End-hydrogen silicone oil embedded with metal ion link segments, and preparation method and use thereof

Abstract

The present application relates to a kind of end hydrogen silicone oil embedded metal ion bond segment and its preparation method and purposes, the end hydrogen silicone oil is used as crosslinking agent, metal ion bond can be introduced into the chemical crosslinking network of silicone rubber, to improve the heat resistance etc. The performance of silicone rubber.The present application also relates to the preparation method of the end hydrogen silicone oil embedded metal ion bond segment, process is simple and fast, cost is low, solve the problem of the metal ion bond of metal compound into the chemical crosslinking network of silicone rubber, provide a convenient synthesis approach for the metal ion bond into the chemical crosslinking network of silicone rubber.In addition, the present application also relates to the purposes of the end hydrogen silicone oil embedded metal ion bond segment as crosslinking agent.

Description

Technical Field

[0001] This invention relates to the field of modified organosilicon polymer technology, specifically to a terminal hydrogen silicone oil with embedded metal ionic bond segments, its preparation method, and its uses. Background Technology

[0002] Silicone rubber is a rubber material with a polysiloxane backbone, widely used in aerospace, automotive, construction, and food industries. With the development of the silicone rubber market and the increasing stringency of operating conditions in recent years, higher requirements have been placed on the various properties of silicone rubber. Research has found that the ionic bonds of metal compounds possess characteristics such as heat resistance and high bond energy. Currently, the main method used is physical doping to introduce metal compounds into silicone rubber to improve its heat resistance and other properties. However, simply physically doping silicone rubber with metal compounds is no longer sufficient to meet the requirements of extreme operating conditions.

[0003] Therefore, how to introduce the ionic bonds of metal compounds into the chemical crosslinking network of silicone rubber to improve the performance of silicone rubber has become an urgent problem to be solved. Summary of the Invention

[0004] In view of the problems in the background art, the present invention provides a terminal hydrogen silicone oil with embedded metal ionic bond segments. This terminal hydrogen silicone oil is used as a crosslinking agent to introduce metal ionic bonds into the chemical crosslinking network of silicone rubber, thereby improving the heat resistance and other properties of silicone rubber.

[0005] In a first aspect, the present invention provides a terminal hydrogen silicone oil with embedded metal ionic bond segments, the structural formula of which is shown in formula (I).

[0006]

[0007] in,

[0008] R1 is selected from one or more of the Group II metal elements and transition metal elements, x is an integer from 1 to 6, y is an integer from 0 to 4, and z is an integer from 0 to 10.

[0009] The hydrogen-terminated silicone oil of the present invention contains metal ionic bonds of metal compounds. When the hydrogen-terminated silicone oil is used as a crosslinking agent to synthesize silicone rubber, the heat resistance and high bond energy of the metal ionic bonds can improve the heat resistance and other properties of the silicone rubber.

[0010] In some embodiments, considering the cost and reactivity of the raw materials, R1 is selected from one or more of calcium, barium, magnesium, and copper. Preferably, R1 is calcium or barium.

[0011] In some embodiments, x can be 1, 2, 3, 4, 5, or 6. y can be 0, 1, 2, 3, or 4. z can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Excessively large values ​​for x, y, and z can increase steric hindrance and reduce reactivity.

[0012] In some specific embodiments, x is 3, y is 0 or 1, and z is an integer from 0 to 3.

[0013] In some specific embodiments, x can be 3, y can be 0 or 1, and z can be 2 or 3.

[0014] Secondly, the present invention provides a method for preparing the terminal hydrogen silicone oil with embedded metal ionic bond segments, comprising the following steps:

[0015] Preparation of (R1CO3) x Oligomers, wherein R1 is selected from one or more of calcium, barium, magnesium, and copper, and x is 1-6;

[0016] To make organic acids CH2=CH(CH2) y COOH and (R1CO3) x The oligomers react to yield terminal vinyl groups (R1CO3). x where y is 0-4;

[0017] End vinyl group (R1CO3) x With terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z The reaction (CH3)2SiH yields terminal hydrogen silicone oil with embedded metal ionic bond segments, where z is 0-10.

