Patent Application
20250206885
The present invention relates to cyclic organopolysiloxanes and more particularly to an organopolysiloxane preparation method for preparing cyclic organopolysiloxanes by depolymerization of organopolysiloxanes in the presence of a catalytic system comprising an alkaline catalyst and a multidentate complexing agent.
The recycling of industrial products and used silicone products is an ongoing issue of concern. The recycling of silicone polymer could enable a 75% reduction in gas emissions (CO, CO2) associated with the silicone industry and a 65% reduction in silicone waste.
One of the recycling routes envisaged is the depolymerization of organopolysiloxanes to produce cyclic organopolysiloxanes (or cyclosiloxane).
The depolymerization of silanol-terminated polydimethylsiloxane (PDMS) in the presence of strong alkali hydroxide or quaternary hydroxide is already known, in particular from U.S. Pat. No. 5,670,689. The reaction is carried out at 140° C. in order to achieve a 90% yield of a mixture of cyclic organopolysiloxanes. However, a high load of catalyst is required, in particular at least 2% by weight relative to the weight of PDMS-OH.
There is therefore an interest in providing an optimised process that enables organopolysiloxane to be depolymerised efficiently and to obtain a good yield of cyclic siloxanes, in particular D3 (hexamethylcyclotrisiloxane), D4 (octamethylcyclotetrasiloxane) and D5 (decamethylcyclopentasiloxane).
One objective of the present patent application is therefore to provide a depolymerization process for the depolymerization of organopolysiloxane in an efficient manner which makes it possible to obtain a good yield of cyclic organopolysiloxanes, in particular D3, D4 and D5.
Another objective of the present application is to provide a catalytic system for implementing this process.
Yet another objective of the present application is to provide a catalytic system that is simple and provides for good reaction kinetics thus being compatible with the industrialisation of the process.
Other objectives will become apparent upon reading the description of the invention that follows below.
These objectives are achieved in the present patent application, which relates to a method for preparing cyclic organopolysiloxane CO by reactive distillation of at least one organopolysiloxane O in the presence of an alkali salt type catalyst selected from the salts of K, Na, Rb or Cs, and of a multidentate complexing agent.
The organopolysiloxane O of the invention may be any type of organopolysiloxane, in particular selected from linear organopolysiloxanes, for example oils, or gums, or branched organopolysiloxanes.
The organopolysiloxane O may in particular be an oil or a gum, and preferably has a dynamic viscosity of between 50 and 600,000 mPa·s at 25° C. or a consistency of between 200 and 2000 expressed in tenths of a millimetre at 25° C.
All the viscosities referred to in the present description correspond to a so-called ‘Newtonian’ dynamic viscosity value at 25° C., i.e. the dynamic viscosity which is measured, in a manner known per se, with a Brookfield viscometer at a shear rate gradient which is sufficiently low for the measured viscosity to be independent of the rate gradient.
The term ‘gum’ is used for organopolysiloxane compounds having viscosities typically greater than 600,000 mPa·s, which corresponds to a molecular weight greater than 260,000 g/mol.
The consistency or penetrability of a gum is determined at 25° C. using a penetrometer of the type PNR12 or an equivalent model which enables a cylindrical head to be applied to the sample under standardised conditions.
These organopolysiloxanes O may comprise one or more functional units such as:
Preferably, the organopolysiloxanes O may comprise one or more functional units such as H, OH, alkenyl (preferably vinyl), aryl, cyclic amine, as defined above.
The organopolysiloxanes O of the invention may be partially cross-linked.
The organopolysiloxanes O of the invention may in particular be waste (used) organopolysiloxanes which have been used, for example, as heat transfer fluids and which ought to be recycled, with the method of the invention thus making it possible to generate cyclic organopolysiloxanes CO that can subsequently be used directly in industrial processes, in particular in new polymerization processes. For example, the organopolysiloxanes O of the invention may be silicone oils in particular terminated with trimethylsilyl, dimethylhydroxysilyl or dimethylvinylsilyl units, or indeed silicone gels. In the event of redeploying waste organopolysiloxanes O, the organopolysiloxane may then contain other elements such as additives, pigments, etc. The inventors have thus shown that the presence of these other elements does not interfere with the depolymerization reaction and the formation of cyclic organopolysiloxanes CO.
According to one embodiment of the invention, the organopolysiloxane O of the invention comprises:
It is understood in the above formulas that, if multiple R groups are present or if multiple R1 groups are present, they may be identical to or different from each other.
