阅读说明：本技术 用于rtv硅橡胶的聚倍半硅氧烷偶联剂合成方法及脱酮肟型硅橡胶 (Synthesis method of polysilsesquioxane coupling agent for RTV (room temperature vulcanized) silicone rubber and deketoxime type silicone rubber ) 是由 陈君行 程小莲 翟晓旭 胡新嵩 李万华 徐文杰 王少辉 钟志贤 张杰龙 于 2021-08-13 设计创作，主要内容包括：本发明公开了一种用于RTV硅橡胶的聚倍半硅氧烷偶联剂合成方法,按重量份计,将20份氨基硅烷偶联剂、20份环氧基硅烷偶联剂、10～20份其它功能性硅烷,1.0～2.0份低沸点水解促进剂以及0.2～1.0份纯水,投入到带搅拌的反应釜中,在釜温65～80℃搅拌下反应1.5～2小时,搅拌转速为60～100rpm；开启真空泵,使所述反应釜在真空度0.09～0.1MPa条件下,釜温80～100℃真空蒸馏0.9-1.1小时,得到透明液体产物即为所述聚倍半硅氧烷偶联剂。使用该方法可使工艺设备简单,原料价廉易得,安全环保,制取的产物可直接作为RTV硅橡胶硅酮胶的增粘剂使用,既减少了生产成本,创造了经济效益,提高了生产效率又减少了环境污染。本发明还公开了一种利用上述聚倍半硅氧烷偶联剂制成的脱酮肟型硅橡胶。(The invention discloses a synthesis method of a polysilsesquioxane coupling agent for RTV (room temperature vulcanized) silicone rubber, which comprises the following steps of putting 20 parts by weight of an aminosilane coupling agent, 20 parts by weight of an epoxy silane coupling agent, 10-20 parts by weight of other functional silanes, 1.0-2.0 parts by weight of a low boiling point hydrolysis promoter and 0.2-1.0 part by weight of pure water into a reaction kettle with stirring, and reacting for 1.5-2 hours under stirring at the kettle temperature of 65-80 ℃ at the stirring rotating speed of 60-100 rpm; and starting a vacuum pump to ensure that the reaction kettle is subjected to vacuum distillation for 0.9 to 1.1 hours at the kettle temperature of 80 to 100 ℃ under the condition that the vacuum degree is 0.09 to 0.1MPa, so as to obtain a transparent liquid product, namely the polysilsesquioxane coupling agent. The method has the advantages of simple process equipment, cheap and easily available raw materials, safety and environmental protection, and the prepared product can be directly used as the tackifier of the RTV silicone rubber silicone adhesive, thereby reducing the production cost, creating economic benefits, improving the production efficiency and reducing the environmental pollution. The invention also discloses a deketoxime type silicon rubber prepared by using the polysilsesquioxane coupling agent.)

1. A synthetic method of polysilsesquioxane coupling agent for RTV silicone rubber, characterized in that the synthetic method comprises the following steps:

1) according to parts by weight, 20 parts of aminosilane coupling agent, 20 parts of epoxy silane coupling agent, 10-20 parts of other functional silanes, 1.0-2.0 parts of low boiling point hydrolysis promoter and 0.2-1.0 part of pure water are put into a reaction kettle with stirring, and the mixture is stirred at the kettle temperature of 65-80 ℃ for 1.5-2 hours, wherein the stirring speed is 60-100 rpm;

2) and starting a vacuum pump to ensure that the reaction kettle is subjected to vacuum distillation for 0.9 to 1.1 hours at the kettle temperature of 80 to 100 ℃ under the condition that the vacuum degree is 0.09 to 0.1MPa, so as to obtain a transparent liquid product, namely the polysilsesquioxane coupling agent.

2. The method of synthesizing a polysilsesquioxane coupling agent for RTV silicone rubber as recited in claim 1, wherein said aminosilane coupling agent is: any one or more of aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrialkoxysilane, 3-phenylaminopropyltrialkoxysilane, aminopropylmethyldialkoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldialkoxysilane, N-N-butyl-3-aminopropyltrialkoxysilane and 3- (diethylenetriamino) propyltrialkoxysilane.

3. The method of synthesizing a polysilsesquioxane coupling agent for RTV silicone rubber as recited in claim 2, wherein said epoxysilane coupling agent is: gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silicon, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane and 3-glycidoxypropyl methyl diethoxy silicon.

