Ring-opening polymerization

Abstract

The present invention provides a method for preparing linear organopolysiloxane OL by a ring-opening polymerization reaction from cyclic organopolysiloxane OC using a basic catalyst B. More specifically, the method according to the present invention makes it possible to obtain linear organopolysiloxane OL with a very low content of cyclic compounds and controlled molar mass. The present invention also relates to composition S1 used in relation to the method of the present invention.

Description

Technical Field

[0001] The present invention relates to a method for preparing a linear organopolysiloxane OL by a ring-opening polymerization reaction in the presence of a cyclic organopolysiloxane OC, a basic catalyst B, and a chain terminator C. More specifically, the method of the present invention provides a linear organopolysiloxane OL with a controlled molar mass and a very low residual content of cyclic organopolysiloxane.

Background Art

[0002] A major challenge for the silicone industry in the coming years is to industrially synthesize organopolysiloxanes with a very low or zero content of residual cyclic compounds.

[0003] To date, the industrial synthesis of organopolysiloxanes by polycondensation or ring-opening polymerization has led to the formation of cyclic organopolysiloxanes, such as octamethyltetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), etc., or other unwanted cyclic organopolysiloxanes. In conventional industrial processes, the content of this unwanted product can reach 10% - 15% of the total mass of the linear organopolysiloxane obtained during synthesis, which corresponds to the thermodynamic equilibrium. Conventionally, this high content of cyclic products requires the implementation of processes that consume large amounts of energy, such as high-temperature and / or vacuum devolatilization steps, to separate these by-products from the obtained linear organopolysiloxane. At the same time, eliminating or at least restricting these processes while improving production efficiency makes it possible to reduce carbon dioxide emissions and thus obtain more environmentally friendly silicone products.

[0004] Therefore, due to economic and energy efficiency reasons, there is a need to develop new solutions to remove or at least limit these costly and time-consuming separation processes.

[0005] Furthermore, cyclic silicones or organopolysiloxanes, such as octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), are subject to and will continue to be subject to restrictions on their use. In addition to the fact that these cyclic compounds pose environmental risks due to their non-biodegradability, they are also suspected of being endocrine disruptors and potential carcinogens. Accordingly, European regulations in 2018 limited the content of D4 and D5 to 0.1% by mass in rinse-off cosmetics. This regulation will soon be introduced not only to other cosmetics but also to other silicone applications. For example, in the electronics field, regulations tend to limit the content of cyclic organopolysiloxanes to less than 100 ppm.

[0006] As a result, there is a need to develop a process that can provide silicone products that do not contain cyclic silicones or have at least a low cyclic silicone content. In particular, we are interested in providing a ring-opening polymerizable composition S that enables the use of such a process. We are also interested in enabling reliable control of the molar mass of the formed product. This possibility enhances the prospects for the use and application of such polymers obtained.

[0007] In the prior art, patent application US2012 / 142956A1 teaches a method for preparing linear organopolysiloxane OL in the presence of a quaternary amine, such as tetramethylammonium hydroxide or choline. Firstly, the examples in patent application US2012 / 142956 disclose that satisfactory yields of linear organopolysiloxane OL cannot be obtained in the presence of choline and its derivatives. Secondly, with regard to testing using tetramethylammonium hydroxide, it is necessary to find alternatives to this catalyst and its derivatives, which are toxic to humans and the environment.

[0008] More recently, patent application WO2018 / 051792 disclosed a method for preparing linear organopolysiloxane OL in the presence of a guanidine derivative as a basic catalyst. However, unlike the catalyst of the present invention, most guanidine derivatives, unlike commercially available choline, need to be synthesized. Furthermore, the method disclosed in patent application WO2018 / 051792 requires the presence of chlorosilane, which is known to be a highly toxic compound.

[0009] The development of this alternative technology will enable the production of more environmentally friendly silicones.

[0010] Furthermore, the present invention solves numerous objectives described below, as well as objectives that become clear from reading the following description of the present invention. [Overview of the project]

[0011] Therefore, one objective of this patent application is to propose a method for preparing linear organopolysiloxane OL by a ring-opening polymerization reaction of cyclic organopolysiloxane OC, wherein the molar mass of the final product can be controlled and the yield of linear organopolysiloxane exceeds 95%, preferably exceeds 98%.

[0012] Another objective of this patent application is to enable control over the properties of the chemical functional groups of the resulting linear organopolysiloxane OL.

[0013] Another object of this patent application is to provide a ring-opening polymerizable composition S that enables this method to be carried out.

[0014] Another objective of this patent application is to propose a low-toxicity, ring-opening polymerizable composition S that is suitable for industrialization of the method.

[0015] Another objective of this patent application is to propose a method that is satisfactory from an industrial standpoint and falls within the realm of chemistry that is considered environmentally friendly.

[0016] Further objectives will become clear from reading the following description of the present invention.

[0017] Surprisingly, the applicant has developed a ring-opening polymerization-capable composition S that meets these expectations. Therefore, the present invention relates to a method for preparing linear organopolysiloxane OL by a ring-opening polymerization reaction, a) A step using a ring-opening polymerizable composition S, wherein the ring-opening polymerizable composition S is i) At least one cyclic organopolysiloxane OC containing three siloxane units, ii) Basic catalyst B of at least one formula (I): [ka] (In the formula, - R1 may be the same or different, and represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. - R2 represents a hydrogen atom or the group -C(=O)-R3, where R3 represents an alkyl group containing 1 to 12 carbon atoms. - X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number from 1 to 6. iii) At least one chain-stopping agent C, Processes including b) Optionally, the next step is to add the same or different chain-stopping agent C or acid A as in step a) to the ring-opening polymerizable composition S. c) Steps to obtain linear organopolysiloxane OL, This includes methods.

[0018] In this case, the basic catalyst B and chain arrestor C allow for control of the molar mass of the final product during the method of the present invention, while simultaneously altering the properties of the terminal chemical functional groups. [Modes for carrying out the invention]

[0019] Silicone, also known as organopolysiloxane, is a polymer material containing alternating atoms of silicon and oxygen, with various organic groups bonded to the silicon atoms.

[0020] In relation to the present invention, the terms "silicone," "silicone product," "silicone polymer," or "organopolysiloxane" refer to polymers containing a siloxane (Si-O-Si) skeleton, which has alternating silicon and oxygen atoms, with various organic groups bonded to the silicon atoms. These silicone polymers can be liquid or solid, depending on their molar mass and degree of polymerization.

