Methylphenylpolysiloxane mixture and method for producing the same
A methylphenylpolysiloxane mixture with increased phenyl groups and functional groups is produced through a controlled reaction of specific methylphenylpolysiloxanes and a Bronsted acid catalyst, enhancing refractive index and compatibility, suitable for coating agents and optical materials.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- SHIN ETSU CHEMICAL CO LTD
- Filing Date
- 2024-10-25
- Publication Date
- 2026-05-13
AI Technical Summary
Existing methods struggle to introduce a large amount of phenyl groups and functional groups with weak basicity, such as acrylic groups, methacrylic groups, and mercapto groups, into methylphenylpolysiloxane, limiting its refractive index and compatibility with organic resins.
A mixture of methylphenylpolysiloxanes represented by specific formulas (1) and (2) is reacted in the presence of a Bronsted acid catalyst, with a controlled catalyst amount and reaction conditions, to produce a methylphenylpolysiloxane mixture with increased phenyl groups and introduced functional groups.
The resulting methylphenylpolysiloxane mixture exhibits a high refractive index and can be used in applications like coating agents and optical materials, with improved compatibility and polymerizable functional groups.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention relates to a methylphenylpolysiloxane mixture and a method for producing the same.
Background Art
[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 having such characteristics, 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 a 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. According to this method, a methylphenylpolysiloxane into which a functional group with weak basicity such as an acrylic group, a methacrylic group, and a mercapto group is 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] In Patent Document 1, it is reported 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. Also by this method, a methylphenylpolysiloxane into which a functional group with weak basicity such as an acrylic group, a methacrylic group, and a mercapto group is introduced can 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 further higher refractive index.
Prior Art Documents
Patent Documents
[0006] [Patent Document 1] Japanese Patent Publication No. 2023-010076 [Overview of the project] [Problems that the invention aims to solve]
[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 functional groups that are sensitive to basics, such as acrylic groups, methacrylic groups, and mercapto groups, have been introduced. [Means for solving the problem]
[0008] In order to solve the above problems, the present invention provides: A mixture of methylphenylpolysiloxanes, (A) Methylphenylpolysiloxane represented by the following formula (1), [ka] (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である。) (B) Methylphenylpolysiloxane represented by the following formula (2) [ka] (In the formula, a, b, and c are the same as above.) The present invention provides a methylphenylpolysiloxane mixture containing and characterized in that 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 the amount of introduced phenyl groups can be increased and functional groups with weak basicity such as acrylic groups, methacrylic groups, and mercapto groups can be introduced.
[0010] Further, a methylphenylpolysiloxane represented by the following formula (3) and
Chemical formula
Chemical formula
[0011] By using such a production 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 the Bronsted acid catalyst used is 5 to 10% by mass based on the total amount (total mass) of the methylphenylpolysiloxane represented by the formula (3) and the disiloxane represented by the formula (4).
[0013] If the amount of the Bronsted acid catalyst used is 5% by mass or more based on the total mass, the end-capping rate will not decrease, and if it is 10% by mass or less, there will be no possibility of undesirable side reactions proceeding. Therefore, it is preferable that the amount is within the above range.
Advantages of the Invention
[0014] As described above, the methylphenylpolysiloxane mixture of the present invention has a high refractive index and has acrylic groups, methacrylic groups, and mercapto groups, which are polymerizable functional groups, and thus can be used in applications such as coating agents, resin modifiers, and optical materials.
Embodiments for Carrying out the Invention
[0015] As described above, there has been a demand for the development of a methylphenylpolysiloxane with a large amount of phenyl groups introduced and with weakly basic functional groups such as acrylic groups, methacrylic groups, and mercapto groups introduced.
[0016] As a result of intensive studies to solve the above problems, the present inventors have found that a mixture of methylphenylpolysiloxanes represented by the following formulas (1) and (2) has a large amount of phenyl groups introduced and can introduce weakly basic functional groups such as acrylic groups, methacrylic groups, and mercapto groups, and have thus completed the present invention.
[0017] That is, the present invention is a methylphenylpolysiloxane mixture, (A) a methylphenylpolysiloxane represented by the following formula (1), and
Chemical Formula
Chemical Formula
[0018] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
[0019] [Methylphenylpolysiloxane mixture] The methylphenylpolysiloxane mixture of the present invention contains, as the component (A), a methylphenylpolysiloxane represented by the following formula (1) and, as the component (B), a methylphenylpolysiloxane represented by the following formula (2). [Chemical formula] (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.)
[0020] In the above formula (1), a is 2 or more, preferably an integer of 2 to 12, b is 3 or more, preferably an integer of 3 to 98, more preferably an integer of 4 to 25, c is 0 or more, preferably an integer of 0 to 10, a < b, 5 ≤ a + b + c ≤ 100, and 5 ≤ a + b + c ≤ 50 is preferable. When a + b + c is greater than 100, the viscosity may increase and the workability may deteriorate.
[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, C6H5- shall refer to a phenyl group.
[0022] [Chemical formula] (In the formula, a, b, and c are the same as above.)
[0023] In the methylphenylpolysiloxane mixture of the present invention, the content of the component (B) is in the range of 0.1 to 5 mol% with respect to 100 mol% of the total amount of the components (A) and (B). Among these, 0.1 to 4 mol% is preferable, and 0.1 to 3 mol% is more preferable. When the content of the component (B) is outside the above range, the effect of the polymerizable functional group cannot be sufficiently exhibited.
