EP3833653A1 - Novel solid presentation form of at least one phenol derivative and process for obtaining same - Google Patents
Novel solid presentation form of at least one phenol derivative and process for obtaining sameInfo
- Publication number
- EP3833653A1 EP3833653A1 EP19746490.2A EP19746490A EP3833653A1 EP 3833653 A1 EP3833653 A1 EP 3833653A1 EP 19746490 A EP19746490 A EP 19746490A EP 3833653 A1 EP3833653 A1 EP 3833653A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chosen
- formula
- compound
- group
- new solid
- 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.)
- Pending
Links
- 239000007787 solid Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims description 32
- 150000002989 phenols Chemical class 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000008188 pellet Substances 0.000 claims description 9
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 8
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 8
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 8
- 235000012141 vanillin Nutrition 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 7
- 229940073505 ethyl vanillin Drugs 0.000 claims description 7
- -1 methoxy, ethoxy Chemical group 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 3
- 238000004320 controlled atmosphere Methods 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 4
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 229960001295 tocopherol Drugs 0.000 description 6
- 239000011732 tocopherol Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003826 tablet Substances 0.000 description 5
- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 4
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 2
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011049 pearl Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003611 tocopherol derivatives Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 231100001032 irritation of the eye Toxicity 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/204—Aromatic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0216—Solid or semisolid forms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/20—Pills, tablets, discs, rods
- A61K9/2072—Pills, tablets, discs, rods characterised by shape, structure or size; Tablets with holes, special break lines or identification marks; Partially coated tablets; Disintegrating flat shaped forms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Definitions
- the present invention relates to a new solid form of at least one phenolic derivative having at least a rounded part and a planar part.
- the present invention also describes a process for the preparation of these solids having at least a rounded part and a flat part.
- the invention also relates to these solids obtained by this preparation process.
- Phenolic derivatives such as vanillin, ethylvanillin, hydroquinone, catechol, para-methoxyphenol, are present in many industrial fields. They are, for example, used in the food industry as flavorings, or in the polymer industry as a polymerization inhibitor.
- Prilling methods for preparing these compounds include cooling droplets of a phenolic compound in a gas stream to solidify them. For certain specific applications, the dissolution rate of these beads could be improved.
- a first aspect of the present invention relates to a new solid form comprising at least one compound of formula (I)
- Ri is chosen from the group consisting of hydrogen, alkyl and alkenyl, preferably Ri is chosen from hydrogen, methyl, ethyl,
- R 2 is chosen from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acyl, preferably R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl,
- the present invention relates to a process for the preparation of a new solid form comprising at least one compound of formula (I) comprising at least the following steps:
- the present invention relates to the new solids capable of being obtained by the process of the present invention. Finally, the present invention relates to the use of these new solids in industry.
- Figures 1 and 2 show two sectional views of an embodiment of a solid compound according to the invention.
- Figure 3 shows a top or bottom view of a solid compound according to the invention.
- Figure 4 is a photo of a para-methoxyphenol tablet according to the present invention obtained on a stainless steel surface (optical microscope, magnification x6.3).
- Figure 5 is a photo of a para-methoxyphenol tablet according to the present invention obtained on a surface coated with PTFE (optical microscope, magnification x 6.3).
- alkyl represents a linear or branched saturated hydrocarbon chain comprising from 1 to 6 carbon atoms.
- alkoxy represents OR where R is an alkyl group as defined above.
- alkenyl represents a linear or branched unsaturated hydrocarbon chain comprising from 1 to 6 carbon atoms and carrying at least one double bond between two carbon atoms.
- alkynyl represents a linear or branched unsaturated hydrocarbon chain comprising from 1 to 6 carbon atoms and carrying at least one triple bond between two carbon atoms.
- ambient temperature means a temperature between 19 ° C and 24 ° C, preferably the ambient temperature is equal to 20 ° C.
- the present invention relates to a new solid form comprising at least one compound of formula (I)
- - n is between 0 and 5, preferably between 0 and 4, and preferably n is equal to 0, 1 or 2,
- - Ri is chosen from the group consisting of hydrogen, alkyl, and alkenyl
- R 2 is selected from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acyl,
- Ri is chosen from hydrogen, methyl, ethyl.
- R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl.
- n 2
- the groups R 2 identical or different, are placed relative to the group ORi, one in the ortho position and the other in the para position.
- the compounds of formula (I) are chosen from the group consisting of hydroquinone, catechol, resorcinol, pyrogallol, 4-tert-butylcatechol, tert-butylhydroquinone, para-methoxyphenol, butylhydroxyanisole, vanillin, ethylvanillin and a compound of vanillin and ethyl vanillin in a molar ratio of 2.
- the compounds of formula (I) are chosen from the group consisting of hydroquinone, catechol, resorcinol, pyrogallol, 4-tert-butylcatechol, tert-butylhydroquinone, para-methoxyphenol, and butylhydroxyanisole.
- the compounds of formula (I) are chosen from the group consisting of vanillin, ethylvanillin and a compound of vanillin and ethylvanillin in a molar ratio of 2.
- the compound of formula (I) is a polymerization inhibitor.
- the compound of formula (I) is a flavor.
- the new solid form can comprise one, two or three compounds of formula (I) as defined above, preferably the new solid form according to the present invention comprises a compound of formula (I) or a mixture of two compounds of formula (I).
- the new solid form according to the invention comprises 2 compounds of formula (I)
- the molar ratio between the 2 compounds is between 1: 99 and 99: 1.
- the molar ratio between the two compounds is 1: 1 or 2: 1.
- the mass ratio is strictly greater than 0% by weight, preferably greater than or equal to 0.1% by weight, more preferably greater than or equal to 5% by weight and strictly less than 100% by weight.
- the new solid form according to the present invention may comprise at least one additive chosen from the group consisting of antioxidants, anti-foam, corrosion inhibitors, rust inhibitors, surfactants, detergents, dispersants, anti-fouling, thinners , viscosants, or acidity correctors.
- the new solid form according to the present invention may comprise at least compound chosen from the group consisting of tocopherol derivatives, preferably a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol, copper complexes having an oxidation state of 2, preferably copper acetate (Cu (OAc) 2) or copper dibutyl dithiocarbamate (CB), 2-sec-Butyl-4,6-dinitrophenol, phenylenediamine, TEMPO, TEMPO-OH, 2 , 4-dimethyl, 6-tertbutylphenol (Topanol A), phenothiazine, butylhydroxyanisole (BHA) and 2,6-ditertbutyl-4-methoxyphenol (DTBHA).
- tocopherol derivatives preferably a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol, copper complexes having an oxidation state of 2, preferably copper
- the new solid shaping according to the present invention comprises:
- tocopherol derivatives preferably a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol, copper complexes having a degree of oxidation of 2, preferably copper acetate (Cu (OAc) 2) or copper dibutyl dithiocarbamate (CB), 2-sec-Butyl- 4,6-dinitrophenol, phenylenediamine, TEMPO, TEMPO-OH, 2,4-dimethyl, 6- tertbutylphenol (Topanol A), phenothiazine, butylhydroxyanisole (BHA) and 2,6-ditertbutyl-4-methoxyphenol (DTBHA).
- Cu copper acetate
- CB copper dibutyl dithiocarbamate
- the new solid form according to the present invention may comprise at least one additive chosen from the group consisting of fatty substances, waxes, sugars, polysaccharides such as starches, maltodextrins, antioxidants.
- the new solid form according to the present invention can be represented schematically as indicated in Figures 1 and 2.
- the distance dl represents the greatest distance between the 2 points A and B of the flat part of the new solid form .
- the distance d2 represents the greatest distance between the planar part and the rounded part.
- the new solid forms of the present invention can be likened to spherical caps.
- the rounded part of these new solid forms is preferably spherical, however it may have imperfections.
- the new solid forms according to the present invention can be qualified as pellets.
- the new solid form has at least one rounded part and a flat part.
- the new solid form has an edge.
- the planar part, seen from above or from below as shown diagrammatically in FIG. 3, of the new solid form can have a shape close to the disc or to the ellipse.
- the volume of the spherical cap can be calculated according to the following formula:
- dl is the diameter of the spherical cap (see Figure 3) and d2 is the thickness of the spherical cap.
- the volume of this portion can therefore be measured according to the following formulas:
- x is strictly greater than 0, preferably greater than or equal to 0.01, and more preferably greater than or equal to 0.02.
- x is strictly less than 1, preferably less than or equal to 0.9, more preferably less than or equal to 0.8. According to a particular aspect, x can be between 0.01 and 0.1.
