Heterogeneous bimetallic platinum catalyst and use thereof in synthesis of γ-chloropropyltrichlorosilane

Abstract

Disclosed in the present invention are a heterogeneous bimetallic platinum catalyst and a use thereof in synthesis of γ-chloropropyltrichlorosilane (γ1). In the present invention, an anthracene skeleton is introduced, a novel bimetallic platinum metal catalyst is synthesized by means of coordination with platinum, and the bimetallic platinum metal catalyst is loaded into high vinyl polybutadiene by means of a Diels-Alder (DA) reaction to prepare the heterogeneous bimetallic platinum catalyst. The novel heterogeneous bimetal platinum catalyst has a synergistic catalytic effect, and high-efficiency and high-selectivity hydrosilylation reaction of non-chloropropene and trichlorosilane is realized. The heterogeneous bimetallic catalyst reported by the present invention has the characteristics of high catalytic efficiency, high selectivity and recyclability, the purity of γ1 reaches 99.5%, and the product yield is as high as 97%.

Description

A heterogeneous bimetallic platinum catalyst and its application in the synthesis of γ-chloropropyltrichlorosilane Technical Field

[0001] The present invention relates to a heterogeneous bimetallic platinum catalyst and application thereof in the synthesis of gamma-chloropropyltrichlorosilane (γ1). Background Art

[0002] Silane coupling agents are essential functional additives in the rubber industry and are the core material of rubber materials. γ-Chloropropyltrichlorosilane (γ1) is the most important intermediate in the synthesis of high-performance silane coupling agents. Industrially, it is typically produced through a hydrosilylation reaction using allyl chloride and trichlorosilane as raw materials in the presence of a platinum catalyst. The selectivity of the hydrosilylation reaction directly determines the quality of the product, while the activity of the reaction determines the cost of the production process. Therefore, the development of metal catalysts for the hydrosilylation reaction is a core technology in the production of γ1 and high-performance silane coupling agents. The development of new, highly efficient, highly selective, and renewable heterogeneous metal catalysts can reduce the activation energy of hydrosilylation, promote the reaction, and improve product selectivity, thereby reducing production costs and energy consumption, improving product purity and quality, and promoting industrial technological upgrading.

[0003] In light of this, the present invention reports a heterogeneous bimetallic platinum catalyst for use in the synthesis of γ-chloropropyltrichlorosilane (γ1). The present invention introduces an anthracene-based ligand and synthesizes several novel bimetallic platinum catalysts by coordinating with platinum. Using the Diels-Alder (DA) reaction, the platinum catalyst is loaded onto high-vinyl polybutadiene to produce a heterogeneous bimetallic platinum catalyst. The heterogeneous catalyst reported in the present invention exhibits high catalytic efficiency, high selectivity, and recyclability. The resulting γ1 is colorless and transparent, with a product purity of 99.5% and a yield as high as 97%.

[0004] Therefore, the heterogeneous bimetallic platinum catalyst reported in the present invention is original and innovative, and has high economic and social benefits for the industrial production of γ-chloropropyltrichlorosilane.

[0005] Summary of the Invention

[0006] The present invention aims to provide a heterogeneous bimetallic platinum catalyst and its application in the synthesis of γ-chloropropyltrichlorosilane (γ1).

[0007] The present invention provides bimetallic platinum metal complexes represented by formulas I-IV:

[0008] The present invention provides a method for preparing the above-mentioned bimetallic complex, comprising the following steps:

[0009] (a) 1,8-dinitroanthraquinone is dissolved in ethanol, sodium sulfide nonahydrate is added, and the mixture is refluxed at 90°C for 6 to 24 hours; after filtering to remove the solvent, the mixture is dissolved in isopropanol, sodium borohydride is added, the mixture is refluxed at 90°C for 6 to 24 hours, and the solvent is filtered to remove to obtain 1,8-diaminoanthracene;

[0010] (b) 1-aminoanthracene is dissolved in ethanol, and 6-methyl-2-pyridinecarboxaldehyde or 6-bromopyridine-2-carboxaldehyde and p-toluenesulfonic acid are added to initiate the reaction. After the reaction is completed, the ligand is filtered and recrystallized to obtain the ligand;

[0011] (c) dissolving the ligand and anhydrous sodium acetate in an organic solvent, adding potassium tetrachloroplatinate or potassium hexachloroplatinate for reaction, washing with water and methanol after the reaction, and recrystallizing to obtain the target complex;

[0012] (d) The metal complex and high-ethylene-content polybutadiene are dissolved in an organic solvent and heated to react. After the reaction is completed, the temperature is lowered and the solvent is removed to obtain the target heterogeneous platinum catalyst.

