CN107033354A - A kind of liquid cage-type silsesquioxane and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of fine chemical preparation, and discloses a liquid cage silsesquioxane and a preparation method thereof. The liquid cage silsesquioxane uses aminoethylaminopropyltrimethoxysilane as a raw material, and firstly undergoes hydrolysis Condensation to synthesize solid aminoethylaminopropyl cage silsesquioxane, and then react with small molecule N,N-diethylamino-1,2-propylene oxide to obtain liquid cage silsesquioxane. The present invention synthesizes aminoethylaminopropyl cage silsesquioxane through aminoethylaminopropyltrimethoxysilane, and prepares liquid silsesquioxane on the basis of aminoethylaminopropyl cage silsesquioxane. Cage silsesquioxane. The prepared liquid cage silsesquioxane has greatly improved its compatibility and dispersion with epoxy resin, which facilitates the construction process. The prepared liquid cage silsesquioxane is used in epoxy The cured resin modification of the resin improves the thermal and mechanical properties of the epoxy resin.

Description

A kind of liquid cage silsesquioxane and preparation method thereof

technical field

The invention belongs to the technical field of fine chemical preparation, and in particular relates to a liquid cage-type silsesquioxane and a preparation method thereof.

Background technique

Cage silsesquioxane (POSS) is a nano-scale inorganic/organic hybrid material composed of Si and O as an internal cage-type inorganic framework and externally connected with organic groups. Due to the structural characteristics of inorganic/organic hybridization and external functional groups, POSS can be used in conjunction with a variety of thermosetting resins to form inorganic/organic hybrid nano-reinforced polymer materials.

High-performance, high-heat-resistant epoxy resin varieties are mainly those multifunctional epoxy resins with heat-resistant skeletons or that can increase cross-linking density. In addition to the influence of the structure of the epoxy resin itself, the influence of the type of curing agent is another important factor for its heat resistance. In general, they either have a stable chemical structure or are multifunctional, and react with epoxy resins to increase the degree of crosslinking and stability of epoxy resins, thereby improving their heat resistance. Amino cage silsesquioxane not only has a silicon cage group with excellent heat resistance, but also can provide a crosslinking density that is difficult to achieve with other curing agents, which greatly improves the heat resistance and mechanical properties of epoxy resins.

Traditional methods of modifying epoxy resins often use thermoplastic resins, rubber elastomers, thermotropic liquid crystal polymers, rigid particles, silicones, etc. to modify epoxy resins, but these modification methods usually improve a certain performance at the same time , loss of additional properties such as rubber toughening usually reduces heat resistance. For this reason, a large number of studies have been carried out on POSS at home and abroad. FrankJ.Feher and others synthesized a series of POSS with different structures, and systematically studied the synthesis conditions of POSS. Dong Xihua and others used aminopropyl cage siloxane (OapPOSS) to modify epoxy resin adhesives. However, most of the cage-type silsesquioxanes (POSS) reported so far are in the state of solid powder, which has poor compatibility with epoxy resins and is difficult to disperse uniformly.

In summary, the problems in the prior art are: the prior art usually loses other properties while improving a certain performance, and the products prepared by the prior art have poor compatibility and dispersibility with epoxy resins, and the environmental Oxygen resins have poor thermal and mechanical properties.

Contents of the invention

Aiming at the problems in the prior art, the invention provides a liquid cage silsesquioxane and a preparation method thereof.

The present invention is achieved in this way, a liquid cage silsesquioxane, the structural formula of the liquid cage silsesquioxane is as follows:

Another object of the present invention is to provide a method for preparing liquid cage silsesquioxane. The preparation method of liquid cage silsesquioxane uses aminoethylaminopropyltrimethoxysilane as a raw material, firstly through hydrolysis and condensation Synthesize solid aminoethylaminopropyl cage silsesquioxane, and then react with small molecule N,N-diethylamino-1,2-epoxypropane to prepare liquid cage silsesquioxane; specifically Include the following steps:

Step 1: Add deionized water, tetrabutylammonium hydroxide, and isopropanol into a round-bottomed flask, stir and heat up, add aminoethylaminopropyltrimethoxysilane dropwise, heat up after stirring, and react; filter to obtain a white powder, Vacuum drying to obtain solid aminoethylaminopropyl cage silsesquioxane;

