Alcohol-soluble polyphenylsilsesquioxane having a high hydroxyl content and a method for preparing the same

Abstract

This application provides an alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content and its preparation method, relating to the field of organosilicon polymer materials technology. The polyphenylsilsesquioxane has the structure shown in Formula I: ; where R is independently any one of phenyl, a combination of phenyl and vinyl, a combination of phenyl and cycloalkyl, or a combination of phenyl, vinyl, and cycloalkyl; a and b are positive integers, and the ratio of a to b is (14:1) to (1:6.5). This alcohol-soluble polyphenylsilsesquioxane has a hydroxyl content in the range of 30-55%, exhibits good alcohol solubility, overcoming the shortcomings of traditional PPSQ, which has extremely low solubility in ethanol and requires processing with toxic solvents. Furthermore, it possesses excellent thermal stability, meeting the requirements of extreme environments.

Description

Technical Field

[0001] This application relates to the field of organosilicon polymer materials technology, and in particular to an alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content and its preparation method. Background Technology

[0002] Polyphenylsilsesquioxane (PPSQ) is a hybrid material that combines the flexibility of organic materials with the heat resistance of inorganic materials, and is widely used in electronic packaging, flame-retardant coatings, and other fields. However, the high hydrophobicity of the phenyl groups and the extremely low content of silanol groups (Si-OH) in traditional PPSQ molecules mean that it is only soluble in toxic solvents such as toluene and tetrahydrofuran (THF), severely limiting its application in green chemistry and biomedical fields. In existing patented technologies, the processing of PPSQ is highly dependent on highly toxic solvents, threatening production safety and hindering sustainable industrial development. For example, Chinese patent CN118561905A explicitly uses toluene to dissolve PPSQ and ethanol to wash the filter cake when preparing PPSQ composite materials. This operation indirectly proves that traditional PPSQ has extremely low solubility in ethanol and must rely on toxic solvents for processing.

[0003] Traditional PPSQ has a high degree of molecular chain condensation, with silanol groups almost exclusively distributed at the end groups and present in extremely low concentrations. This results in insufficient polarity and incompatibility with green solvents such as ethanol. Current methods primarily aim to improve its solubility through blending modification and surface grafting. However, these methods generally suffer from the following drawbacks: sacrificing intrinsic material properties, such as decreased heat resistance; and requiring the addition of crosslinking agents, complicating the process. Therefore, the toxic solvent dependence of traditional PPSQ continues to limit its application expansion. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this application provides an alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content and its preparation method. The polyphenylsilsesquioxane has a hydroxyl content of 30% to 55% and can be dissolved in ethanol, significantly reducing the dependence on toxic solvents in downstream applications.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] According to one aspect of this application, an alcohol-soluble polyphenylsilsesquioxane with a hydroxyl content is provided, having the following structural formula:

[0007] Formula I;

[0008] In Formula I, R is independently any one of phenyl, a combination of phenyl and vinyl, a combination of phenyl and cycloalkyl, or a combination of phenyl, vinyl, and cycloalkyl; the cycloalkyl group is preferably cyclohexyl.

[0009] a and b are positive integers, and the ratio of a to b is (14:1) to (1:6.5).

[0010] According to another aspect of this application, a method for preparing an alcohol-soluble polyphenylsilsesquioxane with a hydroxyl content includes the following steps:

[0011] (a) A silane compound and an organic solvent are mixed to obtain a mixed solution;

[0012] (b) Cool the mixed solution to -10°C, add ice water mixture, and a hydrolysis reaction will occur to obtain the hydrolysis product;

[0013] (c) The hydrolysis product is heated to 10-50°C to carry out a polycondensation reaction to obtain the polycondensation product;

[0014] (d) Remove the solvent from the condensation product, wash, and dry to obtain the final product;

[0015] The silane compound is selected from any one of phenyl silane compounds, combinations of phenyl silane compounds and vinyl silane compounds, combinations of phenyl silane compounds and cycloalkyl silane compounds, and combinations of phenyl silane compounds and vinyl silane compounds and cycloalkyl silane compounds.

[0016] Furthermore, the phenylsilane compound is selected from any one of phenyltrichlorosilane, a combination of phenyltrichlorosilane and phenyltrimethoxysilane, a combination of phenyltrichlorosilane and phenyltriethoxysilane, or a combination of phenyltrichlorosilane and phenyltrimethoxysilane and phenyltriethoxysilane.

[0017] Furthermore, the vinylsilane compound is vinyltrichlorosilane.

[0018] Furthermore, the cycloalkylsilane compound is cyclohexyltriethoxysilane and / or cyclohexyltrichlorosilane.

