Epoxy organic silicon tackifier as well as preparation method and application thereof

Abstract

The invention discloses an epoxy organic silicon tackifier as well as a preparation method and application thereof, and relates to the technical field of tackifiers. The preparation method of the epoxy organic silicon tackifier comprises the following steps: filling an ultra-microporous Pt / SiO2 catalyst into a reactor, and heating to activate the ultra-microporous Pt / SiO2 catalyst; the preparation method comprises the following steps: mixing tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane to obtain a mixed reaction raw material, heating the mixed reaction raw material until the temperature reaches 70-100 DEG C, adding the mixed reaction raw material into a reactor, reacting to generate a synthetic product, and collecting the synthetic product flowing out of the bottom of the reactor, the epoxy group organic silicon tackifier is obtained. According to the preparation method of the epoxy organic silicon tackifier, a solvent does not need to be added in the reaction process, potential safety hazards are avoided, the step of removing the solvent and the catalyst can be omitted, the technological process is simplified, and continuous production of the tackifier can be achieved by adopting the method of the scheme.

Description

Technical Field

[0001] The present invention relates to the technical field of tackifiers, and in particular to an epoxy-based organosilicon tackifier and a preparation method and application thereof. Background Art

[0002] Addition silicone materials are a type of silicone materials that can be crosslinked and vulcanized at room temperature or under heating in the presence of a platinum catalyst, using vinyl-containing polyorganosiloxane as a base polymer and Si-H bond-containing polyorganosiloxane as a crosslinking agent. Addition silicone materials (such as addition-type liquid silicone rubber) are important auxiliary materials in many industries such as LED packaging due to their characteristics of no by-products, extremely low shrinkage, and deep vulcanization during vulcanization. They have many excellent properties and are widely used in the fields of electronics, aerospace, photovoltaic modules, and automobile manufacturing. However, most of the surface groups of addition silicone materials after vulcanization are non-polar organic groups, showing low surface energy and lacking reactive groups. Therefore, the bonding performance of addition silicone materials to metal substrates (such as aluminum, copper, silver, gold, and stainless steel, etc.), polar polymer substrates (such as PET, PBT, PA, PC, and epoxy, etc.) and inorganic non-metallic substrates (such as glass, ceramics, etc.) is very poor, and there is basically no bonding. As a result, water can easily penetrate into electronic devices through the gap between silicone rubber and the substrate during use, causing corrosion and insulation failure. In harsh environments, silicone may even fall off the substrate, causing the electronic devices to lose their sealing protection, seriously hindering their further promotion and application.

[0003] Domestic and foreign researchers have conducted some research on how to improve the adhesion between addition silicone rubber and substrates. Currently, there are three main methods: one is to treat the surface of the substrate to be bonded; the second is to introduce functional groups into the polyorganosilane molecular chain; the third is to introduce tackifiers into the addition silicone rubber system. The operation process of the third method is simpler and easier than the previous two methods, and has broad development prospects.

[0004] At present, the hydrosilylation method is mostly used at home and abroad to synthesize the thickener for addition type silicone rubber. The hydrosilylation method uses the addition reaction between silicon hydrogen bonds and unsaturated bonds to generate a thickener with a specific structure and performance. The hydrosilylation reaction has the advantages of mild conditions, high reaction efficiency and high product purity, so it is widely used in industry. However, there are also some shortcomings in the preparation of thickeners by the hydrosilylation method. For example, the preparation of thickeners by the hydrosilylation method generally requires the use of a large amount of toluene, xylene, etc. as solvents. Toluene and xylene are toxic and flammable substances, which will cause safety hazards in the preparation process of the thickener, cause harm to the health of operators, and may also cause pollution to the surrounding environment; and due to the use of solvents, the preparation process of the thickener also includes the step of removing the solvent, and the process is relatively complicated. At the same time, the preparation of thickeners by the hydrosilylation method generally uses liquid catalysts to catalyze the synthesis of thickeners. After the reaction, the catalyst needs to be removed, which will further increase the complexity of the preparation process. In addition, the current method of preparing a tackifier by the hydrosilylation method generally adopts an intermittent method. For example, Chinese patent application No. 201510367129.0 discloses a method for preparing an addition-type tackifier for silicone rubber, comprising the following steps: (1) adding high hydrogen-containing phenyl silicone oil and toluene to a reactor; (2) heating and adding a liquid catalyst (platinum catalyst) at 60 to 100°C; (3) after mixing evenly, adding KH570 at 60 to 100°C; (4) reacting at 60 to 100°C for more than 1 hour; (3) adding allyl glycidyl ether at 60 to 100°C; (4) reacting at 60 to 100°C for more than 1 hour; (5) removing low boiling substances at 80 to 100°C and a vacuum degree of 0.001 to 0.01 MPa to obtain a tackifier. It can be seen that the above method for preparing the tackifier is carried out discontinuously, that is, after the preparation of the batch of tackifiers is completed, it is necessary to start again from the first step to prepare the second batch of tackifiers. The production efficiency is low and it is difficult to achieve continuous production. Summary of the invention

[0005] In view of the problems raised in the background technology, the purpose of the present invention is to propose a method for preparing an epoxy-based silicone thickener. No solvent needs to be added during the reaction process, which not only avoids safety hazards, but also omits the steps of removing solvents and catalysts, simplifies the process flow, and adopts the method of this scheme to prepare epoxy-based silicone thickeners to achieve continuous production, solving the current problems of using a hydrosilylation method to synthesize thickeners for addition-type silicone rubber, which require the use of solvents, have complex processes, and are difficult to achieve continuous production.

[0006] Another object of the present invention is to provide an epoxy-based silicone tackifier that can be used to prepare addition-type silicone materials to improve the mechanical properties and bonding properties of the addition-type silicone materials.

