CN116925140A - Bidentate phosphine ligand heterogeneous catalyst, preparation method thereof and application thereof in nylon monomer preparation process - Google Patents

Bidentate phosphine ligand heterogeneous catalyst, preparation method thereof and application thereof in nylon monomer preparation process Download PDF

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Publication number
CN116925140A
CN116925140A CN202310597049.9A CN202310597049A CN116925140A CN 116925140 A CN116925140 A CN 116925140A CN 202310597049 A CN202310597049 A CN 202310597049A CN 116925140 A CN116925140 A CN 116925140A
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bidentate phosphine
reaction
modified resin
butadiene
phosphine ligand
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王根林
丁克鸿
徐林
孙延俊
王铖
汪洋
楚肖莉
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Jiangsu Yangnong Chemical Group Co Ltd
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Jiangsu Yangnong Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The application provides a bidentate phosphine ligand heterogeneous catalyst, a preparation method thereof and application thereof in a nylon monomer preparation process. The preparation method comprises the following steps: s1, mixing bidentate phosphine modified resin, a metal salt precursor and an alcohol solution, and performing a first-stage reaction to obtain an intermediate product; wherein the bidentate phosphine modified resin is modified resin with part of side chain benzene rings modified by bidentate phosphine groups in the polystyrene resin; s2, mixing the intermediate product with an acid auxiliary agent, and carrying out a second-stage reaction to obtain the bidentate phosphine ligand catalyst. The bidentate phosphine ligand catalyst prepared by the application is applied to the butadiene carbonylation process, and can be used for achieving good chemical stability and product selectivity and is easy to separate and recycle.

Description

Bidentate phosphine ligand heterogeneous catalyst, preparation method thereof and application thereof in nylon monomer preparation process
Technical Field
The application relates to the technical field of material science, in particular to a bidentate phosphine ligand heterogeneous catalyst, a preparation method thereof and application thereof in a nylon monomer preparation process.
Background
Polyamide is commonly called nylon, and is a thermoplastic resin containing amide (-CONH-) in the repeat structural unit of the molecular main chain, and comprises aliphatic polyamide, aliphatic-aromatic polyamide and aromatic polyamide. The aliphatic polyamide has a plurality of varieties, high yield and wide application, and can be used as fiber or plastic.
Polyamide 66 (nylon 66) was first synthesized in the laboratory in 1935 by the us scientist carsephson and was industrialized in 1939 as a representative product of aliphatic polyamides. The nylon 66 has the advantages of high strength, good rigidity, impact resistance, oil resistance, chemicals resistance, wear resistance, self lubrication and the like, and particularly has excellent hardness, rigidity, heat resistance and creep property, and the nylon 66 has the advantages of easily obtained raw materials and low cost, so that the nylon 66 is widely applied to the fields of industry, clothing, decoration, engineering plastics and the like.
The two polymeric monomers of nylon 66 are hexamethylenediamine and adipic acid. Currently, the main industrial route for the production of adipic acid is the oxidation of a mixture of cyclohexanol and cyclohexanone, which requires the use of an excess of nitric acid during the production process. Because of the corrosiveness of acids, this process requires special equipment and generates large amounts of nitrogen oxides, a major source of stratospheric ozone, with an atmospheric heat absorption capacity approximately 300 times that of carbon dioxide. The method has the defects of large investment, large pollution, long flow and the like.
And the other monomer hexamethylenediamine is mostly prepared by adopting an adiponitrile hydrogenation method, and the adiponitrile synthesis process is mainly a butadiene cyanidation method. In the technology of butadiene cyanidation, patent CN103180290A, CN103012197a and CN103694136a respectively disclose three methods for preparing adiponitrile by butadiene through a three-step method, a two-step method and a one-step method, and although different synthetic methods are used in the processes, the processes essentially use extremely toxic hydrocyanic acid as a raw material, so that a certain risk exists in large-scale production. In the reported patents, the single pass conversion rate of butadiene cyanidation method is about 50-60%, the selectivity is about 70-80%, and the conversion rate and the selectivity are not ideal. The reaction equation of the butadiene cyanidation process route is as follows:
another synthesis process of adiponitrile is to prepare hexamethylenediamine by using butadiene as raw material and synthesizing dimethyl adipate under high pressure in the presence of carbon monoxide and alcohol system and then by amination and dehydration. The research of the process has been carried out for decades, and the biggest difficulty of the process is that during the first-step carbonylation reaction, the substrate butadiene is accompanied with rearrangement of double bond positions during the reaction, so that the reaction product is accompanied with generation of branched-chain C4 and C5 diamine byproducts besides linear-chain C6 diamine, and a carbonylation catalyst with high selectivity is not found all the time in the exploration process.
