Polymerization method by ring opening or polycondensation

Abstract

The present invention relates to a method for producing linear organopolysiloxane OL from (cyclic and / or linear) organopolysiloxane O by a polymerization reaction using a catalytic system AI. More specifically, the method of the present invention can produce linear organopolysiloxane OL with a very low level of residual cyclic organopolysiloxane and a controlled molar mass. The present application also relates to linear organopolysiloxane OL obtained according to various embodiments of the method of the present invention described herein.

Description

[Technical Field]

[0001] The present invention relates to a method for producing linear organopolysiloxane OL by a polymerization reaction using a catalytic system AI, starting from (cyclic and / or linear) organopolysiloxane O. More specifically, the method of the present invention makes it possible to obtain linear organopolysiloxane OL with a very low level of residual cyclic organopolysiloxane and a controlled molar mass. Furthermore, the present invention also relates to catalysts used in catalytic AI systems, which will be described comprehensively below. [Background technology]

[0002] A major challenge for the silicone industry going forward is the industrial synthesis of organopolysiloxanes with extremely low or zero residual cyclic content.

[0003] Industrial synthesis of organopolysiloxanes by polycondensation or ring-opening polymerization has, to date, resulted in the formation of cyclic organopolysiloxanes such as octamethyltetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), or other unwanted cyclic organopolysiloxanes. Conventional industrial processes prefer ring-opening polymerization because it allows the use of monomers that are easy to synthesize and purify and are relatively inexpensive. However, this method also involves the presence of unwanted cyclic products, which can reach a content of 6% to 15% of the total mass of the resulting linear organopolysiloxane, corresponding to thermodynamic equilibrium. Traditionally, due to the high content of cyclic products, energy-intensive processes, such as defloration at high temperatures and / or low pressures, were required to separate these by-products from the linear organopolysiloxane. Eliminating such processes would improve production efficiency and reduce carbon dioxide emissions, resulting in more environmentally friendly silicone products.

[0004] Therefore, from the standpoint of economic and energy efficiency, it is necessary to develop new solutions to eliminate, or at least reduce, such costly and time-consuming separation processes.

[0005] Furthermore, cyclic silicones or cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) are subject to or are expected to be subject to restrictions on use. These cyclic compounds not only pose environmental risks due to their non-biodegradability, but are also suspected of being endocrine disruptors and potential carcinogens.

[0006] Under these circumstances, the 2018 European regulations limited the content of D4 and D5 in rinse-off cosmetics to 0.1% by mass. This regulation will soon be adopted not only in other cosmetics but also in other areas of silicone application, such as the electronics industry.

[0007] Therefore, there is a need to develop a method for obtaining linear organopolysiloxanes that are free of cyclic silicones or have at least a low cyclic silicone content. Providing a novel catalytic system that enables such a method is particularly important. It is also important to reliably control the molar mass of the resulting product. This possibility will broaden the prospects for the use and application of the resulting polymer.

[0008] N-heterocyclic olefins (NHOs) are highly polarized olefins due to their N-heterocyclic aromatic structure. Because they possess strong basicity and nucleophilicity, they are interesting molecules as organocatalysts. In fact, Chinese Patent Application Publications No. 106750227 and 109851765 describe the use of such catalysts in ring-opening polymerization reactions of various cyclic monomers, such as epoxides and cyclic esters. [Prior art documents] [Patent Documents]

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] Therefore, one of the essential objects of the present invention is to realize a polymerization reaction starting from (cyclic and / or linear) organopolysiloxane O and using N-heterocyclic olefins. Therefore, the object of the present invention is to improve the production of organopolysiloxanes by ring-opening polymerization reaction or polycondensation, which is more effective than the catalyst systems used so far, and to improve it by a catalyst system that enables a high yield of linear organopolysiloxanes while suppressing the formation of cyclic organopolysiloxanes by back-biting reaction. The development of this alternative technology enables more environmentally friendly silicone production.

Means for Solving the Problems

[0011] Surprisingly, the applicant has developed a catalyst system that meets these expectations. Therefore, the present invention is at least one catalyst A of the following formula (I):

Chemical formula

[0012] Therefore, one of the objectives of this application is to propose a method for producing linear organopolysiloxane OL by polymerization reaction of organopolysiloxanes, which allows for control of the molar mass of the final product, and the yield of linear organopolysiloxane OL is 90% or more, preferably 95% or more, and more preferably 98% or more.

