Formulations based on bio-sourced polyols

Abstract

BIO-BASED POLYOL FORMULATIONS The present invention relates to formulations for obtaining polymer materials comprising at least one difunctional reagent capable of reacting with a polyol and a polyol capable of reacting with said at least difunctional reagent, said polyol being an aromatic polyol at least partially bio-based. The invention also relates to the use of said formulations for the manufacture of polyurethanes, polyesters, polycarbonates, and epoxy resins, intended for the production of coatings in general, paints, elastomers, sealants, and adhesives. Fig.: none

Description

Title of the invention: Formulations based on bio-sourced polyols

[0001] The invention relates to bio-based polyol formulations usable in the manufacture of polymer resins. More specifically, the present invention relates to bio-based polyol formulations usable in the field of polymers in general and more particularly in the manufacture of polyurethane, polyester, polycarbonate, epoxy, urethane-(meth)acrylate, polyester-(meth)acrylate, epoxy-(meth)acrylate, polyether-(meth)acrylate resins, as well as their silicone and other derivatives.

[0002] Polyol-based formulations are now very widely used and the polyols used are of very diverse natures, depending on the uses for which they are intended, whether in the field of polymers, for example as polymerization reagents, wetting additives, plasticizers, dispersants, smoothers, coalescing agents, emulsifiers, reactive diluents and others, in diverse fields, such as for example paints, coatings, resins, elastomers, sealants, adhesives, flexible and rigid foams to name only the main ones.

[0003] In order to further improve the properties of polyol formulations, the products in which they are used, and in particular to reduce their environmental impact, the industry is constantly looking for polyol-based formulations with properties compatible with the intended uses, while favouring bio-based raw materials.

[0004] There are already many formulations on the market based on bio-based polyols, such as bio-based polyethers, bio-based polyesters from which they are derived, bio-based aromatic polyols, and others, to name only a few typical but non-limiting examples.

[0005] Depending on the intended fields of application, however, there are a number of difficulties associated with the use of such bio-based polyol formulations, for example when used for the manufacture of polyurethane, as indicated, for example, in ACS, Sustainable Chem. Eng., (2021), 9, 10664-10677. Among these difficulties, the most frequently and generally encountered are the following: • difficulties in sourcing raw materials to manufacture polyols, which compete with the food chain. • Reproducibility problems during polyol preparation, • Reactivity problems of bio-based polyols, often low, • Low miscibility of these bio-based polyol formulations with other ingredients ingredients necessary for the manufacture of materials, for example low miscibility with certain isocyanates and other comonomers and / or oligomers, other polyols, surfactants, catalysts or even swelling agents, thus making their uses difficult or limiting.

[0006] Formulations based on bio-sourced polyols are today prepared from natural oils, mainly vegetable or animal, among which we can cite, by way of non-limiting examples, castor oil, palm oil, tall oil (or “tall oil” in English).

[0007] Other formulations based on bio-based polyols are described, for example, in document CN102660014 A, where an ethoxylated / propoxylated cardanol is used in a Mannich reaction to prepare a polyurethane material. In document US2012129963, as in document WO2008017476, a non-alkoxylated formo-cardanol resin is used to synthesize a polyurethane material.

[0008] Document WO2018172222 uses phenolic-type polyols, without any mention of bio-based carbon atoms. Ethoxylated and propoxylated formo-phenolic resins are also described. Document CN103073689 discloses polyols with a very high hydroxyl number, which may be problematic in certain specific applications.

[0009] There therefore remains a need to have compatible and versatile bio-based polyol formulations to be integrated into compositions for obtaining materials, and in particular for obtaining polymers.

[0010] Thus, and according to a first aspect, the invention relates to a formulation for obtaining a polymer material comprising: - at least one difunctional reagent capable of reacting with a polyol, - a polyol capable of reacting with said reagent, at least difunctional, said polyol: * being an aromatic polyol * having a hydroxyl value less than or equal to 200 mg KOH g1, * an average number of features greater than or equal to 2 and, * a content of atoms derived from biomass greater than 30%.

