Cyclic siloxane compounds and methods for producing cyclic siloxane compounds

Abstract

The present invention provides a novel cyclic siloxane compound that can be used as a curable composition and is also useful in reducing carbon dioxide emissions, a curable composition containing the cyclic siloxane compound, a cured product obtained by curing the curable composition, an adhesive containing the curable composition, and a method for producing the cyclic siloxane compound. [Solution] A cyclic siloxane compound having a structure in which a cyclic carbonate group represented by the following formula (5) is present in the molecule. TIFF2026061903000014.tif69140

Description

[Technical Field]

[0001] This invention relates to a novel cyclic siloxane compound and a method for producing a cyclic siloxane compound. [Background technology]

[0002] In recent years, curable compositions have been used as fixatives for optical devices, such as adhesives and encapsulants for optical devices.

[0003] Optical devices include various types of lasers such as semiconductor lasers (LDs), light-emitting elements such as light-emitting diodes (LEDs), photodetectors, composite optical devices, and optical integrated circuits. In recent years, optical devices that emit blue light and white light, which have shorter peak wavelengths, have been developed and are widely used. The brightness of these light-emitting elements with shorter peak wavelengths has increased dramatically, and consequently, the amount of heat generated by these optical devices tends to increase even further.

[0004] However, with the increasing brightness of optical elements in recent years, a problem has arisen where the cured product of the optical element fixing agent is exposed to higher energy light and higher temperatures generated by the optical element for extended periods, causing it to deteriorate and peel off.

[0005] To solve this problem, Patent Documents 1 to 3 propose compositions for fixing photonic devices, in which polysilsesquioxane compounds are the main component.

[0006] Polysilsesquioxane compounds are composed of inorganic silica [SiO2] and organosilicone [(R2SiO)]. n It is an intermediate substance of ], and its formula is: (RSiO 3 / 2 ) n The compound is represented by the formula (wherein R may have substituents, such as an alkyl group or aryl group).

[0007] Polysilsesquioxane compounds have siloxane bonds (bonds between silicon atoms and oxygen atoms) as described above. As other compounds having siloxane bonds, cyclic siloxane compounds are also known. A cyclic siloxane compound refers to a cyclic organic compound having a cyclic molecular structure skeleton formed by siloxane bonds. In Patent Documents 4 and 5, inventions related to cyclic siloxane compounds are disclosed.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0009] By the way, in recent years, along with the growing demand for building a recycling-oriented society, gases such as carbon dioxide, methane, and carbon monoxide have attracted attention as sustainable carbon raw materials. For example, it has been reported that an aliphatic polycarbonate having only aliphatic (non-aromatic) groups in the main chain can be produced by copolymerizing carbon dioxide and an epoxide, and there is interest in chemicals using gases such as carbon dioxide as raw materials and their manufacturing technologies. Since carbon dioxide is considered a cause of global warming, the effective utilization of carbon dioxide discharged from factories in the process of making various materials is helpful for environmental protection.

[0010] The present invention has been made in view of such a situation, and provides a novel cyclic siloxane compound that can be used as a curable composition and is also useful for reducing carbon dioxide emissions, a curable composition containing the cyclic siloxane compound, a cured product obtained by curing the curable composition, an adhesive containing the curable composition, and a method for producing the above cyclic siloxane compound.

Means for Solving the Problems

[0011] First, in order to achieve the above object, the present invention provides a compound represented by the following formula (1)

Chemical formula

[0012] In the above invention (Invention 1), it is preferable that the R 1 is a propylene group (Invention 2).

[0013] In the above invention (Inventions 1 and 2), it is preferable that the R 2 is a methylene group (Invention 3).

[0014] In the above invention (Inventions 1 to 3), it is preferable that the R 3 is a methyl group (Invention 4).

[0015] Second, the present invention provides a curable composition characterized by containing the cyclic siloxane compound (Inventions 1 to 4) (Invention 5).

[0016] Thirdly, the present invention provides a cured product characterized by being obtained by curing the curable composition (Invention 5) (Invention 6).

[0017] Fourthly, the present invention provides an adhesive containing the curable composition (Invention 5) (Invention 7).

