EP3523358A1 - Procédé de fabrication de polyphénols alcoxylés - Google Patents
Procédé de fabrication de polyphénols alcoxylésInfo
- Publication number
- EP3523358A1 EP3523358A1 EP17787506.9A EP17787506A EP3523358A1 EP 3523358 A1 EP3523358 A1 EP 3523358A1 EP 17787506 A EP17787506 A EP 17787506A EP 3523358 A1 EP3523358 A1 EP 3523358A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyphenol
- glycol
- mpa
- lignin
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims abstract description 51
- 235000013824 polyphenols Nutrition 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229920005610 lignin Polymers 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 48
- -1 poly (oxyalkylene glycol Chemical compound 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229920001451 polypropylene glycol Polymers 0.000 claims description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 16
- 229920005611 kraft lignin Polymers 0.000 claims description 8
- 229920001732 Lignosulfonate Polymers 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920001864 tannin Polymers 0.000 claims description 4
- 235000018553 tannin Nutrition 0.000 claims description 4
- 239000001648 tannin Substances 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004117 Lignosulphonate Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 235000019357 lignosulphonate Nutrition 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- ZMWAXVAETNTVAT-UHFFFAOYSA-N 7-n,8-n,5-triphenylphenazin-5-ium-2,3,7,8-tetramine;chloride Chemical compound [Cl-].C=1C=CC=CC=1NC=1C=C2[N+](C=3C=CC=CC=3)=C3C=C(N)C(N)=CC3=NC2=CC=1NC1=CC=CC=C1 ZMWAXVAETNTVAT-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 description 1
- 229940119526 coniferyl alcohol Drugs 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
Definitions
- the invention relates to a process for producing alkoxylated polyphenols, more specifically alkoxylated lignins.
- Lignin is one of the main components of wood, with cellulose and hemicellulose. Lignin is the most abundant biopolymer on Earth after cellulose. It ensures the rigidity of the wood by interpenetrating the cellulose network while conferring resistance to water and some wood pests.
- lignin Although abundant, it is clear that lignin is little valued as such. Until now, and even today, lignin's primary use is energy recovery, particularly through the burning of black liquors. This valuation is important for the economic balance of pulp mills. However, in the face of the drop in pulp production and lignin surpluses, work is being done to improve the value of lignin.
- lignin can be used for the manufacture of polyurethane foam derivatives. Since lignin is a polyphenol, it has a large number of alcohol functional groups capable of reacting, for example with isocyanates to form the polyurethane derivatives. However, since these alcohol functions are difficult to access within this polyphenol, it is necessary to carry out a propoxylation reaction of these functions beforehand, leading to less congested alcohol functions (further from the polyphenol nucleus), and thereby more accessible.
- the process used by different authors consists first of all in a propoxylation of the lignin by reacting the lignin with the propylene oxide in the presence of a catalyst and then reacting the product obtained with example of isocyanate.
- the reaction is initiated around 150 ° C with a strong exotherm which causes a sudden rise in temperature to 250 ° C and pressure of a few bars to more than 20 bar. The authors believe that the reaction is complete when the pressure and temperature decrease and reach a stable plateau.
- propylene oxide may be homopolymerized, as mentioned in EP2816052.
- the propoxylated lignin is then mixed with the poly (propylene) glycols, which can not be readily separated from the propoxylated lignin.
- the product manufactured is a mixture of propoxylated lignin and dispersant, optionally propoxylated, difficult to separate from the propoxylated lignin. It should also be noted that the reaction times are extremely long, the temperature during the reaction is low and the pressure during the reaction used is low.
- the lignin is in solid form. Because of this, it is difficult to engage it in the form of a homogeneous reaction medium. It also tends to generate deposits that can clog different components of an installation, such as for example reactors, pipes, valves, ducts, etc. For this reason, it is also difficult to manipulate on the industrial plan.
- the above references disclose suspending lignin in dispersants, which can solubilize at least in part or all the lignin. However, these processes require subsequent separation steps to isolate the propoxylated lignin from the reaction byproducts of the dispersant with the reactants. In addition, the reaction conditions employed are not necessarily compatible with industrial use.