[0013] Another object of this application is to provide a catalytic AI system for carrying out the present method.

[0014] Another object of this application is to propose a simple and harmless catalyst system suitable for carrying out the present method.

[0015] Further objectives will become clear by reading the following description of the invention. [Modes for carrying out the invention]

[0016] Detailed description of the invention: Silicone, also known as organopolysiloxane, is a polymer material in which silicon and oxygen atoms are arranged alternately, with various organic groups bonded to the silicon atoms.

[0017] In the present invention, "silicone" refers to a silicone, silicone polymer, or organopolysiloxane O composed of a polymer having a siloxane (Si-O-Si) skeleton in which silicon and oxygen atoms are arranged alternately and various organic groups are bonded to the silicon. These silicone polymers may be liquid or solid depending on their molecular weight and degree of polymerization.

[0018] For the purposes of this invention, the reaction mixture refers to all of the reactive chemical species present. Examples include one or more catalysts A, one or more initiators I, one or more organopolysiloxanes O, and / or one or more chain disruptors C.

[0019] For the purposes of this invention, catalyst 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 capable of catalyzing the method of the present invention.

[0020] All viscosities referred to herein correspond to the amount of dynamic viscosity known as "Newton" at 25°C, which is the dynamic viscosity measured by conventional methods using a Brookfield viscometer at a shear rate gradient low enough that the measured viscosity does not depend on the shear rate gradient.

[0021] In the present invention, the organopolysiloxane O present in the reaction mixture is selected from linear organopolysiloxanes alone or in mixtures, cyclic organopolysiloxanes alone or in mixtures, or a mixture of one or more linear organopolysiloxanes and one or more cyclic organopolysiloxanes.

[0022] For the purposes of the present invention, a linear organopolysiloxane is represented by the following formula (II): [ka] Formula II During the ceremony, R 1 They are the same or different. • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 6 carbon atoms, • Aryl groups containing 6 to 18 carbon atoms • Hydroxyl group Represents, or R 2 They are the same or different. • 2 to 6 carbon atoms, preferably an alkenyl group containing vinyl, • Hydroxyl group (OH), Linear or branched alkyl groups containing 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms. This represents, q is an integer from 1 to 2000, preferably from 1 to 500, preferably from 1 to 200, more preferably from 1 to 50. However, at least one base R 2 It is a hydroxyl group (OH).

[0023] For the purposes of this invention, a linear organopolysiloxane is represented by formula (II), where: R 1 They are the same or different. • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 6 carbon atoms, • Aryl groups containing 6 to 18 carbon atoms • Hydroxyl group Represents, or R 2 teeth, • Represents a hydroxyl group (OH), q is an integer between 1 and 500, preferably between 1 and 200, and more preferably between 1 and 50.

[0024] According to one embodiment of the present invention, the method of the present invention uses at least two organopolysiloxanes O selected from the above-mentioned linear organopolysiloxanes.

[0025] According to one embodiment of the present invention, a cyclic organopolysiloxane is represented by the following formula (III): [ka] Formula III In the formula, R is the same or different group representing an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, or an aryl group containing 6 to 18 carbon atoms, and n represents a natural integer from 1 to 2.

[0026] In particular, 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-trioxatricilinane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane (CAS 546-45-2), 2,4,6- Examples of commercially available cyclic organopolysiloxanes include dimethylcyclotrisiloxane (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).

[0027] Advantageously, the cyclic organopolysiloxane is hexamethylcyclotrisiloxane (CAS 541-05-9) or octamethylcyclotetrasiloxane (CAS 556-67-2).

[0028] 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).

[0029] As previously stated, according to one embodiment of the present invention, the method of the present invention uses a mixture of linear and cyclic organopolysiloxanes. These various organopolysiloxanes are defined more comprehensively above.

[0030] In this application, catalyst A is represented by the following formula (IV): [ka] In the formula, the base R1 is the same or different. • Hydrogen atom, • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 6 carbon atoms, • Cycloalkyl groups containing 5 to 8 carbon atoms • Benzyl group or phenyl group This represents, Base R2 is the same or different. • Hydrogen atom, • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group This represents, Base R3 is the same or different. • Hydrogen atom, • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group This represents, Alternatively, the two R3 groups, together with the atom to which they are bonded, form a cyclic hydrocarbon group such as a cycloalkyl or phenyl group of 5 to 8 carbon atoms.