Patent US4575562 describes a process for preparing dimethyl adipate by carbonylation of butadiene, which adopts trialkyl phosphine or triaryl phosphine as ligand and metals such as Pd as active site to prepare monodentate phosphine coordinated metal-phosphine complex, but the monodentate phosphine ligand catalyst has the defect of insufficient reaction selectivity, and the butadiene conversion rate is only 50% and the selectivity is only 70%. The lack of selectivity results in the process being too high in birthday cost and not competitive.
At the end of 2019, the process has obtained a great breakthrough, and a group of Beller subjects reports a pyridine-substituted bidentate phosphine ligand (HeMaRaphos) in Science (2019,366,1514) to regulate and control a one-step synthesis of adipic acid diester products by palladium-catalyzed dihydro esterification of 1, 3-butadiene. The selectivity of the target product is up to 97%, the yield is up to 95%, and the high-efficiency synthesis of 200 g-scale products can be realized. Meanwhile, the catalyst system has good substrate universality and also has good universality for other series of 1, 2-diene and 1, 3-diene synthesized diester compounds. The work provides a low-cost, high-economic benefit and environment-friendly method for directly dicarbonyl synthesizing the adipic acid derivative which is industrially important for the 1, 3-butadiene. In 2021, the subject group also discloses a development work (Angew.chem.int.ed.2021, 60,2) on Angew, and on the basis of the previous work, a simple and easily available bidentate phosphine ligand (1, 2-bis-di-tert-butylphosphinoxylene (dtbpx)) is selected to regulate and control palladium catalysis of 1, 3-diene (or 1, 2-diene) compounds to generate a dihydro esterification reaction, so that adipic acid diester high-added-value chemicals are efficiently synthesized by a one-step method. The catalyst system also has good substrate universality, and different alcohol compounds can be used as solvents to obtain target products with high selectivity. Although the two reports screen bidentate phosphine ligands with high yield and high selectivity and open a process route for preparing adipic diester by one-step carbonylation of butadiene, the homogeneous catalyst has the defects of sensitivity to water and oxygen and difficult preparation, and the homogeneous catalyst always has the problems of difficult separation and low recovery rate, so that industrialization is difficult to realize.
The reaction equation of the butadiene carbonylation process route is as follows:
in view of this, there is a need for a heterogeneous phosphine ligand catalyst with high yields and high selectivity for carbonylation reactions.
Disclosure of Invention
The application mainly aims to provide a bidentate phosphine ligand heterogeneous catalyst, a preparation method thereof and application thereof in a nylon monomer preparation process, so as to solve the problem that a butadiene carbonylation process in the prior art lacks a catalyst which can be used for achieving good chemical stability and product selectivity and is easy to separate and recycle.
In order to achieve the above object, according to one aspect of the present application, there is provided a method for preparing a bidentate phosphine ligand heterogeneous catalyst, comprising the steps of: s1, mixing bidentate phosphine modified resin, a metal salt precursor and an alcohol solution, and performing a first-stage reaction to obtain an intermediate product; wherein the bidentate phosphine modified resin is modified resin with part of side chain benzene rings modified by bidentate phosphine groups in the polystyrene resin; s2, mixing the intermediate product with an acid auxiliary agent, and carrying out a second-stage reaction to obtain the bidentate phosphine ligand heterogeneous catalyst.
Further, the structure of the bidentate phosphine modified resin is as follows:
wherein L is 1 And L 2 Alkylene groups each independently being C1 to C8, preferably C1 to C4; r is R 1 、R 2 、R 3 And R is 4 Each independently is H, pyridinyl or C1-C4 linear or branched alkyl; m is 3 to 10, preferably 3 to 5; n is 1.
Further, the bidentate phosphine modified resin is prepared by the following method: a1, providing a bidentate phosphine ligand containing benzene rings, and carrying out alkylation reaction with ethylene to obtain a bidentate phosphine modified ligand containing vinyl; a2, polymerizing the bidentate phosphine modified ligand containing vinyl and styrene to obtain the bidentate phosphine modified resin.
Further, the metal salt precursor comprises one or more of trifluoroacetate, acetate, chloride, nitrate, sulfate of a group VIII metal; preferably, the group VIII metal comprises one or more of Co, pd, pt, ni and Rh.
Further, the molar ratio of phosphorus atoms in the bidentate phosphine modified resin to metal atoms in the metal salt precursor is (1-20): 1, preferably (1 to 5): 1, a step of; the mole ratio of the acid auxiliary agent to the metal atoms in the metal salt precursor is (2-20): 1, preferably (6 to 12): 1.
further, the alcohol solution is an aqueous solution of fatty alcohol of C1-C6; preferably, the alcohol solution is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, more preferably one or more of methanol, ethanol, n-propanol and n-butanol; preferably, the concentration of the alcohol solution is 30 to 99%, more preferably, the molar ratio of the alcohol in the alcohol solution to the phosphorus atom in the bidentate phosphine-modified resin is (5 to 150): 1, a step of; more preferably, the molar ratio of the alcohol in the alcohol solution to the phosphorus atom in the bidentate phosphine modified resin is (50 to 80): 1.
further, the acid adjuvant includes one or more of benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, fluorosulfonic acid and trifluoromethanesulfonic acid.