- dl and dl ’ are between 300 pm and 10,000 pm, preferably between 500 pm and 5000 pm, more preferably between 500 and 2000 pm; d2 is between 50 pm and 10,000 pm, preferably between 75 pm and 5000 pm and more preferably between 75 pm and 2000 pm.
- the planar part of the new solid forms is a continuous surface.
- the flat surface represents at least 5%, preferably at least 10%, 15%, 20%, 25%, 30%, 40%, 50% of the total surface of the new solid form according to the present invention.
- the flat surface represents at most 95%, preferably at most 90%, 85%, 80%, 75%, 70%, 60%, 55% of the total surface of the new solid form according to the present invention.
- the present invention also relates to a process for the preparation of the new solid forms as defined above by a tableting process.
- the documents US 2017/0326760 and EP1042056 show two devices suitable for the preparation of pellets according to the invention.
- the method comprises at least the following steps:
- Step (a) is a step of placing the droplets on a flat surface.
- the planar surface can be a strip, a plate or a disc.
- the strip or the disc is in motion.
- the belt can be a conveyor belt which rotates around two cylinders.
- the band performs a translational movement.
- the droplets are arranged on the upper part of the conveyor belt.
- the disc can be rotated about an axis.
- the axis of rotation is perpendicular to the ground.
- the droplets are arranged on the surface of the disc, preferably the upper surface.
- the process of the present invention further comprises a step (a1), before step (a) in which the at least one compound of formula (I) is melted.
- step (al) the at least one compound of formula (I) is heated to a temperature between 1 and 50 ° C above its melting point or, in the case of a mixture, of the melting temperature of the compound having the highest melting point, preferably between 1 and 20 ° C above its melting temperature, or the melting temperature of the compound having the highest melting point, and more preferably preferably between 1 and 10 ° C above its melting temperature, or the melting temperature of the compound having the highest melting point.
- the heating temperature can be between 50 ° C and 300 ° C, preferably between 50 ° C and 260 ° C.
- An additive or more additives as defined above can be added to the preparation of the compound in molten form.
- the method of the present invention may also include a step (a2) of forming droplets.
- the droplet formation device can be a perforated cylinder or a perforated plate.
- the droplet formation device is preferably maintained at a temperature greater than or equal to the temperature of step (al).
- the droplet formation device is located above the planar surface so that the droplets can fall on the planar surface.
- step (al) is carried out before step (a2).
- step (a2) of droplet formation is carried out directly after a process for the preparation or purification of the compound of formula (I).
- the compound of formula (I) is in liquid form without requiring a step in which the compound of formula (I) is melted.
- Step (b) is a step of solidifying the droplets on the flat surface.
- the placed surface is cooled to a temperature strictly below the melting temperature of the compound of formula (I) or, in the case of a mixture, strictly below the melting temperature of the compound of formula (I) having the point lowest melting point.
- the flat surface is cooled to a temperature between -50 ° C.
- the planar surface is cooled to a cooling temperature between 10 ° C and room temperature.
- the cooling temperature of the flat surface is uniform over the entire surface.
- the cooling temperature is not uniform over the entire flat surface, the temperature may have a cooling gradient or cooling zones in which the flat surface is cooled to different cooling temperatures.
- the flat surface may have undergone a surface treatment prior to the method according to the present invention.
- the flat surface can also be coated in particular with a non-stick or hydrophobic coating, such as PTFE (polytetrafluoroethylene).
- the flat surface can also have roughness. These treatments or roughness in particular make it possible to improve the separation of the new solid forms according to the present invention at the end of the process. These treatments or roughness also make it possible to improve the mechanical properties of the new solid forms according to the present invention, in particular better resistance to friability during handling.
- the shape of the solids according to the present invention also makes it possible to reduce caking phenomena.
- the new solid forms according to the present invention can adhere to the flat surface.
- the method according to the present invention may include a step in which the new solid forms are removed from the planar surface.
- the device for forming new solid forms according to the present invention may comprise a knife or scraper.
- the process can be carried out in air, under oxygen, or under a controlled atmosphere, in particular the humidity rate can be controlled.
- the process according to the invention can be carried out under dry air, under an inert atmosphere, in particular under nitrogen.
- the level of fine particles having a size less than or equal to 355 mhi is less than or equal to 30%, preferably less than or equal to 20%, more preferably less than or equal to 10% , and even more preferably less than or equal to 0.1% by weight relative to the weight of new solid shaping of formula (I).
- the method according to the present invention can also comprise a step in which the fine particles, having a size less than or equal to 355 mhi, are separated by sieving or by cycloning. Fine particles can be recycled.
- the new solid compounds according to the present invention have a hardness of at least 1N. Hardness can be measured with a penetrometer.
- the new solid compounds according to the present invention have a friability of less than or equal to 15%. This parameter allows easier handling of these new solid compounds compared to the powder, because the formation of mist is avoided or at least reduced.
- the friability can be measured by mixing the new solid forms according to the present invention in a triaxial mixer for 10 minutes, then by measuring the level of particles less than 100 mhi produced. The friability represents the ratio between the mass of particles smaller than 100 ⁇ m produced and the total mass of the new solid forms introduced into the triaxial mixer.
- the new solid forms according to the present invention have good dissolution properties.
- the dissolution rate of these solids is at least equivalent, preferably better, to the dissolution rate of other existing forms of compounds of formula (I).
- the chemical composition of the new solid forms according to the present invention depends on the liquid composition as defined above.
- additives as defined above in the new solid forms according to the present invention can be done during the preparation of the composition comprising at least one compound of formula (I) in liquid form (Step (al )) or during an additional step at the end of the process.
- the new solid forms comprising at least one compound of formula (I) as defined above capable of being obtained according to the method of the invention are also an object of the present invention.
- the present invention relates to the use of these new solid forms comprising at least one compound of formula (I) in the industry, in particular the polymer, food-processing, perfumery or pharmaceutical industry.
- Para-methoxyphenol (PMP) lozenges are prepared.
- the PMP is first melted at 80 ° C. Droplets are then formed and deposited on a strip cooled to 18 ° C.
- Figures 4 and 5 show pellets according to the present invention.
- Example 1 The pellets of Figure 4 were obtained on a stainless steel strip.
- Example 2 The pellets of Figure 5 were obtained on a strip coated with PTFE.
- the dissolution rate corresponds to the time necessary to dissolve 90% of 2 g of pellets / powder / scales in 100 g of water / acrylic acid at 20 ° C stirred at 300 rpm.
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Abstract
The present invention relates to a novel solid presentation form of a phenol derivative, characterized by a rounded portion and a flat portion. The compositions thus obtained have advantageous properties suitable for the storage, handling and flow of the compounds. The present invention also relates to a process for preparing these solids, and to the use thereof, in particular in the polymer and agri-food industries.
Description
NOUVELLE MISE EN FORME SOLIDE D’AU MOINS UN DERIVE PHENOLIQUE ET NEW SOLID SHAPE OF AT LEAST ONE PHENOLIC DERIVATIVE AND
PROCEDE D’OBTENTION PROCESS FOR OBTAINING
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention porte sur une nouvelle mise en forme solide d’au moins un dérivé phénolique présentant au moins une partie arrondie et une partie plane. La présente invention décrit également un procédé de préparation de ces solides présentant au moins une partie arrondie et une partie plane. L’invention porte également sur ces solides obtenus par ce procédé de préparation. The present invention relates to a new solid form of at least one phenolic derivative having at least a rounded part and a planar part. The present invention also describes a process for the preparation of these solids having at least a rounded part and a flat part. The invention also relates to these solids obtained by this preparation process.
ART ANTERIEUR PRIOR ART
Les dérivés phénoliques, tels que la vanilline, l’éthylvanilline, l’hydroquinone, le catéchol, le para-méthoxyphénol, sont présents dans de nombreux domaines industriels. Ils sont, par exemple, utilisés par l’industrie agro-alimentaire en tant qu’arômes, ou dans l’industrie polymère en tant qu’inhibiteur de polymérisation. Phenolic derivatives, such as vanillin, ethylvanillin, hydroquinone, catechol, para-methoxyphenol, are present in many industrial fields. They are, for example, used in the food industry as flavorings, or in the polymer industry as a polymerization inhibitor.
Actuellement ces composés sont principalement vendus sous forme de poudre. Le document WO 2016/033157 décrit des méthodes de mise en forme d’hydroquinone sous forme de poudre cristallisée. Cette poudre est constituée de petites aiguilles cassantes, il en résulte une présence de fines importante qui pose problème notamment pour leur stockage, manipulation, transport. La résistance au mottage de ce produit est certes un peu améliorée, mais la manipulation de ce composé présente des risques notamment d’irritation des yeux, du système respiratoire ou de la peau. Currently these compounds are mainly sold in powder form. Document WO 2016/033157 describes methods for shaping hydroquinone in the form of crystallized powder. This powder consists of small brittle needles, this results in a significant presence of fines which poses a problem in particular for their storage, handling, transport. The caking resistance of this product is certainly slightly improved, but handling this compound poses risks, in particular of irritation of the eyes, the respiratory system or the skin.