[0007] Another object of the present invention is to propose the use of epoxy silicone tackifier in the preparation of addition-type silicone materials.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] A method for preparing an epoxy silicone tackifier comprises the following steps:

[0010] (1) loading an ultra-microporous Pt / SiO2 catalyst into a reactor and heating the reactor to activate the ultra-microporous Pt / SiO2 catalyst;

[0011] (2) Tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane are mixed to obtain a mixed reaction raw material, and when the mixed reaction raw material is heated to a temperature of 70 to 100° C., the mixed reaction raw material is added to the reactor from the top of the reactor, so that the mixed reaction raw material passes through the ultra-microporous Pt / SiO2 catalyst from the top of the reactor, and under the catalytic action of the ultra-microporous Pt / SiO2 catalyst, the mixed reaction raw material reacts in the reactor to generate a synthetic product, and the synthetic product flows out from the bottom of the reactor, and the synthetic product flowing out from the bottom of the reactor is collected to obtain an epoxy silicone adhesion promoter.

[0012] Preferably, in step (2), the molar ratio of tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane in the mixed reaction raw materials is 1:(0.9-1.5):(0.9-1.5).

[0013] Preferably, the ultramicroporous Pt / SiO2 catalyst comprises a SiO2 carrier and a Pt element loaded on the SiO2 carrier;

[0014] The pore size of the ultra-microporous Pt / SiO2 catalyst is 1.0-2.0 nm;

[0015] The specific surface area of ​​the SiO2 carrier is 180 to 300 m 2 / g.

[0016] Preferably, calculated by mass percentage, the content of the Pt element in the ultra-microporous Pt / SiO2 catalyst is 0.03% to 1%.

[0017] Preferably, the ratio of the amount of the mixed reaction raw materials added to the reactor per minute to the loading amount of the ultramicroporous Pt / SiO2 catalyst in the reactor is 0.1 to 2 mL / g.

[0018] Preferably, the reactor is provided with an inner cavity for placing the ultra-microporous Pt / SiO2 catalyst, and the ratio of the width to the length of the inner cavity is 1:20 to 1:50.

[0019] Preferably, in step (2), the content of the epoxy organosilicon tackifier in the synthetic product is detected. When the content of the epoxy organosilicon tackifier in the synthetic product is less than X, the synthetic product is refluxed into the mixed reaction raw materials; when the content of the epoxy organosilicon tackifier in the synthetic product is ≥X, the synthetic product flowing out of the bottom of the reactor is collected to obtain the epoxy organosilicon tackifier, and X is 90% to 99.5%.

[0020] Preferably, the preparation method of the epoxy silicone tackifier further comprises the step of preparing an ultra-microporous Pt / SiO2 catalyst, and the preparation step of the ultra-microporous Pt / SiO2 catalyst is as follows:

[0021] At room temperature, the template is dissolved in water, acetonitrile containing triphenylphosphine and chloroplatinic acid is added, and then a silicon source is added. After stirring for 15 to 24 hours, the reaction is filtered; the filtered solid phase is dried at 60 to 100°C for 1 to 3 hours to obtain a dry intermediate; the dry intermediate is extracted with anhydrous ethanol for 14 to 20 hours, and the obtained solid powder is dried at 60 to 100°C for 12 to 20 hours to obtain an ultra-microporous Pt / SiO2 catalyst.

[0022] Preferably, according to the molecular ratio of the raw material and the oxide, in the preparation steps of the ultra-microporous Pt / SiO2 catalyst:

[0023] The molecular ratio of H2O and SiO2 is 50-200;

[0024] CN － The molecular ratio with SiO2 is 0.3 to 2;

[0025] The molecular ratio of TP and SiO2 is 0.05-0.2;

[0026] The molecular ratio of Pt and SiO2 is 0.0005 to 0.2.

[0027] An epoxy-based organosilicon tackifier is prepared by the above-mentioned preparation method of the epoxy-based organosilicon tackifier, and the chemical structure is as follows:

[0028]

[0029] An application of an epoxy-based organosilicon tackifier in the preparation of an addition-type organosilicon material, wherein the epoxy-based organosilicon tackifier is the above-mentioned epoxy-based organosilicon tackifier.

[0030] Preferably, calculated by mass percentage, the epoxy-based organosilicon tackifier is added to the addition-type organosilicon material in an amount of 0.1% to 5%.

[0031] The above technical solution has the following beneficial effects:

[0032] 1. This technical solution uses an ultra-microporous Pt / SiO2 catalyst to catalyze the silane hydrosilylation reaction with tetramethylcyclotetrasiloxane (D4H), allyl glycidyl ether (AGE) and 3-methacryloxypropylmethyldimethoxysilane (MPMS) as raw materials to prepare a new type of epoxy-based silicone tackifier. Since this technical solution uses an ultra-microporous Pt / SiO2 catalyst as a catalyst, the ultra-microporous Pt / SiO2 catalyst has the advantages of high catalytic activity, mild reaction and good reaction selectivity, so that this technical solution does not need to add solvents in the process of preparing epoxy-based silicone tackifiers. At 70-100°C and under the catalysis of the ultra-microporous Pt / SiO2 catalyst, the epoxy-based silicone tackifier can be directly synthesized, and the synthesized epoxy-based silicone tackifier product produces very few by-products, and basically no addition by-products. The method of the present technical solution for preparing epoxy silicone tackifiers can not only omit the step of removing solvents and catalysts, simplifying the process flow and making the process flow very simple, but also because the present technical solution does not require the use of solvents and does not require the steps of separating solvents and catalysts, a high-purity epoxy silicone tackifier product can be directly obtained, so that the synthesis reaction of the present technical solution can be carried out continuously, and then continuous production can be realized, thereby improving production efficiency.