[0018] The preparation process of this invention is simple, rapid, and low-cost, solving the problem of introducing metal ionic bonds of metal compounds into the chemical crosslinking network of silicone rubber, and providing a convenient synthetic route for introducing metal ionic bonds into the chemical crosslinking network of silicone rubber. This invention overcomes the difficulty in existing technologies where insufficient physical mixing of metal compounds and silicone rubber affects the improvement of the heat resistance and other properties of silicone rubber by the metal compounds. Furthermore, compared to the synthetic difficulty and process complexity of introducing metal compounds into the raw rubber molecular chain, this invention first introduces the metal ionic bonds into the crosslinking agent and then introduces them into the chemical crosslinking network of silicone rubber, greatly reducing the synthetic difficulty and simplifying the synthetic process.

[0019] In some embodiments, the (R1CO3) is prepared. x Oligomers include:

[0020] A metal chloride R1Cl2 and an organic base are dissolved in solvent A to obtain a mixed solution. CO2 gas is then introduced into the mixed solution. After the reaction is complete, the mixture is centrifuged to precipitate (R1CO3). xOligomers;

[0021] Optionally, the organic base includes one or more of triethylamine, diethylamine, tri-n-butylamine, and diisopropylamine;

[0022] Optionally, solvent A includes one or more of ethanol, isopropanol, and n-butanol.

[0023] In some specific embodiments, the (R1CO3) is prepared... x Oligomers include:

[0024] Metal chloride R1Cl2 is dissolved in solvent A, and an organic base is added to prepare a mixed solution. While stirring, CO2 gas is bubbled into the mixed solution. After the mixed solution becomes turbid, CO2 is kept bubbling for 5-15 minutes (e.g., 8-10 minutes), and the mixed solution is stirred continuously (e.g., 20, 30, or 40 minutes) to obtain a transparent or translucent solution containing (R1CO3). X The oligomer solution was centrifuged to precipitate, and then washed to obtain (R1CO3). x Oligomeric gel. Preferably, the product obtained after centrifugation precipitation may be washed multiple times. The washing includes: adding an alcohol solvent such as ethanol to the product obtained after centrifugation, followed by centrifugation.

[0025] In this invention, the (R1CO3) is prepared... x For methods involving oligomers, please refer to Nature 574, 394–398 (2019).

[0026] In some embodiments, the terminal vinyl group (R1CO3) is prepared. x include:

[0027] Under conditions of darkness and at 20-50℃, the organic acid CH2=CH(CH2) is... y COOH and (R1CO3) x The oligomers were reacted in solvent B for 3-10 hours, and centrifuged to obtain terminal vinyl groups (R1CO3). x The reaction process is as follows:

[0028]

[0029] Preferably, the organic acid is CH2=CH(CH2). y COOH and (R1CO3) X The molar ratio of the oligomers can be (2-5):1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, preferably (2-3):1.

[0030] Preferably, solvent B includes at least one of ethanol, isopropanol, and n-butanol. Preferably, solvent B is ethanol.

[0031] Preferably, the reaction temperature can be 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, or 50℃. The reaction time can be 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours. Too low a temperature will affect the reaction rate, while too high a temperature will make the reaction too vigorous and difficult to control.

[0032] Organic acids CH2=CH(CH2) y COOH and (R1CO3) x Oligomers must be reacted under light-protected conditions to avoid side reactions such as acid-base reactions caused by light exposure.

[0033] In some specific embodiments, the terminal vinyl group (R1CO3) is prepared. x include:

[0034] Organic acids CH2=CH(CH2) y COOH is dissolved in solvent B to form solution A, and the (R1CO3) is then dissolved in solvent B. x The oligomer is dissolved in solvent B to form solution B. The freshly prepared solution B is slowly added dropwise to solution A. After the addition is complete, the mixture is stirred and reacted at 20-50°C in the dark for 3-10 hours. The mixture is then centrifuged and washed.