4. The method of synthesizing a polysilsesquioxane coupling agent for RTV silicone rubber as set forth in claim 3, wherein said other functional silanes are: ethyl orthosilicate, propyl trimethoxy silane, phenyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, tetramethoxy silane, tetraethoxy silane, methyl trimethoxy silane, phenyl trimethoxy silane, diphenyl dimethoxy silane, methyl phenyl dimethoxy silane, vinyl trimethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, and 3- (methacryloxy) propyl methyl dimethoxy silane.

5. The method of synthesizing a polysilsesquioxane coupling agent for RTV silicone rubber as set forth in claim 4, wherein said low-boiling hydrolysis facilitator is: any one or more of triethylamine, ethylenediamine, glacial acetic acid, pyridine or diisopropylethylamine.

6. The method for synthesizing a polysilsesquioxane coupling agent for RTV silicone rubber according to any of claims 1 to 5, wherein said pure water is added in an amount of 0.5 to 2.5% by weight based on the total weight of the aminosilane coupling agent and the epoxysilane coupling agent.

7. The method for synthesizing a polysilsesquioxane coupling agent for RTV silicone rubber as set forth in claim 6, wherein 20g of aminopropyltriethoxysilane, 20g of γ - (2, 3-glycidoxy) propyltrimethoxysilane, 20g of ethyl orthosilicate, 0.2g to 1.0g of pure water and 1g of triethylamine are added as hydrolysis accelerators in a 250mL three-necked flask; after the addition is finished, the stirring is started, the rotating speed is 100rpm, and the stirring reaction is carried out for 1.5 hours when the oil bath is heated to 65 ℃; distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a colorless transparent liquid product; a calibration curve y for predicting the viscosity of the polysilsesquioxane coupling agent was obtained, using the amount of water added as the abscissa x and the viscosity of the polysilsesquioxane coupling agent as the ordinate y, of 163.18ln (x) + 329.03.

8. The method for synthesizing a polysilsesquioxane coupling agent for RTV silicone rubber as set forth in any of claims 1-5, wherein said polysilsesquioxane coupling agent has the following specific structural formula:

9. a polysilsesquioxane coupling agent, obtainable by a synthesis process according to any one of claims 1 to 8, having the specific structural formula:

10. the deketoxime type silicon rubber is prepared by mixing the following raw materials in parts by weight at room temperature: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate; the method is characterized in that: the coupling agent is a polysilsesquioxane coupling agent obtained by the synthesis method of any of the preceding claims 1-8.

Technical Field

The invention relates to a synthetic method of polysilsesquioxane coupling agent for RTV (room temperature vulcanized) silicone rubber and deketoxime type silicone rubber, belonging to the technical field of fine chemical engineering.

Background

Silane coupling agents are important industrial additives that can be used to couple organic and inorganic substances, as tackifiers, crosslinkers and curatives for silicone rubbers and resins, and as textile finishes, coating additives, and the like. Because the silane coupling agent has two functional groups of organophilic and inophilic in the middle of the molecule, two materials with different chemical structure types and greatly different affinities can be connected at the interface, and the combination of the paint, the inorganic bottom layer, the pigment, the filler and the polymer is increased.

Polysilsesquioxanes (POSS), particularly cage polysilsesquioxanes, have been extensively studied in polymer materials for reinforcement, toughening, flame retardance, reduction of dielectric constant, proton exchange membranes, and the like. Polysilsesquioxane is generally prepared by hydrolyzing and condensing trichlorosilane or trialkoxysilane, and products with trapezoidal, cage-shaped, irregular and other structures can be obtained by controlling reaction conditions. Polysilsesquioxanes are structurally characterized by cubes consisting of a rigid Si-O-Si backbone inside, and organic substituents on the corners, offering the potential to serve as inorganic-organic hybrid precursors. The organic substituent group positioned on the angle of the polysilsesquioxane can solve the problem of interfacial incompatibility between the organic polymer and the inorganic filler in the traditional system, so that the polysilsesquioxane can be well dispersed in the hybrid polymer. Meanwhile, the introduction of polysilsesquioxane into polymers has been reported in documents, which can improve the high temperature resistance and mechanical properties of the polymers, and increase the flame retardance, oxidation resistance and dielectric properties.