Preferably, in the above formulas, R1, which may be identical or different, represents:
In the present invention:
The organopolysiloxane O may optionally comprise a small quantity of T and Q units. Without intending to be bound by any particular theory, the depolymerization process of the invention may be implemented on organopolysiloxanes O comprising long chains of successive D units. Preferably the organopolysiloxane O according to the invention comprises less than 20%, preferably less than 10%, even more preferentially less than 5%, and even more preferentially less than 2% of T or Q units as defined above relative to the number of total siloxyl units of the organopolysiloxane O.
According to one preferential embodiment, the organopolysiloxane O of the invention is preferably selected from among the compounds having the formula (I):
R1aR(3-a)SiO—(SiR2O)n—(SiR1RO)m—SiR1aR(3-a) (I)
The presence of the group Si—H in the organopolysiloxane O can generate a release of dihydrogen. Therefore, with respect to the device for implementing the method of the invention, in the event of the quantity of the group Si—H being significant, it may be advantageous to provide for a device for managing the release of dihydrogen. In order to avoid having to deploy such a device, the quantity of the group Si—H is preferably less than 20%, preferably less than 10%, more preferably less than 5%, most preferably less than 2% by weight relative to the total weight of organopolysiloxane O.
In a particularly preferred manner, the organopolysiloxane O of the invention is a compound having the formula (I)
In a particularly preferred manner, the organopolysiloxane O of the invention is a compound having the formula (I)
In a particularly preferred manner, the organopolysiloxane O of the invention is a compound having the formula (I)
In a particularly preferred manner, the organopolysiloxane O of the invention is a compound having the formula (I)
In an advantageous manner, the method of the invention may be implemented with organopolysiloxanes O having a dynamic viscosity of between 3 and 20,000,000 mPa·s, preferably between 3 and 6,000,000 mPa·s, for example between 3 and 1,000,000 mPa·s, at 25° C. In a particularly advantageous manner, the method of the invention may be implemented with an organopolysiloxane O or a mixture of organopolysiloxanes O having a dynamic viscosity, of the organopolysiloxane O or of the mixture of organopolysiloxanes O, of between 3 and 1,000,000 mPa·s, preferably between 100 and 60,000 mPa·s, at 25° C. It should therefore be understood that, in an advantageous manner, in order to facilitate the implementation of the method, in the context of mixtures of organopolysiloxanes, the organopolysiloxane O may have variable viscosities to the extent that the viscosity of the mixture is as mentioned above.
In addition, the method of the invention may be implemented in the presence of a solvent. The solvent should be selected from among solvents that solubilise organopolysiloxane O. The solvent may be an alcohol or n-paraffins. Preferably, the alcohol is selected from among fatty alcohols such as n-lauryl alcohol, n-myristyl alcohol, n-palmitic alcohol, n-stearyl alcohol, n-docosanol, or Guerbet alcohols such as 2-octyl 1-dodecanol, 2-decyl 1-tetradecanol. Preferably the n-paraffins are selected from the compounds C16H34, C18H38, C20H42, C22H46, or C24H50. Where a solvent is deployed in the method of the invention, the quantity of solvent added is preferably between 5 and 50% by weight, preferably between 10 and 20% by weight, relative to the weight of organopolysiloxane O. In a particularly advantageous way, in order to facilitate the implementation of the method, the use of a solvent will serve to facilitate the implementation of the method of the invention with organopolysiloxanes O which are more viscous, for example having a viscosity of between 1,000,000 and 20,000,000 mPa·s at 25° C., such that the mixture (organopolysiloxane O+solvent) has a viscosity of between 3 and 1,000,000 mPa·s, preferably between 100 and 60,000 mPa·s at 25° C.
The alkali salt catalyst is an alkali metal salt comprising a metal M, the metal M being selected from K, Na, Rb or Cs, preferably K, Rb or Cs.
Preferably, the said alkali metal salt is selected from among silanolates, hydroxides, alkoxides and siliconates, preferably silanolates.
In the context of the present invention, where reference is made to the term ‘alkali metal salt’, the below terms are to be understood as follows: ‘silanolate’ is a salt derived from a silanol group which is a functional group comprising at least one Si—OH group. Silanolates generally have the formula MOSi(R′)3 with M as defined above; and R′, which may be identical or different, represents a linear or branched alkyl group containing from 1 to 6 carbon atoms, or an alkenyl group containing from 2 to 6 carbon atoms; preferably R′, which may be identical or different, represents methyl or vinyl. ‘siliconate’ is a compound having the formula M (OSi(R3)2)p—OSi(R3)2 with M as defined above; and R3 represents an alkyl group containing from 1 to 6 carbon atoms, preferably methyl; and p represents an integer between 1 and 20, preferably between 1 and 10. ‘hydroxide’ is a group having the formula MOH, with M as defined above. ‘alkoxide’ is a compound having the formula MOAlk, with M as defined above; and Alk represents a linear or branched alkyl containing from 1 to 22 carbon atoms, preferably from 1 to 15 carbon atoms, more preferably from 1 to 12 carbon atoms.