[0035] Preferably, the concentration of solution A is 20-65 mmol / L, for example, it can be 20 mmol / L, 25 mmol / L, 30 mmol / L, 35 mmol / L, 40 mmol / L, 45 mmol / L, 50 mmol / L, 51 mmol / L, 52 mmol / L, 53 mmol / L, 54 mmol / L, 55 mmol / L, 56 mmol / L, 57 mmol / L, 58 mmol / L, 59 mmol / L, 60 mmol / L, 61 mmol / L, 62 mmol / L, 63 mmol / L, 64 mmol / L, or 65 mmol / L. More preferably, the concentration of solution A is 30-40 mmol / L. Too low a concentration results in low yield, while too high a concentration can cause side reactions.

[0036] Preferably, the concentration of solution B is 2-10 mg / mL, for example, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, or 10 mg / mL. More preferably, the concentration of solution B is 3-6 mg / mL.

[0037] Preferably, the centrifugation speed can be 8000-10000 rpm, for example, 8000, 8500, 9000, 9500, or 10000 rpm. High-speed centrifugation is beneficial for better separation of products.

[0038] Preferably, the product obtained after centrifugation may be washed multiple times. The washing includes adding an alcohol solvent, such as ethanol, to the product obtained after centrifugation, followed by further centrifugation.

[0039] Preferably, the mixture is stirred while being added dropwise.

[0040] In some embodiments, the preparation of the terminal hydrogen silicone oil with embedded metal ionic bond segments includes:

[0041] The terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z (CH3)2SiH, the terminal vinyl group (R1CO3) x The hydrosilylation catalyst and co-catalyst are dissolved in solvent C, and the reaction is stirred at 40-120℃ for 1-8 hours. After the reaction is complete, the mixture is cooled, centrifuged, washed, and dried. The reaction process is shown below:

[0042]

[0043] Preferably, the reaction temperature can be 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃ or 120℃. The reaction time can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours.

[0044] Preferably, the terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z (CH3)2SiH and the terminal vinyl group (R1CO3) x The molar ratio can be (2-5):1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, preferably (2-3):1.

[0045] Preferably, the hydrosilylation catalyst comprises at least one of chloroplatinic acid and a Karstedt catalyst. For example, the hydrosilylation catalyst comprises at least one of an isopropanol solution of chloroplatinic acid and an isopropanol solution of a Karstedt catalyst. The concentrations of the isopropanol solution of chloroplatinic acid and the isopropanol solution of the Karstedt catalyst are each 0.01–0.1 mol / L, for example, 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, or 0.1 mol / L, preferably 0.1 mol / L.

[0046] Preferably, the co-catalyst comprises at least one of triphenylphosphine and caprolactam. For example, the co-catalyst comprises at least one of a triphenylphosphine isopropanol solution and a caprolactam isopropanol solution. The concentrations of the triphenylphosphine isopropanol solution and the caprolactam isopropanol solution are each 0.01–0.1 mol / L, for example, 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, or 0.1 mol / L, preferably 0.1 mol / L.

[0047] Preferably, the hydrosilylation catalyst reacts with the terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O). z The molar ratio of (CH3)2SiH can be (10) -5 -10 -6 ):1, for example, it can be 1×10 -5 1. 9×10 -6 1. 8×10 -6 1. 7×10 -6 1. 6×10 -6 1. 5×10 -6 1. 4×10 -6 1, 3×10 -6 1, 2×10 -6 1, 1×10 -6 :1.

[0048] Preferably, the co-catalyst is reacted with the terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O). z The molar ratio of (CH3)2SiH is (10) -5 -10 -6 ):1, for example, it can be 1×10 -5 1. 9×10-6 1. 8×10 -6 1. 7×10 -6 1. 6×10 -6 1. 5×10 -6 1. 4×10 -6 1, 3×10 -6 1, 2×10 -6 1, 1×10 -6 :1.

[0049] Preferably, the solvent C includes isopropanol, n-butanol, toluene, and tetrahydrofuran.

[0050] Preferably, after the reaction is complete, the mixture is allowed to cool naturally to room temperature. In this invention, "room temperature" refers to a temperature of 20-30°C.

[0051] Preferably, the centrifugation speed can be 8000-10000 rpm, for example, 8000, 8500, 9000, 9500, or 10000 rpm. High-speed centrifugation is beneficial for better separation of products.