Des formes alternatives ont été proposées. Le document JP 2000-302716 décrit une technique de granulation qui consiste à faire passer la poudre entre deux rouleaux permettant l’obtention de tablettes puis de concasser ces tablettes de façon à obtenir des granulés. L’inconvénient de ce procédé est que des poussières peuvent subsister, soit en raison du passage au niveau des rouleaux du compacteur, soit par l’attrition des tablettes dans le concasseur. De plus, les granulés sont compacts et leur vitesse de dissolution est très faible par rapport à la poudre initiale.
Les documents EP 0689772 et WO 2004/039758 décrivent la mise en forme de composés phénolique sous forme de perles, en particulier hydroquinone et vanilline par des méthodes de prilling. Ces perles sont hautement sphériques. Cette mise en forme particulière confère aux perles des propriétés intéressantes de résistance à l’attrition, et éviterait ainsi la formation de d’une grande quantité de poussière. Les méthodes de prilling pour préparer ces composés consistent à refroidir des gouttelettes d’un composé phénolique dans un flux gazeux pour les solidifier. Pour certaines applications spécifiques, la vitesse de dissolution de ces billes pourrait être améliorée. Alternative forms have been proposed. The document JP 2000-302716 describes a granulation technique which consists in passing the powder between two rollers allowing the production of tablets and then crushing these tablets so as to obtain granules. The disadvantage of this process is that dust can remain, either due to the passage at the level of the rollers of the compactor, or by the attrition of the tablets in the crusher. In addition, the granules are compact and their dissolution rate is very low compared to the initial powder. Documents EP 0689772 and WO 2004/039758 describe the shaping of phenolic compounds in the form of pearls, in particular hydroquinone and vanillin by prilling methods. These beads are highly spherical. This particular shaping gives the pearls attractive properties of resistance to attrition, and thus would prevent the formation of a large amount of dust. Prilling methods for preparing these compounds include cooling droplets of a phenolic compound in a gas stream to solidify them. For certain specific applications, the dissolution rate of these beads could be improved.
Par ailleurs, malgré les avantages reconnus de ces méthodes alternatives, ces méthodes sont coûteuses. Il est donc souhaitable de proposer d’autres alternatives dont l’impact économique est plus faible tout en maintenant de bonnes propriétés de stockage, manipulation, transport, résistance à l’attrition, au motage, tout en réduisant les risques liés à la santé et à l’environnement en minimisant la présence de poussières et de fines et améliorant les propriétés de solubilité de ces mises en forme. Furthermore, despite the recognized advantages of these alternative methods, these methods are expensive. It is therefore desirable to propose other alternatives whose economic impact is lower while maintaining good properties of storage, handling, transport, resistance to attrition, motage, while reducing the risks linked to health and to the environment by minimizing the presence of dust and fines and improving the solubility properties of these forms.
BREVE DESCRIPTION BRIEF DESCRIPTION
Il est du mérite de la Société Demanderesse d’avoir identifié une nouvelle mise en forme solide présentant l’ensemble des caractéristiques souhaitées précitées et en particulier de bonnes propriétés de solubilité tout en maintenant de bonnes propriétés de résistance à l’attrition. It is to the credit of the Applicant Company to have identified a new solid form having all of the aforementioned desired characteristics and in particular good solubility properties while maintaining good attrition resistance properties.
Un premier aspect de la présente invention porte sur une nouvelle mise en forme solide comprenant au moins un composé de formule (I) A first aspect of the present invention relates to a new solid form comprising at least one compound of formula (I)
Formule (i) Formula (i)
dans lequel : in which :
- n est compris entre 0 et 5, de préférence entre 0 et 4, et préférentiellement n est égal à 0, 1
- Ri est choisi dans le groupe consistant en hydrogène, alkyl, et alcényl, de préférence Ri est choisi parmi hydrogène, méthyl, éthyl, - n is between 0 and 5, preferably between 0 and 4, and preferably n is equal to 0, 1 Ri is chosen from the group consisting of hydrogen, alkyl and alkenyl, preferably Ri is chosen from hydrogen, methyl, ethyl,
- R2 est choisi dans le groupe consistant en hydroxyl, alkyl, alcényl, alcynyl, alkoxy, formyl et acyl, de préférence R2 est choisi parmi hydroxyl, méthyl, éthyl, propyl, méthoxy, éthoxy, et formyl, R 2 is chosen from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acyl, preferably R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl,
et comprenant au moins une partie arrondie et une partie plane. and comprising at least a rounded part and a flat part.
Selon un autre aspect, la présente invention porte sur un procédé de préparation d’une nouvelle mise en forme solide comprenant au moins un composé de formule (I) comprenant au moins les étapes suivantes : According to another aspect, the present invention relates to a process for the preparation of a new solid form comprising at least one compound of formula (I) comprising at least the following steps:
(a) une étape dans laquelle des gouttelettes liquides comprenant au moins un composé de formule (I) sont disposées sur une surface plane, (a) a step in which liquid droplets comprising at least one compound of formula (I) are arranged on a flat surface,
(b) une étape de solidification desdites gouttelettes sur ladite surface. (b) a step of solidifying said droplets on said surface.
Enfin la présente invention porte sur les nouveaux solides susceptibles d’être obtenus par le procédé de la présente invention. Enfin, la présente invention porte sur l’utilisation de ces nouveaux solides dans l’industrie. Finally, the present invention relates to the new solids capable of being obtained by the process of the present invention. Finally, the present invention relates to the use of these new solids in industry.
DESCRIPTION DES FIGURES DESCRIPTION OF THE FIGURES
Figures 1 et 2 représentent deux vues en coupe d’un mode de réalisation d’un composé solide selon l’invention. Figures 1 and 2 show two sectional views of an embodiment of a solid compound according to the invention.
Figure 3 représente une vue de dessus ou de dessous un composé solide selon l’invention. Figure 3 shows a top or bottom view of a solid compound according to the invention.
Figure 4 est une photo d’une pastille de para-méthoxyphénol selon la présente invention obtenu sur une surface en inox (microscope optique, grossissement x6,3). Figure 4 is a photo of a para-methoxyphenol tablet according to the present invention obtained on a stainless steel surface (optical microscope, magnification x6.3).
Figure 5 est une photo d’une pastille de para-méthoxyphénol selon la présente invention obtenu sur une surface revêtue de PTFE (microscope optique, grossissement x6,3). Figure 5 is a photo of a para-methoxyphenol tablet according to the present invention obtained on a surface coated with PTFE (optical microscope, magnification x 6.3).
DESCRIPTION DETAILLEE DETAILED DESCRIPTION
Dans le cadre de la présente invention, et sauf indication contraire, l’expression « compris entre ...et... » inclut les bornes. In the context of the present invention, and unless otherwise indicated, the expression "between ... and ..." includes the terminals.
Dans le cadre de la présente invention, et sauf indication contraire, l’expression « alkyl » représente une chaîne hydrocarbonée saturée linéaire ou branchée comprenant de 1 à 6 atomes de carbone.
Dans le cadre de la présente invention, et sauf indication contraire, l’expression « alkoxy » représente OR où R est un groupement alkyl tel que défini ci-dessus. In the context of the present invention, and unless otherwise indicated, the expression "alkyl" represents a linear or branched saturated hydrocarbon chain comprising from 1 to 6 carbon atoms. In the context of the present invention, and unless otherwise indicated, the expression “alkoxy” represents OR where R is an alkyl group as defined above.
Dans le cadre de la présente invention, et sauf indication contraire, l’expression « alcényl » représente une chaîne hydrocarbonée insaturée linéaire ou branchée comprenant de 1 à 6 atomes de carbone et portant au moins une liaison double entre deux atomes de carbone. In the context of the present invention, and unless otherwise indicated, the expression "alkenyl" represents a linear or branched unsaturated hydrocarbon chain comprising from 1 to 6 carbon atoms and carrying at least one double bond between two carbon atoms.
Dans le cadre de la présente invention, et sauf indication contraire, l’expression « alcynyl » représente une chaîne hydrocarbonée insaturée linéaire ou branchée comprenant de 1 à 6 atomes de carbone et portant au moins une liaison triple entre deux atomes de carbone. In the context of the present invention, and unless otherwise indicated, the expression "alkynyl" represents a linear or branched unsaturated hydrocarbon chain comprising from 1 to 6 carbon atoms and carrying at least one triple bond between two carbon atoms.
