Ring-opening polymerization method

Abstract

The present invention relates to a process for preparing linear organopolysiloxanes OL by ring-opening polymerization of at least one cyclic organopolysiloxane OC in the presence of a catalyst system AI comprising at least one catalyst A of formula (I) and at least one initiator I chosen from alcohols and their derivatives, silanols and their derivatives, or mixtures thereof, and to the use of the linear organopolysiloxanes OL thus obtained in various silicone formulations that can be used, inter alia, in the cosmetics, household cleaners, automotive, and energy sectors.

Description

[Technical Field]

[0001] The present invention relates to a method for preparing linear organopolysiloxanes OL by ring-opening polymerization starting from cyclic organopolysiloxanes OC using a catalyst system AI. More specifically, the method of the present invention provides access to linear organopolysiloxanes OL of controlled molecular weight with extremely low residual levels of cyclic organopolysiloxanes. [Background technology]

[0002] A major challenge for the silicones industry in the coming years will be the industrial synthesis of organopolysiloxanes with very low or no residual cyclic compound content.

[0003] Until now, industrial synthesis of organopolysiloxanes by polycondensation or ring-opening polymerization has been accompanied by the formation of cyclic organopolysiloxanes, such as octamethyltetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), or other unwanted cyclic organopolysiloxanes. In conventional industrial processes, the content of these unwanted products can rise to 10% to 15% by weight of the total mass of the linear organopolysiloxanes obtained in the synthesis, depending on the thermodynamic equilibrium. Traditionally, the high content of these cyclic products has necessitated energy-intensive processes, such as high-temperature and / or high-pressure devolatilization processes, to separate these by-products from the resulting linear organopolysiloxanes.

[0004] Therefore, concerns about economic and energy efficiency necessitate the development of new solutions to eliminate or at least limit these costly and lengthy separation steps.

[0005] Furthermore, cyclic silicones or organopolysiloxanes, such as octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), have and will continue to be subject to restrictions on their use. In addition to the environmental risks posed by the lack of biodegradability of these cyclic compounds, they are also suspected endocrine disruptors and potential carcinogens.

[0006] For this reason, European regulations have limited the content of D4 and D5 in rinse-off cosmetics to 0.1% by weight since 2018. This regulation will soon be introduced in other cosmetic products as well as in silicone applications.

[0007] Therefore, there is a need to provide a process that provides access to linear organopolysiloxanes that are free of cyclic silicones, or at least have a low content of cyclic silicones. In particular, there is interest in providing new catalyst systems that make it possible to operate such processes. There is also interest in enabling reliable control of the molecular weight of the products formed. This possibility would broaden the scope of uses and applications of such resulting polymers.

[0008] In the prior art, the use of phosphorus ylides of formula (Me)C=P(NMe) and their precursors as strong bases of low nucleophilicity in C-alkylation reactions of lactams, succinimides and benzodiazepines was first described in patent application WO-A-98 / 54229.

[0009] Subsequent patent application WO03054058 disclosed the use of this same (Me)2C=P(NMe2)3 catalyst in a polymerization process involving ring-opening of cyclic organopolysiloxanes. This catalyst achieved satisfactory results with yields of 85% to 90%. However, this system did not successfully alter the thermodynamic equilibrium, leading to residual cyclic organopolysiloxane contents on the order of 10% to 15%. Therefore, there is a real need to develop a catalyst system that allows for high yields of linear organopolysiloxanes while limiting the formation of cyclic organopolysiloxanes due to backbiting reactions. Summary of the Invention

[0010] Surprisingly, the Applicant has developed a catalyst system that meets these expectations. The present invention therefore relates to a process for preparing linear organopolysiloxanes OL by ring-opening polymerization of at least one cyclic organopolysiloxane OC in the presence of a catalyst system AI, Catalytic AI, at least one catalyst A of formula (I): [ka] (In the formula, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined together to form a ring; the radicals R1 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two radicals R1 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, the groups R2 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two groups R2 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, the groups R3 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two groups R3 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, provided that the phosphorus atom has at least one heterocyclic amine as a substituent; and At least one initiator I selected from alcohols and their derivatives, silanols and their derivatives, or mixtures thereof Includes:

[0011] Therefore, one object of the present application is to propose a method for preparing linear organopolysiloxanes OL by ring-opening polymerization of cyclic organopolysiloxanes OC, which allows for control of the molecular weight of the final product, with a yield of linear organopolysiloxanes higher than 90%, preferably higher than 95%.

[0012] Another object of the present application is to provide a catalytic system AI for carrying out this method.

[0013] Another object of the present application is to propose a simple and harmless catalytic system suitable for carrying out the above process.

[0014] Further objects will become apparent upon reading the following description of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] Silicones, otherwise known as organopolysiloxanes, are polymeric materials containing alternating atoms of silicon and oxygen, with various organic groups attached to the silicon.

[0016] In the context of the present invention, silicone refers to products made of silicones, silicone polymers or organopolysiloxanes, products made of polymers containing a siloxane backbone with alternating silicon and oxygen atoms (Si-O-Si) to which various organic groups are attached. These silicone polymers can be liquid or solid, depending on the molecular weight and the degree of crosslinking.