Preferably, the alkaline catalyst of the invention is a catalyst having the formula M-X wherein
Preferably, M is selected from K, Rb, Cs; and X is selected from OSiMe3, OSiMe2 Vi (Vi represents vinyl), OH, OSi(Me)2—(OSi(Me)2)p—OSiMe3, where p represents an integer between 1 and 20, preferably between 1 and 10, and O-tBu (tBu represents tert-butyl). Preferably the alkaline catalyst is KOSiMe3 (Potassium Trimethylsilanolate).
In the context of this patent application the term ‘multidentate complexing agent’ is used to refer to a complexing agent for the alkali metal of the alkali salt catalyst, that is to say a complexing agent for K, Na, Rb or Cs, preferably a complexing agent for K, Rb or Cs.
Preferably, the multidentate complexing agents of the invention are selected from crown ethers, cryptands which are diamine macroheterocycles, and OH- or OCH3-terminated polyethylene glycols (PEGs), preferably OCH3-terminated polyethylene glycols, preferably the polyethylene glycols are polyethylene glycol dimethyl ethers. Preferably, the PEGs are soluble in the reaction medium. Consequently, and preferably, the PEGs have a low number average molar mass (Mn), for example between 100 and 2000, preferably between 200 and 1000 g/mol. The number average molar mass (Mn) may be measured by any appropriate technique known to the person skilled in the art, for example by means of steric exclusion chromatography (SEC).
Preferably, the crown ethers contain from 2 to 8 oxygen atoms. The crown ethers are cyclic oligomers of ethylene oxide comprising as the repeating unit a (CH2-CH2-O) group; these crown ethers may be substituted or 2 carbon atoms of a (CH2-CH2-O) unit may be fused with a hydrocarbon ring, in particular cyclohexyl or phenyl.
Preferably, the multidentate complexing agents are selected from:
preferably
preferably
Depending on the alkali metal, and in particular its size, the person skilled in the art would know the multidentate complexing agent that would be appropriate for use.
The alkali salt is used in implementation in catalytic proportions, preferably in an amount of between 0.005 and 1.5% by weight relative to the weight of organopolysiloxane (O), preferably between 0.005 and 0.9%, more preferentially between 0.01 and 0.8%.
Preferably, in the context of the present invention, the alkali salt/multidentate complexing agent molar ratio is between 1/100 and 100/1, preferably between 1/50 and 50/1, more preferably between 1/25 and 25/1, more preferably between 1/10 and 10/1, more preferably between 1/4 and 4/1, preferably between 1/2 and 2/1, preferably greater than or equal to 1, preferably between 1 and 2, for example the ratio is equal to 1.
The method of the invention is implemented at a temperature of between 5° and 200° C., preferably between 6° and 180° C., more preferably between 12° and 160° C.
The method of the invention operationally implements a reactive distillation process.
As is known to the person skilled in the art, reactive distillation consists of combining a separation by distillation and a chemical reaction. The device for implementing the reactive distillation therefore combines a reactor and a distillation system.
The reactive distillation, and the method of the invention, may be implemented based on a continuous or discontinuous—ie batch—process.
Batch reactive distillation combines the advantages of reactive distillation and of the batch (discontinuous) process. The reaction mixture is loaded into the reactor and the reaction products are distilled off as they are produced.
In the case of implementation in continuous mode, the reagents are introduced in a continuous manner.
In one embodiment, the method of the invention, and the reactive distillation, are implemented in a continuous manner. Preferably, the temperature is between 5° and 200° C., preferably between 6° and 180° C., more preferably between 12° and 160° C. Preferably, the pressure is between 0.01 and 50 mbar, preferably between 0.1 and 35 mbar, more preferentially between 5 and 30 mbar.
A person skilled in the art would also know how to adapt the pair of pressure and temperature settings. For example, in one embodiment the pressure is between 0.01 and 50 mbar for a temperature of between 5° and 200° C., preferably the pressure is between 5 and 30 mbar for a temperature of between 12° and 160° C.
In another embodiment, the method of the invention, and the reactive distillation, are implemented in batch mode. Preferably, the temperature is between 5° and 200° C., preferably between 6° and 180° C., more preferably between 12° and 160° C. Preferably, the pressure is between 0.01 and 50 mbar, preferably between 0.1 and 35 mbar, more preferentially between 5 and 30 mbar.