The existing synthetic methods for the polysilsesquioxane compound have the following problems by comprehensively analyzing the current research situation of the polysilsesquioxane: one is that the synthesis usually uses strong acids or strong bases (such as sodium hydroxide, concentrated sulfuric acid, concentrated hydrochloric acid, etc.) as hydrolysis promoters. The use of strong acid and strong base has problems in that purification after completion of the reaction becomes complicated, the reaction system is neutralized to be acidic, and operations such as filtration and liquid separation are performed, increasing the production time and increasing the cost. In addition, tetramethylammonium hydroxide solution is used as a catalyst, but it is expensive and the compound is sensitive to air. Thirdly, adding solvents (ethanol, isopropanol and the like) to react at high temperature (above 80 ℃), the synthesis method needs to use a large amount of solvents, long-time distillation is needed after the reaction is finished, and the high-temperature condition has high energy consumption and does not meet the requirement of green chemistry. Fourthly, the viscosity randomness of the target product in the synthesis process is high, and the coupling agent with the target viscosity is difficult to obtain so as to meet different user requirements.

Disclosure of Invention

One of the purposes of the invention is to provide a method for synthesizing polysilsesquioxane coupling agent for RTV silicone rubber, which can make the process equipment simple, the raw materials are cheap and easy to obtain, the method is safe and environment-friendly, and the prepared product can be directly used as the tackifier of RTV silicone rubber, thereby reducing the production cost, creating economic benefits, improving the production efficiency and reducing the environmental pollution.

The invention provides a synthetic method of a polysilsesquioxane coupling agent for RTV (room temperature vulcanized) silicone rubber, which comprises the following steps of:

1) according to parts by weight, 20 parts of aminosilane coupling agent, 20 parts of epoxy silane coupling agent, 10-20 parts of other functional silanes, 1.0-2.0 parts of low boiling point hydrolysis promoter and 0.2-1.0 part of pure water are put into a reaction kettle with stirring, and the mixture is stirred at the kettle temperature of 65-80 ℃ for 1.5-2 hours, wherein the stirring speed is 60-100 rpm;

2) and starting a vacuum pump to ensure that the reaction kettle is subjected to vacuum distillation for 0.9 to 1.1 hours at the kettle temperature of 80 to 100 ℃ under the condition that the vacuum degree is 0.09 to 0.1MPa, so as to obtain a transparent liquid product, namely the polysilsesquioxane coupling agent.

Preferably, the aminosilane coupling agent is: any one or more of aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrialkoxysilane, 3-phenylaminopropyltrialkoxysilane, aminopropylmethyldialkoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldialkoxysilane, N-N-butyl-3-aminopropyltrialkoxysilane and 3- (diethylenetriamino) propyltrialkoxysilane.

Preferably, the epoxy silane coupling agent is: gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silicon, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane and 3-glycidoxypropyl methyl diethoxy silicon.

Preferably, the other functional silanes are: ethyl orthosilicate, propyl trimethoxy silane, phenyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, tetramethoxy silane, tetraethoxy silane, methyl trimethoxy silane, phenyl trimethoxy silane, diphenyl dimethoxy silane, methyl phenyl dimethoxy silane, vinyl trimethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, and 3- (methacryloxy) propyl methyl dimethoxy silane.

Preferably, the low-boiling hydrolysis promoter is: any one or more of triethylamine, ethylenediamine, pyridine, glacial acetic acid or diisopropylethylamine.

Preferably, the adding amount of the pure water is not more than 2.5 percent of the total weight of the aminosilane coupling agent and the epoxy silane coupling agent; more preferably, the amount of pure water added is not less than 0.5% of the total weight of the aminosilane coupling agent and the epoxysilane coupling agent.

Preferably, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 20g of ethyl orthosilicate, 0.2g to 1.0g of pure water and 1g of triethylamine are added into a 250mL three-neck flask as hydrolysis promoters; after the addition is finished, the stirring is started, the rotating speed is 100rpm, and the stirring reaction is carried out for 1.5 hours when the oil bath is heated to 65 ℃; distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a colorless transparent liquid product; a calibration curve y for predicting the viscosity of the polysilsesquioxane coupling agent was obtained, using the amount of water added as the abscissa x and the viscosity of the polysilsesquioxane coupling agent as the ordinate y, of 163.18ln (x) + 329.03.

