A small obstacle, high boiling point, strong coordination, bulky organic phosphine ligand and preparation and application

Abstract

The application discloses a small-obstacle, high-boiling-point, strong coordination and large-volume organic phosphine ligand, a preparation method and application thereof, and belongs to the technical field of petroleum chemical industry. According to the basic research on the molecular level of the catalytic system of the reactions of the carbonyl synthesis of long-chain olefin to prepare high-grade fatty alcohol and the selective oligomerization of ethylene to prepare 1-octene, new concepts that the catalyst should have small obstacle, strong coordination and high-boiling-point or large volume are discovered, and 30 novel organic phosphine ligands are invented. PH3 (trihydrogen phosphorus) which can generate high-purity phosphine ligand is used as a phosphorus source, a process preparation method of 'ring first and tail later','saturated absorption' and'reaction distillation' integration is invented, and an application example of one of the process preparation methods in a catalytic system for the carbonyl synthesis of n-dodecene to prepare alcohol and the selective tetramerization of ethylene to prepare 1-octene is disclosed.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical catalysis, specifically relating to an organophosphorus ligand with small vacancy, high boiling point, strong coordination or large volume, and its preparation method and application. Background Technology

[0002] US Patent No. 3,418,351. Shell has invented a cobalt-phosphine catalyst and a technology for recycling the catalyst after it completes the single-pass olefin carbonylation synthesis to higher alcohols and the evaporation and separation of the higher alcohol products back into the reactor. The patent holder of this prior art maintains absolute secrecy regarding the structure of the ligands used in industrial production and the industrial manufacturing method. Even in 2023, after more than fifty years of industrial production, no patent for the industrial manufacturing method has been published. However, this catalytic system suffers from drawbacks such as slow reaction rate and high catalyst consumption. To improve these shortcomings, it is necessary to understand the reasons for these drawbacks. Without any prior knowledge of this catalytic system, this invention can only employ a conventional catalytic system composed of tributylphosphine and cobalt naphthenate, starting with fundamental research to explore the basic principles of the microscopic elementary reactions in the carbonylation synthesis of higher alcohols from long-chain olefins.

[0003] The basic research conducted in this invention includes: 1) Xue Shunqing, Li Dagang, Wu Guangxun, and others used high-pressure in-situ IR technology to investigate the elementary reaction steps of olefin carbonyl synthesis to alcohol (aldehyde), confirming that the reaction is completed by the following four steps: ① The olefin molecule is coordinated to HCo(CO)nL. (L is a phosphine ligand) ② The π-coordinated olefin adds to the Co-H bond to generate alkyl cobalt L(CO)nCoR. ③ The coordinated carbon monoxide CO inserts into the Co-R bond to generate L(CO)nCoCOR. ④ L(CO)nCoCOR undergoes hydrogenolysis to generate aldehyde RCHO or the aldehyde group is reduced to an alcohol and HCo(CO)nL. (See Journal of Catalysis, In-situ Infrared Spectroscopic Study on the Generation Mechanism of Cobalt-phosphine Catalysts, Vol. 5, No. 4, pp. 355-362).

[0004] 2) Li Dagang, Xia Chungu, Sun Yanwen, et al. used high-pressure in-situ NMR and IR techniques to capture the signal of MH (M = Rh, Co, Ni), confirming that HM(CO)nL (M = Rh, Co, Ni; L represents phosphine ligand) plays the role of a catalytically active cyclic species. (See *Acta Physico-Chimica Sinica*) In-situ catalytic activity of olefin hydroformylation catalysts 1 (H-NMR Research, Vol. 12, No. 1, pp. 355-362).

[0005] 3) Li Dagang, Kou Yuan, Liu Shufa, and others used high-pressure in-situ IR technology to study and found that the stability of the catalyst is in a positive relationship with the electron-donating ability of the organophosphorus ligand (L). The stronger the coordination ability of the ligand, the better the stability of the catalyst. Its catalytic activity for carbonyl synthesis to alcohols is also higher. Among the known organophosphorus ligands, the trialkyl-coordinated organophosphorus has the strongest coordination ability, and its catalyst with the central cobalt metal exhibits the best stability and the highest catalytic activity. Therefore, it can be determined that to improve the stability of Co-P catalysts, a phosphorus ligand with strong coordination ability is required, and a trialkyl tertiary phosphine with all three substituents being alkyl must be used as the ligand for the central cobalt metal to meet the requirements for catalyst stability. (Molecular Catalysis, Vol. 11, No. 3, "Relationship between Structure and Activity of Organophosphorus Coordination Catalysts, Report No. 2").

[0006] To reduce catalyst consumption, it is necessary to develop high-boiling-point catalysts (at least 50°C higher than the boiling point of the product higher alcohols). To this end, this invention investigated the carbon number of ligands in the synthesis of alcohols from olefin carbonyl groups and its structure-activity relationship. The experimental results are listed in Table 1.

[0007] Table 1. Structural effects of ligands in olefin carbonyl synthesis to alcohol production.

[0008]

[0009] Catalyst: Co-P-KOH, Co concentration: 0.2%, P / Co = 2:1 (mol), solvent: 2EH, reaction temperature: 175℃, reaction pressure: 6MPa, reaction time: 5h.

[0010] Three questions arise regarding the experimental results in Table 1:

[0011] (1) Why do the alcohol yield and olefin conversion decrease significantly when tri-n-butylphosphine (24 carbon atoms) and tri-n-dodecylphosphine (36 carbon atoms) are replaced with tri-n-butylphosphine (12 carbon atoms)? (See Table 1, 1-3)

[0012] (2) When two of the straight-chain alkyl groups of the three alkyl substituents of tertiary phosphine are cyclically linked to form a cyclic secondary phosphine, the Co-P catalyst prepared with this ligand exhibits an alcohol yield that is 7-8 percentage points higher than that of tri-n-butylphosphine. Why then, when the number of carbon atoms of the alkyl substituent in another chain is increased, or even when a fused-ring aromatic hydrocarbon is introduced into the branch, is there no significant effect on the activity of olefin carbonyl synthesis (see 5-10 in Table 1)?

