PROCESS FOR THE PREPARATION OF POLYOLS

专利摘要:
The present invention relates to a process for preparing polyols. In particular, the present invention relates to the one-step preparation of polyols by a process involving a hydrohydroxymethylation reaction from a composition A comprising one or more compounds of formula (I)
公开号:FR3038312A1
申请号:FR1501373
申请日:2015-06-30
公开日:2017-01-06
发明作者:Frederic Hapiot；Eric Monflier；Theodore Vanbesien
申请人:D'artois, University of；Centre National de la Recherche Scientifique CNRS；Pivert SAS；
IPC主号:

专利说明:

Process for the preparation of polvols
Field of the invention The invention relates to a process for preparing polyols, preferably from triglycerides. In particular, the invention relates to a process for the preparation of polyols in a single step by reaction of hydrohydroxymethylation or of reductive hydroformylation.
Technological background of the invention
Polyols are usually produced from petroleum. Polyols are used in many fields * of applications such as textiles, plastics, chemistry, manufacturing industry or the cosmetics industry. The polyols are especially used in the preparation of coatings, adhesives, elastomers, resins or foams.
The polyols are generally prepared via a hydroformylation reaction of alkenes. However, the majority of the methods described in the prior art on this type of approach use ligands difficult to handle in air such as trialkylphosphines or phosphites that degrade in water. A simpler alternative is to use amines as ligands. The use of tertiary amines has been described in the literature for converting terminal alkenes to alcohols via a reductive hydroformylation reaction (Morales Torres et al., Catal. Sci. Technol., 2015, 5, 34-54). Various systematic studies have shown the influence of amine, in terms of structure, basicity and quantity, on the rhodium hydroformylation reaction (Hunter et al., Appl., Catal., 1985, 19, 275-285). . The most recent use of this type of catalytic system dates back to 2012 by Alper et al., (Adv Synth Synth., 2012, 354, 2019-2022) on the synthesis of terminal alcohols from styrene in the presence tertiary diamines as ligand. The production of alcohol by this process using the rhodium-amine catalyst systems has also been described in EP 0014225 and US 4,197,414 but only from light olefins of type 1-hexene.
For heavier olefins, the synthesis of polyols is preferably carried out by an epoxidation reaction as described by WO 2006/012344. Summary of the invention
The present invention allows the preparation of polyols from biosourced compounds, for example from a vegetable oil. The process is particularly advantageous for the selective preparation of polyols from triglycerides with high yield and selectivity.
The present invention relates to a process for preparing polyols from a composition A comprising one or more compounds of formula (I)
wherein R1, R2, R3, R4, R5, Re and R7 are independently of each other, and for R3 and R7 independently for each of the n units, selected from the group consisting of H, -OR15, C1-C10 alkyl substituted or unsubstituted by one or more -OR15 groups, C6-C12 aryl substituted or unsubstituted by one or more -OR15 groups, or C3-C10 cycloalkyl substituted or unsubstituted by one or more -OR15 groups, or a group of formula ( the)
R15 represents H or C1-C10 alkyl optionally substituted with one or more -OH groups a, b, x and y are independently of each other, independently for each group of formula (Ia), independently for each unit ) aC = C- (CH2) b] and independently for each unit [(CH2) xC = C- (CH2) y] p, an integer from 0 to 20, advantageously from 0 to 15, preferably from 0 to and 12; r is an integer from 1 to 10, preferably from 1 to 5; p is an integer between 1 and 10, preferably between 1 and 5; n is an integer from 1 to 7; said method comprising a step a) of contacting with stirring and in an atmosphere of hydrogen and carbon monoxide: • of at least one precatalyst being a complex comprising a transition metal chosen from column 9 of the periodic table of elements, • a tertiary amine, or a non-quaternary ammonium salt thereof, of formula NR8R9R10 wherein Re, R9 and R10 independently of one another are C1-C10 alkyl, C6-C12 aryl; , C3-C10 cycloalkyl or R8 and R9 together with the nitrogen atom to which they are attached form a four-, five- or six-membered heterocycle, and • said composition A comprising one or more compounds of formula (I).
The present process allows the formation of one or more compounds derived from said one or more compounds of formula (I) wherein, for all or part of the carbon-carbon double bonds, a carbon atom of the carbon-carbon double bonds of the Formula (I) has been substituted with one -CH 2 OH group, the other carbon atom of this same carbon double bond being substituted with hydrogen.
Brief description of the figures
Fig. 1 represents a diagram of the synthesis of polyols according to a particular embodiment of the invention,
Fig. 2 represents a 1H NMR spectrum of triolein.
Fig. 3 represents a 1 H NMR spectrum of the product obtained by the process according to a particular embodiment from triolein.
Detailed description of the present invention
The term "substituted" as used in the present invention means that one or more hydrogen atoms of the group to which the term "substituted" refers is replaced by one of the named substituents provided that the normal valence of the atom on which the substitution is considered is not exceeded and that the substitution results in a stable chemical compound, i.e. a compound sufficiently robust to be isolated from a reaction mixture.
The term "alkyl" refers to linear or branched hydrocarbon chains containing the specified number of carbon atoms. For example, C 1 -C 6 alkyl means a linear or branched alkyl group containing at least 1 and at most 6 carbon atoms. The alkyl group may be substituted with unsubstituted aryl, halogen, NO2, CN, SO9H, OH, C1-C10 alkoxy, carbonyl or carboxyl. The term "aryl" refers to an aromatic hydrocarbon ring containing the specified number of carbon atoms substituted or unsubstituted by unsubstituted C1-C10 alkyl, halogen, NO2, CN, SO3H, carbonyl, carboxyl, OH, alkoxy in C1-C10. For example, aryl may be phenyl, naphthyl, anthracyl or phenanthryl. The term "cycloalkyl" refers to a monocyclic or condensed polycyclic non-aromatic hydrocarbon ring having the specified number of carbon atoms. For example, cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. The term "heterocycle" refers to a fused monocyclic or fused polycyclic non-aromatic hydrocarbon ring having the specified number of members, wherein at least one of the carbon atoms is replaced by a phosphorus, sulfur, nitrogen, or nitrogen atom. oxygen. In particular, the term heterocycle as used in the present invention refers to a monocyclic or condensed polycyclic non-aromatic hydrocarbon ring having the specified number of members and wherein at least one of the carbon atoms is replaced by a nitrogen atom. . . According to the present invention, a process for preparing polyols is provided. The present process for the preparation of polyols is carried out from a composition A comprising one or more compounds of formula (I)