[0021] For the purposes of this invention, the term “reaction mixture” refers to all reactive chemical species present in the ring-opening polymerizable composition S described above. Examples include one or more catalysts B, one or more cyclic organopolysiloxanes OC, and a chain arrestor (C).

[0022] All viscosities referred to in this disclosure correspond to the dynamic viscosity value at 25°C known as the “Newtonian,” that is, the dynamic viscosity measured in a self-known manner using a Brookfield viscometer at a shear rate gradient low enough that the measured viscosity does not depend on the rate gradient.

[0023] For the purposes of this invention, the cyclic organopolysiloxane OC is represented by the following formula (II): [ka] In the formula, R may be the same or different, and represents 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 number from 1 to 2.

[0024] Preferably, the cyclic organopolysiloxane OC is represented by the following formula (III): [ka] In the formula, R may be the same or different, and represents 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.

[0025] In particular, commercially available cyclic organopolysiloxanes OCs can be cited, including 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), and 2,2,4-trimethyl-4,6,6-triphenyl-1,3,5,2,4,6-trioxatricilinane (CAS 546-45-2), 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane (CAS 546-45-2), 2,4,6-trimethylcyclotrisiloxane (CAS 13269-39-1), 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 Examples include 2554-06-5), 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (CAS 77-63-4), and octaphenylcyclotetrasiloxane (CAS 546-56-5).

[0026] Advantageously, the cyclic organopolysiloxane OC is hexamethylcyclotrisiloxane (CAS 541-05-9).

[0027] According to one embodiment of the present invention, the method of the present invention uses a combination of at least two cyclic organopolysiloxanes OC containing three siloxane units, for example, hexamethylcyclotrisiloxane (CAS 541-05-9) and 2,4,6-triethenyl-2,4,6-trimethylcyclotrisiloxane (CAS 3901-77-7).

[0028] The introduction of these reagents into the reaction mixture can be carried out simultaneously or sequentially. For example, hexamethylcyclotrisiloxane may be added first, followed by 2,4,6-triethenyl-2,4,6-trimethylcyclotrisiloxane, or vice versa. This procedure is suitable for various cyclic organopolysiloxanes (OCs) containing three siloxane units.

[0029] In the context of this patent application, basic catalyst B is represented by formula (IV): [ka] During the ceremony, R1 may be the same or different, and represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. R2 represents a hydrogen atom or the group -C(=O)-R3, where R3 represents an alkyl group containing 1 to 12 carbon atoms. X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number between 1 and 6.

[0030] Examples of carboxylate anions that can be specifically mentioned include salicylate, oxalate, malonate, glyconate, maleate, and citrate.

[0031] Regarding carbonate anions, bicarbonates and carbonates can be cited.

[0032] For the purposes of this invention, the term "siloxanolate" means an anionic compound of siloxanolate of the following formula (V): [ka] During the ceremony, R 1 They may be the same or they may be 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, - C6~C 18 Aryl group, - Hydroxyl group, or This represents, R 2 They may be the same or they may be 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. This represents, q is an integer between 1 and 20, preferably between 1 and 10, more preferably between 1 and 5, provided that at least one base R 2 This is a hydroxyl group (OH).

[0033] Preferably, the term "siloxanolate" means an anionic compound of formula (V), where, R 1 They may be the same or they may be 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, - A cycloalkyl group containing 5 to 10 carbon atoms, which may be substituted with heteroatoms O, N, S or halides. - C6~C 18 Aryl group, - Hydroxyl group, or This represents, R 2 They are identical, - Hydroxyl group (OH), This represents, q is an integer between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 5.

[0034] In relation to the present invention, the term "silanolate" refers to an anion associated with the compound trimethylsilanol (CAS 1066-40-6) or triethylsilanol (CAS 597-52-4).

[0035] In addition, we can specifically mention the anions associated with silanols represented by formula (VI): [ka] 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 or phenyl group, This represents, The aforementioned group R may be substituted with an alkyl or alkenyl chain of 2 to 6 carbon atoms, a cycloalkyl group, an aryl group, or a heteroatom, such as oxygen, sulfur, or nitrogen.

[0036] Preferably, those skilled in the art can use the compound trimethylsilanol (CAS 1066-40-6) or triethylsilanol (CAS 597-52-4).

[0037] Preferably, the basic catalyst B is represented by formula (VII): [ka] During the ceremony, R1 may be the same or different, and represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number between 1 and 6.

[0038] Preferentially, basic catalyst B is represented by the above formula (VII), where, R1 represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. X represents an anion selected from the group including hydroxyl or silanolate, n is a natural number between 1 and 6.

[0039] According to a particular embodiment of the present invention, the basic catalyst B is represented by the above formula (VII), where, R1 represents an alkyl chain containing one or two carbon atoms. X represents trimethylsilanolate or triethylsilanolate anion. n is equal to 1.

[0040] In particular, basic catalyst B can be selected from choline hydroxide (CAS 123-41-1), choline silanolate, choline lactate (CAS 99150-55-7), triethylcholine hydroxide (CAS 3651-90-9), (2-hydroxyethyl)tripropylammonium hydroxide (CAS 96311-53-4), (2-hydroxyethyl)tributylammonium hydroxide, triethylcholine silanolate, choline bicarbonate (CAS 78-73-9), or choline salicylate (CAS 2016-36-6).

[0041] The molar amount of basic catalyst B used in the method of the present invention is 150 ppm to 4000 ppm, preferably 250 to 2500 ppm, and more preferably 250 ppm to 1500 ppm relative to the molar amount of the reaction mixture.

[0042] According to one embodiment of the present invention, catalyst B is dissolved in a solvent selected from alcohol and water.

[0043] According to one embodiment of the present invention, the alcohol is selected from 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), allyl alcohol (CAS 107-18-6), benzyl alcohol (CAS 100-51-6), 3-buten-1-ol (CAS 627-27-0), long-chain alkyl alcohols, such as undecanol (CAS 112-42-5) or dodecanol (CAS 27342-88-7).

[0044] Preferably, catalyst B is soluble in methanol or water.

[0045] For the purposes of this invention, the chain arresting agent C is selected from H2O, alcohols and their derivatives, or silanols and their derivatives.

[0046] In the context of this patent application, the chain arrester C is selected from H2O or a compound of formula (VIII): [ka] During the ceremony, Y represents a carbon or silicon atom. 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 including 1 to 6 unsaturated carbon-carbon bonds, - an aryl group containing 6 to 18 carbon atoms, preferably phenyl, - benzyl group - a group of formula R 1 c SiO (4-c) / 2 a siloxyl group containing at least 5 units, preferably at least 10 units, of is represented by, where, R 1 may be the same or different, and represents an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, an aryl group containing 6 to 10 carbon atoms, preferably phenyl, c = 0, 1 or 2, and, the aforementioned group R may be unsubstituted or may be substituted by an alkyl chain 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, etc.

