Naturally derived polyol useful for the preparation of polyurethane

Abstract

Naturally derived polyol useful for the preparation of polyurethane. The present invention relates to a process for preparing a polyol comprising: - the epoxidation of at least one unsaturated fatty acid derivative, thereby obtaining at least one epoxidized fatty acid derivative, - the esterification of at least one monoester with a diol, thereby obtaining a diester of diol and epoxidized fatty acid, - the alkoxylation of said diester, thereby obtaining the polyol, or a process in which the epoxidation and esterification steps are reversed, the polyol obtained by this process, its use for the preparation of a polyurethane, the polyurethane obtained, and a vehicle part comprising such a polyurethane. Figure for abstract: none

Description

Title of the invention: Naturally derived polyol useful for the preparation of polyurethane

[0001] The present invention relates to a polyol derived from natural resources, its preparation process and its use for the preparation of polyurethane useful in particular for the preparation of vehicle parts.

[0002] Polyurethanes have many applications. They are prepared from polyol and isocyanate.

[0003] We seek to make polyurethanes and their preparation processes more environmentally friendly by using less fossil-based raw materials to prepare them and more natural-based raw materials, but while retaining the properties of a polyurethane made from fossil-based raw materials, in particular the mechanical properties.

[0004] One of the objectives of the application is to provide a polyol, preferably of natural origin, which makes it possible to prepare a polyurethane whose mechanical properties are analogous to those of a polyurethane prepared exclusively from polyols of fossil origin.

[0005] Another objective of the application is to provide a process for preparing a polyol from fatty acids, preferably of natural origin.

[0006] Another objective of the application is to supply a polyurethane prepared from such a naturally occurring polyol.

[0007] To this end, according to a first object, the invention relates to a process for preparing a polyol of the following formula (I):

[0008] [Chem.l] O 4JL >3^ R5 r- o (f)

[0009] in which:

[0010] - G is a linear, branched or cyclic alkyl comprising from 1 to 100 atoms of carbon and possibly interrupted by one or more oxygen atoms,

[0011] - R4 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n groups of formula (VI):

[0012] [Chem.2] OH

[0013] wherein R6 is a linear or branched alkyl comprising from 1 to 4 carbon atoms,

[0014] - x is an integer from 7 to 23,

[0015] - n is an integer from 1 to 6, preferably from 1 to 3, provided that n is less than or equal to x / 2,

[0016] - R5 is H, a group -(C=O)R4 where R4 is as defined above, or a group -(C=O)R15 in which R15 represents a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m groups of formula (VI) as defined above,

[0017] y is an integer from 7 to 23, and

[0018] m is an integer from 0 to 6, preferably from 0 to 3, provided that:

[0019] - m is less than or equal to y / 2, and

[0020] - when R5 represents a group -(C=O)R15 and m represents 0, the integer n is then from 2 to 6, preferably from 2 to 3,

[0021] from an unsaturated fatty acid derivative of the following formula (II):

[0022] [Chem.3]

[0023] in which:

[0024] - R1 is a linear or branched alkenyl group comprising x carbon atoms and n unsaturations, and

[0025] - x and n are as defined above, and

[0026] - R is H or a linear or branched alkyl comprising 1 to 4 carbon atoms.

[0027] The process allows the preparation of a polyol of formula (I) as defined below. above. The compound of formula (I) is a polyol, as it comprises at least two hydroxyl groups, which allows its use as a starting material for the preparation of polyurethane.

[0028] According to a first alternative, R5 represents H. The polyol then comprises a hydroxyl group as its terminal group. The integer n is then from 1 to 6, preferably from 1 to 3 (provided that n is less than or equal to x / 2). Indeed, n being greater than or equal to At 1, the R4 group includes at least one group with formula (VI), and therefore at least one hydroxyl function. The polyol thus contains at least two hydroxyl groups.

[0029] According to a second alternative, R15 represents a -(C=O)R15 group and m represents 0. Since m is 0, the R15 group is free of a (VI) group, and therefore of a hydroxyl function. In this case, the integer n is then from 2 to 6, preferably from 2 to 3 (provided that n is less than or equal to x / 2). Thus, the R4 group comprises at least two hydroxyl functions, and therefore at least two (VI) groups. The polyol therefore comprises at least two hydroxyl groups.

[0030] According to a third alternative, R5 represents a -(C=O)R15 group and m represents at least 1. The R15 group then comprises at least one group of formula (VI) and therefore at least one hydroxyl function. Since n is greater than or equal to 1, the R4 group also comprises at least one group of formula (VI), and therefore at least one hydroxyl function. The polyol thus comprises at least two hydroxyl groups.

[0031] According to a fourth alternative, R5 represents a -(C=O)R4 group. The compound of formula (I) then comprises two -(C=O)R4 groups and each R4 group comprises at least one hydroxyl group since n is greater than or equal to 1. The polyol therefore comprises at least two hydroxyl groups.

[0032] The process uses as a starting product an unsaturated fatty acid derivative of formula (II), where the fatty acid contains from 8 to 24 carbon atoms (C8 to C24 fatty acid).

[0033] Thus, the radical R1 of the unsaturated fatty acid of formula (II) is a linear or branched alkenyl group comprising x carbon atoms, where x is an integer from 7 to 23 carbon atoms, and n unsaturations (C=C). Alternatively, the radical R1 can be described as a linear or branched alkyl group comprising (x-2n) carbon atoms and interrupted by n groups (C=C). For example, the carbon chain CH3(-CH2)7-CH=CH(-CH2)7- of oleic acid CH3(-CH2)7-CH=CH(-CH2)7-COOH can be described as a linear alkenyl group with 17 carbon atoms and 1 unsaturation (n = 1), or as a linear alkyl group comprising 15 carbon atoms interrupted by 1 group (C=C).