Preferably, the polysilsesquioxane coupling agent has the specific structural formula:

the invention also aims to provide a ketoxime-removing silicone rubber which is prepared by mixing the following raw materials in parts by weight at room temperature: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate; wherein the coupling agent is the polysilsesquioxane coupling agent obtained by the synthesis method.

Compared with the prior art, the invention has beneficial technical effects

(1) In the research process of synthesizing the deketoxime type single-component RTV silicone rubber tackifier, firstly adding a specific organic hydrolysis promoter with low boiling point in the preparation process, wherein the boiling point is less than 130 ℃, and directly removing the organic hydrolysis promoter by vacuumizing after the synthesis is finished; the tackifier obtained by combining the solvent-free synthesis method while adding the low-boiling-point hydrolysis promoter can ensure that the deketoxime type single-component RTV silicone rubber product has good tensile strength and excellent adhesive property, and the surface drying time is short.

(2) The tensile strength of the prepared I-shaped module can be measured by adjusting the addition amount of pure water, and importantly, the polysilsesquioxane coupling agent with different target viscosities can be obtained by simply and exactly optimizing process parameters so as to meet the requirements of different users.

(3) Compared with the synthesis process in the prior art, the process has the advantages that the step processes of neutralization and impurity removal by filtration after the synthesis reaction in the prior art are omitted, the product is directly synthesized without adding a solvent, the solvent cost in production is reduced, the energy consumption for removing the low-boiling-point substance impurities is reduced, the environmental pollution is reduced, the synthesis time is saved, and the synthesis efficiency is improved.

(4) The polysilsesquioxane coupling agent has the advantages that the ideal reaction substance is obtained through countless times of optimized selection, the production process of the product obtained by the process is different from the prior art, the chemical structural formula of the product is different from the prior art, and the polysilsesquioxane coupling agent has large market application and development potential. Particularly, compared with the coupling agent products on the market, the oligomeric coupling agent synthesized by the simple method has improved tensile strength under the condition of the same addition amount, wherein the polysilsesquioxane obtained by taking 3-phenylaminopropyl trialkoxysilane as a raw material has the most obvious improvement on the tensile strength, and the polysilsesquioxane obtained by taking N- (2-aminoethyl) -3-aminopropyltrialkoxysilane as a raw material has higher activity, so that the surface drying time of the silicone sealant can be shortened, and the curing speed can be accelerated.

(5) The synthesis method has the advantages of simple process equipment, cheap and easily available raw materials, safety and environmental protection, and the prepared product can be directly used as the tackifier of the silicone adhesive and can be used for bonding various types of base materials, including bonding of aluminum materials, stainless steel, glass, PMMA, PC, calcium silicate boards and other base materials.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, but the scope of the present invention is not limited to the following embodiments.

Example 1

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 20g of ethyl orthosilicate, 0.2g of pure water and 1g of triethylamine were added as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 1.5 hours with the oil bath warmed to 65 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a colorless transparent liquid product, wherein the coupling agent does not have a viscosity peak in the production of the sizing material, the sizing material does not yellow, and the viscosity is 62mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The surface drying time of the obtained deketoxime type silicon rubber is 31 minutes, and the deep curing speed is 24 hours and 3.51 mm.

Example 2

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 20g of ethyl orthosilicate, 0.5g of pure water and 1g of triethylamine were added as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 1.5 hours with the oil bath warmed to 65 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a colorless transparent liquid product, wherein the coupling agent does not have a viscosity peak in the production of the sizing material, the sizing material does not yellow, and the viscosity is 237mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 30 minutes and the deep curing speed of 24 hours and 3.43 mm.

Example 3

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 20g of ethyl orthosilicate, 0.8g of pure water and 1g of triethylamine were added as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 1.5 hours with the oil bath warmed to 65 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a colorless transparent liquid product, wherein the coupling agent does not have a viscosity peak in the production of the sizing material, the sizing material does not yellow, and the viscosity is 259mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 30 minutes and the deep curing speed of 24 hours and 3.43 mm.

Example 4

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 20g of ethyl orthosilicate, 1g of pure water and 1g of triethylamine were added as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 2 hours with the oil bath warmed to 80 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. The light yellow transparent liquid product is obtained, the coupling agent does not have viscosity peak in the production of sizing material, the sizing material does not yellow, and the viscosity is 346mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 27 minutes and the deep curing speed of 24 hours and 3.31 mm.