[0013] (3) Why is the catalytic activity of short-chain propylene significantly higher than that of long-chain dodecene under the same carbonylation reaction conditions when using the same Co-P catalyst with tri-n-octylphosphine ligand (see Table 1, 2 and 4)?

[0014] If it is confirmed that the first elementary step of this reaction, as described in the basic research of this invention, involves the oxidative addition reaction of the double bond in the alkene with the MH bond in the catalytically active substance, then the three "why" questions can be readily answered. The reason is that the conformation formed by the three straight-chain alkyl substituents of phosphine, due to σ-rotation, creates a momentary steric hindrance to the Co-H bond at the active site of the catalyst, thus preventing the double bond of the long-chain alkene molecule from undergoing the elementary addition reaction. Furthermore, as the number of carbon atoms in the three substituents of the phosphine ligand increases, the steric hindrance to this oxidative addition elementary reaction becomes greater (see Table 1, 2, 3), thus further reducing its catalytic activity. It can be inferred that when the other two substituents are ring-shaped, preventing σ-rotation, this momentary steric hindrance is eliminated. Adding the third substituent at this point only increases the steric hindrance in one direction. In the other two directions, long-chain olefins can still undergo elementary addition reactions with Co-H bonds, thus showing that simply increasing the chain length of an alkyl substituent has no significant effect on its catalytic activity (see Tables 1, 5, 6, 7, and 8). This indicates that the carbonyl synthesis of alcohols from long-chain olefins requires organophosphine ligands with small steric barriers. The concept of small steric barriers is thus proposed.

[0015] The explanation for the third question is that steric hindrance has little effect on the carbonylation of short-chain olefins, hence the higher reactivity of propylene in carbonylation.

[0016] The above fundamental research leads to a new concept: ligands for catalysts used in the carbonyl synthesis of alcohols from long-chain olefins require three key characteristics: small vacancy barriers, high boiling points, and strong coordination. How can organophosphorus ligands possessing all three essential properties be developed?

[0017] The answer is: Transforming the new insights and concepts discovered in the aforementioned basic research into innovative technological ideas: This patent's new understanding of the ligands of catalysts for the carbonyl synthesis of alcohols from long-chain olefins into innovative technological ideas includes:

[0018] 1) The tooth base is made of trivalent P atoms.

[0019] 2) All three substituents of the P atom should be alkyl groups to achieve strong coordination and enhance the stability of the coordination catalyst.

[0020] 3) Two of the three alkane substituents of phosphine are cyclized to form a small vacancy barrier.

[0021] 4) Use an ultra-long chain or high molecular weight inert group as the third substituent to meet the requirements of high boiling point (or large volume) of the catalyst.

[0022] The above ideas led to the following technological inventions. Summary of the Invention

[0023] The purpose of this invention is to overcome the above-mentioned technical deficiencies and provide a solution to the technical problems of poor catalytic effect of organophosphorus ligands in the prior art, and low purity or low yield of catalysts during preparation.

[0024] To achieve the above-mentioned technical objectives, the present invention provides an organophosphorus ligand with small vacancy, high boiling point, strong coordination, or large volume. The organophosphorus ligand consists of a cyclic secondary phosphine group and a high-molecular-weight substituent group. The cyclic secondary phosphine group includes the following structure:

[0025] (1)C5H 10 The structural formula for P is as follows:

[0026]

[0027] (2) C7H10P is 8-phospho-tricyclooctane, with the following structural formula:

[0028]

[0029] (3) The structural formula of P(CH2CH2)3CH is as follows:

[0030]

[0031] (4) The structural formula of P(CH2CH2CH2)3CH is as follows:

[0032]

[0033] (5) The structural formula of P{(CH2CH2)2(CH2CH2CH2)}CH is as follows:

[0034]

[0035] (6) The structural formula of PC4H4 is as follows:

[0036]

[0037] (7)C8H 14 The structural formulas of P for 9-phosphine bicyclic [3, 3, 1]nonane and 9-phosphine bicyclic [4, 2, 1]nonane are as follows:

[0038]

[0039] (8) The structural formula of [(CH2)nP]n=3-11 is as follows:

[0040]

[0041] (9) The structural formula of the phosphane macrobicyclic compound -{C[(CH2)n]3P}n=2-5 is as follows:

[0042]

[0043] (10) The structural formula of silicon-phosphine heterobicyclic-{Si[(CH2)n]3P}n=2-5 is as follows:

[0044]

[0045] (11) The structural formula of the oxygen-phosphine heterocyclic (C2H4O2P) is as follows:

[0046]

[0047] The high molecular weight substituents include the following groups:

[0048] (1) Long-chain alkane group; -C n H 2n+1 n is a positive integer from 1 to 25;

[0049] (2) Aromatic groups: phenyl-C6H5, naphthyl: -C 10 H7;

[0050] (3) Fused ring aromatic groups; anthracene, phenanthrene, pyrene and fluorenyl groups and their alkyl derivatives.

[0051] (4) Alkyl-containing fused-ring aromatic derivatives; -(CH2)nW, n = 2-25 positive integers, W is one of anthraquinone, phenanthrene, pyrene, and fluorene.

