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    • 专利摘要:
    The present invention relates to a hard foam or composition that makes it possible to obtain a hard foam comprising a polyester polyol or a polymer comprising a polyester polyol, said polyester polyol being obtained by a first polycondensation (a) of a C3-C8 - sugar alcohol Z and two C 4 -C 36 diacids Y and Y 'which may be identical or different and a second polycondensation (b) of the product obtained in (a) with two C 2 -C 12 diols X and X' which are identical or different can be.
    公开号:BE1024970B1
    申请号:E20175586
    申请日:2017-08-24
    公开日:2018-09-04
    发明作者:Pierre Etienne Bindschedler；Alexandru Sarbu；Stephanie Laurichesse；Remi Perrin；Pierre Furtwengler；Luc Avérous；Andreas Redl
    申请人:Tereos Starch & Sweeteners Belgium Nv；Centre Nat Rech Scient；Soc Soprema Sas；Univ Strasbourg；
    IPC主号:
    专利说明:

    (73) Holder (s):
    TEREOS STARCH & SWEETENERS BELGIUM NV
    9300, ALST
    Belgium
    Center National de la Recherche Scientifique
    75794, PARIS CEDEX 16
    France
    Société SOPREMASAS 67025, STRASBOURG France
    Université de Strasbourg 67081, STRASBOURG Cedex France (72) Inventor (s):
    BINDSCHEDLER Pierre Etienne 67025 STRASBOURG Belgium
    SARBU Alexandru 67025 STRASBOURG France
    LAURICHESSE Stephanie 67025 STRASBOURG France
    PERRIN Remi 67025 STRASBOURG
    France
    FURTWENGLER Pierre 75794 PARIS Cedex 16 France
    AVÉROUS Luc
    75794 PARIS Cedex 16
    France
    REDL Andreas 9300 AALST Belgium (54) Hard foam comprising a polyester polyol (57) The present invention relates to a hard foam or composition which makes it possible to obtain a hard foam, comprising a polyester polyol or a polymer comprising a polyester polyol, wherein said polyester polyol is obtained by a first polycondensation (a) of a C3-C8 sugar alcohol Z and two C4-C36 diacids 5 Y and Y 'which may be identical or different and a second polycondensation (b) of the obtained in (a) product with two C2-C12 diols X and X 'which can be identical or different.
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    BELGIAN INVENTION PATENT
    FPS Economy, K.M.O., Self-employed & Energy
    Publication number: 1024970 Filing number: BE2017 / 5586
    Intellectual Property Office International classification: C07C 67/08 C08G 63/66 C08G 63/668 C08G 18/42
    Date of issue: 04/09/2018
    The Minister of Economy,
    Having regard to the Paris Convention of 20 March 1883 for the Protection of Industrial Property;
    Having regard to the Law of March 28, 1984 on inventive patents, Article 22, for patent applications filed before September 22, 2014;
    Having regard to Title 1 Invention Patents of Book XI of the Economic Law Code, Article XI.24, for patent applications filed from September 22, 2014;
    Having regard to the Royal Decree of 2 December 1986 on the filing, granting and maintenance of inventive patents, Article 28;
    Having regard to the application for an invention patent received by the Intellectual Property Office on 24/08/2017.
    Whereas for patent applications that fall within the scope of Title 1, Book XI, of the Code of Economic Law (hereinafter WER), in accordance with Article XI.19, § 4, second paragraph, of the WER, the granted patent will be limited. to the patent claims for which the novelty search report was prepared, when the patent application is the subject of a novelty search report indicating a lack of unity of invention as referred to in paragraph 1, and when the applicant does not limit his filing and does not file a divisional application in accordance with the search report.
    Decision:
    Article 1
    TEREOS STARCH & SWEETENERS BELGIUM NV, Burchtstraat 10, 9300 AALST Belgium;
    Center National de la Recherche Scientifique, 3 rue Michel Ange, 75794 PARIS CEDEX 16 France;
    Société SOPREMASAS, 14, rue de Saint-Nazaire, CS 60121, 67025 STRASBOURG France;
    Université de Strasbourg, 4 rue Blaise-Pascal CS 90032, 67081 STRASBOURG Cedex France;
    represented by
    CHIELENS Kristof, Pres. Kennedypark 31c, 8500, KORTRIJK;
    OSTYN Frans, Pres. Kennedypark 31c, 8500, KORTRIJK;
    CARDOON Annelies, Pres. Kennedypark 31c, 8500, KORTRIJK;
    a Belgian invention patent with a term of 20 years, subject to payment of the annual fees as referred to in Article XI.48, § 1 of the Code of Economic Law, for: Hard foam comprising a polyester polyol.
    INVENTOR (S):
    BINDERSCHEDLER Pierre Etienne, 14, rue de Saint-Nazaire, CS 60121, 67025, STRASBOURG;
    SARBU Alexandru, 14, rue de Saint-Nazaire, CS 60121, 67025, STRASBOURG;
    LAURICHESSE Stephanie, 14, rue de Saint-Nazaire, CS 60121, 67025, STRASBOURG;
    PERRIN Remi, 14, rue de Saint-Nazaire, CS 60121, 67025, STRASBOURG;
    FURTWENGLER Pierre, 3, rue Michel-Ange, 75794, PARIS Cedex 16;
    AVÉROUS Luc, 3, rue Michel-Ange, 75794, PARIS Cedex 16;
    REDL Andreas, Burchtstraat 10, 9300, AALST;
    PRIORITY:
    24/08/2016 FR 1601253;
    BREAKDOWN:
    Split from basic application:
    Filing date of the basic application:
    Article 2. - This patent is granted without prior investigation into the patentability of the invention, without warranty of the Merit of the invention, nor of the accuracy of its description and at the risk of the applicant (s).
    Brussels, 04/09/2018,
    With special authorization:
    BE2017 / 5586
    Hard foam comprising a polyester polyol
    Technical area
    The present invention relates to a rigid polyurethane foam comprising a polyester polyol which may be of a biomass origin.
    Previous state of the art
    Polyurethanes (PU) are versatile polymers and are used in various applications such as in vehicles, furniture, building, shoes, acoustic and thermal insulation with a worldwide production of 18 million tons in 2016, by which PU on the 6 th place is below the polymers based on the annual figures for worldwide production.
    Today, the PU industry relies heavily on constituents derived from petroleum, such as polyether polyols obtained from alkoxylation reactions. Isocyanates have historically been obtained from chemical methods with phosgene or diphosgene. Under various laws, in particular the Kyoto Protocol in Europe, it is now mandatory to reduce greenhouse gas emissions from production to the final use of a product. A very clear example of this is the growing focus on the insulation of buildings, in particular the “bio-insulation” of individual and collective spaces. One of the best materials for building insulation is rigid polyurethane foam (PUR), based on the polyaddition of high functionality polyols and polyisocyanurates that carry 2 to 3 isocyanate groups to obtain closed cell materials. The thermal conductivity of PUR foams varies between 20 mW / (mK) and 30 mW / (mK) versus 30 mW / (mK) and 40 mW / (mK) for expanded polystyrene (EPS) or 40 mW / (mK) and 50 mW / (MK) for extruded polystyrene (XPS).
    Today, PUR foams compete with hard polyisocyanurate polyurethane (PUIR) foams that can outperform conventional PUR foams. PUIR foams are based on the high temperature trimerization of diisocyanates to isocyanurate rings, also called triisocyanurate rings (Scheme 1) in the presence of a specific catalyst. The PUIR foam formulation differs slightly from that of PUR foams. An excess of isocyanate function is required to obtain trifunctional isocyanurate rings.
    BE2017 / 5586 .0
    O.
    T> 70 C diisocyanate
    ΊΜ potassium carboxylate catalyst
    isocyanurate ring
    Scheme 1: Trimerization of diisocyanate in the presence of a potassium carboxylate based catalyst
    For example, a polyol with a lower functionality can be used. The PUIR foam net is based on a double chemistry. The polyol reacts with the isocyanate to form polyurethane. Subsequently, the excess polyisocyanates trimerate into isocyanurate rings which underlie the high crosslink density of the final foam. The high cross-linking density of the PUIR foams is their main drawback as it leads to brittleness of the material.
