Methylphenylpolysiloxane mixture and method for producing the same

Abstract

The present invention is a methylphenylpolysiloxane mixture characterized by containing (A) a methylphenylpolysiloxane represented by formula (1), and (B) a methylphenylpolysiloxane represented by formula (2), the content of the component (B) being 0.1-5 mol% based on 100 mol% of the total amount of the components (A) and (B). Thus, provided is a methylphenylpolysiloxane having an increased phenyl group introduction amount, and having a base-sensitive functional group such as an acrylic group, a methacrylic group or a mercapto group introduced in the methylphenylpolysiloxane. (In formula (1), A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group; a is an integer of 2 or more; b is an integer of 3 or more; and c is an integer of 0 or more, where a<b and 5≤a+b+c≤100). (In formula (2), a, b, and c are the same as the aforementioned).

Description

Methylphenylpolysiloxane mixture and method for producing the same

[0001] The present invention relates to a methylphenylpolysiloxane mixture and a method for producing the same.

[0002] It is known that methylphenylpolysiloxane obtained by introducing a phenyl group into dimethylpolysiloxane has improved compatibility with organic resins and a higher refractive index.

[0003] As a method for producing such methylphenylpolysiloxane, for example, an equilibrium copolymerization method using a cyclic siloxane containing a dimethylsiloxy unit and a cyclic siloxane containing a diphenylsiloxy unit as raw materials and an alkali metal catalyst or a silicate catalyst as a catalyst is known. However, it is difficult to simultaneously introduce functional groups with weak basicity such as an acrylic group, a methacrylic group, and a mercapto group by the above method.

[0004] A method is also known in which methylphenylpolysiloxane containing a dimethylsiloxy unit and a diphenylsiloxy unit and having a terminal structure of a silanol group is previously produced, and the silanol group is blocked under acidic conditions. By this method, methylphenylpolysiloxane into which functional groups with weak basicity such as an acrylic group, a methacrylic group, and a mercapto group are introduced can be produced. However, since the silanol group bonded to the diphenylsiloxy unit has a large steric hindrance, it is difficult to efficiently block the terminal.

[0005] Patent Document 1 reports that an equilibrium copolymerization method using an acid catalyst becomes possible by using a specific cyclic siloxane containing a diphenylsiloxy unit as a raw material. By this method, methylphenylpolysiloxane into which functional groups with weak basicity such as an acrylic group, a methacrylic group, and a mercapto group are introduced can also be produced. However, when the cyclic siloxane is used as a raw material, there is a limit to the amount of phenyl group introduced, and it has been difficult to achieve a further increase in refractive index.

[0006] Japanese Unexamined Patent Application Publication No. 2023-010076

[0007] The present invention has been made to solve the above problems, and aims to provide a methylphenylpolysiloxane in which the amount of phenyl groups introduced has been increased, and in which basic-sensitive functional groups such as acrylic groups, methacrylic groups, and mercapto groups have been introduced.

[0008] To solve the above problems, the present invention provides a methylphenylpolysiloxane mixture comprising (A) a methylphenylpolysiloxane represented by the following formula (1), (In the formula, A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group, a is an integer of 2 or more, b is an integer of 3 or more, c is an integer of 0 or more, and a < b, 5 ≤ a + b + c ≤ 100.) (B) Methylphenylpolysiloxane represented by the following formula (2) The present invention provides a methylphenylpolysiloxane mixture containing (wherein a, b, and c are the same as above), wherein the content of component (B) is 0.1 to 5 mol% relative to the total amount of component (A) and component (B) of 100 mol%.

[0009] Such a methylphenylpolysiloxane mixture is preferable because it allows for an increase in the amount of phenyl groups introduced and also allows for the introduction of basic-sensitive functional groups such as acrylic groups, methacrylic groups, and mercapto groups.

[0010] Furthermore, methylphenylpolysiloxane represented by the following formula (3), (In the formula, d is an integer greater than or equal to 2, e is an integer greater than or equal to 3, f is an integer greater than or equal to 0, and d < e and 5 ≤ d + e + f ≤ 100.) Disiloxane represented by the following formula (4) The present invention provides a method for producing a methylphenylpolysiloxane mixture, characterized by reacting (wherein A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group) in the presence of a Brønsted acid catalyst.

