A vanadium catalyst composition and its preparation method and application

Abstract

The present invention relates to the technical field of catalysts for synthesizing ethylene-propylene rubber, and discloses a vanadium catalyst composition, a preparation method thereof and an application thereof, wherein the vanadium catalyst composition is composed of a vanadium complex and an electron donor, wherein the ligand of the vanadium complex is one of fatty alcohols, amines and phosphates, and the electron donor is a sulfoxide compound with a structural formula of R-S(=O)-R', wherein R is selected from one of C1-C3 alkyl, aryl, and C1-C3 alkyl-substituted aryl; and R' is selected from one of C1-C3 alkyl and aromatic alkyl. The present invention adopts an oxidizing electron donor, combined with an aqueous phase extraction method, to synthesize a vanadium catalyst composition with a reactivation function in a one-step method, thereby improving the catalytic efficiency of ethylene / propylene or ethylene / propylene / third monomer copolymerization catalyzed by a non-activator system vanadium catalyst, reducing production costs, and developing different types of ethylene-propylene rubber.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts for synthesizing ethylene-propylene rubber, and in particular to a vanadium catalyst composition and a preparation method and application thereof. Background Art

[0002] At present, EPDM is a synthetic rubber with ethylene and propylene as the main copolymer monomers. It can be divided into EPDM and EPDM according to the presence or absence of a third monomer. EPDM has many excellent properties and is widely used in automotive parts, construction materials, waterproof coiled materials, wires and cables, heat-resistant hoses, advanced sealing materials, lubricant additives, polymer modified materials, and plastic tracks. In particular, automotive parts have an absolute advantage in the domestic and international EPDM consumer market.

[0003] The production of EPDM rubber at home and abroad mostly uses vanadium compounds as the main catalyst, and organic aluminum compounds and activation promoters as co-catalysts. Among them, these vanadium compounds used as the main catalyst are VX3, VX4, VOX3 and VO(OR) 3-n X n , X is a halogen, mainly a chlorine atom. The VOCl3 catalytic system (VOCl3 / Al2Et3Cl3) is commonly used in my country's industrial production, in which the main catalyst VOCl3 is prepared by high-temperature chlorination of V2O5. The large-scale use of chlorine not only harms the health of operators, but also causes serious environmental pollution; and VOCl3 is extremely sensitive to air and water, and is easily decomposed to produce corrosive gases, which increases storage and transportation costs, resulting in many technical disadvantages such as decreased catalytic performance and hydrolysis precipitates blocking the catalyst feeding system. Therefore, Zhang Xuequan et al. developed a new type of efficient, green and environmentally friendly vanadium catalyst (CN200710055981.X). This patent synthesizes vanadium catalysts through a safe and pollution-free aqueous phase extraction method, which has become a research hotspot in recent years. However, the main catalyst vanadium catalyst is gradually reduced to low-valent vanadium under the alkylation of the co-catalyst and deactivated, resulting in low catalytic efficiency, rapid activity decay and high catalyst dosage of the vanadium catalyst. An activator ethyl trichloroacetate (ETCA) is usually used to enhance its catalytic activity. If the activator ethyl trichloroacetate (ETCA) is used in the industrial production process, the difficulty of the post-processing process of EPDM production will be increased, resulting in separation, recovery, water pollution and other related problems, thereby increasing the corresponding production cost.

[0004] The present invention adopts an oxidizing electron donor and combines it with an aqueous phase extraction method to synthesize a vanadium catalyst composition with a reactivation function in a one-step method, thereby improving the catalytic efficiency of ethylene / propylene or ethylene / propylene / third monomer copolymerization catalyzed by a non-activator system vanadium catalyst, reducing production costs, developing different types of ethylene-propylene rubber, and improving my country's ethylene-propylene rubber production capacity and market competitiveness. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a vanadium catalyst composition and a preparation method and application thereof.

[0006] In order to achieve the above object, the technical solution of the present invention is: a vanadium catalyst composition, the vanadium catalyst composition is composed of a vanadium complex and an electron donor, the ligand of the vanadium complex is one of fatty alcohols, amines and phosphates, and the structural formula of the electron donor is shown in formula (I):

[0007]

[0008] In the electron donor, R is selected from one of C1-C3 alkyl, aryl, and aryl substituted by C1-C3 alkyl; and R' is selected from one of C1-C3 alkyl and aromatic alkyl.

