Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/12—Naturally occurring clays or bleaching earth
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
• • 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
  • C08G18/08—Processes
  • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
  • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter

Definitions

• the present invention relates to the field of stable organic compositions comprising zeolites, more particularly stable liquid organic compositions comprising zeolites and very particularly stable compositions of hydroxylated organic liquids or even hydroxylated organic oils, comprising zeolites.
• Such compositions are often and most generally used for drying organic liquids and for example polyols which can then advantageously be used for the synthesis of smooth polyurethanes, the smooth polyurethanes being generally and most often intended for coatings, such as glues, coatings, paints and adhesives.
• Smooth polyurethanes are usually obtained by reaction of said polyols with isocyanates. It is in fact important, often sought after, even essential, to prevent the water present in these polyols from reacting with the isocyanate to form carbon dioxide (CO2) and thus create gas bubbles, or even foam.
• CO2 carbon dioxide
• patent US6051647 seeks to improve the pot life and therefore the effectiveness of a 3A zeolite.
• This document describes a mild acid treatment of a 3A zeolite, in order to modify its pH and thus minimize the effect of this 3A zeolite when it is used as a desiccant for the manufacture of polyurethane (PU) for smooth coatings, that is to say free from foaming phenomena.
• PU polyurethane
• a 50/50 mixture of zeolite crystals and castor oil is used, previously prepared to dry the polyol.
• Patents US8026307 and US8153042 mention the use of phyllosilicates for two-component resins in order to avoid the collapse (“slump” in English) of the shapes prepared using said resins. However, these patents do not mention the use of compositions intended to introduce zeolites into the components of the resins.
• an activated molecular sieve powder in paste is proposed obtained by mixing 48% to 52% by mass of activated synthetic molecular sieve powder, from 30% to 52% by mass of oil of castor oil and from 0 to 20% by weight of a viscosity adjusting agent, generally chosen from glycols.
• a viscosity adjusting agent generally chosen from glycols.
• the teaching of this document and that the viscosity adjustment agent is between 8% and 20%, values which are very high and can harm the quality of the desired product.
• the objective of the present invention is to provide a solution to the problems encountered in the prior art and in particular to provide stable organic compositions comprising zeolite crystals, and in particular stable polyol compositions comprising zeolite crystals having for function the drying, the desiccation of said compositions.
• Another objective is to provide stable liquid compositions of zeolites for the drying of organic compounds, in particular for the drying of organic compounds intended for the preparation of 2K resins, and very particularly for the drying of organic compounds intended for the preparation of PU resins.
• a first subject of the present invention relates to a composition
• a composition comprising:
• hydroxylated oil within the meaning of the present invention is meant any organic fatty compound comprising at least one hydroxyl function, and for example esters of hydroxylated fatty acids, such as for example mono-, di- and tri- glycerides, alone or in mixtures of two or more of them.
• the hydroxylated oil is chosen from mono-, di-, tri-, and poly-hydroxylated oils, alone or as a mixture of two or more of them.
• the composition according to the present invention also comprises crystals of at least one zeolite.
• Zeolites are mineral compounds well known to those skilled in the art and can be natural, artificial or synthetic zeolites. Zeolites are crystallized aluminosilicates, whose crystal structure depends, among other things, on the silicon/aluminum (Si/Al) molar ratio.
• the zeolites in the form of crystals, which can be used in the context of the present invention can be of any type.
• the zeolites are chosen from zeolites of type LTA, FAU, MFI, CHA, SOD, GIS, MOR, RHO, EMT, LTL, preferably from zeolites of type LTA, FAU and MFI and preferably still among LTA and FAU type zeolites.
• the zeolites are chosen from MFI type zeolites.
• the composition of the present invention may comprise crystals of one or more zeolites, depending on the desired effect.
• the zeolite crystals used in the context of the present invention have advantageously previously undergone one or more treatments aimed at reducing the residual water content, or even eliminating free and absorbed water, or even at eliminating possible agents.
• Such treatments are perfectly known to those skilled in the art and include heat treatments, vacuum degassing, vacuum desorptions, and others.
• the residual water content of the zeolite crystals used in the invention is determined by the Karl Fischer method. Zeolite crystals having a residual water content of less than 1% by weight are preferred.
• said at least one zeolite of the composition of the present invention is chosen from zeolites of the LTA, and FAll-X type, and among these, those whose molar ratio Si /AI is between 1.0 and 1.5, limits included.
• said at least one zeolite of the composition of the present invention is chosen from zeolites 3A, 4A, 5A, 13X. According to another embodiment, said at least one zeolite of the composition of the present invention is chosen from MFI, in particular zeolites of the Silicalite-1 type.