wherein R1, R2, R4, R4, R5, R7 and R7 are independently of each other, and for R3 and R7 independently for each of [CR3R7] - units selected from the group consisting of H, -OR15, C1-C10 alkyl optionally substituted with one or more -OR15 groups, C6-C11 aryl optionally substituted with one or more -OR15 groups, or C3-C10 cycloalkyl optionally substituted with one or more -OR15 groups, or a group of formula (la)
R15 is H or C1-C10 alkyl substituted or unsubstituted with one or more -OH groups; a, b, x and y are independently of each other, independently for each group of formula (la), independently for each unit [(CHz) a-OC- (CH 2) b] f and independently for each unit [(CH 2 ) xC = G- (CH 2) y] p; an integer between 0 and 20, advantageously between 0 and 15, preferably between 0 and 12; r is an integer from 1 to 10, preferably from 1 to 5; p is an integer between 1 and 10, preferably between 1 and 5; n is an integer from 1 to 7; said method comprising a step a) of contacting with stirring and in an atmosphere of hydrogen and carbon monoxide: • of at least one precatalyst being a complex comprising a transition metal chosen from column 9 of the periodic table of elements, • a tertiary amine, or a non-quaternary ammonium salt thereof, of formula NR8R9R10 wherein Ra, R8 and R10 independently of one another are C1-C10 alkyl, C6-C12 aryl , C3-C10 cycloalkyl or R8 and R9 together with the nitrogen atom to which they are attached form a four-, five- or six-membered heterocycle, of said composition A comprising one or more compounds of formula (O-
The carbon-carbon double bonds contained in the compound (s) of formula (I), (la) or (II) as described in the present invention may be cis or trans configuration. The term dual carbon-carbon bond (s) encompasses both configurations.
Figure 1 illustrates the process according to a particular embodiment of the present invention involving a hydrohydroxymethylation reaction. The compound (I) is represented by triolein comprising three carbon-carbon double bonds. The process according to the present invention thus allows the preparation of a polyol in which the three carbon-carbon double bonds are hydrohydroxymethylated. The -CH 2 OH group may be carried for each of the carbon-carbon double bonds by any one of the carbon atoms C1 or C2, C'1 or C'2, C "1 or C" 2.
According to a preferred embodiment, said composition A may comprise at least 20% by weight of said one or more compounds of formula (I) on the basis of the total weight of composition A, advantageously at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, in particular at least 60% by weight, more particularly at least 70% by weight, preferably at least 80% by weight.
Preferably, a and x may be independently of each other, independently for each group of formula (Ia), independently for each unit [(CH2) <rC = C- (CH2) b] r and independently for each unit [(CH 2) XC = C- (CH 2) y] p an integer between 1 and 12, advantageously between 2 and 10, preferably between 3 and 9, in particular between 3 and 8 and more particularly between 4 and 8; .
Preferably, b and y may be independently of one another, independently for each group of formula (Ia), independently for each unit [(CH 2) aC = O (CH 1) b] r and independently for each unit [(CH 2 -CC- (CH 2) y] p an integer between 0 and 12, advantageously between 0 and 10, preferably between 0 and 9, in particular between 2 and 9, and more particularly between 3 and 8.
Preferably, n may be an integer between 1 and 7, advantageously between 1 and 5, preferably between 1 and 4, in particular between 1 and 3, and more particularly n is 1.
Preferably, p may be an integer between 1 and 5, advantageously between 1 and 4, preferably between 1 and 3. In particular, p is 1, 2 "or 3, more particularly, p is 1 or 2.
Preferably, r may be an integer between 1 and 5, advantageously between 1 and 4, preferably between 1 and 3. In particular, r is 1, 2 or 3, more particularly, r is 1 or 2.
Advantageously, in said one or more compounds of formula (I), at least one of the substituents R1, R2, R3, R4, R6, R8 and R7 is a group of formula (Ia). Preferably, in said one or more compounds of formula (I), at least two of the substituents R1, R2, R3, R4, R5, R6 and R7 are a group of formula (Ia).
According to a preferred embodiment, said one or more compounds of formula (I) are of formula (II)
wherein a, b, x and y are independently of each other, independently for each group of formula (Ia), independently for each unit [(CHi) aC = C- (CH2) b] r and independently for each unit [ (CH 2) xC = C- (CH 2) y] p, an integer between 0 and 20, advantageously between 0 and 15, preferably between 0 and 12; r is an integer from 1 to 10, preferably from 1 to 5; p is an integer between 1 and 10, preferably between 1 and 5; n is an integer between 1 and 7, preferably between 1 and 4; R1, R2, R9, R4 and R5 are independently of each other, and for R3 independently for each of the units n, selected from the group consisting of H, -OR15, a group of formula (la) as described above C 1 -C 10 alkyl optionally substituted with one or more -OR 15 groups, C 6 -C 12 aryl optionally substituted with one or more -OR 15 groups, or C 3 -C 10 cycloalkyl optionally substituted with one or more -OR 15 groups, in which wherein R 15 is H or C 1 -C 10 alkyl substituted or unsubstituted with one or more -OH groups.
In said one or more compounds of formula (11), a and x may be independently of each other, independently for each unit [(CH 2 -CC- * (CH 2) y] p and independently for each unit [ (CH2) aC = C- (CH2) b] r, an integer between 1 and 12, advantageously between 2 and 10, preferably between 3 and 9, in particular between 3 and 8 and more particularly between 4 and 8.
In said one or more compounds of formula (II), b and y may be independently of each other, independently for each unit [(CH 2) XC = C- (CH 1) y] p and independently for each unit [ (CH2) aC = C- (CH2) b] r, an integer between 0 and 12, advantageously between 0 and 10, preferably between 0 and 9, in particular between 2 and 9, and more particularly between 3 and 8; .
In said one or more compounds of formula (II), n can be an integer between 1 and 7, advantageously between 1 and 5, preferably between 1 and 4, in particular between 1 and 3, and more particularly n is 1. .
In said one or more compounds of formula (II), p may be an integer between 1 and 5, preferably between 1 and 4, preferably between 1 and 3.
In particular, p is 1, 2 or 3, more particularly, p is 1 or 2.
In said one or more compounds of formula (II), r may be an integer between 1 and 5, preferably between 1 and 4, preferably between 1 and 3.
In particular, r is 1, 2 or 3, more particularly, r is 1 or 2.
Preferably, in said one or more compounds of formula (II), the substituents R 1, R 2, R 3, R 4 and R 5 may be independently of each other, and for R 3 independently for each of the units n, selected from the group consisting of H, -OR15, a group of formula (la) as described above, C1-C10 alkyl optionally substituted with one or more -OR15 groups, in which R1S represents H or C1-C10 alkyl substituted or unsubstituted with one or more -OH groups.