[0009] Further, the fatty alcohol is C5~C 18 The fatty alcohol; the phosphate ester is selected from one of di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate 2-ethylhexyl ester, and di(2-ethylhexyl)phosphonic acid; the amine is selected from N 235 、N 1923 , one of tri-n-octylamine.

[0010] Another technical solution of the present invention is: a method for preparing the vanadium catalyst composition, which is prepared by a one-step aqueous phase method, comprising the following steps:

[0011] (1) mixing an extractant, an electron donor and a diluent to obtain an extractant dilution solution; the diluent is a C6-C8 saturated alkane or toluene, and the extractant is a ligand of a vanadium complex;

[0012] (2) mixing the extractant dilution prepared in step (1) with an aqueous solution of an inorganic vanadium compound, performing extraction and phase separation, and obtaining a dilute solution of a vanadium catalyst composition; the inorganic vanadium compound is selected from vanadium pentoxide (V2O5), sodium metavanadate (NaVO3), ammonium metavanadate (NH4VO3), calcium pyrovanadate (Ca2V2O7), calcium orthovanadate (Ca3(VO4)2), sodium hexavanadate (Na2H2V6O 17 ) or both.

[0013] Furthermore, in step (2), an inorganic vanadium compound is used to replace the aqueous solution of the inorganic vanadium compound, and concentrated hydrochloric acid is added to perform extraction and phase separation.

[0014] Furthermore, the method further comprises step (3) of subjecting the dilute solution of the vanadium catalyst composition prepared in step (2) to reduced pressure distillation under the protection of a stabilizer to remove the diluent, thereby obtaining a vanadium catalyst composition.

[0015] Furthermore, the molar ratio of the extractant to the electron donor in step (1) is 1:(0.2-2.0).

[0016] Furthermore, the volume content of the extractant in the extractant dilution solution in step (1) is 20 to 45%.

[0017] Furthermore, in step (2), the pH value of the aqueous solution of the inorganic vanadium compound is adjusted to 1 to 10 with an acid-base solution, the concentration of vanadium element in the aqueous solution of the inorganic vanadium compound is 0.4 to 1.5 mol / L, and the molar ratio of the extractant to the inorganic vanadium compound or the vanadium element in the aqueous solution of the inorganic vanadium compound is (1 to 3.0):1.

[0018] Furthermore, before the extraction and separation in step (2), the volume ratio of the total aqueous phase to the total organic phase is 1:(1-3).

[0019] Furthermore, in step (3), the stabilizer is a C2-C4 fatty acid having a mass concentration of less than 1%; the temperature of the vacuum distillation is 20-70°C, and the time of the vacuum distillation is 0.5-4 hours.

[0020] Another technical solution of the present invention is: an application of the vanadium catalyst composition, wherein the application includes being used for synthesizing ethylene-propylene rubber.

[0021] Furthermore, in an organic solvent, the vanadium catalyst composition and the co-catalyst organoaluminum compound are used to carry out copolymerization of ethylene and propylene to obtain ethylene-propylene-diene rubber.

[0022] Further, the concentration of the vanadium catalyst composition in the organic solvent is 1×10 -4 mol / L~2×10 - 3 mol / L; preferably 3×10 -4 mol / L~1.5×10 -3 mol / L; the molar ratio of ethylene to propylene is 1:(1-5); the organic solvent is selected from one or more of n-hexane, cyclohexane, heptane and toluene; the polymerization temperature is 0-70°C, preferably 20-50°C; the polymerization pressure is 0.1-0.6MPa, preferably 0.3-0.5MPa; the polymerization time is 10-90 minutes, preferably 15-60 minutes.

[0023] Furthermore, after the polymerization reaction is completed, the EPDM rubber is obtained through post-treatment. The post-treatment process is to add the product of the polymerization reaction into a hydrochloric acid-ethanol solution to terminate the polymerization, wherein the mass percentage of hydrochloric acid in the hydrochloric acid-ethanol solution is 5%, wash the sediment with ethanol, and then vacuum dry to obtain the final EPDM rubber.

[0024] Furthermore, in an organic solvent, the vanadium catalyst composition and the co-catalyst organoaluminum compound are used to carry out copolymerization of ethylene, propylene and non-conjugated dienes to prepare ethylene propylene diene monomer rubber.