Further, the temperature of the first stage reaction is 10-40 ℃ and the reaction time is 2-5 h; the reaction temperature of the second stage is 10-40 ℃ and the reaction time is 0.5-2 h.
In order to achieve the above object, according to one aspect of the present application, there is provided a bidentate phosphine ligand heterogeneous catalyst prepared according to the above-mentioned preparation method.
Further, it has the following structure:
wherein L is 1 And L 2 Alkylene groups each independently being C1 to C8, preferably C1 to C4; r is R 1 、R 2 、R 3 And R is 4 Each independently is H, pyridinyl or C1-C4 linear or branched alkyl; m is 3 to 10, preferably 3 to 5; n is 1.
According to another aspect of the present application there is provided a process for the carbonylation of butadiene by the carbonylation of butadiene with a bidentate phosphine ligand heterogeneous catalyst as described above.
Further, the method comprises the steps of: mixing a bidentate phosphine ligand heterogeneous catalyst with an activator, and then introducing butadiene and CO into the mixture to carry out carbonylation reaction; preferably, the activator is one or more of aprotic solvents, aromatic compounds, C5-C8 alkanes and nitriles; more preferably, the activator is one or more of diethyl ether, dimethyl ether, glycol ether, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, n-pentane, n-hexane, n-heptane and acetonitrile.
Further, the molar ratio of the bidentate phosphine ligand heterogeneous catalyst to butadiene is 1 (10-300).
Further, the activator accounts for 50-90%, preferably 70-85% of the total volume of the liquid phase in the carbonylation reaction.
Further, the temperature of the carbonylation reaction is 60 to 200 ℃, preferably 60 to 150 ℃, more preferably 80 to 120 ℃; the pressure of the carbonylation reaction is 0.5-8 MPa, preferably 2-5 MPa; the time of the carbonylation reaction is 5-30 h.
Further, the carbonylation reaction is carried out under an inert atmosphere, preferably N 2 、CO 2 And one or more of Ar, more preferably N 2 And/or Ar.
By applying the technical scheme of the application, the heterogeneous modified metal-resin catalyst is prepared. Compared with a homogeneous catalyst system, the heterogeneous catalyst prepared by the method is easy to recycle and high in stability, and avoids the phenomena of easy deactivation and loss of the homogeneous catalyst in the separation process. Meanwhile, the heterogeneous system phosphine ligand utilized by the application can not only keep the good selectivity of the traditional homogeneous system phosphine ligand system, but also improve the activity of the reaction, and is more suitable for the butadiene carbonylation process. In addition, the carrier adopted by the application is modified resin, and has strong chemical bond action with active metal atoms, so that compared with the common inorganic carrier, the catalyst disclosed by the application is less prone to loss of active components, and has no defect of weakening of the activity of the catalyst due to molding. In particular, when the catalyst of the application is applied to the butadiene carbonylation process, the product can be directly obtained by one-step reaction, the atomic utilization rate is high, the whole process and the post-treatment process are simple and energy-saving, and the industrialization is easy to realize.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
In order to solve the above-mentioned problems in the prior art, according to an aspect of the present application, there is provided a method for preparing a bidentate phosphine ligand heterogeneous catalyst, comprising the steps of: s1, mixing bidentate phosphine modified resin, a metal salt precursor and an alcohol solution, and performing a first-stage reaction to obtain an intermediate product; wherein the bidentate phosphine modified resin is modified resin with part of side chain benzene rings modified by bidentate phosphine groups in the polystyrene resin; s2, mixing the intermediate product with an acid auxiliary agent, and carrying out a second-stage reaction to obtain the bidentate phosphine ligand heterogeneous catalyst.
Compared with a homogeneous catalyst system, the heterogeneous catalyst prepared by the method is easy to recycle and high in stability, and avoids the phenomena of easy deactivation and loss of the homogeneous catalyst in the separation process. Meanwhile, the heterogeneous system phosphine ligand utilized by the application can not only keep the good selectivity of the traditional homogeneous system phosphine ligand system, but also improve the activity of the reaction, and is more suitable for the butadiene carbonylation process. In addition, the carrier adopted by the application is modified resin, and has strong chemical bond action with active metal atoms, so that compared with the common inorganic carrier, the catalyst disclosed by the application is less prone to loss of active components, and has no defect of weakening of the activity of the catalyst due to molding. In particular, when the catalyst of the application is applied to the butadiene carbonylation process, the product can be directly obtained by one-step reaction, the atomic utilization rate is high, the whole process and the post-treatment process are simple and energy-saving, and the industrialization is easy to realize.