[0052] The chemical formula of the organophosphorus ligand is one of those listed in the table below;

[0053]

[0054]

[0055] Wherein, the structural formula is C 18 H 37 -[Si(C2H4)3P], Ph3C-[Si(CH2CH2)3P], C 16 H9-[Si(CH2CH2)3P], C 14 H9-[Si(CH2CH2)3P], C 14 Any organophosphorus ligand in H9-[Si(CH2CH2)3P] can be used to compose a cobalt-phosphine-potassium catalyst in the form of a high carbon alcohol. This catalyst is not sensitive to air and can greatly save production and investment costs.

[0056] This patent discloses a method for preparing tertiary phosphine ligands containing cyclic secondary phosphine and macromolecular substituted groups, as described above. While several prior art methods have been disclosed for laboratory synthesis, no industrial-scale preparation method has been reported. One feature of this patent is the disclosure of a manufacturing process for producing organic tertiary phosphine ligands with cyclic secondary phosphine structures on an industrial scale.

[0057] The technology for industrial-scale manufacturing of tertiary phosphine ligands includes: the selection of phosphorus source materials, the determination of industrial-scale synthesis routes, and the invention of industrial preparation processes.

[0058] This patent focuses on the production of high-purity phosphine ligands, therefore PH3 is preferred as the phosphorus source.

[0059] The industrial-scale synthetic route, as can be seen from the general formula, indicates that the organophosphorus ligands designed based on fundamental research consist of three different structures: dentate groups, phosphine heterocyclic groups, and alkane substituents. A multi-step synthetic process is required to prepare the complete structure.

[0060] To determine a reasonable synthetic route for the industrial preparation of organophosphorus ligands, this invention has specifically developed a high-pressure in-situ NMR pneumatic sample tube, the structure of which is as follows: Figure 1 As shown, it can be used as a miniature autoclave for gas-liquid phase chemical reactions, and also as a sample tube for NMR spectroscopy. (See Li Dagang, Xia Chungu, and Sun Yanwen, CN 88209283.9, 1989; Xia Chungu and Li Dagang, “Research on Pressure In-situ NMR Technology and Its Applications”, Journal of Spectroscopy, Vol.13, No.5, Oct.1996).

[0061] This new experimental technique is used for the synthesis of the patented phosphine ligand, which is highly toxic and extremely sensitive to air. Its outstanding advantage is that it eliminates the need for product separation and post-processing, and allows for the acquisition of NMR signals of the main product and all byproducts at any time, greatly improving the accuracy and efficiency of the experimental results.

[0062] Due to the inherent physicochemical properties of these organophosphine ligands—1) highly toxic, 2) flammable and explosive, 3) extremely sensitive to air, 4) high boiling point, 5) difficult to purify by distillation, and 6) requiring high purity—a complex, oxygen- and water-free synthesis process is necessary. Furthermore, the multi-step synthesis introduces many uncertainties for the industrial-scale preparation of ligands with this unique structure. Therefore, the choice of synthetic route using PH3 as the phosphine source—whether to synthesize the cyclic phosphine first (ringing first) or the high-molecular-weight substituent first (tailing)—becomes a crucial initial issue.

[0063] Because no relevant patents with similar titles for the industrial preparation of organophosphorus compounds have been found in the past fifty years, experimental investigation is necessary to determine the accurate synthetic route. This is to ensure the safety and high efficiency of the industrial manufacturing of highly toxic and air-sensitive organophosphorus ligands.

[0064] The experimental results of investigating the synthetic route of 18-alkyl-9-phosphine bicyclic nonane ligands using high-pressure in-situ NMR technology are listed below. Figure 2 and Figure 3 .Compare Figure 2 and 3 visible, Figure 2 The phosphine ligands synthesized via the "tail-to-loop" method have relatively high impurities. Figure 3 The "ring-first, tail-later" synthetic route yields significantly more phosphine ligands. Therefore, the "ring-first, tail-later" synthetic route is preferred in this invention.

[0065] The so-called "cyclic-tailed" synthetic route is characterized by a two-stage process for manufacturing organophosphorus ligands with small cavities, high boiling points, and strong coordination. (Listed in...) Figure 4 .

[0066] Depend on Figure 4 As can be seen, the first stage involves a free radical addition reaction between phosphine and a non-conjugated straight-chain diene, cyclic diene, or triene, generating a secondary phosphine heterocyclic compound (proximal ring) with a small vacancy barrier function, such as a monocyclic, bicyclic, or tricyclic phosphine. The second stage involves introducing a high-molecular-weight long-chain alkyl or polycyclic aryl group (tailing) into the phosphine heterocyclic compound to generate an organophosphine ligand with a high boiling point or large volume, a trivalent tertiary phosphine.

[0067] In 1996, the inventors of this patent, Yan Xianglan, Li Dagang, and others, published a low-pressure method for preparing organophosphine compounds, authorized by publication number CN1032424C. This method uses a solution saturated with phosphine to carry out free radical addition reactions with various olefins, reducing the reaction pressure from 30.0 MPa to 1.0-3.0 MPa, and achieving better reaction results.

[0068] The inventors of this patent, Li Dagang and Li Song, obtained the patent CN108456228A, "A small-barrier organophosphorus ligand and its preparation method and its application in the production of 1-octene and 1-hexene from ethylene," on October 29, 2020, which also achieved good results.

[0069] This invention is a follow-up to patents CN1032424C and CN108456228A: To improve the efficiency of free radical initiators and the purity of the target product, a tubular reactor with segmented temperature control is designed. The key feature is that one tubular reactor is replaced with three reactors connected in series and parallel, each with its own independently controllable reaction temperature. The temperature control program is that the first reactor has a lower reaction temperature, while the third reactor has a higher temperature. This saturated absorption process is further extended to the synthesis of monocyclic secondary phosphines from linear unsaturated dienes and the one-step production of cyclic organotertiary phosphines from non-conjugated trienes.