In particular, in said one or more compounds of formula (II), the substituents R1, R2, R3, R4 and R5 may be independently of one another, and for Ra independently for each of the units n, selected from the group consisting of H, C1-C10 alkyl substituted or unsubstituted with one or more -OR1S groups, wherein R1S is H.
More particularly, in said one or more compounds of formula (II), the substituents R1, R2, R3, R4 and R5 are hydrogen.
Thus, according to a preferred embodiment, said one or more compounds are of formula (II) in which a and x can be independently of each other, independently for each unit [(CH2) xC = C- (CH2) ) y] P and independently for each unit [(CH2) eC = C- (CH2) b] r, an integer between 1 and 12, advantageously between 2 and 10, preferably between 3 and 9, in particular between 3 and 8 and more particularly between 4 and 8; b and y may be independently of each other, independently for each unit [(CH2) * - C = C- (CH2) y] p and independently for each unit [(CH2) aC = C- (CH2) b] r, an integer between 0 and 12, advantageously between 0 and 10, preferably between 0 and 9, in particular between 2 and 9, and more particularly between 3 and 8; R1, R2, R3, R4 and R5 are hydrogen; p is 1, 2 or 3 independently for each unit [(CH 2) x-C = C- (CH 2) y] P; r is 1, 2 or 3 independently for each unit [(CH 2) a-C = C- (CH 2) b] r; n is 1,
According to a particular embodiment of the present invention, said composition A may consist of one or more compounds of formula (I) or (II).
In the process according to the present invention, the tertiary amine may be of formula NR 8 R 9 R 10 wherein R 8, R 9 and R 10 independently of one another are C 1 -C 10 alkyl, or R 8 and R 9 together with the nitrogen atom to which they are attached a four-, five- or six-membered heterocycle. Advantageously, the tertiary amine may be of formula NReR9R10 in which R8, R9 and R10 independently of one another represent a C1-C10 alkyl, or R8 and Rfl form together with the nitrogen atom to which they are attached a heterocycle selected from the group consisting of azetidine, diazetidine, pyrrolidine, imidazolidine, pyrazolidine, piperidine and piperazine. The imidazolidine and pyrazoidine heterocycles comprise two nitrogen atoms. In the context of the present invention, the two nitrogen atoms of these heterocycles imidazolidine and pyrazolidine are tertiary. Preferably, the tertiary amine may be of formula NR 8 R 9 R 10 wherein R 1, R 9 and R 10 independently of one another are C 1 -C 10 alkyl, or R and R 9 together with the nitrogen atom to which they are attached pyrrolidine or piperidine. In particular, the tertiary amine may be of the formula NR R 9 R 10 in which R 1, R 9 and R 10 independently of one another are C 1 -C 6 alkyl. Tertiary amine can be supported on a resin. Thus, the substituent R10 may be a spacer group between the nitrogen atom of the tertiary amine and the resin. R10 can be C1-C10 alkyl, benzyl, C6-C18 aryl or C3-C10 cycloalkyl.
Preferably, said tertiary amine has a pKa greater than 6, advantageously greater than 7, preferably greater than 8, in particular greater than 9. Preferably, said tertiary amine has a pKa of less than 15, advantageously less than 14, preferably less than 12, in particular less than 11. Said tertiary amine may thus have a pKa of between 6 and 14, advantageously between 8 and 12, preferably between 9 and 11.
The present process is carried out under the pressure of an atmosphere of hydrogen and carbon monoxide. Pressure refers to the sum of the partial pressures of carbon monoxide and hydrogen. The pressure may be between 50 bars and 200 bars, advantageously between 65 bars and 150 bars, preferably between 70 bars and 130 bars, in particular between 75 bars and 120 bars.
Preferably, the molar ratio between carbon monoxide and hydrogen may be between 2: 1 and 1:10, advantageously the molar ratio between carbon monoxide and hydrogen is between 1: 1 and 1: 5 preferably, the molar ratio is between 1: 1 and 1; 3, in particular the molar ratio between carbon monoxide and hydrogen is between 1: 1 and 1: 2.
Preferably, step a) of the present process may be carried out at a temperature of between 60 ° C and 200 ° C, preferably between 70 ° C and 180 ° C, preferably between 80 ° C and 150 ° C. Step a) of the present process may be carried out in the presence of an organic solvent such as aromatic or aliphatic hydrocarbons. For example, the solvent may be toluene, benzene, hexane or heptane.
As mentioned above, the process according to the present invention is carried out in the presence of at least one precatalyst. Said precatalyst is a complex comprising a transition metal chosen from column 9 of the periodic table of the elements. Advantageously, said precatalyst is a complex comprising a transition metal chosen from cobalt or rhodium. Advantageously, the precatalyst is a complex comprising rhodium as a transition metal and one or more ligands. Preferably, at least one of said one or more ligands is selected from CO, acetylacetonate, cyclooctadiene, norbornene, acetate. The precatalyst may be supported on a solid support. The support may be carbon black, SiO 2, ΑΙ 2 O 3, Tip 2, MgO, ZnO, CaCO 3, CaSO 4 or MgSO 4 or a combination thereof. The ratio by weight between the support and the precatalyst may be between 1 and 100.
Preferably, the molar ratio between the tertiary amine of formula NR 8 R 9 R 10 as described above and the transition metal of the complex used as precatalyst in step a) of the present process is greater than 20, advantageously greater than 50, of preferably greater than 100, in particular greater than 200.
Said one or more ligands may also comprise at least one monodentate or bidentate phosphorus ligand comprising at least one C 6 -C 18 aryl substituent substituted in the ortho position with respect to the phosphorus atom or comprising at least one aryloxy substituent in Ce-CiB. Advantageously, said phosphorus ligand may be of formula P (Ar) 3 or (Ar) 2 -P-L-P (Ar) 2, of which Ar is a C 6 -C 6 aryl group; substituted at least in position ortho to the phosphorus atom by a group selected from the group consisting of C1-C6 alkyl, phenyl, benzyl, C3-C6 cycloalkyl, halogen, C1-C6 alkoxyl, C6-aryloxy; and L is a spacer arm selected from the group consisting of C 1 -C 6 alkyl, C 6 -C 13 aryl, C 1 -C 10 cycloalkyl. The expression "ortho-position substituted with respect to the phosphorus atom" means that in the aryl ring, at least one of the two ortho positions with respect to the carbon atom bonded to the phosphorus atom is substituted by one of the groups mentioned. Preferably, said phosphorus ligand may be of formula P (Ar) 3 in which Ar is a C 6 -C 18 aryl group substituted in the ortho position with respect to the phosphorus atom by a group selected from the group consisting of methyl, ethyl , methoxy, phenyl, benzyl, -F, cyclohexyl.
Alternatively, said phosphorus ligand may be of formula P (O-Ar) 3 or (Ar-O) rP-LP (O-Ar) 2 in which Ar is a C 6 -C 18 aryl group substituted or unsubstituted with a group selected from the group consisting of C 1 -C 6 alkyl, C 3 -C 6 alkyl, halogen, C 1 -C 6 alkoxyl, C 6 aryloxy; and L is a spacer arm selected from the group consisting of C1-C18 alkyl, C6-C12 aryl, C3-C10 cycloalkyl. Preferably, said phosphorus ligand can be of formula P (O-Ar) 3 in which Ar is a C 6 aryl substituted or not a methyl, ethyl, methoxy, phenyl, benzyl or cyclohexyl group.