• the size of the zeolite(s) crystals can vary in large proportions. However, for the purposes of the present invention, zeolite crystals whose size is between 0.1 pm and 5 pm, preferably between 0.5 pm and 4 pm, inclusive, are preferred. The size of the crystals corresponds to the number average diameter, calculated from counting on scanning electron microscopy (SEM) images.
• the composition according to the present invention is characterized by the fact that it comprises at least one dispersing agent.
• the dispersing agent promotes and/or allows the zeolite crystals to be kept in suspension in the hydroxylated oil.
• Said at least one dispersing agent used in the composition of the present invention is an organophilic phyllosilicate.
• Phyllosilicates are natural or synthetic minerals from the group of silicates constructed by stacking tetrahedral layers, where the tetrahedra share three out of four vertices, the fourth vertex being connected to an octahedral layer occupied by different cations, for example aluminum cations. , magnesium, iron, titanium, lithium, and others.
• the phyllosilicates which can be used to form the organophilic phyllosilicates which are the dispersing agents of the composition of the present invention can be of any type and in particular natural clays in general, among which we can cite bentonites, palygorskites, sepiolites. , attapulgites, montmorillonites, hydrotalcites, octasilicates, and others and their mixtures of two or more of them in all proportions.
• the phyllosilicate is chosen from fibrous clays and preferably from hormites, the main representatives of which are sepiolite and attapulgite (or palygorskite). Sepiolite and attapulgite are the preferred hormites in the context of the present invention, and most preferably the preferred phyllosilicate is sepiolite.
• Organophilic phyllosilicates also called “organoclays” in English, are generally prepared from natural phyllosilicates which are modified by one or more chemical treatments, generally using an organic compound, most often of the surfactant type, for example nitrogen surfactant, to make them organophilic, as described for example in application WO1999042518.
• organic compounds capable of modifying the phyllosilicates which can be used in the context of the present invention, cationic surfactants are preferred, among which we can cite in particular compounds of the quaternary ammonium type, as described for example in US20200181474.
• said at least one dispersing agent is an organophilic phyllosilicate chosen from bentonites, palygorskites, sepiolites, attapulgites, montmorillonites, hydrotalcites, octasilicates, and preferably chosen from hormites, among which sepiolite is preferred, said organophilic phyllosilicate being functionalized on the surface with one or more compounds chosen from amines, surfactants, silanes, siloxanes and alkyl chains. Mixtures of one or more organophilic phyllosilicates may be used in the composition of the present invention. More preferably, said at least one dispersing agent is a fibrous clay or a mixture of fibrous clays modified with one or more surfactant(s).
• Organophilic phyllosilicates are well known to those skilled in the art and already widely used in numerous fields of application; representatives of these compounds are for example marketed by the company BYK under the general names TIXOGEL®, CLAYTON® or even GARAMITE®.
• the presence of at least one dispersing agent of the organophilic phyllosilicate type makes it possible to greatly limit the sedimentation of zeolite crystals present in a hydroxylated oil, particularly when said crystals are present in quantities greater than 30%, preferably greater than 40%, preferably greater than 50%, by weight, limits included, even after several months of storage.
• composition of the invention is therefore entirely advantageous in numerous fields of application.
• the composition of the present invention allows polyurethane manufacturers to use the composition (oil hydroxylated/zeolite crystals) in their formulation, without it being necessary to redisperse the zeolite crystals in the oil.
• the composition described in this invention can be prepared by any means known per se, and for example by simply mixing its different constituents together.
• the zeolite crystals are added to the hydroxylated oil with shearing stirring at high speed, for example of the order of 1500 rpm, by means of a shearing stirrer, for example of the Rayneri type. , then, still stirring, the dispersing agent is added.
• the dispersing agent can advantageously be added in the form of a mixture in an oil, for example the hydroxylated oil of the composition of the invention.
• the composition can advantageously be degassed, in order to eliminate the air bubbles trapped during its preparation, by any means known per se, and for example by slight heating (for example between 40°C and 80°C) under partial vacuum, for example under 0.2 bar (0.2 kPa).
• This degassing step is advantageously carried out with stirring, preferably low stirring, for example of the order of 200 rpm), until complete or almost complete degassing.
• the composition according to the invention is then in the form of a homogeneous paste, with zeolite crystals in suspension and well dispersed.
• the invention concerns the use of the composition as it has just been defined for the drying of organic compounds, compositions or solutions.
• the invention relates to the use of the composition as it has just been defined for the drying of organic compositions intended for the preparation of 2K resins, and more particularly still for the drying of organic compositions. intended for the preparation of polyurethane resins.