[0033] 2. The ultra-microporous Pt / SiO2 catalyst of the present technical solution is a solid catalyst. The ultra-microporous Pt / SiO2 catalyst is different from the conventional liquid phase catalyst and will not leave the catalyst residue in the product. Therefore, the catalyst of the present technical solution can be used for a long period of time. The catalyst activity remains basically unchanged after continuous use for 100 hours, and it is easy to achieve long-term continuous reaction and production. In addition, the ultra-microporous Pt / SiO2 catalyst of the present technical solution has high activity and mild reaction, so that the present technical solution can directly synthesize the epoxy silicone thickener without the addition of solvent. In the production process, the solvent and catalyst removal steps are omitted, so that the production process can achieve long-term continuous reaction and production, thereby continuously generating epoxy silicone thickener.

[0034] 3. The epoxy silicone tackifier of the present technical solution is used to prepare addition-type silicone materials, which can not only improve the mechanical properties of the addition-type silicone materials, but also greatly improve the bonding properties of the addition-type silicone materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1This is a physical picture of the epoxy-based organosilicon tackifier prepared in Example 1 of the present invention;

[0036] Figure 2 1 is a schematic structural diagram of a continuous reaction device used in preparing an epoxy-based organosilicon tackifier in Example 1 of the present invention;

[0037] Figure 3 is a gas chromatogram of the epoxy organosilicon tackifier prepared in Example 1;

[0038] Figure 4 is the nuclear magnetic resonance image of the epoxy silicone tackifier prepared in Example 1;

[0039] Figure 5 This is a N2 adsorption and desorption diagram of the ultramicroporous Pt / SiO2 catalyst used in Example 1. DETAILED DESCRIPTION

[0040] To make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0041] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. Raw materials used without specifying the manufacturer are all conventional products that can be obtained through commercial purchase.

[0042] The technical solution of the present invention is further explained below in conjunction with the accompanying drawings and specific implementation methods.

[0043] A method for preparing an epoxy silicone tackifier comprises the following steps:

[0044] (1) loading an ultra-microporous Pt / SiO2 catalyst into a reactor and heating the reactor to activate the ultra-microporous Pt / SiO2 catalyst;

[0045] (2) Tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane are mixed to obtain a mixed reaction raw material, and when the mixed reaction raw material is heated to a temperature of 70 to 100° C., the mixed reaction raw material is added to the reactor from the top of the reactor, and the mixed reaction raw material passes through the ultra-microporous Pt / SiO2 catalyst from the top of the reactor. Under the catalytic action of the ultra-microporous Pt / SiO2 catalyst, the mixed reaction raw material reacts to generate a synthetic product, and the synthetic product flows out from the bottom of the reactor, and the synthetic product flowing out from the bottom of the reactor is collected to obtain an epoxy silicone adhesion promoter.

[0046] The ultra-microporous Pt / SiO2 catalyst used in this technical solution is a solid catalyst containing ultra-micropores. The ultra-microporous Pt / SiO2 catalyst uses silicon dioxide as a carrier, and there are tiny pores with a pore size of 1 to 2 nm in the silicon dioxide. Pt is loaded on the silicon dioxide, and preferably contains a certain amount of phosphorus. The ultra-microporous Pt / SiO2 catalyst of this technical solution is a green and efficient hydrosilylation catalyst with high catalytic activity, stable performance, and long-term use. This technical solution uses an ultra-microporous Pt / SiO2 catalyst as a catalyst, and uses tetramethylcyclotetrasiloxane (D4H), allyl glycidyl ether (AGE) and 3-methacryloxypropylmethyldimethoxysilane (MPMS) as raw materials. A new type of epoxy-based organosilicon thickener can be synthesized through a green process continuous method of hydrosilylation. The chemical reaction formula of the process of synthesizing epoxy-based organosilicon thickeners in this technical solution is as follows:

[0047]

[0048] The epoxy-based organosilicon tackifier synthesized by the present technical solution is used in addition-type organosilicon materials (such as addition-type silicone rubber), which can not only improve the mechanical properties of the addition-type organosilicon materials, but also significantly increase the bonding strength between the addition-type organosilicon materials and other substrates.

[0049] It is worth noting that the traditional method of synthesizing organosilicon thickeners by hydrosilylation generally requires the use of flammable and toxic substances such as toluene or xylene as solvents to achieve mild reaction, precise reaction control and minimize the production of by-products. However, the use of solvents such as toluene or xylene not only poses safety hazards, causes harm to the health of operators, and pollutes the surrounding environment, but also requires further removal of the solvent after the reaction is completed, resulting in a relatively complex process, increased energy consumption and production costs, and part of the thickener product will be lost during the solvent removal process; in addition, the use of solvents and liquid catalysts also makes it difficult to achieve continuous production of existing methods for synthesizing organosilicon thickeners, and the production efficiency is low. This technical solution uses an ultra-microporous Pt / SiO2 catalyst to catalyze the silane hydrosilylation reaction using tetramethylcyclotetrasiloxane (D4H), allyl glycidyl ether (AGE) and 3-methacryloxypropylmethyldimethoxysilane (MPMS) as raw materials. Since the present technical solution adopts ultra-microporous Pt / SiO2 catalyst as a catalyst, and the ultra-microporous Pt / SiO2 catalyst has the advantages of high catalytic activity, mild reaction and good reaction selectivity, the present technical solution does not need to add solvent in the process of preparing epoxy silicone thickener, and can directly synthesize epoxy silicone thickener at 70-100°C and under the catalysis of ultra-microporous Pt / SiO2 catalyst, and the synthesized epoxy silicone thickener product produces very few by-products, and basically no added by-products. The method of the present technical solution can not only omit the steps of removing solvent and catalyst, simplify the process flow, and make the process flow very simple, but also because the present technical solution does not need to use solvent and does not need to separate solvent and catalyst, it can directly obtain high-purity epoxy silicone thickener products, so that the synthesis reaction of the present technical solution can be carried out continuously, and then continuous production can be realized, thereby improving production efficiency.