In particular, said phosphorus ligand may be P (OPh) 3, P (C 6 F 5) 3, P (o-MePh) 3, P (o-OMePh) 3.
Alternatively, said one or more ligands also comprise at least one water-soluble monodentate or bidentate phosphonated ligand comprising at least one functional group SO 3 X +, N R- / A, CO 2 X, X representing Li, Na or K; and A representing Cl, Br or I. Advantageously, said phosphorus ligand can be of formula P (Ar) 3 or (Ar) 2-PLP (Ar) 2 in which L is a spacer arm selected from the group consisting of C 1 alkyl -C, C6-C12 aryl, C3-C10 cycloalkyl; and Ar is a C 6 -C 18 aryl substituted by at least one functional group SOaX *, NR 3 * A ', GQ 2 X +, X representing Li, Na or K, and A representing 51 51; Br or I; and optionally substituted with a group selected from the group consisting of CrCe alkyl, phenyl, benzyl, C3-C6 cycloalkyl, halogen, C1-C6 alkoxyl, C6 aryloxy.
According to a particular embodiment, step a) also brings into contact a cyclodextrin -α, -β, -γ methylated having an average degree of substitution of between 0.5 and 2.0 or a cyclodextrin -α, -β , -η hydroxylated having an average degree of substitution of between 0.5 and 0.9. Said cyclodextrin -α, -β, -γ methylated may have an average degree of substitution of between 1.6 and 2.0, or between 0.9 and 1.6 or between 0.5 and 0.9. When a cyclodextrin and a water-soluble phosphorus ligand as mentioned above are used in step a), water is also added at this same step a) to create a biphasic medium comprising an organic phase and an aqueous phase . Before carrying out the reaction, the organic phase consists in particular of the compound of formula (I) or (II) according to the present invention and of the tertiary amine. In this embodiment, the tertiary amine is of the formula NR 8 R 9 R 10 in which R 5, R 8 and R 10 represent, independently of one another, a C 4 -C 10 alkyl. When the process is carried out in the presence of a cyclodextrin, the precatalyst comprising at least one phosphorus monodentate or water-soluble bidentate ligand as defined above. In addition, the process is then carried out under operating conditions allowing the establishment of an emulsion during stirring and decantation of the reaction products after stopping the stirring, preferably the decantation of at least a part of the reaction. of the compound according to the present invention. Advantageously, the proportion of cyclodextrin is between 15 and 40% by weight based on the total weight of water, cyclodextrin and said one or more compounds of formula (I), preferably of formula (II) as described above. above, brought together in step a).
The method according to the present invention may also comprise a recycling step when the process is carried out in biphasic medium. The recycling step comprises degassing the reactor in which the process according to the present invention is carried out, withdrawing the organic phase under a controlled atmosphere, and adding to the reactor composition A comprising one or more compounds of formula ( I) or of formula (II) as described above, tertiary amine NR9R9R10 and optionally one or more ligands as described above. During this recycling step, the temperature may remain constant, i.e., remain at the temperature at which the hydrohydroxymethylation reaction was performed, or be at a temperature above or below the temperature at which the reaction occurs. hydrohydroxymethylation was performed.
According to a particular embodiment of the present invention, said composition A comprising one or more compounds of formula (I), preferably comprising one or more compounds of formula (II), is a vegetable oil having an average number of unsaturations included between 0.5 and 20, advantageously between 0.5 and 15, preferably between 0.5 and 10.
Preferably, said composition A comprising one or more compounds of formula (I), preferably of formula (II), is a vegetable oil having an average number of unsaturations of less than 3.5, advantageously less than 3.4, of preferably less than 3.3, more preferably less than 3.2, in particular less than 3.1, more preferably less than 3.0. Preferably, said vegetable oil has an average number of unsaturations greater than 0.5, advantageously greater than 1, preferably greater than 1.5, more preferably greater than 2.0, in particular greater than 2.5. Said vegetable oil may thus have an average number of unsaturations of between 2.0 and 3.2, advantageously between 2.4 and 3.1, preferably between 2.5 and 3.0, in particular between 2.6 and 2.8.
Alternatively, said composition A comprising one or more compounds of formula (I), preferably of formula (II), is a vegetable oil having an average number of unsaturations of between 4 and 10. Methods Determination of the average number of unsaturations
The average number of unsaturations is determined by 1H NMR in deuterated chloroform (CDCl3); NMR analyzes are performed on a BRUKER 300 MHz device. The average number of unsaturations of a compound is calculated from the integration value of the 1H NMR signal of the olefinic protons located on the fatty acid unit (s) of the compound. The 1 H NMR signal of the olefinic protons is 5.3 ppm. If the signal of the olefinic protons is covered by one or more other protons, a normalization factor is applied to deduce the contribution of this last proton (s) in the integration value and thus obtain an integration value corresponding only to olefinic protons.
In the case of the compounds of formula (II) wherein R 3 is hydrogen in any of the units n, the signal of this hydrogen atom in 1H NMR covers the signal of the olefinic protons; A normalization factor, denoted FN, is thus calculated V 'according to the equation: FN = (value of the integration of a signal / theoretical number of protons of the corresponding signal)
For example, for the case of triglycerides, the normalization factor is calculated from the integration value of the 1H NMR signal corresponding to the protons of the two CH 2 groups of glycerol according to the equation FN = B / 4. Figure 2 shows the 1H NMR spectrum of triolein. The signal B representative of the signal corresponding to the protons of the two CH 2 groups of the glycerol unit has a value of 4 and the normalization factor is therefore 1. The proton CH of the glycerol covers the signal of the olefinic protons. The average number of unsaturations is therefore deduced from the following equation: DBi = (A-FN) / 2 where A corresponds to the integration value of the signal corresponding to the proton CH of glycerol and olefinic protons (as indicated in FIG. Figure 2), and FN is the normalization factor described above.
When the test compound is not a triglyceride, one skilled in the art will adapt the calculation of the normalization factor FN on the basis of another proton or another proton group, for example the protons located in position C or D in Figure 2.
Conversion of the reaction
The conversion of the reaction is given by the following formula;