Step 2, add epichlorohydrin and diethylamine in the flask, slowly add deionized water dropwise; react, then lower the temperature; dissolve sodium hydroxide in water to form a solution and add it to the reaction flask, and continue stirring; Separate the organic phase with a liquid funnel, wash with water, extract and dry to obtain N,N-diethylamino-1,2-propylene oxide;

Step 3, take N,N-diethylamino-1,2-propylene oxide in a four-necked flask, heat up, and dissolve the synthesized aminoethylaminopropyl cage silsesquioxane in methanol; then Slowly add it dropwise into a four-necked flask containing N,N-diethylamino-1,2-epoxypropylene under stirring conditions, and reflux reaction; after the reaction is stopped, the solvent is evaporated and the remaining solvent is dried to obtain a yellow viscous liquid. It is the liquid cage silsesquioxane.

Further, Step 1 specifically includes: adding 10 g of deionized water, 0.21 g of tetrabutylammonium hydroxide, and 31 g of isopropanol into a round bottom flask, stirring and raising the temperature to 30°C, and slowly adding 40.25 g of aminoethylaminopropyl trimethoxy base silane, stirred for 5 hours, then heated to 78°C, and reacted for 19 hours. The white powder was obtained by filtration, and dried in vacuum for 24 hours to obtain solid aminoethylaminopropyl cage silsesquioxane.

Further, step 2 specifically includes: adding 37g of epichlorohydrin and 28.8g of diethylamine into the flask, slowly adding 12g of deionized water dropwise, reacting at 29°C for 6h, then cooling down to 22°C, dissolving 16g of sodium hydroxide in Add 30.4ml of water to the reaction bottle, and continue to stir for 40 minutes; separate the organic phase with a separatory funnel, wash with water, extract, and vacuum dry at 80°C for 24 hours to obtain N,N-diethylamino-1, 2-Propylene oxide.

Further, Step 3 specifically includes: take 5.08g of N,N-diethylamino-1,2-epoxypropane in a four-necked flask, heat up to 70°C, and synthesize 1.76g of aminoethylaminopropyl cage sesqui Siloxane was dissolved in 25.28g of methanol, and then slowly added dropwise to a four-necked flask filled with N,N-diethylamino-1,2-epoxypropylene under stirring conditions, and reflux at 70°C for 4h; stop the reaction Afterwards, the solvent was removed by evaporation, and the remaining solvent was dried at 80°C to obtain a yellow viscous liquid, which was the liquid cage silsesquioxane.

Further, the synthetic route of the liquid cage silsesquioxane chemical formula is specifically:

Another object of the present invention is to provide a rubber prepared by utilizing the above-mentioned liquid cage silsesquioxane.

The advantages and positive effects of the present invention are: the liquid cage silsesquioxane crosslinking agent prepared by the present invention has good compatibility and dispersibility, and the ultraviolet light curing agent prepared by adding cage silsesquioxane Epoxy resin has the characteristics of temperature resistance and high hardness, and its high temperature resistance can reach above 260 °C.

The sample prepared by the present invention is tested and analyzed, and the temperature at 5% thermal weight loss is 380°C, the glass transition temperature is 141°C, the tensile strength is 60MPa, the elongation at break is 80%, and the toughness is 1127Pa.

The present invention has synthesized aminoethylaminopropyl cage silsesquioxane by aminoethylaminopropyl trimethoxysilane, in order to improve the phase of aminoethylaminopropyl cage silsesquioxane and epoxy resin Compatibility and dispersibility, liquid cage silsesquioxane was prepared on the basis of aminoethylaminopropyl cage silsesquioxane. The prepared liquid cage silsesquioxane is used for the curing resin modification of the epoxy resin, and the thermal performance and the mechanical performance of the epoxy resin are improved.

Description of drawings

Fig. 1 is a flowchart of the preparation method of liquid cage silsesquioxane provided by the embodiment of the present invention.

detailed description

In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

The application principle of the present invention will be described in detail below in conjunction with the accompanying drawings.