    The brittleness of PUIR foams is more than offset by their better properties compared to PUR foams, in particular by their higher heat resistance. It has been discovered that the range of the thermal stability of the urethane function depends on their chemical environment and evolves between 120 ° C and 250 ° C. The range of thermal stability of the isocyanurate function also depends on the surrounding chemical function, but is estimated to be between 365 ° C and 500 ° C. The better thermal stability of the isocyanurate functions present in the PUIR foams underlies their better fire resistance compared to PUR foams. The thermal resistance of the PUIR foams compared to that of the PUR foams makes them really interesting for the building insulation sector. The building and construction sector are confronted with new, increasingly drastic standards regarding thermal resistance and fire resistance of the materials used. Despite these better properties, little research has yet been conducted on the PUIR system regarding the replacement of polyol recovered from petroleum with a polyol based on sorbitol recovered from biomass or a formulation containing 100% renewable polyol. Recently, only rapeseed oil, crude glycerol, castor oil, microalgae and tannin-based polyols have been used in PUR-PUIR foam.
    The properties of PUIR foams are mainly linked to their morphology and their internal structure, which has a significant effect on thermal conductivity and mechanical properties. It has been clearly established that the thermal properties of foam materials mainly depend on the content
    BE2017 / 5586 to closed cells and the gas they contain (H. Fleurent and S. Thijs, J. Cell. Plast. 1995, 31,580-599). It is also generally known that the mechanical properties of expanded materials are highly dependent on their density. J. Mills (NJ Mills, J. Cell. Plast., 2011,47, 173-197) has investigated closed-cell polyethylene and polystyrene foams and demonstrated that air contained in the cells contributes significantly to the compression strength of foams with low density. However, the mechanical properties of PUIR foams are not often studied yet. J. Andersons et al. (J. Andersons et al., Mater. Des., 2016, 92, 836-845) have worked on low-density, closed-cell polyisocyanurate foams. They have studied the anisotropy of the compression strength of the foams between the longitudinal and transverse directions when the foam rises. They showed that the ratio between the elastic moduli and the longitudinal and transverse force were about 3 and 1.4, respectively.
    The present invention contemplates the development of a new PUIR foam made from biomass-derived products and more particularly a biomass-derived polyester polyol which can replace the petroleum-derived polyols used for foams on the market in their conventional application . The object of the present invention is to propose a biomass-derived foam that exhibits mechanical and physical properties comparable to that of petroleum-derived foams, for example in terms of cell size, thermal degradation, kinetics, foaming, hardness, compressibility, density or thermal conductivity.
    Detailed description of the invention
    The invention relates to a hard foam or a composition which makes it possible to obtain a hard foam, comprising a polyester polyol obtained by a first polycondensation (a) of a C3-C8 sugar alcohol Z and two C4C36 diacids Y and Y '. which may be identical or different and a second polycondensation (b) of the product obtained in (a) with two C2-C12 diols X and X 'which may be identical or different.
    The invention further relates to a hard foam or a composition which makes it possible to obtain a hard foam, comprising a polyester polyol of general formula Rx-Ry-Z-Ry'-Rx 'in which
    BE2017 / 5586
    - Z is a C3-C8 sugar alcohol, preferably C4-C7, typically C5, C6,
    Ry and Ry diesters are of the formula -OOC-Cn-COO- where n is between 2 and 34, preferably between 3 and 22, typically between 4 and 10,
    -Rx and Rx are C2-C12 mono-alcohols, which may be identical or different, preferably C3-C8, typically C4.
    Typically, the term "foam", as used, for example, in the terms polyurethane foam or polyisocyanurate foam, is understood to mean a compound having a three-dimensional cell structure of the expanded type. Said foam can be hard or soft, with open or closed cells.
    "Hard foam" means a foam that exhibits good compression strength and the internal structure of which has been irreversibly damaged by a change in shape under pressure between 5 and 50%. Usually such foams exhibit glass transition temperatures (Tg) of greater than 100 ° C and often close to 200 ° C. Hard foams are usually foams with a high closed cell content (usually above 90%).
    We are talking about hard polyurethane (PUR), or hard polyisocyanurate (PUIR) for hard polyurethane or polyisocyanurate foams.
    "Closed cell foam" means a foam whose cellular structure includes walls between each cell to form a set of connected and distinct cells that enable the containment of a propellant. A foam is classified as a closed cell foam when it exhibits a maximum of 10% open cells. Typically, the closed cell foams are mainly hard foams.
    "Open cell foam" means a foam, the cell structure of which is formed by a continuous cell matrix with walls open between the cells, preventing the containment of a propellant. Such a foam allows the creation of percolation paths within the cell matrix. Typically, the open cell foams are mainly soft or semi-hard foams.
    The term "polyester polyol" refers to molecules that include hydroxyl groups (diols or sugar alcohols) joined together by ester bonds. For example, in the polyester polyol according to the invention, the molecules X, Y, Z, Y "and X" are interconnected by ester bonds. Typically, the diols X and X "and the sugar alcohol Z are bonded to the two diacids Y and Y" by ester bonds each formed between a
    BE2017 / 5586 acid function of Y or of Y 'and a primary hydroxyl function of Z, X or X'. Advantageously, the pH of the polyester polyol is typically neutral when it is obtained by two successive polycondensations followed by a neutralization step (e.g. with potassium or sodium).
    The polyester polyol according to the invention advantageously has the general chemical formula C a HbO c, where 22 <a <42, 38 <b <78, 14 <c <22.
    Typically, the polyester polyol of the invention has a molecular weight 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. According to the invention, the molar mass of the polyester polyol can be determined by various methods such as steric gel chromatography.
    The polyester polyol advantageously exhibits a hydroxyl number of 300 to 900 mg KOH / g. The hydroxyl number (IOH) can be calculated using the following formula:
    IOH = functionality of the polyester polyol x 56 109.37 / molar mass of the polyester polyol.
    The hydroxyl number corresponds to the number of mg KOH required for the deprotonation of all of the hydroxyl groups present in a gram of polyol. The hydroxyl number can be determined by reverse dosing using potassium, for example, according to standard ASTM 4274-99 in which the colorimetric titration is replaced by pH metric titration.
    By "sugar alcohol" or "polyol" is meant a hydrogenated form of monosaccharide whose carbonyl group (aldehyde or ketone) has been reduced to a primary or secondary hydroxyl. Typically, the sugar alcohol is selected from glycerol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol, and volemitol.
    Diacid means a carbon chain that includes two acid groups. According to the invention, the polyester polyol comprises two diacid molecules Y and Y ". These molecules can be identical or different on C4-C36, preferably C4-C24. Typically, the two diacid molecules are independently selected from butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (tricacetic acid, undecidic acid, undecidic acid), undecic acid (brassylic acid), tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, dimers of fatty acids with up to 36 carbon atoms (C36) or a mixture thereof. Typically Y and Y are C5-C16 or C6-C126
    BE2017 / 5586 diacids. Advantageously, the preferred diacid molecules are independently selected from adipic acid and succinic acid.
    “Diol” means a carbon chain that includes two alcohol groups. According to the invention, the polyester polyol comprises two molecules X and X of diols which can be identical or different. Typically, the diol molecules are independently selected from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8octanediol, 1,10-decanediol, 1,12 dodecanediol and mixtures thereof .
    The polyester polyol according to the invention is advantageously selected 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. Preferably said polyester polyol is selected from bis (1,8-octanediol) sorbitol diadipate, bis (1,10-decanediol) sorbitol diadipate and bis (1,4-butanediol) sorbitol diadipate.
    The invention also relates to a hard foam or a composition which makes it possible to obtain a hard foam, comprising a polyester polyol obtained by a method 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 °, advantageously for 5 to 10 hours:
    i. of a C3-C8 sugar alcohol Z, preferably C4-C7, advantageously C5-C6, typically selected from glycerol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol, ii. two identical or different C4-C36 diacids Y and Y, preferably C5C24,
    Hi. two identical or different C2-C12 diols X and X ', preferably C3C8, typically C4 advantageously, independently selected 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,
    b) optionally a step of neutralizing the free acid functions to neutralize the pH of the polyester polyol (pH = 7), for example, by a base, typically
    BE2017 / 5586 a strong base such as potash, or by a weak base such as sodium carbonate, sodium bicarbonate, potassium carbonate or a C4-C8 mono, bi or tri alcohol such as hexanol; preferably the neutralization step is carried out by adding potassium carbonate or potash.
    Advantageously, the molar ratio (X + X ") / Z between the diols X and X" and the sugar alcohol Z during the polycondensation step is between 1 and 3, preferably between 1.5 and
    2.5 and even more preferably between 1.8 and 2.2.
    Typically, the molar ratio (Y + Y ') / Z between the diacids Y and Y' and the sugar alcohol during the polycondensation step is between 1 and 3, preferably between 1.5 and 2.5, and even more preferably between 1.8 and 2.2.