[0031] In this application, catalyst A is represented by the following formula (V): [ka] During the ceremony, Base R1 is the same or different. • Hydrogen atom, • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 6 carbon atoms, • Cycloalkyl groups containing 5 to 8 carbon atoms • Benzyl group or phenyl group This represents, Base R2 is the same or different. • Hydrogen atom, • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group It represents.

[0032] In this application, catalyst A is represented by the following formula (VI): [ka] During the ceremony, Base R1 is the same or different. • Hydrogen atom, • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 6 carbon atoms, • Benzyl group or phenyl group This represents, Base R2 is the same or different. • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group It represents.

[0033] In this application, catalyst A is represented by the following formula (VII): [ka] During the ceremony, The base R is the same or different. • Hydrogen atom, • A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group It represents.

[0034] According to one embodiment, the method of the present invention is characterized by diluting catalyst A in a solution of alcohol, preferably ethanol.

[0035] This alcohol solution ensures the stability of catalyst A when stored in the atmosphere for extended periods. "Extended period" means a period of more than one week, but can also include periods ranging from one month to several months.

[0036] This embodiment of the present invention demonstrates the robustness of the method of the present invention.

[0037] 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%, more preferably 0.05% to 1%, and even more preferably 0.1% to 0.5%.

[0038] For the purposes of the present invention, initiator I is selected from water, alcohol and its derivatives, or mixtures thereof.

[0039] 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 more preferably 14 to 16.

[0040] 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 is either the same or different. • Hydrogen atom, • Alkyl alkyl groups containing 1 to 12 carbon atoms • Cycloalkyl groups containing 5 to 8 carbon atoms • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group This represents the above, however, the group R may be unsubstituted, or substituted with an alkyl group containing 1 to 12 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, a cycloalkyl group containing 5 to 8 carbon atoms, an aryl group containing 6 to 18 carbon atoms, or a heteroatom such as oxygen, sulfur, or nitrogen.

[0041] According to a preferred embodiment of the present invention, initiator I is represented by a compound of formula (VIII), where, Y represents carbon atoms, R is either the same or different. • Hydrogen atom, • Alkyl alkyl groups containing 1 to 12 carbon atoms • Cycloalkyl groups containing 5 to 8 carbon atoms • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group This represents the above, however, the group R may be unsubstituted, or substituted with an alkyl group containing 1 to 12 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, a cycloalkyl group containing 5 to 8 carbon atoms, an aryl group containing 6 to 18 carbon atoms, or a heteroatom such as oxygen, sulfur, or nitrogen.

[0042] 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.

[0043] 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, and 1,4-butanediol.

[0044] According to one embodiment, initiator I is an alcohol having a pKa of 10 to 16, preferably 12 to 16, and more preferably 14 to 16.

[0045] According to one embodiment, initiator I is an alcohol selected from the following: a long-chain alkyl alcohol such as 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), undecanol (CAS 112-42-5), or dodecanol (CAS 27342-88-7).

[0046] Initiator I is preferably benzyl alcohol (CAS 100-51-6).

[0047] According to another embodiment of the present invention, initiator I is water.

[0048] 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, more preferably 0 to 5, and even more preferably 0 to 2.

[0049] In one embodiment, the method of the present invention is characterized in that the molar ratio of initiator I to the introduced organopolysiloxane O is 0.005% to 10%, preferably 0.01% to 5%, more preferably 0.05% to 2.5%, and even more preferably 0.1% to 1%.

[0050] According to one embodiment, the method of the present invention uses an initiator I represented by the following formula (IX): [ka] Formula IX During the ceremony, R is either the same or different. • Alkyl alkyl groups containing 1 to 12 carbon atoms • Cycloalkyl groups containing 5 to 8 carbon atoms • Alkenyl groups containing 2 to 12 carbon atoms • Benzyl group or phenyl group This represents the above, however, the group R may be unsubstituted, or substituted with an alkyl group containing 1 to 12 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, a cycloalkyl group containing 5 to 8 carbon atoms, an aryl group containing 6 to 18 carbon atoms, or a heteroatom such as oxygen, sulfur, or nitrogen.