[0047] In the context of this patent application, the chain terminator C is selected from H2O or a compound of formula (VIII): Y represents a carbon atom or a silicon atom, R is the same or different, - an alkyl group containing 1 to 12 carbon atoms, - a cycloalkyl group containing 5 to 8 carbon atoms, - an alkenyl group containing 2 to 12 carbon atoms, - an aryl group containing 6 to 18 carbon atoms, preferably phenyl, - benzyl group - a group of formula R 1 c SiO (4-c) / 2 a siloxyl group containing at least 5 units, preferably at least 10 units, of is represented by, where, R 1 These may be the same or different, and represent an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, an aryl group containing 6 to 10 carbon atoms, preferably phenyl, where c=0, 1, or 2.

[0048] In one embodiment of the present invention, the chain arresting agent C is an alcohol or silanol having a pKa of 10 to 16, preferably 12 to 16, and more preferably 14 to 16.

[0049] According to one embodiment of the present invention, the chain arresting agent C is H2O.

[0050] According to one embodiment of the present invention, the chain arrester C is a compound of formula (IX): [ka] During the ceremony, Y represents carbon atoms, 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 or phenyl group This represents, The aforementioned group R may be unsubstituted, or it may be substituted with an alkyl chain 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] According to one embodiment of the present invention, the chain inhibitor C is an alcohol selected from primary alcohols or secondary alcohols. Preferably, the chain inhibitor C is an alcohol selected from primary alcohols.

[0052] According to one embodiment of the present invention, the chain arrester C is an alcohol selected from saturated or unsaturated polyols containing 2 to 6 hydroxyl groups. Examples that can be mentioned include the following polyols: glycerol, pentaerythritol, sorbitol, or 1,4-butanediol.

[0053] According to one embodiment of the present invention, the chain-stopping agent C is an alcohol having a pKa of 10 to 16, preferably 12 to 16, and more preferably 14 to 16.

[0054] According to one embodiment of the present invention, the chain arresting agent C is an alcohol selected from 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), allyl alcohol (CAS 107-18-6), benzyl alcohol (CAS 100-51-6), 3-buten-1-ol (CAS 627-27-0), long-chain alkyl alcohols, such as undecanol (CAS 112-42-5) or dodecanol (CAS 27342-88-7).

[0055] Preferably, the chain inhibitor C is benzyl alcohol (CAS 100-51-6), butanol (CAS 71-36-3), or 3-buten-1-ol (CAS 627-27-0).

[0056] Alternatively, in the context of this patent application, the chain termination agent C contains at least one silanol-terminated functional group.

[0057] Preferably, the chain arrester C containing a silanol-terminated functional group is trimethylsilanol (CAS 1066-40-6), triethylsilanol (CAS 597-52-4), or a mixture thereof.

[0058] According to another embodiment of the present invention, the chain arrester C contains at least one siloxy unit.

[0059] According to another embodiment of the present invention, the chain arrester C containing a terminal silanol chemical functional group contains at least two siloxy units. Alternatively, the chain arrester C containing a terminal silanol functional group contains at least three siloxy units.

[0060] The term "silanol-terminated functional group" refers to a chemical functional group located at the end of a chain formed by a chemical bond between a silicon atom and a hydroxyl group.

[0061] According to one embodiment of the present invention, the chain arresting agent C is represented by formula (X): [ka] During the ceremony, R 1 They may be the same or they may be different. - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be substituted with heteroatoms O, N, S or halides. - Alkenyl groups containing 2 to 6 carbon atoms, - A cycloalkyl group containing 5 to 10 carbon atoms, which may be substituted with heteroatoms O, N, S or halides. - C6~C 18 Aryl group, or - Hydroxyl group, This represents, R 2 They may be the same or they may be different. - Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - Hydroxyl group (OH), or - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, which may be substituted by at least one heteroatom O, N, S or halide, such as a fluorine atom, for example, 1 to 10 fluorine atoms, for example, (C1 to C5)alkyl-CF3 (where the alkyl is linear or branched), This represents, q is an integer between 0 and 20, preferably between 0 and 10, more preferably between 0 and 5, provided that at least one base R 2 This is a hydroxyl group (OH).

[0062] According to one embodiment of the present invention, the chain-stopping agent C is represented by the above formula (X), where, R 1 They may be the same or they may be different. - A linear or branched alkyl group containing 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, which may be substituted with heteroatoms O, N, S or halides. - Alkenyl groups containing 2 to 6 carbon atoms, - A cycloalkyl group containing 5 to 10 carbon atoms, which may be substituted with heteroatoms O, N, S or halides. - C6~C 18 Aryl group, or - Hydroxyl group, This represents, R 2 They are identical, - Hydroxyl group (OH), This represents, q is an integer between 0 and 20, preferably between 0 and 10, and more preferably between 0 and 5.

[0063] In another embodiment, the chain-stopping agent C is represented by the above formula (X), where, R 1 These are identical and represent CH3. R 2 They may be the same or they may be different. - Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - Hydroxyl group (OH), - A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, - C6~C may be substituted. 18 Aryl group, This represents, q is an integer between 0 and 20, preferably between 0 and 10, more preferably between 0 and 5, provided that at least one base R 2 This is a hydroxyl group (OH).

[0064] In another embodiment, the chain-stopping agent C is represented by the above formula (X), where, R 1 These are identical and represent CH3. R 2 They are identical, - Hydroxyl group (OH), This represents, q is an integer between 0 and 20, preferably between 0 and 10, and more preferably between 0 and 5.

[0065] The chain arrester C may be present in the solvent. This is particularly advantageous for dissolving it 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 pentane, n-hexane, n-heptane, n-decane, n-dodecane, isododecane, EXXSOL D60, xylene, toluene, and mixtures thereof.

[0066] Alternatively, the chain arrester C may be present in a polar solvent, such as THF, Me-THF, or CH2Cl2.

[0067] These chain arresters enable the functionalization of linear organopolysiloxanes OL during polymerization. Therefore, for example, linear organopolysiloxanes OL having the same or different terminal chemical functional groups can be obtained.

[0068] According to one embodiment, the method of the present invention is characterized in that, in step a) of the above-described method, the molar ratio of the chain termination agent C to the basic catalyst B used is 0.01 to 600, preferably 0.8 to 300, more preferably 1.5 to 300, more preferably 4 to 200, and more preferably 8 to 100.

