.3.
• the polyester polyol A according to the invention has a viscosity at 25 ° C of 4000 to 25000 mPa.s, preferably between 4500 and 22500 mPa.s, more preferably between 5000 and 20000 mPa.s.
• the polyester polyol A according to the invention has a viscosity at 25 ° C. of 10,000 to 20000 mPa.s.
• the polyester polyol A according to the invention has a viscosity at 25 ° C. of 12000 to 18000 mPa.s.
• the polyester polyol A according to the invention has a viscosity at 25 ° C.
• Viscosity at 25 ° C means the resistance to flow and / or shear of the material at a temperature of 25 ° C. It is measured using a Brookfield RYT DV-II viscometer from Braive-Instruments, in using a pin from the RV range, the RV-5 pin. The spit is dipped so as not to touch the edges or bottom of the measuring beaker. The value is given automatically by the equipment working at a torque between 10 and 100% of the maximum torque of the device. According to one embodiment, the viscosity is determined according to ASTM D4878 standards, in particular ASTM D4878-08.
• said foam further comprises a polyol B, preferably a polyether polyol B or a polyester polyol B having:
• a hydroxyl number (IOH expressed in mg KOH / g) between 80 and 800, preferably between 100 and 700, even more preferably between 120 and 600 typically, between 150 and 350 and / or
• the polyester polyol B has a viscosity at 25 ° C of 500 to 12000 mPa.s. In a preferred embodiment, the polyester polyol B has a viscosity at 25 ° C of 1000 to 12000 mPa.s, 2000 to 10000 mPa.s, or 3000 to 10000 mPa.s, or 2000 to 6000 mPa. s.
• the polyol B has a molar mass (Mn) of between 150 and 3500 g / mol and / or a hydroxyl number (IOH) of between 80 and 800 mg KOH / g and / or a viscosity of less than 50,000 mPa.s. typically, a molar mass (Mn) between 50 and 4000 g / mol and / or a hydroxyl number (IOH) of between 100 and 700 mg KOH / g and / or a viscosity at 25 ° C as described below.
• Mn molar mass
• IOH hydroxyl number
• polyester polyol A and polyol B have a difference in viscosity at 25 ° C of between 500 and 40,000 mPa.s, preferably between 1500 and 30000 mPa.s, more preferably between 2500 and 20000.
• polyester polyol A and polyol B have a difference in viscosity at 25 ° C of 5000 to 15000 mPa.s or 8000 to 12000 mPa.s.
• the polyester polyol A and the polyol B are in a polyol A / polyol B mass ratio of between 5/95 and 50/50.
• the polyester polyol A and the polyol B are in a polyol A / polyol B mass ratio of 10/90 to 45/50.
• the polyester polyol A and the polyol B are in a polyol A / polyol B mass ratio of 25/90 to 45/50.
• the polyester polyol A and the polyol B are in a polyol A / polyol B mass ratio of 35/90 to 45/50.
• 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 potash, for example according to ASTM 4274-99 (1999) in which the colorimetric titration is replaced by a pH-metric titration.
• sugar alcohol as used in the expression “sugar alcohol Z” is meant a hydrogenated form of monosaccharide whose carbonyl group (aldehyde or ketone) has been reduced to a primary or secondary hydroxyl.
• the alcohol sugar is chosen from glycerol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol.
• the sugar alcohol is selected from glycerol, sorbitol, erythritol, xylitol, taraditol, ribitol, dulcitol and mannitol.
• the sugar alcohol is selected from sorbitol, erythritol, xylitol, and mannitol. In one embodiment, the sugar alcohol is selected from glycerol, sorbitol, and mannitol. In a mode of preferential embodiment, the sugar alcohol is selected from sorbitol and mannitol. In a preferred embodiment, the sugar alcohol is sorbitol.
• the composition or the foam according to the invention does not comprise glycerol.
• the polyester polyol A according to the invention is not modified with glycerol or with ethylene glycol.
• the polyester polyol comprises two molecules Y and Y 'of diacid. These molecules may be identical or different in C4 to C36, preferentially C4 to C24.
• the two diacid molecules are independently selected from butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), 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 mixtures thereof.
• butanedioic acid succinic acid
• pentanedioic acid glutaric acid
• adipic acid hexane
• Y and Y 'are C5 to C16 or C6 to C12 diacids.
• the preferred diacid molecules are independently selected from adipic acid and succinic acid.
• Y and Y 'are adipic acid molecules.
• Y and Y 'are not aromatic diacids. In a preferred embodiment, Y and Y 'are not aromatic diacids chosen from phthalic acid, isophthalic acid or terephthalic acid.
• the polyol A typically the polyester polyol A, does not comprise phthalic acid, isophthalic acid terephthalic acid, and their anhydrides, dimethyl terephthalate (DMT) or polyethylene terephthalate (PET) .
• DMT dimethyl terephthalate
• PET polyethylene terephthalate
• the composition according to the invention comprises less than 45% by weight of the composition of phthalic acid, isophthalic acid of terephthalic acid, and their anhydrides, dimethyl terephthalate (DMT) or polyethylene terephthalate (PET). According to one embodiment, the composition according to the invention comprises less than 40% by weight of the composition of phthalic acid, isophthalic acid terephthalic acid, and their anhydrides, dimethyl terephthalate (DMT) or polyethylene terephthalate (PET).
• DMT dimethyl terephthalate
• PET polyethylene terephthalate
• the composition according to the invention comprises less than 30% by weight of the composition of phthalic acid, isophthalic acid of terephthalic acid, and their anhydrides, dimethyl terephthalate (DMT) or polyethylene terephthalate (PET). According to one embodiment, the composition according to the invention comprises less than 25% by weight of the composition of phthalic acid, isophthalic acid terephthalic acid, and their anhydrides, dimethyl terephthalate (DMT) or polyethylene terephthalate (PET).
• DMT dimethyl terephthalate
• PET polyethylene terephthalate
• the composition according to the invention comprises less than 20% by weight of the composition of phthalic acid, isophthalic acid of terephthalic acid, and their anhydrides, dimethyl terephthalate (DMT) or polyethylene terephthalate (PET). According to one embodiment, the composition according to the invention comprises less than 10% by weight of the composition of phthalic acid, isophthalic acid of terephthalic acid, and their anhydrides, dimethyl terephthalate (DMT) or polyethylene terephthalate (PET). According to one embodiment, the composition of the invention comprises less than 5% or less than 2% by weight of the composition of monofunctionalized fatty acids (mono- fatty acids).
• the composition of the invention does not comprise monofunctionalized fatty acids (mono-fatty acids).
• the monofunctionalized fatty acids are chosen from castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grapeseed oil, coconut oil and the like.
• the monofunctionalized fatty acids are preferably chosen from oleic acid, rapeseed oil or soybean oil.
• diol is meant a carbon chain comprising two alcohol groups.
• the polyester polyol comprises two molecules X and X 'of identical or different diols.
• the diol molecules are independently selected from 1,2 ethanediol, 1,3 propanediol, 1,4-butanediol, 1,6 hexanediol, 1,8 octanediol, 1,10 decanediol, 1 , 12 dodecanediol and their mixture.
