CN116284136A - A small space barrier, high boiling point, strong coordination, large volume organic phosphine ligand and its preparation method and application - Google Patents

Abstract

The invention discloses a small-space barrier, high-boiling point, strong-coordination and large-volume organic phosphine ligand, a preparation method and application thereof, and belongs to the technical field of petrochemical industry. According to the basic research of the molecular level of a catalytic system for the reactions of synthesizing higher fatty alcohol by long-chain olefin carbonyl and selectively oligomerizing ethylene to prepare 1-octene and the like by using the novel experimental techniques of high-pressure in-situ IR and high-pressure in-situ NMR, the invention discovers that the catalyst has novel concepts of small air barrier, strong coordination, high boiling point or large volume and the like, and accordingly, 30 organic phosphine ligands with novel structures are invented. By adopting phosphorus tri-hydride (PH 3) capable of generating high-purity phosphine ligand as phosphorus source, the invention discloses a process preparation method integrating 'first ring and then tail', 'saturated absorption' and 'reactive distillation', and an application example of one of them in preparing alcohol by n-dodecene oxo synthesis and preparing 1-octene by ethylene selective tetramerization.

Description

A small space barrier, high boiling point, strong coordination, large-volume organic phosphine ligand and its preparation method and application

technical field

The invention belongs to the field of petrochemical catalysis, and in particular relates to an organic phosphine ligand with small space barrier, high boiling point, strong coordination or large volume, its preparation method and application.

Background technique

U.S.Pat.No.3,418,351. SHELL company invented cobalt-phosphine catalyst and the technology that the catalyst can return to the reactor for recycling after completing the one-way carbonylation of olefins to produce higher alcohols and the evaporation and separation of higher alcohol products. The patentee of this prior art keeps the structure of the ligand used in industry and the industrial method absolutely confidential. Industrial production has reached more than fifty years so far in 2023, and there is no patent announcement of industrial manufacturing method. However, the catalytic system has the disadvantages of slow reaction speed and high catalyst consumption. For improving above-mentioned shortcoming, must find out the reason that produces above-mentioned shortcoming. Without the knowledge of the catalytic system, the present invention can only adopt the conventional catalytic system composed of tributylphosphine and cobalt naphthenate, and start with basic research to explore the method of producing higher alcohols by carbonylation of long-chain olefins Basic laws of microscopic elementary reactions.

The basic research carried out by the present invention includes: 1) Xue Shunqing, Li Dagang, Wu Guangxun, etc. used high-pressure in-situ IR technology to investigate the elementary reaction steps of olefin carbonylation to produce alcohol (aldehyde), and confirmed that the reaction is completed by the following four steps : ①Alkene molecules are coordinated to HCo(CO)nL. (L is a phosphine ligand) ②Addition of π-coordinated alkenes to Co-H bonds produces alkyl cobalt L(CO)nCoR. ③ Coordinated carbon monoxide CO is inserted into the Co-R bond to generate L(CO)nCoCOR. ④L(CO)nCoCOR is hydrogenolyzed to generate aldehyde RCHO or the aldehyde group is reduced to alcohol and HCo(CO)nL. (See Acta Catalytica Sinica, "In-Situ Infrared Spectroscopy Study on the Formation Mechanism of Cobalt-phosphine Catalysts", Volume 5, Issue 4, 355-362).

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), and confirmed that HM(CO)nL (M=Rh, Co, Ni; L represents phosphine Ligands) function as catalytically active cycling species. (See "Acta Physicochemical Sinica", "In-Situ ¹ H-NMR Study on Catalytic Active Substances of Olefin Hydroformylation", Volume 12, Issue 1, 355-362).

3) Li Dagang, Kou Yuan, Liu Shufa, etc. used high-pressure in-situ IR technology to study the stability of the catalyst and the electron-donating ability of the organophosphine ligand (L). The stronger the coordination ability of the ligand, the stronger the catalyst The better the stability. Its oxo-alcohol catalytic activity is also higher. Among the known organophosphine ligands, the organophosphine with the strongest coordination ability is the trialkyl-coordinated organophosphine, and the catalyst coordinated to the central metal cobalt has the best stability and the highest catalytic activity. It can be determined from this: in order to improve the stability of the Co-P catalyst, a phosphine ligand with strong coordination ability is required, and a trialkyl tertiary phosphine whose three substituents are all alkyl must be used as the coordination of the central metal cobalt The body can meet the demand for the qualitative of the catalyst. ("Molecular Catalysis", Volume 11, Issue 3, "The Relationship between the Structure and Activity of Organophosphine Coordination Catalysts, The Second Report").

In order to reduce the consumption quota of the catalyst, it is necessary to develop a catalyst with a high boiling point. (at least 50°C higher than the boiling point of the product higher alcohols) For this reason, the present invention has carried out the investigation of increasing the number of carbon atoms and the structure-activity relationship of the olefin oxo-synthesis alcohol ligand, and the experimental results are listed in Table 1.

Table 1 Structural effects of olefin oxo synthesis alcohol ligands

Catalyst: Co-P-KOH, Co concentration: 0.2%, P/Co=2:1 (mol), solvent: 2EH, reverse temperature: 175°C, reverse pressure: 6MPa, reverse time 5h.

There are three questions about the experimental results in Table 1:

(1) Replace tri-n-butylphosphine ligand (12 carbon atoms) with tri-n-octylphosphine (24 carbon atoms) and tri-n-dodecylphosphine ligand (36 carbon atoms) with high carbon number. Why did the yield of alcohol and the conversion of olefins decrease significantly in sequence (see 1-3 in Table 1)?

(2) When the two straight-chain alkyl groups in the three alkyl substituents of the tertiary phosphine are ringed to form a cyclic secondary phosphine, the Co-P catalyst made with this ligand has a higher alcohol yield than Tri-n-butylphosphine 7-8 percentage points. At this moment, when the number of carbon atoms of the alkyl substituent of another chain is increased, or even when condensed ring aromatics are introduced into the branched chain, why does it have no obvious effect on the activity of olefin oxo synthesis (see 5-10 in Table 1)?

(3) Also use the Co-P catalyst of tri-n-octylphosphine ligand, why under the same carbonylation reaction conditions, the catalytic activity of short-chain propylene is significantly higher than that of long-chain dodecene (see Table 1-2 and 4)?