[0017] For purposes of this invention, reaction mixture refers to the totality of reactive species present, such as one or more catalysts A, one or more initiators I, one or more cyclic organopolysiloxanes OC, and / or one or more chain blocking agents C.

[0018] For the purposes of the present invention, catalyst system AI refers to the combination of catalyst A and initiator I that forms an active species capable of catalyzing the process of the present invention. Heterocyclic amines, by definition, refer to compounds that have at least one heterocyclic ring containing atoms of at least two different elements and at least one amine group. Examples include the following compounds: piperidine, piperazine, pyrrole, pyrrolidine, 4-methylpiperidine.

[0019] All viscosities referred to herein correspond to the dynamic viscosity at 25°C, termed "Newtonian", that is, the quantity of dynamic viscosity conventionally measured using a Brookfield viscometer at a shear rate gradient low enough that the measured viscosity is independent of the velocity gradient.

[0020] For purposes of the present invention, the cyclic organopolysiloxane OC is represented by the following formula (II): [ka] wherein the groups R are the same or different and are hydrogen, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 1 to 6 carbon atoms, or a C6-C 18 and n is a natural number of 1 or 2.

[0021] In particular, commercially available cyclic organopolysiloxanes OC may be mentioned, such as hexamethylcyclotrisiloxane (CAS 541-05-9), 2-ethenyl-2',4,4',6,6'-pentamethylcyclotrisiloxane (CAS 18395-32-9), 2,4,6-triethenyl-2,4,6-trimethylcyclotrisiloxane (CAS 3901-77-7), hexaphenylcyclotrisiloxane (CAS 512-63-0), 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane (CAS 2374-14-3), 2,2,4-trimethyl-4,6,6-triphenyl-1,3,5,2,4,6-trioxatrisilinane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane (CAS 546-45-2), 2,4,6-trimethylcyclotrisiloxane (CAS 13269-39-1), 3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (CAS 3901-77-7), 2-ethenyl-2,4,4,6,6-pentamethylcyclotrisiloxane (CAS 18395-32-9), 2,4,6,8-tetramethylcyclotetrasiloxane (CAS 2370-88-9), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (CAS 2554-06-5), 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (CAS 77-63-4), and octaphenylcyclotetrasiloxane (CAS 546-56-5).

[0022] Advantageously, the cyclic organopolysiloxane OC is hexamethylcyclotrisiloxane (CAS 541-05-9) or octamethylcyclotetrasiloxane (CAS 556-67-2).

[0023] According to one embodiment of the present invention, the method of the present invention uses at least two organopolysiloxanes selected from the following compounds: octamethylcyclotetrasiloxane (CAS 556-67-2), hexamethylcyclotrisiloxane (CAS 541-05-9), and 2,4,6-triethenyl-2,4,6-trimethylcyclotrisiloxane (CAS 3901-77-7).

[0024] In the context of the present application, catalyst A is represented by formula (III): [ka] During the ceremony, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined together to form a ring; the radicals R1 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two radicals R1 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, the groups R2 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two groups R2 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, the groups R3 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two groups R3 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, However, the phosphorus atom has at least one heterocyclic amine as a substituent.

[0025] According to one embodiment of the present invention, catalyst A is represented by formula (IV): [ka] During the ceremony, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined together to form a ring; the radicals R1 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two radicals R1 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, the groups R2 are identical or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably of 1 to 8 carbon atoms, or two groups R2 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, the groups R3 are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and n is a natural number 1, 2 or 3;

[0026] Preferably, catalyst A is represented by formula (V): [ka] During the ceremony, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined together to form a ring; the groups R1 are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, n is the same or different and is a natural number of 1, 2, or 3.

[0027] Preferably, catalyst A is represented by formula (VI): [ka] During the ceremony, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined together to form a ring; n may be the same or different and is a natural number of 1 or 2.

[0028] More preferably, catalyst A is represented by formula (VII): [ka] In the formula, n is a natural number of 1 or 2.

[0029] In one embodiment, the process of the invention is characterized in that the molar ratio of catalyst A to cyclic organopolysiloxane OC is between 0.005% and 2%, preferably between 0.01% and 2%, preferentially between 0.05% and 1%, more preferentially between 0.1% and 1%.

[0030] For the purposes of the present invention, initiator I is selected from alcohols and their derivatives, silanols and their derivatives, or mixtures thereof.

[0031] In the context of the present application, initiator I is selected from compounds of formula (VIII): [ka] During the ceremony, Y represents a carbon atom or a silicon atom; R is the same or different, - hydrogen atoms, - alkyl groups of 1 to 12 carbon atoms, - a cycloalkyl group of 5 to 8 carbon atoms, - an alkenyl group of 1 to 12 carbon atoms, - C6~C 18 an aryl group, preferably phenyl; - benzyl group, - Formula R 1 c SiO (4-c) / 2A siloxyl group having at least 5 units, preferably at least 10 units, of represents where: R 1 are the same or different and represent an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, or an aryl group containing 6 to 10 carbon atoms, preferably phenyl, where c=0, 1 or 2, and when the aforementioned group R is other than a hydrogen atom, the group R may be unsubstituted or substituted by an alkyl or alkenyl chain of 1 to 6 carbon atoms, a cycloalkyl group, an aryl group containing 6 to 10 carbon atoms, or a heteroatom such as oxygen, sulfur or nitrogen.