[0052] Preferably, the product obtained after centrifugation may be washed multiple times. The washing includes adding an alcohol solvent, such as ethanol, to the product obtained after centrifugation, followed by further centrifugation.

[0053] Preferably, the material can be dried at room temperature in a vacuum drying oven for 6-20 hours, for example, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, or 20 hours.

[0054] Thirdly, the present invention provides the use of the terminal hydrogen silicone oil with embedded metal ionic bond segments as a crosslinking agent.

[0055] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0056] 1. This invention provides a terminal hydrogen silicone oil with embedded metal ionic bond segments. This terminal hydrogen silicone oil is used as a crosslinking agent to introduce metal ionic bonds into the chemical crosslinking network of silicone rubber, thereby improving the heat resistance and other properties of silicone rubber.

[0057] 2. The present invention also provides a method for preparing the terminal hydrogen silicone oil with embedded metal ionic bond segments. The process is simple, fast and low in cost, and solves the problem of introducing the metal ionic bonds of metal compounds into the chemical crosslinking network of silicone rubber. It provides a convenient synthetic route for introducing metal ionic bonds into the chemical crosslinking network of silicone rubber. Attached Figure Description

[0058] Figure 1The infrared spectrum of the terminal hydrogen silicone oil with embedded metal ionic bond segments prepared using (CaCO3)3 oligomer, acrylic acid and terminal hydrogen silane in Example 1 is shown. Detailed Implementation

[0059] To make the technical problems, technical solutions, and beneficial effects of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art. In the embodiments, unless otherwise specified, the raw materials used are commercially available, and the methods used in the following embodiments are conventional methods in the art unless otherwise specified.

[0060] Preparation of terminal hydrogen silicone oils with embedded metal ionic bond segments

[0061] Example 1

[0062] (1) Dissolve 2.0 g CaCl2·2H2O in 500 mL of ethanol, add 38 mL of triethylamine to prepare a mixed solution, and while stirring, introduce CO2 gas into the solution. After 5 minutes, the solution becomes turbid. Then, keep the CO2 bubbling for 10 minutes and continue stirring for 30 minutes to obtain a translucent solution containing (CaCO3)3 oligomers. Centrifuge at 10000 rpm to precipitate (CaCO3)3 oligomer gel, and after washing and centrifuging in ethanol several times, finally obtain (CaCO3)3 oligomer gel. Repeat the above steps to obtain four batches of (CaCO3)3 oligomers, which are then collected together.

[0063] (2) 2.3 g of acrylic acid (0.032 mol) was completely dissolved in 500 mL of ethanol to form solution A. 4.8 g of (CaCO3)3 oligomer gel (0.016 mol) was dissolved in 500 mL of ethanol to form solution B. The freshly prepared solution B was slowly added dropwise to solution A while stirring. After the addition was complete, the mixture was stirred for 8 hours at 25 °C in the dark to obtain a mixed solution. The product was obtained by high-speed centrifugation at 10,000 rpm. After washing and centrifugation in ethanol several times, the product terminal vinyl (CaCO3)3 was obtained with a yield of 89.1%.

[0064] (3) Add 7.0 g octamethyldihydrotetrasiloxane (0.025 mol), 5.0 g terminal vinyl (CaCO3)3 (0.012 mol), and 1 μL Karstedt catalyst (10 -7 0.1 mol / L isopropanol solution, 1 μL triphenylphosphine (10 mol) -7A 0.1 mol / L isopropanol solution was dissolved in 200 mL of isopropanol, and the mixture was stirred at 80 °C for 4 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature. The product was obtained by high-speed centrifugation at 10,000 rpm, followed by multiple washings and centrifugations in ethanol. The product was then dried in a vacuum oven at room temperature for 12 hours to obtain terminal hydrogen silicone oil with embedded metal ion bonds, with a yield of 91.0%. Its infrared spectrum is shown below. Figure 1 As shown.