If it is believed that the first elementary step of this reaction is as described in the basic research of the present invention, the double bond in the alkene must carry out the oxidative addition reaction with the M-H bond in the catalytic active substance, then these three why problems can be easily solved . The reason is that the three straight-chain alkyl substituents of the phosphine, due to the conformation formed by the σ-rotational movement, will create an instantaneous steric barrier to the Co-H bond on the active site of the catalyst, thus preventing the double bond of the long-chain olefin molecule from proceeding to the basic unit. Addition reaction. Moreover, as the number of carbon atoms in the three substituents of the phosphine ligand increases, the steric barrier to the oxidative addition elemental reaction will be greater (see Table 1, 1, 2, 3), so its catalytic activity will further decrease. From this, it can be imagined that when the other two substituents are ringed together, it cannot perform σ-rotation, thereby eliminating this instantaneous steric barrier. At this moment, when increasing the number of carbon atoms of the third substituent, it can only increase the steric barrier in one direction. However, long-chain olefins in the other two directions can still carry out basic addition reactions with Co-H bonds, thus showing that the chain length of an alkyl substituent alone has no significant impact on its catalytic activity (see Table 1-5, 6, 7, 8). It can be seen that the oxo-to-alcohol reaction of long-chain olefins requires organophosphine ligands with small steric barriers. The concept of small air barriers was proposed.

The explanation for the third question is that steric barriers have little effect on the carbonylation reaction of short-chain olefins, so the carbonylation reaction activity of propylene is relatively high.

From the above basic research, it can be concluded that the ligands used in the catalysts of long-chain olefin carbonylation to produce alcohol need a new concept with three major characteristics: small space barrier, high boiling point and strong coordination. How can an organophosphine ligand with these three essential properties be developed at the same time?

The answer is: transform the new cognitions and new concepts unearthed in the above-mentioned basic research into the ideas of technological innovation: this patent transforms the new cognitions of the ligands of the catalyst for the carbonylation of long-chain olefins into alcohols into the ideas of technological innovations have:

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

2) The three substituents of the P atom should all be selected from the alkyl group, so as to achieve the requirements of strong coordination and enhanced stability of the coordination catalyst.

3) Two of the three alkane substituents of the phosphine are ringed to form the function of a small space barrier.

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

Produce following technical invention according to above-mentioned idea.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned technical deficiencies and provide a method to solve the technical problems of poor catalytic effect of organophosphorus ligands and low purity or low yield during catalyst preparation in the prior art.

In order to achieve the above technical purpose, the technical scheme of the present invention provides a small space barrier, high boiling point, strong coordination or bulky organic phosphine ligand, the organic phosphine ligand is composed of a cyclic secondary phosphine group and A large molecular weight substituent group, the cyclic secondary phosphine group includes the following structure:

(1) The structural formula of C ₅ H ₁₀ P is as follows:

(2) C7H10P is 8-phosphorus-tricyclooctane, the structural formula is as follows:

(3) The structural formula of P(CH ₂ CH ₂ ) ₃ CH is as follows:

(4) The structural formula of P(CH ₂ CH ₂ CH ₂ ) ₃ CH is as follows:

(5) The structural formula of P{(CH ₂ CH ₂ ) ₂ (CH ₂ CH ₂ CH ₂ )}CH is as follows:

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

(7) C ₈ H ₁₄ P is the structural formula of 9-phosphine bicyclo [3,3.1] nonane and 9-phosphine bicyclo [4,2,1] nonane as follows:

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

(9) The structural formula of phosphine heterobicyclic compound -{C[(CH ₂ )n] ₃ P}n=2-5 is as follows:

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

(11) The structural formula of oxygen-phosphine heteromonocycle (C ₂ H ₄ O ₂ P) is as follows:

The substituting group of described large molecular weight comprises following groups:

(1) Long-chain alkane group; -C _n H _2n+1 , n=a positive integer of 1 to 25;

(2) Aromatic hydrocarbon group: phenyl-C ₆ H ₅ , naphthyl: -C ₁₀ H ₇ ;

(3) Fused ring aromatic groups; anthracenyl, phenanthrenyl, pyrenyl, fluorenyl, etc. and their alkyl derivatives

(4) Alkyl-containing condensed ring aromatic hydrocarbon derivatives; -(CH2)nW, n=2-25 positive integer, W is one of anthracene, phenanthrene, pyrene, and fluorenyl.

Wherein, the chemical formula of the organophosphine ligand is one of the following tables;

Among them, the structural formula is C ₁₈ H ₃₇ -[Si(C ₂ H ₄ ) ₃ P], Ph ₃ C-[Si(CH ₂ CH ₂ ) ₃ P], C ₁₆ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P], C ₁₄ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P], C ₁₄ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P], any organophosphorus ligand can be used The catalyst is not sensitive to air and can greatly save production and investment costs.

A preparation method based on the above-mentioned tertiary phosphine ligands containing ring secondary phosphine and macromolecular group substitutions. The laboratory synthesis method has been disclosed in many prior art, but the preparation method on an industrial scale has not yet been seen. one report. One of the characteristics of this patent is that it discloses a manufacturing process for producing organic tertiary phosphine ligands with a cyclic secondary phosphine structure on an industrial scale.

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

This patent focuses on the production of high-purity phosphine ligands, so preferably PH3 is the phosphorus source.

The determination of the industrial-scale synthesis route can be seen from the general formula that the organic phosphine ligand designed based on basic research is composed of three different structures such as a halide group, a phosphine heterocyclic group and an alkane substituent. The complete structure must be prepared through a multi-step synthetic operation.

In order to determine a reasonable synthetic route for the industrial preparation of organic phosphine ligands, the present invention has successfully developed a high-pressure in-situ NMR pneumatic sample tube. Its structure is shown in Figure 1, and it itself can be used as a miniature autoclave. It can be used for gas-liquid phase chemical reaction, and can also be used as a nuclear magnetic test sample tube for NMR spectrum testing. (See Li Dagang, Xia Chungu, Sun Yanwen CN 88209283.9, 1989; Xia Chungu, Li Dagang "Research on Pressurized In-Situ NMR Technology and Its Application" Journal of Spectroscopy Vol.13, No.5Oct.1996).