[0050] Further explanation, in step (2), the molar ratio of tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane in the mixed reaction raw materials is 1: (0.9-1.5): (0.9-1.5), within this molar ratio range, the yield of the synthesized epoxy silicone adhesion promoter is high. The molar ratio of D4H, AGE and MPMS is exemplarily 1: 0.9: 1.2, 1: 1: 1, 1: 1: 0.9, 1: 1.1: 1.1, 1: 1.2: 1.2, 1: 1.2: 1.5, 1: 1.5: 1.5, but not limited thereto.

[0051] More preferably, tetramethylcyclotetrasiloxane (D4H): allyl glycidyl ether (AGE): 3-methacryloxypropylmethyldimethoxysilane (MPMS) = 1:1.1:1.1 (molar ratio). The technical solution controls the molar ratio of tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane to be 1:1.1:1.1, so that the yield of the synthesized epoxy silicone tackifier is higher.

[0052] Further explanation, the ultra-microporous Pt / SiO2 catalyst includes a SiO2 carrier and a Pt element loaded on the SiO2 carrier;

[0053] The pore size of the ultra-microporous Pt / SiO2 catalyst is 1.0-2.0 nm, exemplified by 1.0 nm, 1.1 nm, 1.2 nm, 1.3 nm, 1.4 nm, 1.5 nm, 1.6 nm, 1.7 nm, 1.8 nm, 1.9 nm, and 2.0 nm, but not limited thereto.

[0054] The specific surface area of ​​the SiO2 carrier is 180 to 300 m 2 / g, exemplarily 180m 2 / g, 190m 2 / g, 200m 2 / g, 220m 2 / g, 250m 2 / g, 280m 2 / g、300m 2 / g, but is not limited to this.

[0055] It is worth noting that there are many tiny pores with a pore size of 1.0 to 2.0 nm in the ultra-microporous Pt / SiO2 catalyst of the present technical solution, which makes the ultra-microporous Pt / SiO2 catalyst have a very large specific surface area of ​​180 to 300 m 2 / g, Pt is adsorbed on the surface of the ultramicroporous Pt / SiO2 catalyst, which can effectively improve the catalytic activity of the catalyst.

[0056] More preferably, the specific surface area of ​​the SiO2 carrier is 200 m 2 / g.

[0057] Calculated by mass percentage, the content of the Pt element in the ultra-microporous Pt / SiO2 catalyst is 0.03% to 1%. The Pt element content within this range has higher catalytic activity.

[0058] More preferably, the content of the Pt element in the ultra-microporous Pt / SiO2 catalyst is 0.05% to 0.2%. The content of the Pt element within this range not only has higher catalytic activity, but also can more effectively synthesize epoxy silicone adhesion promoters and avoid cost waste. The content of the Pt element in the ultra-microporous Pt / SiO2 catalyst is exemplarily 0.05%, 0.06%, 0.7%, 0.8%, 0.9%, 0.10%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.8%, 0.19%, 0.20%, but is not limited thereto.

[0059] Further explanation, the ratio of the amount of the mixed reaction raw materials added to the reactor per minute (V) to the loading amount of the ultramicroporous Pt / SiO2 catalyst in the reactor (M) is 0.1-2 mL / g, which can ensure that the catalytic concentration of the catalyst in the reaction process is within a suitable range, has high catalytic activity, and is conducive to the synthesis of epoxy silicone thickeners.

[0060] It is worth noting that, during the reaction process, the ratio of the amount of the mixed reaction raw materials added to the reactor per minute (V) and the loading amount of the ultramicroporous Pt / SiO2 catalyst in the reactor (M) is a range value. In the initial stage of the reaction, the ratio of V to M is low, that is, in the initial stage of the reaction, the amount of the mixed reaction raw materials added per minute is low, and then as the reaction proceeds, the amount of the mixed reaction raw materials is slowly increased. After the catalytic activity of the catalyst is stabilized, the amount of the mixed reaction raw materials added per minute is controlled within a fixed range, thereby enabling the efficient synthesis of the epoxy silicone thickener.

[0061] More preferably, the ratio of the amount of the mixed reaction raw material added per minute in the reactor (V) to the loading amount of the ultra-microporous Pt / SiO2 catalyst in the reactor (M) is 0.15mL / g to 1.5mL / g, and a high-purity epoxy silicone tackifier can be obtained. If the amount of the mixed reaction raw material added per minute is too much, some unreacted raw materials will exist in the synthetic product. In addition, the flow rate of the mixed reaction raw material in the technical solution can be adjusted in real time. In the early stage of the reaction, due to the low activity of the catalyst, the ratio of V and M can be controlled to 0.15mL / g, and then the flow rate of the mixed reaction raw material is slowly increased. After the catalytic activity of the catalyst is stabilized, the activity of the catalyst is high, and the ratio of V and M can be controlled to 1.5mL / g, thereby improving the reaction efficiency.

[0062] In a preferred embodiment of the present invention, the loading amount of the ultramicroporous Pt / SiO2 catalyst in the reactor is 20g, and the amount of the mixed reaction raw materials added to the reactor per minute can be controlled to be 3mL at the initial stage of the reaction, that is, the flow rate of the mixed reaction raw materials is 3mL / min at this time, and then the flow rate of the mixed reaction raw materials is slowly increased. After the catalytic activity of the catalyst is stabilized, the flow rate of the mixed reaction raw materials is controlled at 30mL / min, that is, at this time the ratio of V and M is 1.5mL / g.