• the diol molecules are independently selected from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and mixtures thereof. According to one embodiment, the diol molecules are identical and chosen from 1,2-ethanediol, 1,3-propanediol and 1,4-butanediol. According to one embodiment, the diol molecules are identical and chosen from 1,3-propanediol and 1,4-diol. butanediol. According to one embodiment, the diol molecules are 1,4-butanediol molecules.
• 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 polyolpolyester is chosen from bis (1,8-octanediol) sorbitol diadipate, bis (1,10 decanediol) sorbitol diadipate and bis (1,4-butanediol) sorbitol diadipate.
• the polyolpolyester A is preferably chosen from bis (1,3-propanediol) -sorbitol diadipate, bis (1,4-butanediol) -sorbitol diadipate, 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,
• the polyolpolyester A is chosen from bis (1,8-octanediol) -sorbitol diadipate, bis (1,10 decanediol) -sorbitol diadipate and bis (1,4-butanediol) -sorbitol-diadipate.
• the polyolpolyester A bis (1,4-butanediol) -sorbitol-diadipate.
• the invention also relates to a rigid foam or composition for obtaining a rigid foam comprising polyols, including a polyester polyol A, said foam having a cell size with a minimum diameter in the transverse direction of between 40 and 400 ⁇ m.
• a foam or composition for obtaining such a foam comprises 5 to 50% preferably 5 to 49% of a polyester polyol A in mass relative to the total mass of polyol typically relative to the total mass of polyester polyol and / or polyol polyether, said polyol polyester A being obtained by a process comprising the following steps: a) a polycondensation step at a temperature between 110 and 200 ° C, preferably 120 to 180 ° C, more preferably 130 and 170 ° C, typically 150 ° C, advantageously for 5 to 10 hours:
• a C 3 to C 8 sugar alcohol preferably C 4 to C 1, advantageously C 5 to C 6, typically chosen from glycerol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol,
• the polyester polyol A is obtained by a process comprising the following steps: c) a polycondensation step at a temperature of between 110 and 200 ° C., preferably 120 to 180 ° C., more preferably 130 and 170 ° C., typically 150 ° C., advantageously for 5 to 10 hours:
• a C4 to Cl preferably C5-C6 alcohol sugar Z selected from sorbitol, erythritol, xylitol, and mannitol,
• two diacids Y and Y 'identical or different C5 to C24 preferably selected from adipic acid and succinic acid
• two diols X and X 'identical or different from C2 to C12 preferably C3 to C8, typically C4, advantageously chosen independently from 1,2 ethanediol, 1,3 propanediol, 1,4-butanediol, 1 , 6 hexanediol, 1,8 octanediol, 1,10 decanediol, 1,12 dodecanediol, 1,4 butanediol and mixtures thereof,
• the diols X and X 'and the alcohol sugar 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 preferentially 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
• the polycondensation step comprises a first polycondensation (a) of the alcohol sugar 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 symmetrical structure.
• the diacids Y and Y ' are identical and / or the diols X and X' are identical.
• the alcohol sugar 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 with a view to their elimination.
• the invention further relates to a rigid foam or a composition for obtaining a rigid foam comprising a polymer comprising polyols of which 5 to 50%, typically 5 to 49% or 6 to 48% by weight of a polyol polyester A on the polyol mass, typically, said polymer is a polyurethane and / or a polyisocyanurate.
• the polymer according to the invention has a molar mass greater than 1.10 6 g / mol.
• the polymer is a crosslinked polymer.
• polyurethane is meant a polymer comprising urethane functions, that is, a urethane polymer. These polymers result essentially from the reaction of polyols, in particular the polyester polyol of the invention and polyisocyanates. These polymers are generally obtained from formulations having an index of from 100 to 150, preferably from 105 to 130 corresponding to an 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 trimerization of polyisocyanates.
• These polymers also known as modified polyurethanes or polyisocyanurate-polyurethane, are generally obtained from formulations having an index of 150 to 700, preferably between 200 and 500, even more preferably between 250-400, ie an NCO / OH ratio of between 1 , 5 and 7, preferably between 2.0 and 5.0, preferably between 2.5 and 4.0.
• said polymer is a mixture of polyurethane and polyisocyanurate. Such a mixture is observed for example when said polymer comprises urethane functional groups and polyisocyanates trimerized to triisocyanuric rings.
• said polymer is a mixture of polyurethane and polyisocyanurate and has an index greater than 150 or less than or equal to 500, corresponding to an NCO / OH ratio greater than 1 or less than or equal to 5.
• NCO / OH ratio is meant, in the sense of the present invention, the ratio between the number of NCO functions of the polyisocyanate and the number of OH functions of the polyols, of any other component comprising OH groups (water, solvents) present in a formulation.
• the ratio NCO / OH is calculated with the following formula:
• Ratio NCO / OH M exp Pi x ME Pi / M exp S Al x ME S Al
• M exp Pi is the mass of the polyisocyanate
• MEPi is the equivalent mass of the polyisocyanate and corresponds to the ratio between the molar mass of the polyisocyanate and the functionality of the polyisocyanate;
• MEOHi is the equivalent mass of each component of the mixture bearing hydroxyl groups and corresponds to the ratio between the molar mass of the component and the functionality of the component.
• urea bond means a disubstituted urea bond, the product of the reaction between a primary amine and an isocyanate functional group of a polyisocyanate.
• the primary amines can be introduced into the composition or are the product of the reaction between a molecule of water and an isocyanate function of a polyisocyanate.
• said rigid foam or composition making it possible to obtain said rigid foam comprising said polyester polyol A according to the invention or said polymer according to the invention, in particular the prepolymer, further comprises a reaction catalyst, a polyisocyanate having a functionality at less than 2, a stabilizer, a blowing agent, and additives.
• polyisocyanate any chemical compound comprising at least two distinct isocyanate chemical (NCO) functions, that is, having "a functionality of at least 2".
• NCO isocyanate chemical
• Functionality is understood to mean, in the sense of the present invention, the total number of reactive isocyanate functions per isocyanate molecule.
• the functionality of a product is evaluated by the titration of the NCO function by a method of dosing the excess dibultylamine with chloridic acid.
• said polyisocyanate has a functionality of 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 and cycloaliphatic polyisocyanates and mixtures thereof.
• 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 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'-diphenylmethane
• the polyisocyanate is chosen from toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (or 4,4'-diphenylmethylene diisocyanate or 4,4'-MDI), polymethylene polyphenylene polyisocyanate (polymeric MDI, pMDI) and their mixture.
• the polyisocyanate is diphenylmethylene polyisocyanate (pMDI).
• reaction catalyst is meant a compound which introduces in a small amount accelerates the kinetics of urethane bond formation (-NH-CO-O-) by reaction between the polyester polyol derived from the invention, the other polyols of the mixture and a polyisocyanate or activates the reaction between a polyisocyanate and water or activates the trimerization of isocyanates.
