WO2016155339A1 - 一种含膦有机混聚物-金属多相催化剂及其方法和应用 - Google Patents

一种含膦有机混聚物-金属多相催化剂及其方法和应用 Download PDF

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WO2016155339A1
WO2016155339A1 PCT/CN2015/095604 CN2015095604W WO2016155339A1 WO 2016155339 A1 WO2016155339 A1 WO 2016155339A1 CN 2015095604 W CN2015095604 W CN 2015095604W WO 2016155339 A1 WO2016155339 A1 WO 2016155339A1
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heterogeneous catalyst
phosphine
ligand
organic
organophosphine ligand
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丁云杰
李存耀
严丽
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中国科学院大连化学物理研究所
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen

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  • the invention belongs to the field of heterogeneous catalysis, and in particular relates to a phosphine-containing organic mixed polymer-metal heterogeneous catalyst and a preparation method and application thereof.
  • the design and synthesis of porous organic materials has gradually become one of the new hotspots in the research of microporous materials.
  • the framework of organic microporous polymers consists of pure organic molecules.
  • the composition is connected to each other by a covalent bond, and has an open pore and an excellent pore property.
  • the pore properties of the material can be regulated by adjusting the structure of the organic molecule.
  • organic microporous polymers are connected by covalent bonds compared to the molecular network structure formed by non-covalent bonds, while the pore properties of the material are maintained, the molecular network The structure is more stable.
  • Hydroformylation of olefins refers to the reaction of olefins and synthesis gas (CO/H 2 ) catalyzed by transition metal carbonyl complexes to form one carbon aldehyde higher than the starting olefins.
  • synthesis gas CO/H 2
  • the aldehyde of the olefin hydroformylation reaction is a very useful chemical intermediate. It can be used to synthesize carboxylic acids and corresponding esters, as well as fatty amines. The most important use is that it can be hydrogenated to alcohol, and the alcohol itself can be used. It is widely used in the field of fine chemicals as an organic solvent, a plasticizer and a surfactant.
  • Table 1 describes the production process conditions and catalytic performance comparisons of the five-generation catalysts that have been industrially applied.
  • the five generations of catalysts that have been industrialized are homogeneous catalysts, and the problem of loss of ligands and metals during the reaction has not been solved.
  • Patent CN1319580A describes a variety of bidentate phosphite ligands with large steric hindrance. These ligands form a homogeneous catalyst with the coordination of Rh and Co, and the hydroformylation of higher olefins. High aldehyde isomer ratio selectivity. However, homogeneous catalysts are difficult to recover and ligand synthesis is difficult.
  • Patent CN1210514A reports a Rh complex catalyst for the hydroformylation of olefins.
  • the Rh complex is a ligand with a multidentate organic nitrogen compound containing at least one tertiary nitrogen group which can be protonated in a weak acid.
  • the catalyst is also facing the problem of being difficult to recycle.
  • a composite catalyst system composed of a Rh complex with a biphenyl skeleton or a binaphthyl skeleton bisphosphine ligand, and a triphenylphosphine or a phosphite triphenyl ester monophosphine ligand is used as a catalyst in a linear olefin hydrogen.
  • the normal aldehyde in the formylation reaction has a higher selectivity, which reduces the amount of the expensive bisphosphine ligand, but the catalytic system is homogeneous and the catalyst cannot be reused.
  • the bisphosphite and triphenylphosphine are also combined with Rh to form a composite catalytic system.
  • the molar ratio of n-butyraldehyde to isobutyraldehyde is more than 20, which significantly prolongs the double sub-
  • the service life of the phosphate ligand significantly reduces the amount of triarylphosphine, but it is also a homogeneous reaction in nature, and it also faces the problem of difficulty in recycling the catalyst.
  • the olefin hydroformylation reaction is currently considered to be the largest homogeneous reaction process in the industry.
  • the annual production of aldehydes and alcohols by olefin hydroformylation is about 9 million tons.
  • the industry currently uses homogeneous catalysts and catalysts. Recycling is difficult and production costs are high.
  • the heterogeneous phase of the olefin hydroformylation homogeneous catalyst is an inevitable trend.
  • the traditional homogeneous catalytic heterogeneous method exposes a series of problems that need to be solved and overcome, especially the poor stability of the catalyst after multiphase, and the loss of active components.
  • an object of the present invention is to provide a phosphine-containing organic polymer-metal heterogeneous catalyst, a preparation method and application thereof.
  • the loading is from 0.01 to 10% by weight (preferably from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight), and the phosphine-containing organic polymer mixture is composed of a polydentate organophosphine ligand containing an olefin group and a monodentate organophosphine group containing an olefin group.
  • the active metal component forms a multi-coordination bond with the exposed P in the hybrid carrier, and the formed catalyst excels in the process of hydroformylation of the olefin to produce a high orthorhombic aldehyde.
  • the olefin group is preferably a vinyl group
  • the olefin group-containing polydentate organophosphine ligand is a vinyl group-containing bidentate phosphite organophosphorus ligand, and the olefin group-containing monodentate organophosphine compound
  • the body is a vinyl-containing triphenylphosphine ligand.
  • the organic hybrid carrier has a multi-stage pore structure, a specific surface area of 100-3000 m 2 /g, and contains macropores, mesopores and micropores (wherein macropores account for 5-50% of the total pore volume, mesopores) 5-50% of the total pore volume, micropores account for 5-50% of the total pore volume), pore volume is 0.1-5.0 cm 3 /g, pore size distribution is 0.2-50.0 nm.
  • the heterogeneous catalyst is a solvothermal polymerization after mixing a polydentate organophosphine ligand with a monodentate organophosphine ligand.