[0063] Further explanation, the reactor is provided with an inner cavity for placing an ultra-microporous Pt / SiO2 catalyst, and the ratio of the width to the length of the inner cavity is 1:20 to 1:50, so that the mixed reaction raw materials are in contact with the catalyst in the reactor for a longer time and the reaction is more complete.

[0064] Further explanation, in step (2), the content of the epoxy silicone tackifier in the synthetic product is detected. When the content of the epoxy silicone tackifier in the synthetic product is less than X, the synthetic product is refluxed into the mixed reaction raw materials; when the content of the epoxy silicone tackifier in the synthetic product is ≥X, the synthetic product flowing out of the bottom of the reactor is collected to obtain the epoxy silicone tackifier, and X is 90% to 99.5%.

[0065] It is worth noting that the technical solution monitors the content of epoxy silicone tackifier in the synthetic product in real time by gas chromatography. When the content of epoxy silicone tackifier in the synthetic product is less than X (90% to 99.5%), it indicates that the synthetic product contains unreacted raw materials. At this time, the synthetic product is pumped into the raw material funnel filled with mixed reaction raw materials by a circulation pump, so that the synthetic product containing unreacted raw materials is refluxed into the mixed reaction raw materials and participates in the reaction again, so that the technical solution forms a reaction cycle system, which is conducive to continuous production. When the content of epoxy silicone tackifier in the synthetic product is ≥X (90% to 99.5%), it indicates that the purity of the epoxy silicone tackifier in the synthetic product is high at this time, and the synthetic product flowing out from the bottom of the reactor can be collected to obtain the epoxy silicone tackifier.

[0066] Preferably, when the content of the epoxy organosilicon tackifier in the synthetic product is ≥95%, the synthetic product flowing out from the bottom of the reactor is collected, and the epoxy organosilicon tackifier obtained has a higher purity.

[0067] More preferably, when the content of the epoxy organosilicon tackifier in the synthetic product is ≥99%, the synthetic product flowing out from the bottom of the reactor is collected, and the epoxy organosilicon tackifier obtained has a higher purity.

[0068] Specifically, the technical solution detects the content of epoxy silicone tackifier in the synthetic product in real time by gas chromatography. In one embodiment of the present invention, the gas chromatograph (GC) conditions are as follows: the injection port is maintained at 280°C, the chromatographic column is maintained at 60°C, the temperature is raised to 120°C at 20°C / min and retained for 2min, the same heating rate is maintained, the temperature is raised to 180°C and retained for 2min, the temperature is raised to 250°C and retained for 2min, and finally the column temperature is raised to 290°C. The carrier gas is high-purity helium, and the gas flow rate is 1ml / min.

[0069] Further explanation, the preparation method of the epoxy silicone tackifier also includes the preparation step of the ultra-microporous Pt / SiO2 catalyst, and the preparation step of the ultra-microporous Pt / SiO2 catalyst is as follows:

[0070] At room temperature, the template is dissolved in water, acetonitrile containing triphenylphosphine and chloroplatinic acid is added, and then a silicon source is added. After stirring for 15 to 24 hours, the reaction is filtered; the filtered solid phase is dried at 60 to 100°C for 1 to 3 hours to obtain a dry intermediate; the dry intermediate is extracted with anhydrous ethanol for 14 to 20 hours, and the obtained solid powder is dried at 60 to 100°C for 12 to 20 hours to obtain an ultra-microporous Pt / SiO2 catalyst.

[0071] It is worth noting that the preparation method of the ultra-microporous Pt / SiO2 catalyst of the present technical solution is green and environmentally friendly, the preparation process is simple, and the ultra-microporous Pt / SiO2 catalyst is directly synthesized in one step. The ultra-microporous Pt / SiO2 catalyst prepared has a small particle size and a high specific surface area of ​​180 to 300 m 2 / g, and the pore size is in the ultra-microporous range of 1 to 2nm. The ultra-microporous Pt / SiO2 catalyst prepared by this technical solution is a very efficient hydrosilylation catalyst with high catalytic activity and long-term use effect. The catalyst activity remains basically unchanged after 100 hours of continuous use. In addition, the ultra-microporous Pt / SiO2 catalyst of this technical solution is mild, efficient, has good reaction selectivity, and produces very few by-products. When used to prepare epoxy silicone thickeners, the synthesized epoxy silicone thickener does not need to be further separated to remove the catalyst, and the step of removing the catalyst is omitted.

[0072] Further explanation: the ultra-microporous Pt / SiO2 catalyst of the present technical solution is a solid catalyst. The ultra-microporous Pt / SiO2 catalyst is different from the conventional liquid phase catalyst and will not leave the catalyst residue in the product. Therefore, the catalyst of the present technical solution can be used for a long period of time. The catalyst activity remains basically unchanged after 100 hours of continuous use, and it is easy to achieve long-term continuous reaction and production. In addition, the ultra-microporous Pt / SiO2 catalyst of the present technical solution has high activity and mild reaction, so that the present technical solution can directly synthesize the epoxy silicone thickener without the addition of solvent. In the production process, the solvent and catalyst removal steps are omitted, so that the production process can achieve long-term continuous reaction and production, thereby continuously generating epoxy silicone thickener.

[0073] Specifically, the raw materials for preparing the ultra-microporous Pt / SiO2 catalyst in the present technical scheme include a template, acetonitrile containing triphenylphosphine and chloroplatinic acid, and a silicon source, wherein the addition of acetonitrile containing triphenylphosphine and chloroplatinic acid can prepare a phosphorus-containing platinum-loaded catalyst; the silicon source serves as a carrier to enable platinum to be loaded on the carrier; the role of the template is to make the pore size of the loaded catalyst reach the nanometer level, so that the pore size of the ultra-microporous Pt / SiO2 catalyst prepared by the present technical scheme can reach 1 to 2 nanometers.