[0034] The integers x and n are related, since x is the number of carbon atoms in the R1 radical of the unsaturated fatty acid of formula (II), and n is its number of unsaturations (C=C). Since one unsaturation requires two carbon atoms, n must be less than or equal to x / 2. In other words:

[0035] when x is 7, n is an integer from 1 to 3,

[0036] when x is 8 or 9, n is an integer from 1 to 4,

[0037] when x is 10 or 11, n is an integer from 1 to 5, and

[0038] where x is an integer from 12 to 24, n is an integer from 1 to 6.

[0039] Two alternative routes are possible for preparing the polyol of formula (I) from the unsaturated fatty acid derivative of formula (II), these two alternatives differing from each other only in the order of the epoxidation and esterification steps.

[0040] According to a first method, the process for preparing the polyol of formula (I) as defined above comprises:

[0041] b) the epoxidation of at least one unsaturated fatty acid derivative of the following formula (II):

[0042] [Chem.4] o

[0043] in which:

[0044] - R1 is a linear or branched alkenyl group comprising x carbon atoms and n unsaturations, and

[0045] - x and n are as defined above, and

[0046] - R is H or a linear or branched alkyl comprising 1 to 4 carbon atoms,

[0047] by which at least one epoxidized fatty acid derivative of the following formula (III) is obtained:

[0048] [Chem.5]

[0049] in which:

[0050] - R is as defined above, and

[0051] - R2 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n epoxide groups of the following formula (IV):

[0052] [Chem.6] ? (JV)

[0053] where x and n are as defined above,

[0054] c) esterification of at least one epoxidized fatty acid derivative of formula (III) with a diol G(OH)2, in which G is as defined above, optionally in the presence of a second fatty acid derivative of the following formula (III'):

[0055] [Chem.7]

[0056] in which:

[0057] - R is as defined above, and

[0058] - R13 is a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m epoxide groups of formula (IV) as defined above, where y and m are as defined above,

[0059] by which at least one epoxidized diol and fatty acid ester of the following formula (V) is obtained:

[0060] [Chem. 8] (V)

[0061] in which:

[0062] R2 and G are as defined above, and

[0063] R3 is H, a group -(C=O)-R2 or a group -(C=O)-R13, in which R2 and R13 are as defined above,

[0064] d) the alkoxylation of said diol and epoxidized fatty acid ester of formula (V) with an alcohol R6OH where R6 is as defined above, by which at least one polyol of formula (I) is obtained.

[0065] The process according to this first method is illustrated in the following diagram 1:

[0066] [Chem.9] o R.JO, qj, epoxydatran where R includes n in saturations C^=C X RO where R" comprises n tonal groups (TV) esterification G(QHj2 essentially X ROO Vj where R" comprises n groups of formulated (iVi atkoxylaifon and R~ represents H or COR ' and:R“ represents H oa COR''

[0067] Scheme 1: Reaction scheme of the process according to the first route

[0068] Alternatively, in a second route of the process for preparing the polyol of formula (I), the epoxidation and esterification steps are reversed.

[0069] Thus, according to this second method, the invention relates to a process for preparing a polyol of formula (I):

[0070] [Chem. 10]

[0071] in which:

[0072] - G is a linear, branched or cyclic alkyl comprising from 1 to 100 atoms of carbon and possibly interrupted by one or more oxygen atoms,

[0073] - R4 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n groups of formula (VI):

[0074] [Chem. 11] OH

[0075] wherein R6 is a linear or branched alkyl comprising from 1 to 4 carbon atoms,

[0076] - x is an integer from 7 to 23,

[0077] - n is an integer from 1 to 6, preferably from 1 to 3, provided that n is less than or equal to x / 2,

[0078] - R5 is H, a group -(C=O)R4 where R4 is as defined above, or a group -(C=O)R15 in which R15 represents a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m groups of formula (VI) as defined above,

[0079] y is an integer from 7 to 23, and

[0080] m is an integer from 0 to 6, preferably from 0 to 3, provided that:

[0081] - m is less than or equal to y / 2, and

[0082] - when R5 represents a group -(C=O)R15 and m represents 0, the integer n is then from 2 to 6, preferably from 2 to 3,

[0083] the process comprising:

[0084] b') the esterification of at least one unsaturated fatty acid derivative of formula (II):

[0085] [Chem. 12] O

[0086] in which:

[0087] - R1 is a linear or branched alkenyl group comprising x carbon atoms and n unsaturations, and

[0088] - x and n are such as defined above, and

[0089] - R is H or a linear or branched alkyl comprising 1 to 4 carbon atoms,

[0090] with a diol G(OH)2, in which G is as defined above, optionally in the presence of a second fatty acid derivative of the following formula (II'):

[0091] [Chem. 13]

[0092] in which:

[0093] - R17 is a linear or branched alkenyl group comprising y carbon atoms and m unsaturations, and

[0094] - R, y and m are as defined above,

[0095] by which at least one diol and unsaturated fatty acid ester of formula is obtained (VII) following:

[0096] [Chem. 14] O II C - ROO' (VH)

[0097] in which:

[0098] R1 and G are as defined above, and

[0099] R7 is H, a group -(C=O)-R', or a group -(C=O)-R'7, in which R1 and R17 are as defined above,

[0100] c') the epoxidation of at least one diol and unsaturated fatty acid ester of formula (VII),

[0101] by which at least one epoxidized diol and fatty acid ester of the following formula (V) is obtained:

[0102] [Chem. 15]

[0103] in which:

[0104] - G is as defined above,

[0105] - R2 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n epoxide groups of the following formula (IV):

[0106] [Chem. 16] O

[0107] where x and n are as defined above,

[0108] - R3 is H, a group -(C=O)-R2 in which R2 is as defined above or a group -(C=O)-R13, in which R13 is a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m epoxide groups of formula (IV) as defined above, where y and m are as defined above,

[0109] d) the alkoxylation of said diol and epoxidized fatty acid ester of formula (V) with an alcohol R6OH where R6 is as defined above, by which at least one polyol of formula (I) is obtained.