Dans le cadre de la présente invention, le terme « comprenant » peut avoir le sens de « consistant ». In the context of the present invention, the term “comprising” can have the meaning of “consistent”.
Dans le cadre de la présente invention, le terme « température ambiante » signifie une température comprise entre l9°C et 24°C, de préférence la température ambiante est égale à 20°C. In the context of the present invention, the term "ambient temperature" means a temperature between 19 ° C and 24 ° C, preferably the ambient temperature is equal to 20 ° C.
Selon un premier aspect, la présente invention porte sur une nouvelle mise en forme solide comprenant au moins un composé de formule (I) According to a first aspect, the present invention relates to a new solid form comprising at least one compound of formula (I)
Formule (i) Formula (i)
dans lequel : in which :
- n est compris entre 0 et 5, de préférence entre 0 et 4, et préférentiellement n est égal à 0, 1 ou 2, - n is between 0 and 5, preferably between 0 and 4, and preferably n is equal to 0, 1 or 2,
- Ri est choisi dans le groupe consistant en hydrogène, alkyl, et alcényl, - Ri is chosen from the group consisting of hydrogen, alkyl, and alkenyl,
- R2 est choisi dans le groupe consistant en hydroxyl, alkyl, alcényl, alcynyl, alkoxy, formyl et acyl, - R 2 is selected from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acyl,
et comprenant au moins une partie arrondie et une partie plane.
Selon un aspect préféré, Ri est choisi parmi hydrogène, méthyl, éthyl. Selon un autre aspect préféré, R2 est choisi parmi hydroxyl, méthyl, éthyl, propyl, méthoxy, éthoxy, et formyl. and comprising at least a rounded part and a flat part. According to a preferred aspect, Ri is chosen from hydrogen, methyl, ethyl. According to another preferred aspect, R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl.
Selon un aspect préféré de la présente invention dans lequel n=2, les groupements R2, identiques ou différents, sont placés par rapport au groupement ORi, l’un en position ortho et l’autre en position para. According to a preferred aspect of the present invention in which n = 2, the groups R 2 , identical or different, are placed relative to the group ORi, one in the ortho position and the other in the para position.
Selon un autre aspect de la présente invention dans lequel n=l, le groupement R2 est placé en position ortho ou para par rapport au groupement ORi . According to another aspect of the present invention in which n = 1, the group R 2 is placed in the ortho or para position relative to the group ORi.
Selon un aspect préféré, les composés de formule (I) sont choisis dans le groupe consistant en hydroquinone, catéchol, résorcinol, pyrogallol, 4-tert-butylcatéchol, tert- butylhydroquinone, para-méthoxyphénol, butylhydroxyanisole, vanilline, éthylvanilline et un composé de vanilline et d’ éthylvanilline dans un rapport molaire de 2. De préférence les composés de formule (I) sont choisis dans le groupe consistant en hydroquinone, catéchol, résorcinol, pyrogallol, 4-tert-butylcatéchol, tert-butylhydroquinone, para-méthoxyphénol, et butylhydroxyanisole. Alternativement les composés de formule (I) sont choisis dans le groupe consistant en vanilline, éthylvanilline et un composé de vanilline et d’ éthylvanilline dans un rapport molaire de 2. According to a preferred aspect, the compounds of formula (I) are chosen from the group consisting of hydroquinone, catechol, resorcinol, pyrogallol, 4-tert-butylcatechol, tert-butylhydroquinone, para-methoxyphenol, butylhydroxyanisole, vanillin, ethylvanillin and a compound of vanillin and ethyl vanillin in a molar ratio of 2. Preferably the compounds of formula (I) are chosen from the group consisting of hydroquinone, catechol, resorcinol, pyrogallol, 4-tert-butylcatechol, tert-butylhydroquinone, para-methoxyphenol, and butylhydroxyanisole. Alternatively, the compounds of formula (I) are chosen from the group consisting of vanillin, ethylvanillin and a compound of vanillin and ethylvanillin in a molar ratio of 2.
Selon un mode de réalisation préféré, le composé de formule (I) est un inhibiteur de polymérisation. According to a preferred embodiment, the compound of formula (I) is a polymerization inhibitor.
Selon un autre mode de réalisation préféré, le composé de formule (I) est un arôme. According to another preferred embodiment, the compound of formula (I) is a flavor.
Selon un aspect de la présente invention, la nouvelle mise en forme solide peut comprendre un, deux ou trois composés de formule (I) tels que définis précédemment, de manière préférée la nouvelle mise en forme solide selon la présente invention comprend un composé de formule (I) ou un mélange de deux composés de formule (I). According to one aspect of the present invention, the new solid form can comprise one, two or three compounds of formula (I) as defined above, preferably the new solid form according to the present invention comprises a compound of formula (I) or a mixture of two compounds of formula (I).
Dans le cas où la nouvelle mise en forme solide selon l’invention comprend 2 composés de formule (I), le ratio molaire entre les 2 composés est compris entre 1 :99 et 99:1. Selon un aspect particulier le ratio molaire entre les deux composés est 1 :1 ou 2: 1. In the case where the new solid form according to the invention comprises 2 compounds of formula (I), the molar ratio between the 2 compounds is between 1: 99 and 99: 1. According to a particular aspect, the molar ratio between the two compounds is 1: 1 or 2: 1.
Dans le cas où la nouvelle mise en forme solide selon l’invention comprend 2 composés de formule (I), le ratio massique est supérieur strictement à 0% en poids, de préférence supérieur ou égal à 0.1% en poids, plus préférentiellement supérieur ou égal à 5% en poids et inférieur strictement à 100% en poids.
Selon un aspect particulier, la nouvelle mise en forme solide selon la présente invention peut comprendre au moins un additif choisi dans le groupe consistant en antioxidants, anti mousse, inhibiteurs de corrosion, inhibiteurs de rouille, surfactants, détergents, dispersants, anti encrassement, fluidifiants, viscosants, ou correcteurs d’acidité. In the case where the new solid form according to the invention comprises 2 compounds of formula (I), the mass ratio is strictly greater than 0% by weight, preferably greater than or equal to 0.1% by weight, more preferably greater than or equal to 5% by weight and strictly less than 100% by weight. According to a particular aspect, the new solid form according to the present invention may comprise at least one additive chosen from the group consisting of antioxidants, anti-foam, corrosion inhibitors, rust inhibitors, surfactants, detergents, dispersants, anti-fouling, thinners , viscosants, or acidity correctors.
Selon un aspect particulier, la nouvelle mise en forme solide selon la présente invention peut comprendre au moins composé choisi dans le groupe constitué de dérivés de tocopherol, préférentiellement a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol, complexes au cuivre ayant un degré d’oxidation de 2, de préférence acétate de cuivre (Cu(OAc)2) ou cuivre dibutyl dithiocarbamate (CB), 2-sec-Butyl-4,6-dinitrophenol, phénylènediamine, TEMPO, TEMPO-OH, 2,4-diméthyl,6-tertbutylphénol (Topanol A), phénothiazine, butylhydroxyanisole (BHA) et 2,6- ditertbutyl-4-methoxyphenol (DTBHA) . According to a particular aspect, the new solid form according to the present invention may comprise at least compound chosen from the group consisting of tocopherol derivatives, preferably a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol, copper complexes having an oxidation state of 2, preferably copper acetate (Cu (OAc) 2) or copper dibutyl dithiocarbamate (CB), 2-sec-Butyl-4,6-dinitrophenol, phenylenediamine, TEMPO, TEMPO-OH, 2 , 4-dimethyl, 6-tertbutylphenol (Topanol A), phenothiazine, butylhydroxyanisole (BHA) and 2,6-ditertbutyl-4-methoxyphenol (DTBHA).
Avantageusement, la nouvelle mise en forme solide selon la présente invention comprend : Advantageously, the new solid shaping according to the present invention comprises:
entre 50 et 100 % en poids du au moins un composé de formule (I) tel que défini précédemment, et between 50 and 100% by weight of the at least one compound of formula (I) as defined above, and
entre 0 % et 50% en poids de au moins un composé choisi dans le groupe constitué de dérivés de tocopherol, préférentiellement a-tocopherol, b-tocopherol, g-tocopherol, d- tocopherol, complexes au cuivre ayant un degré d’oxidation de 2, de préférence acétate de cuivre (Cu(OAc)2) ou cuivre dibutyl dithiocarbamate (CB), 2-sec-Butyl- 4,6-dinitrophenol, phénylènediamine, TEMPO, TEMPO-OH, 2,4-diméthyl,6- tertbutylphénol (Topanol A), phénothiazine, butylhydroxyanisole (BHA) et 2,6- ditertbutyl-4-methoxyphenol (DTBHA) . between 0% and 50% by weight of at least one compound chosen from the group consisting of tocopherol derivatives, preferably a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol, copper complexes having a degree of oxidation of 2, preferably copper acetate (Cu (OAc) 2) or copper dibutyl dithiocarbamate (CB), 2-sec-Butyl- 4,6-dinitrophenol, phenylenediamine, TEMPO, TEMPO-OH, 2,4-dimethyl, 6- tertbutylphenol (Topanol A), phenothiazine, butylhydroxyanisole (BHA) and 2,6-ditertbutyl-4-methoxyphenol (DTBHA).