Specifically, in the first stage reaction, a P-M-P coordination intermediate is obtained. And then, the intermediate product reacts with an acid auxiliary agent to obtain the M-H complex with carbonylation activity.
In a preferred embodiment, the bidentate phosphine modified resin has the following structure:
wherein L is 1 And L 2 Each independently is C 1 ～C 8 Alkylene of (C1-C4) is preferred; r is R 1 、R 2 、R 3 And R is 4 Each independently is H, pyridinyl or C1-C4 linear or branched alkyl; m is 3 to 10, preferably 3 to 5; n is 1.
The inventor prefers the bidentate phosphine modified resin, and the bidentate phosphine group adopts the structure, so that the characteristic that the catalyst and the active group form a strong bond can be better exerted, and the bidentate phosphine modified resin has higher activity on the basis of ensuring higher selectivity, and is more suitable for the carbonylation reaction of long-chain olefin. Meanwhile, the structure can better ensure that the active site of the catalyst is not easy to run off.
Specifically, for example, the P atom and the metal atom in the bidentate phosphine modified resin can form a stable coordination chemical bond, so that the bidentate phosphine ligand heterogeneous catalyst has better chemical stability. The foregoing is by way of example only and should not be construed as limiting the scope of the application.
In a preferred embodiment, the bidentate phosphine modified resin is prepared by the following method: a1, providing a bidentate phosphine ligand containing benzene rings, and carrying out alkylation reaction with ethylene to obtain a bidentate phosphine modified ligand containing vinyl; a2, polymerizing the vinyl-containing bidentate phosphine modified ligand and styrene to obtain the bidentate phosphine modified resin. The bidentate phosphine modified resin prepared by the method has simple and convenient process, and the structure of the bidentate phosphine modified resin is easy to design, so that the bidentate phosphine modified resin is more favorable for being used as a carrier of the bidentate phosphine ligand heterogeneous catalyst.
After the bidentate phosphine modified resin is prepared, it can be characterized by an operator to determine the phosphorus content therein. Or, an operator can calculate and obtain the phosphorus content in the bidentate phosphine modified resin according to the input amount of the reactants.
To better prepare a bidentate phosphine ligand heterogeneous catalyst with good catalytic performance for butadiene carbonylation reactions, in a preferred embodiment, the metal salt precursor comprises one or more of trifluoroacetate, acetate, chloride, nitrate, sulfate of a group VIII metal; preferably, the group VIII metal comprises one or more of Co, pd, pt, ni and Rh.
The metal salt precursor is easy to coordinate with P atoms, and is more favorable for forming a stable metal-bidentate phosphine complex, so that the prepared catalyst has more excellent carbonylation activity.
In a preferred embodiment, the molar ratio of phosphorus atoms in the bidentate phosphine modified resin to metal atoms in the metal salt precursor is (1 to 20): 1, preferably (1 to 5): 1, a step of; the mole ratio of the acid auxiliary agent to the metal atoms in the metal salt precursor is (2-20): 1, preferably (6 to 12): 1. the proportion of the phosphorus and the metal element is more beneficial to preparing the bidentate phosphine ligand heterogeneous catalyst with good catalytic activity. If the ratio is higher than the above ratio, the loss of noble metal is caused; if the ratio is less than the above ratio, the catalyst activity is insufficient. The addition amount of the acid auxiliary agent is more favorable for maintaining the activity of the catalyst, and if the addition amount is higher than the addition amount, the stability of the catalyst is reduced; if the amount is less than the above amount, the catalyst activity is insufficient.
In order to make the alcohol solution more suitable for the environment of the catalyst for catalyzing the carbonylation reaction of butadiene according to the application on the basis of ensuring good catalytic performance, in a preferred embodiment, the alcohol solution is an aqueous solution of a C1-C6 fatty alcohol; preferably, the alcohol solution is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, more preferably one or more of methanol, ethanol, n-propanol and n-butanol; preferably, the weight concentration of the alcohol solution is 30 to 99%, more preferably, the molar ratio of the alcohol in the alcohol solution to the phosphorus atom in the bidentate phosphine-modified resin is (5 to 150): 1, a step of; more preferably, the molar ratio of the alcohol in the alcohol solution to the phosphorus atom in the bidentate phosphine modified resin is (50 to 80): 1. the alcohol solution can well realize the configuration of the catalyst and has good applicability to the carbonylation reaction of the subsequent application.
In a preferred embodiment, the acid adjuvant comprises one or more of benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, fluorosulfonic acid and trifluoromethanesulfonic acid. The acid auxiliary agent has weak coordination capability with metal, and is more suitable for synthesis. In practical applications, the selection of the acid promoter includes, but is not limited to, the above-mentioned range, and a person skilled in the art can select an appropriate acid promoter according to the coordination ability with the metal.
