Furanyl group-containing organopolysiloxane and method for producing same

Abstract

To provide: a furanyl group-containing organopolysiloxane having flexibility and photocrosslinkability due to a (poly)siloxane; and a method for producing the furanyl group-containing organopolysiloxane.SOLUTION: A furanyl group-containing organopolysiloxane is represented by an average composition formula (1) in the figure and has a number-average molecular weight of 500-40,000. [In the formula (1), each R1 is a monovalent hydrocarbon group having 1-10 carbon atoms or the like, or a furanyl group represented by a general formula (2) or (3), provided that at least one R1 in a molecule is a furanyl group represented by the general formula (2) or (3); and a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, and d is a number of 0 or more, provided that 2≤a+b+c+d≤1,000. In the formulas (2) and (3), R2 and R3 represent a hydrogen atom, a monovalent hydrocarbon group having 1-10 carbon atoms, or the like; and a broken line represents a bond.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a furanyl group-containing organopolysiloxane and a method for producing the same. [Background technology]

[0002] Furanyl group-containing organopolysiloxanes are polymers that have the flexibility inherent to (poly)siloxanes as well as the cationic polymerization and Diels-Alder reactivity inherent to the furanyl groups, and are therefore expected to be used in applications such as coating agents, resin modifiers, and self-repairing materials. As a method for producing a furanyl group-containing organopolysiloxane in which a linker containing a carbon atom and / or an oxygen atom is interposed between the furanyl group and the silicon atom, a method using a furanyl compound having an unsaturated bond and an organopolysiloxane having a hydrosilyl group (Patent Document 1) has been disclosed. As a method for producing furanyl group-containing organosiloxane in which the carbon atom of the furan ring is directly bonded to the silicon atom of the organosiloxane, a method using furanyl lithium, cyclotrisiloxane, and triorganohalosilane (Patent Document 2) has been disclosed, but it is limited to an asymmetric siloxane structure. In addition, there are problems such as the use of highly dangerous organolithium species and the necessity of a filtration process for lithium halide after the reaction. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 8-67753 [Patent Document 2] Japanese Patent Application Publication No. 8-119977 Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, an object of the present invention is to provide a furanyl group-containing organopolysiloxane in which the carbon atom of the furan ring is directly bonded to the silicon atom of the organopolysiloxane, and a method for producing the furanyl group-containing organopolysiloxane which can alleviate the above-mentioned problems. [Means for solving the problem]

[0005] The present inventors have conducted intensive research to solve the above problems and have discovered that by utilizing an iridium complex and a hydrogen acceptor, a furanyl group-containing organopolysiloxane can be directly and safely synthesized without producing metal salts as a by-product through an oxidative coupling reaction between a furan compound and a hydrosilyl group-containing organopolysiloxane, thereby completing the present invention.

[0006] That is, the present invention provides the following furanyl group-containing organopolysiloxane and method for producing the same.