[0074] Preferably, the template is an alkylamine with 6 to 14 carbon atoms. The technical solution uses an alkylamine with 6 to 14 carbon atoms as a template, so that the synthesized catalyst reaches nanometer level under the action of the template and can be recovered.

[0075] Preferably, the silicon source is propyl orthosilicate, ethyl orthosilicate or butyl orthosilicate. More preferably, the silicon source is ethyl orthosilicate, which has a lower price.

[0076] More preferably, the preparation method of the ultra-microporous platinum catalyst is as follows: at room temperature, add a certain amount of distilled water to a container, dissolve the template (n-octylamine) in the distilled water, stir, add acetonitrile containing a certain amount of triphenylphosphine and chloroplatinic acid, and quickly add a suitable silicon source (ethyl orthosilicate). The reaction is slightly exothermic, the yellow mist solution is stirred for 18 hours, filtered and filtered, the filtered solid phase is dried at 80°C for 2 hours, and then extracted with absolute anhydrous ethanol in a Soxhlet extractor for 16 hours, and the obtained solid powder is dried at 80°C for 16 hours, which is the ultra-microporous Pt / SiO2 catalyst. The above-mentioned filtered liquid phase can be separated by rotary vacuum to recover more than 99% of the template and more than 99% of the acetonitrile.

[0077] Further explanation, according to the molecular ratio of raw materials and oxides, the preparation steps of ultra-microporous Pt / SiO2 catalyst are:

[0078] The molecular ratio of H2O and SiO2 is 50-200; that is, H2O / SiO2=50-200;

[0079] CN － The molecular ratio of CN to SiO2 is 0.3 to 2; － / SiO2=0.3~2;

[0080] The molecular ratio of TP to SiO2 is 0.05-0.2; that is, TP / SiO2 = 0.05-0.2, where TP is total phosphorus;

[0081] The molecular ratio of Pt to SiO2 is 0.0005 to 0.2, that is, Pt / SiO2 = 0.0005 to 0.2.

[0082] In a preferred embodiment of the present invention, the preparation method of the ultra-microporous platinum catalyst is as follows: at room temperature, 4.1 grams of template agent (n-octylamine) is dissolved in 50 ml of deionized water, and then 50 ml of acetonitrile containing triphenylphosphine and chloroplatinic acid is added, and after stirring to fully mix, 18 grams of silicon source (ethyl orthosilicate) is slowly added dropwise under stirring, and stirring is continued for 18 hours after the dropwise addition is completed, and the mixture is filtered, and the solid phase is taken out and dried at 70° C. for 2 hours to obtain a dry intermediate; the dry intermediate is extracted with absolute anhydrous ethanol through a Soxhlet extractor for 18 hours, and the solid phase is taken out again, and dried at 100° C. for 16 hours to obtain an ultra-microporous Pt / SiO2 catalyst. Wherein, in the 50 ml of acetonitrile in this embodiment, the amounts of dissolved triphenylphosphine and chloroplatinic acid are 0.1833 grams and 0.0722 grams, respectively.

[0083] Specifically, nitrogen was adsorbed as an adsorbate on the surface of the ultra-microporous Pt / SiO2 catalyst sample, and the changes in the adsorption amount and pressure were measured, and then the adsorption isotherm was plotted. Figure 5 As shown, it can be seen from the N2 adsorption-desorption curve of the ultramicroporous Pt / SiO2 catalyst that the curve belongs to a typical Langmuir I type adsorption curve, that is, a typical curve of microporous materials (generally pore size ≤2nm). It can be seen that the present technical solution can produce an ultramicroporous Pt / SiO2 catalyst with a pore size ≤2nm, and through further particle size analysis of the ultramicroporous Pt / SiO2 catalyst, it can be obtained that the pore size of the ultramicroporous Pt / SiO2 catalyst synthesized by the present technical solution is 1.0~2.0nm.

[0084] An epoxy-based organosilicon tackifier is prepared by the above-mentioned preparation method of the epoxy-based organosilicon tackifier, and the chemical structure is as follows:

[0085]

[0086] An application of an epoxy-based organosilicon tackifier in the preparation of an addition-type organosilicon material, wherein the epoxy-based organosilicon tackifier is the above-mentioned epoxy-based organosilicon tackifier.

[0087] The epoxy silicone tackifier of the present technical solution is used to prepare an addition-type silicone material, which can not only improve the mechanical properties of the addition-type silicone material, but also greatly improve the bonding properties of the addition-type silicone material.

[0088] Preferably, the addition type organic silicon material is addition type silicone rubber, but not limited thereto. In one embodiment of the present technical solution, the addition type silicone rubber is a two-component addition type.

[0089] As a further description, the epoxy silicone tackifier is added to the addition silicone material in an amount of 0.1% to 5% by mass, with exemplary amounts being 0.1%, 0.25%, 0.5%, 1%, 2%, 3%, 4%, and 5%.

[0090] Preferably, the epoxy-based silicone tackifier is added to the addition-type silicone material in an amount of 0.1% to 0.5%, which can effectively improve the adhesive properties and mechanical properties of the addition-type silicone material while reducing the cost.

[0091] The present technical solution is further described below in conjunction with embodiments.