For better preparation of bidentate phosphine ligand heterogeneous catalysts, in a preferred embodiment, the temperature of the first stage reaction is 10-40 ℃ and the reaction time is 2-5 hours; the reaction temperature of the second stage is 10-40 ℃ and the reaction time is 0.5-2 h.
The catalyst has simple and convenient preparation process and is easy to industrialize.
According to another aspect of the present application, there is provided a bidentate phosphine ligand heterogeneous catalyst prepared according to the preparation method described above.
In a preferred embodiment, the bidentate phosphine ligand heterogeneous catalyst has the following structure:
wherein L is 1 And L 2 Alkylene groups each independently being C1 to C8, preferably C1 to C4; r is R 1 、R 2 、R 3 And R is 4 Each independently is H, pyridinyl or C1-C4 linear or branched alkyl; m is 3 to 10, preferably 3 to 5; n is 1.
Compared with a homogeneous catalyst system, the heterogeneous catalyst prepared by the method is easy to recycle and high in stability, and avoids the phenomena of easy deactivation and loss of the homogeneous catalyst in the separation process. Meanwhile, the heterogeneous system phosphine ligand utilized by the application can not only keep the good selectivity of the traditional homogeneous system phosphine ligand system, but also improve the activity of the reaction, and is more suitable for the butadiene carbonylation process. In addition, the carrier adopted by the application is modified resin, and has strong chemical bond action with metal atoms, so that compared with common inorganic carriers, the catalyst disclosed by the application is less prone to loss of active components, and has no defect of weakening of catalyst activity caused by molding. In particular, when the catalyst of the application is applied to the butadiene carbonylation process, the product can be directly obtained by one-step reaction, the atomic utilization rate is high, the whole process and the post-treatment process are simple and energy-saving, and the industrialization is easy to realize.
According to a further aspect of the present application there is provided a process for the carbonylation of butadiene by the carbonylation of butadiene catalysed by a bidentate phosphine ligand heterogeneous catalyst as described above.
The catalyst of the application is used for catalyzing the carbonylation reaction of butadiene, has good selectivity, effectively improves the activity of the reaction, directly obtains the product by one-step reaction, has high atomic utilization rate, and has simple and energy-saving whole process and post-treatment process, and is easy to realize industrialization.
In actual operation, the catalyst after the carbonylation of butadiene can be recovered by filtration, light components (alcohols, acids, etc.) in the filtrate can be recovered by distillation for recycling, and adipic acid diester is a heavy component.
In a preferred embodiment, the above method comprises: mixing a bidentate phosphine ligand heterogeneous catalyst with an activator, and then introducing butadiene and CO for carbonylation; preferably, the activator is one or more of aprotic solvents, aromatic compounds, C5-C8 alkanes and nitriles; more preferably, the activator is one or more of diethyl ether, dimethyl ether, glycol ether, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, n-pentane, n-hexane, n-heptane and acetonitrile. The above-mentioned activator acts to activate the catalyst during the carbonylation reaction, and preferably the above-mentioned activator is capable of exerting catalytic activity better.
In a preferred embodiment, the molar ratio of bidentate phosphine ligand heterogeneous catalyst to butadiene is 1 (10 to 300). The ratio of the catalyst to butadiene is preferred to further facilitate the reaction. In actual operation, the molar ratio of bidentate phosphine ligand heterogeneous catalyst to butadiene may be 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190, 1:200, 1:210, 1:220, 1:230, 1:240, 1:250, 1:260, 1:270, 1:280, 1:290, 1:300, or any point value between any two molar ratios thereof.
In a preferred embodiment, the activator comprises from 50 to 90%, preferably from 70 to 85% of the total volume of the liquid phase in the butadiene carbonylation reaction. The above-mentioned amount of the activator is preferable, and the activator can be more effective in activating the catalyst. If the ratio is higher than the above, the product concentration is too low, the separation energy consumption is increased, and if the ratio is lower than the above, the catalyst activity is not sufficiently excited.
In a preferred embodiment, the temperature of the butadiene carbonylation reaction is in the range 60 to 200 ℃, preferably 60 to 150 ℃, more preferably 80 to 120 ℃; the pressure of the butadiene carbonylation reaction is 0.5-8 MPa, preferably 2-5 MPa; the time of the carbonylation reaction of butadiene is 5-30 h.
In actual operation, the operator can maintain the pressure of the reaction system within the above range by introducing CO.
In a preferred embodiment, the butadiene carbonylation reaction is carried out under an inert atmosphere, preferably N 2 、CO 2 And one or more of Ar, more preferably N 2 And/or Ar.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
R in the present embodiment 1 ，R 2 ，R 3 ，R 4 The group is tert-butyl. L (L) 1 And L 2 Is methylene, n is 3-5.