[0032] In the context of the present application, initiators I are selected from compounds of formula (IX): [ka] During the ceremony, Y represents a carbon atom or a silicon atom; R is the same or different, - hydrogen atoms, - alkyl groups of 1 to 12 carbon atoms, - a cycloalkyl group of 5 to 8 carbon atoms, - an alkenyl group of 1 to 12 carbon atoms, - C6~C 18 an aryl group, preferably phenyl; - benzyl group, - Formula R 1 c SiO (4-c) / 2 A siloxyl group having at least 5 units, preferably at least 10 units, of represents where: R 1are the same or different and represent an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, or an aryl group containing 6 to 10 carbon atoms, preferably phenyl, where c=0, 1 or 2.

[0033] In one embodiment of the present invention, initiator I is chosen from alcohols or silanols having a pKa of 10-16, preferably 12-16, preferentially 14-16.

[0034] According to another embodiment of the invention, the initiator I is selected from compounds of formula (X): [ka] During the ceremony, Y represents a carbon atom; R is the same or different, - hydrogen atoms, - alkyl groups of 1 to 12 carbon atoms, - a cycloalkyl group of 5 to 8 carbon atoms, - an alkenyl group of 1 to 12 carbon atoms, - benzyl or phenyl represents Where the aforementioned group R is other than a hydrogen atom, the group R may be unsubstituted or substituted with an alkyl or alkenyl chain of 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, or a heteroatom such as oxygen, sulfur, or nitrogen.

[0035] According to one embodiment, initiator I is an alcohol chosen from primary or secondary alcohols. Initiator I is preferably an alcohol chosen from primary alcohols.

[0036] According to one embodiment, initiator I is an alcohol chosen from saturated or unsaturated polyols having 2 to 6 hydroxyl groups, examples of which include the following polyols, such as glycerol, pentaerythritol, sorbitol or 1,4-butanediol.

[0037] According to one embodiment, initiator I is an alcohol having a pKa of 10-16, preferably a pKa of 12-16, preferentially a pKa of 14-16.

[0038] According to one embodiment, initiator I is selected from the following: methanol (CAS 67-56-1), ethanol (CAS 64-17-5), propanol (CAS 71-23-8), isopropanol (CAS 67-63-0), butanol (CAS 71-36-3), 2-methylpropan-2-ol (CAS 75-65-0), allyl alcohol (CAS 107-18-6), benzyl alcohol (CAS 100-51-6), 3-buten-1-ol (627-27-0), alcohols with long alkyl chains, such as undecanol (CAS 112-42-5) or dodecanol (CAS 27342-88-7).

[0039] According to a preferred embodiment, initiator I is benzyl alcohol (CAS 100-51-6).

[0040] Alternatively, in the context of the present application, initiator I has at least one terminal silanol functional group.

[0041] The initiator I having a terminal silanol functional group preferably has at least one siloxyl unit. The initiator I having a terminal silanol functional group preferentially has at least two siloxyl units. More preferentially, the initiator I having a terminal silanol functional group has at least three siloxyl units.

[0042] Terminal silanol functionality refers to a chemical functionality at the end of a chain formed by a chemical bond between a silicon atom and a hydroxyl group.

[0043] In the process of the present invention, the initiator I is represented by formula (XI): [ka] During the ceremony, R 1 are the same or different, linear or branched alkyl groups containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, optionally substituted by heteroatoms O, N, S or halides, - an alkenyl group containing 2 to 6 carbon atoms, - a cycloalkyl group of 5 to 10 carbon atoms, optionally substituted by heteroatoms O, N, S or halide, - C6~C 18 aryl groups, - a hydroxyl group, or - Hydrogen represents R 2 are the same or different, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - hydroxyl group (OH), a linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, optionally substituted by at least one heteroatom O, N, S or halide, such as a fluorine atom, for example 1 to 10 fluorine atoms, for example (C1-C5) alkyl-CF3, where alkyl is linear or branched, or - Hydrogen represents q is an integer from 0 to 20, preferably from 0 to 10, more preferentially from 0 to 5, provided that at least one group R 2 is a hydroxyl group (OH).

[0044] In the process of the present invention, the initiator I is represented by formula (XI): [ka] During the ceremony, R 1 are the same or different, linear or branched alkyl groups containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, optionally substituted by heteroatoms O, N, S or halides, - an alkenyl group containing 2 to 6 carbon atoms, - a cycloalkyl group of 5 to 10 carbon atoms, optionally substituted by heteroatoms O, N, S or halide, - C6~C 18 aryl groups, - a hydroxyl group, or - Hydrogen represents R 2 are identical, - Hydroxyl group (OH) represents q is an integer of 0 to 20, preferably 0 to 10, and more preferably 0 to 5.