[0007] <1> A furanyl group-containing organopolysiloxane having a number average molecular weight of 500 to 40,000 and represented by the following average composition formula (1): [ka] (In formula (1), R 1 are each independently a group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a furanyl group represented by the following general formula (2) or general formula (3), 1 At least one of the above is a furanyl group represented by the following general formula (2) or (3), in which a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, and d is a number of 0 or more, and 2≦a+b+c+d≦1,000. [ka] (In formulas (2) and (3), R 2 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group; R3 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group. The dashed lines represent bonds. <2> The number average molecular weight is 1,000 to 20,000. <1> 2. The furanyl group-containing organopolysiloxane according to claim 1. <3> d in formula (1) is 0; <1> or <2> 2. The furanyl group-containing organopolysiloxane according to claim 1. <4> Furthermore, c in formula (1) is 0. <3> 2. The furanyl group-containing organopolysiloxane according to claim 1. <5> (A) a furan compound represented by the following general formula (4), (B) a hydrosilyl group-containing organopolysiloxane represented by the following average composition formula (5): reacting in the presence of an iridium complex and a hydrogen acceptor; <1> ~ <4> 2. A method for producing the furanyl group-containing organopolysiloxane according to any one of the above items 1 to 11. [ka] (In formula (4), R 4 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group, 4 At least one of the is a hydrogen atom.) [ka] (In formula (5), R 5 are each independently a group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group, 5 At least one of the is a hydrogen atom. a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, and d is a number of 0 or more, and 2≦a+b+c+d≦1,000. <6> the iridium complex is a complex having, as a ligand, one or more compounds selected from the group consisting of aromatic hydrocarbon compounds having 6 to 30 carbon atoms, heterocyclic compounds having 2 to 30 carbon atoms, hydrocarbon compounds having 1 to 30 carbon atoms and a nitrogen-containing functional group, hydrocarbon compounds having 1 to 30 carbon atoms and an oxygen-containing functional group, hydrocarbon compounds having 1 to 30 carbon atoms and a sulfur-containing functional group, and hydrocarbon compounds having 1 to 30 carbon atoms and a phosphorus-containing functional group; <5> 2. A method for producing the furanyl group-containing organopolysiloxane according to claim 1. <7> The iridium complex is a complex having a heterocyclic compound having 2 to 30 carbon atoms or a hydrocarbon compound having 1 to 30 carbon atoms and a phosphorus-containing functional group as a ligand. <5> or <6> 2. A method for producing the furanyl group-containing organopolysiloxane according to claim 1. <8> The hydrogen acceptor is an aliphatic hydrocarbon compound having 2 to 20 carbon atoms and a carbon-carbon unsaturated bond. <5> ~ <7> 2. A method for producing the furanyl group-containing organopolysiloxane according to any one of the above items 1 to 11. Effect of the Invention

[0008] The furanyl group-containing organopolysiloxane of the present invention can be produced using relatively simple and easily available raw materials such as furan and hydrosilyl group-containing organopolysiloxane, and further, the furanyl group-containing organopolysiloxane can be produced safely without producing metal salts as by-products. Furthermore, since the furanyl group-containing organopolysiloxane of the present invention is a polymer that has the flexibility due to (poly)siloxane, as well as the cationic polymerizability and Diels-Alder reactivity due to the furanyl group, it is useful for applications such as coating agents, resin modifiers, self-repairing materials, etc. Interestingly, the furanyl group-containing organopolysiloxane of the present invention showed significantly higher reactivity in a cationic polymerization reaction using an acid catalyst than a furanyl group-containing organopolysiloxane in which a linker containing a carbon atom and / or an oxygen atom is provided between the furanyl group and the silicon atom. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be described in detail below.

[0010] [Furanyl group-containing organopolysiloxane] The furanyl group-containing organopolysiloxane of the present invention is represented by the following average composition formula (1). [ka] In formula (1), R 1 are each independently a group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a furanyl group represented by the following general formula (2) or general formula (3), 1 At least one of the above is a furanyl group represented by the following general formula (2) or (3), in which a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, and d is a number of 0 or more, and 2≦a+b+c+d≦1,000. [ka] In formulas (2) and (3), R 2 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group; R 3 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group. The dashed lines represent bonds.

[0011] In the above formula (1), R 1 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a furanyl group represented by the following general formula (2) or general formula (3). 1 Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by the formula (I) include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl and tolyl. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. R 1 As the group other than the furanyl group represented by the general formula (2) or (3), an alkyl group, a cycloalkyl group and an aryl group are preferable, and a methyl group and a phenyl group are more preferable.

[0012] In the above general formula (2) and general formula (3), R 2 and R 3 is a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group. 2 or R 3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; and aryl groups such as a phenyl group and a tolyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among these, R 2 and R 3 is preferably a hydrogen atom or an alkyl group.

[0013] Specific structures of general formula (2) and general formula (3) are shown below, but are not limited thereto. [ka] (In the above formula, the dashed lines represent bonds.)