[0110] The process according to this second route is illustrated in the following diagram 2: [YES] [Chem. 17] V [ r ? he G{pH}2 * événfeeDement QÙR compris O n tnsaturatrems .RC=C R Cf 7 _ fet R represented H bu COR O aüoxjîsîOn, JL q R' cK ''û" X. 4 R OH pü R will include grouped of formula {Vf; OH R: o 30 where R. ' comprand n ^saturations where R'comprise fi groups die formatted flW and R " represents H pu COR ' “ X and R Ve present H where COR

[0112] Scheme 2: Reaction scheme of the process according to the second route

[0113] Regardless of the route considered, the R2 group is the result of epoxidation of group R1, meaning that group R2 corresponds to group R1 in which the n C=C unsaturations have been replaced by n groups of formula (IV). The groups of formula (IV) are therefore in the same locations on the alkyl chain of R2 as the unsaturations were on group R1. Similarly, group R4 is the result of the alkoxylation of group R2, meaning that group R4 corresponds to group R2 in which the n groups of formula (IV) have been replaced by n groups of formula (VI). The groups of formula (VI) are therefore also at the same locations on the alkyl of R4 as were the unsaturations of the group R1.

[0114] Regardless of the route considered, the process uses an unsaturated fatty acid derivative of formula (II) as defined above.

[0115] Regardless of the route considered, according to a first alternative, in formula (II), R is H, and the unsaturated fatty acid derivative of formula (II) is then an unsaturated fatty acid of formula (lia):

[0116] [Chem. 18] R ° ÜM

[0117] in which R1 is as defined above.

[0118] Preferably, the group R1 is linear.

[0119] In one embodiment, the group R1 is linear and n represents 1, so that R1 represents H3C-[CH2]r-CH=CH-[CH2]s r-, and the unsaturated fatty acid has the formula (Ilb):

[0120] [Chem. 19] (B),

[0121] in which:

[0122] s represents an integer from 4 to 20, and

[0123] r represents an integer from 0 to s.

[0124] Thus, in this embodiment, in the processes described above (way 1 or 2), R1 represents H3C-[CH2]r-CH=CH-[CH2]s r- with s and r as defined above, and the radical R2 has the formula (XX):

[0125] [Chem.20] {XX)

[0126] with s and r as defined above,

[0127] and the radical R4 has one of the following formulas (XXI) or (XXII):

[0128] [Chem.21] 'O rn । ri* H3C—CH2 — CH -CH - -CH- —| OH s- (XXLj

[0129] [Chem.22] OH HSC—CS- - (XX! I)

[0130] Preferably, the C8-C24 unsaturated fatty acid of formula (lia) or (Ilb) is of natural origin. Among the naturally occurring unsaturated fatty acids are myristoleic acid (14:1), palmitoleic acid (16:1), sapienic acid (16:1), oleic acid (18:1), elaidic acid (18:1), trans-vaccenic acid (18:1), linoleic acid (18:2), linolelaidic acid (18:2), alpha-linolenic acid (18:3), gamma-linolenic acid (18:3), eicosenoic acid (20:1), dihomo-alpha-linolenic acid (20:3), arachidonic acid (20:4), eicosapentaenoic acid (20:5), erucic acid (22:1), docosahexaenoic acid (22:6), and... nervous (24:1).

[0131] For example, mono- or polyunsaturated fatty acids in C8 to C24 from refining processes, for example acid oil, or from the paper industry, for example tallol, can be used as fatty acids of formula (lia).

[0132] When R is H (i.e., when the unsaturated fatty acid derivative has the formula (lia) or (Ilb)), regardless of the process route considered, the process may include, before step b) or step b'), a step a) of preparing at least one unsaturated fatty acid of formula (lia) by hydrolysis of one or more fatty acid esters of an oil. The oil that may be used in step a) may be a vegetable oil, an oil of animal origin, or a used oil, such as recovered oil from the food industry, for example, cooking oil, or oil produced as a by-product in the food industry. The process can thus contribute to the recycling of used oils generally considered waste, which is beneficial for the environment.

[0133] The vegetable oil is typically soybean, palm, sunflower, linseed, rapeseed, camelina, cottonseed, olive, maize, safflower, jatropha, microalgae oil or a mixture thereof.

[0134] Regardless of the route considered, according to a second alternative, in formula (II), R is a linear or branched alkyl comprising 1 to 4 carbon atoms, and the unsaturated fatty acid derivative of formula (II) is then an unsaturated fatty acid monoester of formula (II):

[0135] [Chem.23]

[0136] wherein (Cl-C4)Alk represents a linear or branched alkyl comprising 1 to 4 carbon atoms, in particular a methyl, an ethyl, an isopropyl or a tert-butyl, preferably a methyl.

[0137] Preferably, the group R1 is linear.

[0138] In one embodiment, group R1 is linear and n represents 1, and the unsaturated fatty acid has the formula (Ild):

[0139] [Chem.24] HjC CH -CH my

[0140] in which:

[0141] s represents an integer from 4 to 20, and

[0142] r represents an integer from 0 to s, and

[0143] (Cl-C4)Alk represents a linear or branched alkyl comprising 1 to 4 carbon atoms, in particular a methyl, an ethyl, an isopropyl or a tert-butyl, preferably a methyl.

[0144] Thus, in this embodiment, in the processes described above (way 1 or 2), R1 represents H3C-[CH2]r-CH=CH-[CH2]s r- with s and r as defined above, the radical R2 has the formula (XX) as defined above, and the radical R4 has one of the formulas (XXI) or (XXII) as defined above.

