WO2016155337A1 - 一种内烯烃氢甲酰化制备高正异比醛的方法 - Google Patents

一种内烯烃氢甲酰化制备高正异比醛的方法 Download PDF

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WO2016155337A1
WO2016155337A1 PCT/CN2015/095595 CN2015095595W WO2016155337A1 WO 2016155337 A1 WO2016155337 A1 WO 2016155337A1 CN 2015095595 W CN2015095595 W CN 2015095595W WO 2016155337 A1 WO2016155337 A1 WO 2016155337A1
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olefin
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phosphine
catalyst
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丁云杰
李存耀
严丽
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
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    • 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
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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Definitions

  • 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 continuous development of olefin hydroformylation reaction is mainly driven by the petrochemical industry.
  • the petroleum cracking process and the Fischer-Tropsch synthesis process produce a large amount of olefins, which provide cheap synthetic raw materials for hydroformylation and industrialization.
  • the material base at the same time, the product aldehyde of the olefin hydroformylation reaction is a very useful chemical intermediate, which can be used to synthesize carboxylic acid and corresponding esters, as well as fatty amines.
  • the most important use is that it can be hydrogenated into Alcohols, alcohols themselves can be widely used in the field of fine chemicals as organic solvents, plasticizers and surfactants.
  • Patent CN1319580A describes a plurality of bidentate phosphite ligands with large steric hindrance, which are hydroformylated with higher olefins of a coordinated homogeneous catalyst such as Rh and Co. The selectivity of the ratio. 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.
  • Billig et al. of UCC Corporation (Joint Carbide Corporation) synthesized biphephos ligands, which have excellent performance in the hydroformylation of propylene.
  • Arno Behr and Christian Vogl et al. further systematically studied the formulation using biphephos ligands.
  • a phosphine-containing organic polymer-metal heterogeneous catalyst one, two or three kinds of metals Rh, Co or Ir as active components, a phosphine-containing organic mixture as a carrier, and a metal catalyst in a catalyst
  • 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 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 mixture of a polydentate organophosphine ligand and a monodentate organophosphine ligand, and a solvothermal polymerization method is used to initiate polymerization of an olefin group in the organophosphine ligand by a radical initiator to form
  • the multi-stage pore structure contains a phosphine organic mixed polymer as a carrier, the precursor of the active component and the carrier are stirred in an organic solvent, and the active component forms a multi-coordination bond with the exposed P in the phosphine-containing organic polymer carrier, and is evaporated. After the volatile solvent, a heterogeneous catalyst of the coordination bond type is obtained.
  • 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 prepared P-containing organic hybrid carrier-supporting active metal catalyst is used in the internal olefin hydroformylation reaction, has high catalytic activity and good product selectivity, and can be used for fixed bed, slurry bed, bubbling bed and trickle flow. Bed reaction process.
  • the reaction temperature is 323 to 573 K
  • the reaction pressure is 0.1 to 10.0 MPa
  • the gas space velocity is 100 to 20000 h -1
  • the liquid hourly space velocity is 0.01 to 10.0 h -1 .
  • the main component of the reaction raw material synthesis gas is H 2 and CO, and further contains one or more of N 2 , He, CO 2 and Ar, and the volume content of (H 2 +CO) is 20 to 100%, H 2 .
  • the /CO volume ratio is from 0.5 to 5.0.
  • the raw material internal olefins are mainly derived from C 4 to C 20 olefins in the process of petroleum catalytic cracking, Fischer-Tropsch synthesis, refinery dry gas recovery, etc.
  • the double bonds may be located at positions 2 to 10 of the carbon chain, and also contain C4 to C20.
  • the process and method have strong adaptability, and can be one of C 4 - C 20 internal olefins (including terminal olefins) or several kinds, the purity of the raw materials is 20-100%, and the product is mainly one carbon atom than the raw material olefin. Normal aldehyde.
  • 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.
  • the organophosphine mixed polymer has both the dual functions of a carrier and a ligand, and the active metal component is highly dispersed in the carrier to form 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 coordination-type heterogeneous catalyst is suitable for a reaction process such as a fixed bed, a slurry bed, a bubbling bed and a trickle bed, and the process and method for producing the corresponding aldehyde by hydroformylation of the internal olefin provided by the present invention can be used.
  • a reaction process such as a fixed bed, a slurry bed, a bubbling bed and a trickle bed
  • the internal olefin is first isomerized to a terminal olefin in a hydroformylation reaction, thereby selectively producing a higher value normal aldehyde. It solves the problems of long-term reactivity and selectivity in the process of multi-phase formation of internal olefin hydroformylation, and serious loss of metal components.
  • the heterogeneous catalyst provided by the invention has a good performance in the internal olefin hydroformylation reaction, and the internal olefin is in this class. Under the action of the catalyst, the isomerization to the terminal olefin is first carried out, and the hydroformylation reaction is further carried out to selectively form the corresponding normal aldehyde. Therefore, the product aldehyde has a high aspect ratio and can be higher than 15, and the obtained product has an alkane content. Below 1%, the heterogeneous catalyst has good stability, and the separation of the catalyst from the reactants and products is simple and efficient. The production cost of normal aldehyde is greatly reduced, and a new industrialization technology is provided for the hydroformylation reaction of internal olefins.
  • 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 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 product obtained by liquid separation and the organic phase is evaporated to remove the solvent, and purified by silica gel column chromatography, using silica gel as a stationary phase and ethyl acetate/petroleum ether (volume ratio 1:10) as a mixed solvent.
  • the eluent is finally obtained as a white powdery solid, which 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
  • Example 2 except that 10.0 g of the comonomer tris(4-vinylphenyl)phosphine (L1) was weighed, instead of 2.5 g of the comonomer tris(4-vinylphenyl)phosphine (L1), the rest The catalyst synthesis process was the same as in Example 1.
  • Example 3 the synthesis 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 catalyst synthesis procedure 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 6 the catalyst synthesis 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 catalyst synthesis 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 9 the catalyst synthesis process was the same as in Example 1 except that 1.0 g of styrene was further added as a crosslinking agent.
  • 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 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 1.
  • the catalyst prepared in Examples 1-11 was placed in a 0.5 g fixed bed reactor, and both ends were charged with quartz sand.
  • the micro feed pump is pumped into cis-4-hexene at a flow rate of 0.1 ml/min.
  • the hydroformylation reaction is carried out.
  • 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 2.

