Ring-opening polymerization or polycondensation polymerization method

Abstract

The present invention relates to a method for producing linear organopolysiloxane OL from organopolysiloxane O (cyclic and / or linear) by polymerization reaction using a catalytic system AI. More precisely, the method of the present invention makes it possible to obtain linear organopolysiloxane OL having a controlled molar mass with a very low residual cyclic organopolysiloxane. This application also relates to linear organopolysiloxane OL obtained according to various embodiments of the method of the present invention described above.

Description

[Technical Field]

[0001] The present invention relates to a method for producing linear organopolysiloxane OL by polymerization reaction from organopolysiloxane O (cyclic and / or linear) using a catalytic system AI. More specifically, the method of the present invention provides linear organopolysiloxane OL with controlled molar mass and a very low content of residual cyclic organopolysiloxane.

[0002] The present invention also relates to catalysts used in catalytic AI systems, which will be described in detail below. [Background technology]

[0003] A major challenge for the silicone industry in the coming years will be the industrial synthesis of organopolysiloxanes with very low or zero residual cyclic compound content.

[0004] To date, industrial synthesis of organopolysiloxanes by polycondensation or ring-opening polymerization has resulted in the production of cyclic organopolysiloxanes such as octamethyltetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), or other undesirable cyclic organopolysiloxanes. Conventional industrial processes prefer ring-opening polymerization because it uses monomers that are easily synthesized, purifiable, and consequently inexpensive. However, this method also produces undesirable cyclic products that can account for 6% to 15% of the total mass of the linear organopolysiloxane obtained during synthesis, corresponding to thermodynamic equilibrium. Traditionally, this high content of cyclic products necessitates energy-intensive process steps, such as high-temperature and / or vacuum defloration steps, to separate these by-products from the resulting linear organopolysiloxane. By eliminating these steps and simultaneously improving production efficiency, it becomes possible to reduce carbon dioxide emissions and obtain more environmentally friendly silicone products.

[0005] Therefore, for economic and energy efficiency reasons, it is necessary to develop new solutions to eliminate or at least limit these long and costly separation steps.

[0006] Furthermore, the use of cyclic silicones or organopolysiloxanes such as octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) is restricted and is expected to remain restricted in the future. In addition to the fact that these cyclic compounds are not biodegradable and pose environmental risks, they are endocrine disruptors and are suspected of being potentially carcinogenic.

[0007] Therefore, in 2018, European regulations limited the content of D4 and D5 in rinse-off cosmetics to 0.1% by mass. This regulation is expected to be adopted soon in other cosmetics and silicone application fields such as the electronics industry.

[0008] Consequently, there is a need to develop processes for supplying linear organopolysiloxanes that are free of cyclic silicones or contain at least low levels of cyclic silicones. In particular, there is interest in providing novel catalytic systems that enable such processes. There is also interest in ensuring reliable control over the molar mass of the resulting product. This possibility enhances the potential for utilization and application of the resulting polymers.

[0009] In the prior art, the use of carbene derivatives in the production of organopolysiloxanes by ring-opening polymerization or polycondensation is described in patent application WO2005 / 073279. However, satisfactory results obtained with the catalyst system disclosed in the said patent application cannot satisfy the above-mentioned specifications. [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] In view of such prior art, one of the essential objects of the present invention is to improve the production of organopolysiloxanes by ring-opening polymerization reaction or polycondensation using a catalyst system more effective than those conventionally used, and this catalyst system increases the yield of linear organopolysiloxanes while suppressing the formation of cyclic organopolysiloxanes by retrodecomposition (intramolecular depolymerization) reaction.

[0011] The development of this alternative technology enables the production of more environmentally friendly silicones.

Means for Solving the Problems

[0012] Surprisingly, the applicant has developed a catalyst system that meets these expectations. Accordingly, the present invention relates to a process for producing linear organopolysiloxane OL by polymerizing at least one organopolysiloxane O in the presence of a catalyst system AI, and the catalyst system AI includes the following: - At least one catalyst A of formula (I):

Chemical formula

[0013] Therefore, one of the objectives of this patent application is to propose a process for preparing linear organopolysiloxane OL by polymerization reaction of organopolysiloxanes, in which the molar mass of the final product can be controlled while the yield of linear organopolysiloxane OL exceeds 90%, preferably exceeds 95%, and more preferably exceeds 98%.

[0014] Another objective of this patent application is to provide a catalytic AI system for performing this process.

[0015] Another objective of this patent application is to propose a simple and harmless catalyst system suitable for carrying out the process.