[0011] By using this manufacturing method, the methylphenylpolysiloxane mixture of the present invention can be obtained.

[0012] In the method for producing the methylphenylpolysiloxane mixture, it is preferable that the amount of Brønsted acid catalyst used is 5 to 10% by mass relative to the total amount (total mass) of methylphenylpolysiloxane represented by formula (3) and disiloxane represented by formula (4).

[0013] If the amount of the Brønsted acid catalyst used is 5% by mass or more of the total mass, the end-sealing rate will not decrease, and if it is 10% by mass or less, the possibility of unwanted side reactions proceeding will be eliminated, so it is preferable that the amount used is within the above range.

[0014] As described above, the methylphenylpolysiloxane mixture of the present invention has a high refractive index and contains polymerizable functional groups such as acrylic groups, methacrylic groups, and mercapto groups, making it suitable for use in coatings, resin modifiers, optical materials, and the like.

[0015] As mentioned above, there has been a need for the development of methylphenylpolysiloxanes that have a high amount of phenyl groups introduced, and that also incorporate basic-sensitive functional groups such as acrylic groups, methacrylic groups, and mercapto groups.

[0016] As a result of diligent research to solve the above problems, the inventors have discovered that a mixture of methylphenylpolysiloxanes represented by the following formulas (1) and (2) allows for the introduction of a large amount of phenyl groups and functional groups that are sensitive to basicity, such as acrylic groups, methacrylic groups, and mercapto groups, and have completed the present invention.

[0017] That is, the present invention is a methylphenylpolysiloxane mixture comprising (A) a methylphenylpolysiloxane represented by the following formula (1), (In the formula, A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group, a is an integer of 2 or more, b is an integer of 3 or more, c is an integer of 0 or more, and a < b, 5 ≤ a + b + c ≤ 100.) (B) Methylphenylpolysiloxane represented by the following formula (2) A methylphenylpolysiloxane mixture containing (wherein a, b, and c are the same as above), wherein the content of component (B) is 0.1 to 5 mol% with respect to 100 mol% of the total amount of component (A) and component (B).

[0018] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0019] [Methylphenylpolysiloxane mixture] The methylphenylpolysiloxane mixture of the present invention contains, as component (A), a methylphenylpolysiloxane represented by the following formula (1), and as component (B), a methylphenylpolysiloxane represented by the following formula (2). (In the formula, A is a group selected from (meth)acryloxymethyl group, 3-(meth)acryloxypropyl group, and 3-mercaptopropyl group, a is an integer of 2 or more, b is an integer of 3 or more, c is an integer of 0 or more, and a < b and 5 ≤ a + b + c ≤ 100.)

[0020] In formula (1) above, a is an integer of 2 or more, preferably 2 to 12; b is an integer of 3 or more, preferably 3 to 98, more preferably 4 to 25; c is an integer of 0 or more, preferably 0 to 10; a < b, 5 ≤ a + b + c ≤ 100, and preferably 5 ≤ a + b + c ≤ 50. If a + b + c is greater than 100, the viscosity will increase, which may result in poor workability.

[0021] In the above formula (1), A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group. Also, in this specification, C ６ H ５ The dash (-) represents a phenyl group.

[0022] (In the formula, a, b, and c are the same as above.)

[0023] The methylphenylpolysiloxane mixture of the present invention has a content of component (B) in the range of 0.1 to 5 mol% relative to the total amount of component (A) and component (B) of 100 mol%. Preferably, it is 0.1 to 4 mol%, and more preferably 0.1 to 3 mol%. If the content of component (B) falls outside this range, the effect of the polymerizable functional group cannot be fully exhibited.

[0024] [Method for Producing a Methylphenylpolysiloxane Mixture] The method for producing a methylphenylpolysiloxane mixture of the present invention (hereinafter sometimes abbreviated as "the method for producing the present invention") is characterized by comprising the step of reacting an organosiloxane represented by the following formula (3) with a disiloxane represented by the following formula (4) in the presence of a Brønsted acid catalyst. (In the formula, d is an integer greater than or equal to 2, e is an integer greater than or equal to 3, f is an integer greater than or equal to 0, and d < e and 5 ≤ d + e + f ≤ 100.)