[0013] In the above preparation method, the molar ratio of sodium sulfide nonahydrate to 1,8-dinitroanthraquinone in the process (a) is 2.0-3.0:1, preferably 2.2:1.

[0014] In the process (a), the molar ratio of sodium borohydride to 1,8-dinitroanthraquinone is 5.0-15.0:1, preferably 8:1.

[0015] In the above preparation method, the molar ratio of 6-methyl-2-pyridinecarboxaldehyde or 6-bromopyridine-2-carboxaldehyde to 1-aminoanthracene in the process (b) is 2.1 to 3.0:1, preferably 2.4:1.

[0016] In the above preparation method, the molar ratio of p-toluenesulfonic acid to 1-aminoanthracene in the process (b) is 1 to 8:100, preferably 2:100.

[0017] In the above preparation method, the reaction temperature of the process (b) is 0-40°C, preferably 25°C; and the reaction time is 6-24 hours, preferably 12 hours.

[0018] In the above preparation method, in the process (c), the molar ratio of anhydrous sodium acetate to the ligand is 4.0 to 4.8:1, preferably 4.0:1.

[0019] In the above preparation method, in the process (c), the molar ratio of potassium tetrachloroplatinate or potassium hexachloroplatinate to the ligand is 2.0 to 2.4:1, preferably 2.1:1.

[0020] In the above preparation method, the reaction temperature of the process (c) is 80-140° C., preferably 110° C.; and the reaction time is 2-12 hours, preferably 6 hours.

[0021] In the above preparation method, the solvent used in the process (d) is toluene, xylene, acetonitrile, DMF, chloroform, tetrahydrofuran, preferably toluene.

[0022] In the above preparation method, in the process (d), the reaction temperature is 150-220°C, preferably 180°C; and the reaction time is 2-48 hours, preferably 12 hours.

[0023] The present invention discloses a method for synthesizing γ-chloropropyltrichlorosilane by using the above-mentioned heterogeneous catalyst. The main steps are: premixing allyl chloride and the catalyst, adding trichlorosilane dropwise to carry out a hydrosilylation reaction, filtering and recovering the catalyst after the reaction, and then purifying the reaction product by distillation to obtain γ-chloropropyltrichlorosilane.

[0024] In the above catalytic reaction, the ratio of the chloropropylene to trichlorosilane is 1:1-1.5, preferably 1:1.05.

[0025] In the above catalytic reaction, the amount of the catalyst relative to the allyl chloride is 100 to 10 ppm.

[0026] In the above catalytic reaction, the temperature of the hydrosilylation reaction is 50° C. to 80° C., and the reaction time is 1 to 6 hours. Preferably, the reaction temperature is 60° C., and the reaction time is 3 hours.

[0027] In the above catalytic reaction, the temperature of the distillation purification is 70-90°C.

[0028] The present invention provides the preparation of a heterogeneous bimetallic platinum catalyst and its use in catalyzing the addition reaction of allyl chloride and trichlorosilane. The heterogeneous bimetallic platinum catalyst reported in the present invention has high selectivity, high catalytic efficiency, and recyclability. The resulting γ-chloropropyltrichlorosilane (γ1) has a high yield (up to 97%) and high purity (99.5%). BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is a synthetic route diagram of catalyst I.

[0030] Figure 2 is the NMR spectrum of 1,8-diaminoanthracene. DETAILED DESCRIPTION

[0031] The present invention is further described by way of examples, but the present invention is not limited thereto. The examples of the present invention can enable those skilled in the art to more fully understand the present invention.

[0032] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. The content of 1,2 structure of high vinyl polybutadiene is greater than 80%.

[0033] The present invention is described below with reference to specific embodiments.

[0034] Example 1. Synthesis of anthracene ligand.

[0035] Weigh 12g / 40mmol of 1,8-dinitroanthraquinone and add 100mL of ethanol. Dissolve 38.4g / 0.178mol of sodium sulfide nonahydrate in 120mL of deionized water. Add the resulting mixture to the ethanol solution of 1,8-dinitroanthraquinone and reflux at 90°C for 12 hours. After the reaction, filter and remove the solvent at 0°C. The residue is dissolved in 200mL of isopropanol and 18g / 0.476mol of sodium borohydride is added. Reflux at 90°C for 12 hours. After the reaction, filter and remove the solvent at 0°C. The resulting yellow solid powder is 1,8-diaminoanthracene (7.5g, 36mmol) with a yield of 90%. Weigh 1.04 g / 5 mmol of 1,8-diaminoanthracene, use ethanol as solvent, add 2.4 equivalents of 6-methyl-2-pyridinecarboxaldehyde (2.6 g / 12 mmol) and 12 mg of p-toluenesulfonic acid (1 mol%), react for 12 hours, concentrate the filtrate and recrystallize it, and 1.9 g of ligand is obtained after filtration, with a yield of 92%.