Conv. (%) = ((DBi - DBf) / DBi) * 100 = ((Ai - Af) / (Ai - FN)) * 100 where DBi and DBf are respectively the number of initial and final unsaturations and Ai and Afl integration of the signals A at the beginning and the end of the reaction. The signals A correspond to the 1H NMR signals of the olefinic protons as explained above. If the signal of the olefinic protons is covered by one or more other protons not corresponding to the olefinic protons, a normalization factor FN is applied and calculated as explained above, Determination of the selectivity to alcohol
The selectivities of hydrogenated aldehydes, alcohols and C = C supported by the products of the reaction are determined by integration of the 1H NMR signals. FIG. 3 represents a 1 H NMR spectrum of the product resulting from the implementation of the process according to the invention from triolein. The proton CH2 signal of the hydroxymethyl group (denoted C in FIG. 3) is 3.54 ppm. The alcohol selectivity of the reaction is given by the formula:
Selec. (HHM) (%) = ((C / (2 * FN)) / (DBi - DBf)} * 100 where C represents the integration value of the signal corresponding to the protons CH * of the hydroxymethyl group, FN represents the factor of normalization, DBi and DBf represent the number of initial and final double bonds.
Examples
Example 1
In a reactor, 1 mL of triolein (1 mmol), 5 mL of toluene, 3.9 mg of Rh (CO) 2 (acac) (0.015 mmol), 3 mmol of amine are mixed. The reaction is carried out under a pressure of 80 bar of carbon monoxide and hydrogen (molar ratio 1: 1) for 18 hours at 80 ° C.
Table 1 below shows the results obtained with different tertiary amines.
Table 1 - Catalytic Performance Versus Tertiary Amine
Reaction conditions: triotein: 1 mmol (1 mL, 3 mmol C = C); Rh (CO) & cac: 0.015 mmol (3.9 mg); toluene: 5m! ; amine: 3 mmol (TMEDA and 1,10-phen: 1.5 mmol); CO / H2 pressure (1: 1): 80 bar; temperature: 80 ° C; 18 hours TMEDA: N, N, N ', N'-tetramethylethylenediamine; NMP: N-methyl-2-pyrrolidone; 1,10-phen: 1,10-phenanthroline
The results of Example 1 demonstrate that the use of tertiary amine allows the synthesis of one pot polyols without the use of cocatalyst or other additives under relatively mild catalytic conditions. The use of aliphatic tertiary amines, cyclic or otherwise, allows the majority formation of the desired polyols with excellent conversion and selectivity. However, the use of nitrogen heteroaryls (pyridine and pyrrole) or of amides leads to a hydroformylation reaction without a hydrogenation step thus giving predominantly aldehydes,
EXAMPLE 2 Example 1 was repeated using tributylamine as tertiary amine and varying the pressure to carbon monoxide and hydrogen. The reaction time is 6 hours. Table 2 shows the results obtained.
Table 2 - Catalytic performances as a function of the pressure in synthesis gas
Reaction conditions: triotein: 1 mmol (1 mL, 3 mmol C = C); Rh (CO) 2acac: 0.015 mmol (3.9mg); toluene: 5ml; tributylamine; 3 mmol; CO / Hi (1: 1); temperature: 80 ° C; 6 hours
The total pressure of synthesis gas CO / H2 has an influence on the conversions of hydrohydroxymethylation as well as on the selectivities in final products. As the total pressure increases, conversion and selectivity to alcohol also increase. It should also be noted that as the pressure increases, the hydrogenation selectivity of C = C decreases. However, by substantially increasing the pressure, the first hydroformylation step is favored, followed by the hydrogenation step of the newly formed aldehydes, the hydrogenation of the substrate then having to be slower.
Example 3 Example 1 was repeated in the presence of tributylamine for 6 hours by varying the reaction temperature. Table 3 shows the results obtained.
Table 3 - Catalytic performance as a function of temperature
Reaction conditions: triolene: 1 mmol (1 mL, 3 mmol C-C); Rh (CO) 2acac: 0.015 mmol (3.9mg); toluene: 5ml; tributylamine: 3 mmol; CO / Hz pressure (1: 1): 80 bar; 6 hours
Above 80 ° C, the conversion of triglycerides increases, accompanied by a high activity in hydrogenation of aldehydes produced and surprisingly limiting the hydrogenation of the carbon-carbon double bonds of the substrate.
Example 4 The purpose of Example 4 is to determine the influence of the CO / H2 molar ratio on the hydrohydroxymethylation reaction. Example 1 was reproduced with triethylamine as tertiary amine. The reaction time was set at 6 hours. The results are shown in Table 4 below.
Table 4. Influence of the CO / H2 ratio
Reaction conditions: triolene: 1 mmol (1 mL, 3 mmol C = C); Rh (CO) 2acac: 0.015 mmol (3.9 mg); toluene: 5ml; amine: 3 mmol; total pressure CO / Hz: 80 bar; Temperature: 80 ° C; 6 hours The increase of the hydrogen partial pressure has a surprising effect on the formation of alcohol. The use of a 1: 2 molar ratio of CO / H2 makes it possible to reach stoichiometric proportions of reaction (a molecule of CO used for two molecules of hydrogen) and makes the catalytic system more hydrogenating to reach rapidly the expected polyols. .
Example 5
The present method of preparing polyols has been applied from a natural vegetable oil. Table 5 shows the results obtained.
Table 5. Application to vegetable oils
Reaction conditions: oil: 1 mmol (1 mL); Rh (CO) iacac: 0.015 mmol (3.9 mg); toluene: 5 ml; triethylamine: 3 mmol; CO / H2 pressure (1: 1); 80 bar; Temperature: 80 'C
It emerges from these results that the process according to the invention applies to vegetable oils, that is to say to compositions comprising triglycerides of different structure.
Example 6 Example 1 was reproduced in the presence of a self-emulsifying system. The addition of cyclodextrin, and in particular of CRYSMEB® (CDs methylated in position 2 and having a degree of substitution per glucosidic unit (DS) of 0.8) makes it possible to form a surfactant complex at the oil / water interface. This complex stabilizes the interface makes it possible to put the biphasic system in emulsion and to increase the interface between the two media. The process is carried out in the presence of a precatalyst also comprising a water-soluble phosphine ligand, such as the trisodium salt of the meta-sulphonated tripenylphosphine triphonate (TPPTS). The results are shown in Table 6 below.
Table 6 - Process in a self-emulsifying medium
Reaction conditions: triolene: 1 mmol (1 mL, 3 mmol C = C); Rh (CO) 2ac. 0.015 mmol (3.9 mg); TPPTS: 0.075 mmol (42 mg),; water: 8 ml; CRYSMEB: 2 mmol (2.3 g); amine. 3 mmol; CO / hh pressure (1: 1): 80 bar; Temperature: 80 ° C; 18 hours. The use of cyclodextrin in a self-emulsifying medium makes it possible to effectively convert the initial C = C unsaturations in alcohol function and this with very good selectivity and by limiting the formation of hydrogenation product.
The terms and descriptions used here are for illustrative purposes only and are not limitations. Those skilled in the art will recognize that many variations are possible within the spirit and scope of the invention as described in the following claims and equivalents thereof; in these, all terms must be understood in their broadest sense unless it is
V indicated otherwise.