The specific experimental steps are as follows:
1. to a mechanically stirred autoclave having a volume of 1L was added: 160mL of methanol, 0.02mol of palladium acetate and 0.06mol (calculated by P mol) of modified resin are mixed and stirred; secondly, adding 0.1mol of methanesulfonic acid, mixing and stirring; next, 240mL of toluene is added;
2. after the system is replaced by nitrogen for three times and CO for three times, 1mol of butadiene is introduced into a reaction kettle, and the temperature is raised to 120 ℃;
3. supplementing CO to the pressure of 4MPa, and reacting for 16h, wherein CO is continuously supplemented in the reaction process to maintain the pressure at 4MPa;
the catalyst is separated and recovered after the reaction product is filtered, and the product is analyzed by gas chromatography to calculate the butadiene conversion and the adipic acid diester selectivity.
Example 2
R in the present embodiment 1 ，R 3 ，R 4 The radical being tert-butyl, R 2 Is a pyridyl group. L (L) 1 And L 2 Ethylene, n is 4-6.
The specific experimental steps are as follows:
1. to a mechanically stirred autoclave having a volume of 1L was added: 120mL of methanol, 0.02mol of palladium trifluoroacetate and 0.04mol (calculated by mol P) of modified resin are mixed and stirred; secondly, adding 0.08mol of p-toluenesulfonic acid, mixing and stirring; secondly, 240mL of n-hexane is added;
2. after the system is replaced by nitrogen for three times and CO for three times, 1mol of butadiene is introduced into a reaction kettle, and the temperature is raised to 120 ℃;
3. supplementing CO to the pressure of 5MPa, and reacting for 12h, wherein CO is continuously supplemented in the reaction process to maintain the pressure at 5MPa;
4. the catalyst is separated and recovered after the reaction product is filtered, and the product is analyzed by gas chromatography to calculate the butadiene conversion and the adipic acid diester selectivity.
Example 3
R in the present embodiment 1 ，R 3 The radical being tert-butyl, R 2 ，R 4 Is a pyridyl group. L (L) 1 And L 2 Is methylene, n is 6-8.
The specific experimental steps are as follows:
1. to a mechanically stirred autoclave having a volume of 1L was added: 100mL of methanol, 0.02mol of palladium trifluoroacetate and 0.04mol (calculated by mol P) of modified resin are mixed and stirred; secondly, adding 0.08mol of p-toluenesulfonic acid, mixing and stirring; then 300mL of chlorobenzene is added;
2. after the system is replaced by nitrogen for three times and CO for three times, 1mol of butadiene is introduced into a reaction kettle, and the temperature is raised to 100 ℃;
3. supplementing CO to the pressure of 5MPa, and reacting for 16h, wherein CO is continuously supplemented in the reaction process to maintain the pressure at 5MPa;
4. the catalyst is separated and recovered after the reaction product is filtered, and the product is analyzed by gas chromatography to calculate the butadiene conversion and the adipic acid diester selectivity.
Example 4
The modified resin in this example was the same as in example 3.
The specific experimental steps are as follows:
1. to a mechanically stirred autoclave having a volume of 1L was added: 200mL of n-butanol, 0.02mol of nickel nitrate and 0.06mol (calculated by P mol) of modified resin, and mixing and stirring; secondly, adding 0.12mol of p-trifluoromethanesulfonic acid, mixing and stirring; next, 240mL of toluene is added;
2. after the system is replaced by nitrogen for three times and CO for three times, 1mol of butadiene is introduced into a reaction kettle, and the temperature is raised to 140 ℃;
3. supplementing CO to the pressure of 5MPa, and reacting for 24 hours, wherein CO is continuously supplemented in the reaction process to maintain the pressure at 5MPa;
4. the catalyst is separated and recovered after the reaction product is filtered, and the product is analyzed by gas chromatography to calculate the butadiene conversion and the adipic acid diester selectivity.
Example 5
The modified resin in this example was the same as in example 3.
The specific experimental steps are as follows:
1. to a mechanically stirred autoclave having a volume of 1L was added: 100mL of methanol, 0.02mol of cobalt nitrate and 0.04mol (calculated by P mol) of modified resin are mixed and stirred; secondly, adding 0.08mol of p-trifluoromethanesulfonic acid, mixing and stirring; then 300mL of toluene is added;
2. after the system is replaced by nitrogen for three times and CO for three times, 1mol of butadiene is introduced into a reaction kettle, and the temperature is raised to 140 ℃;
3. supplementing CO to the pressure of 3MPa, and reacting for 24 hours, wherein CO is continuously supplemented in the reaction process to maintain the pressure at 3MPa;
4. the catalyst is separated and recovered after the reaction product is filtered, and the product is analyzed by gas chromatography to calculate the butadiene conversion and the adipic acid diester selectivity.
