Amine type hydroformylation catalyst and preparation method thereof

Abstract

An amine type hydroformylation catalyst and a preparation method thereof, wherein the molecular formula is C 4n H 8(n‑1) N4O4Pd2; The preparation method comprises the following steps: Step 1: Weigh C n H 2n NO and Pd(O2CCH3)2; Step 2: weigh the C n H 2n NO and Pd(O2CCH3)2 are placed in a reactor, and a solvent is added, and the temperature is raised, stirred and refluxed to react; Step 3: After the reaction in Step 2 is completed, the reaction is cooled to room temperature and then filtered, and the filter cake is washed with deionized water; Step 4: After the filter cake is washed, it is filtered, and after the filtration is completed, dichloromethane is added, heated and stirred to dissolve the Pd(O2CCH3)2 in the filter cake for purification; Step 5: After the operation in Step 4 is completed, the reaction is cooled to room temperature and filtered, and the obtained solid is dried and crushed to obtain an amine-type hydroformylation catalyst. The present invention prepares C 4n H 8(n‑1) N4O4Pd2 can reduce the use of palladium metal while ensuring catalytic efficiency. At the same time, palladium metal is cheaper than platinum and rhodium, which can further reduce costs.

Description

Technical Field

[0001] The invention belongs to the field of hydroformylation catalysts, in particular to an amine type hydroformylation catalyst and a preparation method thereof. Background Art

[0002] Hydroformylation is an important chemical reaction, which mainly refers to the process of converting olefins, hydrogen and carbon monoxide into aldehyde compounds under the action of a catalyst. Hydroformylation can be regarded as adding a hydrogen and a formyl group to the C atoms at both ends of the double bond of the olefin, so it is also called hydroformylation reaction.

[0003] At present, the catalysts for the hydroformylation reaction include platinum catalysts, rhodium catalysts, palladium catalysts and cobalt catalysts. Since the metal prices involved in the above-mentioned catalysts are extremely high, how to reduce the usage of the above-mentioned metal catalysts in the current research on catalysts for the hydroformylation reaction is an urgent problem to be solved. Summary of the invention

[0004] The present invention provides an amine type hydroformylation catalyst and a preparation method thereof, which are used to solve the defects in the prior art.

[0005] The present invention is achieved through the following technical solutions:

[0006] An amine-type hydroformylation catalyst having the molecular formula C 4n H 8(n-1) N4O4Pd2.

[0007] In the above-mentioned amine-type hydroformylation catalyst, n is any integer between 4 and 6.

[0008] A method for preparing an amine-type hydroformylation catalyst comprises the following steps:

[0009] Step 1: Weigh C according to the ratio n H 2n NO and Pd(O2CCH3)2;

[0010] Step 2: Weigh the C n H 2n NO and Pd(O2CCH3)2 are placed in a reactor, and a solvent is added, and the temperature is raised, and the mixture is stirred and refluxed to react;

[0011] Step 3: After the reaction in step 2 is completed, cool to room temperature and filter, and wash the obtained filter cake with deionized water;

[0012] Step 4: After the filter cake is washed, filter it. After filtering, add dichloromethane, heat and stir to dissolve the Pd(O2CCH3)2 in the filter cake for purification;

[0013] Step 5: After the operation in step 4 is completed, the mixture is cooled to room temperature and filtered, and the obtained solid is dried and crushed to obtain an amine-type hydroformylation catalyst.

[0014] In the above-mentioned method for preparing an amine-type hydroformylation catalyst, C n H 2n The molar ratio of NO and Pd(O2CCH3)2 is 4-6:1.

[0015] In the above-mentioned method for preparing an amine-type hydroformylation catalyst, the solvent in step 2 is any one of chlorobenzene or toluene.

[0016] In the above-mentioned method for preparing an amine-type hydroformylation catalyst, the reaction temperature of the reactor in step 2 is 130-150° C., and the reaction is carried out for 4-6 hours after the temperature is raised in step 2.

[0017] In the method for preparing an amine-type hydroformylation catalyst as described above, the filter cake after filtration in step 3 is washed 3-4 times with deionized water.

[0018] In the method for preparing an amine-type hydroformylation catalyst as described above, after the filter cake is washed in step 4, it is added to dichloromethane, stirred, heated to 40-50° C., and kept warm and refluxed with stirring for 30-50 minutes.

[0019] In the method for preparing an amine-type hydroformylation catalyst as described above, the drying in step 5 is performed using a negative pressure dryer, the drying temperature is 70-80° C., the vacuum degree is -50 KPa, and the drying time is 30-40 min.

[0020] In the method for preparing an amine-type hydroformylation catalyst as described above, the powder in step 5 is sieved through a 200-mesh sieve for later use.