[0016] Other objectives of the present invention can be understood by reading the following description. [Modes for carrying out the invention]

[0017] Silicone, also known as organopolysiloxane, is a polymer material in which silicon and oxygen atoms are arranged alternately, and various organic radicals are bonded to the silicon atoms.

[0018] In the context of the present invention, the terms "silicone," "silicone product," "silicone polymer," or "organopolysiloxane O" refer to polymers containing a siloxane (Si-O-Si) skeleton in which silicon and oxygen atoms are arranged alternately and various organic radicals are bonded to the silicon. These silicone polymers are liquid or solid depending on their molecular weight and degree of polymerization.

[0019] In the present invention, the term "reaction mixture" means all reactive chemical species present. Examples include catalyst A, initiator I, organopolysiloxane O, and / or chain arrester C.

[0020] In this invention, the term "catalytic system AI" means a system consisting of the following: -Catalyst A alone, or - A combination of catalyst A and at least one initiator I that forms an active species suitable for catalyzing the process of the present invention.

[0021] All viscosities referred to in this disclosure correspond to dynamic viscosity values ​​at 25°C known as "Newtonian" viscosities, i.e., dynamic viscosity measured in a manner known by itself using a Brookfield viscometer at a shear rate gradient low enough that the measured viscosity is independent of the velocity gradient.

[0022] For the purposes of the present invention, the organopolysiloxane O present in the reaction mixture is selected from a linear organopolysiloxane alone or a mixture thereof, a cyclic organopolysiloxane alone or a mixture thereof, or a mixture of one or more linear and cyclic organopolysiloxanes.

[0023] In the present invention, a linear organopolysiloxane is represented by the following formula (II): [ka] During the ceremony, R 1 These can be the same or different, and represent the following: - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. - Alkenyl groups with 2 to 6 carbon atoms, - Aryl groups with 6 to 18 carbon atoms, -hydroxyl group, or R 2 These can be the same or different, and represent the following: - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl group, -Hydroxyl group (OH), - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms. q is an integer from 1 to 2000, preferably from 1 to 500, more preferably from 1 to 200, and even more preferably from 1 to 50, provided that at least one radical R 2 It is a hydroxyl group (OH).

[0024] For the purposes of the present invention, a linear organopolysiloxane is represented by formula (II), where, R 1 These can be the same or different, and represent the following: - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. - Alkenyl groups with 2 to 6 carbon atoms, - Aryl groups with 6 to 18 carbon atoms, -hydroxyl group, or R 2 This represents the following: -Hydroxyl group (OH), q is an integer between 1 and 500, preferably between 1 and 200, and more preferably between 1 and 50.

[0025] According to one embodiment of the present invention, the method of the present invention uses at least two organopolysiloxanes O selected from the linear organopolysiloxanes described above.

[0026] According to one embodiment of the present invention, a cyclic organopolysiloxane is represented by the following formula (III): [ka] In the formula, R may be the same or different, and represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n represents a natural integer from 1 to 2.

[0027] In particular, commercially available cyclic organopolysiloxanes include 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), and hexaphenylcyclotrisiloxane. Lotrisiloxane (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-trioxatrisiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane Examples include 2,4,6-trimethylcyclotrisiloxane (CAS 546-45-2), 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).

[0028] Advantageously, the cyclic organopolysiloxane is hexamethylcyclotrisiloxane (CAS 541-05-9) or octamethylcyclotetrasiloxane (CAS 556-67-2).

[0029] According to one embodiment of the present invention, the method of the present invention uses at least two cyclic 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).

[0030] As described above, according to one embodiment of the present invention, the method of the present invention uses a mixture of linear and cyclic organopolysiloxanes. These different organopolysiloxanes have already been defined in detail.

[0031] In the context of this patent application, catalyst A is represented by formula (IV): [ka] During the ceremony, R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R2 may be the same or different, and represents the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0032] According to one embodiment of the present invention, catalyst A is represented by the following formula (V): [ka] During the ceremony, R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R2 may be the same or different, and represents the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0033] According to one embodiment of the present invention, catalyst A is represented by the following formula (VI): [ka] During the ceremony, R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R2 may be the same or different, and represents the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0034] According to one embodiment of the present invention, catalyst A is represented by the above formula (VI), where: R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, R2 may be the same or different, and represents the following: - Hydrogen atom, - Linear or branched alkyl groups with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0035] According to one embodiment of the present invention, catalyst A is represented by the following formula (VII): [ka] During the ceremony, R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, R2 may be the same or different, and represents the following: - Hydrogen atom, - Linear or branched alkyl groups with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0036] According to one embodiment, the method of the present invention is characterized in that the molar amount of catalyst A relative to organopolysiloxane O is 0.005% to 2%, preferably 0.01% to 2%, preferably 0.05% to 1%, and more preferably 0.1% to 0.5%.