As shown in Figure 1, the preparation method of liquid cage silsesquioxane provided by the embodiment of the present invention specifically includes:

S101: Add deionized water, tetrabutylammonium hydroxide, and isopropanol into a round-bottomed flask, stir and heat up to 30°C, slowly add aminoethylaminopropyltrimethoxysilane dropwise, stir for 5 hours, then heat up to 78°C, Reaction 19h. The white powder was obtained by filtration, and dried in vacuum for 24 hours to obtain solid aminoethylaminopropyl cage silsesquioxane.

S102: Add epichlorohydrin and diethylamine to the flask, slowly add deionized water dropwise, react at 29°C for 6h, then cool down to 22°C, dissolve sodium hydroxide in water to make a solution and add it to the reaction flask, Stirring was continued for another 40 min. Separate the organic phase with a separatory funnel, wash with water, extract and dry to obtain N,N-diethylamino-1,2-propylene oxide.

S103: Take N,N-diethylamino-1,2-propylene oxide in a four-necked flask, heat up to 70°C, and dissolve the synthesized aminoethylaminopropyl cage silsesquioxane in methanol, Then it was slowly added dropwise into a four-necked flask filled with N,N-diethylamino-1,2-propylene oxide under stirring conditions, and refluxed at 70°C for 4h. After the reaction was stopped, the solvent was removed by evaporation, and the remaining solvent was dried at 80°C to obtain a yellow viscous liquid, which was the liquid cage silsesquioxane.

Further, in the preparation method of liquid cage silsesquioxane provided in the embodiment of the present invention, aminoethylaminopropyl trimethoxysilane is used as a raw material, and solid aminoethylaminopropyl cage silsesquioxane is first synthesized by hydrolysis and condensation. Siloxane, and then react with small molecule N,N-diethylamino-1,2-epoxypropylene to prepare liquid cage silsesquioxane. The synthetic route of liquid cage silsesquioxane chemical formula is as follows:

The present invention has synthesized aminoethylaminopropyl cage silsesquioxane by aminoethylaminopropyl trimethoxysilane, in order to improve the phase of aminoethylaminopropyl cage silsesquioxane and epoxy resin Compatibility and dispersibility, liquid cage silsesquioxane was prepared on the basis of aminoethylaminopropyl cage silsesquioxane. The prepared liquid cage silsesquioxane is used for the curing resin modification of the epoxy resin, and the thermal performance and the mechanical performance of the epoxy resin are improved.

The application principle of the present invention will be further described below in conjunction with specific embodiments.

Embodiment one:

(1) Add 10g of deionized water, 0.21g of tetrabutylammonium hydroxide, and 31g of isopropanol into a 500ml round bottom flask, stir and heat up to 30°C, slowly add 40.25g of aminoethylaminopropyltrimethoxysilane dropwise, After stirring for 5 hours, the temperature was raised to 78°C, and the reaction was carried out for 19 hours. The white powder was obtained by filtration, and dried in vacuum for 24 hours to obtain solid aminoethylaminopropyl cage silsesquioxane.

(2) Add 18.5g epichlorohydrin and 14.4 diethylamine into a 250ml round bottom flask, slowly add 6g deionized water dropwise, react at 29°C for 6h, then cool down to 22°C, dissolve 8g sodium hydroxide in 15.2 mL of water was made into a solution and added to the reaction flask, and the stirring was continued for 40 minutes. Separate the organic phase with a separatory funnel, wash with water, extract and dry to obtain N,N-diethylamino-1,2-propylene oxide.

(3) Take 2.54g of N,N-diethylamino-1,2-epoxypropane in a four-necked flask, heat up to 70°C, and dissolve the synthesized 0.88g of aminoethylaminopropyl cage silsesquioxane Add 12.64g of methanol, and slowly add it dropwise into a four-necked flask filled with N,N-diethylamino-1,2-propylene oxide under stirring conditions, and react at reflux at 70°C for 4h. After stopping the reaction, remove the solvent by evaporation, and dry the remaining solvent at 80°C to obtain a yellow viscous liquid, which is the liquid cage silsesquioxane.