[0065] Example 2

[0066] (1) Dissolve 3.0 g BaCl2·2H2O in 500 mL of ethanol, add 38 mL of triethylamine to prepare a mixed solution, and while stirring, introduce CO2 gas into the solution. After 5 minutes, the solution becomes turbid. Then, keep the CO2 bubbling for 10 minutes and continue stirring the solution for 30 minutes to obtain a translucent solution containing (CaCO3)3 oligomers. Centrifuge at 10000 rpm to precipitate (BaCO3)3 oligomers into a gel. After washing and centrifuging in ethanol several times, (BaCO3)3 oligomers into a gel were obtained. Repeat the above steps to obtain four batches of (BaCO3)3 oligomers, which were then collected together.

[0067] (2) 2.3 g of acrylic acid (0.032 mol) was completely dissolved in 500 mL of ethanol to form solution A. 9.4 g of (BaCO3)3 oligomer gel (0.016 mol) was dissolved in 500 mL of ethanol to form solution B. The freshly prepared solution B was slowly added dropwise to solution A while stirring. After the addition was complete, the mixture was stirred at 40 °C in the dark for 5 hours to obtain the product solution. The product was obtained by high-speed centrifugation at 10,000 rpm. After washing and centrifugation in ethanol multiple times, the product terminal vinyl (BaCO3)3 was obtained with a yield of 90.2%.

[0068] (3) Add 9.0 g decamethyldihydropentasiloxane (0.025 mol), 7.0 g terminal vinyl (BaCO3)3 (0.012 mol), and 2 μL Karstedt catalyst (2 × 10⁻⁶ mol) to the mixture. -7 0.1 mol / L isopropanol solution, 2 μL triphenylphosphine (2 × 10⁻⁶ mol / L) - 7A 0.1 mol / L isopropanol solution was dissolved in 200 mL of ethanol and reacted at 80 °C for 8 hours with stirring. After the reaction was complete, the mixture was allowed to cool naturally to room temperature. The product was obtained by high-speed centrifugation at 10,000 rpm, followed by multiple washings and centrifugations in ethanol. The product was then dried in a vacuum drying oven at room temperature for 12 hours to obtain terminal hydrogen silicone oil with embedded metal ion bonds, with a yield of 90.5%. Its infrared spectrum is similar to... Figure 1 similar.

[0069] Example 3

[0070] (1) Dissolve 2.0 g CaCl2·2H2O in 500 mL of ethanol, add 38 mL of triethylamine to prepare a mixed solution, and while stirring, introduce CO2 gas into the solution. After 5 minutes, the solution becomes turbid. Then, keep the CO2 bubbling for 10 minutes and continue stirring the solution for 30 minutes to obtain a translucent solution containing (CaCO3)3 oligomers. Centrifuge at 10000 rpm to precipitate (CaCO3)3 oligomer gel, and after washing and centrifuging in ethanol several times, obtain (CaCO3)3 oligomer gel. Repeat the above steps to obtain four batches of (CaCO3)3 oligomers, and collect them together.

[0071] (2) 3.0 g of vinylacetic acid (0.035 mol) was completely dissolved in 500 mL of ethanol to form solution A. 4.8 g of (CaCO3)3 oligomer gel (0.016 mol) was dissolved in 500 mL of ethanol to form solution B. The freshly prepared solution B was slowly added dropwise to solution A while stirring. After the addition was complete, the mixture was stirred for 8 hours at 25 °C in the dark to obtain the product solution. The product was obtained by high-speed centrifugation at 10,000 rpm. After washing and centrifugation in ethanol several times, the product terminal vinyl (CaCO3)3 was obtained with a yield of 88.7%.

[0072] (3) Add 7.0 g of octamethyldihydrotetrasiloxane (0.025 mol), 5.3 g of terminal vinyl (CaCO3)3 (0.012 mol), and 1 μL of Karstedt catalyst (10 -7 0.1 mol / L isopropanol solution, 1 μL triphenylphosphine (10 mol) -7 A 0.1 mol / L isopropanol solution was dissolved in 200 mL of isopropanol, and the mixture was stirred at 90 °C for 4 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature. The product was obtained by high-speed centrifugation at 10,000 rpm, followed by multiple washings in ethanol and centrifugation. The product was then dried in a vacuum drying oven at room temperature for 12 hours to obtain terminal hydrogen silicone oil with embedded metal ion bonds, with a yield of 89.4%. Its infrared spectrum is similar to... Figure 1 similar.