[0025] In formula (3) above, d is an integer of 2 or more, preferably 2 to 12; e is an integer of 3 or more, preferably 3 to 98, more preferably 4 to 25; and f is an integer of 0 or more, preferably 0 to 10, such that d < e, 5 ≤ d + e + f ≤ 100, and preferably 5 ≤ d + e + f ≤ 50. If d + e + f is greater than 100, the viscosity will increase, which may result in poor workability. (In the formula, A is a group selected from (meth)acryloxymethyl, 3-(meth)acryloxypropyl, and 3-mercaptopropyl groups.)

[0026] In formula (4) above, A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group.

[0027] In this specification, a Brønsted acid catalyst refers to a compound (catalyst) capable of producing a Brønsted acid in a reaction system.

[0028] Examples of Brønsted acid catalysts used in the production method of the present invention include sulfuric acid, trifluoromethanesulfonic acid, and bis(trifluoromethanesulfonyl)imide. Among these Brønsted acid catalysts, sulfuric acid is most preferred. The catalyst can be used alone or in appropriate mixtures of two or more types.

[0029] In the production method of the present invention, the amount of Brønsted acid catalyst used is preferably 5 to 10% by mass, and more preferably 5 to 7% by mass, relative to the total amount (total mass) of methylphenylpolysiloxane represented by formula (3) and disiloxane represented by formula (4). If it is 5% by mass or more, the amount of methylphenylpolysiloxane represented by formula (2) in the resulting methylphenylpolysiloxane mixture will not exceed 5 mol% relative to the total amount of methylphenylpolysiloxane represented by formula (1) and methylphenylpolysiloxane, which is 100 mol%, and there will be no possibility of a decrease in the end-sealing rate. Furthermore, if it is 10% by mass or less, there will be no possibility of unwanted side reactions occurring.

[0030] In the manufacturing method of the present invention, the reaction conditions such as reaction time and the solvent used are not particularly limited, but the reaction time is preferably 1 to 60 hours, more preferably 2 to 48 hours, and most preferably 4 to 24 hours. A solvent may or may not be used, but if used, saturated hydrocarbons such as heptane and octane are preferred.

[0031] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these. In the following examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "mass%", respectively. The apparatus used in the examples is as follows.

[0032] (1) GPC measurement conditions Instrument: HLC-8320GPC manufactured by Tosoh Corporation Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6 mL / min Detector: Differential refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N (6.0 mm I.D. × 15 cm × 1) TSKgel SuperH2500 (6.0 mm I.D. × 15 cm × 1) (both manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 50 μL (THF solution with a concentration of 0.3 mass%) Standard: Monodisperse polystyrene (2) Nuclear magnetic resonance spectrum ( ２９ Si-NMR measurement conditions: Instrument: JEOL ECX500II Solvent: CDCl ３ Internal standard: Tetramethylsilane (TMS)

[0033] [Example 1] 23.0 g of 1,3-bis(methacryloxypropyl)tetramethyldisiloxane and 102.0 g of methylphenylpolysiloxane represented by the following formula (5) were added to a separable flask equipped with a stirrer, dropping funnel, and thermometer, and stirred and mixed. After uniform dissolution of each component, 6.25 g of concentrated sulfuric acid was added dropwise. Since exothermic reactions occur during the dropwise addition, the temperature of the reaction solution was controlled using a water bath to prevent it from exceeding 30°C. After the dropwise addition was complete, stirring was continued for 7 hours in the temperature range of 20-30°C, and the disappearance of the reaction raw materials was confirmed by GPC. Washing with a 10% sodium sulfate aqueous solution was performed and repeated until the pH of the reaction solution reached 7. Dehydration and distillation of low molecular weight components were carried out to obtain the target methylphenylpolysiloxane represented by the following formula (6). ２９ Si-NMR measurements revealed that the mixture contained 2 mol% of methylphenylpolysiloxane represented by the following formula (7). The refractive index of this methylphenylpolysiloxane mixture was 1.531.