[0011] The formulation according to the present invention is particularly suitable for obtaining polymer materials selected from polyurethane, polyester, polycarbonate, epoxy, urethane-(meth)acrylate, polyester-(meth)acrylate, epoxy-(meth)acrylate, and polyether-(meth)acrylate resins, as well as their silicone derivatives and others, to mention only the principal polymer materials that can be obtained from the formulation according to the present invention. The formulation of the present invention is particularly suitable for the preparation of polyurethanes.

[0012] It must be understood that the formulation of the present invention which includes a Aromatic polyol at least partially bio-based allows the preparation of polymers in which the aforementioned aromatic polyol defined above and at least one difunctional reagent are involved.

[0013] Among the difunctional reagents that can be used in the formulation of the present invention, examples include, but are not limited to, at least difunctional isocyanates, at least difunctional carboxylic acids, at least difunctional epoxies, and others. Mixtures of at least difunctional reagents can be considered in the formulation of the present invention.

[0014] According to a preferred embodiment, the formulation of the present invention is particularly suitable for the manufacture of polyurethanes, and the at least difunctional reagent is chosen from at least difunctional isocyanates, preferably from difunctional isocyanates and multifunctional isocyanates.

[0015] The isocyanates that can be used within the scope of the present invention are of any type well known to those skilled in the art, and in particular are organic isocyanates, and more especially difunctional organic isocyanates. Non-limiting examples of such diisocyanates include aliphatic diisocyanates having a hydrocarbon group comprising up to 18 carbon atoms, cycloaliphatic diisocyanates having a hydrocarbon group comprising up to 15 carbon atoms, aromatic diisocyanates having a hydrocarbon group comprising from 6 to 15 carbon atoms, and arylaliphatic diisocyanates having a hydrocarbon group comprising from 8 to 15 carbon atoms. It is understood that two or more at least different difunctional isocyanates may be included in a mixture in the formulation of the present invention, in any proportions.

[0016] Preferred diisocyanates include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, diphenylmethane diisocyanates, particularly diphenylmethane-4,4'-diisocyanate, polymethylenepolyphenyl isocyanates, and mixtures of two or more of these in any proportion. Modified isocyanates that are at least difunctional, such as those comprising one or more carbodiimide groups, methane groups, isocyanurate groups, urea groups, and biuret groups, may also be suitable.

[0017] The polyol capable of reacting with said reagent, at least difunctional in the formulation of the present invention, is an aromatic polyol as previously stated. By aromatic polyol, we mean a polyol comprising at least one aromatic function, preferably an oligomer or polymer whose repeating unit comprises at least one, two, or three aromatic function(s), preferably one or two aromatic function(s), and preferably yet another aromatic function.

[0018] Furthermore, the polyol that can be used in the formulation of the invention exhibits a hydroxyl value (HV) less than or equal to 200 mg KOH g1, preferably less than or equal to 160 mg KOH g1. In one embodiment of the invention, the hydroxyl value is equal to or greater than 30 mg KOH g1, preferably equal to or greater than 50 mg KOH g1. According to a most preferred embodiment of the invention, the polyol that may be used in the formulation of the invention has a hydroxyl value equal to or greater than 30 mg KOH g1 and less than or equal to 200 mg KOH g1, preferably equal to or greater than 50 mg KOH g1 and less than or equal to 160 mg KOH g1.

[0019] The hydroxyl index is a parameter well known to those skilled in the art which can be determined according to the DIN 53240-2 standard.

[0020] The polyol that may be used in the formulation of the invention also has an average number functionality greater than or equal to 2, preferably greater than or equal to 3. The lower the average functionality of the polyol, the more flexible the structures of the resulting polymers will be. Conversely, the higher the average functionality of the polyol, the more rigid the structures of the resulting polymers will be.

[0021] By "number-average functionality," we mean the average number of hydroxyl groups (OH groups) per mole of polyol. More precisely, the number-average functionality (Fou) is calculated according to the following formula: Fou = (Mwp / Mwr) * n0H where: - Mwf represents the number-average molar mass of the aromatic polyol, - Mwr represents the molar mass of the repeating motif in the aromatic polyol, and - n0H represents the number of hydroxyl functions present on the repeating motif, Mwf being determined by size-exclusion chromatography and MwR and n0H being able to be determined by any analytical means well known to those skilled in the art, for example by NMR analysis.