- the present invention aims to provide a solution to solve all of the problems mentioned above.
- the present invention relates to a method of manufacturing at least one alkoxylated polyphenol comprising the following successive steps:
- the method according to the invention can synthesize the alkoxylated polyphenol in good safety conditions, so that it can be carried out on an industrial scale. Indeed, the operating conditions in terms of temperature and pressure are controlled by the method according to the invention. The exothermic reaction is particularly controlled. In addition, the process according to the invention makes it possible to obtain an alkoxylated polyphenol with a good yield and with quite reasonable reaction times that are compatible with industrial use.
- the alkoxylated polyphenol obtained by the process according to the invention can be used crude without purification.
- the process according to the invention also has the advantage of not restricting the use of alkoxylating agent to propylene oxide alone.
- ethylene oxide and / or butylene oxide or mixtures thereof can also be used.
- Step (a): The method according to the invention comprises a step (a) reacting to the at least one polyphenol, at least one alkoxylating agent, at least one catalyst, in the presence of at least one poly (oxyalkylene glycol) as a solvent, at a temperature ranging from 80 ° C. to 200 ° C., preferably at 100 ° C. at 170 ° C, at a pressure of from 0.15 MPa to 2 MPa, preferably from 0.2 MPa to 1.8 MPa.
- the polyphenols used in the process according to the invention can be chosen from tannins, lignins and natural polyphenols different from tannins and lignins.
- said polyphenol is a lignin, preferably chosen from kraft lignin, lignosulphonates and organosolv lignins.
- Kraft lignin is derived from the paper making process of the same name.
- kraft lignin is a combination of three phenolic compounds, coumaryl alcohol, coniferyl alcohol and sinapyl alcohol.
- Nndulin AT TM marketed by the company Ingevity
- the kraft lignin marketed by the company Fibria or the lignin marketed by Stora Enso can be used.
- the lignosulfonates differ structurally from the kraft lignin by the addition of sulphonic functions generally salified, which ensures them better solubility in water.
- Examples of lignosulphonates are lignosulphonates of the Borresperse TM, Ultrazine TM, Ufoxane TM or Vanisperse TM type.
- Organosolv lignins are obtained by chemical etching of woody plants, such as cereal straw, using various solvents, such as formic acid or acetic acid.
- various sources of lignins of the organosolv type there is Biolignin TM marketed by the company CIMV or marketed by the company Fibria.
- the polyphenol used is lignin.
- Alkoxylating agents used in the process according to the invention may be chosen from those of formula (I) below: wherein R 1 is a hydrogen atom or a C 1 -C 6 alkyl radical.
- R 1 denotes a hydrogen atom or a C 1 -C 2 alkyl radical.
- the alkoxylating agent is particularly preferably selected from ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, preferably propylene oxide.
- the mass ratio polyphenol / alkoxylating agent ranges from 0.05 to 2, preferably from 0.1 to 1, more preferably from 0.15 to 0.9, still more preferably from 0.15 to 0.7.
- the catalyst used in the process according to the invention may be chosen from alkali metal hydroxides, sodium or potassium alkoxides, and tertiary amines chosen from trialkylamines and tetramethylguanidine, preferably chosen from among the alkali metal hydroxides.
- the catalyst used in the process according to the invention may be chosen from lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide.
- the catalyst represents from 0.01% to 10% by weight, preferably from 1% to 6% by weight relative to the weight of polyphenol.
- poly (oxyalkylene glycol) is chosen from polypropylene glycol, polybutylene glycol, alternating or random block copolymers obtained from these monomers, and mixtures thereof.
- the alkoxylated polyphenol obtained using this specific poly (oxyalkylene glycol) is advantageously a liquid and homogeneous product.
- the poly (oxyalkylene glycol) used in the process according to the invention is chosen from dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol 220, polypropylene glycol 400 and mixtures thereof, more preferably preferentially selected from polypropylene glycol 220, polypropylene glycol 400 and mixtures thereof.
- the molar mass of the poly (oxyalkylene glycol) is greater than or equal to 100 g. mol "1 , more particularly goes from 100 g mol -1 to 6000 g. mol "1 , and even more preferably from 150 g mol -1 to 2000 g. mol "1 .