[0092] Example 1 uses Figure 2A continuous reaction device is used to prepare epoxy silicone tackifiers. The continuous reaction device includes a raw material hopper 1, a reactor 2, a condensing device 3, a collecting device 4 and a circulating pump 5. The top of the raw material hopper 1 is provided with a feed port, and the bottom is provided with a discharge port. The raw material hopper 1 is used to hold mixed reaction raw materials. The discharge port of the raw material hopper 1 is connected to the feed end of the reactor 2. A peristaltic pump is provided at the bottom of the raw material hopper 1 to control the flow rate of the mixed reaction raw materials entering the reactor 2; the reactor 2 is used to hold an ultra-microporous Pt / SiO2 catalyst 7. Preferably, the bottom of the reactor 2 is provided with a limiter to prevent the ultra-microporous Pt / SiO2 catalyst from going out from the bottom but to allow the synthetic product to flow out smoothly; the reactor The discharge end of the reactor 2 is connected to the feed end of the condensation device 3 through the elbow 6, and the discharge end of the condensation device 3 is connected to the feed end of the collection device 4. The condensation device 3 is used to cool the synthetic product; the collection device 4 is used to collect the synthetic product, and the collection device 4 is provided with a qualified product discharge end and a recovery end. The qualified product discharge end of the collection device 4 is connected to the external thickener collection tank, and the epoxy organic silicon thickener with purity that meets the standard is collected through the thickener collection tank. The recovery end of the collection device 4 is connected to the input end of the circulation pump 5, and the output end of the circulation pump 5 is connected to the reflux end of the raw material funnel 1. The synthetic product with unqualified content of epoxy organic silicon thickener is refluxed to the raw material funnel 1 through the circulation pump 5, and reacts again. Among them, the condensation device 3 used in Example 1 is a condenser, the collection device 4 is a collection container, the reactor 2 is vertically arranged, and the reactor 2 is provided with an inner cavity with a diameter of 10 mm and a length of 400 mm, that is, the ratio of the width and length of the inner cavity is 1:40. The technical solution can heat the ultra-microporous Pt / SiO2 catalyst and the mixed reaction raw materials by microwave heating.

[0093] Example 1

[0094] A method for preparing an epoxy silicone tackifier comprises the following steps:

[0095] (1) 20.02165 g of ultra-microporous Pt / SiO2 catalyst was loaded into a reactor with an inner diameter of 10 mm, and the ultra-microporous Pt / SiO2 catalyst was heated at 100° C. for 30 minutes to activate it; wherein the ultra-microporous Pt / SiO2 catalyst comprises 20 g of SiO2 carrier and 21.65 mg of Pt element, i.e., the content of Pt element in the ultra-microporous Pt / SiO2 catalyst is about 0.108%; the pore size of the SiO2 carrier is 1.0 to 2.0 nm, and the specific surface area is 200 m 2 / g.

[0096] (2) In a raw material funnel, tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane are mixed in a molar ratio of 1:1.1:1.1 to obtain a mixed reaction raw material. After the mixed reaction raw material is heated to a temperature of 100° C., the mixed reaction raw material is added to the reactor from the top of the reactor. At the beginning, the flow rate of the mixed reaction raw material entering the reactor is controlled to be 3 mL / min, and then the flow rate of the mixed reaction raw material is gradually increased to reach 30 mL / min. The mixed reaction raw material passes through the ultra-microporous Pt / SiO2 catalyst from the top of the reactor. Under the catalytic action of the ultra-microporous Pt / SiO2 catalyst, the reaction generates a synthetic product. The synthetic product flows out from the bottom of the reactor, is condensed by a condensing device, and then enters a collecting device. The synthetic product is collected in the collecting device to obtain the synthetic product. The content of epoxy silicone tackifier in the synthetic product is detected by gas chromatography in a timely manner. When the content of epoxy silicone tackifier in the synthetic product is less than 95%, the synthetic product that has not reacted completely is pumped into the raw material funnel through a circulation pump to form a reaction circulation system; when the content of epoxy silicone tackifier in the synthetic product is ≥95%, the material is discharged and the epoxy silicone tackifier product is collected. The actual picture of the epoxy silicone tackifier synthesized in this embodiment is as follows Figure 1 shown.

[0097] Specifically, after 5.5 hours of reaction, a certain amount of the epoxy silicone tackifier product prepared in this embodiment was taken for gas chromatography analysis to calculate the conversion rate of tetramethylcyclotetrasiloxane. Figure 3 The epoxy silicone tackifier product obtained in this embodiment (as shown) contains 0.42% tetramethylcyclotetrasiloxane, 0.07% unknown substances, and 0.35% allyl glycidyl ether; 0.18% 3-methacryloxypropylmethyldimethoxysilane, 98.89% epoxy silicone tackifier, and 0.09% no high boiling products. Calculation shows that the conversion rate of tetramethylcyclotetrasiloxane in this embodiment is 99.58% (i.e., 100%-0.42%=99.58%). By subjecting the epoxy silicone tackifier product to nuclear magnetic resonance analysis (as shown Figure 4 As shown), it can be obtained that the regioselective (i.e., spatial addition) β-E addition product in the epoxy organosilicon tackifier product of this embodiment is greater than 99.6%, which shows that there are no other addition by-products in the epoxy organosilicon tackifier product synthesized by this technical solution.

[0098] Application Example 1

[0099] The epoxy silicone tackifier product prepared in Example 1 is used to prepare addition silicone rubber, and the preparation method of addition silicone rubber adopts the existing process. This application example 1 sets three experimental groups, and the addition amount of epoxy silicone tackifier in the three experimental groups is 0.1%, 0.25% and 0.5% of the total amount of addition silicone rubber respectively; and a control group is set, and no epoxy silicone tackifier is added to the control group. The mechanical properties and bonding properties of the obtained addition silicone rubber of the experimental group and the control group are tested respectively. Among them, the mechanical properties are mainly reflected in tensile strength and elongation at break, and the test is carried out according to the national standard GB / T528-2008, and the tensile strength improvement rate and elongation at break of the experimental group relative to the control group are calculated. The test results are shown in Table 1 below; the bonding performance is mainly reflected in the breaking force and shear strength. With aluminum sheet as the substrate, the addition silicone rubber of the experimental group and the control group are used to bond two aluminum sheets respectively, and the breaking force and shear strength are tested according to the national standard GB / T7124-2008. The test results are shown in Table 1 below.