[0036] Example 2, Synthesis of Catalyst I.

[0037] 2.07 g / 5 mmol of the ligand and 1.6 mg / 20 mmol of anhydrous sodium acetate were weighed, added to 30 mL of toluene, heated to 110°C, and 9.8 g / 10 mmol of potassium tetrachloroplatinate was added, allowing the reaction to proceed for 6 hours. 10 mL of distilled water was then added, filtered, and the residue washed three times with 20 mL of water and once with 20 mL of methanol. The residue was recrystallized from toluene to yield 3.7 g of the platinum complex with a yield of 78%. 1.4 g of the platinum complex and 10 g of high-vinyl polybutadiene were weighed, added to 20 mL of toluene, and heated to 180°C for 12 hours. After the reaction, the reaction was filtered at room temperature and dried under vacuum to yield Catalyst I. ICP analysis revealed a Pt content of 5.0% by mass.

[0038] Example 3, Synthesis of Catalyst II.

[0039] 2.07 g / 5 mmol of the ligand and 1.6 mg / 20 mmol of anhydrous sodium acetate were weighed, added to 30 mL of toluene, heated to 110°C, and then 9.8 g / 10 mmol of potassium chloroplatinate was added and allowed to react for 6 hours. 10 mL of distilled water was then added and filtered, and the residue was washed three times with 20 mL of water and once with 20 mL of methanol. The residue was recrystallized from toluene to yield 4.8 g of the platinum complex with a yield of 79%. 1.9 g of the platinum complex and 10 g of high-vinyl polybutadiene were weighed, added to 20 mL of toluene, and heated to 180°C for 12 hours. After the reaction, the mixture was filtered at room temperature and dried under vacuum to yield Catalyst II. ICP analysis revealed a Pt content of 4.9% by mass.

[0040] Example 4. Synthesis of Catalyst III.

[0041] 2.72 g / 5 mmol of the ligand and 1.6 mg / 20 mmol of anhydrous sodium acetate were weighed, added to 30 mL of toluene, heated to 110°C, and then 9.8 g / 10 mmol of potassium tetrachloroplatinate was added and allowed to react for 6 hours. 10 mL of distilled water was then added and filtered, and the residue was washed three times with 20 mL of water and once with 20 mL of methanol. The residue was recrystallized from toluene to yield 3.9 g of the platinum complex with a yield of 83%. 1.7 g of the platinum complex and 10 g of high-vinyl polybutadiene were weighed, added to 20 mL of toluene, and heated to 180°C for 12 hours. After the reaction, the mixture was filtered at room temperature and dried under vacuum to yield Catalyst I. ICP analysis revealed a Pt content of 5.1% by mass.

[0042] Example 5. Synthesis of Catalyst IV.

[0043] 2.72 g / 5 mmol of the ligand and 1.6 mg / 20 mmol of anhydrous sodium acetate were weighed, added to 30 mL of toluene, heated to 110°C, and then 9.8 g / 10 mmol of potassium chloroplatinate was added and allowed to react for 6 hours. 10 mL of distilled water was then added and filtered, and the residue was washed three times with 20 mL of water and once with 20 mL of methanol. The residue was recrystallized from toluene to yield 4.7 g of the platinum complex with a yield of 77%. 1.9 g of the platinum complex and 10 g of high-vinyl polybutadiene were weighed, added to 20 mL of toluene, and heated to 180°C for 12 hours. After the reaction, the reaction was filtered at room temperature and dried under vacuum to obtain Catalyst IV. ICP analysis revealed a Pt content of 5.1% by mass.

[0044] Example 6: Catalyst I catalyzes the reaction of allyl chloride and trichlorosilane.

[0045] Weigh 10g of allyl chloride and 3mg of Catalyst I, heat to 50°C for 30 minutes, and activate. Then weigh 17.7g of trichlorosilane and add it dropwise to the allyl chloride solution over approximately one hour. Reflux at 60°C for three hours, then evaporate under reduced pressure. Collect the fraction at 70-90°C. The resulting product is γ-chloropropyltrichlorosilane, with a yield of 92%.

[0046] Example 7: Catalyst II catalyzes the reaction of allyl chloride and trichlorosilane.

[0047] Weigh 10g of allyl chloride and 3mg of Catalyst II, heat to 50°C for 30 minutes, and activate. Then weigh 17.7g of trichlorosilane and add it dropwise to the allyl chloride solution over approximately one hour. Reflux at 60°C for three hours, then evaporate under reduced pressure. Collect the fraction at 70-90°C. The resulting product is γ-chloropropyltrichlorosilane, with a yield of 97%.

[0048] Example 8: Catalyst III catalyzes the reaction of allyl chloride and trichlorosilane.