  • the olefin group in the organophosphine ligand is polymerized by a radical initiator to form a phosphine-containing organic polymer having a multi-stage pore structure as a carrier, and the precursor of the active component and the carrier are stirred in an organic solvent, and the activity is stirred.
  • the component forms a multi-coordination bond with the exposed P in the phosphine-containing organic hybrid carrier, and after evaporation of the volatile solvent, a heterogeneous catalyst of a coordination bond type is obtained.
  • the preparation method of the heterogeneous catalyst is:
  • step b) Transfer the mixed solution prepared in the step a) to a synthetic autoclave at 273 to 473 K (preferably 323 to 423 K, more preferably 353 to 403 K), and let it stand for 1 to 100 hours by a solvothermal polymerization method under an inert gas atmosphere. (preferably 1 to 50 hours, more preferably 10 to 30 hours) to carry out a polymerization reaction to obtain a phosphine-containing organic mixed polymer;
  • the mixed polymer obtained in the step b) is vacuum-extracted at room temperature to obtain an organic complex containing bare P having a multi-stage pore structure, that is, a support of the heterogeneous catalyst;
  • the organic hybrid carrier obtained in the step c) is added to the solvent containing the active component precursor, and stirred at 0.1 to ⁇
  • the stirring time is preferably in the range of 0.1 to 50 hours, after which the organic solvent is removed by vacuum to obtain a heterogeneous catalyst.
  • the organic solvent described in the step a) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform;
  • the crosslinking agent is styrene, ethylene, propylene, two One or more of vinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-triethynylbenzene;
  • the free radical initiator is cyclohexanone peroxide One or two or more kinds of dibenzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile.
  • the molar ratio of the monodentate organophosphine ligand to the polydentate organophosphine ligand described in step a) is from 0.01:1 to 100:1 (preferably from 0.1:1 to 10:1, more preferably from 1:1 to 10:1)
  • the molar ratio of the monodentate organophosphine ligand to the crosslinking agent is from 0.01:1 to 10:1 (preferably from 0.1:1 to 10:1, more preferably from 1:1 to 10: 1)
  • the molar ratio of the monodentate organophosphine ligand to the free radical initiator is from 300:1 to 10:1 (preferably from 100:1 to 10:1, more preferably from 100:1 to 20:1), and polymerization is carried out into an organic mixture.
  • the concentration of the monodentate organophosphine ligand in the organic solvent before the polymer is in the range of 0.01 to 1000 g/L (preferably 0.1 to 100 g/L, more
  • the solvent described in the step d) is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform, and the active component is Rh, Co, Ir One, two or three, wherein the precursor of Rh is Rh(CH 3 COO) 2 , RhH(CO)(PPh 3 ) 3 , Rh(CO) 2 (acac), RhCl 3 ; Co(CH 3 COO) 2 , Co(CO) 2 (acac), Co(acac) 2 , CoCl 2 ;
  • the precursor of Ir is Ir(CO) 3 (acac), Ir(CH 3 COO) 3 , Ir ( Acac) 3 , IrCl 4 .
  • the metal loading in the catalyst ranges from 0.01 to 10% by weight (preferably from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight).
  • the properties of the prepared catalyst can be controlled by adjusting various parameters of the catalyst to suit the hydroformylation reaction of different olefins and different processes.
  • the phosphine-containing organic polymer-metal heterogeneous catalyst is used for the hydroformylation of olefins, has high catalytic activity and good stereoselectivity, and can be used in fixed bed, trickle bed, slurry bed and bubbling bed reaction processes. in.
  • the present invention introduces a typical bisphosphine ligand such as an aromatic ring of biphephos into a vinyl (Vinyl) group, that is, a vinyl-containing polydentate organophosphine ligand (Vinyl Biphephos) as a polymerization monomer in an autoclave.
  • a typical bisphosphine ligand such as an aromatic ring of biphephos into a vinyl (Vinyl) group, that is, a vinyl-containing polydentate organophosphine ligand (Vinyl Biphephos) as a polymerization monomer in an autoclave.
  • Exposure of P containing orphaned electrons can form a multi-coordination bond with the active transition metal ion orbit as a catalyst carrier, thereby forming a catalytic active site.
  • the organic phosphine mixed polymer has the dual functions of the carrier and the ligand, and the active metal component is highly dispersed in the carrier, and forms a multi-coordination bond with the high concentration of the exposed P.
  • the active metal component is highly dispersed in the monoatomic form in the organophosphine polymer carrier, which greatly improves the utilization efficiency of the metal. Moreover, the active component is not easily lost, the catalyst has a long service life, and the multidentate phosphine ligand in the skeleton has a remarkable steric effect, and the prepared catalyst can significantly improve the stereoselectivity of the product.
  • the catalyst organic hybrid carrier skeleton provided by the invention contains P, and the organic mixture has the dual functions of the ligand and the carrier; the active metal component can be dispersed in such a large surface area in a single atom or ion manner.
  • the metal utilization efficiency is greatly improved.
  • the monophosphine ligand structural unit in the carrier organophosphine mixed polymer skeleton makes the mixed polymer have a higher P concentration, and easily forms a double or multiple metal-P coordination bond with the active metal component, and the coordination bond has a strong bond. The chemical bonding ability makes the active component not easily lost.
  • the heterogeneous catalyst framework of the present invention contains a multidentate and monodentate organophosphine ligand structural unit, wherein the monodentate organophosphine ligand has a relatively high P on the surface of the mixed polymer, and the polydentate phosphine ligand is With significant steric effect, the active metal atom or ion forms a multi-coordination bond with the exposed P on the mixed polymer, the active component is not easily lost, and the active component of the catalyst is Rh, Co or Ir.