Examples 6 to 10
The modified resin in example 1 was filtered and dried at 80℃for 24 hours, and the dried catalyst was reused in the procedure of example 1, and the recovered catalyst was not charged with palladium acetate, and the amounts of other raw materials were unchanged. The catalyst after the reaction was used by filtration and drying, and was recycled 5 times according to the method, examples 6 to 10 respectively.
Example 11
The difference from example 1 is only that R of the modified resin 1 ，R 2 ，R 3 ，R 4 The group is H.
Example 12
The difference from example 1 is only that the modified resin L 1 Is propylene, L 2 Is propylene.
Example 13
The difference from example 1 is only that the amount of the modified resin (in terms of moles of P) is 0.40mol.
Example 14
The difference from example 1 is only that the amount of the modified resin (in terms of moles of P) is 0.02mol.
Example 15
The only difference from example 1 is that methanesulfonic acid was used in an amount of 0.40mol.
Example 16
The only difference from example 1 is that methanesulfonic acid was used in an amount of 0.04mol.
Example 17
The difference from example 1 is that the amount of methanesulfonic acid used is 0.01mol.
Example 18
The only difference from example 1 is that the amount of methanol used is 8mol.
Example 19
The only difference from example 1 is that the amount of methanol used is 2mol.
Example 20
The only difference from example 1 was that toluene was used in an amount of 1440ml.
Example 21
The only difference from example 1 is that toluene is used in an amount of 160ml.
Example 22
The only difference from example 1 is that toluene was used in an amount of 100ml.
Comparative example 1
Methanol is used as an alcohol raw material, pd (Ac) is used 2 As a precursor, the acid auxiliary agent is methanesulfonic acid, and bis (di-tert-butylphosphino) -o-xylene is used as a ligand to prepare a homogeneous catalyst system, and the specific experimental steps are as follows:
1. to a mechanically stirred autoclave having a volume of 1L, a catalyst system of the following composition was added: 120mL of methanol, 0.02mol of palladium acetate, 0.03mol of bis (di-tert-butylphosphino) -o-xylene, 0.024mol of methanesulfonic acid, and 300mL of toluene;
2. after the system is replaced by nitrogen for three times and CO for three times, 1mol of butadiene is introduced into a reaction kettle, and the temperature is raised to 120 ℃;
3. supplementing CO to the pressure of 4MPa, and reacting for 16h, wherein CO is continuously supplemented in the reaction process to maintain the pressure at 4MPa;
4. the catalyst is separated and recovered after the reaction product is filtered, and the product is analyzed by gas chromatography to calculate the butadiene conversion and the adipic acid diester selectivity.
Comparative examples 2 to 3
The product in comparative example 1 was distilled under reduced pressure at a temperature of 100 ℃ and a vacuum degree of 1KPa, and the remaining 30g of the column bottoms were used as a catalyst mother liquor, and the recovered catalyst mother liquor was continuously used according to the process of comparative example 1 without adding palladium acetate, and the amounts of other raw materials were unchanged. The catalyst mother liquor recovered by distillation was continuously used in the same manner as the product after the reaction, and was recycled 2 times according to the method, which was comparative examples 2 to 3, respectively.
Comparative example 4
The only difference from example 1 is that the modified resin P atom was changed to N atom.
The butadiene conversion and adipic acid diester selectivity of examples 1 to 22 and comparative examples 1 to 4 are shown in table 1.
TABLE 1
Examples Butadiene conversion/% Adipic acid diester selectivity/%
1 99.9 97.1
2 97.8 93.6
3 90.3 94.5
4 84.1 87.0
5 81.5 79.8
6 99.9 97.1
7 99.4 97.3
8 98.8 97.1
9 98.7 96.8
10 98.8 97.0
11 98.1 71.5
12 98.4 89.3
13 99.8 97.0
14 81.0 96.8
15 97.3 97.0
16 87.5 96.9
17 73.4 97.0
18 64.2 95.3
19 93.1 97.0
20 99.9 97.1
21 91.7 87.2
22 85.2 81.1
Comparative example Butadiene conversion/% Adipic acid diester selectivity/%
1 99.3 97.1
2 78.1 96.9
3 57.9 96.7
4 90.7 87.0
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
the catalyst provided by the application has good selectivity and high activity, and still has relatively excellent selectivity and activity after multiple uses. The catalyst prepared by the preferred method is used for the carbonylation reaction of butadiene, the conversion rate of butadiene can reach more than 99 percent, and the selectivity of adipic acid diester can reach more than 97 percent.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (16)

1. A method for preparing a bidentate phosphine ligand heterogeneous catalyst, which is characterized by comprising the following steps:
s1, mixing bidentate phosphine modified resin, a metal salt precursor and an alcohol solution, and performing a first-stage reaction to obtain an intermediate product; wherein the bidentate phosphine modified resin is modified resin with part of side chain benzene rings modified by bidentate phosphine groups in the polystyrene resin;
s2, mixing the intermediate product with an acid auxiliary agent, and carrying out a second-stage reaction to obtain the bidentate phosphine ligand heterogeneous catalyst.