[0037] For the purposes of the present invention, initiator I is selected from water, alcohols and their derivatives, or mixtures thereof.

[0038] According to one embodiment of the present invention, initiator I is selected from alcohols having a pKa of 10 to 16, preferably 12 to 16, and preferably 14 to 16.

[0039] According to one embodiment of the present invention, initiator I is selected from water or a compound of formula (VIII): [ka] During the ceremony, Y represents a carbon or silicon atom. R can be the same or different, and represents the following: - Hydrogen atom, - Alkyl alkyl groups with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group; The radical R may be unsubstituted, or it may be substituted with an alkyl chain having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroatom such as oxygen, sulfur, or nitrogen.

[0040] According to a preferred embodiment of the present invention, initiator I is represented by the compound of formula (VIII) above, where: Y represents a carbon atom. R can be the same or different, and represents the following: - Hydrogen atom, - Alkyl alkyl groups with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, -benzyl group or phenyl group Here, the radical R may be unsubstituted, or it may be substituted with an alkyl chain having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroatom such as oxygen, sulfur, or nitrogen.

[0041] According to one embodiment, initiator I is an alcohol selected from primary alcohols or secondary alcohols. Preferably, initiator I is an alcohol selected from primary alcohols.

[0042] According to one embodiment, initiator I is an alcohol selected from saturated or unsaturated polyols having 2 to 6 hydroxyl groups. Examples include polyols such as glycerol, pentaerythritol, sorbitol, or 1,4-butanediol.

[0043] According to one embodiment, initiator I is an alcohol having a pKa of 10 to 16, preferably 12 to 16, and preferably 14 to 16.

[0044] According to one embodiment, initiator I is an alcohol 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 (CAS 627-27-0), and long-chain alkyl alcohols such as undecanol (CAS 112-42-5) and dodecanol (CAS 27342-88-7).

[0045] Preferably, initiator I is benzyl alcohol (CAS 100-51-6).

[0046] According to another embodiment of the present invention, initiator I is water.

[0047] In one embodiment, the method of the present invention is characterized in that the molar ratio of initiator I to catalyst A is 0 to 20, preferably 0 to 10, preferably 0 to 5, and more preferably 0 to 2.

[0048] In one embodiment, the method of the present invention is characterized in that the molar amount of initiator I relative to the organopolysiloxane O introduced is 0.005% to 10%, preferably 0.01% to 5%, preferably 0.05% to 2.5%, and more preferably 0.1% to 1%.

[0049] According to one embodiment, the method of the present invention uses an initiator I represented by formula (IX): [ka] During the ceremony, R can be the same or different, and represents the following: - Alkyl alkyl groups with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, -benzyl group or phenyl group The radical R may be unsubstituted or may be substituted with an alkyl chain having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroatom such as oxygen, sulfur, or nitrogen.

[0050] Preferably, in the process of the present invention, an initiator I selected from trimethylsilanol (CAS 1066-40-6) or triethylsilanol (CAS 597-52-4) is used.

[0051] In one embodiment of the present invention, the polymerization reaction of at least one organopolysiloxane O also includes at least one chain terminator C.

[0052] According to one embodiment of the present invention, the chain terminator C is represented by formula (X):

Chemical formula

[0053] More specifically, the chain-stopping agent C of the present invention is preferably represented by formula (X), where: R 1 These are identical and represent CH3. R 2 These can be the same or different, and represent the following: - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl group, - A linear or branched alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms. -C6~C replaced by optional selection 18 Aryl group, or - Hydrogen atom, q is an integer between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 5.

[0054] Other stoppers having a siloxane functional group according to the present invention are described on page 264 of "Chemistry and Technology of Silicones," published by Academic Press in 1968. Chain stopper C may be present in a solvent, which is particularly advantageous for dissolving in the reaction mixture. The solvent may be a nonpolar solvent, such as an alkane or aromatic hydrocarbon type organic solvent. Preferably, the solvent is selected from n-hexane, n-heptane, n-decane, n-dodecane, isododecane, EXXSOL D60, xylene, toluene, and mixtures thereof.