• the composition of the present invention finds a use that is entirely suitable for drying polyol compositions intended for the preparation of polyurethane resins.
• composition according to the invention has a completely surprising stability, without sedimentation, or at least without excessive sedimentation, during transport and storage in a pot, for periods of up to one month, even up to two months, even up to three months and even up to 4 months or more.
• the duration from which the sedimentation of the zeolite crystals in the hydroxylated oil is observed can be determined by an accelerated test carried out in a centrifuge.
• the percentage of decantation of the zeolite crystals in the paste is measured by taking the ratio of height of apparent hydroxylated oil to total height of the mixture.
• the estimation of the number average diameter of the zeolite crystals is carried out by observation with a Scanning Electron Microscope (SEM).
• SEM Scanning Electron Microscope
• a set of images is taken at a magnification of at least 5000.
• the diameter of at least 200 crystals is then measured using dedicated software, for example the Smile View software from the publisher LoGraMi. The precision is around 3%.
• a mixture is prepared containing 50% by weight of zeolite crystals and 50% by weight of hydroxylated oil.
• a homogeneous paste of approximately 500 g is obtained.
• it is heated to 60°C under vacuum (0.2 kPa) with gentle stirring (200 rpm) for 1 hour.
• a homogeneous paste with suspended and well-dispersed crystals is obtained.
• Example 2 composition according to the invention
• a composition is prepared as described above in Example 1.
• a mixture is prepared containing 49.75% by weight of zeolite crystals and 49.75% by weight of hydroxylated oil, to which is added 0, 5% dispersing agent.
• 250 g of zeolite from Example 1 are introduced into 125 g of castor oil, under shearing agitation, at high speed, using a Rayneri type mixer at 1500 rpm, in plastic pot. Then, with stirring for 30 min, 2.51 g of dispersing agent, previously dispersed in 125 g of castor oil, is added.
• the dispersing agent is an organophilic montmorillonite dispersant, marketed under the reference CLAYTON® AF by the company BYK.
• a homogeneous paste of approximately 502.5 g is obtained. In order to eliminate the air bubbles trapped in the dough during its preparation, it is heated to 60°C under vacuum (0.2 kPa) with gentle stirring (200 rpm) for 1 hour. A homogeneous paste with suspended and well-dispersed crystals is obtained. The sedimentation rate of the Composition of Example 2 is 8.9%.
• the dispersing agent is an organophilic montmorillonite marketed under the reference Tixogel® MP 250 by the company BYK.
• the sedimentation rate is 8.0%.
• This Composition is also prepared as in Example 2, the dispersing agent being however replaced by an organophilic sepiolite marketed under the reference Garamite® 1958 by the company BYK.
• the sedimentation rate is 6.9%.
• Example 5 comparative example:
• Example 6 This Composition is prepared according to Example 2, with as dispersing agent a dispersing agent of the modified polyglycol polyalkylene imine polyester type, marketed under the reference BYK® 2155 by the company BYK. The observed sedimentation rate is 11.9%.
• Example 6 comparative example:
• the dispersing agent is this time a dispersing agent of the copolymer type functionalized with acid groups, and marketed under the reference Disperbyk® 111 by the company BYK.
• the sedimentation rate is then 22%.
• Example 7 comparative example:
• the composition of this example contains a dispersing agent which is a modified urea solution, marketed under the reference Disperbyk® 7410 by the company BYK. The sedimentation rate is then 13%.
• Example 8 comparative example:
• Comparative Example 8 The Composition of Comparative Example 8 is prepared according to the protocol of Example 2 with a high molecular mass polyacrylic type dispersing agent, marketed under the reference BYK® 430 by the company BYK.
• the sedimentation rate is 12.1%.
• Example 9 comparative example:
• the Composition is prepared according to the protocol of Example 2 with an unmodified sepiolite type clay, marketed under the reference P400 by the company Toisa.
• the sedimentation rate is 17.5%.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Analytical Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Geochemistry & Mineralogy (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
• Treatment Of Liquids With Adsorbents In General (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fats And Perfumes (AREA)

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• 2022
  • 2022-12-19 FR FR2213752A patent/FR3143618B1/fr active Active
• 2023
  • 2023-12-13 KR KR1020257018939A patent/KR20250114928A/ko active Pending
  • 2023-12-13 CN CN202380082190.3A patent/CN120283018A/zh active Pending
  • 2023-12-13 JP JP2025535995A patent/JP2025540425A/ja active Pending
  • 2023-12-13 EP EP23838184.2A patent/EP4638604A1/de active Pending
  • 2023-12-13 WO PCT/FR2023/051999 patent/WO2024134062A1/fr not_active Ceased

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