- the mass ratio polyphenol / poly (oxyalkylene glycol) is less than or equal to 2, preferably less than or equal to 1, more preferably less than or equal to 0.5.
- the polyphenol / poly (oxyalkyleneglycol) mass ratio is greater than or equal to 0.05.
- the polyphenol / poly (oxyalkyleneglycol) mass ratio ranges from 0.05 to 0.5.
- the poly (oxyalkylene glycol) constitutes the only solvent of the reaction medium of step (a).
- Step (a) according to the invention is carried out at a temperature ranging from 80 ° C to 200 ° C, preferably from 100 ° C to 170 ° C.
- the reaction pressure ranges from 0.15 MPa to 2 MPa, preferably from 0.2 MPa to 1.8 MPa, more preferably from 0.2 MPa to 0.6 MPa.
- the duration of step (a) varies from a few minutes to several hours, preferably from 5 minutes to 72 hours, more preferably from 10 minutes to 24 hours, even more preferably from 10 minutes to 12 hours.
- residual alkoxylating agent means an alkoxylating agent which has not reacted.
- said step of removing the residual alkoxylating agent is carried out by cooking, that is to say by maintaining a temperature ranging from 70 ° C. to 170 ° C., preferably from 70 ° C. to 130 ° C, to consume the residual alkoxylating agent, and / or by stripping step under inert gas stream.
- said stripping step may be carried out under steam or under vacuum.
- the residual alkoxylant agent mass content is less than or equal to 1% relative to the weight of alkoxylated polyphenol obtained at the end of step (b), preferentially lower or equal to 0.1%, more preferably less than or equal to 0.01%.
- the alkoxylated polyphenol obtained is in the form of a viscous liquid of dark color.
- the raw product is directly usable as is for the manufacture of rigid polyurethane foam (PU) derivatives, for thermal insulation for example.
- PU polyurethane foam
- the traces of catalyst can be removed by methods known to those skilled in the art.
- the method according to the invention comprises the following successive steps:
- step (a) is carried out at a temperature ranging from 80 ° C to 200 ° C, preferably from 100 ° C to 170 ° C, under a pressure ranging from 0.15 MPa to 2 MPa, preferably from 0.2 MPa to 1.8 MPa.
- the optional step (b) of drying the mixture is carried out by stripping with nitrogen or with steam.
- the method can be implemented in batch, semi-continuous or continuous.
- the method according to the invention is of batch or semi-continuous type.
- step (a) can be decomposed into 3 successive steps:
- the optional step (a2) consists of removing the water possibly formed during the reaction of the catalyst with the polyphenol or brought by the catalyst in aqueous solution.
- This drying step (a2) can be carried out by hot nitrogen stripping, that is to say at a temperature ranging from 50 ° C. to 130 ° C., and optionally under reduced pressure between 0.002 MPa and 0.1 MPa.
- step (a3) the reactor is purged with nitrogen. It is pressurized at a pressure ranging from 0.15 MPa to 0.4 MPa, and the reaction medium is heated with stirring at a temperature ranging from 100 ° C. to 150 ° C.
- the alkoxylating agent or the mixture of alkoxylating agents is then introduced semi-continuously at an introduction rate making it possible to control the temperature and the safety pressure.
- the reaction is carried out at a temperature of from 80 ° C to 200 ° C with a preference of 100 ° C to 170 ° C.
- the pressure varies according to the type of reactor and the filling rate of the latter and varies from 0.15 MPa to 2 MPa.
- step (b) is performed to remove the residual alkoxylating agent, which consists of consuming the remainder of the alkoxylating agent by maintaining the temperature. There is a drop in pressure until the theoretical pressure due to nitrogen alone. It is also possible to carry out a stripping step with an inert gas, such as nitrogen, or with steam and / or under vacuum, to remove the last traces of alkoxylating agent.
- an inert gas such as nitrogen
- a second variant of the process according to the invention is a continuous type process, comprising the following successive steps:
- Step (a1) is carried out by feeding the polyphenol, the poly (oxyalkylene glycol) and the catalyst into a reactor.