[0022] In one embodiment, the average number of functionalities is generally less than 1000, more often less than 500, preferably less than 100, preferably still less than 50 and advantageously less than 20. In a still preferred embodiment, the polyol has an average number of functionalities between 2 and 1000, preferably between 2 and 500, preferably still between 2 and 100, better still between 2 and 50, most often between 2 and 20, for example between 3 and 20, inclusive.

[0023] Finally, the polyol that may be used in the formulation of the invention is at least partly bio-based and, more specifically, said polyol comprises a biomass-derived atom content greater than 30%, as indicated above, and preferably greater than 40%, a content measured according to the standard NF EN 16785-1 (January 2016).

[0024] In a preferred embodiment, the aromatic polyol of the formulation of the present invention is an oligomer or polymer obtained by polycondensation of an aromatic phenol or an aromatic phenol derivative with at least one compound selected from aldehydes and ketones. Aromatic phenol is understood to mean aromatic phenols optionally substituted by one or more hydrocarbon chains. Preferred examples of such aromatic phenols are aromatic phenols that are at least partially or entirely bio-based, such as cardanol, cardol, or methylcardol.

[0025] By "aromatic phenol derivative" is meant the derivatives of the aromatic phenols described above, and in particular the alkoxylates of the aromatic phenols described above, that is to say the aromatic phenols in which at least one hydroxy function is substituted by a (poly)ethoxy, (poly)propoxy, (poly)butoxy, (poly)tetramethylenoxy, and others chain, the chain having from 1 to 100, preferably from 1 to 50 repeating motifs, derived from aromatic phenols obtained according to techniques well known to those skilled in the art and for example by reaction of said aromatic phenols with one or more moles of an epoxy or oxirane type compound, and preferably and respectively among ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran.

[0026] The aldehydes and ketones which can be used to obtain an aromatic phenol oligomer or polymer as indicated above can be of any type well known to those skilled in the art and in particular, and preferably, those chosen from formaldehyde, as well as any hydrocarbon chain aldehyde comprising from 2 to 20 carbon atoms, preferably from 2 to 16 carbon atoms, dimethyl ketone as well as any hydrocarbon chain ketone comprising from 4 to 20 carbon atoms, preferably from 4 to 16 carbon atoms.

[0027] Aromatic phenol oligomers and polymers are particularly preferred, where two aromatic rings are separated by a single carbon atom, itself unsubstituted or possibly substituted by one or two hydrocarbon chains comprising from 2 to 20 carbon atoms, preferably from 2 to 16 carbon atoms.

[0028] Examples of aromatic polyols that have proven particularly suitable for the needs of the present invention are oligomers and polymers obtained by polycondensation of an aromatic phenol or aromatic phenol derivative with formaldehyde. Among these aromatic polyols, those selected from formocardanol resins and alkoxylated formocardanol resins are particularly preferred, where the term "alkoxylated" includes ethoxylated, propoxylated, and butoxylated resins, as well as (poly)tetramethylene ether, obtained, for example, by reaction with tetrahydrofuran, as indicated above. Particularly preferred aromatic phenols are alkoxylated formocardanol resins, and even better, ethoxylated and / or propoxylated formo-cardanol resins.

[0029] Such alkoxylated formo-cardanol resins are well known to those skilled in the art and are commercially available or readily prepared using known methods. For the purposes of the invention, alkoxylated formo-cardanol resins that are bio-based and that comprise a biomass-derived atom content greater than 30%, as previously stated, and preferably greater than 40%, measured according to standard NF EN 16785-1 (January 2016), are particularly preferred.

[0030] The molar ratio of the reactive functions of the polyol(s) relative to the reactive functions of the at least difunctional reactant(s) capable of reacting with said polyol(s) can vary considerably depending on the expected polymerization product and the intended use of said expected polymerization product. However, a molar ratio between 0.7 and 1 is preferred, and even more preferably, a molar ratio between 0.8 and 1.

[0031] The formulation of the present invention may further include other components well known to those skilled in the art, among which, in a completely non-limiting manner, other polyols, other at least functional reagents capable of reacting with the polyol(s), rheological agents, colorants, preservatives, catalysts, foaming agents, non-foaming agents, surfactants, flame retardants, antioxidants, compatibilizing agents, and others, as well as mixtures of two or more of them.