• reaction catalysts are selected from tertiary amines (such as N, N-dimethylcyclohexylamine), tin derivatives (such as tin dibutyldilaurate), ammonium salts (such as methanaminium N, N, N-trimethyl 2,2-dimethylpropanoate) alkali metal carboxylates (such as potassium 2-ethylhexanoate or potassium toctoate) amine ethers (such as bis (2-dimethylaminoethyl) ether), and triazines (such as 1,3,5-Tris (3- (dimethylamino) propyl) hexahydro-1,3,5-triazine).
• tertiary amines such as N, N-dimethylcyclohexylamine
• tin derivatives such as tin dibutyldilaurate
• ammonium salts such as methanaminium N, N, N-trimethyl 2,2-dimethyl
• the catalyst may be a mixture of at least one tertiary amine, at least one potassium carboxylate and at least one triazine.
• the catalyst is a mixture of a tertiary amine, a potassium carboxylate and a triazine.
• the catalyst is a mixture of a tertiary amine, a potassium carboxylate and a triazine; the mass ratio of the amine catalysts on potassium carboxylate being from 0.2 to 2, preferably from 0.5 to 1.5.
• the catalyst is a mixture of a tertiary amine, a potassium carboxylate and a triazine; the mass ratio of triazine and tertiary amine to potassium carboxylate is from 0.2 to 2, preferably from 0.5 to 1.5.
• the catalyst is selected from N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, 1,3,5-tris (3- [dimethylamino] propyl) hexahydro-s-triazine potassium 2-ethylhexanoate and their mixture.
• the catalyst is a mixture of bis (2-dimethylaminoethyl) ether, 1,3,5-tris (3- [dimethylamino] propyl) -hexahydro-s-triazine, and 2-ethylhexanoate.
• potassium; the mass ratio of triazine and tertiary amine on potassium carboxylate is 0.5 to 1.5, preferably 0.5 to 1.
• the invention relates to a composition intended for obtaining a foam having a cell size with a minimum diameter in the transverse direction of between 40 and 400 ⁇ m, and / or an apparent density of between 20 and 80 kg / cm 2.
• m 3 and / or a measurement of the thermal conductivity coefficient of less than 30 mW / (m ⁇ K) comprising said polyester polyol A being obtained by a first polycondensation (a) of a C 3 to C 8 alcohol sugar Z and of two diacids Y and Y 'identical or different at C4 to C36 and a second polycondensation (b) of the product obtained in (a) with two diols X and X' identical or different C2 to C12, or said polyester polyol A being of general formula Rx-Ry-Z-Ry '-Rx' wherein, Z is a C3-C8 alcohol sugar, Ry and Ry 'are diesters of formula -OOC-C n -COO- with
• said composition comprises from 5 to 50%, typically from 5 to 49% or from 6 to 48%, of a polyester polyol A in mass relative to the total mass of polyol, preferably of polyester polyol and / or polyol polyether.
• the composition or the foam according to the invention comprises from 10 to 50% typically 10 to 48% or from 10 to 45% of a polyester polyol A in mass relative to the total mass of polyol, preferably polyol polyester and / or polyol polyether.
• the preferred polyester A polyol is a polyester polyol with a neutral pH and / or comprising a sorbitol as sugar-alcohol Z.
• the polyol Preferred polyester A is bis (1,2-ethanediol) -sorbitol-diadipate, bis (1,6-hexanediol) -sorbitol-diadipate or bis (1,4-butanediol) -sorbitol-diadipate, more preferably bis (1).
• a foam typically comprises, after polymerization, a polymer comprising a polyester polyol A according to the invention, in particular a crosslinked polymer comprising a polyester polyol A, at least one reaction catalyst, at least one blowing agent and a stabilizer.
• blowing agent is meant 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 is chosen from pentane and isomers of pentane, hydrocarbons, hydrofluorocarbons, hydrochlorofluoroolefins, hydrofluoroolefins (HFOs), ethers and their mixtures. Methylal may be mentioned by way of example of an ether-type swelling agent.
• a preferred chemical and physical blowing agent mixture is, for example, a water / isomer mixture of pentane or formic acid / pentane isomer or water / hydrofluoroolefin or pentane / methylal / water isomer or else water / methylal.
• stabilizer is meant, an agent allowing the formation of an emulsion between the polyol and the blowing agent, the nucleation of the expansion sites of the blowing agent, as well as the physical stability of the polymer matrix during progress of the reactions.
• the stabilizer is a surfactant such as polyether.
• 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 DC5000from Air Products), polyalkylene siloxane copolymer (for example Niax L Momentive-6164), polyoxyalkylene methylsiloxane copolymer (for example Niax L-5348 from Momentive), polyetherpolysiloxane copolymer (for example Tegostab B8870 or Tegostab B 1048 from Evonik), polydimethylsiloxane polyether copolymer (for example Tegostab B8526 from Evonik), polyethersiloxane (for example Tegostab B8951 from Evonik), a modified polyether-polysiloxane copolymer (eg Tegostab B8871 from Evonik), a block polyoxyalkylene polysiloxane copolymer (eg Tegostab BF
• the stabilizer is chosen from silicone glycol copolymers, a non-hydrolyzable silicone glycol copolymer, a polyalkylene siloxane copolymer, a polyoxyalkylene methylsiloxane copolymer, a polyetherpolysiloxane copolymer, a polydimethylsiloxane polyether copolymer, a polyether siloxane, and a polyether copolymer. polysiloxane, a block polyoxyalkylene polysiloxane copolymer or mixtures thereof.
• antioxidants chain end neutralization agents at the origin of depolymerization or co-monomer chains capable of stopping the depolymerization propagation
• release agents talc paraffin solution, silicone
• anti-hydrolyses biocides
• anti-UV agents titanium oxide, triazines, benzotriazoles
• flame retardants antimony, phosphorus compounds, boron compounds, nitrogen compounds.
• Flame retardant means a compound that has the property of reducing or preventing the combustion or heating of the materials it impregnates or covers, referred to as flame retardant or fire retardant.
• flame retardant or fire retardant For example, alone or as a mixture, graphite, silicates, boron, halogenated or phosphorus derivatives such as Tris (1-chloro-2-propyl) phosphate (TCPP), triethylene phosphate (PET), triaryl phosphate esters, ammonium polyphosphate, phosphorus red, trishalogenaryl, and their mixture.
• the flame retardant is tris (1-chloro-2-propyl) phosphate.
• composition according to the invention makes it possible to obtain a polyurethane foam, a polyisocyanurate foam or their mixture.
• a first embodiment of the composition according to the invention makes it possible to obtain a closed-cell rigid polyurethane foam is typically formulated with an index between 101 and 200, preferably between 102 and 170, more preferably between 105 and 150 for example 115 or an NCO / OH ratio between 1.01 and 2, preferably between 1.02 and 1.7, more preferably between 1.05 and 1.5, for example 1.2.