This new experimental technology is used for the synthesis research of the highly toxic and air-sensitive phosphine ligand of this patent. Its outstanding advantage is that there is no need for product separation and post-processing operations, and the main product of the reaction and all by-products can be obtained at any time. The NMR signal greatly improves the accuracy and efficiency of the experimental results.

Due to the physical and chemical properties of this type of organophosphine ligands themselves: 1) highly toxic, 2) flammable and explosive, 3) very sensitive to air, 4) high boiling point, 5) difficult to purify by distillation, 6) to the ligand Purity requires high characteristics. It is necessary to adopt more complicated anaerobic and anhydrous anaerobic synthesis operations, and now multi-step synthesis is required, which causes many uncertain factors for the preparation of ligands with this special structure on an industrial scale. How to choose the synthetic route that adopts PH3 as the phosphine source, is to synthesize the cyclic phosphine first (ring first) or the substituent with large molecular weight first (tailing)? becomes the question that must first be determined.

In the past 50 years, no relevant patents related to the synthetic route of industrial preparation of organic phosphine with similar titles have been retrieved, so the choice of an accurate synthetic route must be made through experimental investigation. To ensure the safety and high efficiency of industrial production of highly toxic and air-sensitive organophosphine ligands.

The experimental results of using high-pressure in-situ NMR technology to investigate the synthetic route of 18-alkyl-9-phosphine bicyclononane ligands are shown in Fig. 2 and Fig. 3 . Comparing Figures 2 and 3, it can be seen that the phosphine ligand impurity synthesized in Figure 2 "ring first and then ring" is significantly more than the phosphine ligand prepared in Figure 3 "ring first and then tail". Therefore, the present invention prefers the synthetic route of "ring first and tail later".

The so-called "ring first and tail later" synthetic route is characterized in that it is divided into two sections to complete the whole process of manufacturing organic phosphine ligands with small space barrier, high boiling point and strong coordination. listed in Figure 4.

It can be seen from Figure 4 that the first stage is the free radical addition reaction between phosphine and non-conjugated linear diene, cyclic diene or triene. Generate phosphine-containing monocyclic, bicyclic, or tricyclic secondary phosphine heterocyclic compounds with small space barrier functions (first ring). The second stage is to introduce high-molecular-weight long-chain alkyl groups or polycyclic aryl groups (tailing) into phosphine heterocyclic compounds to generate organic phosphine ligands with high boiling points or large volumes of trivalent tertiary phosphine.

The inventors of this patent, Yan Xianglan and Li Dagang, etc. announced the low-pressure method "Preparation Process of Organic Phosphine Compounds" in 1996, the authorized announcement number is CN1032424C, and the solution that absorbs saturated phosphine is used for free radical addition reaction with various olefins, and the reaction The pressure was reduced from 30.0MPa to 1.0-3.0MPa, and better reaction results were obtained.

The inventors of this patent, Li Dagang and Li Song, authorized CN108456228A "A Small Space Barrier Organic Phosphine Ligand and Its Preparation Method and Its Application in the Production of 1-Octene and 1-Hexene from Ethylene" on October 29, 2020. better effect.

The present invention is a follow-up invention on the basis of two patents CN1032424C and CN108456228A: in order to improve the use efficiency of the free radical initiator and the purity of the target product, a tubular reactor for segmental control of the reaction temperature is designed, which is characterized in that a The tubular reactor is changed to three reactors connected in series and parallel which can individually control the reaction temperature. The temperature control program is that the reaction temperature of the first reactor is relatively low, and the temperature control of the third reactor is relatively high. And this saturated absorption process is extended to the synthesis of monocyclic secondary phosphine from linear unsaturated diolefins and the one-step preparation of cyclic organic tertiary phosphine from non-conjugated trienes.

In the second section, a distillation stirring blowing device and a device for adding initiator at any time are added to improve the distillation efficiency. And it is extended to the preparation of organic tertiary phosphine containing long chain or large molecular weight condensed ring aromatic hydrocarbon derivatives.

The first section of the preparation process is characterized by:

During continuous production, in order to improve the ratio accuracy of phosphine (PH ₃ ) and diolefins, British Patent No. 1,561,674 (1980) describes a continuous preparation process. That is, the process of preparing primary and secondary phosphine from phosphine under high pressure. Firstly, the phosphine, which is a gas under normal conditions, is compressed into liquid phosphine (pressure 8.0-30.0MPa), and the liquid olefin reactants and free radical initiators are accurately dosed according to the reaction gram weight and enter the reactor. The reaction time is 13-15 times of the half-life of the initiator, and the reaction temperature is 90-190°C. In the reaction between phosphine and 1,5-cyclooctadiene, the conversion rate of 1,5-cyclooctadiene is 90%, and the content of 9-phosphine bicyclononane in the product is 96%. The problem with this technology is that the pressure of phosphine is relatively high, 8.0-30.0MPa, and phosphine gas needs to be compressed and liquefied. If there is a little leakage of relatively high-pressure phosphine, it will have serious consequences for the environment and personal safety. At the same time, the maintenance of highly toxic high-pressure equipment is extremely difficult.

The design of the first section of the present invention is divided into four processes including gas-liquid saturated absorption, raw material premixing according to the reaction ratio, reaction process and product gas-liquid separation. The gas-liquid saturated absorption process is to use a gas-liquid mixer to fully mix the reaction solvent at a specific temperature and pressure until the solvent reaches saturation to absorb phosphine. The raw material premixing process is as follows: injecting the solvent saturated with absorbing phosphine into the raw material mixing tank, and keeping the temperature of the mixing tank lower than room temperature by 10-15°C. Since the content of phosphine in the saturated absorption liquid is a function of the absorption temperature and pressure, the proportion of olefins, phosphine and free radical initiators in the reaction liquid can be controlled. The mixed liquid is injected into the first reactor with a cryopump. According to different types of initiators, choose parallel or serial reactors, and set different reaction temperatures for each section. The product separation process is to separate the unreacted phosphine from the liquid phase product under room temperature and vacuum conditions, and then send it to a cryogenic system for storage.