[0024] [Method for producing methylphenylpolysiloxane mixture] The method for producing the methylphenylpolysiloxane mixture of the present invention (hereinafter, may be abbreviated as "the production method of the present invention") includes a 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 Bronsted acid catalyst. [Chemical formula] (In the formula, d is an integer of 2 or more, e is an integer of 3 or more, f is an integer of 0 or more, and d < e, 5 ≤ d + e + f ≤ 100.)
[0025] In the above formula (3), d is 2 or more, preferably an integer of 2 to 12, e is 3 or more, preferably an integer of 3 to 98, more preferably an integer of 4 to 25, f is 0 or more, preferably an integer of 0 to 10, d < e, 5 ≤ d + e + f ≤ 100, and 5 ≤ d + e + f ≤ 50 is preferable. When d + e + f is larger than 100, the viscosity may become high and the workability may deteriorate. [Chemical formula] (In the formula, A is a group selected from a (meth)acryloxymethyl group, a 3-(meth)acryloxypropyl group, and a 3-mercaptopropyl group.)
[0026] In the above formula (4), 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) (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. [Examples]
[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 "% by mass," respectively. The apparatus used in the examples is as follows.
[0032] (1) GPC measurement conditions Equipment: HLC-8320GPC manufactured by Tosoh Corporation Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Differential 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) Standard: Monodisperse polystyrene (2) Nuclear magnetic resonance spectrum ( 29 Si-NMR) measurement conditions Equipment: JEOL ECX500II Solvent: CDCl3 Internal standard: Tetramethylsilane (TMS)
[0033] [Example 1] 23.0 g of 1,3-bis(methacryloxypropyl)tetramethyldisiloxane and 102.0 g of methylphenylpolysiloxane represented by formula (5) below were added to a separable flask equipped with a stirrer, dropping funnel, and thermometer, and stirred and mixed. After homogeneous 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 10% Glauber's salt aqueous solution was repeated until the pH of the reaction solution reached 7. Dehydration and distillation of low molecular weight components were performed to obtain the target methylphenylpolysiloxane represented by formula (6) below. 29 Si-NMR measurements revealed that the mixture contained 2 mol% of methylphenylpolysiloxane represented by formula (7) below. The refractive index of this methylphenylpolysiloxane mixture was 1.531.
[0034] [ka]
[0035] [Example 2] Except for replacing 1,3-bis(methacryloxypropyl)tetramethyldisiloxane used in Synthesis Example 1 above with 1,3-bis(acryloxymethyl)tetramethyldisiloxane and adjusting the reaction ratio, the same procedure as in Example 1 above was carried out to obtain the target methylphenylpolysiloxane represented by the following formula (8). 29 Si-NMR measurements revealed that the mixture contained 2 mol% of methylphenylpolysiloxane represented by formula (7) above. The refractive index of this methylphenylpolysiloxane mixture was 1.534.
[0036] [ka]
[0037] [Example 3] Except for replacing 1,3-bis(methacryloxypropyl)tetramethyldisiloxane used in Synthesis Example 1 above with 1,3-bis(mercaptopropyl)tetramethyldisiloxane and adjusting the reaction ratio, the same procedure as in Example 1 above was carried out to obtain the target methylphenylpolysiloxane represented by the following formula (9). 29 Si-NMR measurements revealed that the mixture contained 0.5 mol% of methylphenylpolysiloxane represented by formula (7) above. The refractive index of this methylphenylpolysiloxane mixture was 1.542.
[0038] [ka]
[0039] [Comparative Example 1] 23.0 g of 1,3-bis(methacryloxypropyl)tetramethyldisiloxane and 102.0 g of methylphenylpolysiloxane represented by formula (10) below were added to a separable flask equipped with a stirrer, dropping funnel, and thermometer, and stirred and mixed. After homogeneous dissolution of each component, 6.25 g of concentrated sulfuric acid was added dropwise. Since exothermic reaction occurs 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 10% Glauber's salt aqueous solution was repeated until the pH of the reaction solution reached 7. Dehydration and distillation of low molecular weight components were performed to obtain methylphenylpolysiloxane represented by formula (11) below. 29 Si-NMR measurements revealed that the compound contains 15 mol% of methylphenylpolysiloxane represented by formula (12) below, indicating that the silanol group blockade was not proceeding efficiently.
[0040] [ka]
[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] [ka]
[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 has substantially the same technical idea as 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 mixture of methylphenylpolysiloxanes, (A) Methylphenylpolysiloxane represented by the following formula (1), 【Chemistry 1】 (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.) (B) Methylphenylpolysiloxane represented by the following formula (2) 【Chemistry 2】 (In the formula, a, b, and c are the same as above.) A methylphenylpolysiloxane mixture characterized by containing and having a content of component (B) of 0.1 to 5 mol% relative to the total amount of component (A) and component (B) of 100 mol%.
2. Methylphenylpolysiloxane represented by the following formula (3), 【Transformation 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) 【Chemistry 4】 (In the formula, A is a group selected from (meth)acryloxymethyl, 3-(meth)acryloxypropyl, and 3-mercaptopropyl groups.) A method for producing a methylphenylpolysiloxane mixture according to claim 1, characterized by reacting the two 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 the Brønsted acid catalyst used is 5 to 10% by mass relative to the total amount (total mass) of the methylphenylpolysiloxane represented by formula (3) and the disiloxane represented by formula (4).