[0018] Fifth, the present invention relates to a method for producing the cyclic siloxane compound (Inventions 1-4), wherein the following formula (2) [ka] (In the formula, x represents an integer between 3 and 6, R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 R represents an alkylene group with 1 to 10 carbon atoms. 3 The present invention provides a manufacturing method characterized by including the step of reacting an epoxy group-containing cyclic siloxane compound having the structure shown in (1) with carbon dioxide to obtain a compound having the structure shown in formula (1). [Effects of the Invention]

[0019] The cyclic siloxane compound according to the present invention can be used as a curable composition and is also useful for reducing carbon dioxide emissions. [Brief explanation of the drawing]

[0020] [Figure 1] This figure shows the 1H NMR measurement results of the cyclic siloxane compound prepared in Example 1. [Figure 2] This figure shows the 1H NMR measurement results of the cyclic siloxane compound prepared in Example 1. [Figure 3] This figure shows the 1H NMR measurement results of the cyclic siloxane compound prepared in Example 1. [Figure 4] This figure shows the 13C NMR measurement results of the cyclic siloxane compound prepared in Example 1. [Figure 5]This figure shows the IR measurement results of the cyclic siloxane compound prepared in Example 1. [Figure 6] This figure shows the LC-MS measurement results of the cyclic siloxane compound prepared in Example 1. [Figure 7] This figure shows the LC-MS measurement results of the cyclic siloxane compound prepared in Example 2. [Modes for carrying out the invention]

[0021] Embodiments of the present invention will be described below. [Cyclic siloxane compounds] The cyclic siloxane compound according to this embodiment is given by formula (1) [ka] (In the formula, n represents an integer from 1 to 6, m represents an integer from 0 to 5, the sum of n and m is an integer from 3 to 6, the order of existence of the units enclosed in parentheses with n and m is arbitrary in formula (1), R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 R represents an alkylene group with 1 to 10 carbon atoms. 3 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) It has the structure shown in [image / diagram].

[0022] As is clear from formula (1) above, the cyclic siloxane compound according to this embodiment contains the following formula (5) within its molecule. [ka] It has cyclic carbonate groups represented by [the symbol]. Therefore, it can interact with these cyclic carbonate groups within or between molecules, and can undergo reactions mediated by these cyclic carbonate groups. As a result, the composition containing the cyclic siloxane compound according to this embodiment becomes curable.

[0023] Furthermore, as will be described later, carbon dioxide can be used as one of the materials when producing the cyclic siloxane compound according to this embodiment. Therefore, the use of the cyclic siloxane compound according to this embodiment is useful in reducing carbon dioxide emissions from the viewpoint of carbon neutrality.

[0024] In the structure shown in formula (1) above, the sum of n and m represents an integer from 3 to 6, as described above, but it is particularly preferable that the integer is from 3 to 5, and even more preferably from 3 to 4. As described above, n is an integer from 1 to 6, and m is an integer from 0 to 5, as described above, but from the viewpoint of easily achieving good curability, it is preferable that n is an integer greater than m, and from the same viewpoint, it is preferable that m is 0 (i.e., all units constituting the cyclic siloxane compound are units to which n is attached in formula (1) above).

[0025] In the structure shown in formula (1) above, R 1 As mentioned above, this is an alkylene group having 1 to 20 carbon atoms, but the number of carbon atoms is particularly preferably 1 to 10, and even more preferably 2 to 9. In particular, R 1 It is preferable that it be a propylene group.

[0026] Furthermore, in the structure shown in formula (1) above, R 2 As mentioned above, this is an alkylene group having 1 to 10 carbon atoms, but the number of carbon atoms is particularly preferably 1 to 5, and more preferably 1 to 3. In particular, R 2 It is preferable that it is a methylene group.

[0027] Furthermore, in the structure shown in formula (1) above, R 3 As described above, this is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but the number of carbon atoms is particularly preferably 1 to 5, and more preferably 1 to 3. In particular, R 3 It is preferable that it be a methyl group.

[0028] The method for producing the cyclic siloxane compound according to this embodiment is not particularly limited, but as mentioned above, it is preferable to produce it using a method that uses carbon dioxide as a material. For example, the method for producing the cyclic siloxane compound according to this embodiment is: The following formula (2) [ka] (In the formula, x represents an integer between 3 and 6, R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 R represents an alkylene group with 1 to 10 carbon atoms. 3 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) A step to obtain a compound having the structure shown in formula (1) above by reacting an epoxy group-containing cyclic siloxane compound having the structure shown with carbon dioxide. It is preferable to include it.

[0029] In equation (2) above, R 1 , R 2 and R 3 The preferred options are the same as those described above for equation (1). Also, as mentioned above, x represents an integer between 3 and 6, but it is particularly preferable that the integer be between 3 and 5, and even more preferably between 3 and 4.

[0030] The reaction between the epoxy group-containing cyclic siloxane compound and carbon dioxide in the above step can be carried out by known methods. For example, the reaction can be carried out by stirring in a system in which the solvent containing the epoxy group-containing cyclic siloxane compound is dissolved is replaced with carbon dioxide gas. At this time, catalysts such as lithium bromide, tetrabutylammonium iodide, and pyridinemethanol may be added to the solvent. The temperature during stirring is preferably 15 to 80°C, particularly preferably 25 to 70°C, and even more preferably 40 to 60°C. Furthermore, the stirring time is preferably 12 to 96 hours, particularly preferably 24 to 96 hours, and even more preferably 36 to 96 hours. After the reaction, the compound shown in formula (1) can be separated from the solvent by appropriate extraction, washing, etc.