[0045] In another embodiment, initiator I is represented by formula (XI), wherein: R 1 are identical and represent CH3, R 2 are the same or different, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - hydroxyl group (OH), - a linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, - Optionally substituted C6-C 18 an aryl group, or - Hydrogen represents q is an integer from 0 to 20, preferably from 0 to 10, more preferentially from 0 to 5, provided that at least one group R 2 is a hydroxyl group (OH).

[0046] In another embodiment, initiator I is represented by formula (XI), wherein: R 1 are identical and represent CH3, R 2 are identical, - Hydroxyl group (OH) represents q is an integer of 0 to 20, preferably 0 to 10, and more preferably 0 to 5.

[0047] The initiator I may be present in a solvent. This is particularly advantageous for dissolving it in the reaction mixture. The solvent may in particular be a non-polar solvent, such as an organic alkane or an aromatic hydrocarbon solvent. The solvent is preferably selected from n-hexane, n-heptane, n-decane, n-dodecane, isododecane, Exxsol D60, xylene, toluene, and mixtures thereof.

[0048] In one embodiment, the process of the invention is characterized in that the molar ratio of initiator I to catalyst A is between 1 and 20, preferably between 3 and 20, preferentially between 5 and 10.

[0049] In one embodiment, the method of the invention is characterized in that the molar ratio of initiator I to cyclic organopolysiloxane OC is between 0.02% and 20%, preferably between 0.25% and 15%, preferentially between 0.5% and 5%, and more preferentially between 0.25% and 2.5%.

[0050] In one embodiment of the present invention, the ring-opening polymerization reaction of at least one cyclic organopolysiloxane OC is carried out in the presence of a catalyst system AI and at least one chain blocking agent C.

[0051] In the method of the present invention, the chain blocking agent C is represented by formula (XII): [ka] During the ceremony, R 1 are the same or different and represent CH3 or phenyl, preferably CH3, R 2are the same or different, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - a linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, optionally substituted by at least one heteroatom O, N, S or halide, such as a fluorine atom, for example 1 to 10 fluorine atoms, for example (C1-C5) alkyl-CF3, where alkyl is linear or branched, - Optionally substituted C5-C 10 cycloalkyl groups, - Optionally substituted C6-C 18 an aryl group, or - hydrogen, represents q is an integer of 1 to 50, preferably 1 to 20, and more preferentially 1 to 10.

[0052] Particularly preferably, the chain blocking agent C of the present invention is represented by formula (XII), in which R 1 are identical and represent CH3, R 2 are the same or different, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - a linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, - Optionally substituted C6-C 18 an aryl group, or - Hydrogen represents q is an integer of 1 to 20, preferably 1 to 10, and more preferentially 1 to 5.

[0053] Other blocking agents having siloxane functional groups according to the present invention are described in the book "Chemistry and Technology of Silicones," published by Academy Press in 1968, p. 264. The chain blocking agent C may be present in a solvent. This is particularly advantageous for dissolving it in the reaction mixture. The solvent may be, in particular, a non-polar solvent, such as an organic alkane or an aromatic hydrocarbon solvent. The solvent is preferably selected from n-hexane, n-heptane, n-decane, n-dodecane, isododecane, Exxsol D60, xylene, toluene, and mixtures thereof.

[0054] In one embodiment, the process of the invention is characterized in that the molar ratio of chain blocking agent C to catalyst A is between 0 and 30, preferably between 0 and 20, preferentially between 0 and 10.

[0055] According to one embodiment of the present invention, the linear organopolysiloxane OL is represented by the formula (XIII) It may be a compound of: [ka] During the ceremony, R is the same or different, alkyl groups containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, an aryl group containing 6 to 10 carbon atoms, preferably phenyl, represents R 1 are the same or different, - an alkyl group containing 1 to 5 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - hydroxyl group (OH), - hydrogen, - C6~C 18 an aryl group, preferably phenyl represents R 2 are the same or different, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - hydroxyl group (OH), - a linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, optionally substituted by at least one heteroatom O, N, S or halide, such as a fluorine atom, for example 1 to 10 fluorine atoms, for example (C1-C5) alkyl-CF3, where alkyl is linear or branched, - Optionally substituted C5-C 10 cycloalkyl groups, - Optionally substituted C6-C 18 aryl groups, - hydrogen, or - Group (OR 3 ) where R 3 teeth, an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably OCH3 or OC2H5; an alkenyl group containing 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms; C6 to C 18 an aryl group or an alkylaryl group, such as a benzyl group; represents q is an integer from 0 to 50, preferably from 0 to 20, more preferably from 0 to 10, and preferably q=0; n2 represents an integer of 10 to 1500, preferably 10 to 1000, more preferably 50 to 1000, and more preferably 100 to 500; m2 represents an integer of 0 to 500, preferably 0 to 100, and more preferably 0 to 50.