Add the synthesized liquid cage silsesquioxane at 3% of the mass of the epoxy resin E-51, mix it evenly with the epoxy resin E-51, pre-react at 70°C for 30 minutes, and then cool down to room temperature. Add 5wt% of photoinitiator diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate, mix well and irradiate for 40s under ultraviolet light, the resin is completely cured.

Embodiment two:

(1) Add 10g of deionized water, 0.21g of tetrabutylammonium hydroxide, and 31g of isopropanol into a 500ml round bottom flask, stir and heat up to 30°C, slowly add 40.25g of aminoethylaminopropyltrimethoxysilane dropwise, After stirring for 5 hours, the temperature was raised to 78°C, and the reaction was carried out for 19 hours. The white powder was obtained by filtration, and dried in vacuum for 24 hours to obtain solid aminoethylaminopropyl cage silsesquioxane.

(2) Add 18.5g epichlorohydrin and 14.4 diethylamine into a 250ml round bottom flask, slowly add 6g deionized water dropwise, react at 29°C for 6h, then cool down to 22°C, dissolve 8g sodium hydroxide in 15.2 mL of water was made into a solution and added to the reaction flask, and the stirring was continued for 40 minutes. Separate the organic phase with a separatory funnel, wash with water, extract and dry to obtain N,N-diethylamino-1,2-propylene oxide.

(3) Take 2.54g of N,N-diethylamino-1,2-epoxypropane in a four-necked flask, heat up to 70°C, and dissolve the synthesized 0.88g of aminoethylaminopropyl cage silsesquioxane Add 12.64g of methanol, and slowly add it dropwise into a four-necked flask filled with N,N-diethylamino-1,2-propylene oxide under stirring conditions, and react at reflux at 70°C for 4h. After stopping the reaction, remove the solvent by evaporation, and dry the remaining solvent at 80°C to obtain a yellow viscous liquid, which is the liquid cage silsesquioxane.

Add the synthesized liquid cage silsesquioxane at 5% of the mass of the epoxy resin E-51, mix it evenly with the epoxy resin E-51, pre-react at 70° C. for 30 minutes, and then cool down to room temperature. Add 5wt% of photoinitiator diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate, mix well and irradiate for 40s under ultraviolet light, the resin is completely cured.

Embodiment three:

(1) Add 10g of deionized water, 0.21g of tetrabutylammonium hydroxide, and 31g of isopropanol into a 500ml round bottom flask, stir and heat up to 30°C, slowly add 40.25g of aminoethylaminopropyltrimethoxysilane dropwise, After stirring for 5 hours, the temperature was raised to 78°C, and the reaction was carried out for 19 hours. The white powder was obtained by filtration, and dried in vacuum for 24 hours to obtain solid aminoethylaminopropyl cage silsesquioxane.

(2) Add 18.5g epichlorohydrin and 14.4 diethylamine into a 250ml round bottom flask, slowly add 6g deionized water dropwise, react at 29°C for 6h, then cool down to 22°C, dissolve 8g sodium hydroxide in 15.2 mL of water was made into a solution and added to the reaction flask, and the stirring was continued for 40 minutes. Separate the organic phase with a separatory funnel, wash with water, extract and dry to obtain N,N-diethylamino-1,2-propylene oxide.

(3) Take 2.54g of N,N-diethylamino-1,2-epoxypropane in a four-necked flask, heat up to 70°C, and dissolve the synthesized 0.88g of aminoethylaminopropyl cage silsesquioxane Add 12.64g of methanol, and slowly add it dropwise into a four-necked flask filled with N,N-diethylamino-1,2-propylene oxide under stirring conditions, and react at reflux at 70°C for 4h. After stopping the reaction, remove the solvent by evaporation, and dry the remaining solvent at 80°C to obtain a yellow viscous liquid, which is the liquid cage silsesquioxane.

Add the synthesized liquid cage silsesquioxane at 8% of the mass of the epoxy resin E-51, mix it evenly with the epoxy resin E-51, pre-react at 70°C for 30 minutes, and then cool down to room temperature. Add 5wt% of photoinitiator diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate, mix well and irradiate for 40s under ultraviolet light, the resin is completely cured.