• such a composition comprises:
• At least 1 to 100 parts preferably from 40 to 100 parts, even more preferably between 80 to 100 parts of polyols, of which 5 to 50%, preferably 5 to 49% or 6 to 48% of a polyester polyol A by mass; relative to the total mass of polyol,
• 150 to 500 parts preferably from 160 to 425 parts, even more preferably between 180 and 375 parts of at least one polyisocyanate,
• At least one catalyst typically an amine catalyst such as dimethylcyclohexyleamine,
• 0.5 to 15 parts of at least one swelling agent typically 0.5 to 12 parts, preferably 0.6 to 10 parts, more preferably 0.7 to 9 parts of a chemical blowing agent such as water and / or 0 to 60 parts, preferably 0.5 to 30 parts, even more preferably 1 to 25 parts of a physical blowing agent such as isopentane derivatives,
• a stabilizer such as a polyether-polysiloxane copolymer and
• the composition comprises:
• the composition comprises:
• At least one catalyst typically an amine catalyst such as dimethylcyclohexyleamine,
• % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• composition may comprise:
• w / w From 0.1 to 3.2% (w / w), preferentially from 0.1 to 2.4% (w / w), more preferably from 0.1 to 1.9% (w / w), at least one catalyst, typically an amine catalyst such as dimethylcyclohexyleamine, From 0.1 to 7.3% (w / w), preferentially from 0.1 to 4.7% (w / w), more preferably from 0.1 to 3.3% (w / w), a chemical blowing agent,
• amine catalyst such as dimethylcyclohexyleamine
• % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• a closed cell rigid polyurethane foam according to the first variant comprises for example 100 parts of polyol, 270 parts of a polyisocyanate, 2 parts of an amine catalyst such as dimethylcyclohexyleamine, 6 parts of a blowing agent such as water, 2.5 parts of a stabilizer such as a polyether-polysiloxane copolymer and 10 parts of a flame retardant.
• the composition may comprise about 25.6% (w / w) of polyols as described above, about 69.1% (w / w) of a polyisocyanate, about 0.5% (w / w) an amine catalyst such as dimethylcyclohexyleamine, about 1.5% (w / w) of a chemical blowing agent such as water, about 0.6% (w / w) of a stabilizer such as polyether-polysiloxane copolymer and about 2.6% (w / w) of a flame retardant; % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• At least one catalyst typically an amine catalyst such as dimethylcyclohexyleamine,
• % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• a second embodiment of a composition that makes it possible to obtain a rigid closed cell polyisocyanurate foam is typically formulated with a minimum index of 200, ie an NCO / OH ratio greater than 2.0, preferably an index of between 250 and 450, even more preferably between 300 and 400, ie an NCO / OH ratio preferably between 2.5 and 4.5, more preferably between 3.0 and 4.0.
• a composition for obtaining a rigid closed cell polyisocyanurate foam comprises
• 60 to 100 parts preferably 70 to 100 parts even more preferably between 80 and 100 parts of polyols, 5 to 50% of which typically 5 to 49% or 6 to 48% by weight of polyester polyol A on the polyol mass, 100 to 700 parts, preferably from 120 to 650 parts, even more preferably between 150 and 575 parts of at least one polyisocyanate,
• 0.1 to 13 parts preferably from 0.5 to 12 parts, even more preferably between 1 and 11 parts of at least one catalyst, preferably two catalysts, typically an amine catalyst and a potassium carboxylate (for example in a ratio of amine catalyst / potassium carboxylate of 0.2 to 2),
• the composition comprises:
• the composition comprises:
• % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• a composition for obtaining a rigid closed cell polyisocyanurate foam comprises, for example, 85 parts of polyols of which 5 to 50%, typically 5 to 49% or 6 to 48% by weight of polyester polyol A on the mass.
• polyols 550 parts of a polyisocyanate such as diphenylmethylene polyisocyanate; 1.6 parts of an amine catalyst such as bis (2-dimethylaminoethyl) ether; 7 parts of a potassium carboxylate such as, for example, potassium 2-ethylhexanoate; 0.8 parts of a triazine such as 1,3,5-tri (3- [dimethylamino] propyl) hexahydro-s-triazine; 45 parts of a blowing agent such as an isomer of pentane; 2.5 parts of a stabilizer and 15 parts of a flame retardant.
• a polyisocyanate such as diphenylmethylene polyisocyanate
• an amine catalyst such
• the composition may comprise about 12% (w / w) of polyols as described above, about 77.8% (w / w) of a polyisocyanate such as diphenylmethylene polyisocyanate, about 0.2 % (w / w) of an amine catalyst such as N, N-dimethylcyclohexyleamine, about 1% (w / w) of a potassium carboxylate such as, for example, potassium 2-ethylhexanoate, about 0.1% (w / w) of a triazine such as 1 , 3,5-tri (3 - [dimethylamino] propyl) hexahydro-s-triazine, about 0.1% (w / w) of a blowing agent such as pentane isomer, about 0.4% ( p / p) of a stabilizer and about 2.1% (w / w) of a flame retardant;
• a polyisocyanate such as dipheny
• % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• polyols consisting of 5 to 50% of a polyester polyol A as described above, preferably bis (1,4-butanediol) -sorbitol-diadipate and 50 to 95% of a polyester polyol B as described above , based on the weight of the total polyols;
• At least one polyisocyanate typically polymeric 4,4'-methylenebis (phenylisocyanate); the isocyanate / hydroxyl molar ratio in the composition (NCO / OH) being from 3.0 to 4.0, typically 3.2; and from 0.1 to 0.5% (w / w), typically about 0.23% (w / w) of at least one catalyst; % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• polyols consisting of 5 to 50% of a polyester polyol A as described above, preferably bis (1,4-butanediol) -sorbitol-diadipate and 50 to 95% of a polyester polyol B as described above , based on the weight of the total polyols;
• At least one polyisocyanate typically polymeric 4,4'-methylenebis (phenylisocyanate); the isocyanate / hydroxyl molar ratio in the composition (NCO / OH) being from 3.0 to 4.0, typically 3.2; and from 0.1 to 0.2% (w / w), typically about 0.12% (w / w) of a potassium carboxylate catalyst, typically potassium 2-ethylhexanoate;
• a triazine catalyst typically 1,3,5-tri (3- [dimethylamino] propyl) hexahydro-s-triazine; from 0.01 to 0.05% (w / w), typically about 0.03% (w / w) of a tertiary amine catalyst, typically N, N-dimethylcyclohexyleamine; % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• polyols consisting of 5 to 45% of a polyester polyol A as described above, typically bis (1,4-butanediol) sorbitol diadipate and 55 to 95% of a polyester polyol B as described above, relative to the weight of the total polyols;
• At least one polyisocyanate typically polymeric 4,4'-methylenebis (phenylisocyanate); the isocyanate / hydroxyl molar ratio in the composition (NCO / OH) being from 3.0 to 4.0, typically 3.2; and from 0.1 to 0.5% (w / w), typically about 0.23% (w / w) of at least one catalyst; % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• polyols consisting of 10 to 45% of a polyester polyol A as described above, typically bis (1,4-butanediol) sorbitol diadipate and 55 to 90% of a polyester B polyol as described above, relative to the weight of the total polyols; at least one polyisocyanate, as previously described, typically polymeric 4,4'-methylenebis (phenylisocyanate); the molar ratio isocyanate / hydroxyl in the composition (NCO / OH) being from 3.0 to 4.0, typically 3.2; and
• w / w from 0.1 to 0.5% (w / w), typically about 0.23% (w / w) of at least one catalyst; % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• polyols consisting of 10 to 45%, or 15 to 45% of a polyester polyol A as described above, typically bis (1,4-butanediol) sorbitol-diadipate and 55 to 90% or 55 to 85% respectively a polyester polyol B as described above, relative to the weight of the total polyols;
• At least one polyisocyanate typically polymeric 4,4'-methylenebis (phenylisocyanate); the isocyanate / hydroxyl molar ratio in the composition (NCO / OH) being from 3.0 to 4.0, typically 3.2; and
• w / w from 0.1 to 0.5% (w / w), typically about 0.23% (w / w) of at least one catalyst; % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• the composition comprises:
• polyols consisting of 10 to 45%, or 15 to 45% of a polyester polyol A as described above, typically bis (1,4-butanediol) sorbitol-diadipate and 55 to 90% or 55 to 85% respectively a polyester polyol B as described above, relative to the weight of the total polyols;
• At least one polyisocyanate typically polymeric 4,4'-methylenebis (phenylisocyanate); the isocyanate / hydroxyl molar ratio in the composition (NCO / OH) being from 3.0 to 4.0, typically 3.2; and from 0.1 to 0.2% (w / w), typically about 0.12% (w / w) of a potassium carboxylate catalyst, typically potassium 2-ethylhexanoate;
• a triazine catalyst typically 1,3,5-tri (3- [dimethylamino] propyl) hexahydro-s-triazine;
• w / w from 0.01 to 0.05% (w / w), typically about 0.03% (w / w) of a tertiary amine catalyst, typically N, N-dimethylcyclohexyleamine; % (w / w) designating the relative concentration by weight relative to the weight of the total composition.