[0055] In one embodiment, the method of the present invention is characterized in that the molar ratio of chain stopper C to catalyst A is 0 to 30, preferably 0 to 20, and preferably 0 to 10.

[0056] According to one embodiment of the present invention, a linear organopolysiloxane OL may be a compound of formula (XI): [ka] During the ceremony, R can be the same or different, and represents the following: - 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 groups, - Aryl group having 6 to 10 carbon atoms, preferably phenyl, R 1 These can be the same or different, and represent the following: - Alkyl alkyl groups with 1 to 5 carbon atoms, - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl, -Hydroxyl group (OH), -hydrogen, -C6~C 18 Aryl group, preferably phenyl, R 2 These can be the same or different, and represent the following: - Alkenyl group having 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 with at least one heteroatom O, N, or S, or a halide such as a fluorine atom, for example, 1 to 10 fluorine atoms, e.g., (C1 to C5)alkyl-CF3, where the alkyl is linear or branched. -C5~C can be replaced by any option. 10 Cycloalkyl groups, -C6~C can be replaced by any option. 18 Aryl group, or - Hydrogen atom, or -Base (OR 3 ), here, R 3 This represents the following: C6-C 18 Aryl group or alkylaryl group (such as benzyl group), q is an integer between 0 and 50, preferably between 0 and 20, more preferably between 0 and 10, and preferably q = 0. n2 represents an integer between 10 and 10000, preferably between 10 and 5000, preferably between 10 and 1000, and more preferably between 10 and 500. m2 represents an integer between 0 and 5000, preferably between 0 and 1000, and more preferably between 0 and 100.

[0057] According to a preferred embodiment of the present invention, the linear organopolysiloxane OL is a compound of formula (XI): During the ceremony, R may be the same or different, and represents CH3 or phenyl, preferably CH3; R 1 These may be the same or different, and represent the following bases: - Alkyl alkyl groups with 1 to 5 carbon atoms, - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl, -C6~C 18 Aryl group, preferably phenyl, - Hydrogen atom; R 2 These may be the same or different, and represent the following bases: - Alkyl alkyl groups with 1 to 6 carbon atoms, - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl, -Hydroxyl group (OH), -C6~C 18 Aryl group, - Hydrogen atom; -Base (OR 3 ), here, R 3 This represents the following: Alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or benzyl groups, q is an integer between 0 and 50, preferably between 0 and 20, more preferably between 0 and 10; preferably q = 0. n2 represents an integer between 10 and 10000, preferably between 10 and 5000, preferably between 10 and 1000, and more preferably between 10 and 500. m2 represents an integer between 0 and 5000, preferably between 0 and 1000, and more preferably between 0 and 100.

[0058] According to a particularly preferred embodiment of the present invention, the linear organopolysiloxane OL of the present invention is a compound of formula (XI), wherein: R may be the same or different, and represents CH3 or a phenyl group, preferably CH3. R 1 These may be the same or different, and represent CH3, a phenyl group, or a vinyl group; R 2 These can be the same or different, and represent the following: - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl, -Hydroxyl group (OH), - A linear or branched alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms. - Arbitrarily substituted C6~C 18 Aryl group, or - Hydrogen atom; -Base (OR 3 ), here, R 3 This represents the following: Alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or benzyl groups, q is 0; n2 represents an integer between 10 and 10000, preferably between 10 and 5000, preferably between 10 and 1000, and even more preferably between 10 and 500; m2 represents an integer between 0 and 5000, preferably between 0 and 1000, and more preferably between 0 and 100.

[0059] According to a particularly preferred embodiment of the present invention, the linear organopolysiloxane OL of the present invention is a compound of formula (XII), wherein: R may be the same or different, and represents CH3 or phenyl, preferably CH3. R 1 These may be the same or different, and represent CH3, phenyl, or vinyl; R2 These are identical and represent the following base: - A linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl, -Hydroxyl group (OH), -Base (OR 3 ), here, R 3 This represents the following: Alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or benzyl groups, q is 0; n2 represents an integer between 10 and 5000, preferably between 10 and 1000, and more preferably between 10 and 500; m2 represents an integer between 0 and 1000, preferably between 0 and 500, and more preferably between 0 and 100.

[0060] The linear organopolysiloxane OL of the present invention is characterized in that its degree of polymerization is strictly greater than the degree of polymerization of organopolysiloxane O introduced into the reaction mixture.

[0061] According to one embodiment of the method of the present invention, the linear organopolysiloxane OL of the present invention is characterized in that its degree of polymerization is at least 2 times, at least 3 times, or at least 5 times greater than the degree of polymerization of the organopolysiloxane O introduced into the reaction mixture.