[0100] Table 1 Mechanical properties test results

[0101]

[0102] As can be seen from Table 1, the application of the epoxy silicone tackifier prepared in Example 1 to the preparation of addition silicone rubber can not only greatly improve the bonding performance of the addition silicone rubber, but also has a high activity on the mechanical properties of the addition silicone rubber. Specifically, it can be seen from the mechanical properties data in Table 1 that the tensile strength and elongation at break of the addition silicone rubber with the addition of epoxy silicone tackifier are significantly improved, especially when the addition amount of epoxy silicone tackifier is 0.5%, the tensile strength of the addition silicone rubber is increased by 20.51%, and the elongation at break is increased by 19.86%. It can be seen from the bonding performance data in Table 1 that the use of epoxy silicone tackifier in addition silicone rubber can greatly improve the bonding performance of addition silicone rubber, especially when the addition amount of epoxy silicone tackifier is 0.5%, the breaking force is increased by 254.6%, and the shear strength is increased by 255.2%.

[0103] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A method for preparing an epoxy silicone tackifier, characterized in that: The steps include: (1) loading an ultra-microporous Pt / SiO2 catalyst into a reactor and heating the reactor to activate the ultra-microporous Pt / SiO2 catalyst; (2) Tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane are mixed to obtain a mixed reaction raw material, and when the mixed reaction raw material is heated to a temperature of 70 to 100° C., the mixed reaction raw material is added to the reactor from the top of the reactor, and the mixed reaction raw material passes through the ultra-microporous Pt / SiO2 catalyst from the top of the reactor. Under the catalytic action of the ultra-microporous Pt / SiO2 catalyst, the mixed reaction raw material reacts to generate a synthetic product, and the synthetic product flows out from the bottom of the reactor, and the synthetic product flowing out from the bottom of the reactor is collected to obtain an epoxy silicone adhesion promoter.

2. The method for preparing the epoxy-based organosilicon tackifier according to claim 1, characterized in that: In step (2), the molar ratio of tetramethylcyclotetrasiloxane, allyl glycidyl ether and 3-methacryloxypropylmethyldimethoxysilane in the mixed reaction raw materials is 1:(0.9-1.5):(0.9-1.5).

3. The method for preparing the epoxy-based organosilicon tackifier according to claim 1, characterized in that: The ultra-microporous Pt / SiO2 catalyst comprises a SiO2 carrier and a Pt element loaded on the SiO2 carrier; The pore size of the SiO2 carrier is 1.0 to 2.0 nm; The specific surface area of ​​the SiO2 carrier is 180 to 300 m 2 / g.

4. The method for preparing the epoxy-based organosilicon tackifier according to claim 1, characterized in that: Calculated by mass percentage, the content of the Pt element in the ultra-microporous Pt / SiO2 catalyst is 0.03% to 1%.

5. The method for preparing the epoxy silicone tackifier according to claim 1, characterized in that: The ratio of the amount of the mixed reaction raw materials added to the reactor per minute to the loading amount of the ultra-microporous Pt / SiO2 catalyst in the reactor is 0.1 to 2 mL / g.

6. The method for preparing the epoxy-based organosilicon tackifier according to claim 5, characterized in that: The reactor is provided with an inner cavity for placing an ultra-microporous Pt / SiO2 catalyst, and the ratio of the width to the length of the inner cavity is 1:20 to 1:

50.

7. The method for preparing the epoxy-based organosilicon tackifier according to claim 1, characterized in that: In step (1), the ultra-microporous Pt / SiO2 catalyst is loaded into a reactor and heated at 70 to 100° C. for 20 to 40 minutes to activate the ultra-microporous Pt / SiO2 catalyst; In step (2), the content of the epoxy silicone tackifier in the synthetic product is detected. When the content of the epoxy silicone tackifier in the synthetic product is less than X, the synthetic product is refluxed into the mixed reaction raw materials; when the content of the epoxy silicone tackifier in the synthetic product is ≥X, the synthetic product flowing out of the bottom of the reactor is collected to obtain the epoxy silicone tackifier, and X is 90% to 99.5%.

8. The method for preparing the epoxy-based organosilicon tackifier according to claim 1, characterized in that: The preparation method of the epoxy silicone tackifier also includes the preparation step of an ultra-microporous Pt / SiO2 catalyst, and the preparation step of the ultra-microporous Pt / SiO2 catalyst is as follows: At room temperature, the template is dissolved in water, acetonitrile containing triphenylphosphine and chloroplatinic acid is added, and then a silicon source is added. After stirring for 15 to 24 hours, the reaction is filtered; the filtered solid phase is dried at 60 to 100°C for 1 to 3 hours to obtain a dry intermediate; the dry intermediate is extracted with anhydrous ethanol for 14 to 20 hours, and the obtained solid powder is dried at 60 to 100°C for 12 to 20 hours to obtain an ultra-microporous Pt / SiO2 catalyst.

9. An epoxy silicone tackifier, characterized in that: It is prepared by the preparation method of the epoxy silicone tackifier according to any one of claims 1 to 8, and its chemical structure is as follows:

10. Use of an epoxy-based organosilicon tackifier in the preparation of an addition-type organosilicon material, characterized in that: The epoxy-based silicone tackifier is the epoxy-based silicone tackifier according to claim 9; Calculated by mass percentage, the epoxy-based organosilicon tackifier is added to the addition-type organosilicon material in an amount of 0.1% to 5%.

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