[0051] The method of the present invention preferably uses initiator I selected from trimethylsilanol (CAS 1066-40-6) or triethylsilanol (CAS 597-52-4).

[0052] In one embodiment of the present invention, the polymerization reaction of at least one organopolysiloxane O further comprises at least one chain-blocking agent C.

[0053] Therefore, according to one embodiment of the present invention, the method uses a catalyst system AI and a chain terminator C.

[0054] More specifically, according to one embodiment of the present invention, the method uses a catalyst A and a chain terminator C.

[0055] Alternatively, according to one embodiment of the present invention, the method uses a catalyst A, an initiator I, and a chain terminator C. According to one embodiment of the present invention, the chain terminator C is represented by the following formula (X):

Chemical formula

[0056] Particularly preferably, the chain terminator C of the present invention is represented by the formula (X), in which R 1 are the same or different and represent CH3; R 2 are the same or different and ·an alkenyl group containing 2 to 6 carbon atoms, preferably containing vinyl, • A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. • C6-C may be substituted. 18 Aryl group, or • Hydrogen atom This represents, q is an integer between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 5.

[0057] Other chain-blocking agents having a siloxane functional group according to the present invention are described on page 264 of the document "Chemistry and Technology of Silicones," published by Academie Press in 1968. Chain-blocking agent C may be present in a solvent, which is particularly advantageous for dissolution in the reaction mixture. The solvent may be a nonpolar solvent, such as an organoalkane or 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.

[0058] In one embodiment, the method of the present invention is characterized in that the molar ratio of chain-breaking agent C to catalyst A is 0 to 30, preferably 0 to 20, and more preferably 0 to 10. According to one embodiment of the present invention, the linear organopolysiloxane OL may be a compound of the following formula (XI): [ka] Formula XI During the ceremony, R is either 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 a phenyl group. This represents, R 1 They are the same or different. • Alkyl alkyl groups containing 1 to 5 carbon atoms • Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, • Hydroxyl group (OH), • Hydrogen atom, ·C6-C 18 Aryl group, preferably phenyl This represents, R 2 They are the same or different. • 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, which may be substituted with at least one heteroatom O, N, S or a halide such as a fluorine atom, for example 1 to 10 fluorine atoms, for example (C1-C5)alkyl-CF3 (where the alkyl is linear or branched). • C5-C may be substituted. 10 Cycloalkyl groups, • C6-C may be substituted. 18 Aryl group, • Hydrogen atom, or Base (OR 3 ) This represents, where R 3 This includes 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, and C6-C 18 Represents an alkylaryl group such as an aryl group or a benzyl group; 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, 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 preferred embodiment of the present invention, the linear organopolysiloxane OL is a compound of formula (XI), where, R is the same or different, representing CH3 or phenyl, preferably CH3; R 1 They are the same or different. • Alkyl alkyl groups containing 1 to 5 carbon atoms • Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, ·C6-C 18 Aryl group, preferably phenyl, • Hydrogen atom It represents; R 2 They are the same or different. • Alkyl alkyl groups containing 1 to 6 carbon atoms • Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, • Hydroxyl group (OH), ·C6-C 18 Aryl group, • Hydrogen atom, Base (OR 3 ) This represents, where R 3 This represents an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or a benzyl group; 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, 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.

[0060] According to one particularly preferred embodiment of the present invention, the linear organopolysiloxane OL of the present invention is a compound of formula (XI), wherein, R is the same or different, representing CH3 or phenyl, preferably CH3; R 1 These are identical or different, representing CH3, phenyl, or vinyl; R 2They are the same or different. • 2 to 6 carbon atoms, preferably an alkenyl group containing vinyl, • Hydroxyl group (OH), • A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. • C6-C may be substituted. 18 Aryl group, or • Hydrogen atom, ·Base (OR 3 ) This represents, where R 3 This represents an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or a benzyl group; q is 0; n2 represents an integer between 10 and 10000, preferably between 10 and 5000, preferably between 10 and 1000, 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.