[0069] According to one embodiment, the method of the present invention is characterized in that, in step a), the molar ratio of cyclic organopolysiloxane OC to chain arrester C used is 1 to 20000, preferably 2 to 5000, preferredly 2 to 1400, preferredly 4 to 700, more preferably 4 to 300, and still preferredly 10 to 150.

[0070] According to one embodiment of the present invention, the linear organopolysiloxane OL is a compound of formula (XI): [ka] During the ceremony, R may be the same or may be different. - Alkyl groups containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl - An aryl group containing 6 to 10 carbon atoms, preferably phenyl, This represents, R 1 They may be the same or they may be different. - Alkyl alkyl groups containing 1 to 5 carbon atoms, - Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - Hydroxyl group (OH), or - C6~C 18 Aryl group, preferably phenyl, This represents, R 2 They may be the same or they may be 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 by at least one heteroatom O, N, S or halide, such as a fluorine atom, for example, 1 to 10 fluorine atoms, for example, (C1 to 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, or Alternatively, base (O-R3) This represents, where R3 is, 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 OCH3 or OC2H5, alkenyl groups containing 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, C6-C 18 Aryl or alkylaryl groups, for example, benzyl groups, This represents, 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 25000, preferably between 10 and 5000, preferably between 10 and 1500, preferably between 50 and 1000, and more preferably between 100 and 500. m2 represents an integer between 0 and 100, preferably between 0 and 50, and more preferably between 0 and 30, and preferably m2 = 0.

[0071] 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 They may be the same or they may be 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, This represents, R 2 They may be the same or they may be 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, - Base (OR 3 ) This represents, where R 3 teeth, Alkyl groups containing 1 to 10 carbon atoms, alkenyl groups containing 2 to 10 carbon atoms, or benzyl groups, This represents, 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 1500, preferably between 10 and 1000, preferably between 50 and 1000, and more preferably between 100 and 500. m2 represents an integer between 0 and 500, preferably between 0 and 100, and more preferably between 0 and 50.

[0072] 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 phenyl, preferably CH3. R 1 These may be the same or different, and represent CH3, phenyl, or vinyl. R 2 They may be the same or they may be different. - Alkenyl group containing 2 to 6 carbon atoms, preferably vinyl, - Hydroxyl group (OH), - A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. - C6~C may be substituted. 18 Aryl group, or - Group (O-R3) This represents, where R3 is, Alkyl groups containing 1 to 10 carbon atoms, alkenyl groups containing 2 to 10 carbon atoms, or benzyl groups, This represents, q is equal to 0, n2 represents an integer between 10 and 1500, preferably between 10 and 1000, preferably between 50 and 1000, and more preferably between 100 and 500. m2 represents an integer between 0 and 500, preferably between 0 and 100, and more preferably between 0 and 50.

[0073] According to one embodiment of the present invention, the linear organopolysiloxane OL of the present invention represented by the above formula (XI) is R 2 These are compounds that are identical. In other words, linear organopolysiloxane OL is homotelechelic.

[0074] For clarification, the term "homotelechelic linear organopolysiloxane OL" refers to a linear organopolysiloxane having identical terminal chemical functional groups.

[0075] Similarly, according to one embodiment of the present invention, the linear organopolysiloxane OL of the present invention represented by formula (XI) is R 2 These are different compounds. In other words, linear organopolysiloxanes OL are heterotelechelic.

[0076] For clarification, the term "hetero-telechelic linear organopolysiloxane OL" refers to a linear organopolysiloxane with different terminal chemical functional groups.

[0077] For the present invention, the mass-average molar mass and number-average molar mass (M, respectively) of different linear organopolysiloxanes OL w and M n(often abbreviated as ) can be determined by size exclusion chromatography (SEC) at 35°C in a solvent such as toluene, in the presence of a polystyrene standard.

[0078] 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 5 to 28,000, preferably 5 to 7,000, preferably 5 to 4,000, preferentially 15 to 2,000, more preferably 20 to 1,000, and still preferentially 20 to 400.

[0079] According to one embodiment of the present invention, the linear organopolysiloxane OL of the present invention has a mass-average molar mass M w The present invention is characterized in that the amount may be 500 to 2,000,000 g / mol, preferably 500 to 500,000 g / mol, preferably 500 to 300,000 g / mol, preferentially 1,000 to 150,000 g / mol, more preferably 1,000 to 100,000 g / mol, and even more preferably 5,000 to 40,000 g / mol.

[0080] 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 present invention is characterized in that the amount may be 500 to 2,000,000 g / mol, preferably 500 to 500,000 g / mol, preferably 500 to 300,000 g / mol, preferentially 1,000 to 150,000 g / mol, more preferably 1,000 to 100,000 g / mol, and even more preferably 5,000 to 40,000 g / mol.

[0081] 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 1,000 to 500,000 mPa·s at 25°C, preferentially 1,000 to 100,000 mPa·s, and even more preferentially 10,000 to 80,000 mPa·s at 25°C.

[0082] In the context of this patent application, the mass percentage or weight percentage of 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 size exclusion chromatography (SEC) analysis.

[0083] Hereinafter, the total of linear organopolysiloxane OL and cyclic organopolysiloxane OC at the end of the method of the present invention will be referred to as the reaction product.

[0084] 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 preferentially 0.5% or less, based on the total mass of the reaction product.

[0085] 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 preferentially 0.5% or less, based on the total mass of the reaction product.

[0086] Preferably, the method of the present invention is carried out without using any solvent other than the amount necessary to solubilize and / or dissolve catalyst B in the reaction medium.

[0087] This embodiment is particularly advantageous because it allows for satisfactory results when carrying out the method of the present invention while eliminating the need for solvent use and the subsequent treatment or recycling of the solvent.

[0088] However, in another embodiment, the method of the present invention is carried out in a nonpolar solvent. The solvent may be an organic solvent, such as an alkane or aromatic hydrocarbon.

[0089] Preferably, the solvent is selected from n-hexane, n-heptane, n-decane, n-dodecane, isododecane, EXXSOL D60, xylene, toluene, and mixtures thereof.

[0090] Alternatively, the method of the present invention is carried out in a polar solvent. The solvent may be an organic solvent in particular, such as THF or Me-THF.

[0091] In one embodiment, the method of the present invention is characterized in that the mass ratio of cyclic organopolysiloxane OC to the mass of the solvent used is 0.5 to 50, preferably 1.5 to 15, and more preferably 3 to 10, relative to the mass of the solvent used.