In this embodiment, the reaction and heating begin at atmospheric pressure and then after a period of 10 to 120 min, preferably 30 to 60 min, after the temperature has been reached, the reactive distillation begins at a pressure of between 0.01 and 50 mbar, preferably between 0.1 and 35 mbar, more preferentially between 5 and 30 mbar.
The method of the present invention may be implemented either with or without the presence of a solvent, in particular of the alcohol type. Preferably, the alcohol is selected from fatty alcohols such as n-lauryl alcohol, n-myristyl alcohol, n-palmitic alcohol, n-stearyl alcohol, n-docosanol, or Guerbet alcohols such as 2-octyl 1-dodecanol, 2-decyl 1-tetradecanol. The solvent may also be selected from the group of n-paraffins such as the compounds C16H34, C18H38, C20H42, C22H46, C24H50. Where a solvent is deployed in the method of the invention, the quantity of solvent added is preferably between 5 and 50% by weight, preferably between 10 and 20% by weight, relative to the weight of organopolysiloxane.
The cyclic organopolysiloxanes CO (or cyclic organopolysiloxanes) obtained by the method of the invention are preferably the compounds D3, D4 or D5. Preferably, the cyclic organopolysiloxanes CO obtained are obtained as a mixture comprising more than 95% by weight of a mixture of the compounds D3, D4 or D5, preferably from 95 to 99%, relative to the total weight of cyclic organopolysiloxanes CO produced.
Preferably the predominant compound obtained by the method of the invention is the compound D4. Preferably, the method of the invention makes it possible to obtain a yield of D4 of at least 80% by weight.
The compounds D3, D4 and D5 are preferably compounds having the following formulae:
As mentioned above, the starting organopolysiloxane O may include functional groups described by the group R1 described above. In these cases, at least one of the methyl groups of the compounds D3, D4 and/or D5 may be substituted by at least one of the R1s.
According to one embodiment, in order to facilitate the recycling of the compounds D3, D4 and D5, as well as their reuse in industrial processes, in particular polymerization processes, these compounds preferably comprise less than 10%, preferably less than 5%, preferably less than 2, and even more preferentially less than 0.2% by weight of the functional groups described by the group R1 as previously discussed above, relative to the total weight of the compounds D3, D4 and D5.
The method of the invention makes it possible preferably to obtain a mass yield of cyclic organopolysiloxanes CO that is greater than 85%, preferably greater than 95% and possibly up to 99% by weight.
Optionally, the compounds D3, D4 and D5 may be separated in particular by distillation, for example by distillation with numerous theoretical plates.
In a particularly advantageous manner, the compounds D3, D4 and D5 obtained by the method of the invention can be used directly in other industrial processes so as to be polymerised and thereby produce novel oils and gums.
The present invention also relates to the use of a catalytic system comprising an alkali salt selected from the salts of K, Na, Rb or Cs, and a multidentate complexing agent, for the depolymerization of organopolysiloxanes O in order to produce cyclic organopolysiloxanes CO.
According to one embodiment, the alkali salt for the above-mentioned use is as defined above.
According to one embodiment, the multidentate complexing agent for the above-mentioned use is as defined above.
Preferably, the multidentate complexing agents used for the depolymerization of organopolysiloxanes O are selected from crown ethers, cryptands which are diamine macroheterocycles and OH- or OCH3-terminated polyethylene glycols (PEGs), preferably OCH3-terminated polyethylene glycols, preferably the polyethylene glycols are polyethylene glycol dimethyl ethers. Preferably, the PEGs are soluble in the reaction medium. Consequently, and preferably, the PEGs have a low number average molar mass (Mn), for example between 100 and 2000, preferably between 200 and 1000 g/mol.
Preferably, the crown ethers contain from 2 to 8 oxygen atoms. The crown ethers are cyclic oligomers of ethylene oxide comprising as the repeating unit a (CH2—CH2—O) group; these crown ethers may be substituted or 2 carbon atoms of a (CH2—CH2—O) unit may be fused with a hydrocarbon ring, in particular cyclohexyl or phenyl.
Preferably, the multidentate complexing agents used for the depolymerization of organopolysiloxanes O are selected from:
preferably
preferably
According to one preferred use, the alkali salt used for the depolymerization of organopolysiloxanes O is used in implementation in catalytic proportions, preferably in an amount of between 0.005 and 1.5% by weight relative to the weight of organopolysiloxane (O), preferably between 0.005 and 0.9%, more preferentially between 0.01 and 0.8%.