- the reactor may be a stirred tank or a mixing device such as an extruder. This step can be carried out continuously with a continuous feed of the reagents and a continuous withdrawal of the reaction mixture formed.
- reaction mixture produced can then be sent continuously to step (a3).
- step (a3) the reaction mixture resulting from step (a1) or optionally step (a2) and at least one alkoxylating agent are continuously added to a reactor system, which may consist of a continuous stirred tank or a cascade of continuous stirred tanks or an extruder.
- a reactor system which may consist of a continuous stirred tank or a cascade of continuous stirred tanks or an extruder.
- the crude alkoxylated polyphenol is withdrawn continuously from the reactor system.
- step (a3) comprises a cascade of 2 to 6 continuous stirred tanks.
- the first tank is fed continuously with the reaction mixture from step (a1) or step (a2) and each subsequent tank is fed continuously with the stream withdrawn from the preceding tank.
- each continuous stirred tank is fed continuously with a portion of the flow of alkoxylating agent, in order to obtain a tighter polydispersity of alkoxylated polyphenol product.
- the process according to the invention comprises a step (c) of recovering the alkoxylated polyphenol obtained at the end of step (b).
- the present invention also relates to an alkoxylated polyphenol obtainable by the process according to the invention.
- the invention also relates to the use of poly (oxyalkylene glycol) as a solvent in a process for producing alkoxylated polyphenols, especially such as that defined above.
- the present invention finally relates to the use of the alkoxylated polyphenol obtained by the process according to the invention for producing polyurethanes, polyesters, nonionic or cationic surfactants, biosourced precursors of carbon fiber.
- the temperature is gradually increased with stirring of the reaction medium to 80 ° C. Nitrogen is re-pressurized to 0.25 MPa and then a 50 g fraction of propylene oxide is introduced. The temperature is gradually raised to a temperature of 120 ° C., at which temperature it is possible to observe the attachment of the reaction.
- the entire propylene oxide, ie 488 g, is introduced at a temperature ranging from 120 ° C. to 130 ° C., at a maximum pressure of 0.6 MPa and at an average flow rate of 140 g. h "1.
- the temperature was maintained at 130 ° C until a pressure stage.
- the mixture is stirred for one hour so that all of the propylene oxide is consumed, then stripping the residue with nitrogen for 1 hour at 80 ° C.
- 1,125 g of product are recovered in the form of a dark viscous liquid.
- the product is homogeneous and does not contain unreacted lignin grain. Its hydroxyl number (IOH) is 290 mg KOH.g -1 .
- the leak tests are also carried out.
- the temperature is gradually increased with stirring of the reaction medium to 80 ° C. Nitrogen is re-pressurized to 0.25 MPa and then a fraction of 50 g of propylene oxide is introduced.
- the temperature is gradually raised to a temperature of 130 ° C., at which temperature it is possible to observe the attachment of the reaction.
- the entire propylene oxide ie 500 g, is introduced at a temperature ranging from 130 ° C. to 140 ° C. and at a maximum pressure of 0.6 MPa at an average flow rate of 85 g. h "1.
- the temperature is maintained at 130 ° C. until reaching a pressure level. of addition, it is left stirring for one hour so that all of the propylene oxide is consumed, then stripped the residue with nitrogen for 1 hour at 80 ° C.
- Recovering 1100 g of product in the form of a dark viscous liquid The product is homogeneous and does not contain unreacted lignin grain. Its hydroxyl number (IOH) is 202 mg KOH.g -1 .