[0034]

[0035] [Example 2] The same procedure as in Example 1 was carried out, except that 1,3-bis(methacryloxypropyl)tetramethyldisiloxane used in Example 1 was replaced with 1,3-bis(acryloxymethyl)tetramethyldisiloxane and the reaction ratio was adjusted, to obtain the target methylphenylpolysiloxane represented by the following formula (8).２９ As a result of Si-NMR measurement, it contained 2 mol% of the methylphenylpolysiloxane represented by the above formula (7). The refractive index of this methylphenylpolysiloxane mixture was 1.534.

[0036]

[0037] [Example 3] The 1,3-bis(methacryloxypropyl)tetramethyldisiloxane used in Example 1 above was changed to 1,3-bis(mercaptopropyl)tetramethyldisiloxane, and the same operations as in Example 1 above were carried out except for adjusting the reaction ratio, to obtain the target methylphenylpolysiloxane represented by the following formula (9). ２９ As a result of Si-NMR measurement, it contained 0.5 mol% of the methylphenylpolysiloxane represented by the above formula (7). The refractive index of this methylphenylpolysiloxane mixture was 1.542.

[0038]

[0039] [Comparative Example 1] 23.0 g of 1,3-bis(methacryloxypropyl)tetramethyldisiloxane and 102.0 g of the methylphenylpolysiloxane represented by the following formula (10) were charged into a separable flask equipped with a stirrer, a dropping funnel and a thermometer, and stirred and mixed. After uniform dissolution of each component, 6.25 g of concentrated sulfuric acid was dropped. Since heat generation occurred due to the dropping reaction, the temperature of the reaction solution was controlled using a water bath so as not to exceed 30°C. After completion of dropping, stirring was continued for 7 hours in the temperature range of 20 to 30°C, and disappearance of the reaction raw materials was confirmed by GPC. Washing was carried out with a 10% aqueous sodium sulfate solution until the pH of the reaction solution reached 7. Dehydration and distillation of low molecular components were carried out to obtain the methylphenylpolysiloxane represented by the following formula (1). ２９ As a result of Si-NMR measurement, it contained 15 mol% of the methylphenylpolysiloxane represented by the following formula (12), and it was found that the blocking of the silanol groups did not proceed efficiently.

[0040]

[0041] [Comparative Example 2] In a separable flask equipped with a stirrer, dropping funnel, and thermometer, 47.0 g of 1,3-bis(methacryloxypropyl)tetramethyldisiloxane, 253.0 g of 2,2,4,4-tetramethyl-6,6-diphenylcyclotrisiloxane, and 0.6 g of trifluoromethanesulfonic acid were charged, and the reaction was carried out at 20°C for 4 hours under a nitrogen atmosphere. Then, 3.6 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 20°C for 2 hours, and the white precipitate was filtered off by pressure filtration. The obtained crude product was distilled off under reduced pressure at an internal temperature of 160°C and 3 mmHg to synthesize methylphenylpolysiloxane represented by the following formula (13). The refractive index of this methylphenylpolysiloxane was 1.510, which was lower than that of the methylphenylpolysiloxane obtained in Example 1.

[0042]

[0043] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are merely illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A methylphenylpolysiloxane mixture comprising (A) a methylphenylpolysiloxane represented by the following formula (1), (In the formula, A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group, a is an integer of 2 or more, b is an integer of 3 or more, c is an integer of 0 or more, and a < b, 5 ≤ a + b + c ≤ 100.) (B) Methylphenylpolysiloxane represented by the following formula (2) A methylphenylpolysiloxane mixture containing (wherein a, b, and c are the same as above), wherein the content of component (B) is 0.1 to 5 mol% with respect to 100 mol% of the total amount of component (A) and component (B).

2. Methylphenylpolysiloxane represented by the following formula (3), (In the formula, d is an integer greater than or equal to 2, e is an integer greater than or equal to 3, f is an integer greater than or equal to 0, and d < e and 5 ≤ d + e + f ≤ 100.) Disiloxane represented by the following formula (4) A method for producing a methylphenylpolysiloxane mixture according to claim 1, characterized by reacting (wherein A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group) in the presence of a Brønsted acid catalyst.

3. The method for producing a methylphenylpolysiloxane mixture according to claim 2, characterized in that the amount of Brønsted acid catalyst used is 5 to 10% by mass relative to the total amount (total mass) of methylphenylpolysiloxane represented by formula (3) and disiloxane represented by formula (4).

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