    In one embodiment, the molar ratio (X + X ') / (Y + Y') between the diols X and X 'and the diacids Y and Y' during the polycondensation step is between 0.5 and 2, preferably between 0.7 and 2 1.5 and even more preferably between 0.8 and 1.2.
    Advantageously, the polycondensation step comprises a first polycondensation (a) of the sugar alcohol Z and the diacids Y and Y "and a second polycondensation (b) of the product obtained in (a) with the diols X and X". Polyester polyol having this symmetrical structure can be obtained by this two-step polycondensation. Typically, the diacids Y and Y are identical and / or the diols X and X are identical.
    In one embodiment, the sugar alcohol Z is mixed with the or the molecules of diacid Y and Y 'and then incubated for more than an hour, more preferably between 2 and 5 hours, even more preferably between 2.5 and 4 hours, typically for 3 hours. The or molecules of diol X and X 'are added to the mixture in a second step and then incubated for more than 4 hours, preferably between 5 and 10 hours, typically between 5.5 and 7 hours. Preferably, the polycondensation is carried out under vacuum.
    Advantageously, the molecules of diacid Y and Y "react during the polycondensation step with the primary alcohols of the molecules of sugar alcohol Z and then of the diols X and X". The water molecules from the reaction are collected for elimination.
    The invention further relates to a hard foam or a composition which makes it possible to obtain a hard foam, comprising a polymer comprising the polyester polyol according to the invention, said polymer typically being a polyurethane and / or a polyisocyanurate.
    BE2017 / 5586
    Advantageously, the polymer according to the invention has a molar mass of more than 1.7x10 6 g / mol. Typically, the polymer is a cross-linked polymer.
    By "polyurethane" is meant a polymer that includes urethane functions, in other words, a urethane polymer. These polymers mainly result from the reaction of polyols, in particular the polyester polyol according to the invention and polyisocyanates. These polymers are generally obtained from formulations having an index of 100 to 150, preferably 105 to 130, corresponding to NCO / OH ratio between 1 and 1.5, preferably between 1.05 and 1.3.
    By "polyisocyanurate" is meant the polymers resulting from the reaction of polyols, especially of the polyester polyol of the invention and polyisocyanates, which further contain urethane bonds, other kinds of functional groups, in particular triisocyanation rings formed by trimerization of polyisocyanates. These polymers, commonly also referred to as modified polyurethanes or polyisocyanurate polyurethanes, are usually obtained from formulations having an index of 150 to 700, preferably between 200 and 500, even more preferably between 250 and 400, or an NCO / OH ratio between 1.5 and 7, preferably between 2.0 and 5.0, preferably between 2.5 and 4.0.
    According to the invention, said polymer is a mixture of polyurethane and polyisocyanurate. Such a mixture is observed, for example, when said polymer comprises urethane functions and polyisocyanates trimerized to triisocyanurate rings. Typically, said polymer is a mixture of polyurethane and polyisocyanurate, and exhibits an index of greater than 100 or less than or equal to 400, corresponding to an NCO / OH ratio greater than 1 or less than or equal to 4.
    By "NCO / OH ratio", within the meaning of the present invention, is meant the ratio between the number of NCO functions of the polyisocyanate and the number of OH functions of the polyester polyol, of the co-polyols and of any other component comprising OH groups (water, solvents) present in a form. The NCO / OH ratio is calculated using the following formula:
    Ratio NCO / OH = M exp Pi x ME Pi / M exp SAI x ME SAI where:
    M exp Pi is the mass of the polyisocyanate;
    MexpSAI is the mass of the sugar alcohol;
    BE2017 / 5586
    ME SAI is the equivalent mass of the sugar alcohol and corresponds to the ratio between the molar mass of the sugar alcohol and the functionality of the sugar alcohol;
    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.
    For the purposes of the present invention, "urea bond" is understood to be a disubstituted urea bond, or the product of the reaction between a primary amine and an isocyanate function of a polyisocyanate. The primary amines can be introduced into the composition or are the product of the reaction between a water molecule and an isocyanate function of a polyisocyanate.
    Typically, said hard foam or said composition which permits to obtain said hard foam, comprising said polyester polyol of the invention or said polymer of the invention, in particular the prepolymer, further comprises a reaction catalyst, a polyisocyanate having a functionality at least equal is on 2, a stabilizer, a blowing agent, optionally, a co-polyol and additives.
    By "co-polyol" is meant a compound bearing two hydroxyl functions (type diol) or more (polyol) added to the composition comprising the polyester polyol, to adjust its properties such as functionality or viscosity, to create cross-linking knots or act as a chain extender. The foam according to the invention comprises at least one C2-C8 copolyol, preferably C2 to C7, advantageously C2 to C6. The at least one copolyol is advantageously selected from ethylene glycol, glycerol, 1,4-butanediol, butane-1,3-diol, 1,3-propanediol, propane-1,2-diol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propylene glycol, 3-oxapentane-1,5-diol, 2- [2- (2-hydroxyethoxy) ethoxy] -ethanol, benzene-1,2,4-triol, benzene-1,2 , 3-triol, benzene-1,3,5-triol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol. Preferably, the at least one copolyol is selected from glycerol, ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,5-pentanediol, 1,2-propylene glycol, 3-oxapentane-1,5-diol and sorbitol, wherein the preferred at least one copolyol is selected from glycerol, ethylene glycol, 1,4-butanediol and sorbitol.
    Typically, the copolyol (s) is / are added in a polyester polyol / copolyol ratio of 70/30 to 99/1, preferably 75/25 to 95/5, even more preferably, 80/20 and 92/8, typically, 82/8 and 90/10, for example 85/15.
    BE2017 / 5586
    According to the invention, the composition comprises two copolyols, typically a C2 copolyol and a C3 copolyol or a C2 copolyol and a C4 copolyol or a C2 copolyol and a C5 copolyol polyol or a C2-co-polyol and a C6-co-polyol or a C3-co-polyol and a C5co-polyol or a C3-co-polyol and a C4-co-polyol or a C3-co-polyol and a C6 copolyol or a C5 copolyol and a C6 copolyol, or two C3 copolyols or two C5 copolyols or two C6 copolyols.
    Advantageously, the composition comprises at least one C2 copolyol, typically two copolyols, for example a C2 copolyol and a C3, C4, C5 or C6 copolyol, typically ethylene glycol and glycerol, ethylene glycol and erythritol, ethylene glycol and xylitol, ethylene glycol and araditol, ethylene glycol and ribitol, ethylene glycol and dulcitol, ethylene glycol and mannitol, ethylene glycol and 1,4-butanediol, ethylene glycol and 1,3-propanediol and 1,4-butanediol, or ethylene glycol and volemitol.
    Advantageously, the composition comprises two copolyols, typically in a ratio of C2 / C6 or C2 / C5 or C2 / C6 or C2 / C3 or C3 / C6 or C3 / C5 or C5 / C6 between 95/05 to 50 / 50, preferably, 90/10 to 55/45, preferably 87/13 to 60/40, more preferably 85/15 to 62/38, even more preferably 80/20 to 65/35.
    "Polyisocyanate" means any chemical compound that includes at least two distinct chemical isocyanate (NCO) functions, in other words, "having a functionality at least equal to 2". When the polyisocyanate has a functionality of 2, this is called a diisocyanate. For the purposes of the present invention, functionality is understood to mean the total number of reactive isocyanate functions per isocyanate molecule. The functionality of a product is determined by the titration of the NCO function via a method of back-titration of excess dibultylamine by hydrochloric acid. Typically said polyisocyanate has a functionality between 2 and 5, preferably between 2.5 and 3.5, even more preferably between 2.7 and 3.3. Advantageously, said polyisocyanate is selected from aromatic, aliphatic, cycloaliphatic polyisocyanates and their mixtures. For example, mention may be made of: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6toluene diisocyanate, m-phenyl diisocyanate, p -phenyl diisocyanate, cis / trans cyclohexane diisocyanate hexamethylene diisocyanate, m- and p-tetramethylxylylene diisocyanate, mxylylene, p-xylylene diisocyanate, naphthalene-m, m-diisocyanate, 1, 3,5-hexamethyl mesitylene triisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4'-diphenyl-methane diisocyanate, 4,4'-di-isocyanabiphenylene 3,3'-dimethoxy-4, 4'-diphenyl diisocyanate, 3,3'dimethyl-4,4'-diphenyl diisocyanate, 4,4,4-triphenylmethane triisocyanate, toluene-2,4,6m-triisocyanate, 4.4 dimethyl-diphenyl-methane-2,2 ', 5,5'-tetraisocyanate, and aliphatic
    BE2017 / 5586 isocyanates such as 4,4'-diphenylmethane diisocyanate hydrogen, hydrogenated toluene diisocyanate (TDI) and hydrogenated meta and paraxylene diisocyanate of tetramethylxylylene diisocyanate (TMXDIO isocyanate, product of American Cyanamid co, Wayne .), 3: 1 meta-tetramethylxylylene diisocyanate / trimethylolpropane (Cythane 3160® isocyanate, of the American company American Cyanamid Co.), multifunctional molecules such as diphenylmethylene poly-diisocyanate (pMDI) and analogs thereof. Typically, the polyisocyanate is selected from toluene diisocyanate (TDI), 4,4'diphenylmethane diisocyanate (or 4,4'-diphenylmethylene diisocyanate or 4,4'-MDI), polymethylene polyphenylene polyisocyanate (polymer MDI, pMDI) and mixtures thereof.