[0073] Preparation of organic-inorganic polymer materials

[0074] Example 4

[0075] Organic-inorganic polymer materials were prepared using the terminal hydrogen silicone oil with embedded metal ion bonds prepared in Example 1 as a crosslinking agent. The specific steps are as follows: 100 parts by weight of methyl vinyl raw rubber, 40 parts by weight of fumed silica, 3 parts by weight of hydroxyl silicone oil, and 5 parts by weight of the terminal hydrogen silicone oil with embedded metal ion bonds prepared in Example 1 were weighed and mixed on a two-roll mill for 15 minutes. Then, 1 part of inhibitor masterbatch and 2 parts of platinum catalyst masterbatch (Pt was calculated as 1 × 10⁻⁶ of the rubber mass) were added. －6 The mixture was thoroughly mixed on a two-roll mill to form a compound. Finally, it was vulcanized at 150°C and 5MPa for 10 minutes to obtain silicone rubber test pieces.

[0076] Example 5

[0077] The organic-inorganic polymer material was prepared using the terminal hydrogen silicone oil with embedded metal ion bonds prepared in Example 2 as a crosslinking agent. The specific steps are as follows:

[0078] Weigh out 100 parts by weight of methyl vinyl raw rubber, 40 parts by weight of fumed silica, 3 parts by weight of hydroxyl silicone oil, and 5 parts by weight of terminal hydrogen silicone oil with embedded metal ion bond segments prepared in Example 2. Mix them on a two-roll mill for 15 minutes, then add 1 part of inhibitor masterbatch and 2 parts of platinum catalyst masterbatch (Pt is 1×10⁻⁶ of the rubber compound mass). －6 The mixture was thoroughly mixed on a two-roll mill to form a compound. Finally, it was vulcanized at 150°C and 5MPa for 10 minutes to obtain silicone rubber test pieces.

[0079] Example 6

[0080] The organic-inorganic polymer material was prepared using the terminal hydrogen silicone oil with embedded metal ion bond segments prepared in Example 3 as a crosslinking agent. The specific steps are as follows:

[0081] Weigh out 100 parts by weight of methyl vinyl raw rubber, 40 parts by weight of fumed silica, 3 parts by weight of hydroxyl silicone oil, and 5 parts by weight of terminal hydrogen silicone oil with embedded metal ion bond segments prepared in Example 3. Mix them on a two-roll mill for 15 minutes, then add 1 part of inhibitor and 2 parts of platinum catalyst masterbatch (Pt is 1×10⁻⁶ of the rubber compound mass). －6 The mixture was thoroughly mixed on a two-roll mill to form a compound. Finally, it was vulcanized at 150°C and 5MPa for 10 minutes to obtain silicone rubber test pieces.

[0082] Comparative Example 1

[0083] The specific steps for preparing organic-inorganic polymer materials using terminal hydrogen silicone oil without metal ion-bonded chain segments as a crosslinking agent are as follows:

[0084] Weigh out 100 parts by weight of methyl vinyl raw rubber, 40 parts by weight of fumed silica, 3 parts by weight of hydroxyl silicone oil and 5 parts by weight of terminal hydrogen silicone oil, and mix them on a two-roll mill for 15 minutes. Then add 1 part of inhibitor masterbatch and 2 parts of platinum catalyst masterbatch (Pt is 1×10⁻⁶ of the rubber compound mass). －6 The mixture was thoroughly mixed on a two-roll mill to form a compound. Finally, it was vulcanized at 150°C and 5MPa for 10 minutes to obtain silicone rubber test pieces.

[0085] Performance testing of organic-inorganic polymer materials

[0086] Heat resistance test: The tensile strength and elongation at break of the silicone rubber specimens in the above examples and comparative examples were tested according to the national standard GB / T 528. The heat resistance was judged by comparing the performance before and after aging in hot air at 300℃ for 70h.

[0087] The test results are shown in Table 1 below.