Selon un autre aspect particulier, la nouvelle mise en forme solide selon la présente invention peut comprendre au moins un additif choisi dans le groupe constitué des corps gras, des cires, des sucres, des polysaccharides tels que amidons, maltodextrines, des anti-oxidants. According to another particular aspect, the new solid form according to the present invention may comprise at least one additive chosen from the group consisting of fatty substances, waxes, sugars, polysaccharides such as starches, maltodextrins, antioxidants.
La nouvelle mise en forme solide selon la présente invention peut être représentée schématiquement telle qu’indiqué aux Figures 1 et 2. La distance dl représente la plus grande distance entre les 2 points A et B de la partie plane de la nouvelle mise en forme solide. La distance d2 représente la plus grande distance entre la partie plane et la partie arrondie. Les nouvelles mises en forme solides de la présente invention sont assimilables à des calottes sphériques.
La partie arrondie de ces nouvelles mises en forme solides est préférablement sphérique, cependant elle peut présenter des imperfections. Les nouvelles mises en forme solides selon la présente invention peuvent être qualifiées de pastilles. The new solid form according to the present invention can be represented schematically as indicated in Figures 1 and 2. The distance dl represents the greatest distance between the 2 points A and B of the flat part of the new solid form . The distance d2 represents the greatest distance between the planar part and the rounded part. The new solid forms of the present invention can be likened to spherical caps. The rounded part of these new solid forms is preferably spherical, however it may have imperfections. The new solid forms according to the present invention can be qualified as pellets.
Selon la présente invention, la nouvelle forme solide présente une au moins une partie arrondie et une partie plane. Ainsi selon la présente invention, la nouvelle forme solide présente un bord. According to the present invention, the new solid form has at least one rounded part and a flat part. Thus according to the present invention, the new solid form has an edge.
Selon un aspect particulier de la présente invention, la partie plane, vue de dessus ou de dessous telle que représentée schématiquement à la Figure 3, de la nouvelle mise en forme solide peut avoir une forme proche du disque ou de l’ellipse. According to a particular aspect of the present invention, the planar part, seen from above or from below as shown diagrammatically in FIG. 3, of the new solid form can have a shape close to the disc or to the ellipse.
Le volume de la calotte sphérique peut être calculé selon la formule suivante :
The volume of the spherical cap can be calculated according to the following formula:
dans laquelle dl est le diamètre de la calotte sphérique (voir Figure 3) et d2 est l’épaisseur de la calotte sphérique. where dl is the diameter of the spherical cap (see Figure 3) and d2 is the thickness of the spherical cap.
La nouvelle forme solide selon la présente invention peut donc être assimilée à une portion de sphère de rayon r (V = 4pG3/3) ou une portion d’ellipsoide (V = 4 abc/3, où a, b et c sont les longueurs des demi-axes de l’ellipsoïde). Le volume de cette portion peut donc être mesuré selon les formules suivantes : The new solid form of the present invention can therefore be likened to a portion of sphere of radius r (V 4PG = 3/3) or a portion of ellipsoid (V abc = 4/3, where a, b and c are the lengths of the semi-axes of the ellipsoid). The volume of this portion can therefore be measured according to the following formulas:
4p r3 4uabc 4p r 3 4uabc
V = - x ou V = - x V = - x or V = - x
3 3 3 3
dans lesquelles x est strictement supérieur à 0, de préférence supérieur ou égal à 0,01, et plus préférentiellement supérieur ou égal à 0,02. x est strictement inférieur à 1, de préférence inférieur ou égal à 0,9, plus préférentiellement inférieur ou égal à 0,8. Selon un aspect particulier, x peut être compris entre 0,01 et 0,1. in which x is strictly greater than 0, preferably greater than or equal to 0.01, and more preferably greater than or equal to 0.02. x is strictly less than 1, preferably less than or equal to 0.9, more preferably less than or equal to 0.8. According to a particular aspect, x can be between 0.01 and 0.1.
Selon un aspect particulier de la présente invention, dl et dl’, identiques ou différents, sont compris entre 300 pm et 10000 pm, de préférence entre 500 pm et 5000 pm, plus préférentiellement entre 500 et 2000 pm; d2 est compris entre 50 pm et 10000 pm, de préférence compris entre 75 pm et 5000 pm et plus préférentiellement entre 75 pm et 2000 pm. According to a particular aspect of the present invention, dl and dl ’, identical or different, are between 300 pm and 10,000 pm, preferably between 500 pm and 5000 pm, more preferably between 500 and 2000 pm; d2 is between 50 pm and 10,000 pm, preferably between 75 pm and 5000 pm and more preferably between 75 pm and 2000 pm.
Selon la présente invention, la partie plane des nouvelles formes solides est une surface continue. De préférence la surface plane représente au moins 5%, de préférence au moins 10%,
15%, 20%, 25%, 30%, 40%, 50% de la surface totale de la nouvelle forme solide selon la présente invention. De préférence la surface plane représente au plus 95%, de préférence au plus 90%, 85%, 80%, 75%, 70%, 60%, 55% de la surface totale de la nouvelle forme solide selon la présente invention. According to the present invention, the planar part of the new solid forms is a continuous surface. Preferably the flat surface represents at least 5%, preferably at least 10%, 15%, 20%, 25%, 30%, 40%, 50% of the total surface of the new solid form according to the present invention. Preferably the flat surface represents at most 95%, preferably at most 90%, 85%, 80%, 75%, 70%, 60%, 55% of the total surface of the new solid form according to the present invention.
La présente invention porte également sur un procédé de préparation des nouvelles mises en forme solides tels que définies précédemment par un procédé de pastillage. Les documents US 2017/0326760 et EP1042056 présentent deux dispositifs adaptés pour la préparation de pastilles selon l’invention. The present invention also relates to a process for the preparation of the new solid forms as defined above by a tableting process. The documents US 2017/0326760 and EP1042056 show two devices suitable for the preparation of pellets according to the invention.
Selon un aspect particulier, le procédé comprend au moins les étapes suivantes : According to a particular aspect, the method comprises at least the following steps:
(a) une étape dans laquelle des gouttelettes liquides comprenant au moins un composé de formule (I) sont disposées sur une surface plane, (a) a step in which liquid droplets comprising at least one compound of formula (I) are arranged on a flat surface,
(b) une étape de solidification desdites gouttelettes sur ladite surface. (b) a step of solidifying said droplets on said surface.
L’étape (a) est une étape de disposition des gouttelettes sur une surface plane. Dans le cadre de la présente invention, la surface plane peut être une bande, une plaque ou un disque. De préférence la bande ou le disque est en mouvement. Step (a) is a step of placing the droplets on a flat surface. In the context of the present invention, the planar surface can be a strip, a plate or a disc. Preferably the strip or the disc is in motion.
La bande peut être une bande de transport qui tourne autour de deux cylindres. La bande effectue un mouvement de translation. Les gouttelettes sont disposées sur la partie supérieure de la bande de transport. The belt can be a conveyor belt which rotates around two cylinders. The band performs a translational movement. The droplets are arranged on the upper part of the conveyor belt.
Alternativement, le disque peut être en rotation autour d’un axe. De préférence, l’axe de rotation est perpendiculaire au sol. Les gouttelettes sont disposées sur la surface du disque, de préférence la surface supérieure. Alternatively, the disc can be rotated about an axis. Preferably, the axis of rotation is perpendicular to the ground. The droplets are arranged on the surface of the disc, preferably the upper surface.
Avantageusement, le procédé de la présente invention comprend en outre une étape (al), avant l’étape (a) dans laquelle le au moins un composé de formule (I) est fondu. Lors de l’étape (al), le au moins un composé de formule (I) est chauffé à une température comprise entre 1 et 50°C au-dessus de sa température de fusion ou, dans le cas d’un mélange, de la température de fusion du composé présentant le point de fusion le plus élevé, de préférence entre 1 et 20°C au- dessus de sa température de fusion, ou de la température de fusion du composé présentant le point de fusion le plus élevé, et plus préférentiellement de préférence entre 1 et l0°C au-dessus de sa température de fusion, ou de la température de fusion du composé présentant le point de fusion le plus élevé. Généralement la température du chauffage peut être comprise entre 50°C et 300°C, de préférence entre 50°C et 260°C.