The process of the second workshop is characterized in that:

The second section of the present invention involves a tailing reaction, that is, the phosphine heterocyclic secondary phosphine product obtained in the first section is introduced into a large molecular weight linear terminal alkene or an aromatic hydrocarbon group to obtain a high boiling point or large volume tertiary phosphine. The content of the invention is to adopt a stirred tank integrating anaerobic and water-absent reaction-distillation, and to complete the tailing reaction by intermittent operation. Since the target product has the highest boiling point, the reaction is distilled under reduced pressure to evaporate the solvent, unreacted phosphine heterocyclic secondary phosphine, and low-boiling point impurities. The remaining liquid at the bottom of the tank is the tertiary phosphine target product of this patent with small air barrier, high boiling point, strong coordination or large volume. In order to improve the efficiency of distillation and separation, a distillation stirring blowing device is added or a molecular distillation device is used. This process can be extended for tailing large molecular weight condensed aromatic hydrocarbons.

Fig. 5 is composed of the first and second two sections to prepare small space barrier, high boiling point, strong coordination or bulky organic tertiary phosphine ligand. The operation of the whole flow process includes the following steps;

1) Pre-mixing the solvent with the non-conjugated diene or triene in proportion;

2) Use a powerful gas-liquid mixer to saturate and absorb the phosphonane in the liquid phase at a fixed temperature of 5°C and a fixed pressure;

3) The saturated absorption mixed liquid and the initiator are simultaneously pumped into the pipeline reactor, and the reaction of phosphine and olefin is carried out at a fixed temperature of 50-150° C. and a pressure of 0-10 MPa. Azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanonitrile, azoisobutyrocyanoformamide, azobicyclohexylcarbonitrile, azobisisobutyric acid dimethyl Esters, etc., but not limited to the above initiators. The molar ratio of initiator to olefin is 0.01 to 1;

4) The reaction liquid is separated from gas and liquid, and the unreacted phosphine is recovered and entered into the cryogenic section;

5) The bicyclic secondary phosphine product obtained in step 3) is sent to a batch-operated reactor and an initiator is added to carry out a second step reaction with a terminal olefin or a derivative thereof with a large molecular weight to obtain a compound with a small space barrier, a high boiling point, a strong Coordinated organic tertiary phosphine;

6) Vacuum distillation in situ after the reaction to separate the solvent, unreacted cyclic secondary phosphine, large molecular weight olefins and low boiling point impurities, etc., and the residue at the bottom of the still is the target product tertiary phosphine.

Based on the application of the organophosphine ligand described above, the organophosphine ligand can be applied to a cobalt-phosphine-potassium three-way catalyst system or a chromium-phosphorus-activator three-way catalyst system. Wherein the cobalt-phosphine-potassium three-way catalytic system includes the organic tertiary phosphine ligand, zero-valent cobalt metal, potassium hydroxide; under the following operating conditions of _H2 :CO=2:1 (mol) synthesis gas :

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

Described chromium-phosphorus-activator ternary system catalyst system comprises organic tertiary phosphine ligand, chromium source, activator; Reaction condition is as follows:

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

Based on the organophosphine ligands used in the cobalt-phosphine-potassium three-way catalytic system described above, it can also be extended to small molecules to prepare macromolecular compounds, such as the selective tetramerization of ethylene to 1-octene catalysts. Ligand. Because the transition metal coordination catalyst for this catalytic reaction also shows that the smaller the vacancy barrier of itself, the more conducive to the formation of macromolecules. Otherwise, the large vacancy barrier of the coordination catalyst itself will interfere with the self-assembly of small molecules to large molecules. (See Li Dagang and Li Song "A Small Space Barrier Organophosphine Ligand and Its Preparation Method and Its Application in the Production of 1-Octene and 1-Hexene from Ethylene", CN108456228A, authorized date October 19, 2020)

The invention inherits the small space barrier ligand technology of CN108456228A and develops a small space barrier strong coordination large-volume organic phosphine ligand, which is used to adjust the molecular self-assembly when the chromium center forms a catalyst. Make it form a monodentate phosphine with small vacancy barrier, large enough volume and strong coordination ability, so that two identical ligands cannot self-assemble in the angular coordination region, and can only form a linear double ligand as (Figure 5). bit configuration. Therefore, four π-ethylenes can form a single active center to achieve the goal of improving the selectivity of 1-octene.

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

1-1. The general structure of the monocyclic small space barrier organic phosphine ligand is as follows:

Table 2 Monocyclic Small Space Barrier Organophosphine Ligands

1-2. The molecular structure of the silicon lantern-shaped small space barrier with high boiling point and strong coordination phosphine ligand is as follows:

Table 3 Silicon lantern-shaped small space barrier, high boiling point, strong coordination phosphine ligands

1-3. Small space barrier, high boiling point and strong coordination phosphine ligand with lantern structure, the general structure formula is as follows:

Table 4 Lantern structure small space barrier high boiling point strong coordination phosphine ligand

1-4. The general structural formula of the tricyclic small space barrier organic phosphine ligand is as follows:

Table 5 Structure of tricyclic small space barrier organophosphine ligand

1-5. The general structural formula of bicyclic small space barrier and high boiling organic phosphine ligand is as follows:

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Table 6 Bicyclic Small Space Barrier High Boiling Organic Phosphine Ligands

Description of drawings

FIG. 1 is a schematic structural view of a high-pressure in-situ NMR pneumatic sample tube provided by the present invention.

Fig. 2 is the in situ NMR31P spectrum of the "tail first ring" product in comparative example 1 in the specific embodiment.

Fig. 3 is the in-situ NMR31P spectrum of the "ring first, tail later" product in Example 1 of the specific embodiment.

Fig. 4 is a schematic structural diagram of a preparation device for a small space barrier, high boiling point, strong coordination, and large volume organic phosphine ligand in the present invention.

Fig. 5 is a catalytic coordination diagram of ethylene tetramerization to 1-octene of an organophosphine ligand with small space barrier, high boiling point, strong coordination and large volume in the present invention.

Among them: 1. Air source; 2. Vacuum pump; 3. Inflatable valve; 4. Pressure gauge; 5. Test tube; 6. Heating tube; 7. Temperature control; 8-1. Premix tank; 8-2. Saturated absorption 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 still; 8-9, condenser.