权利要求:
Claims (10)
[1" id="c-fr-0001]
claims
A process for preparing polyols from a composition A comprising one or more compounds of formula (I)

wherein R1, R2, R3, R4, R5, Re and R7 are independently of each other, and for R3 and R7 independently for each of n, selected from the group consisting of -C10 substituted or not by one or more -OR15 groups, Cb-C12 aryl substituted or not by one or more -OR15 groups, or C3-C10 cycloalkyl substituted or unsubstituted by one or more -OR15 groups, or a group of formula

R15 represents H or C1-C10 alkyl optionally substituted with one or more -OH groups a, b, x and y are independently of each other, independently for each group of formula (la), independently for each unit [(CH2 ) aC = C- (CH2) b] and independently for each unit [(CH2)> .- C = C- (CH2) y] p, an integer between 0 and 20, advantageously between 0 and 15, of preferably between 0 and 12; r is an integer from 1 to 10, preferably from 1 to 5; p is an integer between 1 and 10, preferably between 1 and 5; n is an integer from 1 to 7; said method comprising a step a) of contacting with stirring and under an atmosphere of hydrogen and carbon monoxide: • at least one precatalyst being a complex comprising a transition metal chosen from column 9 of the periodic table, A tertiary amine, or a non-quaternary ammonium salt thereof, of formula NR 8 R 9 R 10 in which R 1, R 9 and R 10 represent, independently of each other, a C 1 -C 10 alkyl or C 1 -C 12 aryl, C3-C10 cycloalkyl or R8 and Ra form together with the nitrogen atom to which they are attached a four-, five- or six-membered heterocycle; of said composition A comprising said compound of formula (I).
[2" id="c-fr-0002]
2. Method according to any one of the preceding claims characterized in that step a) is carried out at a temperature between 70 ° C and 180 * 0, preferably between 80 ° C and 150 * 0.
[3" id="c-fr-0003]
3. Process according to any one of the preceding claims, characterized in that the said at least one compound of formula (I) is of formula (II)