[0031] As described above, the cyclic siloxane compound according to this embodiment has cyclic carbonate groups, and therefore exhibits curability due to interactions between these cyclic carbonate groups within or between molecules, or through reactions with amine compounds mediated by these cyclic carbonate groups.

[0032] The curable composition according to this embodiment contains the cyclic siloxane compound according to this embodiment, and may optionally contain other components. Here, the curable composition may contain various cyclic siloxane compounds with different structures. Examples of other components include silane coupling agents, fillers, amine compounds, and the like.

[0033] The amount of the cyclic siloxane compound according to this embodiment in the curable composition according to this embodiment is preferably 1 to 30% by mass, particularly preferably 1 to 20% by mass, and even more preferably 1 to 10% by mass.

[0034] The curable composition according to this embodiment can be cured by heating if it contains the cyclic siloxane compound and amine compound according to this embodiment. The heating conditions are set appropriately according to the composition of the curable composition, etc., but for example, heating at a temperature of 25 to 200°C is preferred, particularly heating at a temperature of 110 to 180°C, and even more preferably heating at a temperature of 120 to 150°C. The heating time is preferably 30 to 300 minutes, particularly 60 to 180 minutes, and even more preferably 90 to 120 minutes.

[0035] By using the curable composition according to this embodiment, a cured product having a desired shape can be obtained. By forming the curable composition according to this embodiment into a sheet and curing it, a sheet-like cured product can be obtained. The cured product obtained by curing the curable composition according to this embodiment can be used, for example, as a sealing material, adhesive, bonding agent, film, protective film, sealant, etc.

[0036] The embodiments described above are provided to facilitate understanding of the present invention and are not intended to limit it. Accordingly, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention. [Examples]

[0037] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0038] [Example 1] The following formula (3) [ka] 100 parts by mass of methylpropylglycidyl cyclic siloxane having the structure shown and 2.8 parts by mass of lithium bromide were added to 150 parts by mass of N-N'-dimethylformamide, and the mixture was reacted at 50°C for 60 hours while stirring under conditions of carbon dioxide gas purging. The compound of formula (3) above is the same as formula (2) above, where x is 4 and R 1 is an n-propylene group, R 2 The methylene group is R 3 This corresponds to a compound in which the atom is a hydrogen atom.

[0039] Subsequently, ethyl acetate and purified water were added to extract the organic layer, and the resulting organic layer was washed with purified water. The washed organic layer was then dried using anhydrous magnesium sulfate. After that, the anhydrous magnesium sulfate was filtered, and the ethyl acetate was removed by vacuum distillation to obtain a pale yellow liquid.

[0040] The resulting pale yellow liquid was treated as shown in Test Example 1 below. 1 1H NMR measurement and 13 By performing 13C NMR measurements, IR measurements as described in Test Example 2 below, and LC-MS measurements as described in Test Example 3 below, the following equation (4) is obtained. [ka] It was confirmed that compound A is a cyclic siloxane compound having a cyclic carbonate group with the structure shown in formula (4). In particular, LC-MS measurement revealed that only a peak at m / z 895.2328 was observed, confirming that this matches the molecular weight of cyclic siloxane compound A having a cyclic carbonate group with the structure of formula (4) above, to which a sodium ion has been added. Note that in the compound of formula (4) above, n is 4, m is 0, and R 1 is an n-propylene group, R 2 The methylene group is R 3 This corresponds to a compound in which the atom is a hydrogen atom.

[0041] Furthermore, the analysis confirmed that in cyclic siloxane compound A, all of the epoxy groups in formula (3) used as the material were replaced with cyclic carbonate groups. Figures 1-3 also show... 1 The results of the 1H NMR measurement are shown. In particular, Figure 2 is a magnified view of the region enclosed by the dashed line labeled "A" in Figure 1, and Figure 3 is a magnified view of the region enclosed by the dashed line labeled "B" in Figure 1. In Figures 2 and 3, peaks originating from the hydrogen atoms located at a~g and g' of the cyclic siloxane compound A shown in Figure 2 could be confirmed, respectively. Furthermore, in Figure 4, 13 The results of the 13C NMR measurement are shown. In Figure 4, peaks originating from carbon atoms 1-8 of the cyclic siloxane compound A shown in Figure 4 could be identified. Figure 5 shows the results of the IR measurement. Figure 6 shows the results of the MS measurement.