[0145] When R is a linear or branched alkyl comprising 1 to 4 carbon atoms, regardless of the route of the process considered, the process may include, before step b) or step b'):

[0146] - either a step a') of preparing at least one unsaturated fatty acid monoester of formula (Ile) (or (Ild)) by transesterification, with an alcohol of formula HO-(C1-C4)Alk, of at least one fatty acid ester, preferably by transesterification of the triglycerides of an oil,

[0147] - either a step a”) of preparing at least one unsaturated fatty acid monoester of formula (Ile) by esterification, with an alcohol of formula HO-(Cl-C4)Alk, of at least one fatty acid, in particular at least one fatty acid as listed above, preferably a fatty acid of formula (lia), particularly preferably a fatty acid of formula (Ilb). In particular, unsaturated fatty acid monoesters of formula (Ile) or (Ilb) can be obtained by esterification of the unsaturated fatty acid of formula (lia) or (Ilb) respectively with an alcohol of formula HO-(Cl-C4)Alk.

[0148] The oil that can be used in step a') may in particular be an oil such as described above for step a).

[0149] Regardless of the method used, it can be carried out using a single compound of formula (II), or using a mixture comprising, in addition to the unsaturated fatty acid derivative of formula (II), another unsaturated fatty acid derivative of formula (II), a saturated fatty acid derivative, or a mixture thereof. It is particularly carried out using such a mixture when the starting product of the process is an oil, notably as defined above, or is derived from an oil (by hydrolysis or transesterification).

[0150] When the process is carried out according to the first route and with a single compound of formula (II), esterification c) is generally not performed in the presence of a second fatty acid derivative of formula (III') as defined above, and esterification c) leads to a compound of formula (V) as defined above in which R3 is H or a -(C=O)-R2 group. Esterification c) of the process according to route 1 then leads to:

[0151] - to a diol and epoxidized fatty acid monoester of the following formula (Va) (when R3 is H):

[0152] [Chem.25]

[0153] in which G and R2 are as defined above,

[0154] - to a diol and epoxidized fatty acid diester, of the following formula (V[3] (when R3 East -(C=O)-R2):

[0155] [Chem.26]

[0156] in which G and R2 are as defined above,

[0157] - or a mixture of these.

[0158] The following diagram 3 illustrates the process according to route 1 implemented with an oleic acid derivative as a compound of formula (II).

[0160] Scheme 3: Reaction scheme of the process according to route 1 using oleic acid as an unsaturated fatty acid derivative of formula (II).

[0161] When the process is carried out according to the first method and is carried out with a mixture comprising at least two compounds corresponding to formula (II) but of different natures from each other (or from each other when there are more than two), typically with two R1 radicals of distinct natures:

[0162] - during step b) of epoxidation, each compound corresponding to formula (II) is epoxylated and a mixture comprising at least two compounds of formula (III) is obtained, namely:

[0163] - the compound of formula (III), and

[0164] - at least one compound of formula (III') as defined above, and in which R13 is a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m epoxide groups of formula (IV) as defined above, where y is an integer from 7 to 23 and m is an integer from 1 to 6, preferably from 1 to 3, provided that m is less than or equal to y / 2, and

[0165] - esterification c) is carried out in the presence of a second fatty acid derivative epoxide of formula (III'), and leads to:

[0166] - a compound of formula (V) in which R3 is a -(C=O)-R13 group where the radical R13 is a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m epoxide groups of formula (IV) as defined above, where y is an integer from 7 to 23 and m is an integer from 1 to 6, preferably from 1 to 3, provided that m is less than or equal to y / 2 (this compound is the product of the diesterification of the diol G(OH)2 with on the one hand the epoxide fatty acid derivative of formula (III), and on the other hand the second fatty acid derivative of formula (III')),

[0167] - a compound of formula (V) in which R3 is a -(C=O)-R2 group where the radical R2 is as defined above (this compound is the product of the diesterification of the diol G(OH)2 with two epoxidized fatty acid derivatives of formula (III),

[0168] - possibly to a compound of formula (V) in which R3 is H (product of the monoesterification of the diol G(OH)2 with the compound of formula (III)),

[0169] - each of these compounds will react during the next alkoxylation step.

[0170] By way of example, a process according to route 1 may be cited using an oleic acid derivative and a linoleic acid derivative as a mixture comprising at least two compounds corresponding to formula (II).

[0171] When the process is carried out according to the first method and is carried out with a mixture comprising, in addition to the unsaturated fatty acid derivative of formula (II), a saturated fatty acid, the latter preferably has the formula (III') as defined above in which the radical R13 is a linear or branched alkyl comprising y carbon atoms where y is an integer from 7 to 23 (so m is 0):

[0172] - during step b) of epoxidation, the saturated fatty acid derivative of formula (III') is inert (since it is free of unsaturation). Also, epoxidation b) leads to a mixture:

[0173] - of an epoxidized fatty acid derivative of formula (III) as defined above and

[0174] - of a saturated fatty acid derivative of formula (III') in which the radical R13 is a linear or branched alkyl comprising y carbon atoms where y is an integer from 7 to 23.

[0175] - esterification c) is carried out in the presence of a second fatty acid derivative of formula (III'), and leads to:

[0176] - a compound of formula (V) in which R3 is a linear or branched alkyl comprising y carbon atoms where y is an integer from 7 to 23 (this compound is the product of the diesterification of the diol G(OH)2 with on the one hand the epoxidized fatty acid derivative of formula (III), and on the other hand the second fatty acid derivative of formula (IID),

[0177] - a compound of formula (V) in which R3 is a -(C=O)-R2 group where the radical R2 is as defined above (this compound is the product of the diesterification of the diol G(OH)2 with two epoxidized fatty acid derivatives of formula (III)),

[0178] - possibly to a compound of formula (V) in which R3 is H (product of the monoesterification of the diol G(OH)2 with the compound of formula (III)),

[0179] - each of these compounds will react during the next alkoxylation step.

[0180] By way of example, a process according to route 1 may be cited using an oleic acid derivative and a lauric acid derivative as a mixture comprising a compound of formula (II) and a saturated fatty acid derivative of formula (III').