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Example 1

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, its molecular formula is C ₁₈ H ₃₇ -PC ₅ H ₁₀ , the equipment used in its preparation process is shown in Figure 5, and its preparation method includes the following steps ;

(1) Inject degassed n-pentadiene at a flow rate of 5.56mol/h and a degassed solvent of 15.2mol/h into the premixing tank 8-1 for mixing, and pump it with a metering pump at a flow rate of 2.0kg/h into the saturated absorber 8-2, and at the same time, use the initiator feeder a 8-3 to add azobisisobutyronitrile initiator and keep the temperature at 5±3°C, and the pressure of the injected phosphine trihydride gas is kept at 1.6MPa. Start the gas-liquid mixer to make the liquid reach saturated absorption pH ₃ . The saturated absorption liquid is stored in the absorption liquid storage tank under the condition of 5±3°C and 1.6MPa. Use a diaphragm feed pump to inject the saturated absorption mixture into the tubular reactor 8-4 at a flow rate of 2.01kg/h, and use a water bath 8-5 to keep the temperature in the pipeline at 70-80°C and the pressure at 3.0MPa. The mixed liquid flows into the gas-liquid separator 8-6 from the outlet of the tubular reactor 8-4, where the unreacted very small amount of phosphine gas is separated and returned to be stored in the liquid nitrogen cryogenic storage purifier. 1. The conversion rate of 5-cyclooctadiene is 92%, and the concentration of polycyclic phosphonanes generated in the reaction solution by capillary chromatography is 25-30% by weight, and the selectivity is >90%.

(2) After the reaction still 8-8 is degassed and purified to an oxygen content lower than 3ppm, the reaction starts the batching operation, and the initiator feeder b 8-7 adds the initiator, and the reaction starting raw material proportioning reaches the following standard (mol %):

Toluene solvent: initiator: octadecene-1: cyclic secondary phosphine = 35:2.0:42:21. Reaction start pressure: 0.5MPa high-purity nitrogen. Reaction temperature: Different initiators have different reaction degrees: 60-190°C. Reaction time: The reaction solution is sampled and analyzed twice at an interval of 30 minutes, and the target product is no longer increased to terminate the reaction, and condensed in the condenser 8-9.

After the reaction is completed, the in-situ normal and vacuum distillation are used to distill out: solvent, unreacted cyclic secondary phosphine, large molecular weight olefin and low boiling point impurities, etc. The bottom residue is the target product tertiary phosphine. The two-step reaction is based on the 1,4-pentadiene raw material, and the total molar yield of the target product is not less than 70%.

Comparative example 1

The steps (2) and (1) in the examples were exchanged, the preparation method of "tail first and then ring", and then the purity and yield of the products obtained in Example 1 and Comparative Example 1 were analyzed.

The in-situ NMR31P spectrum in Comparative Example 1 is shown in FIG. 2 , and the in-situ NMR31P spectrum in Example 1 is shown in FIG. 3 .

It can be seen that the purity of the target product of the "first ring and then tail" process is higher; while the final product of the "first tail and then ring" process contains more impurities. The comparison between the two processes of "ring first and then tail" and "tail first and then ring" is as follows;

Preparation Process Total reaction time (h) The total yield of organic phosphine Organophosphine Product Purity Total alcohol yield loop first 20 60-70% >95% 84-85% end to end loop 13 90% 83% 72-73%

Example 2

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, trityl-ethyl-6-phosphine monocyclohexane [(Ph) ₃ CC ₂ H ₄ -Ph ₃ C-CH ₂ CH ₂ -PC ₅ H ₁₀ ], the preparation method is the same as that in the example, the difference is that in this example, tritylethylene is used instead of octadecene.

Example 3

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is trityl-6-phosphine monocyclohexane (Ph3C-P-C5H10), the first step secondary phosphine product-6-phosphine monocyclohexane Cyclohexane directly takes the product of Example 1. The second step is to prepare trityl-6-phosphine monocyclohexane tertiary phosphine by Wurz method.

Operation steps: Take _{2.0 mol} of the HPC ₇ H ₁₂ ring secondary phosphine prepared in Example 1, add 1.6 M BuLi (4.5 L, 7.2 mol ) in hexane, the temperature was kept at -78°C and stirred for 40min. Thereafter, 2 L of a THF solution containing 2.6 mol of 1-bromotriphenylmethane (Ph ₃ CBr) was added. The mixture was allowed to warm to room temperature overnight. Extract with 40L of anhydrous ether, and dry the organic phase with sodium carbonate. C ₅ H ₁₀ PC-CPh ₃ was obtained by vacuum distillation with a yield of 60%.

Example 4

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is the preparation method of 1-pyrenyl-6-phosphine monocyclohexane (C ₁₆ H ₉ -PC ₅ H ₁₀ ) Preparation method and examples In the same way as 3, the title product 1-pyrenyl-6-phosphine monocyclohexane can be prepared only by replacing Ph ₃ CBr with bromopyrene 1-Br-C ₁₆ H ₉ with a yield of 61%.

Example 5

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1-pyrenyl-ethyl-6-phosphine monocyclohexane C ₁₆ H ₉ -CH ₂ CH ₂ -PC ₅ H ₁₀ , prepared The method was the same as in Example 2 except that 1-vinylpyrene was used instead of tritylethylene. The target product yield was 59%.

Example 6

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 9-anthracenyl-ethyl-6-phosphine monocyclohexane 9-C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₅ H ₁₀ The preparation method, except that tritylethylene is replaced with 9-vinyl-anthracene, all the other operations are the same as in Example 2. The target product yield was 58%.

Example 7

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is an industrial preparation method for 9-phenanthrenyl-6-phosphine monocyclohexane 9-C ₁₄ H ₉ -PC ₅ H ₁₀ , except for Except that 9-bromo-phenanthrene replaced 1-bromotriphenylmethane, other operations were the same as in Example 3. The target product yield was 58%.

Example 8

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1-phenanthrenyl-ethyl-6-phosphine monocyclohexane (C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₅ H ₁₀ ) .

The preparation method of C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₅ H ₁₀ is the same as in Example 2 except that 9-vinyl-phenanthrene is used instead of tritylethylene. The target product yield was 58%.