2. The method of claim 1, wherein the bidentate phosphine modified resin has the following structure:
wherein L is 1 And L 2 Alkylene groups each independently being C1 to C8, preferably C1 to C4; r is R 1 、R 2 、R 3 And R is 4 Each independently is H, pyridinyl or C1-C4 linear or branched alkyl; m is 3 to 10, preferably 3 to 5; n is1。
3. The preparation method according to claim 1 or 2, wherein the bidentate phosphine modified resin is prepared by the following method:
a1, providing a bidentate phosphine ligand containing benzene rings, and carrying out alkylation reaction with ethylene to obtain a bidentate phosphine modified ligand containing vinyl;
a2, polymerizing the vinyl-containing bidentate phosphine modified ligand and styrene to obtain the bidentate phosphine modified resin.
4. A method of preparation according to any one of claims 1 to 3 wherein the metal salt precursor comprises one or more of the group VIII metal trifluoroacetate, acetate, chloride, nitrate, sulfate;
preferably, the group VIII metal comprises one or more of Co, pd, pt, ni and Rh.
5. The production method according to any one of claims 1 to 4, wherein a molar ratio of phosphorus atoms in the bidentate phosphine-modified resin to metal atoms in the metal salt precursor is (1 to 20): 1, preferably (1 to 5): 1, a step of; the molar ratio of the acid auxiliary agent to the metal atoms in the metal salt precursor is (2-20): 1, preferably (6 to 12): 1.
6. the production method according to any one of claims 1 to 5, wherein the alcohol solution is an aqueous solution of a C1 to C6 fatty alcohol; preferably, the alcohol solution is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, more preferably one or more of methanol, ethanol, n-propanol and n-butanol; preferably, the alcohol solution has a weight concentration of 30 to 99%, more preferably, the molar ratio of the alcohol in the alcohol solution to the phosphorus atom in the bidentate phosphine-modified resin is (5 to 150): 1, a step of; more preferably, the molar ratio of the alcohol in the alcohol solution to the phosphorus atom in the bidentate phosphine-modified resin is (50 to 80): 1.
7. the production method according to any one of claims 1 to 6, wherein the acid auxiliary agent comprises one or more of benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, fluorosulfonic acid, and trifluoromethanesulfonic acid.
8. The preparation method according to any one of claims 1 to 7, wherein the temperature of the first stage reaction is 10 to 40 ℃ and the reaction time is 2 to 5 hours; the temperature of the second stage reaction is 10-40 ℃ and the reaction time is 0.5-2 h.
9. A bidentate phosphine ligand heterogeneous catalyst prepared according to the preparation method of any one of claims 1 to 8.
10. The bidentate phosphine ligand heterogeneous catalyst according to claim 9, characterized by having the following structure:
wherein L is 1 And L 2 Alkylene groups each independently being C1 to C8, preferably C1 to C4; r is R 1 、R 2 、R 3 And R is 4 Each independently is H, pyridinyl or C1-C4 linear or branched alkyl; m is 3 to 10, preferably 3 to 5; n is 1.
11. A process for the carbonylation of butadiene wherein the carbonylation of butadiene is catalysed by a bidentate phosphine ligand heterogeneous catalyst according to claim 9 or claim 10.
12. The method according to claim 11, characterized in that the method comprises: mixing the bidentate phosphine ligand heterogeneous catalyst with an activator, and then introducing butadiene and CO into the mixture to carry out the carbonylation reaction; preferably, the activator is one or more of aprotic solvents, aromatic compounds, C5-C8 alkanes and nitriles; more preferably, the activator is one or more of diethyl ether, dimethyl ether, glycol ether, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, n-pentane, n-hexane, n-heptane and acetonitrile.
13. The process according to claim 11 or 12, characterized in that the molar ratio of the bidentate phosphine ligand heterogeneous catalyst to the butadiene is 1 (10-300).
14. The process according to claim 11, characterized in that the activator comprises 50-90%, preferably 70-85% of the total volume of liquid phase in the carbonylation reaction.
15. Process according to any one of claims 11 to 14, characterized in that the temperature of the carbonylation reaction is 60 to 200 ℃, preferably 60 to 150 ℃, more preferably 80 to 120 ℃; the pressure of the carbonylation reaction is 0.5-8 MPa, preferably 2-5 MPa; the time of the carbonylation reaction is 5-30 h.
16. The process according to any one of claims 11 to 15, characterized in that the carbonylation reaction is carried out under an inert atmosphere, preferably N 2 、CO 2 And one or more of Ar, more preferably N 2 And/or Ar.
CN202310597049.9A 2023-05-24 2023-05-24 Bidentate phosphine ligand heterogeneous catalyst, preparation method thereof and application thereof in nylon monomer preparation process Pending CN116925140A (en)

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