[0061] According to one particularly preferred embodiment of the present invention, the linear organopolysiloxane OL of the present invention is a compound of formula (XII), wherein, R is the same or different, representing CH3 or phenyl, preferably CH3; R 1 These are identical or different, representing CH3, phenyl, or vinyl; base R 2 They are the same or different. • A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. • Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, • Hydroxyl group (OH), ·Base (OR 3 ) This represents, where R 3 This represents an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or a benzyl group; q is 0; n2 represents an integer between 10 and 5000, preferably between 10 and 1000, 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.

[0062] 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.

[0063] 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 the degree of polymerization of the organopolysiloxane O introduced into the reaction mixture.

[0064] For the purposes of this invention, the mass-average molar mass and number-average molar mass (M) of various linear organopolysiloxanes OL are required. w and M n (Abbreviated as ) can be determined by size exclusion chromatography (SEC) in the presence of a polystyrene standard in a solvent such as toluene at 35°C.

[0065] 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 n The characteristic feature is that the concentration is 500 to 1,000,000 g / mol, preferably 500 to 500,000 g / mol, more preferably 500 to 1,000,000 g / mol, and even more preferably 500 to 50,000 g / mol.

[0066] 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 1,000,000 mPa·s at 25°C.

[0067] In this application, the mass percentage or weight percentage of cyclic organopolysiloxane (such as D4) in the product obtained by 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 method of the present invention can be measured by a chromatogram obtained from analysis by size exclusion chromatography (SEC).

[0068] In the following, the term "products resulting from the reaction" refers to the total amount of linear organopolysiloxane OL and organopolysiloxane OC at the end of the process of the present invention.

[0069] In one embodiment, the method according to the present invention is characterized in that the content of cyclic organopolysiloxane OC is less than 4%, preferably 2% or less, more preferably 1% or less, and even more preferably 0.5% or less, based on the total mass of the product obtained from the reaction.

[0070] In one embodiment, the method according to the present invention is characterized in that the content of octamethylcyclotetrasiloxane (D4) is 4% or less, preferably 2% or less, more preferably 1% or less, and even more preferably 0.5% or less, based on the total mass of the product produced from the reaction.

[0071] In one embodiment, the method according to the present invention is carried out in a nonpolar solvent. The solvent may be an organic solvent, particularly an alkane, an aromatic hydrocarbon, or an alcohol such as ethanol.

[0072] The solvent is preferably selected from n-hexane, n-heptane, n-decane, n-dodecane, cyclohexane, isododecane, Exxsol D60, xylene, toluene, and mixtures thereof.

[0073] 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.

[0074] Advantageously, and preferably, the reaction is carried out at a temperature of 50°C to 250°C, preferably 70°C to 170°C, and more preferably 80°C to 150°C.

[0075] According to one embodiment, the reaction time is 1 to 72 hours, preferably 8 to 72 hours, and more preferably 18 to 72 hours. Those skilled in the art will know how to appropriately adjust these parameters depending on the properties of the reactor and the chemical species used.

[0076] Furthermore, this application relates to linear organopolysiloxane OL obtained by various embodiments of the method of the present invention described above. Furthermore, this application relates to a silicone composition containing organopolysiloxane OL obtained by various embodiments of the method of the present invention described above.

[0077] Furthermore, this application relates to a composition for carrying out the method of the present invention, and comprises the following: • At least one cyclic organopolysiloxane O, as defined above, • The catalyst system AI defined above, and optionally a chain-breaking agent C as defined above.

[0078] Furthermore, this application relates to the use of 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 maintenance products, automobiles, and energy.

[0079] Furthermore, this application relates to the use of catalyst A for carrying out polymerization reactions by ring-opening or polycondensation in the presence of (cyclic and / or linear) organopolysiloxane O. Furthermore, this application also relates to the use of catalyst system AI for carrying out polymerization reactions by ring-opening or polycondensation in the presence of (cyclic and / or linear) organopolysiloxane O. [Examples]

[0080] Organopolysiloxanes used in the examples: Cyclic organopolysiloxane O1:octamethylcyclotetrasiloxane (CAS 556-67-2) Linear organopolysiloxane O2: [ka] (n=8) Catalyst A used in the example: Catalyst A1: [ka] Catalyst A comp1 : [ka]

[0081] Initiators used in the examples: Initiator I1: Benzyl alcohol (CAS 100-51-6) Chain disruptors used in the examples: Chain disruptor C 1 : Divinyltetramethyldisiloxane (CAS 2627-95-4) Chain disruptor C 2 : Hexamethyldisiloxane (CAS 107-46-0)

[0082] In the following examples, the residual mass % of cyclic organopolysiloxane OC and the mass % 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 This is determined by the same-size exclusion chromatography (SEC) method.