[0062] For the purposes of the present invention, the mass-average molar mass (M) of different linear organopolysiloxanes OL is used. w and M n The number-average molar mass (as shown by) can be measured by size exclusion chromatography (SEC) in a solvent such as toluene at 35°C in the presence of a polystyrene standard.

[0063] According to one embodiment of the method of the present invention, the linear organopolysiloxane OL of the present invention has a number-average molar mass M nThe compound is characterized by having a concentration of 500 to 1,000,000 g / mol, preferably 500 to 500,000 g / mol, preferably 500 to 100,000 g / mol, and even more preferably 500 to 50,000 g / mol.

[0064] According to one embodiment of the method of the present invention, the linear organopolysiloxane OL of the present invention is characterized in that its dynamic viscosity is 100 to 1,000,000 mPa·s at 25°C, preferably 100 to 500,000 mPa·s at 25°C, and more preferably 100 to 100,000 mPa·s at 25°C.

[0065] In the context of this patent application, the mass percentage or weight percentage of cyclic organopolysiloxane (e.g., D4) in the product obtained according to the method of the present invention is quantitative. 29 It can be measured by Si NMR spectroscopy. Alternatively, the mass percentage or weight percentage of D4 in the product obtained by the process of the present invention can be measured by a chromatogram obtained from size exclusion chromatography (SEC) analysis.

[0066] Hereinafter, the reaction product is defined as the sum of linear organopolysiloxane OL and organopolysiloxane OC at the end of the method of the present invention.

[0067] In one embodiment, the method according to the present invention is characterized in that the content of cyclic organopolysiloxane OC is less than 2%, preferably 1% or less, and preferably 0.5% or less, based on the total mass of the reaction product.

[0068] In one embodiment, the method according to the present invention is characterized in that the content of octamethylcyclotetrasiloxane (D4) is less than 2%, preferably 1% or less, and preferably 0.5% or less, relative to the total mass of the reaction product.

[0069] In one embodiment, the method of the present invention is carried out in a nonpolar solvent. Examples of solvents include alkane or aromatic hydrocarbon type organic solvents, or alcohols such as ethanol.

[0070] Preferably, the solvent is selected from n-hexane, n-heptane, n-decane, n-dodecane, cyclohexane, isododecane, EXXSOL D60, xylene, toluene, and mixtures thereof.

[0071] According to one embodiment of the present invention, the amount of solvent used in the method of the present invention is the minimum amount required to dissolve catalyst A in the reaction mixture. Therefore, the catalyst can be dissolved in ethanol or toluene.

[0072] Advantageously and preferably, the reaction is carried out at a temperature of 50°C to 170°C, preferably 80°C to 150°C, and more preferably 80°C to 110°C.

[0073] According to the method of the present invention, the reaction time is between 1 hour and 72 hours, preferably between 8 hours and 72 hours, and more preferably between 18 hours and 72 hours. Those skilled in the art will know how to adapt these parameters depending on the properties of the reactor and the species used.

[0074] This patent application also relates to linear organopolysiloxane OLs obtained according to various embodiments of the method of the present invention described above. The present invention also relates to silicone compositions comprising organopolysiloxane OLs obtained according to various embodiments of the method of the present invention described above.

[0075] This patent application also relates to a composition for carrying out the method of the present invention, and comprises the following components: - At least one cyclic organopolysiloxane O as defined above, -Catalyst AI as defined above, -and optionally, a chain arrestor C as defined above.

[0076] The present invention also relates to using organopolysiloxane OL obtained by the method of the present invention as an ingredient that can be directly used in various silicone formulations useful in fields such as cosmetics, household detergents, automobiles, and energy.

[0077] This patent application also relates to catalyst A, which is represented by the following formula (XII): [ka] During the ceremony, R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R2 may be the same or different, and represents the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0078] According to one embodiment, catalyst A is represented by the following formula (XIII): [ka] During the ceremony, R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R2 may be the same or different, and represents the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0079] More specifically, the present invention relates to catalyst A represented by the following formula (XIV): [ka] During the ceremony, R1 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, -hydroxyl group, R2 may be the same or different, and represents the following: - Hydrogen atom, - A linear or branched alkyl chain with 1 to 12 carbon atoms. - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

[0080] This patent application also relates to the use of catalysts defined according to formulas (XII, XIII, and XIV) as ring-opening polymerization or polycondensation catalysts. [Examples]