• a tertiary amine catalyst typically N, N-dimethylcyclohexyleamine
• the invention also relates to a rigid foam panel or block comprising the rigid foam of the invention, typically for the thermal or sound insulation including buildings or cryogenic insulation of refrigerators, tank of gas boats, or for filling or buoyancy aid such as in buoyancy aids (girdles or waistcoats ..) or water sports.
• the panels may incorporate on and under siding permeable or expansion gas-tight facings to reduce diffusion thereof and, therefore, to have improved thermal conductivity properties after aging, or the panels may be manufactured with or without facings or finishing coatings.
• panel means a structure 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 from 15 to 500mm; 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 an area of 600 x 600mm, 1200 x 600mm or 1000 x 1200 mm for a thickness of 20 to 250mm.
• Block is understood to mean a structure of any geometrical, cubic parallelepiped shape, star or cylindrical, with or without recess (s), of a volume between 1 cm 3 to 100 m 3 , preferably 10 cm 3 to 70 m 3 , more preferably 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 rigid foam block according to the invention.
• the invention furthermore relates to a method for improving the insulating power and / or improving the compressive strength, and / or increasing the Young's moduli, and / or decreasing the size of the cells and in particular the minimum diameter of the cell size and / or the reduction of the thermal conductivity of a rigid foam comprising polyols, of which a polyester polyol A by the use of 5 to 50% of said polyester polyol A in mass relative to the total mass of polyols, preferably relative to the total weight of polyester polyol and / or polyol polyether, said polyester polyol A being obtained by a first polycondensation (a) of a C3 to C8 alcohol sugar Z and two diacids Y and Y 'identical or different C4 to C36 and a second polycondensation (b) of the product obtained in (a) with two diols X and X' identical or different C2 to C12 or said polyester polyol A being of general formula Rx -Ry-Z-R
• Young's modulus is meant the value of the constant defined by the ratio of the stress to the deformation applied to a material in the limit of elastic deformation of the latter.
• the invention also relates to a method of reducing lead time and / or reducing time off and / or reducing the time difference between lead time and time out and / or improvement method aesthetic characteristics including a reduction of surface irregularities of a rigid foam by G use in said rigid foam or in a composition allowing obtaining such a rigid foam of 5 to 50% by weight of a polyester polyol A on the total mass of polyol of said foam or said composition.
• the foam comprising the polyester polyol A according to the invention has a reduction of the gap between the lead time and the tack free time of 40%, a decrease of the cell size of said foam by 44%.
• cream time is meant the time during which the reaction medium changes color and starts to expand, this time corresponds to the moment when the reaction between the polyisocyanates and the water and / or polyols begins, once all the constituents of the foam were mixed.
• primer time is meant the time of formation of the polymer yarns during the removal of a control stick introduced into the reaction medium; corresponding to the beginning of the crosslinking of the polyurethane network and / or polyisocyanurate.
• bad luck time we mean the time at the end of which the surface of the foam no longer adheres to the surface of a control stick; corresponding to the macroscopic end of the crosslinking of the polymeric network of polyurethane and / or polyisocyanurate.
• the cream times, lead time and time off are well known to those skilled in the art and are for example described in Polyurethane and related foams: chemistry and technology, K. Ashida, CRC press, 2006
• the invention relates to a method thermal, acoustic or cryogenic insulation, in particular of buildings, of conduits for the transport of fluids or a method of filling (cracks or free space), of sealing (of structures, cracks, etc.), sealing or improving the floatation (typically buoyancy aids or water sports) of an object or a building by the deposit or introduction of blocks or rigid foam panels according to the invention or by in situ projection of a rigid foam or a composition for obtaining a rigid foam according to the invention.
• the invention also relates to a process for obtaining a rigid foam, typically polyurethane or polyisocyanurate comprising:
• Figure 1 Evolution of (a) temperature, (b) expansion profile, (c) normalized height (H / Hmax) as a function of time during P IR foaming.
• Figure 2 Evolution of the characteristic times (cream, thread, out of bad luck) of foaming of the PIR foams according to the rate of B AS AB.
• Figure 3 SEM images of REF foam, X40 magnification: (a) in the direction transverse to the expansion of the foam, (b) in the direction of expansion (from bottom to top).
• Figure 4 PIR foam cell diameters.
• Figure 4A minimum diameter distribution in the transverse direction
• Figure 4B maximum diameter distribution in the transverse direction
• Figure 4C minimum diameter distribution in the longitudinal direction
• Figure 4D Distribution of the maximum diameter in the longitudinal direction.
• Figure 5 Distribution of cell diameters in the direction transverse to the expansion of different PIR foams.
• Figure 6 FTIR spectra of foams.
• Figure 6A REF, PU-90/10/0-KE, PU-75/25 / 0-
• Figure 7 ATG curves of PIR foams under reconstituted air.
• Figure 8 DTGA curves of PIR foams in reconstituted air.
• Figure 9 Stress-strain curves of the foams in the longitudinal direction of the REF at PU-35/65/0-KE.
• Figure 10 Stress-strain curves in the transverse direction for REF foams to PU-35/65/0-KE.
• Figure 11 Evolution of the Young's moduli in the longitudinal (top) and transverse (bottom) directions as a function of the B AS AB level. Examples
• the polyisocyanate used is polymeric 4,4'-methylenebis (phenylisocyanate) (called pMDI, BorsodChem's Ongronat 2500 commercial range).