wherein a, b, x and y are independently of each other, independently for each group of formula (la), independently for each unit [(CH2) aC = C- (CH2) b] r and independently for each unit [ (CH2) xC = C- (CH2) y] P, an integer between 0 and 20, advantageously between 0 and 15, preferably between 0 and 12; p is independently for each unit [(CH2) x-C = C- (CH2) y] p an integer of from 1 to 5; r is independently for each unit [(CH2) a-C = C- (CH2) b] r an integer of from 1 to 5; R1, R2, R3, R1 * and R5 are independently of each other, and for R3 independently for each n, selected from the group consisting of H, -OR15, C1-C10 alkyl substituted or unsubstituted by one or more -OR15 groups, or a group of formula (la) as described above, R1S represents H or C1-C10 alkyl optionally substituted with one or more -OH groups; n is an integer between 1 and 4,
[4" id="c-fr-0004]
4. Method according to the preceding claim characterized in that said at least one compound of formula (I) is of formula (II) in which a and x can be independently of each other, independently for each unit [(CH 2 ) xC = C- (CH2) y] P and independently for each unit [(CH2) a'C = C- (CH2) b] f, an integer between 1 and 12, preferably between 2 and 10, preferably between 3 and 9, in particular between 3 and 8 and more particularly between 4 and 8; b and y may be independently of each other, independently for each unit [(CH2) xC = C- (CH2) y] p and independently for each unit [(CH2) aC = C- (CH2) b] r, an integer between 0 and 12, advantageously between 0 and 10, preferably between 0 and 9, in particular between 2 and 9, and more particularly between 3 and 8; R1, Rz, R3, R4 and R5 are hydrogen; p is 1,2 or 3 independently for each unit [(CH2) x-C = C- (CH2) y] p; r is 1, 2 or 3 independently for each unit [(CH2) a-C-C- (CH2) [,] r; n is 1.
[5" id="c-fr-0005]
5. Process according to any one of the preceding claims, characterized in that the tertiary amine is of formula NR8R9R10 in which R8, R8 and R10 independently of one another represent a C1-C10 alkyl, or Rs and R® form together with the nitrogen atom to which they are attached a heterocycle azetidine, diazetidine, pyrrolidine, imidazolidine or pyrazolidine; preferably R8, R8 and R10 independently of one another are C1-C10 alkyl, or R8 and R8 together with the nitrogen atom to which they are attached form a pyrrolidine.
[6" id="c-fr-0006]
6. Process according to any one of the preceding claims, characterized in that the precatalyst is a complex comprising rhodium as a transition metal and one or more ligands; preferably at least one of said one or more ligands is selected from CO, acetylacetonate, cyclooctadiene, norbornene and acetate.
[7" id="c-fr-0007]
7. Process according to any one of the preceding claims, characterized in that it is carried out under pressure with an atmosphere of hydrogen and carbon monoxide, said pressure being between 50 bars and 200 bars, advantageously between 65 bars and 150 bars, preferably between 70 bars and 130 bars, in particular between 75 bars and 120 bars.
[8" id="c-fr-0008]
8. Process according to any one of the preceding claims, characterized in that the molar ratio between carbon monoxide and hydrogen is between 2: 1 and 1: 10, advantageously the molar ratio between carbon monoxide and carbon monoxide. hydrogen is between 1: 1 and 1: 5, preferably the molar ratio is between 1: 1 and 1: 3, in particular the molar ratio between carbon monoxide and hydrogen is between 1: 1 and 1 : 2.
[9" id="c-fr-0009]
9. Process according to any one of the preceding claims, characterized in that the molar ratio between the amine and the transition metal is greater than 20, advantageously greater than 50, preferably greater than 100, in particular greater than 200.
[10" id="c-fr-0010]
10. Process according to any one of the preceding claims, characterized in that the said composition A comprising one or more compounds of formula (I) is a vegetable oil having an average number of unsaturations of less than 3.5, advantageously less than 3, 4, preferably less than 3.3, more preferably less than 3.2, in particular less than 3.1, more preferably less than 3.0.