[0181] When the process is carried out according to the second route and with a single compound of formula (II), esterification b') is generally not performed in the presence of a second fatty acid derivative of formula (II') as defined above, and esterification b') leads to a compound of formula (VII) as defined above in which R7 is H or a -(C=O)-R' group. Thus, esterification of the process according to route 2 leads to:

[0182] - to a diol and epoxidized fatty acid monoester of the following formula (Vlla) (when R7 is H):

[0183] [Chem.28] O ...G .. . H ROQ (VHa)

[0184] in which G and R1 are as defined above,

[0185] - to a diol and epoxidized fatty acid diester of the following formula (VII[3] (when R7 East -(C=O)-R'):

[0186] [Chem.29] OO AaX KUUK

[0187] in which G and R1 are as defined above,

[0188] - or a mixture of these.

[0189] The following diagram 4 illustrates the process according to route 2 implemented with an oleic acid derivative as the sole compound of formula (II).

[0190] [Chem.30]

[0191] Scheme 4: Reaction scheme of the process according to route 2 using oleic acid as an unsaturated fatty acid derivative of formula (II).

[0192] When the process is carried out according to the second route and is carried out with a mixture comprising at least two compounds corresponding to formula (II) but of different natures from each other (or from each other when there are more than two), typically with two R1 radicals of distinct natures:

[0193] - esterification b') is carried out in the presence of a second fatty acid derivative of formula (II'), and leads to:

[0194] - a compound of formula (VII) in which R7 is a -(C=O)-R'7 group where the radical R17 is a linear or branched alkenyl group comprising y carbon atoms and m unsaturations, where y is an integer from 7 to 23 and m is an integer from 1 to 6, preferably from 1 to 3, provided that m is less than or equal to y / 2 (this compound is the product of the diesterification of the diol G(OH)2 with on the one hand the unsaturated fatty acid derivative of formula (II), and on the other hand the second fatty acid derivative of formula (ID),

[0195] - a compound of formula (VII) in which R7 is a -(C=O)-R' group where the radical R1 is as defined above (this compound is the product of the diesterization of the diol G(OH)2 with two unsaturated fatty acid derivatives of formula (II),

[0196] - possibly to a compound of formula (VII) in which R7 is H (product of of the monoesterification of the diol G(OH)2 with the compound of formula (II)),

[0197] - each of these compounds will react in the following steps c) epoxidation and d) of alkoxylation.

[0198] By way of example, a process according to route 2 may be cited using an oleic acid derivative and a linoleic acid derivative as a mixture comprising at least two compounds corresponding to formula (II).

[0199] When the process is carried out according to the second route and is carried out with a mixture comprising, in addition to the unsaturated fatty acid derivative of formula (II), a saturated fatty acid derivative, the latter preferably has the formula (II') as defined above in which the radical R17 is a linear or branched alkyl comprising y carbon atoms where y is an integer from 7 to 23 (so m is 0):

[0200] - esterification b') is carried out in the presence of this second fatty acid derivative saturated with formula (II'), and leads to:

[0201] - a compound of formula (VII) in which R7 is a -(C=O)-R'7 group where the radical R17 is a linear or branched alkyl comprising y carbon atoms where y is an integer from 7 to 23 (this compound is the product of the diesterification of the diol G(OH)2 with on the one hand the unsaturated fatty acid derivative of formula (II), and on the other hand the second saturated fatty acid derivative of formula (II')),

[0202] - a compound of formula (VII) in which R7 is a -(C=O)-R' group where the radical R1 is as defined above (this compound is the product of the diesterization of the diol G(OH)2 with two unsaturated fatty acid derivatives of formula (II)),

[0203] - possibly to a compound of formula (VII) in which R7 is H (product of of the monoesterification of the diol G(OH)2 with the compound of formula (II)),

[0204] - each of these compounds will react in the following steps c) epoxidation and d) of alkoxylation.

[0205] By way of example, a process according to route 2 may be cited using an oleic acid derivative and a lauric acid derivative as a mixture comprising a compound of formula (II) and a saturated fatty acid derivative of formula (III').

[0206] Regardless of the method and embodiment considered, epoxidation is preferably carried out with hydrogen peroxide and formic acid, preferably at a temperature of 50 to 90°, for example 60 to 80°C.

[0207] Regardless of the process route and embodiment considered, the esterification can be catalyzed, for example, by Ti(OBu)4. The molar ratio of fatty acid derivative(s) to diol G(OH)2 is, for example, from 1 / 1 to 2 / 1. The higher this ratio, the higher the diester / monoester ratio.

[0208] Esterification can be a transesterification. More specifically, in route 1 of the process, when R is H in formula (III), step c) is an esterification, whereas when R is a linear or branched alkyl group comprising 1 to 4 carbon atoms in formula (III), step c) is a transesterification. Similarly, in route 2 of the process, when R is H in formula (II), step b') is an esterification, whereas when R is a linear or branched alkyl group comprising 1 to 4 carbon atoms in formula (II'), step b') is a transesterification.

[0209] Regardless of the method and embodiment considered, G is a linear, branched, or cyclic alkylene, or, alternatively, the alkyl radical of group G is interrupted by one or more oxygen atoms and thus comprises one or more ether groups. Two oxygen atoms are generally not adjacent, so the polyol of formula (I) is generally free of a peroxide group (-OO-). It may then be a monoether or polyether, typically an alkylene polyoxide, in particular propylene polyoxide, or an ethylene polyoxide, in particular ethylene polyoxide of formula -[O-CH2-CH2]p- where p is an integer from 2 to 100.

[0210] Preferably, the diol G(OH)2 used for transesterification is a polyethylene glycol comprising from 2 to 50 units, a poly(propanediol) comprising from 2 to 33 units or a dimer diol type compound of the following formula (X):

[0211] [Chem.31] marketed under the name Pripol 2033.

[0212] In a particularly preferred manner, the diol is a polyethylene glycol with a weight molecular mass of 200 to 4000 g / mol and G is a polyethylene oxide of formula -[O-CH2-CH2]P- where p is an integer from 4 to 91.