[0019] Preferably, the silane compound is phenyltrichlorosilane; or

[0020] A molar ratio of phenyltrichlorosilane to vinyltrichlorosilane of 10:(1–1.25); or

[0021] A molar ratio of 10:(1–1.25) of phenyltrichlorosilane, phenyltrimethoxysilane / phenyltriethoxysilane; or

[0022] phenyltrichlorosilane, vinyltrichlorosilane, phenyltrimethoxysilane / phenyltriethoxysilane in a molar ratio of 9:1:(1–1.25); or

[0023] Phenylacetyltrichlorosilane, phenyltrimethoxysilane / phenyltriethoxysilane, and cyclohexyltriethoxysilane are present in a molar ratio of 10:(1-1.25):(0.5-1).

[0024] Furthermore, the organic solvent is selected from any one or a combination of dichloromethane, chloroform, methyl isobutyl ketone, acetone, and toluene. The amount of organic solvent used is not specifically limited, as long as it can dissolve the silane compound; preferably, the mass ratio of the silane compound to the volume of the organic solvent is 1 g: 2-10 mL, more preferably 1 g: 2.6-8 mL.

[0025] Furthermore, the mass ratio of the ice-water mixture to the silane compound is (0.5-10):1, preferably (0.5-6):1.

[0026] Furthermore, the hydrolysis reaction is carried out at a temperature of -10 to 0°C for a duration of 2 to 4 hours.

[0027] Furthermore, the temperature of the polycondensation reaction is 10–50°C, and the reaction time is 1–7 hours.

[0028] Compared with the prior art, this application has, but is not limited to, the following beneficial effects:

[0029] 1. This application provides a method for preparing alcohol-soluble polyphenylsilsesquioxane (PPSQ). First, phenyltrichlorosilane and other silane compounds are hydrolyzed at low temperature. After hydrolysis, the solution becomes acidic, and then polycondensation is performed to obtain PPSQ. Under acidic conditions, the polycondensation product PPSQ retains a large amount of uncondensed Si-OH in its molecular chain. While retaining its excellent heat resistance, the hydroxyl content of PPSQ is adjusted to the range of 30-55%, so that it forms a stable dissolution-dispersion system in ethanol (the solubility reaches 15g / 100g ethanol at 70℃), completely breaking through the barrier of traditional PPSQ being insoluble in ethanol.

[0030] 2. The downstream products processed by PPSQ in this application can directly use ethanol (an FDA-recognized safe solvent), achieving non-toxicity, reducing VOC emissions by more than 80%, and reducing environmental pollution.

[0031] 3. The PPSQ of this application also has excellent thermal stability, which can meet the requirements of extreme environments.

[0032] 4. The PPSQ of this application can be applied to environmentally friendly coatings, medical materials, and high-end electronic packaging materials. In addition, PPSQ contains abundant active sites, which can be further grafted and modified or bonded to fillers for the development of antibacterial, conductive and other special materials, thus expanding the application fields. Attached Figure Description

[0033] Figure 1 This is a structural diagram of the polyphenylsilsesquioxane prepared in Example 1 of this application;

[0034] Figure 2This is the FT-IR spectrum of the polyphenylsilsesquioxane prepared in Example 1 of this application;

[0035] Figure 3 It is the polyphenylsilsesquioxane prepared in Example 1 of this application. 1 H NMR spectrum;

[0036] Figure 4 It is the polyphenylsilsesquioxane prepared in Example 1 of this application. 13 C NMR spectrum;

[0037] Figure 5 It is the solid polyphenylsilsesquioxane prepared in Example 1 of this application. 29 Si NMR spectrum;

[0038] Figure 6 This is the TG spectrum of the polyphenylsilsesquioxane prepared in Example 1 of this application. Detailed Implementation

[0039] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of this application, but do not limit this application in any way. The following content is merely an exemplary description of the scope of protection claimed in this application, and those skilled in the art can make various changes and modifications to the invention based on the disclosed content, which should also fall within the scope of protection claimed in this application.

[0040] The present application will be further described below by way of specific embodiments. Unless otherwise specified, all chemical reagents used in the embodiments of this application are obtained through conventional commercial means.

[0041] Example 1

[0042] This embodiment provides a method for preparing an alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content, comprising the following steps:

[0043] 85g of phenyltrichlorosilane was dissolved in 240mL of methyl isobutyl ketone to obtain a mixed solution. The mixed solution was cooled to -10℃, and 101g of ice-water mixture was added to the above mixed solution. The polycondensation reaction was carried out at 50℃ for 1h. After washing, rotary evaporation, and drying, a white powder solid was obtained, which is polyphenylsilsesquioxane.