[0092] Advantageously and preferably, the reaction is carried out at a temperature of 25°C to 150°C, preferably 35°C to 100°C, and more preferably 35°C to 80°C.

[0093] According to the method of the present invention, the reaction time is 1 minute to 48 hours, preferably 1 minute to 18 hours, more preferably 1 minute to 8 hours, even more preferably 1 minute to 2 hours, and even more preferably 1 minute to 1 hour.

[0094] Those skilled in the art will know how to adapt these parameters according to the properties of the reactor and species used.

[0095] Furthermore, the method defined by the present invention may subsequently include step b), which involves adding the same or a different chain-stopping agent C or acid A as in step a) to the ring-opening polymerizable composition S.

[0096] Step b) of the present invention provides adaptability for controlling the properties of terminal chemical functional groups and, furthermore, for controlling the molar mass of the product OL.

[0097] Specifically, depending on the properties of step b) of the method described above, it is possible to obtain homotelechelic or heterotelechelic linear organopolysiloxane OL.

[0098] For clarification, the term "homotelechelic linear organopolysiloxane OL" refers to a linear organopolysiloxane having identical terminal chemical functional groups.

[0099] The term "hetero-telechelic linear organopolysiloxane OL" refers to a linear organopolysiloxane with different terminal chemical functional groups.

[0100] According to one embodiment of the present invention, the method also includes step b), which is defined as subsequently adding the same chain arrester C introduced in step a) described above.

[0101] This embodiment makes it possible to obtain homotelechelic linear organopolysiloxane OL and, at the same time, to control the molar mass of the product thus obtained.

[0102] According to one embodiment of the present invention, the method also includes step b), which is defined as subsequently adding a chain arresting agent C different from the one introduced in step a) described above.

[0103] This embodiment provides control over both the molar mass and the properties of the terminal chemical functional groups of the product OL. In this way, heterotelechelic linear organopolysiloxane OL is obtained.

[0104] According to one embodiment of the present invention, the method of the present invention is characterized in that the molar ratio of the chain termination agent C to the basic catalyst B used in step b) is 1 to 200, preferably 1 to 100, and more preferably 20 to 100.

[0105] According to one embodiment of the present invention, the method of the present invention is characterized in that the molar ratio of cyclic organopolysiloxane OC to chain arrester C used in step b) is 1 to 100, preferably 5 to 80, and more preferably 10 to 50.

[0106] Alternatively, step b) of the method of the present invention includes the step of subsequently adding acid A to the ring-opening polymerizable composition S.

[0107] Step b) allows for the neutralization of the basic catalyst B, thereby stopping the polymerization reaction carried out according to the method of the present invention.

[0108] This embodiment also provides control over the properties of the terminal chemical functional groups of the product OL. In this way, heterotelechelic linear organopolysiloxane OL is obtained.

[0109] According to one embodiment of the method of the present invention, the acid A introduced in step b) of the method described above is selected from acids, such as organic acids, Lewis acids, functionalized organohalosilanes, ion exchange resins, or mineral acids.

[0110] Regarding organic acids, examples include carboxylic acid derivatives, such as propionic acid, glycolic acid, valeric acid, butyric acid, caproic acid, caprylic acid, capric acid, octanoic acid, lauric acid, myristic acid, stearic acid, palmitic acid, oleic acid, undecylenic acid, or other carboxylic acid derivatives.

[0111] Preferably, acid A is selected from the group consisting of carboxylic acid derivatives or mineral polyacids.

[0112] For the purposes of this invention, the term "mineral polyacid" refers to a compound formed from hydrogen and one or more other elements (excluding carbon), which, unlike monoacids that can release only one proton, has the ability to release multiple protons in aqueous solution. Examples that can be mentioned include phosphoric acid, sulfuric acid, and oxonium ions.

[0113] According to one embodiment of the present invention, acid A is phosphoric acid.

[0114] According to one embodiment of the present invention, acid A has a pKa of 1 to 13, preferably 1.5 to 10, and more preferably 2 to 8.

[0115] It is obvious that those skilled in the art know how to adapt the properties and amount of acid A introduced in order to satisfy the requirements of the method of the present invention.

[0116] According to a particular embodiment, step b) of the method of the present invention includes adding the same or different chain-stopping agent C and acid A as those in step a) to a ring-opening polymerizable composition S.

[0117] According to one embodiment of the method of the present invention, step b) is performed 2 to 45 minutes after step a) of the method described above, preferably 2 to 30 minutes after, and more preferably 2 to 15 minutes after step a) of the method described above.

[0118] In step c) of the method of the present invention, linear organopolysiloxane OL is obtained.

[0119] Step c) may also include one or more steps of filtration, evaporation, or distillation to produce the linear organopolysiloxane OL.

[0120] Those skilled in the art will know how to carry out these processing steps and how to adapt their operating conditions to satisfy the requirements of the method of the present invention.

[0121] Furthermore, this patent application relates to linear organopolysiloxane OL obtained by various embodiments of the method of the present invention described above. It also relates to a silicone composition comprising organopolysiloxane OL obtained by various embodiments of the method of the present invention described above.

[0122] Furthermore, this patent application relates to composition S1, i) At least one cyclic organopolysiloxane OC containing three siloxane units, ii) Basic catalyst B of at least one formula (XII): [ka] (In the formula, - R1 may be the same or different, and represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. - R2 represents a hydrogen atom or the group -C(=O)-R3, where R3 represents an alkyl group containing 1 to 12 carbon atoms. - X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number between 1 and 6. iii) At least one chain-stopping agent C, This relates to composition S1, which includes [a certain element].

[0123] According to one embodiment of the present invention, this patent application also relates to composition S1, i) At least one cyclic organopolysiloxane OC containing three siloxane units, ii) Basic catalyst B of at least one formula (XIII): [ka] (In the formula, - R1 may be the same or different, and represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. - X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number between 1 and 6. This relates to composition S1, which includes [a certain element].

[0124] Furthermore, this patent 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 cleaning products, automobiles, and energy.

[0125] Finally, this patent application relates to a basic catalyst B represented by formula (XIV): [ka] During the ceremony, - R1 may be the same or different, and represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. - X represents a siloxanolate or silanolate anion, n is a natural number between 1 and 6.

[0126] Preferably, the basic catalyst B is represented by the above formula (XIV), where, - R1 may be the same or different, and represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. - X represents a cyranolate anion, n is a natural number between 1 and 6.