[0014] In the above formula (1), a is 2 or more, preferably a number from 2 to 12, b is 0 or more, preferably a number from 1 to 998, more preferably a number from 5 to 500, c is 0 or more, preferably a number from 0 to 10, d is 0 or more, preferably a number from 0 to 5, and 2≦a+b+c+d≦1,000, preferably 2≦a+b+c+d≦800, more preferably 3≦a+b+c+d≦800, and even more preferably 4≦a+b+c+d≦500. If a+b+c+d is more than 1,000, the viscosity of the furanyl group-containing organopolysiloxane increases, which may result in poor workability.

[0015] The molecular weight of the furanyl group-containing organopolysiloxane of the present invention is 500 to 40,000 in number average molecular weight, preferably 1,000 to 20,000, and more preferably 1,000 to 10,000. If the molecular weight is less than 500, the properties such as flexibility derived from the (poly)siloxane may not be expressed, and if it exceeds 40,000, the viscosity of the furanyl group-containing organopolysiloxane may increase, which is not preferable as it may cause poor workability. The number average molecular weight is a value obtained by GPC (gel permeation chromatography) analysis using polystyrene as a standard substance under the following conditions. [Measurement conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N(6.0mmI.D.×15cm×1) TSKgel SuperH2500(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (THF solution with a concentration of 0.3% by mass)

[0016] [Method for producing furanyl group-containing organopolysiloxane] The method for producing a furanyl group-containing organopolysiloxane of the present invention (hereinafter sometimes abbreviated as "the production method of the present invention") comprises the step of reacting "a furan compound having one or more C-H bonds" with "a hydrosilyl group-containing organopolysiloxane" in the presence of an "iridium complex" and a "hydrogen acceptor".

[0017] The present inventors conducted extensive research in search of a safe method for producing furanyl group-containing organopolysiloxanes that does not produce metal salts as by-products, and as a result, discovered that furanyl group-containing organopolysiloxanes can be synthesized directly by the oxidative coupling reaction of a furan compound with a hydrosilyl group-containing organopolysiloxane, utilizing an iridium complex and a hydrogen acceptor.

[0018] (Furan compounds with one or more C-H bonds) The furan compound having one or more C-H bonds is represented by the following general formula (4). [ka] In formula (4), R 4 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group, 4 At least one of the is a hydrogen atom. R 4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; and aryl groups such as a phenyl group and a tolyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among these, R 4 is preferably a hydrogen atom or an alkyl group.

[0019] (Hydrosilyl-containing organopolysiloxane) As the hydrosilyl group-containing organopolysiloxane, one represented by the following average composition formula (5) can be used. [ka] In formula (5), R 5are each independently a group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group, 5 At least one of the above is a hydrogen atom. a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, and d is a number of 0 or more, and 2≦a+b+c+d≦1,000. R 5 Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by the formula (1) include alkyl groups such as methyl, ethyl, propyl and butyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; and aryl groups such as phenyl and tolyl groups, and examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy and butoxy groups. Among these, alkyl groups, cycloalkyl groups and aryl groups are preferred, and methyl and phenyl groups are more preferred.

[0020] (Iridium complex) The type of iridium complex used in the manufacturing method of the present invention is not particularly limited, and known iridium complexes can be appropriately used.For example, the ligand coordinated to iridium atom can be exemplified by aromatic hydrocarbon compounds having the structure of benzene, naphthalene, etc.; heterocyclic compounds having the structure of thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, phenanthroline, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, etc.; hydrocarbon compounds having nitrogen-containing functional groups such as alkylamino group, arylamino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, imino group, etc.; hydrocarbon compounds having oxygen-containing functional groups such as alkoxy group, aryloxy group, acyloxy group, silyloxy group, carbonyl group, ether group, etc.; hydrocarbon compounds having sulfur-containing functional groups such as alkylthio group, arylthio group, thioether group, etc.; and hydrocarbon compounds having phosphorus-containing functional groups such as dialkylphosphino group, diarylphosphino group, trialkylphosphine, triarylphosphine, phosphinine group, etc. The ligand of the iridium complex in the production method of the present invention is at least one compound selected from the group consisting of an aromatic hydrocarbon compound having 6 to 30 carbon atoms, preferably 6 to 26 carbon atoms, and more preferably 10 to 24 carbon atoms; a heterocyclic compound having 2 to 30 carbon atoms, preferably 2 to 16 carbon atoms; a hydrocarbon compound having 1 to 30 carbon atoms, preferably 3 to 16 carbon atoms, and having a nitrogen-containing functional group; a hydrocarbon compound having 1 to 30 carbon atoms, preferably 3 to 16 carbon atoms, and having an oxygen-containing functional group; a hydrocarbon compound having 1 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and having a sulfur-containing functional group; and a hydrocarbon compound having 1 to 30 carbon atoms, preferably 3 to 27 carbon atoms, and having a phosphorus-containing functional group. Among these ligands, a heterocyclic compound having 2 to 30 carbon atoms or a hydrocarbon compound having 1 to 30 carbon atoms and a phosphorus-containing functional group is preferred, and specifically, 2-methyl-1,10-phenanthroline, 4,4'-di-tert-butylbipyridine (dtbpy), 2,2'-bipyridyl, and 1,3-bis(diphenylphosphino)propane (dppp) are more preferred.