[0070] The second stage added a distillation stirring and blowing device and a device for replenishing initiator at any time to improve distillation efficiency. It also expanded its application to the preparation of organotertiary phosphine derivatives containing long-chain or high-molecular-weight fused-ring aromatic hydrocarbons.

[0071] The characteristics of the first stage of the preparation process are as follows:

[0072] To improve the accuracy of the ratio of phosphine (PH3) to dienes in continuous production, British Patent 1,561,674 (1980) describes a continuous preparation process. This process involves preparing primary and secondary phosphine from phosphine under high pressure. First, phosphine, which is gaseous at normal conditions, is compressed into liquid phosphine (pressure 8.0–30.0 MPa). This liquid phosphine, along with liquid olefin reactants and a free radical initiator, is precisely proportioned according to the molecular weight of the reactants and introduced into the reactor. The reaction time is 13–15 times the half-life of the initiator, and the reaction temperature is 90–190 °C. In the reaction of phosphine with 1,5-cyclooctadiene, the conversion rate of 1,5-cyclooctadiene is 90%, and the product contains 96% 9-phosphine-bicyclononane. A problem with this technology is the high pressure of the phosphine (8.0–30.0 MPa), requiring the phosphine gas to be compressed and liquefied. Even a small leak of phosphine under high pressure can have serious consequences for the environment and personal safety. At the same time, the maintenance of high-pressure equipment containing highly toxic substances is extremely difficult.

[0073] The first stage of this invention is designed with four processes: gas-liquid saturation absorption, raw material premixing according to the reaction ratio, reaction process, and product gas-liquid separation. The gas-liquid saturation absorption process uses a gas-liquid mixer to thoroughly mix the reaction solvent at a specific temperature and pressure until the solvent is saturated to absorb phosphine. The raw material premixing process involves injecting the saturated phosphine-absorbing solvent into a raw material mixing tank, maintaining the tank temperature 10-15°C below room temperature. Since the phosphine content in the saturated absorbent is a function of absorption temperature and pressure, the ratio of olefins to phosphine and free radical initiators in the reaction solution can be controlled. The mixture is injected into the first reactor using a cryogenic pump. Depending on the type of initiator, parallel or serial reactors are selected, and different reaction temperatures are set for each stage. The product separation process involves separating unreacted phosphine from the liquid product under room temperature and vacuum conditions and then storing it in a cryogenic system.

[0074] The characteristics of the process in the second stage are:

[0075] The second stage of this invention involves a tailing reaction, whereby the phosphonoheterocyclic secondary phosphine product obtained in the first stage is introduced with a high-molecular-weight straight-chain terminal alkene or aromatic group to obtain a high-boiling-point or large-volume tertiary phosphine. The invention employs an oxygen- and water-free integrated reaction-distillation stirred tank, with intermittent operation to complete the tailing reaction. Since the target product has the highest boiling point, vacuum distillation is performed after the reaction to remove the solvent, unreacted phosphonoheterocyclic secondary phosphine, and low-boiling-point impurities. The remaining liquid at the bottom of the tank is the small-barrier, high-boiling-point, strongly coordinated, or large-volume tertiary phosphine target product of this patent. To improve distillation separation efficiency, a distillation stirring and blowing device or a molecular distillation device is added. This process can be extended to tailing high-molecular-weight polycyclic aromatic hydrocarbons.

[0076] Figure 5 The process of preparing small-barrier, high-boiling-point, strongly coordinated or large-volume organic tertiary phosphine ligands, consisting of the first and second stages, includes the following steps.

[0077] 1) Mix the solvent with a non-conjugated diene or triene in a pre-mixed ratio;

[0078] 2) At a fixed temperature of 5℃ and a fixed pressure, a powerful gas-liquid mixer is used to saturate the phosphine in the liquid phase;

[0079] 3) The saturated absorbent mixture and initiator are simultaneously pumped into a pipeline reactor, and the reaction of phosphine with olefins is carried out at a fixed temperature of 50–150℃ and a pressure of 0–10 MPa. Initiators may include, but are not limited to, azobisisobutyronitrile, azobisisopentanolitrile, azobisisoheptanenitrile, azoisobutylcyanoformamide, azobiscyclohexylformitrile, and dimethyl azobisisobutyrate. The molar ratio of initiator to olefin is 0.01–1.

[0080] 4) The reaction liquid is separated into gas and liquid phases, and the unreacted phosphine is recovered and sent to the cryogenic section;

[0081] 5) The bicyclic secondary phosphine product obtained in step 3) is fed into a batch-operated reactor and an initiator is added to carry out a second-step reaction with a high molecular weight terminal alkene or its derivative to obtain an organic tertiary phosphine with small vacancy, high boiling point and strong coordination.

[0082] 6) After the reaction, in-situ vacuum distillation is performed to separate the solvent, unreacted cyclic secondary phosphine, high molecular weight olefins and low boiling point impurities. The residue at the bottom of the vessel is the target product, tertiary phosphine.

[0083] Based on the applications of the organophosphine ligands described above, these ligands can be applied to cobalt-phosphine-potassium ternary catalytic systems and / or chromium-phosphine-activator ternary catalytic systems. The cobalt-phosphine-potassium ternary catalytic system comprises the aforementioned organophosphine ligand, zero-valent cobalt metal, and potassium hydroxide; under the following operating conditions with H2:CO = 2:1 (mol) syngas:

[0084] Catalyst: Co-P-KOH, Co concentration: 0.01~1.0%, P / Co=2∶1(mol), solvent: 2EH, reaction temperature: 100~250℃, reaction pressure: 3~10MPa, reaction time: 3~10h.