Example 9

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is phenyl-4-silicon-1-phosphine bicyclo-[2,2,2]-octane C ₆ H ₅ -[Si(CH ₂ CH ₂ ) ₃ P] preparation method:

To a Schlenk vessel containing P(CH ₂ CH ₂ ) ₃ SiH in THF (3 ml) was added 1.6M BuLi (4.5 ml, 7.2 mmol) in hexane within 5 min, and the temperature was kept at -78°C and stirred for 40 min. Thereafter, 2 ml of a THF solution containing 2.6 mmol of 1-bromobenzene (PhBr) was added. The mixture was allowed to warm to room temperature overnight. Extract with 40ml of anhydrous ether, and dry the organic phase with sodium carbonate. C ₆ H ₅ -[Si(CH ₂ CH ₂ ) ₃ P] was obtained by vacuum distillation. Yield 50%.

C ₆ H ₅ -[Si(CH ₂ CH ₂ CH ₂ ) ₃ P, C ₆ H ₅ -{[Si[(CH ₂ )n] ₃ }P n=2～5 and other derivatives preparation method and above method same.

Example 10

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 18-alkyl-4-silicon-1-phosphine bicyclo[2,2,2]octane C ₁₈ H ₃₇ -[Si(C The preparation method of ₂ H ₄ ) ₃ P] is the same as in Example 09, except that 18-ene-1 is used instead of 1-bromobenzene, and the rest is the same as in Example 09.

Example 11

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is Ph ₃ C-[Si(CH ₂ CH ₂ ) ₃ P] The preparation method is the same as in Example 09, except that bromotriphenyl is used The base is substituted for 1-bromobenzene, and the rest are the same as in Example 09. Yield 70% of the title product.

Example 12

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1-pyrenyl-4-silicon-1-phosphine bicyclo[2,2,2]octane C ₁₆ H ₉ -[Si( The preparation method of CH ₂ CH ₂ ) ₃ P] is the same as in Example 09, except that 1-bromopyrenyl is used instead of 1-bromobenzene, and the rest is the same as in Example 09. Yield 60% of title product.

Example 13

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 9-anthracenyl-4-silicon-1-phosphine bicyclo[2,2,2]octane C ₁₄ H ₉ -[Si(CH The preparation method of ₂ CH ₂ ) ₃ P] is the same as in Example 09, except that 9-bromoanthracene is used instead of 1-bromobenzene, and the rest is the same as in Example 09. Yield 62% of title product.

Example 14

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1-phenanthrenyl-4-silicon-1-phosphine bicyclo[2,2,2]octane C ₁₄ H ₉ -[Si(CH The preparation method of ₂ CH ₂ ) ₃ P] is the same as in Example 09, except that 1-bromophenanthrenyl is used instead of 1-bromobenzene, and the rest is the same as in Example 09. The yield of the title product was 59%.

Example 15

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 18-alkyl-4-carbon-1-phosphine-bicyclo[2,2,2]octane C ₁₈ H ₃₇ -[C( C ₂ H ₄ ) ₃ P] or CnHn+1-[C ₂ H ₄ ) m] ₃ P, n=1～40; m=2～5, the preparation method is the same as that of Example 10, except that Except that 1-phosphine-bicyclo[2,2,2]octane was substituted for 4-silicon-1-phosphine-bicyclo[2,2,2]octane, the rest of the operations were the same as in Example 10. Yield 60% of title product.

Example 16

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is trityl-4-carbon-1-phosphine-bicyclo[2,2,2]octane Ph ₃ C-[C(CH The preparation method of ₂ CH ₂ ) ₃ P] is the same as that of Example 10, except that bromotriphenylmethane is used instead of 18-ene-1, and the rest of the operations are the same as in Example 10. Yield 57% of the title product.

Example 17

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1-pyrenyl-4-carbon-1-phosphine-bicyclo[2,2,2]octane ₁₆ H ₉ -[C(CH ₂ CH ₂ ) ₃ P], the preparation method is the same as that of Example 16, except that bromotriphenylmethane is replaced by 1-bromopyrene, and the rest of the operations are the same as in Example 10. Yield 60% of title product.

Example 18

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 9-anthracenyl-4-carbon-1-phosphine-bicyclo[2,2,2]octane C ₁₄ H ₉ -[C( The preparation method of CH ₂ CH ₂ ) ₃ P] is the same as that of Example 16, except that bromotriphenylmethane is replaced by 1-bromoanthracene, and the rest of the operations are the same as in Example 16. Yield 57% of the title product.

Example 19

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1-phenanthrenyl-4-carbon-1-phosphine-bicyclo[2,2,2]octane C ₁₄ H ₉ --[C The preparation method of (CH ₂ CH ₂ ) ₃ P] is the same as that of Example 16, except that bromotriphenylmethane is replaced by 1-bromophenanthrene, and the rest of the operations are the same as in Example 10. Yield 60% of title product.

Example 20

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, the preparation method of octadecyl-8-phosphine tricyclooctane C ₁₈ H ₃₇ -(PC ₇ H ₁₀ ) except using norbornanol di Same as Example 1 except that ene is substituted for pentadiene. The yield of the title product was 72%.

Example 21

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is a preparation method of trityl-ethyl-8-phosphine tricyclooctane Ph ₃ C-CH ₂ CH ₂ -PC ₇ H ₁₀ It is the same as Example 20 except that octadecene-1 is substituted with benzyl. The yield of the title product was 65%.

Example 22

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is the preparation of 1-pyrenyl-ethyl-8-phosphine tricyclooctane C ₁₆ H ₉ -CH ₂ CH ₂ -PC ₇ H ₁₀ The method is the same as in Example 20 except that 1-vinylpyrene is used instead of octadecene-1. The yield of the title product was 60%.

Example 23

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is the preparation method of 9-anthracenyl-8-phosphine tricyclooctane C ₁₄ H ₉ -PC ₇ H ₁₀ except using 9 bromo-anthracene Except for replacing bromotriphenylmethane and norbornene for pentadiene, other operations are the same as in Example 03. The yield of the title product was 59%.

Example 24

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1-phenanthryl-ethyl-8-phosphine tricyclooctane C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₇ H ₁₀ The preparation method is the same as that of Example 20 except that 1-ethylene-phenanthrene-substituted octadecene-1 is used. The yield of the title product was 57%.

Example 25

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is trityl-ethyl-9-phosphine-bicyclononane, C ₁₈ H ₃₇ -PC ₈ H ₁₄ Preparation method and examples 1, the difference is that 1.5-cyclooctadiene replaces pentadiene, and tritylethylene replaces octadecene. The two-step reaction is calculated based on 1,5-cyclooctadiene raw material, and the total molar yield is 70%.