[0127] Basic catalyst B is represented by the above formula (XIV), where, - R1 may be the same or different, and represents an alkyl chain containing one or two carbon atoms. - X represents trimethylsilanolate or triethylsilanolate anion, n is equal to 1. [Examples]

[0128] The cyclic organopolysiloxane used as an example : Cyclic organopolysiloxane OC1:Hexamethylcyclotrisiloxane (CAS 541-05-9) Cyclic organopolysiloxane OC2:2,4,6-triethenyl-2,4,6-trimethylcyclotrisiloxane (CAS 3901-77-7) Comparative Cyclic Organopolysiloxane OC comp1 Octamethylcyclotetrasiloxane (CAS 556-67-2)

[0129] Basic catalyst B used in the example : Catalyst B1: Commercially available choline hydroxide (CAS 123-41-1) diluted in water or methanol. [ka] Catalyst B2: Choline trimethylsilanolate (13%), synthesized in connection with the present invention and diluted in 1,3-buten-1-ol (CAS 627-27-0). [ka] Catalyst B3: Triethylcholine trimethylsilanolate (13%), synthesized in connection with the present invention and diluted in 1,3-buten-1-ol (CAS 627-27-0). [ka] Catalyst B4: Choline bicarbonate (CAS 78-73-9) [ka] Catalyst B5: Choline salicylate (CAS 2016-36-6) [ka] Catalyst B comp1 Triazabicyclodecene CAS (5807-14-7) [ka] Catalyst B comp2 KOSiMe3 (CAS 10519-96-7) (13% by mass) diluted in 1,3-buten-1-ol (CAS 627-27-0) Catalyst B comp3 :KOSiMe3(CAS 10519-96-7) Catalyst B comp4 : Corinchloride (CAS 67-48-1) [ka] Catalyst B comp5 Tetramethylammonium hydroxide (CAS 75-59-2)

[0130] Chain arresting agent used in the example : Chain Suppressant C comp1Divinyltetramethyldisiloxane (CAS 2627-95-4) Chain inhibitor C1: Benzyl alcohol (CAS 100-51-6) Chain inhibitor C2: 1,3-buten-1-ol (CAS 627-27-0) Chain arresting agent C3: Triethylsilanol (CAS 597-52-4) Chain arresting agent C4: Trimethylsilanol (CAS 1066-40-6) Chain arresting agent C5:H2O Chain arresting agent C6: n-butanol (CAS 71-36-3)

[0131] In the context of the examples described below, the residual mass percentage of cyclic organopolysiloxane OC (D3 or D4, D5, and D6) and the mass percentage of linear organopolysiloxane OL obtained by the method of the present invention are measured by size exclusion chromatography (SEC) at 35°C in a solvent such as toluene, in the presence of a polystyrene standard.

[0132] Similarly, the number-average molar mass M of various linear organopolysiloxanes OL according to the present invention n This is determined by same-size exclusion chromatography (SEC).

[0133] Example 1: Catalyst B 2 and B 3 synthesis : A 100 mL round-bottom flask is filled with a solution of corinium chloride or ethyl corinium chloride (1.2 eq, dissolved at 15% by mass in 3-buten-1-ol alcohol) and a solution of potassium silanolate (1.0 eq, dissolved at 25% by mass in 3-buten-1-ol alcohol).

[0134] The resulting turbid reaction medium is mixed by magnetic stirring at room temperature for 2 hours. After filtration, catalyst B2 or B3 is obtained as a clear solution of 13% by weight in alcohol 3-buten-1-ol.

[0135] Example 2: General protocol for polymerization method as defined by the present invention : The cyclic organopolysiloxane OC, basic catalyst B, and chain stopper C are introduced into a 500 mL reactor under an inert atmosphere (argon). The reaction mixture is maintained at 70°C for 1 hour with stirring. The sample is collected, 1 1H NMR and 29 Analysis is performed by Si NMR.

[0136] Example 3a: Screening of different basic catalysts B for carrying out the method of the present invention : In this example, the reaction mixture consists of cyclic organopolysiloxane OC1 (10 g), basic catalyst B (5-9 mg), and a chain arrestor (OC / C ratio of 15 or 21). Throughout this example, the chain arrestor C is 1,3-buten-1-ol (CAS 627-27-0) (C2). The reaction mixture is maintained at 70°C with stirring. A sample is taken, 1 1H NMR and 29 Analysis is performed by Si NMR.

[0137] The type of catalyst B, reaction time, molar amount of catalyst B, and the various products obtained upon completion of ring-opening polymerization are listed in Table 1 below.

[0138] [Table 1]

[0139] The additional tests were repeated with an OC / C molar ratio equal to 15.

[0140] [Table 2]

[0141] The molar ppm of catalyst B was calculated according to the following calculation:

[0142]

number

[0143] The table above shows that basic catalyst B of the present invention enables ring-opening polymerization, where conversion reaches its maximum within 10-30 minutes and the amount of by-products (in this case, residual cyclic compounds) is low.

[0144] In the remaining examples, these by-products are collectively referred to as residual OC. Note that the only satisfactory comparative catalyst (B) comp5 Unlike the present invention, this catalyst is toxic and biotoxic.

[0145] Example 3b: Cyclic organopolysiloxane OC comp1 Comparative example in the presence of : In the first example, the reaction mixture, in the presence of C5, is a comparative cyclic organopolysiloxane OC comp1 It consists of (octamethylcyclotetrasiloxane) and basic catalyst B1.

[0146] In this example, the reaction mixture is kept at a temperature of 70°C while being stirred for 1 hour. The sample is then collected. 1 1H NMR and 29 Analysis is performed by Si NMR.

[0147] Under the above conditions, 12% of the product OL (88% OC) comp1 ) obtain.

[0148] The second trial involved comparative cyclic organopolysiloxane OC comp1 The reaction is carried out with a reaction mixture containing (octamethylcyclotetrasiloxane), basic catalyst B2, and chain arrestor C2 (OC / C ratio of 21).

[0149] In this example, the reaction mixture is maintained at a predetermined temperature while being stirred. The sample is then collected. 1 1H NMR and 29 Analysis is performed by Si NMR.

[0150] At 70°C, with catalyst B2, the yield after 4 hours of reaction is 0%.

[0151] When the experiment is repeated with B2 and the reaction medium is heated at 135°C for 4 hours, 10% of the product OL (and 90% of OC comp1 ) is obtained.

[0152] Example 4: Effect of the type of chain arresting agent C on the method of the present invention : Using cyclic organopolysiloxane OC1 (250 g), basic catalyst B1 (950 μmol), and chain terminator C (52.7 mmol), the protocol of Example 2 is carried out. The reaction mixture is maintained at 70°C while stirring for 1 hour. The molar ratio OC1 / C is equal to 21.