• Various catalysts such as N, N-dimethylcyclohexylamine (called DMCHA) from BorsodChem, 1,3,5-tris (3- [dimethylamino] propyl) -hexahydro-s-triazine (called triazine, trade name Tegoamin C41 from Evonik) ), bis (2-dimethylaminoethyl) ether (named BDMAEE, trade name Lupragen N205 from BASF), 15% by weight.
• a solution of potassium 2-ethylhexanoate was used (called KE, trade name K-ZERO 3000 from Momentive).
• the flame retardant is Shekoy's tris (1-chloro-2-propyl) phosphate (TCPP).
• the surfactant used is based on polyether polysiloxane (called PDMS, trade name TEGOSTAB® B84501 from Evonik).
• Ethylene glycol (EG) was obtained from Alfa Aesar (99% purity).
• Inventec isopentane has been used as a physical blowing agent. All of these chemicals were used as received without further purification.
• the petroleum-based polyol is an aromatic polyester polyol obtained from phthalic anhydride (Stepanpol® PS-2412, from Stepan). This polyol is used as a conventional reference and is also called petrosourced polyol thereafter.
• the biosourced polyester polyol (B AS AB) was synthesized from sorbitol according to a
• the polyester polyol B AS AB results from a two-step esterification between sorbitol, adipic acid and 1,4-butanediol (1,4 BDO).
• the first step is the reaction of sorbitol with two equivalents of adipic acid relative to sorbitol.
• the second step is the addition of a molar equivalent of 1.4 BDO to adipic acid.
• the reaction was carried out in bulk without catalyst at 150 ° C. This specific process leads to a linear polyester polyol.
• the properties of B AS AB and the petroleum-based polyol are compared in Table 1. Voltage Rating
• Polyester (secondary primary mg (mN / m)
• the reaction is carried out in a sealed stainless steel reactor equipped with a U-shaped stirring flask, a Dean Stark having an outlet at the top of the condenser to be able to link a vacuum pump and a low output to recover the condensates, an inlet and an outlet of inert gas.
• sorbitol and adipic acid are introduced in powder form in a 1/2 molar ratio (sorbitol / adipic acid).
• the reactor is placed in an inert atmosphere and is then started in heating. When the temperature reaches 100.degree. C., stirring is progressively started up to 1 pmrpm. When the temperature reaches 150 ° C, the reaction is started and continued for 3 hours.
• 1,4 butanediol (hereinafter called diol) is introduced into the reactor in a molar ratio (1,4 / butanediol / sorbitol) 2.2 / 1.
• the temperature of the reaction medium returns to 150 ° C. (stirring still maintained at 170 rpm, inert atmosphere).
• a passage under partial vacuum is carried out under partial vacuum for a period of one minute and the atmospheric pressure is brought under an inert atmosphere.
• a new partial vacuum flush is carried out for 2 minutes then the atmospheric pressure is brought under an inert atmosphere.
• the isocyanate / hydroxyl molar ratio (NCO / OH) was maintained at 3.2 in all IRP formulations. To determine the amount of isocyanate, all the reactive hydroxyl groups are taken into account, ie the polyols, the water and some solvents used in the composition of the catalysts. A mixture containing polyols, catalysts, surfactant (PDMS), flame retardant (TCPP), blowing agent (isopentane) and water was prepared. In each formulation the amounts (Table 2) of water, TCPP and surfactants were held constant at 0.9, 15 and 2.5 parts by weight (pbw), respectively. The total amount of polyol was maintained at 100pp. The amount of blowing agent was adjusted to obtain equivalent foam bulk densities.
• PDMS surfactant
• TCPP flame retardant
• blowing agent isopentane
• the mixture was stirred mechanically until a fine white emulsion was obtained with incorporation of the blowing agent.
• the temperatures of the various components were adjusted to 20 ° C.
• the correct amount of polyisocyanate was rapidly added using a syringe into the emulsion.
• the entire reaction mixture was vigorously stirred for 5 seconds.
• the foam foams freely in a 250 ml disposable beaker at room temperature (controlled at 20 ° C) or in a Foamat.
• the main characteristic reaction times, ie cream time, lead time, and time out, were recorded. Prior to further analysis, the foam samples were stored at room temperature for three days to achieve complete structural and dimensional stability without shrinkage.
• Some foams have been prepared with a partial substitution of the polyester polyols which have been hydrosourced by the biosourced polyol, BAS AB.
• the substitution ratio was 0 (REF, REF) to 65% by weight.
• PIR foams were labeled according to the ratio of petroleum-based polyol (% by weight of polyols) / B AS AB (% by weight of polyols) / EG (% by weight) as REF, PU-90/10/0-KE, PU-75/25/0-KE, PU-65/35/0-KE, PU-55/45/0-KE, PU-45/55/0-KE and PU-35/65/0-KE.
• Detailed formulations are presented in Table 2.
• Thermogravimetric (TGA) analyzes were performed using an instrument from TA: TGA Q5000 at high resolution in reconstituted air (flow rate 25 mL / min). 1-3 mg samples were warmed from room temperature to 700 ° C (10 ° C / min). The main characteristic degradation temperatures are those of the maximum of the weight loss curve (DTG) (Tdeg, max) and the characteristic temperatures at which 50% (Td eg 50%) and 100% (Tde gi oo%) have been reported. .
• Infrared spectroscopy was carried out with a Nicolet 380 Fourier transform infrared spectrometer used in reflection mode equipped with an ATR diamond module (FTIR-ATR). An atmospheric white was collected before each sample analysis (64 scans, resolution 4 cm -1 ). All spectra were normalized on the CH elongation peak at 2950 cm -1.
• Foam temperature, expansions, flow rates, apparent density and pressure were recorded with a Foamat FPM 150 (Messtechnik GmbH) equipped with cylindrical vessels 180 mm high and 150 mm in diameter, d an LR 2-40 PFT ultrasonic probe / K type thermocouple, and a FPM 150 pressure sensor. The data was recorded and analyzed with specific software.
• the closed cell count was determined using a Quantachrome Instruments Ultrapyc 1200 based on the gas expansion technique (Boyle's Law). Cubic foam samples (approximately 2.5 x 2.5 x 2.5 cm3) were cut for the first measurement and then the sample was again cut into eight pieces and the measurement again. The second measure corrects closed cell contents based on closed cells that have been damaged due to sample cutting. Measurements were made according to EN ISO4590 (October 2016) and ASTM 6226 (January 2015).
• the fire resistance of foams was evaluated according to the standardized method EN ISO 11925-2 (February 2013).
• This flammability test consists of a small direct exposure to the flame (20 mm high) of a flat foam sample for 15 s in a controlled airflow combustion chamber. This flammability test is evaluated by measuring the maximum propagation of the flame on the flat surface of the foam. The result of the test is positive if the propagation of the flame stops before reaching 15 cm high on the foam sample.
• the morphology of the foam cells was observed with Jeol JSM-IT100 (SEM) scanning electron microscope. Cubic foam samples were cut with a microtome slide and analyzed in two characteristic orientations: parallel and perpendicular to the rising direction of the foam. Using the ImageJ software (Open Source Processing Program), the Average cell size was measured as the cell aspect ratio defined by eq.1.