Example 5

In a 250mL three-necked flask, 20g N- (2-aminoethyl) -3-aminopropyltrialkoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 20g of propyltrimethoxysilane, 0.5g of pure water and 1g of ethylenediamine were charged as a hydrolysis accelerator. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 2 hours with the oil bath warmed to 65 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. The colorless transparent liquid product is obtained, the coupling agent does not have viscosity peak in the production of sizing material, the sizing material does not yellow, and the viscosity is 79mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 23 minutes and the deep curing speed of 24 hours and 4.92 mm.

Example 6

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 10g of ethyl orthosilicate, 0.5g of pure water and 1g of glacial acetic acid were added as hydrolysis promoters. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 2 hours with the oil bath warmed to 80 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. The light yellow transparent liquid product is obtained, the coupling agent does not have viscosity peak in the production of sizing material, the sizing material does not yellow, and the viscosity is 250mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained ketoxime-removing silicone rubber is used for preparing ketoxime-removing silicone rubber, the surface drying time is 27 minutes, and the deep curing speed is 24 hours and 3.32 mm.

Example 7

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 10g of phenyltrimethoxy, 0.5g of pure water and 1g of triethylamine were added as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 1.5 hours with the oil bath warmed to 65 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. The colorless transparent liquid product is obtained, the coupling agent does not have viscosity peak in the production of sizing material, the sizing material does not yellow, and the viscosity is 86mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has surface drying time of 33 minutes and deep curing speed of 24 hours and 3.59 mm.

Example 8

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 10g of ethyl orthosilicate, 0.5g of pure water and 1g of triethylamine were added as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 1.5 hours with the oil bath warmed to 65 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. The colorless transparent liquid product is obtained, and the viscosity peak of the tackifier does not appear in the production of sizing materials, the sizing materials are not yellowed, and the viscosity is 81mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 30 minutes and the deep curing speed of 24 hours and 3.55 mm.

Example 9

In a 250mL three-necked flask, 20g N- (2-aminoethyl) -3-aminopropyltrialkoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 20g of phenyltrimethoxy, 0.5g of pure water and 2g of triethylamine were charged as a hydrolysis accelerator. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 2 hours with the oil bath warmed to 80 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. The colorless transparent liquid product is obtained, the viscosity peak of the tackifier does not appear in the production of sizing materials, the sizing materials are not yellowed, and the viscosity is 260mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 25 minutes and the deep curing speed of 24 hours and 4.36 mm.

Example 10

In a 250mL three-necked flask, 20g of aminopropyltriethoxysilane, 20g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane and 20g of ethyl orthosilicate, 0.5g of pure water and 1g of triethylamine were added as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 2 hours with the oil bath warmed to 80 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. A colorless transparent liquid product is obtained, the viscosity peak of the tackifier does not appear in the production of sizing materials, the sizing materials are not yellowed, and the viscosity is 347mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 27 minutes and the deep curing speed of 24 hours and 3.35 mm.

Example 11

In a 250mL three-necked flask, 20g of 3-phenylaminopropyltrialkoxysilane, 20g of γ - (2, 3-glycidoxy) propyltrimethoxysilane and 20g of γ -methacryloxypropyltrimethoxysilane, 0.5g of pure water and 1g of triethylamine were charged as hydrolysis accelerators. After the addition was complete, the stirring was turned on at 100rpm and the reaction was stirred for 2 hours with the oil bath warmed to 80 ℃. And (3) distilling after the reaction is finished, and distilling for 1 hour at the vacuum degree of 0.09-0.1 MPa and the temperature of 80 ℃ to obtain a product. The colorless transparent liquid product is obtained, the viscosity peak of the tackifier does not appear in the production of sizing materials, the sizing materials are not yellowed, and the viscosity is 88mPa & s.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 25 minutes and the deep curing speed of 24 hours and 4.22 mm.

Comparative example 1

New blue sky 1162 was used as a coupling agent for comparison.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The surface drying time of the obtained deketoxime type silicon rubber is 34 minutes, and the deep curing speed is 24 hours and 3.59 mm.