[0153] The following table describes the type of chain terminator, the molar mass of the resulting linear organopolysiloxane OL, and the mass percentage of the residual cyclic organopolysiloxane OC resulting from the method of the present invention.

[0154]

Table 3

[0155] Test 1 shows that with conventional chain terminators such as C comp1 , the molar mass of the resulting product cannot be adjusted. Furthermore, it can be seen that the percentage of cyclic by-products (residual cyclic organopolysiloxane OC) is higher than that obtained under the conditions of the claimed method. Specifically, the presence of chain terminator C in Tests 2 - 5, as claimed according to the method of the present invention, provides a very low content of cyclic by-products (<1%). Furthermore, these chain terminators make it possible to adjust the molar mass of the resulting product OL and to control the nature of the terminal chemical functional groups. Therefore, the results shown in the above table indicate that the method of the present invention is versatile and can be used in the case of different chain terminators C defined according to the present invention.

[0156] Example 5: Effect of the amount of chain-stopping agent C on the method of the present invention : In the context of this example, the protocol of Example 2 is followed using cyclic organopolysiloxane OC1 (250 g), basic catalyst B1 (950 μmol), and chain arrester C4 (in the amount specified in the table below). The reaction mixture is maintained at 70°C with stirring for 1 hour.

[0157] The following table shows the molar ratio of OC1 to moles of C, the molecular weight of the resulting product OL, and the mass percentage of the residual cyclic organopolysiloxane OC produced by the method of the present invention.

[0158] [Table 4]

[0159] The amount of chain arrestor C introduced into the reaction mixture allows for control over the molecular weight of the resulting linear product OL.

[0160] Example 6: Formation of homotelechelic or heterotelechelic organopolysiloxanes In the context of this example, the protocol of Example 2 is followed using cyclic organopolysiloxane OC1 (250 g), basic catalyst B1 (950 μmol), and chain arrester C4 (52.7 mmol). The reaction mixture is maintained at 70°C with stirring for several minutes to 1 hour. Then, a sample is taken, 1 1H NMR and 29 Analysis is performed by Si NMR. In this example, the initial molar ratio OC1 / C is the same in each test and equals 21.

[0161] [Table 5]

[0162] The tests described in the table above involve different steps of the method of the present invention.

[0163] First, Test 1 comprises only step a) of the method of the present invention. This test makes it possible to obtain homotelechelic linear organopolysiloxane OL.

[0164] For the sake of certainty, the term "homo-telechelic linear organopolysiloxane OL" means a linear organopolysiloxane having the same terminal chemical functional groups.

[0165] Test 2 includes step a) of the method of the present invention and any step b) of the aforementioned method. In the context of this example, step b) is constituted by adding the same chain terminator C4 later. In Test 2, adding this chain terminator C4 later is carried out after a reaction for several minutes (8 - 15 minutes). In this way, a homo-telechelic linear organopolysiloxane OL is obtained. This embodiment (Test 2) enables controlling the molar mass of the product OL.

[0166] Finally, Test 3 includes step a) of the method of the present invention and subsequent step b) of the aforementioned method. In this test, step b) consists of adding an acid (H3PO4), which thereby Heterotelechelic linear organopolysiloxane OL makes it possible to obtain.

[0167] Thus, these different strategies detailed in the above table can affect the nature of the terminal chemical functional groups of the resulting linear organopolysiloxane OL depending on the nature of the reaction inhibition (adding a second chain terminator or adding an acid to the reaction medium). In this way, the various 1 H NMR and 29 Si NMR spectra of the linear organopolysiloxane OL obtained in Tests 1 - 3 support these results.

[0168] Example 7: Formation of short α,ω-hydroxypolydimethylsiloxane in a solvent medium : In the context of this example, the protocol of Example 2 is carried out using cyclic organopolysiloxane OC1 (250 g), basic catalyst B1 (950 μmol), and chain terminator C5 (52.7 mmol).

[0169] To obtain an α,ω-hydroxy polydimethylsiloxane oil with a low number-average molar mass M n , the chain terminator C is mixed with a solvent (80 mL) such as Me-THF, and the reaction mixture is heated to 45°C. Samples are collected and1 1H NMR and 29 Analysis is performed by Si NMR.

[0170] Under these operating conditions, a linear organopolysiloxane OL containing two hydroxyl functional groups at the chain terminus is obtained, where the number-average molar mass M is n The concentration is 6900 g / mol, and the mass percentage of residual cyclic organopolysiloxane OC is 1.2%.

[0171] This test demonstrates the applicability of the method of the present invention and the number-average molar mass M n Confirm the possibility of obtaining α,ω-hydroxypolydimethylsiloxane oil with low hydroxyl content.

[0172] Example 8: Block copolymer : Characterization of V and D triads of copolymers by NMR : 29 Microstructure analysis by Si NMR is a highly effective analytical method for determining the structure and microstructure of linear organopolysiloxanes OL. It allows for the distinction between D and V units, which are generated by the homopolymerization of introduced cyclic organopolysiloxanes OC1 and OC2, respectively.

[0173] Therefore, the distribution of V units in the silicone chain is determined according to the distribution of VVV, DVV (or VVD), and DVD triads. These triads are determined by the presence of triplets characteristic of VVV, DVV (or VVD), and DVD units. 29 Clearly identified by Si NMR. For the purposes of this patent application, the triads VVV, DVV (or VVD), and DVD refer to the following units: VVV Triad: [ka] DVV (or VVD) triad: [ka] DVD Triad: [ka] The DDD, DDV, and VDV triads are constructed similarly.

[0174] In the context of this example, the term "statistical product" refers to the linear organopolysiloxane OL having a random distribution of vinyl units (V) obtained by the method of the present invention.

[0175] On the other hand, for the purposes of this invention, the term "block copolymer" refers to a linear organopolysiloxane OL having a non-random distribution of vinyl units (V) obtained by the method of this invention.

[0176] In the context of this example, the method of the present invention is carried out in six different embodiments.

[0177] The cyclic organopolysiloxane OC, basic catalyst B (800 ppm), and chain arrester C are introduced into a vial under an inert atmosphere (argon). The reaction mixture is maintained at 70°C with stirring for 1 hour. The sample is collected, 1 1H NMR and 29 Analysis is performed by Si NMR.