[0049] Weigh 10g of allyl chloride and 3mg of Catalyst III, heat to 50°C for 30 minutes, and activate. Then weigh 17.7g of trichlorosilane and add it dropwise to the allyl chloride solution over approximately one hour. Reflux at 60°C for three hours, then evaporate under reduced pressure. Collect the fraction at 70-90°C. The resulting product is γ-chloropropyltrichlorosilane, with a yield of 94%.

[0050] Example 9: Catalyst IV catalyzes the reaction of allyl chloride and trichlorosilane.

[0051] Weigh 10g of allyl chloride and 3mg of Catalyst IV, heat to 50°C for 30 minutes, and activate. Then weigh 17.7g of trichlorosilane and add it dropwise to the allyl chloride solution over approximately one hour. Reflux at 60°C for three hours, then evaporate under reduced pressure. Collect the fraction at 70-90°C. The resulting product is γ-chloropropyltrichlorosilane, with a yield of 96%.

[0052] Example 10: The recovered catalyst II catalyzes the reaction of allyl chloride and trichlorosilane.

Claims

1. A heterogeneous bimetallic platinum catalyst, characterized in that: The structural formula of the heterogeneous heterogeneous bimetallic platinum catalyst is one of the following:

2. The method for preparing the heterogeneous bimetallic platinum catalyst according to claim 1 comprises the following steps: (a) 1,8-dinitroanthraquinone is dissolved in ethanol, sodium sulfide nonahydrate is added, and the mixture is refluxed at 90°C for 6-24 hours; after filtering and removing the solvent, the mixture is dissolved in isopropanol, sodium borohydride is added, the mixture is refluxed at 90°C for 6-24 hours, and the solvent is filtered and removed to obtain 1,8-diaminoanthracene; (b) 1-aminoanthracene is dissolved in ethanol, 6-methyl-2-pyridinecarboxaldehyde or 6-bromopyridine-2-carboxaldehyde and p-toluenesulfonic acid are added to start the reaction, and after the reaction, the mixture is filtered and recrystallized to obtain a ligand; (c) The ligand and anhydrous sodium acetate are dissolved in an organic solvent, potassium tetrachloroplatinate or potassium hexachloroplatinate is added to react, and after the reaction, the mixture is washed with water and methanol, and recrystallized to obtain a target complex; (d) The metal complex and high-ethylene-content polybutadiene are dissolved in an organic solvent and heated to react, and after the reaction, the temperature is lowered and the solvent is removed to obtain a target heterogeneous platinum catalyst.

3. The preparation method according to claim 2, characterized in that: The molar ratio of sodium sulfide nonahydrate to 1,8-dinitroanthraquinone in the step (a) is 2.0-3.0:1; the molar ratio of sodium borohydride to 1,8-dinitroanthraquinone in the step (a) is 5.0-15.0:

1.

4. The preparation method according to claim 2, characterized in that: In the step (b), the molar ratio of 6-methyl-2-pyridinecarboxaldehyde or 6-bromopyridine-2-carboxaldehyde to 1-aminoanthracene is 2.1-3:1; the molar ratio of p-toluenesulfonic acid to 1-aminoanthracene is 0.5-4:100; the reaction temperature of the step (b) is 0-40°C, and the reaction time is 6-24 hours.

5. The preparation method according to claim 2, characterized in that: The molar ratio of anhydrous sodium acetate to the ligand in the step (c) is 4.0-4.8:1; the molar ratio of potassium tetrachloroplatinate or potassium hexachloroplatinate to the ligand in the step (c) is 2.0-2.4:1; the reaction temperature in the step (c) is 80-140° C., and the reaction time is 2-12 hours.

6. The preparation method according to claim 2, characterized in that: The solvent used in the step (d) is selected from toluene, xylene, acetonitrile, DMF, chloroform, and tetrahydrofuran; the reaction temperature of the step (d) is 150-220° C., and the reaction time is 2-48 hours.

7. A method for synthesizing γ-chloropropyltrichlorosilane (γ1) using a heterogeneous bimetallic platinum catalyst, characterized in that: The method comprises the following steps: premixing allyl chloride and a catalyst, adding trichlorosilane dropwise to carry out a hydrosilylation reaction, filtering and recovering the catalyst after the reaction is finished, and then purifying the reaction product by distillation to obtain γ-chloropropyltrichlorosilane (γ1).

8. According to claim 7, it is characterized in that The ratio of allyl chloride to trichlorosilane is 1:1-1.5; the amount of the heterogeneous bimetallic platinum catalyst relative to allyl chloride is 100-10 ppm; the temperature of the hydrosilylation reaction is 50-80°C, and the reaction time is 1-6 hours; the temperature of the distillation purification is 70-90°C.

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