[0056] According to one preferred embodiment of the present invention, the linear organopolysiloxane OL is a compound of formula (XIII), During the ceremony, R are identical or different and represent CH3 or phenyl, preferably CH3; R 1 are the same or different, - an alkyl group containing 1 to 5 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - C6~C 18 an aryl group, preferably phenyl; - Hydrogen represents R 2 are the same or different, - an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - hydroxyl group (OH), - C6~C 18 aryl groups, - hydrogen, - Group (OR 3 ) where R 3 teeth, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or a benzyl group represents q is an integer from 0 to 50, preferably from 0 to 20, more preferably from 0 to 10, and preferably q=0; n2 represents an integer of 10 to 1500, preferably 10 to 1000, more preferably 50 to 1000, and more preferably 100 to 500; m2 represents an integer of 0 to 500, preferably 0 to 100, and more preferably 0 to 50.

[0057] According to one particularly preferred embodiment of the present invention, the linear organopolysiloxane OL of the present invention is a compound of formula (XIII), in which R are identical or different and represent CH3 or phenyl, preferably CH3; R 1 are the same or different and represent CH, phenyl or vinyl, R 2 are the same or different, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - hydroxyl group (OH), - a linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, - Optionally substituted C6-C 18 an aryl group, or - hydrogen, - Group (OR 3 ) where R 3 teeth, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or a benzyl group represents q is 0, n2 represents an integer of 10 to 1500, preferably 10 to 1000, more preferably 50 to 1000, and more preferably 100 to 500; m2 represents an integer of 0 to 500, preferably 0 to 100, and more preferably 0 to 50.

[0058] According to one particularly preferred embodiment of the present invention, the linear organopolysiloxane OL of the present invention is a compound of formula (XIII), in which R are identical or different and represent CH3 or phenyl, preferably CH3; R 1 are the same or different and represent CH, phenyl or vinyl, base R 2 are identical, - a linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - hydroxyl group (OH), - Group (OR 3 ) where R 3 teeth, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or a benzyl group represents q is 0, n2 represents an integer of 10 to 1500, preferably 10 to 1000, more preferably 50 to 1000, and more preferably 100 to 500; m2 represents an integer of 0 to 500, preferably 0 to 100, and more preferably 0 to 50.

[0059] For the purposes of the present invention, the weight average molecular weight and number average molecular weight (M, respectively) of various linear organopolysiloxanes OL are w and M n ) can be determined by size exclusion chromatography (SEC) at 35° C. in a solvent such as toluene in the presence of polystyrene standards.

[0060] According to one embodiment of the process of the present invention, the linear organopolysiloxane OL of the present invention is characterized in that it has a degree of polymerization of 2 to 2000, preferably 4 to 1000, preferentially 4 to 500 and more preferentially 10 to 100.

[0061] According to one embodiment of the process of the invention, the linear organopolysiloxanes OL of the invention have a mass average molecular weight M of 500 to 150,000 g / mol, preferably 1,000 to 150,000 g / mol, preferentially 1,000 to 100,000 g / mol and more preferentially 5,000 to 30,000 g / mol. w The present invention is characterized by having the following.

[0062] According to one embodiment of the process of the invention, the linear organopolysiloxanes OL of the invention have a number average molecular weight M of 500 to 150,000 g / mol, preferably 1,000 to 100,000 g / mol, preferentially 1,000 to 70,000 g / mol and more preferentially 2,500 to 30,000 g / mol. n The present invention is characterized by having the following.

[0063] According to one embodiment of the method of the present invention, the linear organopolysiloxane OL of the present invention is characterized in that it has a dynamic viscosity of 100 to 100,000 mPa·s at 25°C, preferably 1,000 to 80,000 mPa·s at 25°C, more preferentially 10,000 to 70,000 mPa·s at 25°C.

[0064] In the context of this application, the mass percentage or weight percentage of cyclic organopolysiloxanes (e.g., D4, etc.) in the products obtained by the process of the present invention is not considered to be quantitative. 29 The mass or weight percentage of D4 in the product obtained by the method of the present invention can be measured by Si NMR spectroscopy. Alternatively, the mass or weight percentage of D4 in the product obtained by the method of the present invention can be measured by chromatograms resulting from analysis by size exclusion chromatography (SEC).

[0065] The product resulting from the reaction will hereinafter refer to the sum of the linear organopolysiloxane OL and the cyclic organopolysiloxane OC at the end of the process of the invention.

[0066] In one embodiment, the process according to the invention is characterized in that the content of cyclic organopolysiloxanes OC is less than 2%, preferably less than or equal to 1% and preferentially less than or equal to 0.5%, relative to the total mass of the product resulting from the reaction.

[0067] In one embodiment, the process according to the invention is characterized in that the content of octamethylcyclotetrasiloxane (D4) is less than 2%, preferably less than or equal to 1%, and preferentially less than or equal to 0.5%, relative to the total mass of the products resulting from the reaction.

[0068] In one embodiment, the process according to the invention is carried out in a non-polar solvent, which may in particular be an organic alkane or aromatic hydrocarbon solvent.