Un additif ou plusieurs additifs tels que définis ci-dessus peut être ajouté à la préparation du composé sous forme fondu. Advantageously, the process of the present invention further comprises a step (a1), before step (a) in which the at least one compound of formula (I) is melted. During step (al), the at least one compound of formula (I) is heated to a temperature between 1 and 50 ° C above its melting point or, in the case of a mixture, of the melting temperature of the compound having the highest melting point, preferably between 1 and 20 ° C above its melting temperature, or the melting temperature of the compound having the highest melting point, and more preferably preferably between 1 and 10 ° C above its melting temperature, or the melting temperature of the compound having the highest melting point. Generally the heating temperature can be between 50 ° C and 300 ° C, preferably between 50 ° C and 260 ° C. An additive or more additives as defined above can be added to the preparation of the compound in molten form.
Le procédé de la présente invention peut également comprendre une étape (a2) consistant à former des gouttelettes. Le dispositif de formation des gouttelettes peut être un cylindre perforé ou une plaque perforée. Le dispositif de formation des gouttelettes est de préférence maintenu à une température supérieure ou égale à la température de l’étape (al). De préférence, le dispositif de formation des gouttelettes est situé au-dessus de la surface plane de manière à ce que les gouttelettes puissent tomber sur la surface plane. The method of the present invention may also include a step (a2) of forming droplets. The droplet formation device can be a perforated cylinder or a perforated plate. The droplet formation device is preferably maintained at a temperature greater than or equal to the temperature of step (al). Preferably, the droplet formation device is located above the planar surface so that the droplets can fall on the planar surface.
Selon un aspect particulier l’étape (al) est réalisée avant l’étape (a2). Selon un autre aspect, l’étape (a2) de formation des gouttelettes est réalisée directement à l’issue d’un procédé de préparation ou de purification de composé de formule (I). Dans ce mode de réalisation, le composé de formule (I) est sous forme liquide sans nécessiter d’étape dans lequel le composé de formule (I) est fondu. According to a particular aspect, step (al) is carried out before step (a2). According to another aspect, step (a2) of droplet formation is carried out directly after a process for the preparation or purification of the compound of formula (I). In this embodiment, the compound of formula (I) is in liquid form without requiring a step in which the compound of formula (I) is melted.
L’étape (b) est une étape de solidification des gouttelettes sur la surface plane. Avantageusement la surface place est refroidie à une température strictement inférieure à la température de fusion du composé de formule (I) ou, dans le cas d’un mélange, inférieure strictement à la température de fusion du composé de formule (I) ayant le point de fusion le plus bas. Avantageusement la surface plane est refroidie à une température comprise entre -50°C et une température inférieure strictement à la température de fusion du composé de formule (I) ou, dans le cas d’un mélange, inférieure strictement à la température de fusion du composé de formule (I) ayant le point de fusion le plus bas, de préférence à une température comprise entre 0°C et une température inférieure strictement à la température de fusion du composé de formule (I) ou, dans le cas d’un mélange, inférieure strictement à la température de fusion du composé de formule (I) ayant le point de fusion le plus bas, et plus préférentiellement à une température comprise entre l0°C et une température inférieure strictement à la température de fusion du composé de formule (I) ou, dans le cas d’un mélange, inférieure strictement à la température de fusion du composé de formule (I) ayant le point de fusion le plus bas. De préférence la surface plane est refroidie à une température de refroidissement comprise entre l0°C et la température ambiante. Step (b) is a step of solidifying the droplets on the flat surface. Advantageously, the placed surface is cooled to a temperature strictly below the melting temperature of the compound of formula (I) or, in the case of a mixture, strictly below the melting temperature of the compound of formula (I) having the point lowest melting point. Advantageously, the flat surface is cooled to a temperature between -50 ° C. and a temperature strictly below the melting temperature of the compound of formula (I) or, in the case of a mixture, strictly below the melting temperature of the compound of formula (I) having the lowest melting point, preferably at a temperature between 0 ° C and a temperature strictly below the melting temperature of the compound of formula (I) or, in the case of a mixture, strictly below the melting temperature of the compound of formula (I) having the lowest melting point, and more preferably at a temperature between 10 ° C. and a temperature strictly below the melting temperature of the compound of formula (I) or, in the case of a mixture, strictly lower than the melting temperature of the compound of formula (I) having the lowest melting point. Preferably the planar surface is cooled to a cooling temperature between 10 ° C and room temperature.
Selon un aspect particulier de la présente invention la température de refroidissement de la surface plane est uniforme sur toute la surface place. Selon un autre aspect particulier la
température de refroidissement n’est pas uniforme sur toute la surface plane, la température peut présenter un gradient de refroidissement ou des zones de refroidissement dans lesquelles la surface plane est refroidie à différentes températures de refroidissement. According to a particular aspect of the present invention, the cooling temperature of the flat surface is uniform over the entire surface. According to another particular aspect the cooling temperature is not uniform over the entire flat surface, the temperature may have a cooling gradient or cooling zones in which the flat surface is cooled to different cooling temperatures.
Selon un aspect particulier, la surface plane peut avoir subi un traitement de surface préalable au procédé selon la présente invention. La surface plane peut également être revêtue notamment par un revêtement antiadhésif ou hydrophobe, tel que le PTFE (polytetrafluoroethylene). La surface plane peut également présenter des rugosités. Ces traitements ou rugosités permettent notamment d’améliorer le décollement des nouvelles formes solides selon la présente invention à l’issue du procédé. Ces traitements ou rugosités permettent également d’améliorer les propriétés mécaniques des nouvelles formes solides selon la présente invention, notamment une meilleure résistance à la friabilité lors des manipulations. La forme des solides selon la présente invention permet également de réduire les phénomènes de mottage. According to a particular aspect, the flat surface may have undergone a surface treatment prior to the method according to the present invention. The flat surface can also be coated in particular with a non-stick or hydrophobic coating, such as PTFE (polytetrafluoroethylene). The flat surface can also have roughness. These treatments or roughness in particular make it possible to improve the separation of the new solid forms according to the present invention at the end of the process. These treatments or roughness also make it possible to improve the mechanical properties of the new solid forms according to the present invention, in particular better resistance to friability during handling. The shape of the solids according to the present invention also makes it possible to reduce caking phenomena.
A l’issue de l’étape (b) de solidification, les nouvelles mises en forme solides selon la présente invention peuvent adhérer à la surface plane. Le procédé selon la présente invention peut comprendre une étape dans laquelle les nouvelles mises en forme solides sont retirées de la surface plane. Le dispositif de formations des nouvelles mises en forme solides selon la présente invention peut comprendre un couteau ou racloir. At the end of the solidification step (b), the new solid forms according to the present invention can adhere to the flat surface. The method according to the present invention may include a step in which the new solid forms are removed from the planar surface. The device for forming new solid forms according to the present invention may comprise a knife or scraper.
Selon un aspect particulier de la présente invention, le procédé peut être réalisé à l’air, sous oxygène, ou sous atmosphère contrôlée, en particulier le taux d’humidité peut être contrôlé. Le procédé selon l’invention peut être réalisé sous air sec, sous atmosphère inerte, en particulier sous azote. According to a particular aspect of the present invention, the process can be carried out in air, under oxygen, or under a controlled atmosphere, in particular the humidity rate can be controlled. The process according to the invention can be carried out under dry air, under an inert atmosphere, in particular under nitrogen.
A l’issue du procédé selon la présente invention, le taux de particules fines ayant une taille inférieure ou égal à 355 mhi est inférieur ou égal à 30%, de préférence inférieur ou égal à 20%, plus préférentiellement inférieur ou égal à 10%, et encore plus préférentiellement inférieur ou égal à 0,1% en poids par rapport au poids de nouvelle mise en forme solide de formule (I). At the end of the process according to the present invention, the level of fine particles having a size less than or equal to 355 mhi is less than or equal to 30%, preferably less than or equal to 20%, more preferably less than or equal to 10% , and even more preferably less than or equal to 0.1% by weight relative to the weight of new solid shaping of formula (I).
Le procédé selon la présente invention peut également comprendre une étape dans laquelle les particules fines, ayant une taille inférieure ou égale à 355 mhi, sont séparées par tamisage ou par cyclonage. Les particules fines peuvent être recyclées. The method according to the present invention can also comprise a step in which the fine particles, having a size less than or equal to 355 mhi, are separated by sieving or by cycloning. Fine particles can be recycled.