[0085] The chromium-phosphorus-activator ternary catalyst system comprises an organic tertiary phosphine ligand, a chromium source, and an activator; the reaction conditions are as follows:

[0086] Chromium isooctanoate:phosphine ligand:activator = 1:2:500 (mol); solvent: methylcyclohexane; reaction temperature: 50-180℃, reaction pressure: 4.0-8.0MPa, reaction time: 1-5h.

[0087] Based on the organophosphine ligands described above for use in the cobalt-phosphine-potassium ternary catalytic system, similar applications can be extended to the preparation of macromolecular compounds from small molecules, such as ligands for the selective tetramerization of ethylene to 1-octene. This is because the smaller the vacancy barrier of the transition metal coordination catalyst in this catalytic reaction, the more favorable it is for the formation of macromolecules. Otherwise, a large vacancy barrier in the coordination catalyst itself will interfere with the self-assembly of small molecules into macromolecules. (See Li Dagang and Li Song, "A Small-Vacancy Organophosphine Ligand and Its Preparation Method and Its Application in the Production of 1-Octene and 1-Hexene from Ethylene", CN108456228A, authorized on October 19, 2020)

[0088] This invention inherits the small-barrier ligand technology from CN108456228A and develops it into a small-barrier, strongly coordinated, large-volume organophosphine ligand, used to modulate molecular self-assembly during catalyst formation at the chromium center. This results in a monodentate phosphine with a small barrier, sufficiently large volume, and strong coordination ability, preventing two identical ligands from self-assembling in an angular coordination region, and instead forming ligands such as (…). Figure 5 A linear dual-coordination configuration allows four π-ethylene groups to form a single active center, thereby improving the selectivity of 1-octene.

[0089] The structural innovations of phosphine ligands used in the catalytic system for the selective tetramerization of Cr-based ethylene to octene are listed in Tables 2-6.

[0090] 1-1. The general structural formula of a monocyclic small-barrier organophosphorus ligand is as follows:

[0091]

[0092] Table 2. Organophosphorus ligands with small cavities on a single ring

[0093]

[0094]

[0095] 1-2. The general molecular formula of silicon-containing lantern-shaped small vacancy barrier high-boiling-point strongly coordinated phosphine ligands is as follows:

[0096]

[0097] Table 3. Silicon-containing lantern-shaped small vacuoles, high boiling point, and strongly coordinated phosphine ligands.

[0098]

[0099] 1-3. Lantern-shaped, small-barrier, high-boiling-point, strongly coordinated phosphine ligands, with the following general structural formula:

[0100]

[0101] Table 4. Small Barrier High-Boiling-Point Strongly Coordinated Phosphine Ligands in Lantern Structure

[0102]

[0103] 1-4. The general structural formula of tricyclic small-barrier organophosphorus ligands is as follows:

[0104]

[0105] Table 5. Structure of Organophosphorus Ligands with Tricyclic Small Barrier

[0106]

[0107] 1-5. The general structural formulas of bicyclic small-barrier high-boiling-point organophosphorus ligands are as follows:

[0108] or / and

[0109] Table 6 Bicyclic Small Barrier High-Boiling-Point Organophosphine Ligands

[0110] Attached Figure Description

[0111] Figure 1 This is a schematic diagram of the structure of a high-pressure in-situ NMR pneumatic sample tube provided by the present invention.

[0112] Figure 2 The in-situ NMR 31P spectrum of the "tail-first, ring-later" product in Comparative Example 1 is shown in the specific implementation.

[0113] Figure 3 The in-situ NMR 31P spectrum of the "ring-tail" product in Example 1 of the specific implementation method is shown.

[0114] Figure 4 This is a schematic diagram of the structure of an apparatus for preparing organophosphorus ligands with small cavities, high boiling points, strong coordination, and large volume, according to the present invention.

[0115] Figure 5 This is a coordination diagram of the ethylene tetramerization of 1-octene by an organophosphorus ligand with small cavities, high boiling point, strong coordination, and large volume, as described in this invention.

[0116] The components include: 1. Gas source; 2. Vacuum pump; 3. Gas filling valve; 4. Pressure gauge; 5. Test tube; 6. Heating tube; 7. Temperature control; 8-1. Premixing vessel; 8-2. Saturated absorber; 8-3. Initiator feeder a; 8-4. Tubular reactor; 8-5. Water bath; 8-6. Gas-liquid separator; 8-7. Initiator feeder b; 8-8. Reaction distillation vessel; 8-9. Condenser. Detailed Implementation

[0117] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0118] Example 1

[0119] An organic tertiary phosphine ligand with a cyclic secondary phosphine group, its molecular formula is C 18 H 37 -P-C5H 10 The equipment used in its preparation process, such as Figure 5 As shown, its preparation method includes the following steps;

[0120] (1) Degassed n-pentadiene was injected into a premixing reactor 8-1 at a flow rate of 5.56 mol / h and degassed solvent at a flow rate of 15.2 mol / h. The mixture was then pumped into a saturated absorber 8-2 at a flow rate of 2.0 kg / h using a metering pump. Simultaneously, azobisisobutyronitrile (AIBN) initiator was added using initiator feeder a 8-3 while maintaining a temperature of 5±3℃. Phosphorus trihydrogenate gas was injected at a pressure of 1.6 MPa. The gas-liquid mixer was started to bring the liquid to saturation absorption pH 3. The saturated absorbent was stored in an absorbent storage tank at 5±3℃ and 1.6 MPa. The saturated absorbent mixture was injected into a tubular reactor 8-4 at a flow rate of 2.01 kg / h using a diaphragm feed pump. A water bath 8-5 was used to maintain the temperature in the pipeline at 70–80℃ and the pressure at 3.0 MPa. The mixture flows from the outlet of tubular reactor 8-4 into gas-liquid separator 8-6, where a very small amount of unreacted phosphorus trihydrogenase gas is separated and returned to the liquid nitrogen cryogenic storage and purification unit. The conversion rate of 1,5-cyclooctadiene is 92%, and the concentration of polycyclic phosphine generated in the reaction solution, analyzed by capillary chromatography, is 25-30% (by weight), with a selectivity >90%.