[0069] The solvent is preferably selected from n-hexane, n-heptane, n-decane, n-dodecane, isododecane, Exxsol D60, xylene, toluene, and mixtures thereof.

[0070] In one embodiment, the process of the invention is characterized in that the mass ratio, mass of cyclic organopolysiloxane OC to mass of solvent used, is between 1 and 500, preferably between 1 and 100 and preferentially between 5 and 50.

[0071] Advantageously and preferably, the reaction is carried out at a temperature between 50°C and 150°C, preferably between 50 and 100°C, more preferentially between 60 and 80°C, for example 80°C.

[0072] According to the method of the present invention, the reaction time is from 2 hours to 48 hours, preferably from 8 hours to 36 hours, more preferentially from 8 hours to 18 hours.

[0073] A person skilled in the art will know how to adapt these parameters depending on the reactor used and the nature of the species.

[0074] The present application also relates to linear organopolysiloxanes OL obtained by the various embodiments of the process of the invention described above.

[0075] The present application also provides a composition for carrying out the method of the present invention, comprising: at least one cyclic organopolysiloxane OC, - a catalytic AI as defined above, and optionally a chain blocking agent C The present invention relates to a composition comprising:

[0076] The present application also relates to the use of the organopolysiloxane OL obtained by the process of the present invention as a directly applicable ingredient in a variety of silicone formulations useful in fields such as cosmetics, household maintenance products, automotive and energy.

[0077] The present application also relates to a catalyst A represented by the following formula (XIV): [ka] During the ceremony, R represents an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined by groups to form a ring, the groups R1 are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, n is the same or different and is a natural number of 1, 2, or 3.

[0078] More specifically, the present invention relates to a catalyst A represented by the following formula (XV): [ka] In the formula, n is a natural number of 1 or 2.

[0079] The present application also relates to the use of the catalysts defined according to formula (XIV and XV) as catalysts for ring-opening polymerization or polycondensation. [Example]

[0080] Cyclic organopolysiloxanes used in the examples: Cyclic organopolysiloxane OC1: Hexamethylcyclotrisiloxane (CAS 541-05-9) Cyclic organopolysiloxane OC2: Octamethylcyclotetrasiloxane (CAS 556-67-2)

[0081] Catalyst A used in the example: Catalyst A1: [ka] Catalyst A2: [ka] Catalyst A comp1 : [ka]

[0082] Initiators used in the examples: Initiator I1: Benzyl alcohol (CAS 100-51-6) Initiator I2: [ka] n=8

[0083] Chain blocking agents used in the examples: Chain Blocking Agent C 1 : Divinyltetramethyldisiloxane (CAS 2627-95-4).

[0084] In the context of the examples described below, the residual mass percentages of cyclic organopolysiloxanes OC and of linear organopolysiloxanes OL obtained by the process of the invention are measured by size exclusion chromatography (SEC) in a solvent such as toluene in the presence of polystyrene standards at 35° C. Similarly, the number average molecular weights M of the various linear organopolysiloxanes according to the invention are n is determined by the same size exclusion chromatography (SEC) method.

[0085] In the context of the examples set forth below, the weight percentage of residual cyclic organopolysiloxane is the weight percentage of cyclic organopolysiloxane at the end of a process carried out in accordance with the present invention.

[0086] Example 1: Catalyst A of the present invention 1 and A 2 Synthesis of: Catalyst A of the present invention 1 Synthesis of: Synthesis of intermediate compound 1: [ka] A solution of tris(1-pyrrolidinyl)phosphine (1.00 g, 4.15 mmol) in 30 mL of diethoxymethane (DEM) was mixed with 2-iodopropane (1.06 g, 6.23 mmol) at ambient temperature. The solution was stirred at 40 °C for 7 days. A white precipitate formed, and after filtration and recrystallization from acetonitrile at ambient temperature, compound 1 was obtained in the form of a white solid (1.45 g, 85%).

[0087] Catalyst A of the present invention 1 The second step: A suspension of compound 1 in THF (20 mL) was mixed with KHMDS powder (0.52 g, 2.63 mmol) at ambient temperature. The solution was stirred at ambient temperature for 1 hour. The solution was then filtered and subsequently evaporated by rotary evaporation.

[0088] The product thus formed was extracted twice with pentane (2 x 15 mL). Evaporation of pentane under vacuum gave a colorless liquid, which is catalyst A1 of the present invention (0.56 g, 75%). [ka]

[0089] Catalyst A of the present invention 2 Synthesis of: A solution of tripiperidinophosphine (3.00 g, 10.59 mmol) in 30 mL of diethoxymethane (DEM) was mixed with 2-iodopropane (2.70 g, 15.88 mmol) at ambient temperature. The solution was stirred at 40 °C for 7 days. A white precipitate formed, and after filtration and recrystallization from acetonitrile at ambient temperature, compound 2 was obtained in the form of a white solid (3.70 g, 77.0%). [ka]

[0090] Catalyst A of the present invention 2 The second step: A suspension of compound 2 in THF (20 mL) was mixed with KH (53 mg, 1.32 mmol) at ambient temperature. The solution was stirred at ambient temperature for 12 hours. The solution was then filtered and subsequently evaporated by rotary evaporation.