Mechanical Properties of Liquid Cage Silsesquioxane Modified Epoxy Resin

components E-51 epoxy resin Embodiment one Embodiment two Embodiment three Tensile strength (MPa) 55 60 70 78 Toughness (Pa) 1024 1125 1127 1196

Thermal Properties of Liquid Cage Silsesquioxane Modified Epoxy Resin

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.

Claims (7)

1. a liquid cage type silsesquioxane, characterized in that, the structural formula of the liquid cage type silsesquioxane is as follows: 2. a method for preparing liquid cage silsesquioxane as claimed in claim 1, wherein the method for preparing liquid cage silsesquioxane takes aminoethylaminopropyltrimethoxysilane as raw material , first synthesize solid aminoethylaminopropyl cage-type silsesquioxane by hydrolysis and condensation, and then react with small molecule N,N-diethylamino-1,2-epoxypropane to prepare liquid cage-type silsesquioxane Siloxane; Specifically comprise the following steps: Step 1: Add deionized water, tetrabutylammonium hydroxide, and isopropanol into a round-bottomed flask, stir and heat up, add aminoethylaminopropyltrimethoxysilane dropwise, heat up after stirring, and react; filter to obtain a white powder, Vacuum drying to obtain solid aminoethylaminopropyl cage silsesquioxane; Step 2, add epichlorohydrin and diethylamine in the flask, slowly add deionized water dropwise; react, then lower the temperature; dissolve sodium hydroxide in water to form a solution and add it to the reaction flask, and continue stirring; Separate the organic phase with a liquid funnel, wash with water, extract and dry to obtain N,N-diethylamino-1,2-propylene oxide; Step 3, take N,N-diethylamino-1,2-propylene oxide in a four-necked flask, heat up, and dissolve the synthesized aminoethylaminopropyl cage silsesquioxane in methanol; then Slowly add it dropwise into a four-necked flask containing N,N-diethylamino-1,2-epoxypropylene under stirring conditions, and reflux reaction; after the reaction is stopped, the solvent is evaporated and the remaining solvent is dried to obtain a yellow viscous liquid. It is the liquid cage silsesquioxane. 3. the method for preparing liquid cage silsesquioxane as claimed in claim 2, is characterized in that, step one specifically comprises: add deionized water, tetrabutylammonium hydroxide, Virahol in round bottom flask, three The mass ratio is 8-15:0.18-0.24:25-35, stir and heat up to 30°C, slowly add 40.25g of aminoethylaminopropyltrimethoxysilane dropwise, stir for 5h, then heat up to 78°C, react for 19h; filter A white powder was obtained and dried in vacuum for 24 hours to obtain solid aminoethylaminopropyl cage silsesquioxane. 4. The method for preparing liquid cage-type silsesquioxane as claimed in claim 2, wherein step 2 specifically comprises: adding 37g epichlorohydrin and 28.8g diethylamine in a flask, slowly adding 12g dropwise to remove Ionized water, react at 29°C for 6h, then cool down to 22°C, dissolve 16g of sodium hydroxide in 30.4ml of water to make a solution, add it to the reaction flask, and continue stirring for 40min; separate the organic phase with a separatory funnel, and wash with water , extraction, and vacuum drying at 80°C for 24 hours to obtain N,N-diethylamino-1,2-propylene oxide. 5. The method for preparing liquid cage silsesquioxane as claimed in claim 2, wherein step 3 specifically comprises: taking 5.08gN,N-diethylamino-1,2-propylene oxide in a four-necked flask In , heat up to 70°C, dissolve 1.76g of aminoethylaminopropyl cage silsesquioxane synthesized in 25.28g of methanol, and then slowly add it dropwise to the -In a four-necked flask of 1,2-propylene oxide, reflux at 70°C for 4 hours; evaporate the solvent after stopping the reaction, and dry the remaining solvent at 80°C to obtain a yellow viscous liquid, which is the liquid cage sesquite silicone. 6. the preparation method of liquid cage silsesquioxane as claimed in claim 2, is characterized in that, described liquid cage silsesquioxane chemical molecular formula synthetic route is specifically: 7. A rubber prepared by utilizing the liquid cage silsesquioxane according to claim 1.