• n is the number of cells measured for a given sample.
• the hardness of the foam was measured with a Hilderbrand Shore 00 hardness tester according to ASTM D 2240 (January 2005). Each sample was tested ten times, the average value of the measurements and the standard deviations were determined.
• the quasi-static compression tests were carried out with an Instron compression testing machine (El 000, USA), equipped with a 1 kN load cell, 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 x 25 x 25 mm 3 .
• the samples were tested in the longitudinal direction (corresponding to the dilation) 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 limit as the first maximum of the stress curve.
• the thermal conductivity was measured from the heat flow conduction according to EN 12667 (July 2001).
• the installation consists of a heating element with two thermocouples to determine the temperatures on the front and back faces.
• the device is also equipped with dedicated sensors for measuring heating time and cycle time. The heating and cycling times are used to correct the maximum thermal conduction flux necessary for the determination of the thermal conductivity coefficient, by means of the Fourier law, used in steady-state thermal conduction. Plates of different materials, measuring 300 x 400 x 3 mm 3 , were used for the determination of the thermal conductivity coefficient.
• the solubility parameter of Hansen is characterized as follows. A small amount of polyol was poured into a 5 ml flask which was then filled with the desired solvent. The flasks were placed in an ultrasonic bath for 1 hour, then the solubility of the polyols was evaluated visually 3 hours later and confirmed after 24 hours. The corresponding results (soluble or insoluble) were collected. The Hansen solubility parameters and the predicted compatibility of the two polyols were determined by modeling their solubility sphere with the HSPiP software. IL Results and discussion
• the Hansen solubility parameters for the petroleum-based polyol and B AS AB were determined according to a previously described protocol, by qualitatively measuring their dissolutions in fourteen known solvents. Table 3 lists the solvents used and their three Hansen parameters (i) the dispersion parameter ( ⁇ d), (ii) the polar parameter (dr) and (iii) the hydrogen bonding parameter ( ⁇ h). These parameters are used to determine a solubility sphere with the HSPiP software.
• the solubility score expresses the total solubility of the polyol in the solvent with a score of 1. When the polyol is insoluble or partially soluble, the result obtained is 0.
• Table 3 Set of solvents used to model the solubility spheres and their Hansen parameter and the solubility score of B AS AB and the petroleum-based polyol
• the Petro-Rough PIR foam (REF) has short reaction times, as shown in Table 4.
• the characteristic times recorded for the REF were 10, 60 and 148 s for the cream, yarn and out-of-foul time respectively.
• PIR foam has a typical collar due to the second expansion step induced by the trimerization of isocyanates. This second step is also visible on the Foamat measurements, presented in figure 1, b.
• the expansion rate of the foam begins to decrease after 30 s of reaction and increases again after 60s of reaction.
• the temperature curve of the foam ( Figure 1-a) also shows a local plateau at 50 s with an increase to 150 ° C, which is related to the trimerization of isocyanates. The same phenomenon is visible in Figure l-c. After 50 s, a change of slope is observed and the standardized height increases rapidly from 80 to 100% with the trimerization of isocyanates.
• FIG. 2 shows the evolution of the characteristic times of cream, yarn and pimp of foams REF, PU-90/10/0-KE, PU-75/25 / 0-KE, PU65 / 35/0-KE, PU-55/45/0-KE, PU-45/55/0-KE and PU-35/65/0-KE plotted as a function of biosourced polyol content 0%, 10%, 25%, 35%, 45%, 55%, 65%. It can be seen in FIG. 2 that the cream times increase slightly with the increase in the B AS AB content. This seems to be related to the lower reactivity of the secondary hydroxyls of B AS AB.
• Figure 1-a shows the temperature of the foam as a function of time.
• the exothermicity of the reaction between polyol and isocyanate is higher for REF as well as for PU-90/10/0-KE foam.
• the temperature curves show a point of inflection around 70 ° C followed by an increase in temperature for all the foams observed. This is related to the exothermicity of the catalyzed isocyanate trimerization reaction and the formation of the PIR network.
• Figure 1b shows the expansion profile of the foam.
• the foaming rate is influenced by the expansion of the gas, so it is expected that its evolution has similarities with the evolution of the temperature of the foam.
• Increasing the biobased polyol content delayed the temperature rise and decelerated the expansion of the foam.
• the peak of the foaming speed becomes wider and its maximum decreases from 3.5 (REF) to 1.5 mm / s (PU-35/65/0-KE).
• the second increase in the foaming rate related to the trimerization of isocyanates is therefore delayed.
• the evolution of the standardized height of the foams (H / Hmax) as a function of time is presented in FIG.
• the second increase in normalized height is related to the foaming rate and trimerization of the isocyanurate.
• Figure 3 shows the SEM images of the REF foam in the transverse and longitudinal directions with respect to the rise of the foam.
• a typical honeycomb structure in the transverse direction is clearly observed.
• Stretching cells in the longitudinal direction is characteristic of a partially free expansion foaming process performed in an open cylindrical container (Hawkins, MC, 2005. J. Cell. Plast. 4J 267-285). This is really visible thanks to the anisotropic coefficient R of all the PIR foams presented in Table 5.
• the coefficients R are close to 2.0 in the longitudinal direction (oval shape), whereas in the transverse direction, R is close to 1 , 2 (close to the spherical shape).
• Figure 4-a, b shows the cell size distribution of PIR foams in the transverse direction for substitution rates of the petroleum-based polyol polyester up to PU-55/45/0-KE.
• the cell size distributions are narrow and the mean cell diameters decrease progressively as the B AS AB content in the foam increases to PU-65/35/0-KE.
• PIR foam with 45% by weight substitution (PU-55/45/0-KE) marks the change of trend as its cell diameters increase over PU-65/35/0-KE .
• Figure 5 shows the cell size distribution of the IRP foams in transverse directions determined by electron microscopy having average cell sizes smaller than the REF.
• the PU-90/10/0-KE to PU-55/45/0-KE foams also have a narrower cell distribution. Foams with a BASAB content greater than 45% by weight have larger cells than REF, in agreement with the change of trend observed on PU-45/55/0-KE.
• the inventors of the present invention consider, without wishing to be limited by theory, that the surface tension of B AS AB (Table 1) is greater than that of the second petroleum-based polyol. This increase slows the growth of bubbles according to the Laplace equation (2) because the pressure inside the bubble must exceed the surface tension to grow (Minogue, E., 2000. An in-situ study of nucleation process
• PU-90/10/0-KE to PU-65/35/0-KE have closed cell levels greater than 90%.
• the closed cell count of the PU-55/45/0-KE, PU-45/55/0-KE and PU-35/65/0-KE foam samples falls to 87, 47 and 28%, respectively.
• These foams have lower foaming temperatures and longer reaction times based on the results mentioned above. This means that the cell walls can not withstand gas expansion and collapse during foam expansion (Septevani, AA, Evans, DAC, Chaleat, C., Martin, DJ., Annamalai, PK, 2015. Ind Crops Prod 66, 16-26).
• Table 6 displays the Shore 00 hardness data. Shore 00 hardness results can be divided into two main populations.