[0021] The amount (mass) of the iridium complex used in the production method of the present invention is not particularly limited and is appropriately selected depending on the purpose, and is preferably 100 to 20,000 ppm, more preferably 300 to 15,000 ppm, and most preferably 500 to 10,000 ppm relative to the amount (mass) of the hydrosilyl group-containing organopolysiloxane used. If it is within the above range, the reaction can proceed efficiently.

[0022] In the manufacturing method of the present invention, the method of preparing the iridium complex is not particularly limited, and it may be prepared by reacting a precursor containing iridium (hereinafter, sometimes abbreviated as "iridium-containing precursor") with a ligand, or the iridium complex may be formed in a reaction vessel in which a furan compound and a hydrosilyl group-containing organopolysiloxane are reacted with an iridium-containing precursor and a ligand. Since the operation is simple, it is preferable to form the iridium complex in a reaction vessel in which a furan compound and a hydrosilyl group-containing organopolysiloxane are reacted. The type of iridium-containing precursor is not particularly limited, and commercially available known precursors can be appropriately used. Specific examples include [Ir(OMe)(cod)]2, [Ir(OH)(cod)]2, [IrCl(cod)]2, and [Ir(OAc)(cod)]2 (wherein cod refers to 1,5-cyclooctadiene). Furthermore, the amount of the ligand used when preparing the iridium complex (amount of substance [mol]) is preferably 1 to 25 times, more preferably 5 to 20 times, and most preferably 10 to 15 times the amount of the iridium-containing precursor used (amount of substance [mol]).

[0023] (hydrogen acceptor) The hydrogen acceptor used in the production method of the present invention is not particularly limited in type as long as it is a substance capable of incorporating two or more hydrogen atoms through a chemical reaction. Specific examples of hydrogen acceptors include aliphatic hydrocarbon compounds having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and having a carbon-carbon unsaturated bond capable of incorporating hydrogen atoms through an addition reaction. Specific examples of aliphatic hydrocarbon compounds having a carbon-carbon unsaturated bond include cyclohexene, norbornene, 1-octene, trans-stilbene, 1,5-cyclooctadiene, phenylacetylene, and diphenylacetylene, and it is preferable to use one or more of these aliphatic hydrocarbon compounds.

[0024] The amount of hydrogen acceptor used in the production method of the present invention (amount of substance [mol]) is not particularly limited and should be appropriately selected depending on the purpose. The amount of hydrogen acceptor used (amount of substance [mol]) is preferably 1 to 30 times, more preferably 2 to 7 times, and most preferably 3 to 6 times the amount of hydrosilyl group-containing organopolysiloxane used (amount of substance [mol]). If it is within the above range, the reaction can proceed efficiently.