    By "reaction catalyst" is meant a compound which, when introduced in a small amount, accelerates the kinetics of the formation of the urethane bond (-NHCO-O-) by reaction between the polyester polyol of the invention and a polyisocyanate or the reaction between a polyisocyanate and activates water or activates the trimerization of isocyanates. Typically, the reaction catalysts are selected from tertiary amines (such as dimethylcyclohexane), tin derivatives (such as tin dibutyl dilaurate), ammonium salts (such as methaneamine, 2,2-dimethylpropanoate-N, N, N-trimethyl), alkali metal carboxylates (such as potassium 2-ethylhexoanoate) or potassium 2-ethyl octanoate , amine ethers (such as bis (2-dimethylaminoethyl) ether), and triazines (such as 1,3,5-Tris (3dimethylamino) propyl)) hexahydro-1,3,5-triazine).
    A composition intended to obtain a foam advantageously comprises said polyester polyol according to the invention or said polymer according to the invention, in particular the prepolymer, at least one reaction catalyst, at least one polyisocyanate with a functionality at least equal to 2 , at least one blowing agent and optionally, a stabilizing agent, a fire retardant, a copolyol.
    When the composition is a foam or a composition which makes it possible to obtain a foam, the preferred polyester polyol is advantageously a polyester polyol having a neutral pH and / or it comprises a sorbitol such as sugar alcohol Z. Typically, the preferred polyester polyol is (1,2 ethanediol) sorbitol diadipate, bis (1,6 hexanediol) sorbitol diadipate or bis (1,4 butanediol) sorbitol diadipate, more preferably bis (1,4 butanediol) sorbitol diadipate, or bis (1,6 hexanediol) sorbitol diadipate.
    According to the invention, a foam after polymerization typically comprises a polymer according to the invention, in particular a cross-linked polymer, at least one reaction catalyst, at least one blowing agent, a stabilizing agent, and optionally at least one copolyol.
    BE2017 / 5586
    By "blowing agent" is meant a compound which, by chemical and / or physical action, causes an expansion of a composition during a foaming step. Typically, the chemical blowing agent is selected from water, formic acid, phthalic anhydride and acetic acid. The physical blowing agent is selected from pentane and isomers of pentane, hydrocarbons, fluorinated hydrocarbons, the hydrochlorofluoro olefins, hydrofluoroolefins (HFO), ethers and mixtures thereof. We can mention methylal as an example of an ether type blowing agent. According to the invention, a preferred chemical and physical blowing agent mixture is, for example, a mixture of water / pentane isomer or formic acid / pentane isomer or water / hydrofluoroolefins or pentane isomer / methylal / water or water / methylal.
    "Stabilizer" is understood to mean an agent that allows 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 the progress of the reactions. Typically, the stabilizers are selected from any of the glycol silicone copolymers (e.g., Dabco DC198 or DC193, marketed by Air Products), non-hydrolyzable glycol silicone copolymer (e.g., DC5000 from Air Products), siloxane-polyalkylene copolymer (e.g. Niax L-6164 from Momentive), polyoxyalkylene-methylsiloxane copolymer (e.g. Niax L-5348 from Momentive), polyether polysiloxane copolymer (e.g. Tegostab B8870 or Tegostab B1048 from Evonik), polyether polydimethylsiloxane copolymer from Evonik), polyether siloxane (e.g. Tegostab B8951 from Evonik), a modified polyether-polysiloxane copolymer (e.g. Tegostab B8871 from Evonik), a polyoxyalkylene-polysiloxane block copolymer (e.g. Tegostab BF 2370 from Evonik) and derivatives or mixtures thereof.
    “Additives” include agents such as antioxidants (neutralization agents of the chain ends that are the origin of the depolymerization or comonomer chains capable of stopping the depolymerization extension), demoulding agents (talc, paraffin solution, silicone), anti-hydrolysis agents, biocides, anti-UV agents (titanium oxide, triazines, benzotriazoles) and / or fire retardants (antimony, phosphorus, boron, nitrogen compounds).
    “Fire retardant” means a compound that has the property of limiting or preventing the combustion or heating of the materials it impregnates or covers; we also speak of flame or fire retardant. For example, alone or in a mixture, we can use graphite, silicates, boron, halogen or phosphorus derivatives such as Tris (1-chloro-2-propyl) phosphate (TCPP), triethylene phosphate (TEP), triaryl13
    BE2017 / 5586 Phosphate esters, ammonium polyphosphate, red phosphorus, trishalogeenaryl, and their mixtures.
    An example of a composition according to the invention which makes it possible to obtain a closed-cell hard polyurethane foam is typically formulated with an index between 101 and 200, preferably between 102 and 170, even more preferably between 105 and 150, for example 115 in other words, an NCO / OH ratio contains between 1.01 and 2, preferably between 1.02 and 1.7, even more preferably between 1.05 and 1.5, for example 1.2.
    Typically, such a composition includes:
    • at least 1 to 100 parts, preferably 40 to 100 parts, even more preferably between 80 to 100 parts of a polyester polyol according to the invention, • 0 to 70 parts, preferably 1 to 50 parts, even more preferably between 2 and 30 parts of at least one copolyol, 150 to 500 parts, preferably 160 to 425 parts, even more preferably between 180 and 375 parts of at least one polyisocyanate, 0.5 to 5 parts of at least one catalyst, typically of an amine catalyst such as dimethylcyclohexylamine, 0.5 to 15 parts of at least one blowing agent, typically 0.5 to 12 parts, preferably 0.6 to 10 parts, even 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, 0 to 5 parts of a stabilizing agent such as a polyether-silicone copolymer and • 0 to 20 parts of a fire retardant means.
    For example, a closed cell hard polyurethane foam includes 100 parts of a polyester polyol, 270 parts of a polyisocyanate, 2 parts of an amine catalyst such as dimethylcyclohexylamine, 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.
    BE2017 / 5586
    An example of a composition which allows to obtain a closed cell hard polyisocyanurate foam is typically formulated with a minimum index of 200, i.e. an NCO / OH ratio greater than 2.0, preferably an index between 250 and 450, even more preferably between 300 and 400, in other words an NCO / OH ratio preferably between 2.5 and 4.5, even more preferably between 3.0 and 4.0.
    A composition allowing to obtain a closed cell hard polyisocyanurate foam comprises: • 60 to 100 parts, preferably 70 to 100 parts, even more preferably between 80 and 100 parts of the polyester polyol of the invention, • 0 to 50 parts, preferably 1 to 40 parts, even more preferably between 5 and 20 parts of a copolyol, • 100 to 700 parts, preferably 120 to 650 parts, even more preferably between 150 and 575 parts of at least one polyisocyanate, • 0.1 to 13 parts, preferably 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 amine catalyst / potassium carboxylate ratio of 0.2 to 2), 0 to 80 parts, preferably 5 to 70 parts, even more preferably 10 to 60 parts of at least one blowing agent such as a pentane isomer, • 0 to 8 parts, preferably 1 to 7 parts, even more preferably between 1.5 and 6 parts of a stabilizing agent, • 0 to 30 parts, preferably 5 to 25 parts, even more preferably between 10 and 20 parts of a fire retardant.
    Typically, a composition allowing to obtain a closed cell hard polyisocyanurate foam comprises, for example, 85 parts of the polyester polyol of the invention; 15 parts of a copolyol such as ethylene glycol; 550 parts of a polyisocyanate such as diphenylmethylene poly-diisocyanate; 1.6 parts of an amine catalyst such as bis (2-dimethylaminoethyl) ether; 7 parts of a potassium carboxylate such as 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 a
    BE2017 / 5586 pentane isomer; 2.5 parts of a stabilizer and 15 parts of a flame retardant medium.