  • the mixed polymer has a high specific surface area multi-stage pore structure, and has the dual functions of a carrier and a ligand.
  • the active metal component is highly dispersed in a monoatomic form in the pore or surface of the organic phosphine polymer carrier, thereby improving Utilization efficiency of metal components.
  • the coordination bond type heterogeneous catalyst is suitable for reaction processes such as fixed bed, slurry bed, bubbling bed and trickle bed, and the multi-stage pore structure containing phosphine organic polymer-metal heterogeneous catalyst provided by the invention is applied Hydroformylation of olefins can significantly increase the conversion of olefins and the selectivity of normal aldehydes, and can solve the long-term stability and selectivity of the olefin hydroformylation reaction, and the loss of metal components. problem.
  • the olefin hydroformylation reaction product using the catalyst has a high aspect ratio, reduces the cost of industrial production of olefin hydroformylation, has good catalyst stability, and is simple and efficient in separating reactants and products from catalysts.
  • New industrial technology is provided for the production of olefin hydroformylation.
  • Figure A shows a typical olefin-based functionalized bisphosphine ligand
  • Figure B shows a schematic diagram of Vinyl Biphephos.
  • Figure 2 is a schematic diagram of the Vinyl Biphephos polymerization technology route.
  • Figure 3 is a schematic diagram of a typical monodentate organophosphine ligand and a multidentate organophosphine ligand and a crosslinking agent used in the polymerization, wherein L1-L16 is a monodentate organophosphine ligand, and L17-L19 is a multidentate organic Phosphine ligands, L20 and L21 are crosslinkers.
  • Figure 4 is a 1 H spectrum of Vinyl Biphephos ligand.
  • Figure 5 shows the 13 C spectrum of the Vinyl Biphephos ligand.
  • Figure 6 is a 31 P spectrum of Vinyl Biphephos ligand.
  • Figure 7 is a high resolution mass spectrum of Vinyl Biphephos ligand.
  • Figure 8 is a graph showing the thermogravimetric curve of the catalyst synthesized in Example 1 under a N 2 atmosphere.
  • the typical monophosphine ligand tris(4-vinylphenyl)phosphine (L1) is synthesized by adding magnesium powder to a 500 ml three-neck round bottom flask with magnetic stirrer in an ice water bath and a nitrogen atmosphere. g, a mixed solution of p-bromostyrene and anhydrous diethyl ether (18.3 g of p-bromostyrene + 100 ml of anhydrous diethyl ether) was added dropwise, and the resulting reaction mixture was stirred at room temperature for 2 hours to complete the reaction.
  • a mixed solution of phosphorus trichloride and anhydrous diethyl ether (4.6 g of phosphorus trichloride + 10 ml of anhydrous diethyl ether) was added dropwise under ice water, and the obtained mixture was stirred at room temperature for 2 hr. 50 ml of deionized water was added to the reaction system under ice-water bath, and the mixture was reacted at room temperature for 2 hours. The organic phase is separated and the organic phase is evaporated to remove the solvent.
  • the obtained primary product is purified by silica gel column chromatography, that is, a mixed solvent of silica gel as a stationary phase and ethyl acetate/petroleum ether (volume ratio 1:10) is used as an eluent, and finally a white powdery solid is obtained, that is, It is tris(4-vinylphenyl)phosphine (L1).
  • the typical bisphosphine ligand Vinyl Biphephos (Fig. 1) is synthesized according to the literature (Org. Lett., 2009, 11, 971).
  • B In an ice water bath and a nitrogen atmosphere, 7.6 g of A, 50 mg of DMAP (4-dimethylaminopyridine) and 32 mg of acetic anhydride were sequentially added to a 500 ml three-necked flask, and after fully reacting, it was purified by a silica gel column to obtain C: C and The reaction is purified by silica gel column to obtain D: Reducing D with LiH 4 Al in the presence of KOH in an ethanol solution yields
  • E In a 500 ml three-necked flask, 100 ml of toluene, 10 ml of triethylamine, and then 3.5 g of E and 5.0 g of B were added in an ice water bath under a nitrogen atmosphere, and the reaction was sufficiently stirred at room temperature for 2
  • FIG. 2 is a schematic diagram of the Vinyl Biphephos organic hybrid carrier polymerization technology route. 3.13 mg of acetylacetone tricarbonyl ruthenium was weighed and dissolved in 10.0 ml of tetrahydrofuran solvent, 1.0 g of the above-prepared organic polymer mixture was added, and the mixture was stirred at 298 K under an inert gas atmosphere for 24 hours, and then vacuumed at room temperature. The solvent is removed to obtain a coordination-bonded heterogeneous catalyst for the hydroformylation of an olefin.
  • Example 2 in addition to weighing 10.0 grams of comonomer tris(4-vinylphenyl)phosphine (L1) instead of 2.5 grams of comonomer tris(4-vinylphenyl)phosphine, the rest of the catalyst synthesis process The same as in the first embodiment.
  • Example 3 the preparation process of the remaining catalyst was the same as in Example 1 except that 0.1 g of a radical initiator azobisisobutyronitrile was weighed instead of 1.0 g of a radical initiator azobisisobutyronitrile.
  • Example 4 the preparation of the remaining catalyst was the same as in Example 1 except that 50.0 ml of tetrahydrofuran solvent was used instead of 100.0 ml of tetrahydrofuran solvent.
  • Example 5 the preparation process of the remaining catalyst was the same as that of Example 1 except that 100.0 ml of a dichloromethane solvent was used instead of 100.0 ml of a tetrahydrofuran solvent.