[0091] The product thus formed was extracted twice with pentane (2 x 10 mL). Evaporation of pentane under vacuum gave a colorless liquid, which is catalyst A2 of the present invention (0.102 g, 47%). [ka]

[0092] Example 2: General protocol for carrying out the method of the present invention: Catalyst system AI is formed by combining catalyst A (e.g., A1 and A2) (1 equivalent, 0.061 mmol) with n equivalents of initiator I (e.g., I1 or I2, etc.). The table below shows various molar ratios I / A. This newly formed catalyst system AI, containing 0.025 mmol (0.5 mol%) of catalyst A, is mixed into a solution containing cyclic organopolysiloxane OC1 or OC2 (5.07 mmol) and toluene as a solvent.

[0093] Optionally, a chain blocking agent, such as C1, is added to the reaction mixture.

[0094] The reaction mixture is then heated at 80° C. for 18 hours.

[0095] Example 3a: Test on D4: In the context of this example, the general protocol of Example 2 was used. In this example, octamethylcyclotetrasiloxane OC2 (CAS 556-67-2) was used. The following table lists the various catalysts used and the properties of the product OL obtained by the method of the present invention.

[0096] [Table 1]

[0097] It can be noted that in the presence of catalysts A1 and A2 described according to the method of the present invention, more than 80% of linear organopolysiloxanes OL are obtained, and in particular in the presence of catalyst A1, the product OL thus obtained has a cyclic organopolysiloxane content of less than 1%.

[0098] Example 3b: Test on D3: In the context of this example, the general protocol of Example 2 was used. In this example, hexamethylcyclotrisiloxane OC1 (CAS 541-05-9) was used. The following table lists the various catalysts used and the properties of the product OL obtained by the method of the present invention.

[0099] [Table 2]

[0100] It can be noted that in the presence of catalysts A1 and A2 described according to the method of the present invention, more than 95% of linear organopolysiloxane OL is obtained, and in particular, in the presence of catalyst A1, a product OL is obtained having a residual cyclic organopolysiloxane content of less than 1%.

[0101] Example 4: Tests on D4, influence of the molar ratio I / A: In the context of this example, the general protocol of Example 2 was used. In this example, octamethylcyclotetrasiloxane OC2 (CAS 556-67-2) was used. The following table lists the various molar ratios used and the properties of the product OL obtained by the method of the present invention.

[0102] [Table 3]

[0103] It can be observed that the molar ratio I / A affects the number average molecular weight of the product OL obtained by the method of the present invention. Using the information disclosed in this invention, one skilled in the art can use the method of the present invention to obtain the desired number average molecular weight M while controlling the cyclic compound content. n The reader will know how to adapt these parameters to obtain an organopolysiloxane OL having the following structure:

[0104] Example 5a: Tests on D4, influence of the ratio C / A: In the context of this example, the general protocol of Example 2 was used. In this example, octamethylcyclotetrasiloxane OC2 (CAS 556-67-2) was used. The following table lists the molar ratio of the chain blocking agent used relative to the molar amount of catalyst A used, and the properties of the product OL obtained by the method of the present invention. In the context of this example, the molar ratio I / A is 5.

[0105] [Table 4]

[0106] These various tests were carried out to determine the number average molecular weight (M n Varying the amount of chain blocking agent C affects the molecular weight of the product obtained by the method of the present invention.

[0107] Furthermore, it is possible to note that the products obtained by the process of the invention have a very low mass percentage of cyclic organopolysiloxanes (less than 1% by mass relative to the total mass of the organopolysiloxane OL obtained).

[0108] Example 5b: Tests on D4, influence of the ratio C / A: In the context of this example, the general protocol of Example 2 was used. In this example, octamethylcyclotetrasiloxane OC2 (CAS 556-67-2) was used. The following table lists the molar ratio of the chain blocking agent used relative to the molar amount of catalyst A used, and the properties of product OL obtained by the method of the present invention. In this particular example, the amount of catalyst A used is 1.00 mol% relative to the amount of OC2 used, in contrast to the other examples. In the context of this example, the molar ratio I / A is 5.

[0109] [Table 5]

[0110] The conclusions that can be drawn from these results are the same as those obtained in Example 5a) above.

Claims

1. 1. A process for preparing linear organopolysiloxanes OL by ring-opening polymerization of at least one cyclic organopolysiloxane OC in the presence of a catalyst system AI, comprising: said catalyst system AI being At least one catalyst A of formula (I): 【Chemistry 1】 (In the formula, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined together to form a ring; group R 1 are the same or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or two groups R 1 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, group R 2 are the same or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or two groups R 2 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, group R 3 are the same or different and represent an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or two groups R 3 together with the nitrogen atom to which they are attached form a heterocyclic amine of 5 to 10 atoms, provided that the phosphorus atom has at least one heterocyclic amine as a substituent; and at least one initiator I selected from alcohols and their derivatives, silanols and their derivatives, or mixtures thereof; A method comprising:

2. The cyclic organopolysiloxane OC is represented by formula (II): 【Chemistry 2】 wherein the groups R are the same or different and are hydrogen, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 1 to 6 carbon atoms, or C 6 ~C 18 and n is a natural number of 1 or 2. The method of claim 1 , wherein:

3. The catalyst A is represented by the following formula (V): 【Transformation 3】 (In the formula, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be linked by a group to form a ring, group R 1 are the same or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, n may be the same or different and is a natural number of 1, 2, or 3. The method of claim 1 or 2, wherein the

4. The catalyst A is represented by the following formula (VI): 【Chemistry 4】 (In the formula, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be linked by a group to form a ring, n may be the same or different and is a natural number of 1 or 2.