Comparative example 2

Wound 1146 was used as a coupling agent control.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyl ketoxime silane, 1 part of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The obtained deketoxime type silicon rubber has the surface drying time of 32 minutes and the deep curing speed of 24 hours and 3.38 mm.

Comparative example 3

KH-550 and KH-560 mixed solutions (non-oligomers) were used as coupling agent comparisons.

The preparation method of the deketoxime type silicone rubber comprises the following steps: 100 parts of 107 glue, 150 parts of nano calcium, 11 parts of methyl silicone oil, 10 parts of methyl tributyl ketoxime silane, 2 parts of vinyl tributyroxime silane, KH-5500.5 parts of coupling agent, KH-5600.5 parts of coupling agent and 0.05 part of dibutyl tin dilaurate at room temperature. The surface drying time of the obtained deketoxime type silicon rubber is 31 minutes, and the deep curing speed is 24 hours and 3.48 mm.

The performance of the deketoxime type silicone sealants prepared in the examples 1-11 and the comparative examples 1-3 is tested by referring to GB/T13477.5-2002, GB/T29595-2013 and JC/T882-2001, and the test results are shown in Table 1. Wherein, the detection method adopted by the surface drying time refers to the method B in GB/T13477.5-2002 for testing (filling the sample into a mould frame, scraping by a scraper, and contacting the finger with three different parts until no sample is adhered to the finger); the curing speed is detected by taking a proper amount of prepared sealant to fill in a test template with a thickness gradient groove according to GB/T29595-2013, placing the test template under 60% RH, vulcanizing the test template at room temperature for 24h, then tearing off the thinnest part of the thickness gradient of the sealing clamp until the sealant adheres to the template, and measuring the thickness of the vertical section of the test template. The tensile strength is detected by referring to JC/T882-2001 and testing by a microcomputer controlled electronic universal tester (the tensile speed is 10 mm/min).

In the results in table 1, groups 1 to 4 explore the influence of adding different amounts of water on the synthesis of the polysilsesquioxane coupling agent, the viscosity of the obtained polysilsesquioxane coupling agent is increased along with the increase of the addition amount of water and the change of other conditions, the use amount of other components is fixed, a known curve fitting method is adopted according to the rising trend of the use amount of other components, the addition amount of water is used as an abscissa x, the viscosity of the polysilsesquioxane coupling agent is used as an ordinate y, and a standard curve y which is 163.18ln (x) +329.03 for predicting the viscosity of the polysilsesquioxane coupling agent corresponding to the target production process can be obtained, and the accuracy of a prediction model can be further improved by increasing the data sample amount. The amount of water added should in principle not be less than 0.5% of the system. And when the amount of water added is more than 2.5% of the system, the silane coupling agent is easily hydrolyzed completely to be unusable, so the amount of water added should be controlled. In addition, as the addition amount of water increases, the surface drying time of the corresponding silicone adhesive added with the polysilsesquioxane coupling agent is slightly shortened, and the measured tensile strength of the prepared I-shaped module is also increased, which can be interpreted as that the polysilsesquioxane coupling agent with higher polymerization degree has better wetting effect on the surface of the base material, so that the bonding capacity is improved. Comparing example 2 with example 9, varying the amount of hydrolysis promoter had little effect on the viscosity of the polysilsesquioxane coupling agent.

The results in Table 1 show that the oligomer coupling agent synthesized by the simple method can reduce the production cost and simultaneously enable the ketoxime-removed silicone rubber to have excellent adhesive property, and compared with the results of comparative examples, the tensile strength of the oligomeric coupling agent is improved under the condition of the same addition amount compared with the coupling agent products on the market, wherein the improvement of the tensile strength of the polysilsesquioxane obtained by taking 3-phenylaminopropyltrialkoxysilane as the raw material is most obvious, and the polysilsesquioxane obtained by taking N- (2-aminoethyl) -3-aminopropyltrialkoxysilane as the raw material has higher activity, so that the surface drying time of the silicone sealant can be shortened and the curing speed can be accelerated. Can be used for bonding various substrates, including aluminum materials, stainless steel, glass, PMMA, PC, calcium silicate boards and the like. The surface drying time and the deep curing speed are normal, the difference with the products on the market is basically avoided, and the method is suitable for being applied to the field of assembly type buildings.

TABLE 1 polysilsesquioxane coupling agent used to prepare silicone sealants results

Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.