  • Example 6 the rest of the catalyst preparation process was the same as in Example 1 except that the 393 K polymerization temperature was used instead of the 373 K polymerization temperature.
  • Example 7 the rest of the catalyst preparation process was the same as in Example 1 except that the polymerization time of 12 h was used instead of the polymerization time of 24 h.
  • Example 8 the remaining catalyst preparation process was the same as in Example 1 except that 10.0 g of L20 was further added as a crosslinking agent.
  • Example 9 except for the further addition of 1.0 g of styrene as a crosslinking agent, the rest of the catalyst preparation process was the same as in Example 1.
  • Example 10 14.05 mg of acetylacetone dicarbonyl cobalt was added in place of acetylacetone tricarbonyl hydrazine in 10.0 ml of tetrahydrofuran solvent, and the rest of the catalyst synthesis process was the same as in Example 1.
  • Example 11 2.05 mg of acetylacetone tricarbonyl hydrazine was weighed in place of acetylacetone tricarbonyl hydrazine in 10.0 ml of tetrahydrofuran solvent, and the rest of the catalyst synthesis process was the same as in Example 1.
  • the catalyst prepared above was placed in a fixed bed reactor of 0.5 g, and both ends were charged with quartz sand.
  • the micro feed pump was pumped into 1-octene at a flow rate of 0.1 ml/min.
  • Hydroformylation reaction The reaction was collected in an ice bath cooled collection tank.
  • the obtained liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector using n-propanol as an internal standard.
  • the tail gas from the collection tank was analyzed online using an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector.
  • the reaction results are shown in Table 1.
  • the catalyst prepared above was placed in a fixed bed reactor of 0.5 g, and both ends were charged with quartz sand.
  • the micro feed pump pumps 2-octene at a flow rate of 0.1 ml/min.
  • Hydroformylation reaction The reaction was collected in an ice bath cooled collection tank.
  • the obtained liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector using n-propanol as an internal standard.
  • the tail gas from the collection tank was analyzed online using an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector.
  • the reaction results are shown in Table 3.

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Abstract

一种多级孔结构含膦有机混聚物-金属多相催化剂及其制备方法和在烯烃氢甲酰化反应中的应用，多相催化剂以金属Rh、Co或Ir作为活性组分，以多级孔结构含膦有机混聚物作为载体，含膦有机混聚物由多齿有机膦配体和单齿有机膦配体共聚而成，获得的催化剂稳定性较高。

Description

一种含膦有机混聚物-金属多相催化剂及其方法和应用 技术领域
本发明属于多相催化领域，具体涉及一种含膦有机混聚物-金属多相催化剂及其制备方法和应用。
背景技术