[0021] The advantages of the present invention are: the present invention prepares C 4n H 8(n-1) N4O4Pd2 can reduce the use of palladium metal while ensuring catalytic efficiency. At the same time, palladium metal is cheaper than platinum and rhodium, which can further reduce costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0023] Figure 1 is the reaction formula of Example 1 of the present invention;

[0024] Figure 2 is the reaction formula of Example 2 of the present invention;

[0025] Figure 3 It is the reaction formula of Example 3 of the present invention. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] An amine-type hydroformylation catalyst having the molecular formula C 4n H 8(n-1) N4O4Pd2.

[0028] Specifically, n described in this embodiment is any integer between 4 and 6.

[0029] A method for preparing an amine-type hydroformylation catalyst comprises the following steps:

[0030] Step 1: Weigh C according to the ratio n H 2n NO and Pd(O2CCH3)2;

[0031] Step 2: Weigh the C n H 2n NO and Pd(O2CCH3)2 are placed in a reactor, and a solvent is added, and the temperature is raised, and the mixture is stirred and refluxed to react;

[0032] Step 3: After the reaction in step 2 is completed, cool to room temperature and filter, and wash the obtained filter cake with deionized water;

[0033] Step 4: After the filter cake is washed, filter it. After filtering, add dichloromethane, heat and stir to dissolve the Pd(O2CCH3)2 in the filter cake for purification;

[0034] Step 5: After the operation in step 4 is completed, the mixture is cooled to room temperature and filtered, and the obtained solid is dried and crushed to obtain an amine-type hydroformylation catalyst.

[0035] Specifically, C in step 1 of this embodiment n H 2n The molar ratio of NO and Pd(O2CCH3)2 is 4-6:1.

[0036] More specifically, the solvent in step 2 described in this embodiment is any one of chlorobenzene or toluene.

[0037] More specifically, the reaction temperature of the reactor in step 2 of this embodiment is 130-150° C., and the reaction is carried out for 4-6 hours after the heating in step 2 is completed.

[0038] Furthermore, the filter cake after filtration in step 3 of this embodiment is washed 3-4 times with deionized water.

[0039] Furthermore, after the filter cake in step 4 of this embodiment is washed, it is added to dichloromethane, stirred and heated to 40-50°C, and refluxed and stirred for 30-50 minutes. Refluxing through a condenser increases the rate at which Pd(O2CCH3)2 dissolves in dichloromethane, thereby improving the purification efficiency.

[0040] Furthermore, the drying in step five of this embodiment is performed using a negative pressure dryer, the drying temperature is 70-80°C, the vacuum degree is -50KPa, and the drying time is 30-40min.

[0041] Furthermore, the powder in step 5 of this embodiment is sieved through a 200-mesh sieve for later use.

[0042] Example 1

[0043] like Figure 1 As shown:

[0044] Step 1: Weigh C4H8NO and Pd(O2CCH3)2 in a molar ratio of 4:1;

[0045] Step 2: put the weighed C4H8NO and Pd(O2CCH3)2 into a reactor, add chlorobenzene or toluene, heat to 150°C, stir and reflux to react, and react for 4 hours after heating;

[0046] Step 3: After the reaction in step 2 is completed, cool to room temperature and filter, and wash the obtained filter cake with deionized water three times;

[0047] Step 4: After the filter cake is washed, filter it. After filtering, add dichloromethane and heat it to 50°C, keep it warm and reflux and stir for 30 minutes;

[0048] Step 5: After the operation in step 4 is completed, the solid is cooled to room temperature and filtered. The solid is dried in a negative pressure dryer at a drying temperature of 70°C, a vacuum degree of -50 KPa, and a drying time of 40 min. After drying, the solid is crushed through a 200-mesh sieve to obtain an amine-type hydroformylation catalyst (C 16 H 24 N4O4Pd2).

[0049] Example 2

[0050] like Figure 2 As shown:

[0051] Step 1: Weigh C6H2O in a molar ratio of 6:1 12 NO and Pd(O2CCH3)2;

[0052] Step 2: Weigh the C6H 12 NO and Pd(O2CCH3)2 were placed in a reactor, chlorobenzene or toluene was added, the temperature was raised to 150°C, and the mixture was stirred under reflux for reaction. After the temperature was raised, the reaction lasted for 4 hours.

[0053] Step 3: After the reaction in step 2 is completed, cool to room temperature and filter, and wash the obtained filter cake with deionized water 4 times;

[0054] Step 4: After the filter cake is washed, filter it. After filtering, add dichloromethane and heat it to 50°C, keep it warm and reflux and stir for 30 minutes;

[0055] Step 5: After the operation in step 4 is completed, the solid is cooled to room temperature and filtered. The solid is dried in a negative pressure dryer at a drying temperature of 80°C, a vacuum degree of -50KPa, and a drying time of 30 minutes. After drying, the solid is crushed and passed through a 200-mesh sieve to obtain an amine-type hydroformylation catalyst (C 24 H 40 N4O4Pd2).