Les nouveaux composés solides selon la présente invention présente une dureté d’au moins 1N. La dureté peut être mesurée avec un pénétromètre.
Avantageusement, les nouveaux composés solides selon la présente invention présentent une friabilité inférieure ou égale à 15%. Ce paramètre permet une manipulation facilitée de ces nouveaux composés solides par rapport à la poudre, car la formation de brouillard est évitée ou au moins réduite. La friabilité peut être mesurée en mélangeant les nouvelles mises en forme solides selon la présente invention dans un mixeur triaxial pendant 10 minutes, puis en mesurant le taux de particules inférieures à 100 mhi produites. La friabilité représente le rapport entre la masse de particules inférieures à 100 pm produites et la masse totale des nouvelles mises en forme solides introduites dans le mixeur triaxial. The new solid compounds according to the present invention have a hardness of at least 1N. Hardness can be measured with a penetrometer. Advantageously, the new solid compounds according to the present invention have a friability of less than or equal to 15%. This parameter allows easier handling of these new solid compounds compared to the powder, because the formation of mist is avoided or at least reduced. The friability can be measured by mixing the new solid forms according to the present invention in a triaxial mixer for 10 minutes, then by measuring the level of particles less than 100 mhi produced. The friability represents the ratio between the mass of particles smaller than 100 μm produced and the total mass of the new solid forms introduced into the triaxial mixer.
Les nouvelles mises en forme solides selon la présente invention présente de bonnes propriétés de dissolution. La vitesse de dissolution de ces solides est au moins équivalente, de préférence meilleure, à la vitesse de dissolution d’autres formes existantes de composés de formule (I). The new solid forms according to the present invention have good dissolution properties. The dissolution rate of these solids is at least equivalent, preferably better, to the dissolution rate of other existing forms of compounds of formula (I).
La composition chimique des nouvelles mises en forme solides selon la présente invention dépend de la composition liquide telle que définie ci-dessus. The chemical composition of the new solid forms according to the present invention depends on the liquid composition as defined above.
L’ajout d’additifs tels que définis ci-dessus dans les nouvelles mises en forme solides selon la présente invention peut se faire lors de la préparation de la composition comprenant au moins un composé de formule (I) sous forme liquide (Etape (al)) ou lors d’une étape supplémentaire à l’issue du procédé. The addition of additives as defined above in the new solid forms according to the present invention can be done during the preparation of the composition comprising at least one compound of formula (I) in liquid form (Step (al )) or during an additional step at the end of the process.
Les nouvelles mises en forme solides comprenant au moins un composé de formule (I) tel que défini précédemment susceptibles d’être obtenus selon le procédé de l’invention sont également un objet de la présente invention. The new solid forms comprising at least one compound of formula (I) as defined above capable of being obtained according to the method of the invention are also an object of the present invention.
Enfin la présente invention porte sur l’utilisation de ces nouvelles mises en forme solides comprenant au moins un composé de formule (I) dans l’industrie, en particulier l’industrie polymère, agro-alimentaire, parfumerie ou pharmaceutique. Finally, the present invention relates to the use of these new solid forms comprising at least one compound of formula (I) in the industry, in particular the polymer, food-processing, perfumery or pharmaceutical industry.
Exemple Example
Des pastilles de para-méthoxyphénol (PMP) sont préparées. Le PMP est d’abord fondu à 80°C. Des gouttelettes sont ensuite formées et déposées sur une bande refroidie à l8°C. Para-methoxyphenol (PMP) lozenges are prepared. The PMP is first melted at 80 ° C. Droplets are then formed and deposited on a strip cooled to 18 ° C.
Les Figures 4 et 5 montrent des pastilles selon la présente invention.
Exemple 1 : Les pastilles de la figure 4 ont été obtenues sur une bande en inox. Figures 4 and 5 show pellets according to the present invention. Example 1: The pellets of Figure 4 were obtained on a stainless steel strip.
Exemple 2 : Les pastilles de la figure 5 ont été obtenues sur une bande revêtue de PTFE. Example 2: The pellets of Figure 5 were obtained on a strip coated with PTFE.
La résistance au mottage est acquise visuellement après conservation de l’échantillon pendant 7 jours à 35°C Clumping resistance is visually acquired after storage of the sample for 7 days at 35 ° C
La vitesse de dissolution correspond au temps nécessaire pour dissoudre 90% de 2g de pastilles/poudre/écailles dans 100 g d’eau/acide acrylique à 20°C agité à 300 tours par minute.
The dissolution rate corresponds to the time necessary to dissolve 90% of 2 g of pellets / powder / scales in 100 g of water / acrylic acid at 20 ° C stirred at 300 rpm.
Claims
1. Nouvelle mise en forme solide comprenant au moins un composé de formule (I) 1. New solid form comprising at least one compound of formula (I)
Formule (i) Formula (i)
dans lequel : in which :
- n est compris entre 0 et 5, de préférence entre 0 et 4, et préférentiellement n est égal à 0, 1 ou 2, - n is between 0 and 5, preferably between 0 and 4, and preferably n is equal to 0, 1 or 2,
- Ri est choisi dans le groupe consistant en hydrogène, alkyl, et alcényl, de préférence Rl est choisi parmi hydrogène, méthyl, éthyl. - Ri is chosen from the group consisting of hydrogen, alkyl, and alkenyl, preferably R1 is chosen from hydrogen, methyl, ethyl.
- R2 est choisi dans le groupe consistant en hydroxyl, alkyl, alcényl, alcynyl, alkoxy, formyl et acétyl, de préférence R2 est choisi parmi hydroxyl, méthyl, éthyl, propyl, méthoxy, éthoxy, et formyl, R 2 is chosen from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acetyl, preferably R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl,
et comprenant au moins une partie arrondie et une partie plane. and comprising at least a rounded part and a flat part.
2. Nouvelle mise en forme solide selon la revendication 1 caractérisée en ce que le composé de formule (I) est choisi dans le groupe consistant en hydroquinone, catéchol, résorcinol, pyrogallol, 4-tert-butylcatéchol, tert-butylhydroquinone, para-méthoxyphénol, butylhydroxyanisole, vanilline, éthylvanilline et un composé de vanilline et d’éthylvanilline dans un rapport molaire de 2. 2. New solid form according to claim 1 characterized in that the compound of formula (I) is chosen from the group consisting of hydroquinone, catechol, resorcinol, pyrogallol, 4-tert-butylcatechol, tert-butylhydroquinone, para-methoxyphenol , butylhydroxyanisole, vanillin, ethylvanillin and a compound of vanillin and ethylvanillin in a molar ratio of 2.
3. Pastilles d’au moins un composé de formule (I)
3. Tablets of at least one compound of formula (I)
Formule (i) Formula (i)
dans lequel : in which :
- n est compris entre 0 et 5, de préférence entre 0 et 4, et préférentiellement n est égal à 0, 1 ou 2, - n is between 0 and 5, preferably between 0 and 4, and preferably n is equal to 0, 1 or 2,
- Ri est choisi dans le groupe consistant en hydrogène, alkyl, et alcényl, de préférence Rl est choisi parmi hydrogène, méthyl, éthyl. - Ri is chosen from the group consisting of hydrogen, alkyl, and alkenyl, preferably R1 is chosen from hydrogen, methyl, ethyl.
- R2 est choisi dans le groupe consistant en hydroxyl, alkyl, alcényl, alcynyl, alkoxy, formyl et acétyl, de préférence R2 est choisi parmi hydroxyl, méthyl, éthyl, propyl, méthoxy, éthoxy, et formyl. - R 2 is chosen from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acetyl, preferably R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl.
4. Calotte sphérique d’au moins un composé de formule (I) 4. Spherical cap of at least one compound of formula (I)
Formule (i) Formula (i)
dans lequel : in which :
- n est compris entre 0 et 5, de préférence entre 0 et 4, et préférentiellement n est égal à 0, 1 ou 2, - n is between 0 and 5, preferably between 0 and 4, and preferably n is equal to 0, 1 or 2,
- Ri est choisi dans le groupe consistant en hydrogène, alkyl, et alcényl, de préférence Rl est choisi parmi hydrogène, méthyl, éthyl.
- R2 est choisi dans le groupe consistant en hydroxyl, alkyl, alcényl, alcynyl, alkoxy, formyl et acétyl, de préférence R2 est choisi parmi hydroxyl, méthyl, éthyl, propyl, méthoxy, éthoxy, et formyl. - Ri is chosen from the group consisting of hydrogen, alkyl, and alkenyl, preferably R1 is chosen from hydrogen, methyl, ethyl. - R 2 is chosen from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acetyl, preferably R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl.