[0213] Regardless of the method and embodiment considered, the method includes an alkoxylation that leads to the opening of the epoxide function(s). This opening can be on either of the carbon atoms of the epoxide, so that the group with formula (VI) can be in either (VI) or (VI') orientation relative to the rest of the carbon chain:

[0214] [Chem.32]

[0216] and this for all compounds that contain one or more (VI) groups. Reaction schemes 3 and 4 above illustrate the two directions of opening of the epoxide function using oleic acid as a starting material.

[0217] The alcohol R6OH used is such that R6 is a linear or branched alkyl comprising from 1 to 4 carbon atoms. Preferably, the alcohol is methanol, ethanol, or isopropanol. Ethanol is particularly preferred.

[0218] The process may include, after esterification, a step of purifying the polyol of formula (I) or the mixture of polyols of formula (I), for example by distillation.

[0219] According to a second object, the invention relates to a polyol of formula (I) capable of being obtained by one of the processes described above, or a mixture of polyols of formula (I) capable of being obtained by one of the processes described above.

[0220] The embodiments defined above for the first object are of course applicable.

[0221] The polyol of formula (I) may include radicals derived from a naturally occurring mono- or diunsaturated fatty acid. Thus, such a polyol of formula (I) has a lower carbon footprint than a polyol whose radicals are derived from fossil fuels. The polyol of formula (I) advantageously consists of radicals of which at least 5% by weight are of natural origin. This is referred to as "biocontent."

[0222] The polyol of formula (I) preferably has:

[0223] - a hydroxyl value of 20 to 100 mg KOH / g such that measured according to method A of standard NF EN ISO 14900 of 2023,

[0224] - an acid value less than or equal to 1.5 mg KOH / g such that measured according to standard NF EN ISO 660 of 2020, preferably less than or equal to 1.0 mg KOH / g, and / or

[0225] - a viscosity at 20°C of 500 to 5000 mPa.s at a shear rate of 0.1 to 100 s1.

[0226] According to a third object, the invention relates to a process for preparing a polyurethane comprising the polymerization of a diisocyanate and a polyol of formula (I) or a mixture of polyols of formula (I).

[0227] The embodiments defined above for the first object are of course applicable. For example, the polymerization can be carried out from an isocyanate and a mixture of polyols of formula (I') or (I”) as defined above.

[0228] The polymerization can be carried out in the absence of a polyol other than the polyol of formula (I), or alternatively, using a mixture of at least one polyol of formula (I) and at least one other polyol that does not correspond to formula (I), for example, a polyol of fossil origin. For example, the polymerization can be carried out from one or more polyol(s) of formula (I) as defined above, other polyol(s) that do not correspond to formula (I), and a diisocyanate, with a mass proportion of polyol(s) of formula (I) of 10 to 50% by weight, preferably 20 to 40% by weight, relative to the sum of polyol(s) of formula (I) and other polyol(s).

[0229] Polymerization may include foaming of the polyurethane. The usual foaming parameters are applicable.

[0230] Polymerization can be carried out in the presence of one or more additives chosen from among catalysts, surfactants, stabilizing agents and flame retardants, and possibly in the presence of water.

[0231] According to a fourth object, the invention relates to a polyurethane, foamed or non-foamed, which can be obtained by this process.

[0232] The embodiments defined above for the other objects are of course applicable.

[0233] Polyurethane can be a rigid or flexible foam.

[0234] This polyurethane, foamed or non-foamed, can be used in various applications, for example as a coating, adhesive, sealant, or for preparing parts or parts of parts. A preferred application is the preparation of vehicle parts, preferably interior vehicle parts. The vehicle could, for example, be a car, truck, bus, tractor, airplane, or train. The flexible polyurethane can, for example, be used in A cushion, a seat back, a headrest, or a flexible foam pad. Rigid polyurethane can, for example, be used as a seat back shell.

[0235] Thus, according to a fifth object, the invention relates to a vehicle interior part comprising a polyurethane as defined above.

[0236] The invention is illustrated by the following examples. Examples

[0237] Example 1: Process for preparing a polyol from vegetable oils

[0238] Rapeseed oil (ITERG) was transesterified with methanol. In addition, used cooking oil was transesterified with methanol. The methyl esters thus obtained were distilled using a short-path falling-film evaporator. The fatty acid content of each of the two oils is given in Table 1. The major fatty acid in rapeseed oil is erucic acid, and transesterification therefore leads to a mixture of methyl esters consisting mainly of erucic acid methyl ester. The major fatty acid in cooking oil is oleic acid, and transesterification therefore leads to a mixture of methyl esters consisting mainly of oleic acid methyl ester.

[0239] [Tables 1] Fatty acid rapeseed oil cooking oil Myristic acid 0.1 0.1 Palmitic acid 3.3 7.0 Palmitoleic acid 0.2 0.2 Stearic acid 1.0 3.3 Trans Cl8:1 acid 0 0.2 Oleic acid 15.3 49.8 Trans Cl8:2 acid 0 0.4 Linoleic acid 13.8 36.5 Linolenic acid 8.3 0.8 Arachidic acid 0.8 0.3 Eicosenoic acid 7.0 0.3 Behenic acid 0.7 0.7 Erucic acid 47.2 0 C22:1 acid 0.8 0 Lignoceric acid 0.4 0.3 Nervonic acid 1.0 0 Unidentified 0.5 0 Average number n of installations per fatty acid 1.2 1.3

[0240] Table 1: Nature of fatty acids present in oils.

[0241] Each methyl ester mixture was epoxidized with hydrogen peroxide and formic acid at 70°C, then transesterified with PEG200 in the presence of Ti(OBu)4 with a molar ratio of epoxidized methyl ester / PEG200 of 2 / 1, and then alkoxylated with ethanol.

[0242] Scheme 5 below illustrates one of the reactions using cooking oil as a starting material, namely that with methyl ester of oleic acid. .PEG2O0. HQ

[0244] Scheme 5: Reaction scheme from oleic acid methyl ester as compound of formula (II), and PEG 200n as diol G(OH)2 and ethanol as alcohol R6OH.