• PU-90/10/0-KE to PU-65/35/0-KE have values similar to the REF.
• the Shore 00 hardness results are similar to those of REF for PU-90/10/0-KE to PU-55/45/0-KE foams with similar stiffness to REF.
• Other foams have a slightly lower Shore 00 hardness indicating a decrease in rigidity.
• the bulk density values shown in Table 7 are similar for all PIR formulations except samples PU-45/55/0-KE and PU-35/65/0-KE. Since the swelling agent content is kept constant in each formulation, the densifications of PU-45/55/0-KE and PU-35/65/0-KE are related to their lower foaming reactivity, resulting in lower temperatures decreasing the expansion ratio of the blowing agent.
• the signals at 2955 cm 1 and 2276 cm 1 are respectively attributed to the stretching of the CH bond of the polyurethane backbone and unreacted residual NCO groups.
• the signal at 1596 cm -1 corresponds to the Ph-H stretch of the phenyl groups of pMDI.
• the bending signal of the NH groups is located at 1509 cm 1 .
• the stretching of the C-O bonds is located at 1220 cm 1 .
• the strong signal at 1408 cm 1 is attributed to isocyanurate rings, typical of PIR foams.
• FIGS 7-8 show the TGA and DTG curves of all PIR foams. All PIR foams have a conventional two-step weight loss (Sheridan, JE, Haines, CA, 1971. J. Cell Plast 7, 135-139). PIR foams with higher B AS AB content (PU-45/55/0-KE, PU-35/65/0-KE) have better thermal stability than REF. Table 8 shows the maximum temperatures of the curve derived from weight loss: Tdegmaxi and Tde g max2. Tdegmaxi are in the range of 200 to 300 ° C. T deg max 2 is observed around 500 ° C for all substituted PIR foams.
• T deg max corresponds to the decomposition of the urethane bond.
• the mechanism of decomposition of the urethane bond is generally described as three simultaneous processes such as (i) dissociation of isocyanate and alcohol, (ii) the formation of primary and secondary amines and (iii) the formation of olefins (Javni, L, Petrovi, ZS, Guo, A., Fuller, R., 2000. J. Appl. Polym Sci 77, 1723-1734).
• T deg max 2 is more pronounced than the first T deg max and is assigned to the dual degradation of isocyanurate and cleavage of the carbon bond (Sheridan, JE, Haines, CA, 1971. J. Cell. Plast.
• the first weight loss is less important because of the isocyanurate groups.
• the isocyanurate groups are more thermally stable than furethane due to the absence of labile hydrogen and the corresponding degradation is then mainly due to cleavage of the carbon bond (Sheridan, JE, Haines, CA, 1971. J. Cell. Plast. 7, 135-139).
• Table 8 presents two temperatures corresponding to 50% respectively (Tdeg 50%) and 100% (Tde g 100%) of PIR foams weight loss.
• Tdeg 50% and Td% i oo% are similar for all PIR foam formulations, except for the PIR PU-35/65/0-KE sample which have Td eg greater than 50% and T deg oo % .
• the aromatic petrosourced polyol has an aromatic structure and it is well known that aromaticity provides a higher fire resistance, favoring surface carbonization, which reduces the flammability (Celzard, A., Fierro, V., Amaral- Labat, G., Pizzi, A., Torero, J., 2011. Polym. Degrad. Stab. 96, 477-482).
• ATG DTG ATG DTG
• Figures 9 and 10 show the stress-strain curves of all PIR foams, obtained in the longitudinal and transverse directions. As described above, in the longitudinal direction (FIG. 9), the stress increases linearly with the deformation (due to the elastic behavior of the foams) before reaching the elastic threshold. After the elastic limit, the stress remains almost constant due to the collapse of the cells of the foam.
• the lowest Young's modulus ratio of PU-65/35/0-KE reflects the least anisotropic behavior. This observation is in agreement with previous results concerning the anisotropic coefficient R of foam cells (presented in Table 5) because PU-65/35/0-KE has the smallest value of R. In the longitudinal direction, it is clear that the mechanical properties, including the Young's modulus and the yield strength, presented in Table 9, successively describe two main trends. The Young's modulus and the yield strength increase first when the biobased polyol concentration increases from 0 to 25% by weight (foam samples REF to PU-75/25/0-KE), where a loading threshold is reached.
• the size of the foam cells decreased when the amount of B AS AB was increased. This leads to good load distribution, combined with closed cell contents, resulting in increased performance.
• the gas enclosed in the cells generates pressure resistant to the compressive load, improving the mechanical properties of the foam.
• Figure 11 shows the evolution of the Young's modulus in the transverse (E T ) and longitudinal (E L ) directions. This evolution is consistent with the Gibson and Ashby bass scale (LJ Gibson, MF Ashby, Cellular Solids: Structure and Properties, Cambridge University Press, 1997, LJ Gibson et al., Failure surfaces for cellular materials under Multiaxial Loads I. Modeling, Int.J.Mech.Sc.
• Table 9 Thermal and Mechanical Conductivity Parameters of the Different Foams PIR, EL: Young's Modulus in the Longitudinal Direction, AND: Young's Modulus in the Transverse Direction, CL Strain Value in the Longitudinal Direction, CT Stress Value in the Direction transversal, I Coefficient of thermal conductivity in longitudinal direction, CS (10 / Y) Compressive strength.
• the coefficient of thermal conductivity in the longitudinal expansion direction of foams decreased slightly as the amount of biosourced polyol increased.
• the corresponding values are between 22 and 24 mW / (mK) for REF, PU-90/10/0-KE, PU-75/25/0-KE and PU-65/35/0-KE ,.
• the conductivity value of 22 mW / (mK) for the PU-75/25/0-KE foam is remarkable.
• the thermal conductivity is mainly influenced by the decrease in cell size.
• the smallest cell size influences the extinction coefficient (K) of the radiation expressed by equations (4) and (5) (Hejna, A., Kosmela, P., Kirpluks, M., Cabulis, U. , Klein, M., Haponiuk, J., Piszczyk, L., 2017b J. Polym Environ, Septevani, AA, Evans, DAC, Chaleat, C., Martin, DJ, Annamalai, PK, 2015. Ind. Prod 66, 16-26).
• the lower thermal conductivity of the PU-75/25/0-KE foam sample is a consequence of the combined effect of the closed cell content and the reduction of cell size compared to the REF. .
• the thermal conductivity remains constant around 23 mW / (m> ⁇ K).
• PIR foams have a high content of closed cells (greater than 90%) and a decrease in average cell size of 44% compared to the petro-hardened reference.
• the characteristics of the cells observed and in particular the presence of fine cells is a key parameter of a foam because they improve the thermal conductivity as well as the mechanical properties of the foam.
• the partial substitution of a polyosourced polyol by a biosourced polyol allows the observation of a foam having a compressive strength increased by 95% and a thermal conductivity decreased by 2 mW / (mK).
• an increased Young's modulus of 96 and 142% is observed in the longitudinal and transverse direction, respectively, when the content of biosourced polyols is optimal.
• the developed biosourced PIR foams meet the main requirements related to the targeted application areas (thermal insulation) such as: i. good fire resistance,

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