[0032] Examples of additional polyols which have proven particularly suitable for the needs of the present invention are, without limitation, poly-etherpolyols, for example those obtained by condensation of an alkylene oxide or a mixture of alkylene oxides with glycerol, ethylene glycol, trimethyl-olpropane, pentaerythritol, neopentyl glycol, isosorbide, polyester polyols, for example those obtained from polycarboxylic acids, in particular oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, terephthalic acid, with glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, neopentyl glycol and others.

[0033] Polyetherpolyols obtained by adding alkylene oxides, in particular ethylene oxide and / or propylene oxide, to aromatic amines, in particular the mixture of 2,4-toluene diamine and 2,6-toluene diamine, may also be suitable as additional polyols which may be added to the formulation of the present invention.

[0034] The aromatic polyols described above offer numerous advantages, including compatibility with other polyols that may be present in the formulation and, more generally, with all other components of the formulation according to the invention, while being at least partially bio- sourced.

[0035] According to a second aspect, the invention relates to the use of an aromatic polyol as described above for the manufacture of polymers, in particular with one or more at least difunctional reagents, and optionally one or more additives chosen from among wetting additives, plasticizing agents, dispersing agents, smoothing agents, coalescing agents, emulsifiers, and reactive diluents, to name only the main additives commonly used and well known to those skilled in the art.

[0036] The use according to the invention finds numerous applications in a wide variety of fields, including, but not limited to, the polymer production industry, the production of coatings in general, the production of paints, the production of elastomers, and the production of sealants and adhesives, to name only the main products of interest. According to one embodiment, the polyols defined above are particularly well suited as a component of a formulation according to the invention intended for the manufacture of polymers, and preferably for the manufacture of polyurethane, polyester, polycarbonate, epoxy, urethane-(meth)acrylate, polyester-(meth)acrylate, epoxy-(meth)acrylate, and polyether-(meth)acrylate resins, as well as their silicone derivatives, and very advantageously for the preparation of polyurethanes.

[0037] The polyurethane obtained from the formulation of the present invention has numerous possible uses in various industrial fields, including, but not limited to, coatings in general, paints, adhesives, sealants, and elastomers. The polyurethanes thus produced can be in any form well known to those skilled in the art, and in particular in liquid form, as flexible foam or rigid foam, and other forms.

[0038] The invention is now illustrated by means of the following examples, which in no way limit the invention, the scope of which is defined by the claims annexed to this description. Examples

[0039] Example 1: Synthesis of an aromatic polyol Step 1:

[0040] In a 4-liter nitrogen-inerted three-necked flask, cardanol (1854 g, 6.2 mol) and para-formaldehyde (146 g, 4.9 mol) are loaded at room temperature. The mixture is heated to 80°C, and then 8.9 grams of 32% HCl are added. The reaction is maintained at 80°C for 30 minutes and then heated to 110°C (distillation apparatus). The reaction is maintained for 4 hours, and then a gradual vacuum is applied (15 kPa). The reaction is maintained for 1 hour and 30 minutes at 120°C. After returning to atmospheric pressure and 80°C, 11.1 grams of KOH are added. After stirring for one hour, the mixture is cooled and the product is collected without further treatment. The resulting polymer has a number-average weight of 1300 g mol⁻¹, determined by NMR. Step 2:

[0041] In an alkoxylation reactor, 1200 g of the product obtained in Step 1 and 10.6 g of KOH are introduced. They are dehydrated under vacuum at 110°C for one hour to achieve a water content of less than 0.1%. The reactor is purged with nitrogen and the stirring speed is set at 1100 rpm*. The reaction medium is heated to 155-160°C. Ethylene oxide (1293 g) is introduced slowly while cooling to maintain the reactor at the set temperature. Once all the ethylene oxide has been introduced and the pressure has stabilized, the medium is cooled to 70°C and 6.8 g of acetic acid are added.

[0042] The polymer obtained has a hydroxyl value of 84 mg KOH g1, an average number functionality of 4.2, and a bio-based atom content of 45%. This polyol is named Polyol A, and it conforms to the polyol of the formulation of the present invention.