[0025] (Reaction conditions) In the production method of the present invention, the reaction conditions such as the reaction temperature, reaction time, and the solvent used are not particularly limited. The reaction temperature is preferably 25 to 200° C., more preferably 70 to 150° C., and most preferably 80 to 100° C. If the reaction temperature is within the above range, the furanyl group-containing organopolysiloxane can be produced efficiently. The reaction time is preferably from 1 to 60 hours, more preferably from 2 to 48 hours, and most preferably from 4 to 24 hours. A solvent may or may not be used, but when both the furan compound and the hydrosilyl group-containing organopolysiloxane are solid at the reaction temperature, it is preferable to use a solvent. The solvent to be used is not particularly limited as long as it dissolves both the furan compound and the hydrosilyl group-containing organopolysiloxane, and specific examples include tetrahydrofuran, decane, octane, etc. EXAMPLES

[0026] The present invention will be described in more detail below with reference to examples, but the examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited to the specific examples shown below.

[0027] As described in the examples 1 H-NMR was measured using AVANCE-III 400MHz (BRUKER) with deuterated chloroform as the solvent and TMS (tetramethylsilane) as the standard substance. The values ​​in parentheses are integral ratios. The number average molecular weight is a value obtained by GPC (gel permeation chromatography) analysis using polystyrene as a standard substance under the following conditions. [Measurement conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N(6.0mmI.D.×15cm×1) TSKgel SuperH2500(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (THF solution with a concentration of 0.3% by mass) In the structural formulae described in the following examples, Me represents a methyl group.

[0028] <Example 1> In a 100 mL separable flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet tube, 0.06 g of 2-methyl-1,10-phenanthroline, 6.44 g of 2-butylfuran, 3.41 g of cyclohexene, 5.00 g of tetrahydrofuran, and 50.00 g of organopolysiloxane containing hydrosilyl groups at both ends represented by the following average formula (7) were charged, and then 20.1 g of [Ir(OMe)(cod)] was added under stirring at 25°C under a nitrogen atmosphere, and the mixture was heated to reflux at 80 to 100°C for 8 hours. Thereafter, low boiling point substances were distilled off under reduced pressure at an internal temperature of 80°C, yielding a brown transparent liquid at a yield of 92%. This product was, 1 It was confirmed by H-NMR that the compound was the compound represented by the following average formula (8), and the number average molecular weight was 9,500. 1 The H-NMR data is shown below. 0.07ppm(930H), 0.91ppm(6H), 1.34ppm(4H), 1.58ppm(4H), 2.63ppm(4H), 5.94ppm(2H), 6.57ppm(2H) [ka] [ka]

[0029] <Example 2> In a 100 mL separable flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet tube, 0.06 g of 2-methyl-1,10-phenanthroline, 4.98 g of 2,5-dimethylfuran, 3.41 g of cyclohexene, 5.00 g of tetrahydrofuran, and 50.00 g of organopolysiloxane containing hydrosilyl groups at both ends represented by the above average formula (7) were charged, and then 20.1 g of [Ir(OMe)(cod)] was added under stirring at 25°C under a nitrogen atmosphere, and the mixture was heated to reflux at 80 to 100°C for 8 hours. Thereafter, low boiling point substances were distilled off under reduced pressure at an internal temperature of 80°C, yielding a brown transparent liquid at a yield of 95%. This product was, 1 It was confirmed by H-NMR that the compound represented by the following average formula (9) had a number average molecular weight of 5,800. 1 The H-NMR data is shown below. 0.07ppm(600H), 2.23ppm(6H), 2.31ppm(6H), 5.82ppm(2H) [ka]

[0030] <Example 3> In a 100 mL separable flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet tube, 0.03 g of 2-methyl-1,10-phenanthroline, 3.34 g of furan, 3.23 g of cyclohexene, 2.50 g of tetrahydrofuran, and 25.00 g of a terminal hydrosilyl-containing branched organopolysiloxane represented by the following average formula (10) were charged, and then 20.05 g of [Ir(OMe)(cod)] was added under stirring at 25°C under a nitrogen atmosphere, and the mixture was heated to reflux at 80 to 100°C for 8 hours. Thereafter, low boiling point substances were distilled off under reduced pressure at an internal temperature of 80°C, yielding a brown transparent liquid at a yield of 90%. This product was,1 It was confirmed by H-NMR that the compound was the compound represented by the following average formula (11), and the number average molecular weight was 3,500. 1 The H-NMR data is shown below. 0.07ppm(481H), 6.37ppm(3H), 6.66ppm(3H), 7.62ppm(3H) [ka] [ka]