    The invention also relates to a hard foam panel or block comprising the hard foam according to the invention, typically for thermal or acoustic insulation, in particular of buildings, or cryogenic insulation of refrigerators, tanks of gas tankers, or for filling or assisting when buoyant as in means that aid in buoyancy (belt or vest ...) or water sports.
    By "panel" is meant a rectangle of approximately parallelepiped shape having relatively smooth surfaces and having the following dimensions, from 0.3 to 50 m 2 surface for a thickness of 10 to 1000 mm, preferably of 0 , 5 to 20 m 2 surface for a thickness of 15 to 500 mm; even more preferably 0.8 to 15 m 2 of surface for a thickness of 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 600 mm or 1200 x 600 mm for a thickness of 20 to 250 mm.
    “Block” means a structure of any possible geometric shape, cube, parallelepiped, star or cylinder, with or without recess (es), with a volume between 1 cm 3 to 100 m 3 , preferably 10 cm 3 to 70 m 3 , even 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 hard foam panel or block according to the invention.
    The invention relates to a method for thermal, acoustic or cryogenic insulation, in particular of buildings, pipes for transporting fluids or a method for filling (cracks or free space), rendering them impermeable (structures, cracks .. .), buoyancy sealing or enhancement (typically of buoyancy or water sports aids) by depositing or introducing foam blocks or panels of the invention or by injecting or injecting a hard foam or composition which makes it possible to obtain a hard foam according to the invention.
    The invention also relates to a method of obtaining a hard foam, typically of polyurethane or polyisocyanurate, comprising:
    BE2017 / 5586 • a step of obtaining a polyester polyol according to the invention or a polymer according to the invention, in particular a pre-polymer according to the invention, • a step of adding at least one polyisocyanate, at least one blowing agent, a stabilizer and at least one reaction catalyst, and • a polymerization step.
    Although they have different meanings, the terms include, "contain", "consist of" and their derivatives have been used interchangeably in the description of the invention and may be substituted for one another. The invention will be more clearly understood by reading the following figures and examples, which are given by way of example only.
    FIGURES
    Figure 1: Profile of the formation of PUIR foam, extracted from petroleum: a. Temperature, b. expansion rate, c. normalized maximum height of the foam
    Figure 2: Evolution of the temperature of the reaction medium during the foaming of the reference and of two foams B1-K0 and B2-PC recovered from biomass. Figure 3: View of the PUIR foams: a) 100/0, b) B1-K0 , c) B2-PC
    Figure 4: MEB negatives of the PUIR foam 100 / o: a) transverse to the expansion of the foam, b) longitudinal to the expansion of the foam Figure 5: FTIR spectrum of the PUIR foams 100 / 0, 35/65, B1-K0 and B2-PC
    Examples
    I. Material and working method
    a. Chemical products
    The petroleum-derived polyester polyol is an aromatic polyester based on modified phthalic anhydride from STEPANP (STEPANPOL® PS-2412), called petroleum-derived polyol. The polyester polyol (BASAB) recovered from biomass
    BE2017 / 5586 obtained from sorbitol according to an esterification process described in our patent application FR 16/01253. The properties of the polyols obtained from petroleum and from biomass are summarized in table 1. The D-sorbitol is sold by TEREOS SYRAL (sorbitol more than 98%, water less than 0.5%, reducing sugars less than 0.1% ), 1,4-butanediol (99%) is sold by SIGMA ALDRICH, adipic acid (99%) is sold by ACROS ORGANICS. The polyisocyanate is 4,4'-methylene bis (phenyl isocuyanate) (MDI) polymer and the Ν, Ν-dimethylcyclohexylamine (DMCHA, catalyst) is from BORSODCHEM (Ongronat 2500). Various raw catalysts such as 1,3,510 tris (3- [dimethylamino] propyl) -hexahydro-s-triazine supplied by EVONIK (Tegoamin C41), bis (2-dimethylaminoethyl) ether of BASF (Lupragen N205), 15 wt% . Solution of potassium octate (Ko) and 40% by weight. A potassium carboxylate in ethylene glycol (Pc) from EVONIK was used. The fire-resistant agent used is the phosphate of tris- (1-chloro-2-propyl) (TCPP) from SHEKOY, the surfactant is polydimethylsiloxane (B84501) from
    EVONIK and the ethylene glycol (EG) was obtained from ALFA AESAR (purity 99%). INVENTEC isopentane was used as a blowing agent. All these chemicals were used as received without further purification.
    Hydroxyl number (mg KOH / g) Acid value (mg KOH / g) Viscosity (25 ° C, mPa.s) Primaryhydroxyl Secondaryhydroxyl Surface tension(mN / m) From petroleum 230-250 1.9-2.5 4000 2 0 33.6 ± 0.9 wonBASAB 490-510 Less than 3 14,000 2 4 40 ± 0.8
    Table 1: Important properties of the polyester polyol and of
    0 the BASAB
    b. General procedure for obtaining the BASAB
    The reaction is carried out in an impermeable stainless steel reactor equipped with a U-shaped stirring blade, a Dean Stark which has an outlet at the top of the condenser
    5 shows for connection thereto a vacuum pump and a bottom outlet for collecting the condensates, an inlet and an outlet for inert gas. Powdered adipic acid and sorbitol are introduced into the reactor in a 1/2 mol ratio (sorbitol / adipic acid). The reactor is placed in an inert atmosphere after which the heating is started. When the temperature reaches 100 ° C, the stirring becomes gradual
    0 on started up to 170 rpm. When the temperature reaches 150 ° C, the reaction is started and continued for 3 hours. After 3 hours, 1,4-butanediol (hereinafter called diol) is introduced into the reactor in a molar ratio (1,4-butanediol / sorbitol) of 2.2 / 1. The temperature
    BE2017 / 5586 of the reaction medium returns to 150 ° C (still stirring at 170 rpm, inert atmosphere). 2:30 after the return to 150 ° C, a passage under partial vacuum is carried out under partial vacuum for one minute, after which atmospheric pressure is restored under inert atmosphere. 4:30 after the addition of diols, a new flush is performed under partial vacuum for 2 minutes, after which atmospheric pressure is restored under inert atmosphere. 6h15 minutes after the introduction of the diol (in other words, a total reaction time of 9h15min at 150 ° C), the reactor is stopped and the reaction product is warm-collected to have minimal loss in the transfer of material from the reaction to the package of the product.
    c. General method for preparing PUIR foams
    The isocyanate / hydroxyl (NCO / OH) molar ratio was kept at 3.2 in all PUIR formulations. To determine the amount of isocyanate, all reactive hydroxyl groups are taken into account, i.e. the polyols, the water and the solvents from the selected catalyst charge. Based on the two-component foaming process, a first mixture is prepared comprising: polyols, catalysts, surfactants (polydimethylsiloxane, B84501), flame retardants (TCPP), a blowing agent (isopentane) and water. In each preparation, the number of parts (p) of water, TCPP, surfactants is constant in particular 0.9 p, 15 p, 2.5 p, respectively, and the total amount of polyol never exceeds 100 p. The amount of blowing agent was kept constant at 24 µ to obtain foams of comparable densities. The mixture was stirred mechanically until a white fine emulsion was obtained with total blowing agent uptake. The mixture and temperature of the polyisocyanates were checked and adjusted and adjusted to 20 ° C. Then, with an emulsion syringe, the appropriate amount of polyisocyanate was added to obtain an NCO / OH ratio of 3.2. The complete reaction mixture was run for 5 sec. stirred vigorously and the foam was allowed to expand freely in a 250 ml disposable beaker at room temperature (controlled at 20 ° C) or in a FOAMAT device. The characteristic constants of the kinetics of foam formation were recorded, in particular the time to cream foam, the time to filamentary foam and the time to tack free foam. Prior to analysis, the foam samples were kept at room temperature for three days to obtain complete dimensional stability (absence of shrinkage).
    BE2017 / 5586
    A formulation containing only petroleum-derived polyester polyol was used as the reference formulation (Table 1). This formulation is converted to formulations containing 65% and 100% (equal to 65 p and 100 p, respectively) BASAB, noted as 35/65 and 0/100 (PS2412 / BASAB), respectively. Subsequently, the formulation was optimized in formulations containing 85% (equal to 85 µ) BASAB. The formulations containing the BASAB are presented in Table 3.