多孔有机材料的设计和合成逐渐成为微孔材料研究领域新的热点之一，与传统的无机微孔材料与有机-金属配位聚合物相比，有机微孔聚合物的骨架由纯粹的有机分子构成，相互通过共价键连接，具有开放的孔道与优异的孔性质。更重要的是，由于有机化学合成方法的多样性，为有机分子网络的构建提供了丰富的合成路径和架构方式，可以通过有目的地引入功能化的有机分子使最终的材料具有相应的性质，通过调节有机分子的结构可以调控材料的孔性质。除此以外，在大多数情况下，与通过非共价键连接成的分子网络结构脆弱相比，有机微孔聚合物都是通过共价键连接，在材料孔性质得到保持的同时，分子网络结构更加稳固。
烯烃氢甲酰化反应(Hydroformylation，又称OXO-Synthesis)是指过渡金属羰基配合物催化下的烯烃与合成气(CO/H2)生成比原料烯烃高一个碳的醛的反应，是最早实现工业生产的匀相络合催化过程。烯烃氢甲酰化反应的产品醛是很有用的化学中间体，它可以用来合成羧酸及相应的酯，以及脂肪胺等，最重要的用途是它可加氢转化成醇，醇本身可作为有机溶剂、增塑剂和表面活性剂等广泛应用于精细化工领域。
表1叙述了已经工业应用的五代催化剂的生产工艺条件和催化性能比较，已经工业化的五代催化剂均为均相催化剂，始终没有解决反应过程中配体及金属的流失问题。
专利CN1319580A叙述了具有较大空间位阻的多种双齿亚磷酸酯配体，这些配体与Rh和Co等配位形成的均相催化剂，其高碳烯烃的氢甲酰化反应，具有较高醛正异比的选择性。但是均相催化剂不易回收且配体合成较为困难。
专利CN1210514A报道了烯烃氢甲酰化反应的Rh络合物催化剂，Rh络合物是采用多齿的有机氮化合物作配体，配体中含至少一个能在弱酸中被质子化的叔氮基，但是催化剂同样面临不易回收的问题。
专利CN102911021A中，利用Rh配合物与联苯骨架或联萘骨架双膦配体，以及三苯基膦或亚磷酸酯三苯酯单膦配体组成的复合催化体系为催化剂，在直链烯烃氢甲酰化反应中正构醛具有较高的选择性，这样降低了价格昂贵的双膦配体的用量，但是催化体系还是均相的，催化剂无法重复利用。
专利CN1986055A中同样利用双亚磷酸酯和三苯基膦与Rh配合，组成复合催化体系，在丙烯的氢甲酰化反应中，正丁醛和异丁醛摩尔比大于20，显著延长了双亚磷酸酯配体的使用寿命，明显减少三芳基膦的用量，但是本质上还是均相反应，同样面临催化剂回收利用困难的问题。
表1已经工业应用的五代催化剂的生产工艺条件和催化性能比较
Figure PCTCN2015095604-appb-000001
烯烃氢甲酰化反应目前被认为是工业上规模最大的均相反应过程，每年通过烯烃氢甲酰化反应生产的醛和醇约为900万吨，工业上目前使用的是均相催化剂，催化剂回收利用困难，生产成本很高。烯烃氢甲酰化反应均相催化剂的多相化是发展的必然趋势。但是传统的均相催化多相化方法暴露出一系列需要解决和克服的问题，尤其是多相化后催化剂稳定性差，活性组分流失严重等。
发明内容
为了解决上述问题，本发明的目的在于提供一种含膦有机混聚物-金属多相催化剂及其制备方法和应用。
本发明的技术方案为：
一种含膦有机混聚物-金属多相催化剂，以金属Rh、Co或Ir中的一种、两种、三种作为活性组分，以含膦有机混聚物为载体，催化剂中金属担载量为0.01～10wt％(优选0.1～5wt％，更优选为0.1～2wt％)，含膦有机混聚物由含有烯烃基的多齿有机膦配体和含有烯烃基的单齿有机膦配体(典型的含乙烯基的单膦双膦配体合成方法详见文献Chem.Commun.,2014,50,11844和J.Am.Chem.Soc.,2015,137,5204)共聚而成。活性金属组分与混聚物载体中裸露的P形成多重配位键，形成的催化剂在烯烃氢甲酰化生产高正异比醛工艺中表现优良。
所述的烯烃基优选为乙烯基，所述的含有烯烃基的多齿有机膦配体为含乙烯基的二齿亚磷酸酯有机磷配体，所述的含有烯烃基的单齿有机膦配体为含乙烯基的三苯基膦配体。
所述的有机混聚物载体具有多级孔结构，比表面积为100～3000m2/g，同时含有大孔、中孔和微孔(其中大孔占总孔容的5-50％、中孔占总孔容的5-50％、微孔占总孔容的5-50％)，孔容为0.1～5.0cm3/g，孔径分布在0.2～50.0nm。
所述的多相催化剂是将多齿有机膦配体和单齿有机膦配体混合后，采用溶剂热聚合 法，经自由基引发剂引发有机膦配体中的烯烃基发生聚合反应，生成具有多级孔结构含膦有机混聚物作为载体，活性组分的前驱体与载体在有机溶剂中搅拌，活性组分与含膦有机混聚物载体中裸露的P形成多重配位键，蒸去挥发性溶剂后，得到配位键型的多相催化剂。
多相催化剂的制备方法为：
a)在273～473K(优选273～353K，更优选280～300K)，惰性气体气氛下，在有机溶剂中，加入单齿有机膦配体和多齿有机膦配体、添加或不添加交联剂、再加入自由基引发剂，混合后，将混合物搅拌0.1～100小时，优选的搅拌时间范围为0.1～50小时；
b)将步骤a)制得的混合溶液转移至合成高压釜中，273～473K(优选323～423K更优选353～403K)，惰性气体气氛下，采用溶剂热聚合法，静置1～100小时(优选1～50小时，更优选10～30小时)进行聚合反应，得到一种含膦有机混聚物；
c)将步骤b)得到的混聚物，在室温条件下真空抽除溶剂，即得到具有多级孔结构的含有裸露P的有机混聚物，即所述多相催化剂的载体；
d)在273～473K(优选273～353K，更优选280～300K)，惰性气体气氛下，在含有活性组分前驱体的溶剂中，加入步骤c)得到的有机混聚物载体，搅拌0.1～100小时，优选搅拌时间范围0.1～50小时，之后，真空抽除有机溶剂，得到多相催化剂。
步骤a)中所述的有机溶剂为苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上；所述的交联剂为苯乙烯、乙烯、丙烯、二乙烯基苯、二甲氧基甲烷、二碘甲烷、多聚甲醛或1,3,5-三乙炔基苯中的一种或两种以上；所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或两种以上。