[0044] Figure 1 The figure shows the structural formula of the polyphenylsilsesquioxane prepared in this embodiment, where T2 and T3 correspond to... Figure 5 Chemical shifts of two types of silicon atoms.

[0045] Figure 2 This is the FT-IR spectrum of the polyphenylsilsesquioxane of this application. As can be seen from the figure, at 3625 cm⁻¹... -13390cm -1 The absorption peak at 3064 cm⁻¹ corresponds to the stretching vibration of Si-OH. -1 The absorption peak at 1433 cm⁻¹ corresponds to the CH stretching vibration on the aromatic ring. -1 The absorption peak at that point is due to the C-C stretching vibration of the aromatic ring.

[0046] Figure 3 The polyphenylsilsesquioxane of this application 1 The 1H NMR spectrum is shown in the figure. The 2.5 ppm peak is the solvent peak (DMSO), and the 7.41 ppm signal peak is the H on the benzene ring.

[0047] Figure 4 The polyphenylsilsesquioxane of this application 13 The C NMR spectrum shows that the three signal peaks at 133.4 ppm, 130.5 ppm, and 127.7 ppm are all C on the benzene ring.

[0048] Figure 5 The solid polyphenylsilsesquioxane of this application 29 The Si NMR spectrum shows two signal peaks, -67.83 ppm and -77.00 ppm, corresponding to two different chemical shifts of silicon atoms, such as... Figure 1 As shown, they are named T2 and T3 respectively. After integral calculation, the hydroxyl content is 48%, indicating that the synthesized polyphenylsilsesquioxane has a high hydroxyl content.

[0049] Figure 6 The TG spectrum of polyphenylsilsesquioxane under a nitrogen atmosphere, with a 5% thermogravimetric temperature (T). 5% The temperature is 512.35℃, and the 10% thermal weight loss temperature (T) is... 10% The temperature is 553.60℃, and the 20% thermal weight loss temperature (T) is... 20% The temperature was 622.59℃, and the maximum thermal weight loss temperature (T) was... max The temperature is 569.08℃, and the residual weight at 1000℃ is 77.04%, indicating excellent heat resistance.

[0050] Tests showed that the synthesized polyphenyl silsesquioxane (PPSQ) with high hydroxyl content had a solubility of 15 g / 100 g ethanol at 70 °C.

[0051] Example 2

[0052] This embodiment provides another method for preparing alcohol-soluble polyphenyl silsesquioxane with high hydroxyl content, including the following steps: dissolving 4g of vinyltrichlorosilane and 52g of phenyltrichlorosilane (molar ratio 1:10) in 163mL of methyl isobutyl ketone to obtain a mixed solution, cooling the mixed solution to -10℃; adding 83g of ice-water mixture to the above mixed solution, reacting at 10℃ for 7h, rotary evaporating and drying to obtain the final product.

[0053] Example 3

[0054] This embodiment provides another method for preparing alcohol-soluble polyphenyl silsesquioxane with high hydroxyl content, including the following steps: dissolving 6.2g of vinyltrichlorosilane and 52g of phenyltrichlorosilane (molar ratio 1.25:10) in 175mL of methyl isobutyl ketone to obtain a mixed solution, cooling the mixed solution to -10℃; adding 83g of ice-water mixture to the above mixed solution, reacting at 50℃ for 3h, and then rotary evaporating and drying after the reaction is complete to obtain the product.

[0055] Example 4

[0056] This embodiment provides another method for preparing alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content, including the following steps: dissolving 20g of phenyltrimethoxysilane and 169g of phenyltrichlorosilane (molar ratio 1.25:10) in 492mL of methyl isobutyl ketone to obtain a mixed solution, cooling the mixed solution to -10℃; adding 162g of ice-water mixture to the above mixed solution, reacting at 50℃ for 3h, then raising the temperature to 50℃ for 2h, and after the reaction is complete, rotary evaporation and drying to obtain a white powder solid.

[0057] Example 5

[0058] This embodiment provides another method for preparing alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content, comprising the following steps: dissolving 19g of phenyltriethoxysilane and 169g of phenyltrichlorosilane (molar ratio 1:10) in 1012mL of toluene to obtain a mixed solution, cooling the mixed solution to -10℃; adding 108g of ice-water mixture to the above mixed solution, reacting at 50℃ for 1h; rotary evaporation and drying to obtain a white powdery solid.