10. The method of any one of the preceding claims, represented by:

5. 10. The method according to any one of the preceding claims, wherein the molar ratio of catalyst A to cyclic organopolysiloxane OC is between 0.005% and 2%, preferably between 0.01% and 2%, preferentially between 0.05% and 1%, more preferentially between 0.1% and 1%.

6. The initiator I is a compound of formula (VIII): 【Transformation 5】 (In the formula, Y represents a carbon atom or a silicon atom; R are the same or different, hydrogen atoms, an alkyl group of 1 to 12 carbon atoms; a cycloalkyl group of 5 to 8 carbon atoms, alkenyl groups of 1 to 12 carbon atoms; an aryl group of 6 to 10 carbon atoms, preferably phenyl; Formula R 1 c SiO (4-c) / 2 a siloxyl group having at least 5 units, preferably at least 10 units, of represents Here, R 1 are the same or different and represent an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, or an aryl group containing 6 to 10 carbon atoms, preferably phenyl, where c=0, 1 or 2, and if the group R is other than a hydrogen atom, the group R may be unsubstituted or substituted by an alkyl or alkenyl chain of 1 to 6 carbon atoms, a cycloalkyl group, an aryl group containing 6 to 10 carbon atoms, or a heteroatom such as oxygen, sulfur or nitrogen.

10. The method of any one of the preceding claims, selected from:

7. 10. The method according to any one of the preceding claims, wherein the initiator I is an alcohol or silanol having a pKa of 10 to 16, preferably a pKa of 12 to 16, preferentially a pKa of 14 to 16.

8. 10. The process according to any one of the preceding claims, wherein the molar ratio of said initiator I to said catalyst A is between 1 and 20, preferably between 3 and 20, preferentially between 5 and 10.

9. 10. The method according to any one of the preceding claims, wherein the molar ratio of the initiator I to the cyclic organopolysiloxane OC is between 0.02% and 20%, preferably between 0.25% and 15%, preferentially between 0.5% and 5%, more preferentially between 0.25% and 2.5%.

10. 10. The process according to claim 1, wherein the ring-opening polymerization reaction of the at least one cyclic organopolysiloxane OC is carried out in the presence of a catalyst system AI and at least one chain blocking agent C.

11. The chain blocking agent C is represented by formula (XII): 【Transformation 6】 (In the formula, R 1 are identical, and CH 3 represents R 2 are the same or different, alkenyl groups containing 2 to 6 carbon atoms, preferably vinyl; a linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms; Optionally substituted C 6 ~C 18 an aryl group, or hydrogen represents q is an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5. The method of claim 10, wherein the

12. 10. The method according to claim 1, wherein the linear organopolysiloxane OL has a degree of polymerization of 2 to 2000, preferably 4 to 1000, preferentially 4 to 500 and more preferentially 10 to 100.

13. The linear organopolysiloxane OL has a weight average molecular weight M of 500 to 150,000 g / mol, preferably 1,000 to 150,000 g / mol, preferentially 1,000 to 100,000 g / mol, more preferentially 5,000 to 30,000 g / mol. w 10. The method according to any one of the preceding claims, characterized in that it comprises:

14. 10. The method according to any one of the preceding claims, wherein the content of cyclic organopolysiloxanes OC is less than 2%, preferably less than or equal to 1%, and preferentially less than or equal to 0.5% by weight relative to the total weight of the product obtained from the reaction.

15. A composition for carrying out the method according to claims 1 to 14, comprising at least one cyclic organopolysiloxane OC, A catalytic system AI according to claim 1, and Optionally, a chain blocking agent C A composition comprising:

16. Use of the linear organopolysiloxane OL obtained as claimed in any one of claims 1 to 14 as a compound that can be directly used in various silicone formulations useful in the fields of cosmetics, household maintenance products, automobiles and energy, etc.

17. The following formula (XIV): 【Transformation 7】 (In the formula, the groups R are identical or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be joined together to form a ring; group R 1 are the same or different and represent a hydrogen atom or an alkyl chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, n may be the same or different and is a natural number of 1, 2, or 3. Catalyst A represented by:

18. The following formula (XV): 【Transformation 8】 (In the formula, n is a natural number of 1 or 2.) Catalyst A according to claim 17, represented by:

19. 19. Use of catalyst A according to claims 17 and 18 as a catalyst for ring-opening polymerization or polycondensation.

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