[0031] Comparative Example 1: Synthesis of furanyl group-containing organopolysiloxane containing a linker According to the examples described in Patent Document 1, a furanyl group-containing organopolysiloxane represented by the following average formula (12) was synthesized. [ka]

[0032] Comparative Example 2: Synthesis of furanyl group-containing asymmetric siloxane According to the examples described in Patent Document 2, a furanyl group asymmetric disiloxane represented by the following formula (13) was synthesized. [ka]

[0033] <Cationic polymerization evaluation> One part of concentrated sulfuric acid was added to 99 parts of each of the organo(poly)siloxanes represented by formulas (8), (9), (11), (12) and (13) obtained in the above Examples or Comparative Examples, and cationic polymerization was carried out at room temperature. The results are shown in Table 1. Curability was evaluated according to the following criteria. 〇: Hardens and becomes gel-like △: Partially hardened ×: Not hardened, paste-like

[0034] [Table 1]

[0035] As shown in Table 1, the furanyl group-containing organopolysiloxane of the present invention exhibited excellent cationic polymerization properties.

Claims

1. A furanyl group-containing organopolysiloxane having a number average molecular weight of 500 to 40,000 and represented by the following average composition formula (1): 【Chemistry 1】 (In formula (1), R 1 are each independently a group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a furanyl group represented by the following general formula (2) or general formula (3), 1 At least one of the groups is a furanyl group represented by the following general formula (2) or (3), in which a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, and d is a number of 0 or more, and 2≦a+b+c+d≦1,000. 【Chemistry 2】 (In formulas (2) and (3), R 2 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group; R 3 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group. The dashed lines represent bonds.

2. 2. The furanyl group-containing organopolysiloxane according to claim 1, which has a number average molecular weight of 1,000 to 20,000.

3. 3. The furanyl group-containing organopolysiloxane according to claim 1, wherein d in formula (1) is 0.

4. The furanyl group-containing organopolysiloxane according to claim 3, wherein c in formula (1) is 0.

5. (A) a furan compound represented by the following general formula (4), (B) a hydrosilyl group-containing organopolysiloxane represented by the following average composition formula (5):

5. A method for producing a furanyl group-containing organopolysiloxane according to claim 1, comprising a step of reacting an iridium complex with a hydrogen acceptor in the presence of the iridium complex, wherein the iridium complex is a complex having as a ligand one or more compounds selected from the group consisting of aromatic hydrocarbon compounds having 6 to 30 carbon atoms, heterocyclic compounds having 2 to 30 carbon atoms, hydrocarbon compounds having 1 to 30 carbon atoms and a nitrogen-containing functional group, hydrocarbon compounds having 1 to 30 carbon atoms and an oxygen-containing functional group, hydrocarbon compounds having 1 to 30 carbon atoms and a sulfur-containing functional group, and hydrocarbon compounds having 1 to 30 carbon atoms and a phosphorus-containing functional group. 【Chemistry 3】 (In formula (4), R 4 are each independently a group selected from a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group, 4 At least one of the is a hydrogen atom. 【Chemistry 4】 (In formula (5), R 5 are each independently a group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group, 5 At least one of the above is a hydrogen atom. a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, and d is a number of 0 or more, and 2≦a+b+c+d≦1,000.

6. 6. The method for producing a furanyl group-containing organopolysiloxane according to claim 5, wherein the iridium complex is a complex having a heterocyclic compound having 2 to 30 carbon atoms or a hydrocarbon compound having 1 to 30 carbon atoms and a phosphorus-containing functional group as a ligand.

7. 7. The method for producing a furanyl group-containing organopolysiloxane according to claim 5 or 6, wherein the hydrogen acceptor is an aliphatic hydrocarbon compound having 2 to 20 carbon atoms and a carbon-carbon unsaturated bond.

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