[0042] [Example 2] A pale yellow liquid was obtained in the same manner as in Example 1, except that the reaction time was changed to 24 hours at 50°C. The obtained pale yellow liquid was then subjected to the following test as described in Test Example 1 below. 1 1H NMR measurement and 13 By performing 13C NMR measurements, IR measurements as described in Test Example 2 below, and LC-MS measurements as described in Test Example 3 below, it was confirmed that the compound was formed in a mixed state containing cyclic siloxane compound A having a cyclic carbonate group with the structure of formula (4) above, cyclic siloxane compound B having a cyclic carbonate group with the structure of formula (5) below, cyclic siloxane compound C having a cyclic carbonate group with the structure of formula (6) below, and cyclic siloxane compound D having a cyclic carbonate group with the structure of formula (7) below. In particular, as shown in the LC-MS measurement results in Figure 7, peaks at m / z 895.2332, 851.2435, 807.2539, and 763.2637 were observed. These peaks correspond to the molecular weights obtained when sodium ions are added to cyclic siloxane compounds in which the epoxy groups in formula (3) above are substituted with 4, 3, 2, and 1 cyclic carbonate groups, respectively.

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] Furthermore, analysis revealed that 10% of the epoxy groups from formula (3) used as the raw material remained in the resulting mixture of cyclic siloxane compounds.

[0047] [Test Example 1] (NMR Measurement) (1) 1 H-NMR measurement Under the following conditions 1 1H-NMR measurements were performed. Equipment: Bruker Corporation, product name "Biospin Avance 500") 1 H-NMR resonance frequency: 500MHz Probe: 5mmφ solution probe Measurement temperature: room temperature (25℃) Repeat time: 1s Total number of times: 16

[0048] 1 The samples for H-NMR measurement were prepared under the following conditions. Silane compound concentration: 3% Measurement solvent: CDCl3

[0049] (2) 13 C-NMR measurement Under the following conditions 13 1C-NMR measurements were performed. Equipment: Bruker Corporation, product name "Biospin Avance 500") 13 C-NMR resonance frequency: 500MHz Probe: 5mmφ solution probe Measurement temperature: room temperature (25℃) Repeat time: 1s Total number of times: 1024

[0050] 13 The samples for 1C-NMR measurement were prepared under the following conditions. Silane compound concentration: 3% Measurement solvent: CDCl3

[0051] [Test Example 2] (IR Measurement) The IR spectrum was obtained using a Fourier transform infrared spectrophotometer (PerkinElmer Spectrum100) at wavenumbers 4000–400 cm⁻¹. -1 Measurements were taken within the specified range.

[0052] [Test Example 3] (LC-MS measurement) The sample was diluted with methanol to approximately 1 mg / mL, and then diluted 10-fold, 100-fold, or 1000-fold with methanol for measurement. Mass calibration was then performed using polyethylene glycol (PEG) and tetrabutylammonium (TBA) as external standards. Equipment: Hitachi High-Technologies Corporation, Mass Spectrometer "Nano Frontier eLD" Autosampler "LaChrom ELITE L-2200" Liquid delivery unit "LaChrom ELITE L-2100" UV detector "LaChrom ELITE L-2400" Column oven "LaChrom ELITE L-2300" Mobile phase: methanol (flow rate: 0.3 mL / min) Measurement method: Flow injection method Mode: ESI-MS positive ion It is primarily detected as a sodium adduct (+22.9 g / mol). [Industrial applicability]

[0053] The cyclic siloxane compounds of the present invention can be suitably used as materials for curable compositions.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, n represents an integer from 1 to 6, m represents an integer from 0 to 5, the sum of n and m is an integer from 3 to 6, the order of existence of the units enclosed in parentheses with n and m is arbitrary in formula (1), R １ R represents an alkylene group with 1 to 20 carbon atoms. ２ R represents an alkylene group with 1 to 10 carbon atoms. ３ (This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) A cyclic siloxane compound characterized by having the structure shown.

2. The aforementioned R １ The cyclic siloxane compound according to claim 1, characterized in that it is a propylene group.

3. The aforementioned R ２ The cyclic siloxane compound according to claim 1, characterized in that it is a methylene group.

4. The aforementioned R ３ The cyclic siloxane compound according to claim 1, characterized in that it is a methyl group.

5. A curable composition characterized by containing a cyclic siloxane compound according to any one of claims 1 to 4.

6. A cured product characterized by being obtained by curing the curable composition described in claim 5.

7. An adhesive containing the curable composition described in claim 5.

8. A method for producing a cyclic siloxane compound according to any one of claims 1 to 4, The following formula (2) 【Chemistry 2】 (wherein, x represents an integer of 3 to 6, and R １ represents an alkylene group having 1 to 20 carbon atoms, and R ２ represents an alkylene group having 1 to 10 carbon atoms, and R ３ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) A manufacturing method characterized by comprising the step of reacting an epoxy group-containing cyclic siloxane compound having the structure shown in (1) with carbon dioxide to obtain a compound having the structure shown in formula (1).

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