[0178] In the context of the various tests A, B, and C described below, the introduced cyclic organopolysiloxanes are OC1 (5 g, 70 mol%) and OC2 (2.5 g, 30 mol%). The basic catalyst B1 is dissolved in methanol, and the chain arrestor is C4. Test A This procedure is performed by simultaneously introducing the cyclic organopolysiloxanes OC1 and OC2. Test B The reaction is carried out with cyclic organopolysiloxane OC1, and then cyclic organopolysiloxane OC2 is introduced approximately 10 minutes after the start of the reaction. Test C The first step is performed with cyclic organopolysiloxane OC2, followed by the introduction of cyclic organopolysiloxane OC1 approximately 10 minutes after the start of the reaction.

[0179] In the context of the various tests D, E, and F described below, the introduced cyclic organopolysiloxanes are OC1 (5 g, 80 mol%) and OC2 (1.7 g, 20 mol%). The basic catalyst B1 is soluble in water, and the chain arrestor is C6. Test D This is carried out using the cyclic organopolysiloxanes OC1 and OC2, which are introduced simultaneously. Test E The reaction is carried out using cyclic organopolysiloxane OC1, and then cyclic organopolysiloxane OC2 is introduced approximately 10 minutes after the start of the reaction. Test F This is carried out using the cyclic organopolysiloxane OC2, and then, approximately 10 minutes after the start of the reaction, the cyclic organopolysiloxane OC1 is introduced.

[0180] [Table 6]

[0181] Therefore, experimental data measured under the above conditions show a tendency to form block copolymers under these specific experimental conditions. As a result, the method of the present invention allows for control of the structure of the resulting linear organopolysiloxane OL, in addition to controlling the properties of terminal chemical functional groups as discussed in prior examples.

[0182] Characterization of units present at the ends of chains in tests A, B, and C. : The above 29 Si NMR microstructure analysis also allowed for the identification of units observed at the chain ends in experiments A, B, and C. In other words, this enabled the evaluation of the possible effects of the order of addition of cyclic organopolysiloxane OC on the properties of the units observed at the chain ends.

[0183] In the table below, the acronym HO-D represents the following units: [ka]

[0184] The acronym (Me)3SiO-D represents the following units: [ka]

[0185] Similarly, the acronym HO-V represents the following units: [ka]

[0186] Finally, the acronym (Me)3SiO-V represents the following units: [ka]

[0187] The results obtained are listed in the table below.

[0188] [Table 7]

[0189] Thus, in the case of the chain arrester C4, different distributions of units present at the chain ends are observed according to embodiments of the method of the present invention (tests A, B, or C). Specifically, the table above shows that the order in which the cyclic organopolysiloxane OC is added strongly influences the properties of the "terminal" units. Furthermore, the chain arrester C4 allows for complete control over the properties of the units present at the chain ends.

Claims

1. A method for preparing linear organopolysiloxane OL by a ring-opening polymerization reaction, a) A step in which a ring-opening polymerizable composition S is used, wherein the ring-opening polymerizable composition S is i) At least one cyclic organopolysiloxane OC containing three siloxane units, ii) Basic catalyst B of at least one formula (I): 【Chemistry 1】 (In the formula, R 1 These may be the same or different, and represent an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. R 2 is a hydrogen atom or group -C(=O)-R 3 This represents, and here, R 3 This represents an alkyl group containing 1 to 12 carbon atoms. X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number from 1 to 6. iii) At least one chain-stopping agent C, Processes including b) Optionally, subsequently add the same or different chain-stopping agent C or acid A as in step a) to the ring-opening polymerizable composition S. c) Steps to obtain the linear organopolysiloxane OL, Methods that include...

2. The cyclic organopolysiloxane OC is defined by formula (II): 【Chemistry 2】 (In the formula, R may be the same or different, and represents 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.) The method of the prior claim as represented by

3. The basic catalyst B is of formula (III): 【Transformation 3】 (In the formula, R 1 This represents an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number between 1 and 6. The method according to any one of the prior claims, as represented by:

4. The method according to any one of the preceding claims, wherein the molar amount of the basic catalyst B relative to the molar amount of the reaction mixture is 150 ppm to 4000 ppm, preferably 250 to 2500 ppm, more preferably 250 to 1500 ppm, relative to the molar amount of the reaction mixture.

5. The chain-stopping agent C is H 2 Compounds of formula (VIII) or O: 【Chemistry 4】 (In the formula, Y represents a carbon or silicon atom. 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, including 1 to 6 unsaturated carbon-carbon bonds, An aryl group containing 6 to 18 carbon atoms, preferably phenyl, benzyl group, Formula R 1 c SiO (4-c) / 2 A siloxyl group containing at least 5 units, preferably at least 10 units This represents, Here, R 1 These may be the same or different, and represent an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, an aryl group containing 6 to 10 carbon atoms, preferably phenyl, where c = 0, 1 or 2, and The group R may be unsubstituted, or it may be substituted with an alkyl chain 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. A method according to any one of the prior claims, selected from the following.

6. The method according to any one of the preceding claims, wherein the chain-stopping agent C is an alcohol or silanol having a pKa of 10 to 16, preferably 12 to 16, and more preferably 14 to 16.

7. The method according to any one of the preceding claims, wherein in step a), the molar ratio of the chain arrester C to the basic catalyst B used is 0.01 to 600, preferably 0.8 to 300, more preferably 1.5 to 300, more preferably 4 to 200, and more preferably 8 to 100.

8. The method according to any one of the preceding claims, wherein in step a), the molar ratio of the cyclic organopolysiloxane OC to the chain arrester C used is 1 to 20,000, preferably 2 to 5,000, more preferably 2 to 1,400, more preferably 4 to 700, more preferably 4 to 300, and even more preferably 10 to 150.

9. The method according to any one of the preceding claims, wherein in step b), the molar ratio of the cyclic organopolysiloxane OC to the chain arrester C used in this step is 1 to 100, preferably 10 to 80, and more preferably 10 to 50.

10. i) At least one cyclic organopolysiloxane OC containing three siloxane units, ii) Basic catalyst B of at least one formula (XII): 【Transformation 5】 (In the formula, R 1 These may be the same or different, and represent an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. R 2 is a hydrogen atom or group -C(=O)-R 3 This represents, and here, R 3 This represents an alkyl group containing 1 to 12 carbon atoms. X represents an anion selected from the group including carboxylates and their derivatives, carbonates and their derivatives, hydroxyl, siloxanolate, and silanolate. n is a natural number from 1 to 6. iii) At least one chain-stopping agent C, Composition S1, which includes the above.

11. Formula (XIV): 【Transformation 6】 (In the formula, R 1 These may be the same or different, and represent an alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. X represents siloxanolate or silanolate anion, n is a natural number between 1 and 6. Catalyst B is represented by [this].

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