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1659586A FR3056985B1 (fr) | 2016-10-04 | 2016-10-04 | Procede de fabrication de polyphenols alcoxyles |
PCT/FR2017/052722 WO2018065728A1 (fr) | 2016-10-04 | 2017-10-03 | Procédé de fabrication de polyphénols alcoxylés |
Publications (1)
Publication Number | Publication Date |
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EP3523358A1 true EP3523358A1 (fr) | 2019-08-14 |
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ID=57796504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP17787506.9A Withdrawn EP3523358A1 (fr) | 2016-10-04 | 2017-10-03 | Procédé de fabrication de polyphénols alcoxylés |
Country Status (9)
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US (1) | US20210284807A1 (fr) |
EP (1) | EP3523358A1 (fr) |
CN (1) | CN109790294A (fr) |
BR (1) | BR112019006038A2 (fr) |
CA (1) | CA3038306C (fr) |
FR (1) | FR3056985B1 (fr) |
MX (1) | MX2019003621A (fr) |
RU (1) | RU2727972C1 (fr) |
WO (1) | WO2018065728A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2019099405A1 (fr) * | 2017-11-14 | 2019-05-23 | Hexion Research Belgium S.A. | Lignine alcoxylée pour applications de polyuréthane |
FR3125820B1 (fr) | 2021-07-30 | 2024-01-19 | Soprema | Procédé de fabrication d'un mélange de polyphénols alcoxylés et utilisation de ce mélange. |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US3546199A (en) * | 1967-02-06 | 1970-12-08 | Kaiser Aluminium Chem Corp | Process for producing polyoxyalkylene ether-polyols from lignin |
DE19648724A1 (de) * | 1996-11-25 | 1998-05-28 | Basf Ag | Lignin-haltige Polyhydroxylverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Polyurethanen sowie Verfahren zur Herstellung der Polyurethane |
US8853299B2 (en) * | 2009-10-06 | 2014-10-07 | Amcol International Corp. | Lignite-based urethane resins with enhanced suspension properties and foundry sand binder performance |
CN101696261B (zh) * | 2009-10-29 | 2011-12-07 | 华南理工大学 | 一种木质素聚氨酯及其制备方法 |
EP2809677B1 (fr) * | 2012-02-02 | 2017-05-17 | Annikki GmbH | Procédé de production de polyols |
US20140200324A1 (en) | 2013-01-11 | 2014-07-17 | Pittsburg State University | Production of polyols using distillers grains and proteins and lignin extracted from distillers grains |
JP6518236B2 (ja) * | 2013-06-18 | 2019-05-22 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | タンニン含有ポリオール、その製造および使用方法 |
LV14722B (lv) | 2013-06-20 | 2013-10-20 | LATVIJAS VALSTS KOKSNES ĶĪMIJAS INSTITŪTS, Atvasināta publiska persona | Siltumizolācijas materiālu iegūšanas paņēmiens |
CA2932275C (fr) * | 2013-12-05 | 2021-12-28 | Stora Enso Oyj | Composition sous la forme d'un polyol de lignine, son procede de production et utilisation |
CN105622957B (zh) * | 2014-11-05 | 2018-05-04 | 中国石油化工集团公司 | 一种木质素聚醚多元醇的制备方法 |
-
2016
- 2016-10-04 FR FR1659586A patent/FR3056985B1/fr not_active Expired - Fee Related
-
2017
- 2017-10-03 RU RU2019111667A patent/RU2727972C1/ru active
- 2017-10-03 CN CN201780061757.3A patent/CN109790294A/zh active Pending
- 2017-10-03 CA CA3038306A patent/CA3038306C/fr active Active
- 2017-10-03 MX MX2019003621A patent/MX2019003621A/es unknown
- 2017-10-03 US US16/338,854 patent/US20210284807A1/en not_active Abandoned
- 2017-10-03 WO PCT/FR2017/052722 patent/WO2018065728A1/fr unknown
- 2017-10-03 BR BR112019006038A patent/BR112019006038A2/pt not_active Application Discontinuation
- 2017-10-03 EP EP17787506.9A patent/EP3523358A1/fr not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
US20210284807A1 (en) | 2021-09-16 |
FR3056985B1 (fr) | 2020-06-19 |
WO2018065728A1 (fr) | 2018-04-12 |
BR112019006038A2 (pt) | 2019-06-25 |
RU2727972C1 (ru) | 2020-07-28 |
CN109790294A (zh) | 2019-05-21 |
FR3056985A1 (fr) | 2018-04-06 |
CA3038306C (fr) | 2021-03-16 |
MX2019003621A (es) | 2019-07-04 |
CA3038306A1 (fr) | 2018-04-12 |
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