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

Abstract

The present invention discloses a heterogeneous bimetallic platinum catalyst and its application in the synthesis of γ-chloropropyltrichlorosilane (γ1). The present invention introduces an anthracene skeleton, synthesizes a novel bimetallic platinum metal catalyst by coordination with platinum, and uses Diels-Alder (DA) reaction to load the bimetallic platinum metal catalyst into high vinyl polybutadiene to prepare a heterogeneous bimetallic platinum catalyst. The novel heterogeneous bimetallic platinum catalyst has a synergistic catalytic effect, and realizes the efficient and highly selective hydrogen silicon addition reaction of non-chloropropylene and trichlorosilane. The heterogeneous bimetallic catalyst reported in the present invention has the characteristics of high catalytic efficiency, high selectivity and recyclable reuse, and the purity of the obtained γ1 reaches 99.5%, and the product yield is as high as 97%.

Description

Technical Field

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

[0002] Silane coupling agent is an indispensable functional additive in the rubber industry and the soul material of rubber materials. Among them, γ-chloropropyltrichlorosilane (γ1) is the most important intermediate in the synthesis of high-performance silane coupling agent. In industry, allyl chloride and trichlorosilane are usually used as raw materials, and it is prepared by hydrosilylation reaction under the action of platinum catalyst. During the reaction process, the selectivity of the hydrosilylation reaction directly determines the quality of the product, and the activity of the reaction determines the cost of the production process. Therefore, the research and development of metal catalysts for hydrosilylation reaction is the core technology of the production process of γ1 and high-performance silane coupling agents. The development of new high-efficiency, highly selective, and renewable heterogeneous metal catalysts can reduce the activation energy of hydrosilylation, promote the reaction and improve the selectivity of the product, thereby reducing production costs and energy consumption, improving product purity and quality, and is conducive to promoting industrial technology upgrades.

[0003] In view of this, the present invention reports a heterogeneous bimetallic platinum catalyst and applies it to the synthesis process of γ-chloropropyltrichlorosilane (γ1). The present invention introduces an anthracene skeleton ligand, and synthesizes several types of novel bimetallic platinum catalysts by coordinating with platinum. The platinum catalyst is loaded into high vinyl polybutadiene by Diels-Alder (DA) reaction to obtain a heterogeneous bimetallic platinum catalyst. The heterogeneous catalyst reported in the present invention has the characteristics of high catalytic efficiency, high selectivity, and recyclable reuse. The obtained γ1 is colorless and transparent, the product purity reaches 99.5%, and the yield is 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. Summary of the invention

[0005] The purpose of the present invention is to provide a heterogeneous bimetallic platinum catalyst and its application in the synthesis of γ-chloropropyltrichlorosilane (γ1).

[0006] The present invention provides a bimetallic platinum metal complex as shown in Formula I-IV:

[0007]

[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 start the reaction. After the reaction is completed, the ligand is obtained by filtering and recrystallization;

[0011] (c) dissolving the ligand and anhydrous sodium acetate in an organic solvent, adding potassium tetrachloroplatinate or potassium hexachloroplatinate to react, 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 reduced 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; 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; 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; the reaction time is 2-48 hours, preferably 12 hours.

[0023] The present invention adopts the method for catalyzing the synthesis of γ-chloropropyltrichlorosilane by the heterogeneous catalyst, and 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 is completed, and then purifying the reaction product by distillation to obtain γ-chloropropyltrichlorosilane.

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

[0025] In the above catalytic reaction, the amount of the catalyst relative to 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 application in catalyzing the addition reaction of allyl chloride and trichlorosilane. The heterogeneous bimetallic platinum catalyst reported in the present invention has the characteristics of high selectivity, high catalytic efficiency and recyclable reuse, and the obtained γ-chloropropyltrichlorosilane (γ1) has a high yield (up to 97%) and a high purity (99.5%). BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the synthetic route of catalyst I.

[0030] Figure 2 This 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 understand the present invention more comprehensively.

[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 ligands.

[0035] Weigh 12g / 40mmol of 1,8-dinitroanthraquinone and add 100mL of ethanol; weigh 38.4g / 0.178mol of sodium sulfide nonahydrate and dissolve it in 120mL of deionized water, then add it to the ethanol solution of 1,8-dinitroanthraquinone and reflux at 90℃ for 12 hours. After the reaction is completed, filter and remove the solvent at 0 degrees, dissolve the residue in 200mL of isopropanol, add 18g / 0.476mol of sodium borohydride, and reflux at 90℃ for 12 hours. After the reaction is completed, filter and remove the solvent at 0 degrees, and 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, and 1.9 g of ligand is obtained after filtration, with a yield of 92%.

[0036] Example 2, Synthesis of Catalyst I.

[0037] Weigh 2.07g / 5mmol of ligand and 1.6mg / 20mmol of anhydrous sodium acetate, add 30mL of toluene, heat to 110°C, add 9.8g / 10mmol of potassium tetrachloroplatinate and react for 6 hours. Then add 10mL of distilled water and filter, wash the filter residue with 20mL of water 3 times and 20mL of methanol once. The residue is recrystallized in toluene to obtain 3.7g of platinum complex with a yield of 78%. Weigh 1.4g of platinum complex and 10g of high vinyl polybutadiene, add 20mL of toluene, heat to 180°C and react for 12 hours. After the reaction is completed, filter at room temperature and vacuum dry to obtain catalyst I. The mass percentage of Pt measured by ICP is 5.0%.