[0081] Organopolysiloxanes used in the examples: Cyclic organopolysiloxane O1:Hexamethylcyclotrisiloxane (CAS 541-05-9) Cyclic organopolysiloxane O2:octamethylcyclotetrasiloxane (CAS 556-67-2) Linear organopolysiloxane O3: [ka]

[0082] Catalyst A used in the example: Catalyst A1: [ka] Catalyst A2: [ka] Catalyst A3: [ka] Catalyst A comp1 : [ka] Initiators used in the examples: Initiator I1: Benzyl alcohol (CAS 100-51-6) Initiator I2: Ethanol (CAS 64-17-5) Initiator I3:H2O Chain inhibitors used in the examples: Chain inhibitor C1: Divinyltetramethyldisiloxane (CAS 2627-95-4).

[0083] In the following examples, the residual mass percentage of cyclic organopolysiloxane OC and the mass percentage of linear organopolysiloxane OL obtained by the method of the present invention are measured by size exclusion chromatography (SEC) in a solvent such as toluene at 35°C in the presence of a polystyrene standard. Similarly, the number-average molar mass (M) of various linear organopolysiloxanes OL according to the present invention is measured. n(as indicated by the notation) is determined by same-size exclusion chromatography (SEC).

[0084] In the following embodiments, the mass percentage of residual cyclic organopolysiloxane is defined as the mass percentage of cyclic organopolysiloxane at the end of the process used in accordance with the present invention.

[0085] Example 1: Catalyst A of the present invention 1 、A 2 and A 3 Synthesis of: In the first step, the precursor shown in the following reaction equation is obtained by reacting iodine (1.4 equivalents) with imidazole (1.5 equivalents), and this is added to a solution of Ph3P (1.3 equivalents) in dichloromethane (50 mL) while stirring at room temperature for 5 minutes. Next, the alcohol precursor (i x Add (1.0 equivalent) of dichloromethane (10 mL) solution to the reaction mixture using a syringe and stir overnight at room temperature. Next, wash the reaction mixture with aqueous Na2SO3 solution (2 × 100 mL), and rinse this aqueous phase twice with dichloromethane (2 × 100 mL). Combine the organic phases and dry (Na2SO4). After filtration, evaporate the obtained organic phase using a rotary evaporator. The resulting crude product is purified by flash chromatography (1 / 9 siRNA / petroleum ether) to obtain a yellow oily substance. The yields of each iodination intermediate are as follows: [ka]

[0086] In the second step, the product synthesized in the previous step (1.2 equivalents) is added to a solution of 1-(tert-butyl)-1H-imidazole (1 equivalent) in toluene (20 mL). The reaction medium is placed under an argon stream and stirred overnight at 80°C. After removing the solvent, the crude reaction product is washed with distilled ether (3 × 10 mL), dried under vacuum, and then converted to b using the following reaction equation. x A white solid imidazole salt is obtained, as shown.

[0087] The yields obtained for each of these intermediates are as follows: [ka]

[0088] In the final stage, product b generated in the previous stage is used. x Dissolve in 20 mL of THF and add KHMDS (1 equivalent) to the reaction mixture. Stir the reaction mixture at room temperature for 1 hour. Remove the solvent, extract the product with pentane, and filter. After vacuum drying, catalysts A1, A2, or A3 are obtained as white solids. The synthesis yields of these catalysts are as follows: [ka]

[0089] Example 2: A general protocol for performing the process of the present invention: The catalytic AI system is formed by a combination of catalyst A (e.g., A1, A2, or A3) (1 equivalent, 0.025 mmol) and initiator I (e.g., I1, I2, or I3) in amounts from 0 to n equivalents. The table below shows different I / A molar ratios.

[0090] The newly formed catalyst system AI is mixed with a solution containing organopolysiloxane O1, O2, or O3 (5.07 mmol). The content of catalyst A is 0.5 mol% relative to organopolysiloxane O. Optionally, a chain arrester such as C1 is added to the reaction mixture. The reaction mixture is then heated to the temperature and time shown in each example of the present invention.

[0091] Example 3a: Organopolysiloxane O 2 Implementation of the present invention method in the presence of In this example, the general protocol of Example 2 was followed. In this example, organopolysiloxane O2 (CAS 556-67-2) was used. The initiator was I1, and the molar ratio I / A was equal to 1. The reaction mixture was heated at 80°C for 16 hours.

[0092] The following table describes the characteristics of the various catalysts used and the product OL obtained according to the method of the present invention.