[0121] (2) After the oxygen content in the reaction distillation vessel 8-8 is degassed and purified to below 3 ppm, the reaction begins the batching operation. The initiator is added through initiator feeder b 8-7, and the initial raw material ratio of the reaction reaches the following standard (mol%):

[0122] Toluene solvent: initiator: octadecene-1: cyclic secondary phosphine = 35: 2.0: 42: 21. Initial reaction pressure: 0.5 MPa high-purity nitrogen. Reaction temperature: 60–190 °C depending on the initiator. Reaction time: Samples of the reaction solution were taken and analyzed twice at 30-minute intervals. The reaction was terminated when the target product no longer increased, and the solution was condensed in condensers 8 and 9.

[0123] After the reaction, in-situ atmospheric and vacuum distillation is performed to remove the solvent, unreacted cyclic secondary phosphine, high molecular weight olefins, and low-boiling-point impurities. The residue at the bottom of the reactor is the target product, tertiary phosphine. Based on a 1,4-pentadiene starting material, the overall molar yield of the target product in the two-step reaction is no less than 70%.

[0124] Comparative Example 1

[0125] By swapping steps (2) and (1) in the examples, a "tail-first, ring-later" preparation method was adopted, and then the purity and yield of the products obtained in Example 1 and Comparative Example 1 were analyzed.

[0126] The in-situ NMR 31P spectrum in Comparative Example 1 is as follows: Figure 2 As shown, the in-situ NMR 31P spectrum in Example 1 is as follows: Figure 3 As shown.

[0127] It is evident that the "ring-first, tail-later" process yields a higher purity target product, while the "tail-first, ring-later" process produces a final product with more impurities. A comparison of the two processes is as follows:

[0128] First ring then tail 20 60-70％ >95％ 84～85％ Tail first, then ring 13 90％ 83％ 72～73％

[0129] Example 2

[0130] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is triphenylmethyl-ethyl-6-phosphine monocyclohexane [(Ph)3C-C2H4-Ph3C-CH2CH2-P-C5H 10 The preparation method is the same as in the example, except that in this example, triphenylmethylethylene is used instead of octadecene.

[0131] Example 3

[0132] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is triphenylmethyl-6-phosphine monocyclohexane (Ph3C-P-C5H10). The secondary phosphine product, -6-phosphine monocyclohexane, was obtained directly from the product of Example 1 in the first step. The tertiary phosphine, triphenylmethyl-6-phosphine monocyclohexane, was prepared using the Woltz process.

[0133] Operating steps: Take the HPC7H prepared in Example 1 12 2.0 mol of cyclophosphine, to a solution containing HPC7H 12 A 1.6 M hexane solution of 4.5 L (7.2 mol) BuLi was added to a Schlenk container containing 3 mL of THF solution over 5 min, and the mixture was stirred at -78 °C for 40 min. Then, 2 L of a THF solution containing 2.6 mol of 1-bromotriphenylmethane (Ph3CBr) was added. The mixture was allowed to rise to room temperature overnight. Extraction was performed with 40 L of anhydrous diethyl ether, and the organic phase was dried over sodium carbonate. C5H was obtained by vacuum distillation. 10 PC-CPh3, yield 60%.

[0134] Example 4

[0135] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-pyrene-6-phosphine monocyclohexane (C 16 H9-P-C5H 10 The preparation method is the same as in Example 3, except that 1-Br-C bromopyrene is used. 16 The title product 1-pyrene-6-phosphine monocyclohexane can be prepared by substituting H9 for Ph3CBr, with a yield of 61%.

[0136] Example 5

[0137] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-pyrene-ethyl-6-phosphine monocyclohexane C16 H9-CH2CH2-PC5H 10 The preparation method was the same as in Example 2, except that 1-vinylpyrene was used instead of triphenylmethylethylene. The yield of the target product was 59%.

[0138] Example 6

[0139] An organotertiary phosphine ligand with a cyclic secondary phosphine group is 9-anthrayl-ethyl-6-phosphine monocyclohexane 9-C 14 H9-CH2CH2-PC5H 10 The preparation method was the same as in Example 2, except that 9-vinyl-anthracene was used instead of triphenylmethylethylene. The yield of the target product was 58%.

[0140] Example 7

[0141] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 9-phenanthyl-6-phosphine monocyclohexane 9-C. 14 H9-PC5H 10 The industrial preparation method is the same as in Example 3, except that 1-bromotriphenylmethane is replaced with 9-bromo-phenanthroline. The yield of the target product was 58%.

[0142] Example 8

[0143] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-phenanthrene-ethyl-6-phosphine monocyclohexane (C 14 H9-CH2CH2-PC5H 10 ).

[0144] C 14 H9-CH2CH2-PC5H 10 The preparation method was the same as in Example 2, except that 9-vinyl-phenanthrene was used instead of triphenylmethylethylene. The yield of the target product was 58%.

[0145] Example 9

[0146] A method for preparing an organic tertiary phosphine ligand with a cyclic secondary phosphine group, namely phenyl-4-silyl-1-phosphine bicyclo-[2,2,2]-octane C6H5-[Si(CH2CH2)3P]:

[0147] A 1.6 M hexane solution of BuLi (4.5 mL, 7.2 mmol) was added over 5 min to a Schlenk container containing a 3 mL THF solution of P(CH2CH2)3SiH, and the mixture was stirred at -78 °C for 40 min. Then, 2 mL of a THF solution containing 2.6 mmol of 1-bromobenzene (PhBr) was added. The mixture was allowed to rise to room temperature overnight. Extraction was performed with 40 mL of anhydrous diethyl ether, and the organic phase was dried over sodium carbonate. C6H5-[Si(CH2CH2)3P] was obtained by vacuum distillation. Yield: 50%.