    Number of parts Polyols extracted from petroleum 100 C41 0.3 Catalyst N205 0.12 KO 3 water 1 others Surfactant 2.5 Fire retardant 15
    Table 2: Formulation of the PUIR foams, expressed in number of parts
    d. Characterizations
    The thermogravimetric analyzes (TGA) were performed using a TA Hi-Res TGA Q5000 device under reconstituted air (flow rate 25 ml / min.). Samples from 1 to 3 mg were heated from room temperature to 700 ° C (10 ° C / min). The main characteristic breakdown temperatures are those at the maximum of the derived weight loss curve (DTG) (Td eg , max) and characteristic temperatures corresponding to 50% (Td eg 5o%) and 100% (Td eg ioo%) weight loss have been reported .
    The infrared spectrometry was performed with an infrared spectrometer with Fourier Transform Nicolet 380 used in reflection mode equipped with an ATR2 0 diamond module (FTIR-ATR). An atmospheric background was collected for the analysis of all samples (64 scans, resolution 4 cm -1 ). All spectra were normalized to a draw peak CH at 2950 cm -1 .
    The temperature of the foams, the expansion rates and heights, the density and the pressure were recorded using a FOAMAT FPM 150 (Messtechnik
    5 GmbH) equipped with cylindrical holders with a height of 180 mm and a diameter of 150 mm, an LR2-40 PFT ultrasonic probe for recording the foam heights, a NiCr / thermocouple Ni type K and a pressure sensor 150 FPM. The data was recorded and analyzed with specific software.
    BE2017 / 5586
    The closed cell contents were determined using an Ultrapyc 1200e from Quantachrome Instruments, based on the gas expansion technique (Boyle's law). Cuboid foam samples (approximately 2.5 cm x 2.5 cm x 2.5 cm) were cut for the first measurement, then the sample was cut again into eight pieces and the measurement repeated. The second step allows to correct the contents of the closed cells in function of the cells damaged by cutting the sample. The measurements were performed according to standards EN ISO4590 and ASTM 6226.
    The cell morphology of the foams was observed with an electron emission scanning electron microscope (SEM) JEOL JSM-IT100. The cubic foam samples were cut with a microtome blade and analyzed in two characteristic directions: longitudinal and transverse to the direction of rise of the foams. Using the ImageJ software (Open Source processing program), the average cell size was measured as the aspect ratio of the cell defined by Eq. 1 22.
    Y- Dfi ax
    R = ~ y nZ-ι D ™ m i = l where ÜFmax and ÜFmin are the maximum and minimum Feret diameters, n is the number of cells measured for a given sample.
    II. Results and discussion
    a. Kinetics of the PUIR reference foam
    The petroleum-derived PUIR reference foam (100/0) shows rapid foaming. Its characteristic times can be found in Table 3.
    To evaluate the foam formation kinetics of these different formulations, the characteristic times of the cream foam, filamentary foam and tack free foam were measured.
    The time of creaming forms the beginning of the polyaddition reaction between the isocyanate functions applied by the polyisocyanate and the water, or the alcohol groups applied by the entirety of polyols, copolyols or additives present in the formulation. The time of creaming is characterized by a color change of the reaction medium prior to the expansion of the foam.
    BE2017 / 5586
    The moment of filament formation starts the formation of the polymer net of polyurethane and / or polyisocyanurate. It is characterized by the formation of adhesive thread when physical contact is made with the expanding foam.
    The moment when the foam becomes tack-free, the polymerization of the polyurethane and / or polyisocyanurate network on the surface of the foam ends. It is characterized by a foam that no longer feels sticky.
    The characteristic times recorded for 100/0 are 10 sec, 60 sec, and 148 sec, respectively, for the time of creaming, the time of threading, and the time when the foam becomes tack-free. The macroscopic appearance of such a PUIR foam is characteristic (Figure 3a) and shows a typical collar generated by the second growth of the foam during the trimerization of the isocyanates. This second growth is clearly visible on the Foamat measurements shown in Figure 1b. The expansion rate of the foam begins to decrease after a 30 sec reaction and again increases after a 60 sec reaction. The temperature curve of the foam (Figure 1a) also shows an inflection point at 50 sec and rises to 150 ° C, corresponding to the trimerization of the isocyanates. The same phenomenon can be seen in Figure 1c, which shows the maximum height of the foam. After 50 sec, a change in slope is observed and the maximum height rapidly increases 80 to 100% with the trimerization of the isocyanates.
    b. Kinetics of the PUIR foams containing BASAB
    Two formulations, similar to the reference (100/0), containing PS 2412 only, were prepared with the following polyester polyol ratios: 35/65 and 0/100 (parts / parts) PS 2412 / BASAB (Table 3). From the analysis of the time of creaming of the 35/65 and 0/100 formulations, we can determine that the onset of the polyaddition reaction between the polyols and the polyisocyanates has shifted by 9 and 14 seconds, respectively, relative to the reference. The time to threading of the 0/100 foam is not measurable as it may coincide with the time when the foam becomes tack free and exceeds 300 sec, while at the reference the time when the foam becomes tack free is 148 sec. The comparison of these two moments when the foam becomes tack-free clearly shows that the mixture of catalysts commonly used for the formulation containing 100% petroleum-derived polyol is not equally suitable for the formulation containing 100% biomass-derived polyol according to the invention. In other words, the exotherm of the polyaddition reaction is different and leads to a lower activity of
    BE2017 / 5586 the catalysts. The activation of these catalysts is at the origin of the rate at which the polyurethane net is formed, and at the origin of the formation of the triisocyanurate rings.
    Surprisingly, the 35/65 formulation exhibits a threading time that is 48 sec shorter than that of the reference. This means that the 35 parts PS 2412 are sufficient to maintain the activation of the traditional catalyst mixture. The larger and unusual functionality of the BASAB for a PUIR formulation also makes it possible to reach the characteristic moment when the foam becomes tack-free more quickly.
    Two formulations identical to the control formulation were prepared replacing the reference PS 2412 poyol with BASAB. Foams with good properties for the 35/65 foam could be obtained. However, with a total replacement, the 0/100 foams exhibit relatively slow measured characteristic times to foam.
    In other words, the best results are obtained by using a combination of a co-polyol with BASAB. EG was chosen because, as a short diol, it was found to be very reactive to stimulate the onset of the first exothermic reaction and enhance the reaction between the BASAB and the polyisocyanate molecules. After several tests with BASAB / EG ratios, the ratio showed 85 wt% / 15
    0 wt% best result in PUIR foam formulation.
    Two catalysts were compared: potassium octoate (Ko) and potassium carboxylate (Pc). The latter, smaller catalyst exhibits greater mobility and thus greater activity in the medium.
    The resulting optimized formulations being a B1-K0 formulation comprising 100% biomass-derived polyester polyol (85 parts BASAB and 15 parts ethylene glycol) and potassium octoate (Ko) and a B2-PC formulation comprising 100% polyester-polyol ( 85 parts of BASAB and 15 parts of ethylene glycol) and potassium carboxylate (Pc) are shown in Table 3. The reference formulation (100/0) contains 100% petroleum-derived polyester polyol (PS 2412) and potassium octoate (Ko).
    Reference(100/0) 35/65 0/100 B1-K0 B2-PC PS 2412 100 a 35 0 o a 0 a Wording BASAB o a 65 100 85 a 85 EG o a 0 0 15 a 15 a
    BE2017 / 5586
    Ko 0.12 b 0.12 b 0.12 b 0.17 b 0 b N205 0.03 b 0.03 b 0.03 b 0.08 b 0.22 b Tegoamine C41 0.08 b 0.08 b 0.08 b 0.21 b 0.11 b Pc 0 b 0 b 0 b 0 b 0.97 b Time to 10 19 24 12 11 creaming (s) Characteristic times,, J filament (s) 60 76 n.m 134 82 Time to tack free 148 100 > 300 166 120 foam (s)
    Table 3: Catalyst content and characteristic times of the different PUIR foams. a : expressed in shares relative to the final product, b : expressed in percent relative to the final product, nm: not measurable.
    The B1-K0 formulation, which is catalyzed with the same catalyst as the reference but in greater amount, shows a time to cream formation relatively comparable to that of the latter (Table 3). B1-K0, however, exhibits a time to filament which shows a delay of 74 sec compared to that of the reference and an delay of 18 sec in time to tack free foam. The results thus show that the formulation B1-K0 shows different characteristics with regard to the characteristic times, compared to the reference. These differences, especially the extension of the characteristic times, are an advantage in the formation of hard PUIR foam in block, formed in molds.
    On the other hand, the formulation B2-PC recovered from biomass exhibits a catalyst different from that of the reference. We find that the time to creaming of this formulation as well as the time to filming are closer to the times of the reference formulation, while the time to tack free foam of B2-PC 28 is faster than that of the reference. The results thus show that the formulation B2-PC shows different characteristics with regard to the characteristic times, compared to B1-K0. The fact that this formulation has shorter characteristic times comparable to those
    0 of the reference, is an advantage for the methods of in-line production of rigid PUIR foam insulation panels.