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Abstract

本发明公开了一种内烯烃氢甲酰化制高正异比醛的方法,所述方法使用的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，以多级孔结构含膦有机混聚物作为载体，含膦有机混聚物由含有烯烃基的多齿有机膦配体和单齿有机膦配体共聚而成。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器中。本发明提供的多相催化剂在内烯烃氢甲酰化反应中具有很好的表现，内烯烃在此类催化剂的作用下先异构化为端基烯烃，再发生氢甲酰化反应选择性地生成相应的正构醛，因此产品醛的正异比高，可高于15，得到的产物中烷烃含量低于1％。

Description

一种内烯烃氢甲酰化制备高正异比醛的方法 技术领域
本发明属于多相催化及精细化工领域，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其在内烯烃氢甲酰化制高正异比醛生产中的应用。
背景技术
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不断发展主要得益于石油化学工业的推动，石油裂解工艺及Fischer-Tropsch合成工艺产生大量的烯烃，为氢甲酰化反应提供了廉价的合成原料，使其工业化具备了物质基础；同时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。
专利CN1319580A叙述了具有较大空间位阻的多种二齿亚磷酸酯配体，这些配体与Rh和Co等配位均相催化剂的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。
2001年，Holger Klein等人(Angew.Chem.Int.Ed.2001,40,No.18)合成了NAPHOS型的均相配体，该类配体与Rh络合后在端基烯烃及内烯烃氢甲酰化反应中取得了很好的选择性(产品醛的正异比很高)。但是催化体系本质上还是均相反应，催化剂回收困难，高碳烯烃包括内烯烃氢甲酰化反应成本很高。
UCC公司(联合碳化物公司)的Billig等人合成了Biphephos配体，该配体在丙烯氢甲酰化反应中性能优异，Arno Behr及Christian Vogl等人利用Biphephos配体进一步系统地研究了该配体与Rh配合后催化内烯烃及端基烯烃的氢甲酰反应(Journal of Molecular Catalysis A:Chemical,2003,206,179-184；2005,232,41-44；2005,226,215–219)，产物醛的立体选择性好，并且Arno Behr及Christian Vogl还在两相烯烃氢甲酰化方面做了一些探索工作。但是始终没有从根本上解决均相催化剂多相化的问题，催化剂失活很快，并且没有实现催化剂的循环使用。
内烯烃的氢甲酰化一直是研究的难点与热点，化学工作者们在应用于内烯烃氢甲酰化反应的均相的多齿配体合成方面倾注了大量心血，但目前还没有专门针对于内烯烃氢甲酰化反应的多相催化剂及工艺出现。
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在内烯烃氢甲酰化制高正异比醛生产中的应用。
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共聚(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)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，形成的催化剂在内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％)。
制备出的含P有机混聚物载体负载活性金属的催化剂用于内烯烃氢甲酰化反应中，催化活性高，产品选择性好，可用于固定床，浆态床，鼓泡床和滴流床反应工艺中。反应温度323～573K，反应压力0.1～10.0MPa，气体空速100～20000h-1,液时空速0.01～10.0h-1。反应原料合成气的主要组分为H2和CO，还含有N2、He、CO2、Ar中的一种或二种以上，(H2+CO)体积含量为20～100％，H2/CO体积比为0.5～5.0。原料内烯烃主要来源于石油催化裂解、费托合成、炼厂干气回收等过程的C4～C20的烯烃，双键可以位于碳链的2～10号位置上，还含有C4～C20的烷烃中的一种或二种以上。本工艺及方法原料适应性强，可以为C4～C20内烯烃中的一种(包括端基烯烃)或几种，原料纯度为20～100％，产品主要为比原料烯烃多一个碳原子的正构醛。
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，活性金属组分可能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，本发明所提供的内烯烃氢甲酰化生产相应醛的工艺及方法，可使用固定床，浆态床，鼓泡床和滴流床等反应工艺，内烯烃在氢甲酰化反应首先异构化为端基烯烃，进而选择性的生成附加值较高的正构醛，可以解决内烯烃氢甲酰化反应多相化过程中长期存在的反应活性和选择性差，以及金属组分流失严重等问题。
本发明提供的多相催化剂在内烯烃氢甲酰化反应中具有很好的表现，内烯烃在此类 催化剂的作用下先异构化为端基烯烃，再发生氢甲酰化反应选择性地生成相应的正构醛，因此产品醛的正异比高，可高于15，得到的产物中烷烃含量低于1％，该多相催化剂稳定性好，催化剂与反应物、产品的分离简单而且高效。大大降低了正构醛的生产成本，为内烯烃氢甲酰化反应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 PCTCN2015095595-appb-000001