5. Procédé de préparation d’une nouvelle mise en forme solide, d’une pastille ou d’une calotte sphérique comprenant au moins un composé de formule (I) tels que définis aux revendications 1 à 4 comprenant au moins les étapes consécutives suivantes : 5. Method for preparing a new solid form, a pellet or a spherical cap comprising at least one compound of formula (I) as defined in claims 1 to 4 comprising at least the following consecutive steps:
(a) une étape dans laquelle des gouttelettes liquides comprenant au moins un composé de formule (I) sont disposées sur une surface plane, (a) a step in which liquid droplets comprising at least one compound of formula (I) are arranged on a flat surface,
(b) une étape de solidification desdites gouttelettes sur ladite surface. (b) a step of solidifying said droplets on said surface.
6. Procédé de préparation d’une nouvelle mise en forme solide selon la revendication 5 dans lequel la surface plane est une bande, une plaque ou un disque. 6. A method of preparing a new solid form according to claim 5 wherein the planar surface is a strip, a plate or a disc.
7. Procédé de préparation selon la revendication 5 à 6 comprenant en outre avant l’étape (a) une étape (al) dans laquelle le au moins un composé de formule (I) est chauffé à une température comprise entre 1 et 50°C au-dessus de sa température de fusion de préférence entre 1 et 20°C au-dessus de sa température de fusion, et plus préférentiellement de préférence entre 1 et l0°C au-dessus de sa température de fusion. 7. The preparation method according to claim 5 to 6 further comprising before step (a) a step (al) in which the at least one compound of formula (I) is heated to a temperature between 1 and 50 ° C above its melting temperature preferably between 1 and 20 ° C above its melting temperature, and more preferably preferably between 1 and 10 ° C above its melting temperature.
8. Procédé de préparation selon l’une quelconque des revendications 5 à 7 comprenant une étape (a2) précédant l’étape (a) consistant à former des gouttelettes. 8. Preparation process according to any one of claims 5 to 7 comprising a step (a2) preceding step (a) consisting in forming droplets.
9. Procédé selon l’une quelconque des revendications 5 à 8 dans lequel la surface plane est refroidie à une température inférieure strictement à la température de fusion du composé de formule (I) pour permettre la solidification desdites gouttelettes. 9. Method according to any one of claims 5 to 8 wherein the flat surface is cooled to a temperature strictly below the melting temperature of the compound of formula (I) to allow the solidification of said droplets.
10. Procédé selon l’une quelconque des revendications 5 à 9 réalisé à l’air, sous oxygène, air appauvri en oxygène, atmosphère contrôlée, atmosphère inerte, en particulier sous azote. 10. Method according to any one of claims 5 to 9 carried out in air, under oxygen, air depleted in oxygen, controlled atmosphere, inert atmosphere, in particular under nitrogen.
11. Nouvelle mise en forme solide comprenant au moins une partie arrondie et une partie plane, pastille ou calotte sphérique comprenant au moins un composé de formule (I)
11. New solid shaping comprising at least one rounded part and a flat part, pellet or spherical cap comprising at least one compound of formula (I)
Formule (i) Formula (i)
dans lequel : in which :
- n est compris entre 0 et 5, de préférence entre 0 et 4, et préférentiellement n est égal à 0, 1 ou 2, - n is between 0 and 5, preferably between 0 and 4, and preferably n is equal to 0, 1 or 2,
- Ri est choisi dans le groupe consistant en hydrogène, alkyl, et alcényl, de préférence Rl est choisi parmi hydrogène, méthyl, éthyl. - Ri is chosen from the group consisting of hydrogen, alkyl, and alkenyl, preferably R1 is chosen from hydrogen, methyl, ethyl.
- R2 est choisi dans le groupe consistant en hydroxyl, alkyl, alcényl, alcynyl, alkoxy, formyl et acétyl, de préférence R2 est choisi parmi hydroxyl, méthyl, éthyl, propyl, méthoxy, éthoxy, et formyl, R 2 is chosen from the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, formyl and acetyl, preferably R 2 is chosen from hydroxyl, methyl, ethyl, propyl, methoxy, ethoxy, and formyl,
susceptibles d’être obtenu selon le procédé défini aux revendications 5 à 10. capable of being obtained according to the process defined in claims 5 to 10.
12. Utilisation d’une nouvelle mise en forme solide, pastille ou calotte sphérique tels que définis aux revendications 1 à 4 dans l’industrie, en particulier l’industrie polymère, agro- alimentaire, parfumerie, ou pharmaceutique.
12. Use of a new solid form, pellet or spherical cap as defined in claims 1 to 4 in the industry, in particular the polymer industry, food industry, perfumery, or pharmaceutical.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1857419A FR3084886B1 (en) | 2018-08-09 | 2018-08-09 | NEW SOLID FORMATION OF AT LEAST ONE PHENOLIC DERIVATIVE AND PROCESS FOR OBTAINING |
| PCT/EP2019/070872 WO2020030541A1 (en) | 2018-08-09 | 2019-08-02 | Novel solid presentation form of at least one phenol derivative and process for obtaining same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3833653A1 true EP3833653A1 (en) | 2021-06-16 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19746490.2A Pending EP3833653A1 (en) | 2018-08-09 | 2019-08-02 | Novel solid presentation form of at least one phenol derivative and process for obtaining same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20210292262A1 (en) |
| EP (1) | EP3833653A1 (en) |
| JP (1) | JP2021534120A (en) |
| CN (1) | CN112566889A (en) |
| FR (1) | FR3084886B1 (en) |
| WO (1) | WO2020030541A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754523B (en) * | 2021-09-29 | 2023-11-07 | 潍坊裕凯化工有限公司 | Method for separating out methyl octabromoether crystal |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5827604A (en) * | 1981-08-07 | 1983-02-18 | Sumitomo Chem Co Ltd | Method for solidifying substance difficult to solidify |
| JPS5910333A (en) * | 1982-07-12 | 1984-01-19 | Nippon Kagaku Sangyo Kk | Method for granulating organic metallic salt |
| FR2721803B1 (en) * | 1994-06-29 | 1996-09-06 | Rhone Poulenc Chimie | ETHYLVANILLIN VANILLIN PEARLS AND THEIR PROCESS |
| NL1007904C2 (en) | 1997-12-24 | 1999-06-25 | Goudsche Machinefabriek Bv | Method and device for forming granulate from a melt of chemical products. |
| JP2000302716A (en) | 1999-04-23 | 2000-10-31 | Mitsui Chemicals Inc | Production of granular phenols |
| JP2004075507A (en) * | 2002-08-09 | 2004-03-11 | Yamanaka Hutech Corp | Method of manufacturing granular gallium trichloride |
| FR2846324B1 (en) | 2002-10-28 | 2006-07-07 | Rhodia Chimie Sa | PEARLS OF A PHENOLIC COMPOUND AND PROCESS FOR OBTAINING THEM |
| JP2014118350A (en) * | 2012-12-13 | 2014-06-30 | Seiko Kagaku Kk | GRANULAR p-METHOXYPHENOL, AND PRODUCTION METHOD THEREOF |
| US20160060196A1 (en) | 2014-08-26 | 2016-03-03 | Eastman Chemical Company | Crystallized hydroquinone and methods of making |
| FR3026021B1 (en) * | 2014-09-18 | 2016-10-28 | Rhodia Operations | METHOD FOR UNLOADING LIQUID STATE OF OXIDIZABLE COMPOUND |
| DE102014224736B4 (en) * | 2014-12-03 | 2017-10-19 | Sandvik Materials Technology Deutschland Gmbh | Apparatus and method for pasting a flowable product |
-
2018
- 2018-08-09 FR FR1857419A patent/FR3084886B1/en active Active
-
2019
- 2019-08-02 US US17/266,238 patent/US20210292262A1/en active Pending
- 2019-08-02 CN CN201980053287.5A patent/CN112566889A/en active Pending
- 2019-08-02 EP EP19746490.2A patent/EP3833653A1/en active Pending
- 2019-08-02 JP JP2021506743A patent/JP2021534120A/en active Pending
- 2019-08-02 WO PCT/EP2019/070872 patent/WO2020030541A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR3084886A1 (en) | 2020-02-14 |
| US20210292262A1 (en) | 2021-09-23 |
| CN112566889A (en) | 2021-03-26 |
| FR3084886B1 (en) | 2021-07-16 |
| JP2021534120A (en) | 2021-12-09 |
| WO2020030541A1 (en) | 2020-02-13 |
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