[0083] In the following examples, the mass percentage of residual cyclic organopolysiloxane is the mass percentage of cyclic organopolysiloxane at the end of the method carried out according to the present invention.

[0084] Example 1: A 1 Synthesis of catalysts of the present invention, such as: In the first step, iodomethane (3.7 mL, 59.3 mmol, 1.5 eq) and 1,2-dimethylimidazole (3.8 g, 39.5 mmol, 1 eq) were added to a solvent such as acetonitrile at ambient temperature and reacted to obtain precursor a, as shown in the following reaction scheme. After stirring for 1 hour, precipitated product a was obtained. x The product was recovered by filtration and washed with Et2O (2 × 10 mL). After drying under vacuum, product a x This was obtained as a white solid (8.9 g, 95%). [ka]

[0085] In the second step, product a (2 g, 8.5 mmol, 1 eq) synthesized in the previous step was added to a suspension of potassium hydride (0.67 g, 17 mmol, 2 eq) in Et2O (30 mL). The reaction mixture was placed under an argon stream and stirred at room temperature for 2 days. The resulting solution was filtered and dried under vacuum to obtain product A1 as a white solid (0.72 g, 78%). [ka]

[0086] Example 2: General protocol for carrying out the method of the present invention: The catalytic AI system is formed by combining catalyst A (e.g., A1) (1 eq, 0.025 mmol) with 0 to n equivalents of initiator I (e.g., I1). The following tables show various molar ratios I / A. The newly formed catalyst system AI is mixed with a solution containing organopolysiloxane O1 or O2 (5.07 mmol). The content of catalyst A is 0.5 mol% relative to organopolysiloxane O. A chain-breaking agent such as C1 or C2 is added to the reaction mixture as appropriate. The reaction mixture is then heated at 80°C for the time specified in each example of the present invention.

[0087] Example 3: 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 adopted. In this example, organopolysiloxane O1 (CAS 556-67-2) was used. The initiator was I1, and the molar ratio I / A was 1. The reaction mixture was heated at 80°C for 48 hours for tests 1 and 2, and for 72 hours for test 3.

[0088] The following table shows the properties of the various catalysts used and the product OL obtained by the method of the present invention. [Table 1]

[0089] In the presence of catalysts described according to the method of the present invention, such as A1, the residual level of cyclic organopolysiloxane is compared to comparative catalyst A comp1 Note that a lower product OL is obtained than that of the previous product.

[0090] Example 4: Implementation of the method of the present invention with different I / A ratios: In this example, the general protocol of Example 2 was adopted. In this example, organopolysiloxane O1 (CAS 556-67-2), initiator I1, and catalyst A1 were used. The various tests described in the following examples were carried out at 80°C for 72 hours. The following table shows the properties of the various initiators I used and the product OL obtained by the method of the present invention. [Table 2]

[0091] The method of the present invention is versatile, and as shown in the table above, satisfactory results can be observed at various I / A ratios.

[0092] Example 5: Implementation of the present invention without using an initiator: In this example, the general protocol of Example 2 was adopted. In this example, organopolysiloxane O1 (CAS 556-67-2), catalyst A1, and chain disruptor C1 were used. In these tests, the reaction mixture was heated at a temperature of 80°C for 72 hours. The following table shows the molar ratio of the chain-breaking agent used to the molar amount of catalyst A used, and the properties of the product OL obtained by the method of the present invention.

[0093] [Table 3]

[0094] Even without using an initiator, the method of the present invention produces a linear organopolysiloxane OL with a very low mass percentage of residual cyclic organopolysiloxane OC.

[0095] These tests were repeated under the same operating conditions using the chain-breaking agent C2. The following table shows the molar ratio of the chain-breaking agent C2 used to the molar amount of catalyst A used, and the properties of the product OL obtained by the method of the present invention.

[0096] [Table 4]

[0097] Under these operating conditions, the method of the present invention produces a linear organopolysiloxane OL with a very low mass percentage of residual cyclic organopolysiloxane OC. Alternatively, this method can be carried out at 150°C for 24 hours, as shown in the table below. This table shows the molar ratio of the chain-breaking agent C1 used to the molar amount of catalyst A used, and the properties of the product OL obtained by the method of the present invention.