[0043] Example 2: Miscibility in a polyol formulation

[0044] Formulated polyol compositions are prepared containing a mixture of polyol, a blowing agent, and a catalyst mixture. All formulations have the same quantities of blowing agent and catalyst. The polyols used have the characteristics shown in Table 1 below: [Table 1] Polyol IOH (mgKOH g-1) Functionality Bio-based atom content (%) Polyol M420 415 4 0 Polyol A® 84 4.2 45 Polyol B® 440 4 78 Polyol C4) 475 4 60 (1) Non-bio-based polyol, marketed by PCI (not part of the invention)

[0045] (2) Bio-based polyol A according to the invention, prepared according to Example 1

[0046] (3) Bio-based polyol B (not part of the invention), GX9102 marketed by Cardolite

[0047] (4) Bio-based polyol C (not part of the invention), GX9103 marketed by Cardolite

[0048] Formulation 1 does not contain a bio-based polyol. Formulation 2 substitutes a polyols of formulation 1 are replaced by a bio-based polyol A according to the invention. formulations 3 and 4 also contain bio-based polyols B and C in quantities equivalent to formulation 2, but whose properties do not conform to the invention.

[0049] The formulated polyols comprising the additional components and the blowing agent are presented in Table 2 below and expressed in pph. [Tables 2] Formulation # 1 2 3 4 Terate HT 5510® 55 55 55 55 Voranol CP 450® 22.5 22.5 22.5 22.5 Polyol M420 22.5 Polyol A 22.5 Polyol B 22.5 Polyol C 22.5 (1,1,3,3-tetramethylguanidine)® 7.23 6.42 7.31 7.41 DABCO T120® 0.29 0.26 0.29 0.29 Tegostab B84711® 1.47 1.5 1.48 1.5 Tris-(l-chloro-2-propyl) phosphate(10) 19.4 17.2 19.62 19.91 Added Water 1.66 1.47 1.68 1.7 1233zd 14.45 12.82 14.6 14.82 TOTAL B-SIDE 144.5 139.67 144.98 145.63 (5) Polyester polyol marketed by Invista (IOH = 250-265)

[0050] (6) Polyether polyol marketed by Dow

[0051] (7) Amino catalyst marketed by Sigma-Aldrich

[0052] (8) Metallic catalyst marketed by Evonik

[0053] (9) Foam stabilizer marketed by Dow

[0054] (10) Flame retardant (tris (l-chloro-2-propyl) phosphate)

[0055] The formulations are prepared by successively adding the desired quantity of each component and left to stand for 72 hours at room temperature. The possible appearance of several phases is observed, as indicated in Table 3 below. [Tables 3] Formulation # 1 2 3 4 Miscibility miscible miscible biphasic biphasic

[0056] The formulations are prepared and aged for 7 days at 50°C. Polyurethane foams are prepared using the formulations described in Table 2 above and adding the isocyanates as indicated in Table 4 below. [Table 4] Formulation # 1 2 3 4 Ongronat 2100(11) 143.52 115.94 146.17 149.85 ROH index'121 119 119 119 119 B / A(13' 1.01 1.20 0.99 0.97 Blowing agent rate (% wt) 5 5 5 5 (11) Isocyanate marketed by BorsodChem

[0057] (12) molar ratio [(NCO functions) / (OH functions)] x 100

[0058] (13) weight ratio (formulated polyols / isocyanates)

[0059] The growth kinetics of the foam are presented in Table 5 below. The free growth reaction profile is defined by the terms and definitions specified in standard NF EN 14315-1.

[0060] Cream time is the time elapsed between the start of the mixing procedure and the start of the foam growth (measured in seconds).

[0061] The yarn time is the time elapsed between the moment when the procedure of stirring the mixed components begins and the moment when, by means of a rod applied to the surface of the foam, a polymer chain can be extracted from the surface of the foam (measured in seconds).

[0062] The tack-free time is the time elapsed between the moment when the procedure of stirring the mixed components begins and the moment when, by means of a rod applied to the surface of the foam, it is established that the surface is no longer tacky (measured in seconds). [Tables 5] Formulation # 1 2 3 4 Creaming time(s) 5 4 5 6 Threading time(s) 12 12 26 25 Tack-free time(s) 16 15 37 34

[0063] It is noted that formulation 2 has identical reactivity to formulation 1. Formulations 3 and 4 have significantly lower reactivities and cannot can be used as a replacement for formulation 1.