[0059] Example 6

[0060] This embodiment provides another method for preparing alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content, comprising the following steps: dissolving 10g of phenyltrimethoxysilane, 8g of vinyltrichlorosilane, and 95g of phenyltrichlorosilane (molar ratio 1:1:9) in 937mL of methyl isobutyl ketone to obtain a mixed solution; cooling the mixed solution to -10°C, adding 71g of an ice-water mixture to the above mixed solution, and reacting at 10°C for 7h. The mixture is then rotary evaporated and dried to obtain a white powdery solid.

[0061] Example 7

[0062] This embodiment provides another method for preparing alcohol-soluble polyphenyl silsesquioxane with high hydroxyl content, including the following steps: dissolving 4g vinyltrichlorosilane, 3g cyclohexyltriethoxysilane and 52g phenyltrichlorosilane (molar ratio of feed: 1:0.5:10) in 163mL methyl isobutyl ketone to obtain a mixed solution, cooling the mixed solution to -10℃; adding 83g ice-water mixture to the above mixed solution, reacting at 10℃ for 7h, rotary evaporating and drying to obtain the final product.

[0063] Example 8

[0064] The difference from Example 2 is that the molar ratio of vinyltrichlorosilane to phenyltrichlorosilane is 1.5:10.

[0065] Example 9

[0066] The difference from Example 4 is that the molar ratio of phenyltrimethoxysilane and phenyltrichlorosilane is 1.5:10.

[0067] Comparative Example 1

[0068] The polyphenylsilsesquioxane of this comparative example was prepared by the following method: 106 g of phenyltrichlorosilane was dissolved in 148 g of diethyl ether, 27 g of water was added, and the reaction was carried out for 1 h. Then, 138 g of toluene was added, the temperature was raised to 55 °C, the mixture was washed with water, and rotary evaporated to obtain a prepolymer. 50 g of the prepolymer containing 3 ml of KOH in a methanol solution (2 wt‰) was added to a reaction vessel, nitrogen gas was introduced, and the reaction was carried out at 70 °C for 0.5 h. The temperature was then raised to 250 °C and the reaction was carried out for 1 h. The mixture was filtered to obtain a powdered solid. The polyphenylsilsesquioxane obtained in this comparative example has a hydroxyl content of 0 and an ethanol solubility of 0 at 70 °C.

[0069] The hydroxyl content, solubility, and 5% thermal weight loss temperature (T) of the polyphenylsilsesquioxane obtained in the above examples are as follows: 5% Maximum thermal weight loss temperature (T) max ) and the residual weight at 1000℃.

[0070] Table 1

[0071]

[0072] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, this application is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of this application without departing from the scope of this application should be within the protection scope of this application.

Claims

1. A method for preparing an alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content, characterized in that, Includes the following steps: (a) A silane compound and an organic solvent are mixed to obtain a mixed solution; (b) Cool the mixed solution to -10°C, add ice water mixture to cause hydrolysis reaction, the temperature of hydrolysis reaction is -10 to 0°C, and the hydrolysis product is obtained; (c) The hydrolysis product is heated to 10-50°C to carry out a polycondensation reaction to obtain the polycondensation product; (d) Remove the solvent from the condensation product, wash, and dry to obtain the final product; Wherein, the silane compound is phenyltrichlorosilane; or A molar ratio of phenyltrichlorosilane to vinyltrichlorosilane of 10:(1–1.25); or A molar ratio of 10:(1–1.25) of phenyltrichlorosilane, phenyltrimethoxysilane / phenyltriethoxysilane; or phenyltrichlorosilane, vinyltrichlorosilane, phenyltrimethoxysilane / phenyltriethoxysilane in a molar ratio of 9:1:(1–1.25); or Phenylacetyltrichlorosilane, phenyltrimethoxysilane / phenyltriethoxysilane, and cyclohexyltriethoxysilane in a molar ratio of 10:(1~1.25):(0.5~1); The alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content has the structure shown in Formula I: Equation I; In Formula I, R is independently any one of phenyl, a combination of phenyl and vinyl, or a combination of phenyl and cyclohexyl; a and b are positive integers, and the ratio of a to b is (14:1) to (1:6.5). The hydroxyl content of the alcohol-soluble polyphenylsilsesquioxane with high hydroxyl content is 30% to 55%.

2. The preparation method according to claim 1, characterized in that, The organic solvent is selected from any one or a combination of dichloromethane, chloroform, methyl isobutyl ketone, acetone, and toluene.

3. The preparation method according to claim 1, characterized in that, The mass ratio of the ice-water mixture to the silane compound is (0.5–10):

1.

4. The preparation method according to claim 1, characterized in that, The hydrolysis reaction takes 2 to 4 hours.

5. The preparation method according to claim 1, characterized in that, The temperature of the polycondensation reaction is 10–50℃, and the reaction time is 1–7 hours.

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