[0088] Table 1

[0089]

[0090] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A terminal hydrogen silicone oil with embedded metal ionic bond segments, characterized in that, The structural formula of the hydrogen-terminated silicone oil is shown in formula (I). Equation (I) Where R1 is selected from one or more of calcium and barium, x is an integer from 1 to 6, y is an integer from 0 to 4, and z is an integer from 0 to 10.

2. The terminal hydrogen silicone oil with embedded metal ionic bond segments according to claim 1, characterized in that, x is 3, y is 0 or 1, and z is an integer between 0 and 3.

3. The method for preparing the terminal hydrogen silicone oil with embedded metal ionic bond segments according to any one of claims 1-2, characterized in that, Includes the following steps: Preparation of (R1CO3) x Oligomers, wherein R1 is selected from one or more of calcium and barium, and x is 1-6; To make organic acids CH2=CH(CH2) y COOH and (R1CO3) x The oligomers react to yield terminal vinyl groups (R1CO3). x where y is 0-4; End vinyl group (R1CO3) x With terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z The reaction (CH3)2SiH yields terminal hydrogen silicone oil with embedded metal ionic bond segments, where z is 0-10.

4. The preparation method according to claim 3, characterized in that, Preparation of the terminal vinyl group (R1CO3) x include: Under conditions of darkness and at 20-50℃, the organic acid CH2=CH(CH2) is... y COOH and (R1CO3) x The oligomers were reacted in solvent B for 3-10 hours, and centrifuged to obtain terminal vinyl groups (R1CO3). x The reaction process is as follows: ； The organic acid CH2=CH(CH2) y COOH and (R1CO3) X The molar ratio of oligomers is (2-5):1; Solvent B includes at least one of ethanol, isopropanol, and n-butanol.

5. The preparation method according to claim 4, characterized in that, Preparation of the terminal vinyl group (R1CO3) x include: Organic acids CH2=CH(CH2) y COOH is dissolved in solvent B to form solution A, and the (R1CO3) is then dissolved in solvent B. x The oligomer is dissolved in solvent B to form solution B. The freshly prepared solution B is slowly added dropwise to solution A. After the addition is complete, the mixture is stirred and reacted at 20-50°C in the dark for 3-10 hours. The mixture is then centrifuged and washed. The concentration of solution A is 20-65 mmol / L; The concentration of solution B is 2-10 mg / mL.

6. The preparation method according to claim 3 or 4, characterized in that, The preparation of the terminal hydrogen silicone oil with embedded metal ionic bond segments includes: The terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z (CH3)2SiH, the terminal vinyl group (R1CO3) x The hydrosilylation catalyst and co-catalyst are dissolved in solvent C, and the reaction is stirred at 40-120℃ for 1-8 hours. After the reaction is complete, the mixture is cooled, centrifuged, washed, and dried. The reaction process is shown below: 。 7. The preparation method according to claim 6, characterized in that, The terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z (CH3)2SiH and the terminal vinyl group (R1CO3) x The molar ratio is (2-5):1; The hydrosilylation catalyst includes at least one of chloroplatinic acid and Karstedt catalyst. The co-catalyst includes at least one of triphenylphosphine and caprolactam; The hydrosilylation catalyst and the terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z The molar ratio of (CH3)2SiH is (10) -5 -10 -6 ):1; The co-catalyst and the terminal hydrogen silane HSi(CH3)2O(Si(CH3)2O) z The molar ratio of (CH3)2SiH is (10) -5 -10 -6 ):1; The solvent C includes isopropanol, n-butanol, toluene, and tetrahydrofuran.

8. The preparation method according to claim 3 or 4, characterized in that, Preparation of (R1CO3) x Oligomers include: A metal chloride R1Cl2 and an organic base are dissolved in solvent A to obtain a mixed solution. CO2 gas is then introduced into the mixed solution. After the reaction is complete, the mixture is centrifuged to precipitate (R1CO3). x Oligomers; The organic base includes one or more of triethylamine and diisopropylamine; Solvent A includes one or more of ethanol, isopropanol, and n-butanol.

9. Use of the terminal hydrogen silicone oil with embedded metal ionic bond segments as described in any one of claims 1-2 as a crosslinking agent.

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