    Apart from the characteristic times, the main difference between these formulations is macroscopic.
    The characteristics of the foams of the previous formulations were
    Namely compared. This shows that the B2-PC foam has a characteristic surface, with a smooth outer layer, similar to the reference, while B1-K0 has an irregular surface (Figure 3, b and c) (presence of cracks and bubbles).
    BE2017 / 5586
    The main hypothesis that can explain these differences in surface area between the B1-K0 foam on the one hand and the B2-PC and reference foams on the other is based on the differences in time to filament formation. Namely, the time to 134-sec of B1-K0 is longer than that of B2-PC, which is 82 sec.
    Since formulations B1-K0 and B2-PC contain the same polymer, the longer time to filament reflects a longer time to obtain the same degree of polymerization, and thus an instability or brittleness of the material during this polymerization step. This brittleness causes the walls of the cells to collapse under the pressure of the expanding gases, causing cracks and bubbles visible on the surface of the foam. This is done before the foam cures and the end of the polymerization, ie before the end of the foaming.
    The evolution of the internal temperature of the foams during foaming was evaluated (Figure 2). This clearly shows that the temperature of the B1-PC foam rises faster than that of the B1-K0 foam. This reflects greater reactivity of the reaction medium, perhaps due to the choice of the catalysts. Furthermore, the B1-K0 sample exhibits a foaming temperature lower at each point than that of the other two foams. The curve of the foaming temperature of B1-PC exhibits a profile similar to that of the reference, up to the characteristic inflection point of the latter, corresponding to the trimerization of the isocyanates.
    Finally, we note that the global kinetics of the B2-PC PUIR foam are very close to that of the reference foam and that the foaming temperature is 140 ° C, which is similar to the foaming temperature of the petroleum derived reference foam.
    The better foaming reactivity and thus the better foaming kinetics was obtained by increasing the foaming temperature (in particular by the change in catalyst), by increasing the amount of BASAB in the mixture and by adding a copolyol.
    Thus, these results demonstrate that a formulation of PUIR foam comprising biomass-derived polyester polyols and exhibiting characteristics comparable to that of a petroleum-based polyester polyols formulation can be obtained. Such a formulation is particularly advantageous for rapid and continuous in-line production of foam blocks or panels. On the other hand, these results also show that other types of PUIR formulations also come from biomass
    BE2017 / 5586 recovered polyester polyols and exhibit slower foaming characteristics than the reference foam based on petroleum-derived polyester polyol can be obtained. Such formulations are advantageous for the production of foam in a molded block. The polyester polyol (BASAB) recovered from biomass is special in that it provides the ability to adjust the foam characteristics or kinetics of the foam according to the desired applications or manufacturing methods.
    c. Closed cell content and foam morphology
    The morphologies of the resulting foams were yellowed by SEM. Figure 4 shows the SEM images of samples of the PUIR reference foam cut in the longitudinal and transverse direction relative to the rise of the foam after the foaming. In the transverse direction, a typical honeycomb structure is clearly noticeable. The longitudinal stretching of the cell is characteristic of a partially free foaming performed in an open cylindrical container (M. C. Hawkins, J. Cell. Plast., 2005, 41, 267-285). Using the SEM observations, the anisotropic coefficients R of the studied PUIR foams: 100/0, 35/65, 0/100, B1-K0 B2-PC could be measured (Table 4).
    The anisotropic coefficients (R) represent the shape of the cells of a foam. The coefficient R is the ratio of the two measurable maximum diameters in a cell. For example, a perfectly round cell will have a coefficient R equal to 1 (all diameters are identical in a circle). An elongated oval-shaped cell, on the other hand, will exhibit a coefficient R greater than 1. In the present study, the coefficients R are determined in two different planes. In this way, the shape of the cells can be evaluated in a cross section across the direction of expansion of the PUIR foams and also in the longitudinal direction of the expansion of the PUIR foams.
    We find that the coefficients R of the formulations 100/0, B1-K0 and B2-PC in the longitudinal direction are close to 1.8. This means that the cells of the foam have an oval shape. In the direction transverse to the rise of the foam, the calculated coefficient R is closer to 1.2. This indicates that the shape of the cells is closer to the spherical shape here. The 35/65 and 1/100 formulations exhibit less similar coefficients R. The large cell size distribution of these foams, which translates into significant standard deviations from the entirety of their Feret diameters in the longitudinal and transverse directions, results in cells with very anisotropic shapes.
    BE2017 / 5586
    If we compare the reference foam to the 34/65 and 0/100 foams, the latter display cells about 2 to 4 times larger than the petroleum-based reference 100% polyol in all directions studied. The size of the cells is a criterion that influences the final properties of a PUIR5 foam. For example, larger cells offer less good heat insulating properties.
    If we compare the reference foam with the biomass-derived PUIR foams B1-K0 and B2-PC, the latter show cells with sizes almost equal to those of the reference in all directions (Table 4). Compared to 35/65 and
    0/100 formulations have significantly smaller cell sizes. This significant gain on the recovered from biomass is an advantage for its use in the field of building thermal insulation, for example.
    _
    100/0 35/65 0/100 B1-K0 B2-PC Feret max, DF max 408 ± 643 ± 860 ± 524 ± 521 ± (p.m) 117 189 170 215 123 Longitudinal Feret min, Df 171 1 2 * * * 223 ± 518 550 ± 295 ± 298 ± direction (p.m) 44 ± 147 130 112 67 R = D F max / D F min 1.83 1.25 1.56 1.78 1.75 Feret max, DF max 275 ± 940 ± 1240 ± 386 ± 448 ± (p.m) 72 260 380 123 122 Transverse Feret min, Df 171 7 242 ± 420 ± 990 ± 324 ± 347 ± direction (p.m) 72 90 300 116 122 R = F D max / Df 171 '17 1.14 2.24 1.25 1.19 1.29
    Table 4: Feret diameter and anisotropy coefficient (R) of all PUIR foams in the longitudinal and transverse directions relative to the expansion direction of the foams
    The previous study of the kinetic foaming profiles has shown
    0 that the temperatures reached by the reaction medium during the foaming process are lower for the foams B1-K0 and B2-PC. These low temperatures are responsible for a delay in the trimerization of the isocyanates, which is the cause of the lower reaction rates (longer time to filament formation). The longer time for filament formation leads to an increase in the coalescence of the gas bubbles
    BE2017 / 5586 prior to the full polymerization of the polyurethane and polyisocyanurate net of the foam, which explains why larger cell sizes are observed for the foams recovered from biomass.
    d. Properties of the foams: density, closed cell content and chemical composition (FT-IR)
    100 /0 35/65 0/100 B1-K0 B2-PC Apparent density 31.1 39.8 n.b. 33.8 ± 2 32.8 ± 0.8 (kg / m 3)Content closed 95 <50 <50 86 85 cells (%)
    Table 5: Properties of the PUIR foams. note: not determined
    The apparent density for the foams in Table 5 is comparable for all PUIR formulations, and is between 31 and 40 kg / m 3 . The 35/65 foam exhibits the highest apparent density (39.8 kg / m 3 ) and is also the foam that exhibits the lowest foaming temperature. The low foaming temperature has limited the expansion of the blowing agent, resulting in a slightly denser foam than the others. The foams B1-K0 and B2-PC, with optimized formulation, do not exhibit this characteristic since their density is closer to that of the reference.
    To confirm the chemical nature of the resulting foams, an infrared spectrometry (FT-IR) analysis was performed. The FT-IR spectra of the formulated foams are shown in Figure 5. All foams show characteristic peaks as the stretching vibrations of the NH groups, at 3400-3200 cm -1, and the stretching vibrations of the C = O bond present in the urethane groups at 1705 cm -1 . The signals observed at 2955 cm -1 and 2276 cm -1 are attributed respectively to the stretch of the CH bond of the polyurethane backbone and to the remaining unreacted NCO groups. The signal at 1596 cm -1 corresponds to the Ar-H stretch in the phenyl groups from the polymer polyisocyanate. The bulging signal of the NH groups is at 1509 cm -1 and the CO elongation at 1220 cm -1 . Then, a strong signal at 1408 cm -1 is attributed to the presence of isocyanurate rings typical of the PUIR foam formulation.