步骤a)中所述的单齿有机膦配体和多齿有机膦配体的摩尔比为0.01:1～100:1(优选0.1:1～10:1，更优选1:1～10:1)，在交联剂添加的情况下，单齿有机膦配体与交联剂的摩尔比为0.01:1～10:1(优选0.1:1～10:1，更优选1:1～10:1)，单齿有机膦配体与自由基引发剂的摩尔比为300:1～10:1(优选100:1～10:1，更优选100:1～20:1)，聚合成有机混聚物前，单齿有机膦配体在有机溶剂中的浓度范围为0.01～1000g/L(优选0.1～100g/L，更优选1～100g/L)。
步骤d)中所述的溶剂为水、苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上，所述的活性组分为Rh、Co、Ir中的一种、两种或三种，其中Rh的前驱体为Rh(CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3；Co的前驱体为Co(CH3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2；Ir的前驱体为Ir(CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4。催化剂中金属担载量范围为0.01～10wt％(优选0.1～5wt％，更优选为0.1～2wt％)。
本发明制备时，可通过调变催化剂的各项参数进而来控制制备出的催化剂的性能，以适用于不同烯烃，不同工艺的氢甲酰化反应。此类含膦有机混聚物-金属多相催化剂用于烯烃氢甲酰化反应，催化活性高，产品立体选择性好，可用于固定床，滴流床，浆态床和鼓泡床反应工艺中。所述烯烃结构式为R-C＝C-R’(其中R为H，C1～C20的烷基，R’为H或R1-C＝C-R2，R1＝-(CH2)n-(n＝1～10)，R2为C1-C10的烷基)或
Figure PCTCN2015095604-appb-000002
(n＝1～10)
本发明的反应原理：
本发明将典型的双膦配体比如Biphephos的芳环上引入乙烯基(Vinyl)基团，即一种含有乙烯基的多齿有机膦配体(Vinyl Biphephos)作为聚合单体，在高压釜中利用溶剂热聚合法，与单齿有机膦配体比如三(4-乙烯基苯)基膦共聚形成具有高表面积和多级孔道结构的有机混聚物，由于该有机混聚物骨架中具有大量暴露含有孤对电子的P，可作为催化剂载体与活性过渡金属离子空轨道形成多重配位键，进而形成催化活性位。在该 催化剂中，有机膦混聚物同时具备载体和配体的双重功能，活性金属组分高分散于该载体中，与高浓度裸露P形成多重配位键。活性金属组分以单原子形式高分散于有机膦混聚物载体中，大大提高了金属的利用效率。且活性组分不易流失，催化剂寿命长，骨架中的多齿膦配体具有显著的立体效应，制备出来的催化剂可显著提高产物的立体选择性。
本发明所提供的催化剂有机混聚物载体骨架中含有P，有机混聚物兼具配体和载体的双重功能；活性金属组分能够以单原子或离子的方式分散在这种大表面积多级孔结构有机混聚物载体中，大大提高了金属利用效率。载体有机膦混聚物骨架中的单膦配体结构单元使混聚物具有较高P浓度，容易与活性金属组分形成二重或多重金属-P配位键，该配位键具有较强的化学键合能力，使得活性组分不易流失。
本发明的有益效果为：
本发明所述的多相催化剂骨架中含有多齿和单齿有机膦配体结构单元，其中单齿有机膦配体使混聚物的表面上存在较高裸露的P，多齿膦配体则具有显著的立体效应，活性金属原子或离子与混聚物上的裸露P形成多重配位键，活性组分不易流失，催化剂的活性组分为Rh、Co或Ir，此类催化剂具有较高的立体选择性，混聚物具有高比表面积多级孔结构，具备载体和配体的双重功能，活性金属组分以单原子形式高分散于有机膦混聚物载体孔道中或表面上，提高了金属组分的利用效率。
此类配位键型多相催化剂适用于固定床，浆态床，鼓泡床和滴流床等反应工艺，本发明所提供的多级孔结构含膦有机聚合物-金属多相催化剂应用于烯烃氢甲酰化反应，能够显著提高烯烃的转化率和正构醛的选择性，可以解决烯烃氢甲酰化反应多相化过程中长期存在的稳定性和选择性差，以及金属组分流失严重等问题。同时使用该催化剂的烯烃氢甲酰化反应的产品具有较高的正异比，降低了烯烃氢甲酰化工业生产的成本，催化剂稳定性好，反应物和产品与催化剂的分离简单而且高效，为烯烃氢甲酰化生产提供了新的工业化技术。
附图说明
图1中，A图为典型的烯烃基功能化的双膦配体，B图为Vinyl Biphephos结构示意图。
图2是Vinyl Biphephos聚合技术路线示意图。
图3是聚合中用到的典型的单齿有机膦配体和多齿有机膦配体及交联剂的示意图，其中，L1-L16为单齿有机膦配体，L17-L19为多齿有机膦配体，L20和L21为交联剂。
图4为Vinyl Biphephos配体的1H谱。
图5为Vinyl Biphephos配体的13C谱。
图6为Vinyl Biphephos配体的31P谱。
图7为Vinyl Biphephos配体的高分辨质谱。
图8为N2氛围下实施例1合成的催化剂热重曲线。
具体实施方式
下述实施例对本发明进行更好的说明，但不限制本发明所要保护的范围。
典型的单膦配体三(4-乙烯基苯)基膦(L1)合成过程为：在冰水浴和氮气氛围下，向带有磁搅拌子的500ml三口圆底烧瓶中，依次加入镁粉2.5g，逐滴加入对溴苯乙烯和无水乙醚的混合溶液(18.3g对溴苯乙烯+100ml无水乙醚)，所得反应混合物在室温条件下搅拌2小时使反应完全。冰水浴下逐滴加入三氯化磷和无水乙醚的混合溶液(4.6g三氯化磷+10ml无水乙醚)，所得反应混合物在室温下搅拌2小时。冰水浴下向反应体系中加入50ml去离子水，室温下反应2小时。分液取有机相，有机相蒸发掉溶剂后制 得的初级产品，经硅胶柱层析提纯，即用硅胶作固定相，乙酸乙酯/石油醚(体积比1:10)组成的混合溶剂作洗脱液，最终可得白色粉末状固体，即为三(4-乙烯基苯)基膦(L1)。
典型的双膦配体Vinyl Biphephos(附图1)合成过程为：依据文献(Org.Lett.,2009,11,971)可得中间物A：
Figure PCTCN2015095604-appb-000003
和B：
Figure PCTCN2015095604-appb-000004
在冰水浴和氮气氛围下，500ml三口烧瓶中，依次加入7.6gA，50mg DMAP(4-二甲氨基吡啶)和32mg醋酸酐，充分反应后经硅胶柱纯化后可得C：
Figure PCTCN2015095604-appb-000005