[0038] Example 3. Synthesis of Catalyst II.

[0039] Weigh 2.07g / 5mmol of ligand and 1.6mg / 20mmol of anhydrous sodium acetate, add 30mL of toluene, heat to 110℃, add 9.8g / 10mmol of potassium chloroplatinate and react for 6 hours. Then add 10mL of distilled water and filter, wash the filter residue with 20mL of water 3 times and 20mL of methanol once. The residue is recrystallized in toluene to obtain 4.8g of platinum complex with a yield of 79%. Weigh 1.9g of platinum complex and 10g of high vinyl polybutadiene, add 20mL of toluene, heat to 180℃ and react for 12 hours. After the reaction, filter at room temperature and vacuum dry to obtain catalyst II. The mass percentage of Pt measured by ICP is 4.9%.

[0040] Example 4. Synthesis of Catalyst III.

[0041] Weigh 2.72g / 5mmol of ligand and 1.6mg / 20mmol of anhydrous sodium acetate, add 30mL of toluene, heat to 110°C, add 9.8g / 10mmol of potassium tetrachloroplatinate and react for 6 hours. Then add 10mL of distilled water and filter, wash the filter residue with 20mL of water 3 times and 20mL of methanol once. The residue is recrystallized in toluene to obtain 3.9g of platinum complex with a yield of 83%. Weigh 1.7g of platinum complex and 10g of high vinyl polybutadiene, add 20mL of toluene, heat to 180°C and react for 12 hours. After the reaction, filter at room temperature and vacuum dry to obtain catalyst I. The mass percentage of Pt measured by ICP is 5.1%.

[0042] Example 5. Synthesis of Catalyst IV.

[0043] Weigh 2.72g / 5mmol of ligand and 1.6mg / 20mmol of anhydrous sodium acetate, add 30mL of toluene, heat to 110℃, add 9.8g / 10mmol of potassium chloroplatinate and react for 6 hours. Then add 10mL of distilled water and filter, wash the filter residue with 20mL of water 3 times and 20mL of methanol once. The residue is recrystallized in toluene to obtain 4.7g of platinum complex with a yield of 77%. Weigh 1.9g of platinum complex and 10g of high vinyl polybutadiene, add 20mL of toluene, heat to 180℃ and react for 12 hours. After the reaction, filter at room temperature and vacuum dry to obtain catalyst IV. The mass percentage of Pt measured by ICP is 5.1%.

[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℃ for activation for 30 minutes; weigh 17.7g of trichlorosilane, add dropwise to the allyl chloride solution for about 1 hour. After reflux reaction at 60℃ for 3 hours, perform vacuum distillation and collect the fraction at 70-90℃. The obtained product is γ-chloropropyltrichlorosilane, and the reaction yield is 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℃ for activation for 30 minutes; weigh 17.7g of trichlorosilane, add dropwise to the allyl chloride solution for about 1 hour. After reflux reaction at 60℃ for 3 hours, perform vacuum distillation and collect the fraction at 70-90℃. The obtained product is γ-chloropropyltrichlorosilane, and the reaction yield is 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℃ for activation for 30 minutes; weigh 17.7g of trichlorosilane, add dropwise to the allyl chloride solution for about 1 hour. After reflux reaction at 60℃ for 3 hours, perform vacuum distillation and collect the fraction at 70-90℃. The obtained product is γ-chloropropyltrichlorosilane, and the reaction yield is 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℃ for activation for 30 minutes; weigh 17.7g of trichlorosilane, add dropwise to the allyl chloride solution for about 1 hour. After reflux reaction at 60℃ for 3 hours, perform vacuum distillation and collect the fraction at 70-90℃. The obtained product is γ-chloropropyltrichlorosilane, and the reaction yield is 96%.

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

[0053] Cycle times Reaction temperature Reaction time Yield 1 60℃ 3 hours 97％ 2 60℃ 3 hours 97％ 3 60℃ 3 hours 96％ 4 60℃ 3 hours 95％ 5 60℃ 3 hours 95％

Claims

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

2. A method for preparing the heterogeneous bimetallic platinum catalyst according to claim 1, comprising 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) 1,8-diaminoanthracene 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 metal complex; (d) The target 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 bimetallic 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 1,8-diaminoanthracene is 2.1-3:1; the molar ratio of p-toluenesulfonic acid to 1,8-diaminoanthracene 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 any one of 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 following steps are involved: Allyl chloride and the heterogeneous bimetallic platinum catalyst according to claim 1 are premixed, trichlorosilane is added dropwise to carry out a hydrosilylation reaction, and after the reaction is completed, the catalyst is filtered and recovered, and then the reaction product is purified by distillation to obtain γ-chloropropyltrichlorosilane (γ1).

8. The method for synthesizing γ-chloropropyltrichlorosilane (γ1) according to claim 7, 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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