Example 26

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is the preparation of 1-pyrenyl-ethyl-9-phosphine bicyclo-nonane C ₁₆ H ₉ -CH ₂ CH ₂ -PC ₈ H ₁₄ The method is the same as in Example 25 except that 1-vinylpyrene replaces tritylethylene. The yield of the target product was 58%.

Example 27

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 1 8-alkyl-9-phosphine bicyclo-nonane Ph ₃ C-CH ₂ CH ₂ -PC ₈ H ₁₄ The preparation method is the same as the example 25. The title product was obtained by simply substituting octadecene for tritylethylene. Yield 59%.

Example 28

An organic tertiary phosphine ligand with a cyclic secondary phosphine group, which is 9-anthracenyl-ethyl-9-phosphine bicyclo-nonane 9-C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₈ H ₁₄ The manufacturing method is the same as in Example 25. Only by substituting 9-vinylanthracene, trityl-ethylene, the title product can be obtained in a yield of 55%.

Example 29

An application of an organic tertiary phosphine ligand, applied to a chromium-phosphorus-activator ternary system catalyst system, the chromium-phosphorus-activator ternary system catalyst system organic tertiary phosphine ligand, chromium source, and activator .

Operation method:

A stainless steel autoclave with a volume of 500ml, after cleaning, vacuum-dry at 120°C for three hours, and cool to room temperature. Dissolve (1) chromium source material (Cr), (2) organophosphine ligand (L) and (3) activator (A) in specified amount of dry methyl Cyclohexane solvent and stored in a 100ml syringe, sealed with silicone rubber. At room temperature, first inject (1) and (2) into the autoclave, immediately fill with 0.3MPa ethylene, stir and replace three times. Use a micro-oxygen analyzer to detect the oxygen content in the ethylene gas phase in the kettle, and it is required to be below 3ppm. After passing the test, add the activator (3) with a pressure bomb under the atmosphere of ethylene, immediately pressurize to 2.5MPa with ethylene, and quickly raise the temperature to the design temperature (40-80°C), control the reaction pressure to 5.0MPa, and the stirring speed is >500rpm , reacted for 30 minutes to stop the reaction. The autoclave was cooled to 0 °C. After trapping the discharged gas phase, add an appropriate amount of isooctyl alcohol or 30ml of 10% HCl to kill the activator. The liquid sample was taken for chromatographic analysis, the organic phase product was weighed, and the filtered by-product PE was dried and weighed. Calculate the amount of gas, liquid and solid three products, catalytic activity, product distribution percentage and purity of 1-octene and 1-hexene.

Chromium source materials can be selected individually: CrCl ₃ (THF) ₃ , CrCl ₂ (THF) ₂ , Cr(acac) ₃ , Cr(HA) ₃ .

The activator (A) can be selected separately: methylaluminoxanes (MAO or MMAO-3A), (2) alkylaluminums (triethylaluminum or triisobutylaluminum), (3) DMAO. Or choose the mixture of (1)+(3).

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

Catalyst system in this example catalyzes ethylene oligomerization reaction evaluation result

Catalytic system: chromium: phosphine ligand: activator = 1:2:500 (mol)

Reaction temperature: 45°C, reaction pressure: 4.0MPa, reaction time: 30min.

Example 30

An application of an organic tertiary phosphine ligand, the cobalt-phosphine-potassium three-way catalytic system includes the organic tertiary phosphine ligand, zero-valent cobalt metal, and potassium hydroxide.

Clean the 1.0L autoclave with 2EH solvent, vacuum inhale the 2EH solution of cobalt isooctanoate, organic tertiary phosphine ligand and potassium hydroxide, and replace it with vacuum until the oxygen content of the synthesis gas in the autoclave reaches 1 mg/m ³ . Pressurize to 3.0Mpa, stir and heat up to 170°C, press 1-12ene after 30min, keep the pressure at 6.0MPa, keep the temperature at 180-190°C, react for 5h, cool to room temperature and press out the reaction solution, weigh and use a capillary Chromatographic analysis of liquid phase products.

The catalytic effects of organic phosphine ligands used in Co~P catalyst olefin carbonylation to produce alcohol are as follows;

Catalyst: Co-P-KOH, Co concentration: 0.2%, P:Co=2:1 (mol), solvent: 2EH, reverse temperature: 180-190°C, reverse pressure: 6.0MPa, reverse time 5h.

The specific embodiments of the present invention described above do not constitute a limitation to the protection scope of the present invention. Any other corresponding changes and modifications made according to the technical concept of the present invention shall be included in the protection scope of the claims of the present invention.

Claims (9)

1. A small empty barrier, high boiling, strongly coordinating, bulky organophosphine ligand, characterized in that the organophosphine ligand consists of one cyclic secondary phosphine group and one substituent of high molecular weight, the cyclic secondary phosphine group comprising the structure:

(1)C ₅ H ₁₀ the structural formula of P is as follows:

(2) C7H10P is 8-phosphorus-tricyclic octane, and the structural formula is as follows:

(3)P(CH ₂ CH ₂ ) ₃ the structural formula of CH is as follows:

(4)P(CH ₂ CH ₂ CH ₂ ) ₃ the structural formula of CH is as follows:

(5)P{(CH ₂ CH ₂ ) ₂ (CH ₂ CH ₂ CH ₂ ) The structural formula of the CH is as follows:

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

(7)C ₈ H ₁₄ p is 9-phosphinodibicyclo [3,3.1 ]]Nonane and 9-phosphabicyclo [ 4.2.1 ]]The structural formula of nonane is as follows:

(8) The structural formula of [ (CH 2) nP ] n=3-11 is as follows:

(9) Phosphine heteromacrocyclic compound- { C [ (CH) ₂ )n] ₃ The structural formula of P } n=2-5 is as follows:

(10) The structural formula of the silicon-phosphabicyclo- { Si [ (CH 2) n ]3p } n=2-5 is as follows:

(11) Oxa-phosphine heteromonocyclic ring (C) ₂ H ₄ O ₂ The structural formula of P) is as follows:

the high molecular weight substituent groups include the following groups:

(1) Long chain alkyl groups: -C _n H _2n+1 N=a positive integer from 1 to 25;

(2) Aromatic hydrocarbon group: phenyl-C ₆ H ₅ The method comprises the steps of carrying out a first treatment on the surface of the Naphthyl: -C10H7;

(3) Condensed ring aromatic groups; anthryl, phenanthryl, pyrenyl, fluorenyl and alkyl derivatives thereof

(4) Alkyl-containing polycyclic aromatic hydrocarbon derivatives; - (CH 2) nW, n=a positive integer of 2 to 25, W being one of anthraquinone, phenanthrene, pyrene, and fluorenyl.