C与
Figure PCTCN2015095604-appb-000006
反应并用硅胶柱纯化可得D：
Figure PCTCN2015095604-appb-000007
用乙醇溶液中，KOH存在下用LiH4Al还原D可得E：
Figure PCTCN2015095604-appb-000008
在冰水浴和氮气氛围下，500ml三口烧瓶中加入100ml甲苯，10ml三乙胺，随后加入3.5g E和5.0g B，室温下充分搅拌反应2h。用硅胶作固定相，乙酸乙酯/石油醚(体积比1:10)组成的混合溶剂作洗脱液，最终可得灰色粉末状固体，即为Vinyl Biphephos。
实施例1
在298K和惰性气体保护氛围下，将10.0克Vinyl Biphephos单体(附图1)溶于100.0ml四氢呋喃溶剂中，同时加入2.5g共单体三(4-乙烯基苯)基膦(L1)，向上述溶液中加入1.0克自由基引发剂偶氮二异丁腈，搅拌2小时。将搅拌好的溶液移至高压釜中，于373K和惰性气体保护氛围下利用溶剂热聚合法聚合24h。待上述聚合后的溶液冷却至室温，室温条件真空抽走溶剂，即得到由Vinyl Biphephos和三(4-乙烯基苯)基膦有机单体共聚的有机膦混聚物。图2为Vinyl Biphephos有机混聚物载体聚合技术路线的示意图。称取3.13毫克乙酰丙酮三羰基铑溶于10.0ml四氢呋喃溶剂中，加入1.0克上述制得的有机混聚物，将此混合物在298K和惰性气体保护氛围下搅拌24小时，然后在室温条件下真空抽走溶剂，即获得应用于烯烃氢甲酰化反应的配位键型多相催化剂。
实施例2
在实施例2中，除了称取10.0克共单体三(4-乙烯基苯)基膦(L1)，替代2.5克共单体三(4-乙烯基苯)基膦，其余的催化剂合成过程与实施例1相同。
实施例3
在实施例3中，除了称取0.1克自由基引发剂偶氮二异丁腈替代1.0克自由基引发剂偶氮二异丁腈外，其余的催化剂制备过程与实施例1相同。
实施例4
在实施例4中，除了用50.0ml四氢呋喃溶剂替代100.0ml四氢呋喃溶剂外，其余的催化剂制备过程与实施例1相同。
实施例5
在实施例5中，除了用100.0ml二氯甲烷溶剂替代100.0ml四氢呋喃溶剂外，其余的催化剂制备过程与实施例1相同。
实施例6
在实施例6中，除了用393K聚合温度替代373K聚合温度外，其余的催化剂制备过程与实施例1相同。
实施例7
在实施例7中，除了用12h聚合时间替代24h聚合时间外，其余的催化剂制备过程与实施例1相同。
实施例8
在实施例8中，除了再加入10.0克L20作为交联剂外，其其余的催化剂制备过程与实施例1相同。
实施例9
在实施例9中，除了再加入1.0克苯乙烯作为交联剂外，其余的催化剂制备过程与实施例1相同。
实施例10
在实施例10中,称取14.05毫克乙酰丙酮二羰基钴替代乙酰丙酮三羰基铑溶于10.0ml四氢呋喃溶剂外，其余的催化剂合成过程与实施例1相同。
实施例11
在实施例11中,称取2.05毫克乙酰丙酮三羰基铱替代乙酰丙酮三羰基铑溶于10.0ml四氢呋喃溶剂外，其余的催化剂合成过程与实施例1相同。
实施例12
将上述制备的催化剂0.5g固定床反应器中，两端装入石英砂。微量进料泵泵入1-辛烯，其流量为0.1ml/min，质量流量计控制合成气(体积比H2:CO＝1:1)空速1000h-1，在373K，1MPa条件下进行氢甲酰化反应。反应经冰浴冷却的收集罐收集。所获得液体产品采用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析，采用正丙醇作内标。收集罐出来的尾气采用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析。反应结果列于表1。
实施例13
将上述制备的催化剂0.5g装入到固定床反应器中，两端装入石英砂。通入反应混合气(体积比H2:CO:C3H6＝1:1:1)，在393K，1.0MPa，反应混合气空速2000h-1条件下进行氢甲酰化反应。反应经一个装有60ml冷却的去离子水的收集罐吸收收集，反应产物全部溶于收集罐的水中。所获得水溶液采用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析，采用乙醇作内标。经水吸收后反应尾气采用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析。反应结果列于表2。
实施例14
将上述制备的催化剂0.5g固定床反应器中，两端装入石英砂。微量进料泵泵入2-辛烯，其流量为0.1ml/min，质量流量计控制合成气(体积比H2:CO＝1:1)空速1000h-1，在373K，1MPa条件下进行氢甲酰化反应。反应经冰浴冷却的收集罐收集。所获得液体产品采用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析，采用正丙醇作内标。收集罐出来的尾气采用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析。反应结果列于表3。
表1实施例1-11中合成的催化剂比表面积和1-辛烯反应数据
Figure PCTCN2015095604-appb-000009
Figure PCTCN2015095604-appb-000010
*实验条件为100℃，1MPa，1-辛烯流量为0.1ml/min，合成气(CO:H2＝1:1)空速1000h-1，TOF计算时认为所有的金属均是活性位点。**表示反应温度为230℃,实施例10的活性组分为Co,实施例11的活性组分为Ir。
表2实施例1-11中合成的催化剂比表面积和丙烯反应数据
Figure PCTCN2015095604-appb-000011
*实验条件为120℃，1MPa，配气(丙烯:CO:H2＝1:1:1)空速2000h-1，TOF计算时认为所有的金属均是活性位点。**表示反应温度为230℃,实施例10的活性组分为Co,实施例11的活性组分为Ir。
表3实施例1-11中合成的催化剂比表面积和2-辛烯反应数据
Figure PCTCN2015095604-appb-000012
Figure PCTCN2015095604-appb-000013