[0093] [Table 1]

[0094] It should be noted that, according to the method of the present invention, in the presence of the catalyst described as A2, product OL with a cyclic organopolysiloxane content of less than 1% can be obtained under these operating conditions.

[0095] In the table below, the process of the present invention was repeated at 110°C for 2 days using catalysts A1 and A3 of the present invention. The initiator was I1, and the molar ratio I / A was 1.

[0096] [Table 2]

[0097] These tests resulted in the generation of linear organopolysiloxane OL with a mass percentage exceeding 99% of the reaction product.

[0098] Example 3b: Organopolysiloxane O 1 Implementation of the method of the present invention in the presence of: In this example, the general protocol of Example 2 was followed. Organopolysiloxane O1 (CAS 541-05-9) was used. The initiator was I1. In Test 1 in the table below, the reaction mixture was heated at 110°C for 24 hours.

[0099] In Test 2 shown in the table below, the reaction mixture was heated at 80°C for 16 hours. The table below shows the characteristics of the various catalysts used, the I / A molar ratios used, and the product OL obtained according to the method of the present invention.

[0100] [Table 3]

[0101] It should be noted that in the presence of catalysts A1 and A2 described according to the method of the present invention, linear organopolysiloxane OL with a purity of over 99% can be obtained.

[0102] Example 4: Implementation of the process of the present invention using different initiators I: In this embodiment, the general protocol of Example 2 was used.

[0103] In this example, organopolysiloxane O2 (CAS 556-67-2) and catalyst A2 were used. The molar ratio I / A was 1.

[0104] The various tests described in the following examples were carried out at a temperature of 80°C for 16 hours. The following table shows the characteristics of the various initiators I used and the OL products obtained according to the method of the present invention.

[0105] [Table 4]

[0106] The method of the present invention is versatile, and as shown in the table above, satisfactory results can be obtained even when using different initiators.

[0107] Example 5: Effect of different C / A molar ratios in the process of the present invention: In this embodiment, the general protocol of Example 2 was used.

[0108] In this example, organopolysiloxane O2 (CAS 556-67-2), catalyst A1, initiator I1, and chain arrestor C1 were used.

[0109] In these tests, the reaction mixture was heated at a temperature of 80°C for 48 hours.

[0110] The following table shows the molar ratio of chain arrester C to the molar amount of catalyst A used, and the characteristics of product OL obtained according to the method of the present invention. In this embodiment, the molar ratio I / A is 5.

[0111] [Table 5]

[0112] These various tests determine the number-average molar mass (M) of the linear organopolysiloxane OL obtained according to the method of the present invention. n This demonstrates the control of ).

[0113] Changes in the amount of chain arrester C affect the molar mass of the product obtained according to the method of the present invention.

[0114] Furthermore, it should be noted that the product OL obtained according to the method of the present invention has a very low mass percentage of residual cyclic organopolysiloxane OC (less than 1% by mass relative to the total mass of the reaction product).

[0115] Example 6: Implementation of the process of the present invention without an initiator: In this example, the general protocol of Example 2 was used. In this example, organopolysiloxane O2 (CAS 556-67-2), catalyst A1, and chain arrestor C1 were used. In these tests, the reaction mixture was heated at a temperature of 110°C for 48 hours.

[0116] The following table shows the molar ratio of the chain termination agent used to the molar amount of catalyst A used, and the characteristics of the product OL obtained according to the method of the present invention.

[0117] [Table 6]

[0118] According to the method of the present invention, a linear organopolysiloxane OL can be obtained that does not contain any residual cyclic organopolysiloxane OC, or has a very low mass percentage of residual cyclic organopolysiloxane OC, even without an initiator.

[0119] Example 7: Polycondensation reaction: Organopolysiloxane O without initiator 3 The present invention method carried out in the presence of: In this example, catalyst A1 (0.5 mol%, 0.0137 mmol) is mixed with a solution containing organopolysiloxane O3 (2.73 mmol).

[0120] Optionally, a chain arrester such as C1 may be added to the reaction mixture, as shown in the table below.

[0121] The reaction mixture was heated at 110°C for 48 hours. The following table shows the molar ratio of the chain arrester C1 used to the molar amount of catalyst A used, and the characteristics of the product OL obtained according to the method of the present invention.

[0122] [Table 7]

[0123] As shown in the table above, this example demonstrates that the process of the present invention yields very satisfactory results in polycondensation reactions.