[0056] Example 3

[0057] like Figure 3 As shown:

[0058] Step 1: Weigh C4H8NO and Pd(O2CCH3)2 in a molar ratio of 5:1;

[0059] Step 2: put the weighed C4H8NO and Pd(O2CCH3)2 into a reactor, add chlorobenzene or toluene, heat to 140°C, stir and reflux to react, and react for 5 hours after heating;

[0060] Step 3: After the reaction in step 2 is completed, cool to room temperature and filter, and wash the obtained filter cake with deionized water 4 times;

[0061] Step 4: After the filter cake is washed, filter it. After filtering, add dichloromethane and heat it to 45°C, keep it warm and reflux and stir for 40 minutes;

[0062] Step 5: After the operation in step 4 is completed, the solid is cooled to room temperature and filtered. The solid is dried in a negative pressure dryer at a drying temperature of 75°C, a vacuum degree of -50 KPa, and a drying time of 35 min. After drying, the solid is crushed through a 200-mesh sieve to obtain an amine-type hydroformylation catalyst (C 20 H 32 N4O4Pd2).

[0063] Verification test

[0064] The conventional commercially available palladium metal catalyst (denoted as the control group) and the amine-type hydroformylation catalyst prepared in Examples 1-3 were used to carry out multiple hydroformylation reactions under the same conditions, and the reaction time and yield were recorded. The results are shown in Table 1.

[0065] Group Average reaction time (h) Average yield (%) Example 1 3.56 86.9 Example 2 3.61 87.2 Example 3 3.47 87.3 Control group 3.57 87.1

[0066] Table 1

[0067] As can be seen from the data in Table 1, the amine-type hydroformylation catalysts prepared in Examples 1-3 of the present invention can obtain similar yields as the palladium metal catalyst in the control group within a similar reaction time, so their catalytic efficiency is equivalent. However, the use cost of the amine-type hydroformylation catalyst prepared in the present invention is significantly lower than that of the palladium metal catalyst, and the use amount of the palladium element can be effectively reduced, thereby saving production costs and allowing the palladium element to be fully utilized.

[0068] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An amine-type hydroformylation catalyst, characterized in that: Its molecular formula C 4n H 8(n-1) N4O4Pd2.

2. An amine-type hydroformylation catalyst according to claim 1, characterized in that: The n is any integer between 4 and 6.

3. A method for preparing an amine-type hydroformylation catalyst, characterized in that: The steps include: Step 1: Weigh C according to the ratio n H 2n NO and Pd(O2CCH3)2; Step 2: Weigh the C n H 2n NO and Pd(O2CCH3)2 are placed in a reactor, and a solvent is added, and the temperature is raised, and the mixture is stirred and refluxed to react; Step 3: After the reaction in step 2 is completed, cool to room temperature and filter, and wash the obtained filter cake with deionized water; Step 4: After the filter cake is washed, filter it. After filtering, add dichloromethane, heat and stir to dissolve the Pd(O2CCH3)2 in the filter cake for purification; Step 5: After the operation in step 4 is completed, the mixture is cooled to room temperature and filtered, and the obtained solid is dried and crushed to obtain an amine-type hydroformylation catalyst.

4. The method for preparing an amine-type hydroformylation catalyst according to claim 3, characterized in that: C in step 1 n H 2n The molar ratio of NO and Pd(O2CCH3)2 is 4-6:

1.

5. The method for preparing an amine-type hydroformylation catalyst according to claim 3, characterized in that: The solvent in step 2 is any one of chlorobenzene or toluene.

6. The method for preparing an amine-type hydroformylation catalyst according to claim 3, characterized in that: The reaction temperature of the reactor in step 2 is 130-150° C., and the reaction is carried out for 4-6 hours after the heating in step 2 is completed.

7. The method for preparing an amine-type hydroformylation catalyst according to claim 3, characterized in that: The filter cake after filtering in the step 3 is washed 3-4 times with deionized water.

8. The method for preparing an amine-type hydroformylation catalyst according to claim 3, characterized in that: After the filter cake is washed in step 4, it is added into dichloromethane, stirred and heated to 40-50° C., and then kept under reflux and stirred for 30-50 minutes.

9. The method for preparing an amine-type hydroformylation catalyst according to claim 3, characterized in that: The drying in step 5 is carried out in a negative pressure dryer, the drying temperature is 70-80°C, the vacuum degree is -50KPa, and the drying time is 30-40min.

10. The method for preparing an amine-type hydroformylation catalyst according to claim 3, characterized in that: After the pulverization in step 5, the product is sieved through a 200-mesh sieve for later use.

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