*实验条件为100℃，1MPa，2-辛烯流量为0.1ml/min，合成气(CO:H2＝1:1)空速1000h-1，TOF计算时认为所有的金属均是活性位点。**表示反应温度为230℃。实施例10的活性组分为Co,实施例11的活性组分为Ir。

Claims (10)

  1. 一种含膦有机混聚物-金属多相催化剂，其特征在于:所述多相催化剂中以金属Rh、Co或Ir中的一种、两种、三种作为活性组分，以含膦有机混聚物为载体，含膦有机混聚物由含有烯烃基的多齿有机膦配体和含有烯烃基的单齿有机膦配体共聚而成，催化剂中金属担载量范围为0.01～10wt％。
  2. 按照权利要求1所述的多相催化剂，其特征在于：所述的烯烃基为乙烯基官能团。
  3. 按照权利要求1或2所述的多相催化剂，其特征在于：所述的含有烯烃基的多齿有机膦配体为含有乙烯基的二齿亚磷酸酯有机磷配体，所述的含有烯烃基的单齿有机膦配体为含有乙烯基的三苯基膦配体。
  4. 按照权利要求1所述的多相催化剂，其特征在于：所述的有机混聚物载体具有多级孔结构，比表面积为100～3000m2/g，孔容为0.1～5.0cm3/g，孔径分布在0.2～50.0nm。
  5. 一种权利要求1-4任一所述多相催化剂的制备方法，其特征在于：所述的多相催化剂是将多齿有机膦配体和单齿有机膦配体混合后，采用溶剂热聚合法，经自由基引发剂引发有机膦配体中的烯烃基发生聚合反应，生成具有多级孔结构含膦有机混聚物作为载体，活性组分的前驱体与载体在有机溶剂中搅拌，活性组分与含膦有机混聚物载体中裸露的P形成多重配位键，蒸去挥发性溶剂后，得到配位键型的多相催化剂。
  6. 按照权利要求5所述多相催化剂的制备方法，其特征在于：
    a)在273～473K，惰性气体气氛下，在有机溶剂中，加入单齿有机膦配体和多齿有机膦配体、添加或不添加交联剂、再加入自由基引发剂，混合后，将混合物搅拌0.1～100小时，优选的搅拌时间范围为0.1～50小时；
    b)将步骤a)制得的混合溶液转移至合成高压釜中，273～473K，惰性气体气氛下，采用溶剂热聚合法，静置1～100小时进行聚合反应，得到一种含膦有机混聚物；
    c)将步骤b)得到的混聚物，在室温条件下真空抽除溶剂，即得到具有多级孔结构的含有裸露P的有机混聚物，即所述多相催化剂的载体；
    d)在273～473K，惰性气体气氛下，在含有活性组分前驱体的溶剂中，加入步骤c)得到的有机混聚物载体，搅拌0.1～100小时，优选搅拌时间范围0.1～50小时，之后，真空抽除有机溶剂，得到多相催化剂。
  7. 按照权利要求6所述的制备方法，其特征在于：步骤a)中所述的有机溶剂为苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上；所述的交联剂为苯乙烯、乙烯、丙烯、二乙烯基苯、二甲氧基甲烷、二碘甲烷、多聚甲醛或1,3,5-三乙炔基苯中的一种或两种以上；所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或两种以上。
  8. 按照权利要求6所述的制备方法，其特征在于：步骤a)中所述的单齿有机膦配体和多齿有机膦配体的摩尔比为0.01:1～100:1，在交联剂添加的情况下，单齿有机膦配体与交联剂的摩尔比为0.01:1～10:1，单齿有机膦配体与自由基引发剂的摩尔比为300:1～10:1，聚合成有机混聚物前，单齿有机膦配体在有机溶剂中的浓度范围为0.01-1000g/L。
  9. 按照权利要求6所述的制备方法，其特征在于：步骤d)中所述的溶剂为水、苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上，所述的活性组分为Rh、Co、Ir中的一种或两种以上，其中Rh的前驱体为Rh(CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3；Co的前驱体为Co(CH3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2；Ir的前驱体为Ir(CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4，催化剂中金属担载量范围为0.01～10wt％。
  10. 按照权利要求1-4任一所述多相催化剂在烯烃氢甲酰化反应中的应用。
PCT/CN2015/095604 2015-04-03 2015-11-26 一种含膦有机混聚物-金属多相催化剂及其方法和应用 WO2016155339A1 (zh)

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CN110982105B (zh) * 2019-11-06 2022-07-29 华侨大学 一种负载钌纳米粒子的催化剂
CN112898138B (zh) * 2019-12-03 2022-09-27 中国科学院大连化学物理研究所 一种费托产物高值化利用的方法
CN112892604B (zh) * 2019-12-03 2022-09-20 中国科学院大连化学物理研究所 一种有机胺和co2多相催化制甲酰胺的方法
CN113877635B (zh) * 2021-10-27 2024-02-06 南京延长反应技术研究院有限公司 一种铱基催化剂及其制备方法、醛化方法
CN116178623A (zh) * 2021-11-26 2023-05-30 中国科学院大连化学物理研究所 一种膦配体有机聚合物和应用
CN115873221B (zh) * 2021-12-17 2024-06-04 浙江新和成股份有限公司 一种含磷聚合物及其制备方法和应用
CN116410390B (zh) * 2021-12-31 2024-05-10 中国石油天然气股份有限公司 有机膦配体聚合物及二齿膦配体共聚物催化剂的制备方法
CN114591159B (zh) * 2022-03-10 2023-04-07 中国科学院大连化学物理研究所 利用氧化膦聚合物负载型催化剂进行内烯烃氢甲酰化反应的方法

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