Preferably, in the context of the above-mentioned use, the alkali salt/multidentate complexing agent molar ratio is between 1/100 and 100/1, preferably between 1/50 and 50/1, more preferably between 1/25 and 25/1, more preferably between 1/10 and 10/1, more preferably between 1/4 and 4/1, preferably between 1/2 and 2/1, preferably greater than or equal to 1, preferably between 1 and 2, for example the ratio is equal to 1.
According to one embodiment, the above-mentioned use is effectively implemented by means of reactive distillation.
The present application will hereinafter be described using the following examples.
n=70 viscosity 100 mPa·s
n=100 viscosity 350 mPa·s
n=100 (waste oil used as a heating bath for a number of years) viscosity 350 mPa·s
n=180 viscosity 1000 mPa·s
viscosity 100 mPa·s
viscosity 450 mPa·s
viscosity 100 mPa·s
the viscosity of the mixture is less than 60,000 mPa·s
viscosity 250 mPa·s
with 5% of Si-Ph units relative to the total number of units and a viscosity of 60,000 mPa·s
with n=between 1 and 10
In a flask (50 mL) topped with a vigorous column, the organopolysiloxane, alkali salt and multidentate complexing agent are introduced and heated at temperature T for a period of 30 minutes to 1 hour. The reaction mixture is then distilled under reduced pressure for a period of 20-25 minutes.
In the results reported in the tables of the examples:
The protocol described in Example 1 is implemented with KOSiMe3 (SA1) being used as the alkali salt and a crown ether 18-6 (CM1). The reaction mixture is heated for a period of 30 minutes prior to reactive distillation (temperature and pressure as mentioned above).
The organopolysiloxane used is organopolysiloxane O1.
The results are compiled in Table 1 below
These results show that the method of the invention effectively enables depolymerization and formation of cyclic organopolysiloxane, with the method in particular exhibiting selectivity for the compounds D4. In an advantageous manner, the method of the invention requires a small amount of catalyst.
The protocol described in Example 1 is implemented with KX being used as the alkali salt, and a crown ether 18-6 (CM1). The reaction mixture is heated for a period of 1 h prior to reactive distillation at a temperature of 140° C. and a pressure of 10 mbar for a period of 20-25 min.
The organopolysiloxane is O1.
The results are compiled in Table 2 below.
These results show that the method of the invention may be implemented with different alkali salts while at the same time maintaining the selectivity for D4 production.
The protocol described in Example 1 is implemented with KOSiMe3 (SA1) being used as the alkali salt, and a multidentate complexing agent. The reaction mixture is heated for a period of 1 h prior to reactive distillation at a temperature of 140° C. and a pressure of 10 mbar for a period of 20-25 min.
The organopolysiloxane is O1.
The results are compiled in Table 3 below.
These results show that the method of the invention may be implemented with different complexing agents with good yields.
The protocol described in Example 1 is implemented with KOSiMe3 (SA1) being used as the alkali salt and a crown ether 18-6 (CM1). The reaction mixture is heated for a period of 1 hour prior to reactive distillation, at a temperature of 140° C. and a pressure of 10 mbar for a period of 20-25 min.
The results are compiled in Table 4 below.
The results show that the method of the invention makes it possible to process a variety of organopolysiloxanes while at the same time achieving good yields and a high degree of selectivity, particularly for D4. The examples also show that the method of the Invention makes it possible to process waste (used) silicone oils, gums and cross-linked silicone gels.
The protocol described in Example 1 is implemented with different catalyst/catalytic systems, at a temperature of 140° C. The reaction mixture is heated for a period of 30 minutes prior to reactive distillation at a temperature of 140° C. and a pressure of 10 mbar for a period of 20-25 min.
The organopolysiloxane is O1.
The results are compiled in Table 5 below.
These results show that the catalytic system of the invention makes it possible to obtain a very high yield of cyclo siloxane.
The protocol described in Example 1 is implemented with different catalytic systems. The reaction mixture is heated to 150° C. for a period of 30 minutes prior to reactive distillation at a temperature of 150° C. and a pressure of 5 mbar for a period of 30 minutes.
The organopolysiloxane is an oil derived from chlorosilane hydrolysis reaction by-products comprising at least 95% of an organopolysiloxane which comprises approximately 2% of the group Si—H, and other reaction products such as residues of the reaction product, the catalyst, etc.
The results are compiled in Table 6 below.
These results show that the catalytic system of the invention makes it possible to obtain cyclosiloxane with oils derived from industrially generated by-products and therefore of complex composition.
| Number | Date | Country | Kind |
|---|---|---|---|
| 22 02507 | Mar 2022 | FR | national |
| 22 14489 | Dec 2022 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2023/057124 | 3/21/2023 | WO |