[0124] Example 8: O 2 and O 3 The present invention process carried out in the presence of: In this example, catalyst A1 (0.5 mol%, 0.0136 mmol) was mixed with a solution containing a mixture of organopolysiloxanes O2 (1.36 mmol) and O3 (1.36 mmol). The reaction mixture was heated at 110°C for 48 hours.

[0125] In this way, 99.9% of the linear organopolysiloxane OL was obtained (only 0.1% of the cyclic organopolysiloxane OC remained). The molar mass of the obtained product OL was 75,000 g / mol.

Claims

1. A process for producing a linear organopolysiloxane OL by polymerizing at least one organopolysiloxane O in the presence of a catalytic system AI, wherein the catalytic system AI includes the following: - At least one catalyst A of formula (I): 【Chemistry 1】 During the ceremony, R 1 These can be the same or different, and represent the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, - Hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R 2 These can be the same or different, and represent the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - benzyl group or phenyl group, and at least one initiator I, at the discretion of the party.

2. The process according to claim 1, wherein the organopolysiloxane O is selected from a linear organopolysiloxane alone or a mixture thereof; a cyclic organopolysiloxane alone or a mixture thereof; or a mixture of one or more linear and cyclic organopolysiloxanes.

3. The catalyst A is represented by the following formula (VI) in the process according to claim 1 or 2: 【Chemistry 2】 During the ceremony, R 1 These can be the same or different, and represent the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, - Hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R 2 These can be the same or different, and represent the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

4. The process according to any one of claims 1 to 3, wherein the molar amount of catalyst A relative to organopolysiloxane O is 0.005% to 2%, preferably 0.01% to 2%, preferably 0.05% to 1%, and more preferably 0.1% to 0.5%.

5. The initiator I is selected from water or a compound of formula (VIII) in the process according to any one of claims 1 to 4: 【Transformation 3】 During the ceremony, Y represents a carbon atom or a silicon atom. R may be the same or different, and represents the following: - Hydrogen atom, - Alkyl alkyl groups with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group; The radical R may be unsubstituted, or it may be substituted with an alkyl chain having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroatom such as oxygen, sulfur, or nitrogen.

6. The process according to any one of claims 1 to 5, wherein at least one chain termination agent C represented by formula (X) is added during the polymerization reaction of at least one organopolysiloxane O: 【Chemistry 4】 During the ceremony, R 1 CH may be the same or different, 3 Or a phenyl group, preferably CH 3 Represents; R 2 These can be the same or different, and represent the following: - Alkenyl group having 2 to 6 carbon atoms, preferably vinyl, - an alkyl group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, linear or branched, optionally with at least one heteroatom O, N or S, or a halide such as a fluorine atom, for example substituted with 1 to 10 fluorine atoms, for example (C 1 ~C 5 )alkyl-CF 3 where alkyl is linear or branched - C is replaced by choice. 5 ~C 10 Cycloalkyl groups, - C is replaced by choice. 6 ~C 18 Aryl group, or - Hydrogen atom; q is an integer from 1 to 50, preferably from 1 to 20, and more preferably from 1 to 10.

7. A silicone composition comprising a linear organopolysiloxane OL obtained by the method described in any one of claims 1 to 6.

8. A composition for carrying out the processes defined in claims 1 to 7, - At least one cyclic organopolysiloxane O as defined in claim 1 or 2, - Catalyst system AI as defined in claim 1, 3, 4, or 5, and optionally, chain arresting agent C as defined in claim 6. A composition containing the following:

9. Catalyst A, represented by the following formula (XIII): 【Transformation 5】 During the ceremony, R 1 These can be the same or different, and represent the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, - Hydroxyl group, - Alkoxyl groups with 1 to 6 carbon atoms, - Thiol group or thioether group having 1 to 6 carbon atoms, - Amino group or aminoalkyl group having 1 to 6 carbon atoms, R 2 These can be the same or different, and represent the following: - Hydrogen atom, - Alkyl chains with 1 to 12 carbon atoms, - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

10. Catalyst A, represented by the following formula (XIV): 【Transformation 6】 During the ceremony, R 1 These can be the same or different, and represent the following: - Hydrogen atom, - A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (optionally substituted with heteroatoms O, N, S or halides), - Alkenyl groups with 2 to 6 carbon atoms, - Hydroxyl group, R 2 These can be the same or different, and represent the following: - Hydrogen atom, - A linear or branched alkyl chain having 1 to 12 carbon atoms. - Cycloalkyl groups with 5 to 8 carbon atoms, - Alkenyl groups with 2 to 12 carbon atoms, - Benzyl group or phenyl group.

Images