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ES2734263T3|2019-12-05|

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

GB2046266A|1979-04-07|1980-11-12|Henkel Kgaa|Process for the production of nonadecane diols|

---

WO2003093215A1|2002-04-29|2003-11-13|Dow Global Technologies Inc.|Intergrated chemical processes for industrial utilization of seed oils|

---

US20050070620A1|2003-09-30|2005-03-31|Ron Herrington|Flexible polyurethane foams prepared using modified vegetable oil-based polyols|

---

US4197414A|1977-06-06|1980-04-08|The Dow Chemical Company|Amine-resin supported rhodium-cobalt bimetallic clusters as novel hydroformylation catalysts|

---

EP0014225A1|1979-02-13|1980-08-20|The Dow Chemical Company|Amine-resin supported rhodium-cobalt bimetallic clusters as hydroformylation catalysts, their preparation and oxo process utilising such a catalyst|

---

PL1797057T3|2004-06-25|2019-02-28|Pittsburg State University|Modified vegetable oil-based polyols|EP3844293A1|2018-08-30|2021-07-07|Checkerspot, Inc.|Hydroformylated triglycerides and uses thereof|

---

WO2020167745A1|2019-02-11|2020-08-20|Checkerspot, Inc.|Triglyceride oil compositions|

---

WO2020193681A1|2019-03-26|2020-10-01|Novogy, Inc.|Derivatives of 10-methylene lipids, process for preparing such derivatives and use thereof|

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优先权:

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申请号 | 申请日 | 专利标题

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FR1501373A|FR3038312B1|2015-06-30|2015-06-30|PROCESS FOR THE PREPARATION OF POLYOLS|FR1501373A| FR3038312B1|2015-06-30|2015-06-30|PROCESS FOR THE PREPARATION OF POLYOLS|

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CA2987682A| CA2987682A1|2015-06-30|2016-06-15|Process for preparing polyols|

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EP16732992.9A| EP3317247B1|2015-06-30|2016-06-15|Process for preparing polyols|

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US15/569,880| US10138200B2|2015-06-30|2016-06-15|Process for preparing polyols|

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JP2017566860A| JP2018522865A|2015-06-30|2016-06-15|Process for preparing polyols|

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ES16732992T| ES2734263T3|2015-06-30|2016-06-15|Polyol Preparation Procedure|

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PCT/EP2016/063718| WO2017001194A1|2015-06-30|2016-06-15|Process for preparing polyols|