[0098] [Table 5]

[0099] The results obtained in the table above confirm the versatility of the method of the present invention.

[0100] Example 6: Stability of the catalyst in ethanol solution: Catalyst A1 (80 mg) was placed in an ethanol solution (1 mL) and left in the air for one month. Before use, the ethanol was removed under vacuum. After this step, the general protocol of Example 2 was repeated at 80°C for 62 hours in the presence of O1.

[0101] The following table shows the molar ratio of the chain-breaking agent C1 used to the molar amount of catalyst A used, and the properties of the product OL obtained by the method of the present invention.

[0102] [Table 6]

[0103] The results in the table above confirm the stability of the catalyst in ethanol solution for one month. These satisfactory results confirm the robustness of the catalyst system used in the present invention.

[0104] Example 7: Polycondensation reaction: Organopolysiloxane O without the use of an initiator 2 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 O2 (2.73 mmol). As appropriate, add chain-breaking agents such as C1 to the reaction mixture, as shown in the table below. The reaction mixture was heated at 80°C for 48 hours. The following table shows the molar ratio of the chain-breaking agent C1 used to the molar amount of catalyst A used, and the properties of the product OL obtained by the method of the present invention.

[0105] [Table 7]

[0106] As shown in the table above, this embodiment demonstrates that the method of the present invention yields very satisfactory results for polycondensation reactions.

Claims

1. At least one catalyst A of the following formula (I): 【Chemistry 1】 (In the formula, group R 1 They are the same or different. Hydrogen atom, - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. - Alkenyl groups containing 2 to 6 carbon atoms, ・Cycloalkyl groups containing 5 to 8 carbon atoms, Benzyl group or phenyl group This represents, group R 2 They are the same or different. Hydrogen atom, - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. - Alkenyl groups containing 2 to 12 carbon atoms, Benzyl group or phenyl group This represents, group R 3 They are the same or different. Hydrogen atom, - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. - Alkenyl groups containing 2 to 12 carbon atoms, Benzyl group or phenyl group This represents, Alternatively, two bases R 3 These atoms, along with the atoms to which they are bonded, form a cyclic hydrocarbon group of 5 to 8 carbon atoms, such as a cycloalkyl or phenyl group. and optionally at least one initiator I A method for producing a linear organopolysiloxane OL by polymerization of at least one organopolysiloxane O in the presence of a catalyst system AI containing [a specific component].

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

3. The method according to claim 1 or 2, wherein the catalyst A is represented by the following formula (VI): 【Chemistry 2】 In the formula, the group R 1 They are the same or different. Hydrogen atom, - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. - Alkenyl groups containing 2 to 6 carbon atoms, Benzyl group or phenyl group This represents, group R 2 They are the same or different. - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. - Alkenyl groups containing 2 to 12 carbon atoms, Benzyl group or phenyl group It represents.

4. The method 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%, more preferably 0.05% to 1%, and even more preferably 0.1% to 0.5%.

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

6. The method according to any one of claims 1 to 5, wherein the molar ratio of initiator I to catalyst A is 0 to 20, preferably 0 to 10, more preferably 0 to 5, and even more preferably 0 to 2.

7. The polymerization reaction of at least one organopolysiloxane O is as follows (X): 【Chemistry 4】 Formula X This includes adding at least one chain-blocking agent C represented by the formula, where, R 1 is the same or different, CH 3 or phenyl, preferably CH 3 represents; R 2 They are the same or different. ・Alkenyl groups 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, and a halide such as at least one heteroatom O, N, S or fluorine atom, for example 1 to 10 fluorine atoms, for example (C 1 -C 5 ) Alkyl-CF 3 (The alkyl group may be linear or branched.) - C may be substituted. 5 -C 10 Cycloalkyl groups, - C may be substituted. 6 -C 18 Aryl group, or Hydrogen atom It represents; q is an integer from 1 to 50, preferably from 1 to 20, and more preferably from 1 to 10.

8. The method according to any one of claims 1 to 7, wherein the molar ratio of the chain-breaking agent C to the catalyst A is 0 to 30, preferably 0 to 20, and more preferably 0 to 10.

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

Images