[0148] The preparation methods for derivatives such as C6H5-[Si(CH2CH2CH2)3P and C6H5-{[Si[(CH2)n]3}P n=2~5 are the same as those described above.

[0149] Example 10

[0150] An organotertiary phosphine ligand with a cyclic secondary phosphine group is an 18-alkyl-4-silyl-1-phosphine bicyclo[2,2,2]octane C 18 H 37 The preparation method of -[Si(C2H4)3P] is the same as that of Example 09, except that 18-ene-1 is used instead of 1-bromobenzene.

[0151] Example 11

[0152] An organic tertiary phosphine ligand with a cyclic secondary phosphine group, Ph3C-[Si(CH2CH2)3P], was prepared using the same method as in Example 09, except that a bromotriphenyl group was used instead of 1-bromobenzene. The yield of the title product was 70%.

[0153] Example 12

[0154] An organotertiary phosphine ligand with a cyclic secondary phosphine group is a 1-pyrene-4-silyl-1-phosphine bicyclic [2,2,2]octane C 16 The preparation method of H9-[Si(CH2CH2)3P] is the same as in Example 09, except that 1-bromopyrene is used instead of 1-bromobenzene. The yield of the title product is 60%.

[0155] Example 13

[0156] An organotertiary phosphine ligand with a cyclic secondary phosphine group is a 9-anthrayl-4-silyl-1-phosphine bicyclic [2,2,2]octane C 14 The preparation method of H9-[Si(CH2CH2)3P] is the same as in Example 09, except that 9-bromoanthracene is used instead of 1-bromobenzene. The yield of the title product is 62%.

[0157] Example 14

[0158] An organotertiary phosphine ligand with a cyclic secondary phosphine group is 1-phenanthyl-4-silyl-1-phosphine bicyclo[2,2,2]octane C. 14 The preparation method of H9-[Si(CH2CH2)3P] is the same as in Example 09, except that 1-bromophenanthroline is used instead of 1-bromobenzene. The yield of the title product is 59%.

[0159] Example 15

[0160] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 18-alkyl-4-carbon-1-phosphine-bicyclo[2,2,2]octane C. 18 H 37 The preparation method of -[C(C2H4)3P] or CnHn+1-[C2H4)m]3P, n=1~40; m=2~5, is the same as that in Example 10, except that 1-phosphine-bicyclo[2,2,2]octane is used instead of 4-silicon-1-phosphine-bicyclo[2,2,2]octane. The yield of the title product is 60%.

[0161] Example 16

[0162] An organic tertiary phosphine ligand with a cyclic secondary phosphine group, triphenylmethyl-4-carbon-1-phosphine-bicyclo[2,2,2]octane Ph3C-[C(CH2CH2)3P], was prepared by the same method as in Example 10, except that 18-ene-1 was replaced with bromotriphenylmethane. The yield of the title product was 57%.

[0163] Example 17

[0164] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-pyrene-4-carbon-1-phosphine-bicyclo[2,2,2]octane. 16 The preparation method of H9-[C(CH2CH2)3P] is the same as that in Example 16, except that 1-bromopyrene is used instead of bromotriphenylmethane. All other operations are the same as in Example 10. The yield of the title product is 60%.

[0165] Example 18

[0166] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 9-anthrayl-4-carbon-1-phosphine-bicyclo[2,2,2]octane C. 14The preparation method of H9-[C(CH2CH2)3P] is the same as that in Example 16, except that 1-bromoanthracene is used instead of bromotriphenylmethane. All other operations are identical to those in Example 16. The yield of the title product is 57%.

[0167] Example 19

[0168] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-phenanthrene-4-carbon-1-phosphine-bicyclo[2,2,2]octane C. 14 The preparation method of H9--[C(CH2CH2)3P] is the same as that in Example 16, except that 1-bromophenanthrene is used instead of bromotriphenylmethane. All other operations are the same as in Example 10. The yield of the title product is 60%.

[0169] Example 20

[0170] An organic tertiary phosphine ligand with a cyclic secondary phosphine group, namely octadecyl-8-phosphine tricyclooctane C 18 H 37 -(PC7H 10 The preparation method is the same as in Example 1, except that norbornene is used instead of pentadiene. Title compound yield: 72%.

[0171] Example 21

[0172] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is triphenylmethyl-ethyl-8-phosphine tricyclooctane Ph3C-CH2CH2-P-C7H 10 The preparation method is the same as in Example 20, except that octadecene-1 is substituted with benzyl. The yield of the title compound is 65%.

[0173] Example 22

[0174] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-pyrene-ethyl-8-phosphine tricyclooctane C. 16 H9-CH2CH2-PC7H 10 The preparation method is the same as in Example 20, except that 1-vinylpyrene is used instead of octadecene-1. The yield of the title compound is 60%.

[0175] Example 23

[0176] An organotertiary phosphine ligand with a cyclic secondary phosphine group, namely 9-anthrayl-8-phosphine tricyclooctane C 14 H9-P-C7H 10 The preparation method is the same as in Example 03, except that 9-bromo-anthracene is replaced with bromotriphenylmethane and norbornene is replaced with pentadiene. The yield of the title compound is 59%.

[0177] Example 24

[0178] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-phenanthrene-ethyl-8-phosphine tricyclooctane C. 14 H9-CH2CH2-PC7H 10 The preparation method is the same as in Example 20, except that 1-ethylene-phenanthrene is substituted for octadecene-1. The yield of the title compound is 57%.