2. The organophosphine ligand according to claim 1, which isCharacterized in that the organic phosphine ligand has the chemical formula of C ₁₈ H ₃₇ -P-C ₅ H ₁₀ 、Ph ₃ C-CH ₂ CH ₂ -P-C ₅ H ₁₀ 、Ph ₃ C--P-C ₅ H ₁₀ 、C ₁₆ H ₉ --P-C ₅ H ₁₀ 、C ₁₆ H ₉ -CH ₂ CH ₂ -PC ₅ H ₁₀ 、9-C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₅ H ₁₀ 、C ₁₄ H ₉ -PC ₅ H ₁₀ 、

C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₅ H ₁₀ 、C ₆ H ₅ -[Si(CH ₂ CH ₂ ) ₃ P]、C ₆ H ₅ -[Si(CH ₂ CH ₂ CH ₂ ) ₃ P]、C ₆ H ₅ -{[Si[(CH ₂ ) _n ] ₃ }P n＝2-5、C ₁₈ H ₃₇ -[Si(C ₂ H ₄ ) ₃ P]、Ph ₃ C-[Si(CH ₂ CH ₂ ) ₃ P]、C ₁₆ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P]、C ₁₄ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P]、C ₁₄ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P]、C ₁₈ H ₃₇ -[C(C ₂ H ₄ ) ₃ P]、C _n H _n+1 -[C ₂ H ₄ ) _m ] ₃ P n =a positive integer from 1 to 40; m=positive integer from 2 to 5, ph ₃ C-[C(CH ₂ CH ₂ ) ₃ P]、1-C ₁₆ H ₉ -[C(CH ₂ CH ₂ ) ₃ P]、9-C ₁₄ H ₉ --[C(CH ₂ CH ₂ ) ₃ P]、1-C ₁₄ H ₉ --[C(CH ₂ CH ₂ ) ₃ P]、C ₁₈ H ₃₇ -P-C ₇ H ₁₀ 、Ph ₃ C-CH ₂ CH ₂ -P-C ₇ H ₁₀ 、1-C ₁₆ H ₉ -CH ₂ CH ₂ -PC ₇ H ₁₀ 、9-C ₁₄ H ₉ -PC ₇ H ₁₀ 、C ₁₄ H ₉ -CH ₂ CH ₂ -PC ₇ H ₁₀ 、C ₁₈ H ₃₇ -P-C ₈ H ₁₄ 、Ph ₃ C-CH ₂ CH ₂ -P-C ₈ H ₁₄ 、C _n H _2n+1 -P-C ₈ H ₁₄ 、C ₁₄ H ₉ -CH ₂ CH ₂ -P-C ₈ H ₁₄ 、C ₁₄ H ₉ -CH ₂ CH ₂ -P-C ₈ H ₁₄ 、C ₁₆ H ₉ -CH ₂ CH ₂ -P-C ₈ H ₁₄ One of them.

3. A high carbon cobalt-phosphine-potassium alkoxide based catalyst based on an organic phosphine ligand according to claim 1 or 2, wherein the formula is: c (C) ₁₈ H ₃₇ -[Si(C ₂ H ₄ ) ₃ P]、Ph ₃ C-[Si(CH ₂ CH ₂ ) ₃ P]、C ₁₆ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P]、C ₁₄ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P]、C ₁₄ H ₉ -[Si(CH ₂ CH ₂ ) ₃ P]The organic phosphorus ligand of the catalyst can be used as a catalyst for synthesizing high-carbon alcohol cobalt-phosphine-potassium.

4. A process for preparing an organic phosphine ligand according to any one of claims 1 to 3, wherein the cyclic phosphine structure is synthesized from phosphine as a raw material, and then an inert group having a large molecular weight is attached.

5. The process of claim 4, wherein the synthesis of the cyclic phosphine structure is carried out by pre-absorbing the phosphine in a solvent and a reactant, and the phosphine is converted from a gas phase to a liquid phase.

6. The method of preparation according to claim 4 or 5, comprising the steps of;

1) Mixing solvent and non-conjugated diene or triene in proportion in advance;

2) The phosphine alkane is saturated and absorbed in the liquid phase by strong gas-liquid mixing to obtain saturated absorption mixed liquid

3) Pumping the saturated absorption mixed solution and an initiator into a pipeline reactor simultaneously to react phosphine with olefin to obtain a dicyclic secondary phosphine product;

4) Feeding the dicyclic secondary phosphine product obtained in the step 3) into a reaction kettle operated intermittently, adding an initiator and terminal alkene or derivative with large molecular weight for a second reaction to obtain organic tertiary phosphine;

5) And (3) carrying out in-situ vacuum distillation after the reaction, and separating out solvent, unreacted cyclic secondary phosphine, high-molecular-weight olefin and low-boiling-point impurities, wherein the residue at the bottom of the kettle is the target product tertiary phosphine.

7. The preparation method according to claim 6, wherein the initiator in the step 3) is one of azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanenitrile, azoi Ding Qingji formamide, azodicyclohexyl carbonitrile and dimethyl azodiisobutyrate, and the molar ratio of the initiator to olefin is 0.01-1.

8. Use of an organophosphine ligand according to any one of claims 1 to 2, wherein the organophosphine ligand is applicable to a cobalt-phosphine-potassium three-way catalyst system comprising the organophosphine ligand, zero-valent cobalt metal, potassium hydroxide and/or a chromium-phosphorus-activator three-way catalyst system; the chromium-phosphorus-activator three-way catalyst system comprises an organic tertiary phosphine ligand, a chromium source and an activator.

9. The use according to claim 8, wherein the organophosphine ligand is applicable to ethylene selective tetramerization 1-octene catalyst system.

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