[0245] Scheme 5 does not illustrate all the reactions that take place during the process. For one thing, oleic acid methyl ester is not the only compound of formula (II) in the cooking oil, and other compounds of formula (II) (linoleic acid ester, for example) will also react. Furthermore, during esterification, diesters formed with different radicals will be produced, for example, a diester derived from oleic acid and linoleic acid, and also a diester derived from oleic acid and palmitic acid, as illustrated in the diagram below:

[0246] [Chem.35]

[0247] In practice, a complex mixture is obtained.

[0248] The properties of the prepared formula (I) polyol mixtures are given in Table 2.

[0249] [Tables2] Property Unit Method Polysaccharide mixture of formula (I) obtained from rapeseed oil Polysaccharide mixture of formula (I) obtained from cooking oil Hydroxy value mg KOH / g NF EN ISO 1 4900 - Method A 80.9 78.8 Acid value mg KOH / g NF EN ISO 6 60 0.50 0.51 075 Viscosity (20°C) rnPa.s 1324 1279 Water content % by weight Karl Fischer 0.04 0.03 Volatile content % by weight 0.66 0.15 Mw g / mol PS 3131 2877 Mn g / mol PS 1702 1642 Polydispersity index IP - 1.84 1.75 Content of natural origin ("biocontent") % by weight 80 80

[0250] Table 2: Properties of the prepared polyol mixtures of formula (I)

[0251] Example 2: preparation of a polyurethane according to the invention

[0252] A polymerization was carried out between a diisocyanate (ISO 135 / 161 (BASF)), a polyol (Rokopol 6010 (Rokita)) and the mixture of compounds of formula (I) obtained by esterification of PG3 and hydrolysate from cooking oil obtained in Example 1, with a mass proportion of mixture of Example 1 / (mixture of Example 1 + polyol) of 30%, and in the presence of water, a catalyst (DABCO NE 300 and Polycat 15 (Evonik)) and surfactants (Tegostab B 8715 LF2) and diethanolamine. Diisocyanate represented 38% by weight of the mixture, polyol 51.3% by weight of the mixture, catalysts 0.1 and 1% by weight of the mixture respectively, surfactant 1% of the mixture, water 1.9% of the mixture and diethanolamine 1% of the mixture.

[0253] Foam formed and expanded freely. The observed reactivity was similar to that of a comparative foam obtained by polymerization of diisocyanate and polyol, in the absence of polyol of formula (I). The reactivity was observed in particular by comparing the evolution of the foam height as a function of the polymerization time, as shown in Table 3 below.

[0254] [Tables3] Formulation Rise Height (mm) Rise Time (s) Maximum Speed ​​(mm / s) Reference 228 95 3.9 Foam a mixture of compound of formula 1 218 88 3.7

[0255] Table 3: Foam rise height, rise time and foam rise speed

[0256] The content of units derived from formula (I) polyols in the prepared polyurethane foam was 17% by weight.

[0257] The mechanical properties, in particular the density of the polyurethane foam according to the invention and that of the comparative foam, were similar.

[0258] Polyurethane foam blocks according to Example 2 and with a density of 60 kg / m3 were thus prepared. Their mechanical properties, in particular the compression set under constant height (DIN EN ISO 1856, method A) and the tear resistance (DIN EN ISO 1798, type IA) of the polyurethane foam according to the invention and that of the comparative foam, were similar for a similar hardness (DIN EN ISO 3386-1) at the same density of 60 kg.m3 (DIN EN ISO 845), as shown in Table 4.

[0259] [Tables4] Formulation Density (kg.m3) Hardness (kPa) Deformation set (%) Tear resistance (N.cm-1) Reference 61 5.2 2.1 13 Foam a mixture of compound of formula 1 59 5.8 2.5 19

[0260] Table 4: Properties of foams

Claims

Demands

1. Process for preparing a polyol of the following formula (I): [Chem.36] O in which: - G is a linear, branched or cyclic alkyl group comprising from 1 to 100 carbon atoms and possibly interrupted by one or more oxygen atoms, - R4 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n groups of formula (VI): [Chem.37] OH (V!), in which R6 is a linear or branched alkyl comprising 1 to 4 carbon atoms, - x is an integer from 7 to 23, - n is an integer from 1 to 6, preferably from 1 to 3, provided that n is less than or equal to x / 2, - R5 is H, a -(C=O)R4 group where R4 is as defined above, or a -(C=O)R15 group in which R15 represents a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m formula groups (VI) as defined above, y is an integer from 7 to 23, and m is an integer from 0 to 6, preferably from 0 to 3, provided that: - m is less than or equal to y / 2, and - when R5 represents a group -(C=O)R15 and m represents 0, the integer n is then from 2 to 6, preferably from 2 to 3, the process comprising: b) the epoxidation of at least one unsaturated fatty acid derivative of the following formula (II): [Chem.38] in which: - R1 is a linear or branched alkenyl group comprising x carbon atoms and n unsaturations, and - x and n are as defined above, and - R is H or a linear or branched alkyl group comprising 1 to 4 carbon atoms, by which at least one epoxidized fatty acid derivative is obtained formula (III) as follows: [Chem.39] in which: - R is as defined above, and - R2 is a linear or branched alkyl group comprising (x-2n) atoms of carbon and interrupted by n epoxide groups of the following formula (IV): [Chem.40] o 1 / \ j x ï (IV) where x and n are as defined above, c) esterification of at least one epoxidized fatty acid derivative of formula (III) with a diol G(OH)2, in which G is as defined above, optionally in the presence of a second fatty acid derivative of the following formula (III'): [Chem.41] in which: - R is as defined above, and - R13 is a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m epoxide groups of formula (IV) as defined above, where y and m are as defined above, whereby at least one epoxide diol and fatty acid ester of the following formula (V) is obtained: [Chem.42] (V)