[0179] Example 25

[0180] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is triphenylmethyl-ethyl-9-phosphine-bicyclononane, C 18 H 37 -P-C8H 14 The preparation method is the same as in Example 1, except that 1,5-cyclooctadiene replaces pentadiene and triphenylmethylethylene replaces octadecene. The total molar yield of the two-step reaction, based on 1,5-cyclooctadiene as the starting material, is 70%.

[0181] Example 26

[0182] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1-pyrene-ethyl-9-phosphine bicyclo-nonane C. 16 H9-CH2CH2-P-C8H 14 The preparation method is the same as in Example 25, except that 1-vinylpyrene is replaced with triphenylmethylethylene. The yield of the target product is 58%.

[0183] Example 27

[0184] An organic tertiary phosphine ligand with a cyclic secondary phosphine group is 1,8-alkyl-9-phosphine bicyclo-nonane Ph3C-CH2CH2-P-C8H. 14 The preparation method is the same as in Example 25, except that octadecene is used instead of triphenylmethylethylene to obtain the title product. Yield: 59%.

[0185] Example 28

[0186] An organotertiary phosphine ligand with a cyclic secondary phosphine group is 9-anthrayl-ethyl-9-phosphine bicyclo-nonane 9-C. 14 H9-CH2CH2-P-C8H 14 The manufacturing method is the same as in Example 25. The title product can be obtained by replacing only 9-vinylanthracene with triphenylmethyl-ethylene, with a yield of 55%.

[0187] Example 29

[0188] An application of an organic tertiary phosphine ligand is disclosed in a chromium-phosphorus-activator ternary catalyst system, wherein the chromium-phosphorus-activator ternary catalyst system comprises an organic tertiary phosphine ligand, a chromium source, and an activator.

[0189] Operating instructions:

[0190] A 500ml stainless steel autoclave was cleaned and vacuum-dried at 120℃ for three hours, then cooled to room temperature. In a glove box, (1) chromium source material (Cr), (2) organophosphorus ligand (L), and (3) activator (A) were dissolved in a specified amount of dry methylcyclohexane solvent according to the required molar ratio and stored in 100ml syringes, sealed with silicone rubber. At room temperature, (1) and (2) were first injected into the autoclave, and 0.3MPa ethylene was immediately introduced, followed by three stirring and displacement cycles. The oxygen content in the ethylene gas phase inside the autoclave was measured using a micro-oxygen analyzer, and was required to be below 3ppm. After passing the test, activator (3) was added using a pressure bomb under an ethylene atmosphere, and ethylene was immediately introduced to pressurize to 2.5MPa. The temperature was rapidly increased to the design temperature (40-80℃), the reaction pressure was controlled at 5.0MPa, the stirring speed was >500rpm, and the reaction was stopped after 30 minutes. The autoclave was then cooled to 0℃. After capturing the emitted gas phase, add an appropriate amount of isooctanol or 30 ml of 10% HCl to kill the activator. Take a liquid sample for chromatographic analysis, weigh the organic phase product, and dry and weigh the filtered byproduct PE. Calculate the amounts of gaseous, liquid, and solid products, catalytic activity, product distribution percentage, and the purity of 1-octene and 1-hexene.

[0191] Chromium source materials can be selected individually: CrCl3(THF)3, CrCl2(THF)2, Cr(acac)3, Cr(HA)3.

[0192] The activator (A) can be selected alone: ​​(2) methylaluminoxane (MAO or MMAO-3A), (3) alkylaluminum (triethylaluminum or triisobutylaluminum), or (4) DMAO. Alternatively, a mixture of (1) and (3) can be selected.

[0193] (Al) / Cr is 100-500 (mol); L / Cr is 2 / 1 (mol); Chromium concentration: 30 mmol

[0194] Evaluation results of the catalyst system for ethylene oligomerization reaction in this embodiment

[0195]

[0196]

[0197] Catalytic system: Chromium : Phosphine ligand : Activator = 1 : 2 : 500 (mol)

[0198] Reaction temperature: 45℃, reaction pressure: 4.0MPa, reaction time: 30min.

[0199] Example 30

[0200] An application of an organic tertiary phosphine ligand, wherein the cobalt-phosphine-potassium ternary catalytic system comprises the organic tertiary phosphine ligand, zero-valent cobalt metal, and potassium hydroxide.

[0201] After cleaning the 1.0L autoclave with 2EH solvent, a 2EH solution of cobalt isooctanoate, organophosphine ligand, and potassium hydroxide was vacuum-filled. The autoclave was then evacuated and purged until the oxygen content of the synthesis gas inside reached 1 mg / m³. 3 Pressurize to 3.0 MPa, stir and heat to 170°C, and after 30 min, press in 1-12 olefins. Maintain pressure at 6.0 MPa and temperature at 180–190°C. After reacting for 5 h, cool to room temperature and press out the reaction solution. Weigh and analyze the liquid phase product using capillary chromatography.

[0202] The catalytic effects of organophosphorus ligands in the carbonyl synthesis of olefins to alcohols using Co-P catalysts are as follows;

[0203]

[0204] Catalyst: Co-P-KOH, Co concentration: 0.2%, P∶Co=2∶1 (mol), solvent: 2EH, reaction temperature: 180-190℃, reaction pressure: 6.0MPa, reaction time: 5h.

[0205] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. An organophosphorus ligand with small vacancy, high boiling point, strong coordination, and large volume, characterized in that, The organophosphine ligand structure is selected from:

2. An application based on the organophosphorus ligand of claim 1, characterized in that, The organophosphine ligand is used in a catalytic system for the selective tetramerization of ethylene to prepare 1-octene.

3. The application according to claim 2, characterized in that, The catalytic system is a chromium-phosphorus-activator ternary catalyst system, which includes the organophosphorus ligand, chromium source and activator.

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