    From this we can therefore conclude that the foams obtained, and in particular the foams based on polyester polyol obtained from biomass, have a chemical composition similar to that of the foam based on 100%
    BE2017 / 5586 petroleum extracted polyester polyol. This means that the differences in characteristic times or foaming temperatures observed have not prevented the proper formation of a PUIR net in all formulations.
    e. Thermal resistance of the foams
    The thermal stability of the samples from the PUIR foams was studied by thermogravimetric analysis of the TGA and DTGA curves of all PUIR foams (not shown). All PUIR foams exhibit classic two-stage weight loss. The PUIR foams B1-K0 and B2-PC exhibit a thermal stability higher than that of the reference foam. Table 6 shows the temperatures at the maximum of the curve derived from the weight loss: Td eg maxi and Td eg max2. Td eg maxi is close to 300 ° C for the three foams. Td eg max2 is observed at a temperature of 523 ° C for the reference foam, while foams B1-K0 and B1-PC exhibit higher Td eg max2 of 538 and 534 ° C, respectively.
    In addition, they exhibit a shoulder on the DTGA curve at over 600 ° C. The first Td eg maxi corresponds to the decomposition of the urethane bond. The urethane linkage decomposition mechanism has been widely described as a simultaneous dissociation of the isocyanate and alcohol, the formation of a primary and secondary amine, and the formation of olefins. The second Td eg max2 is more pronounced than the first Td eg maxi and is linked to the double breakdown of the isocyanurate and the cleavage of the carbon-carbon bonds (JE Sheridan and CA Haines, J. Cell. Plast., 1971, 7, 135-139). The first weight loss is less significant because an isocyanurate bond exists. Isocyanurates are more thermally stable than urethane due to the absence of labile hydrogen and therefore the second weight loss is mainly due to the carbon-carbon splitting (HE Reymore et al., N. J. Cell. Plast., 1975, 11, 328-344 ). In the specific case of B1-K0 and B2-PC, Td eg max2 is higher, which is attributed to their higher concentration of BASAB compared to the reference. The higher OH value of the BASAB compared to the PS 2412 results in a higher formation of urethane bonds and the cross-linking of the PUIR network (AA Septevani, et al Ind. Crops Prod., 2015, 66, 16-26; I Javni, ZS et al., J. Appl. Polym. Sci., 2000, 77, 1723-1734) making it more resistant to thermal degradation.
    Table 6 also shows two temperatures corresponding to 50% (Td eg 50%) and 100% (Td eg 100%) weight loss of the PUIR foams, respectively. Td eg so% and Td eg ioo%. The latter are comparable between the reference foams and B1-K0. Sample B2PC shows a higher Td eg so% and Td eg wo% than that of the reference foam, which is consistent with the previous observations. In addition, formulation B2-PC makes it possible to use a
    BE2017 / 5586 foam with a better temperature resistance than the reference foam based on polyester polyol obtained from petroleum.
    Sample TGA TGD Tdeq50% (C) Tdeq100% (° C) Tdeq maxi Tdeq max2 0% 448 645 301 523 (Reference)B1-K0-PC 458 632 300 538 B2-PC 499 690 295 534
    Table 6: Degradation temperatures at 95% and 50% weight loss of samples of PUIR5 foams
    Closed-cell PUIR foams based on the total replacement of a petroleum-derived polyester polyol with the biomass-derived polyester polyol were prepared with success. The optimization of the formulation has made it possible to obtain a foaming kinetics comparable to that of the petroleum-derived reference foam. The Study was conducted using two different catalysts. The PUIR foams have a high closed cell content, which is extremely interesting to meet the thermal insulation characteristics. Finally, the most notable point relates to the biomass-derived PUIR foams that exhibit a thermal breakdown stability higher than that of the petroleum-derived reference foam.
    BE2017 / 5586
    权利要求:
    Claims (13)
    [1]
    CONCLUSIONS
    A hard foam or composition permitting to obtain a hard foam comprising a polyester polyol or a polymer comprising a polyester polyol, said polyester polyol being obtained by a first polycondensation (a) of a C3-C8 sugar alcohol Z and two C4 -C36 diacids Y and Y 'which may be identical or different and a second polycondensation (b) of the product obtained in (a) with two C2-C12 diols X and X' which may be identical or different.
    [2]
    2. A hard foam or composition which makes it possible to obtain a hard foam, comprising a polyester polyol or a polymer comprising a polyester polyol, said polyester polyol having the general formula Rx-Ry-Z-Ry'-Rx ", in which
    - Z is a C3-C8 sugar alcohol, preferably C4-C7, typically C5-C6,
    - Ry and Ry 'diesters are of the formula -OOC-C n -COO- where n is between 2 and 34, preferably between 3 and 22, typically between 4 and 10,
    -Rx and Rx are C2-C12 mono-alcohols, which may be identical or different, preferably C3-C8, typically C4.
    [3]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 and 2, characterized in that the sugar alcohol Z is selected from glycerol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol.
    [4]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 3, characterized in that the diacids Y and Y 'are independently selected 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.
    [5]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 4, characterized in that the diols X and X '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 mixtures thereof.
    BE2017 / 5586
    [6]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 5, comprising at least one reaction catalyst, at least one blowing agent, a stabilizing agent, at least one polyisocyanate with a functionality of at least equal to 2, optionally, at least one copolyol.
    [7]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 6, characterized in that it comprises at least one C2-C8 copolyol.
    [8]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 7, characterized in that it has a polyester polyol / co-polyol (s) ratio of from 70/30 to 99/1, preferably 75/25 to 95/5.
    [9]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 8, characterized in that the at least one copolyol is selected from ethylene glycol, glycerol, 1,4-butanediol, butane-1,3-diol,
    1,3-propanediol, propane-1,2-diol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propylene glycol, 3oxapentane-1,5-diol, 2- [2- (2-hydroxyethoxy) ethoxy] -ethanol, benzene-1,2,4-triol, benzene 1,2,3-triol, benzene-1,3,5-triol, sorbitol, erythritol, xylitol, araditol, ribitol, dulcitol, mannitol and volemitol.
    [10]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 9, characterized in that it comprises:
    at least 1 to 100 parts of a polyester polyol according to the invention,
    0 to 70 parts of at least one copolyol, preferably from 1 to 50 parts of at least one copolyol,
    150 to 500 parts of a polyisocyanate,
    0.5 to 5 parts of a catalyst, typically an amine catalyst,
    0.5 to 15 parts of a blowing agent, typically 0.5 to 12 parts, preferably of a chemical blowing agent,
    0 to 5 parts of a stabilizer such as a polyether-silicone copolymer, and
    0 to 20 parts of a fire retardant.
    BE2017 / 5586
    [11]
    Hard foam or composition permitting obtaining a hard foam according to any one of claims 1 to 9, characterized in that it is 0.5 to
    [12]
    12 parts of chemical blowing agent such as water and 0 to 60 parts of a physical blowing agent.
    12. Hard foam panel or block comprising a hard foam according to any one of claims 1 to 11.
    [13]
    13. Method of thermal, acoustic or cryogenic insulation or method of filling, impermeability, sealing or improving the buoyancy of a building or object by depositing or introducing hard blocks or panels
    Foam according to claim 12 or by spraying or injecting a hard foam or an composition which makes it possible to obtain a hard foam according to any one of claims 1 to 11.
    BE2017 / 5586
    a.
    ISO
    160
    140
    P 120
    ICO σ
    v e
    co
    d.
    120.00
    100.00
    80.00
    60.00
    40.00
    20.00
    0.00
    Max. Height (%)
    100
    150
    Time (s)
    200 250 300
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    同族专利:
    公开号 | 公开日
    BE1024923B1|2018-08-22|
    US11180605B2|2021-11-23|
    BE1024969A1|2018-08-29|
    CN109843847A|2019-06-04|
    BR112019003666A2|2019-05-21|
    FR3055335B1|2020-03-27|
    WO2018037376A1|2018-03-01|
    US20190194379A1|2019-06-27|
    EP3504179B1|2022-03-16|
    CA3034943A1|2018-03-01|
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    CA3034942A1|2018-03-01|
    EP3504179A1|2019-07-03|
    CA3036188A1|2018-03-01|
    FR3055335A1|2018-03-02|
    BE1024970A1|2018-08-29|
    US20190194380A1|2019-06-27|
    FR3070393A1|2019-03-01|
    BE1024923A1|2018-08-10|
    WO2018037373A1|2018-03-01|
    BE1024969B1|2018-09-04|
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    FR3070392B1|2019-09-06|
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    法律状态:
    2018-10-25| FG| Patent granted|Effective date: 20180904 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1601253A|FR3055335B1|2016-08-24|2016-08-24|PROCESS FOR THE PRODUCTION OF POLYOL POLYESTERS AND THEIR USE IN POLYURETHANE|
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