2. in which: R2 and G are as defined above, and R3 is H, a -(C=O)-R2 group or a -(C=O)-R13 group, in which R2 and R13 are as defined above, d) the alkoxylation of said diol and epoxidized fatty acid ester of formula (V) with an alcohol R6OH where R6 is as defined above, by which at least one polyol of formula (I) is obtained. Process for preparing a polyol of formula (I): [Chem.43] in which: - G is a linear, branched or cyclic alkyl group comprising from 1 to 100 carbon atoms and possibly interrupted by one or more oxygen atoms, - R4 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n groups of formula (VI): [Chem.44] OH in which R6 is a linear or branched alkyl comprising 1 to 4 carbon atoms, - x is an integer from 7 to 23, - n is an integer from 1 to 6, preferably from 1 to 3, provided that n is less than or equal to x / 2, - R5 is H, a group -(C=O)R4 where R4 is as defined above, or a group -(C=O)R15 in which R15 represents a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m formula groups (VI) as defined above, y is an integer from 7 to 23, and m is an integer from 0 to 6, preferably from 0 to 3, provided that: - m is less than or equal to y / 2, and - when R5 represents a group -(C=O)R15 and m represents 0, the integer n is then from 2 to 6, preferably from 2 to 3, the process comprising: b') the esterification of at least one unsaturated fatty acid derivative of formula (II): [Chem.45] in which: - R1 is a linear or branched alkenyl group comprising x carbon atoms and n unsaturations, and - x and n are as defined above, and - R is H or a linear or branched alkyl group comprising 1 to 4 carbon atoms, with a diol G(OH)2, in which G is as defined above, possibly in the presence of a second fatty acid derivative of the following formula (II'): [Chem.46] in which: - R17 is a linear or branched alkenyl group comprising y carbon atoms and m unsaturations, and - R, y and m are as defined above, by which at least one ester of diol and unsaturated fatty acid of the following formula (VII) is obtained: [Chem.47] in which: R1 and G are as defined above, and R7 is H, a -(C=O)-R' group, or a -(C=O)-R17 group, in which R1 and R17 are as defined above, c') the epoxidation of at least one diol-unsaturated fatty acid ester of formula (VII), by which at least one epoxidized diol-fatty acid ester of the following formula (V) is obtained: [Chem.48] (V) in which: - G is as defined above, - R2 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n epoxide groups of the following formula (IV): [Chem.49] o Ï (IV) where x and n are as defined above, - R3 is H, a -(C=O)-R2 group in which R2 is as defined above or a -(C=O)-R13 group, in which R13 is a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m epoxide groups of formula (IV) as defined above, where y and m are as defined above, d) the alkoxylation of said diol and epoxide fatty acid ester of formula (V) with an alcohol R6OH where R6 is as defined above, by which is obtained at least one polyol of formula (I).

3. Method according to claim 1 or 2, wherein the radical R1 represents H3C-[CH2]r-CH=CH-[CH2]s r-, where s represents an integer from 4 to 20, and r represents an integer from 0 to s.

4. A process according to any one of claims 1 to 3, wherein the alcohol G(OH)2 is polyethylene glycol comprising from 2 to 50 units, a poly(propanediol) comprising from 2 to 33 units, or a diol dimer-type compound of the following formula (X): [Chem. 50] X / \ / x / x 'S y OH \ /

5. (X). A method according to any one of claims 1 to 4, wherein the unsaturated fatty acid derivative of formula (II) is an unsaturated fatty acid of formula (Ia): [Chem.51] O in which R1 is a linear or branched alkenyl group comprising x carbon atoms and n unsaturations, the process comprising, before step b) or before step b'), a step a) of preparing at least one unsaturated fatty acid of formula (lia) by hydrolysis of at least one fatty acid ester of an oil.

6. A method according to any one of claims 1 to 4, wherein the unsaturated fatty acid derivative of formula (II) is an unsaturated fatty acid monoester of formula (IIe): [Chem. 52] O (G1-C4}A9t R' (Ifâ in which R1 is a linear or branched alkenyl group comprising x carbon atoms and n unsaturations and (Cl-C4)Alk represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms, the process comprising, before step b) or before step b'), - either a step a') of preparation of at least one unsaturated fatty acid monoester of formula (Ile) by transesterification, with an alcohol of formula HO-(Cl-C4)Alk, of at least one fatty acid ester, - or a step a”) of preparation of at least one unsaturated fatty acid monoester of formula (Ile) by esterification, with an alcohol of formula HO-(Cl-C4)Alk, of at least one fatty acid.

7. Polyol of formula (I): [Chem.53] 4JL JA R 0 O' 0) in which: - G is a linear, branched or cyclic alkyl comprising from 1 to 100 carbon atoms and optionally interrupted by one or more oxygen atoms, - R4 is a linear or branched alkyl comprising (x-2n) carbon atoms and interrupted by n groups of formula (VI): [Chem. 54] OH R'O (VI), in which R6 is a linear or branched alkyl comprising from 1 to 4 carbon atoms, - x is an integer from 7 to 23, - n is an integer from 1 to 6, preferably from 1 to 3, provided that n is less than or equal to x / 2, - R5 is H, a -(C=O)R4 group where R4 is as defined above, or a -(C=O)R15 group in which R15 represents a linear or branched alkyl comprising (y-2m) carbon atoms and interrupted by m groups of formula (VI) as defined above, y is an integer from 7 to 23, and m is an integer from 0 to 6, preferably from 0 to 3, provided that: - m is less than or equal to y / 2, and - when R represents a -(C=O)R15 group and m represents 0, the integer n is then from 2 to 6, preferably from 2 to 3, or a mixture of polyols of formula (I), obtained by the process according to any one of claims 1 to A

8. U. A process for preparing a polyurethane comprising the polymerization of a diisocyanate, a polyol or a mixture of polyols according to claim 7, and optionally of a polyol which does not conform to formula (I).

9.

10. Polyurethane obtained by the process according to claim 8. Vehicle part, preferably an interior vehicle part, comprising the polyurethane according to claim 9.