和B：
Figure PCTCN2015095595-appb-000002
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 PCTCN2015095595-appb-000003
C与
Figure PCTCN2015095595-appb-000004
反应并用硅胶柱纯化可得D：
Figure PCTCN2015095595-appb-000005
用乙醇溶液中，KOH存在下用LiH4Al还原D可得E：
Figure PCTCN2015095595-appb-000006
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进行聚合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载体。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克由Vinyl Biphephos和三(4-乙烯基苯)基膦共聚得到的有机混聚物载体，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，即获得应用于内烯烃氢甲酰化反应的优良催化剂。
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(L1)，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，其余的催化剂合成过程与实施例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，其余的催化剂合成过程与实施例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，其余的催化剂合成过程与实施例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，其余的催化剂合成过程与实施例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，其余的催化剂合成过程与实施例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，其余的催化剂合成过程与实施例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，其余的催化剂合成过程与实施例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1。
实施例13
将实施例1-11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cis-4-己烯，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2。
表1 实施例1-13中合成的催化剂比表面积和2-辛烯反应数据
Figure PCTCN2015095595-appb-000007
*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。
表2 实施例1-13中合成的催化剂比表面积和cis-4-己烯反应数据
Figure PCTCN2015095595-appb-000008
*实验条件为100℃，1MPa，cis-4-己烯流量为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. 一种内烯烃氢甲酰化制备高正异比醛的方法，其特征在于：在含膦有机混聚物-金属多相催化剂存在下进行反应，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所述的方法,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所述的方法,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所述的方法，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. 按照权利要求1所述的方法，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所述的方法，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；
    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％。
  8. 按照权利要求6所述的方法，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1所述的方法，其特征在于：内烯烃的氢甲酰化反应，反应温度为 323～573K，反应压力为0.1～10.0MPa，气体空速为100～20000h-1,液时空速为0.01～10.0h-1，反应原料合成气的主要组分为H2和CO，(H2+CO)体积含量为20～100％，H2/CO体积比为0.5～5.0，原料内烯烃为C4～C20的烯烃，双键位于碳链的2～10号位置上，内烯烃原料纯度为20～100％，产品主要为比原料烯烃多一个碳原子的正构醛。
  10. 按照权利要求9所述的方法，其特征在于：混合气中还含有N2、He、CO2、Ar中的一种或二种以上；原料内烯烃中还含有C4～C20的烷烃中的一种或二种以上。
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