Claims

Demands

1. Formulation for obtaining a polymeric material comprising at least one difunctional reagent capable of reacting with a polyol and a polyol capable of reacting with said at least one difunctional reagent, said polyol: * being an aromatic polyol * having a hydroxyl number less than or equal to 160 mg KOH g1, determined according to DIN 53240-2 * a number-average functionality greater than or equal to 2, and, * a biomass atom content greater than 30%, content measured according to NF EN 16785-1 of January 2016, the number-average functionality (FOH) being calculated according to the following formula: Foh = (MwP / Mwr) * n0H, in which: - MwP represents the number-average molar mass of the aromatic polyol, - Mwr represents the molar mass of the repeating unit in the aromatic polyol, and - n0H represents the number of hydroxyl groups present on the repeating unit,MwP is determined by size exclusion chromatography, and MwR and n0H are determined by NMR analysis.

2. Formulation according to claim 1, for obtaining polymer materials selected from polyurethane, polyester, polycarbonate, epoxy, urethane-(meth)acrylates, polyester-(meth)acrylates, epoxy-(meth)acrylates, polyether-(meth)acrylates resins, as well as their silicone derivatives and preferably for obtaining polyurethanes.

3. Formulation according to claim 1 or claim 2, wherein the polyol capable of reacting with said at least difunctional reagent is a polyol comprising at least one aromatic function, preferably an oligomer or polymer whose repeating motif comprises at least one, two or three aromatic function(s), preferably one or two aromatic function(s), and preferably yet another aromatic function.

4. Formulation according to any one of the preceding claims, wherein the polyol that may be used in the formulation of the invention has a hydroxyl number (OHN) equal to or greater than 30 mg KOH g1, preferably still equal to or greater than 50 mg KOH g1, and more particularly a hydroxyl index equal to or greater than 30 mg KOH g1 and less than or equal to 160 mg KOH g1, preferably equal to or greater than 50 mg KOH g1 and less than or equal to 160 mg KOH g1.

5. Formulation according to any one of the preceding claims, wherein the polyol has a number average functionality greater than or equal to 2, preferably greater than or equal to 3.

6. Formulation according to any one of the preceding claims, wherein the polyol has a number average functionality between 2 and 1000, preferably between 2 and 500, more preferably between 2 and 100, better still between 2 and 50, most often between 2 and 20, for example between 3 and 20, inclusive.

7. Formulation according to any one of the preceding claims, wherein the polyol comprises a biomass-derived atom content greater than 40%.

8. Formulation according to any one of the preceding claims, wherein the aromatic polyol is selected from alkoxylated formo-cardanol resins, preferably ethoxylated and / or propoxylated formo-cardanol resins.

9. Formulation according to any one of the preceding claims, wherein the difunctional reagent is selected from at least difunctional isocyanates, at least difunctional carboxylic acids and at least difunctional epoxies, and preferably from at least difunctional isocyanates.

10. Formulation according to any one of the preceding claims, for the manufacture of polyurethanes, wherein the least difunctional reagent is selected from the least difunctional isocyanates, preferably from the difunctional isocyanates and the multifunctional isocyanates.

11. Formulation according to the preceding claim, wherein the isocyanates are difunctional organic isocyanates selected from aliphatic diisocyanates having a hydrocarbon group comprising up to 18 carbon atoms, cycloaliphatic diisocyanates having a hydrocarbon group comprising up to 15 carbon atoms, aromatic diisocyanates having a hydrocarbon group comprising from 6 to 15 carbon atoms, and arylaliphatic diisocyanates having a hydrocarbon group comprising 8 to 15 carbon atoms, as well as mixtures of two or more of them in any proportions.

12. Use of a formulation according to any one of claims 1 to 10, for the manufacture of polyurethane, polyester, polycarbonate, epoxy, urethane-(meth)acrylates, polyester-(meth)acrylates, epoxy-(meth)acrylates, polyether-(meth)acrylates resins, as well as their silicone derivatives, and advantageously for the preparation of polyurethanes.

13. Use according to claim 12, for the production of coatings in general, paints, elastomers, sealants and adhesives.