[0025] Further, the concentration of the vanadium catalyst composition in the organic solvent is 1×10 -4 mol / L~2×10 - 3 mol / L; preferably 3×10 -4 mol / L~1.5×10 -3 mol / L; the molar ratio of ethylene to propylene is 1:(1-4); the non-conjugated diene is selected from dicyclopentadiene (DCPD), ethylidene norbornene (ENB), 5-vinyl-2-norbornene (VNB), 4-ethylene-1-cyclohexene (VCH) or 1,4-hexadiene (HD); the amount of the non-conjugated diene added is 1-10% of the mass fraction of the final product EPDM rubber; the organic solvent is selected from one or more of n-hexane, cyclohexane, heptane and toluene; the temperature of the polymerization reaction is 0-70°C, preferably 20-50°C; the pressure of the polymerization reaction is 0.1-0.6MPa, preferably 0.3-0.5MPa; the time of the polymerization reaction is 10-90 minutes, preferably 15-60 minutes.

[0026] Furthermore, after the polymerization reaction is completed, EPDM rubber is obtained through post-treatment; the post-treatment process is to add the product of the polymerization reaction into a hydrochloric acid-ethanol solution to terminate the polymerization, the mass percentage of hydrochloric acid in the hydrochloric acid-ethanol solution is 5%, and the precipitate is washed with ethanol and then vacuum dried to obtain the final EPDM rubber.

[0027] Furthermore, the organic aluminum compound is selected from at least one of triethylaluminum trichloride (Al2(C2H5)3Cl3), ethylaluminum dichloride (AlC2H5Cl2), diethylaluminum monochloride (Al(C2H5)2Cl) and isobutylaluminum dichloride (AlC4H9Cl2).

[0028] The present invention does not impose any particular restriction on the usage ratio of the main catalyst vanadium catalyst composition to the co-catalyst, and it can be selected according to the routine selection of those skilled in the art.

[0029] Beneficial effects of the present invention: The vanadium catalyst composition of the present invention comprises a vanadium complex and a sulfoxide compound electron donor. The vanadium catalyst composition has good stability in water and air, a long storage time, and high catalytic activity. By introducing an electron donor into the vanadium complex, the vanadium metal active center can be stabilized, the life of the vanadium catalyst can be extended, the catalytic activity and the third monomer insertion rate can be improved, which is conducive to replacing the industrial catalyst VOCl3 and implementing it in industrial equipment as a vanadium catalyst for the production of ethylene-propylene rubber; the preparation method of the vanadium catalyst composition of the present invention is simple, safe to use, and the reaction conditions are mild, which overcomes many drawbacks of the existing industrial catalyst VOCl3 in the preparation and use process, has a high third monomer insertion rate, and reduces the production cost of ethylene-propylene rubber; experimental results show that the ethylene, propylene, and third monomer copolymer obtained by catalysis thereof has a third monomer conversion rate of up to 90%. In addition, the vanadium catalyst composition of the present invention can be used to develop different types of ethylene-propylene rubber, thereby improving the production capacity and market competitiveness of ethylene-propylene rubber in my country. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the 1HNMR spectrum of the vanadium catalyst composition prepared in Example 1.

[0031] Figure 2 It is the DSC spectrum of the EPDM rubber prepared in Examples 8-11.

[0032] Figure 3 It is the GPC spectrum of EPDM rubber prepared in Example 12 and Comparative Example 1.

[0033] Figure 4 This is a polymerization temperature curve of the EPDM rubber prepared in Example 20 and Comparative Example 2. DETAILED DESCRIPTION

[0034] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0035] Embodiment 1:

[0036] A method for preparing a vanadium catalyst composition comprises the following steps: adding 100 mL of pure water and 37 g of NaVO3 into a 1000 mL beaker to prepare a slurry solution, then diluting the solution to 400 mL with pure water, and heating the solution to fully dissolve the NaVO3; adding 48.2 g of Na2SO3 to the solution in batches, stirring the solution evenly, and then dripping 90 mL of a sulfuric acid aqueous solution having a volume ratio of sulfuric acid to water of 1:1 (V:V), stirring the solution at 95°C for 60 minutes, and the solution turns dark blue; cooling the solution to room temperature, filtering the solution with a funnel to filter out insoluble matter, and adding deionized water to dilute the solution to 500 mL to obtain an inorganic vanadium compound solution.

[0037] Take 16 mL of L P204 extractant, add 6.2 g of electron donor dimethyl sulfoxide, and dilute to 60 mL with hexane to obtain an extractant dilution solution.

[0038] Add 60mL of the above extractant dilution and 10mL of 6mol / LNaOH solution to the separatory funnel, place the separatory funnel on a Conrad oscillator and shake for 5min, then add 50mL of the above inorganic vanadium compound solution, and shake on the Conrad oscillator for 20min to fully mix the two phases. Then let it stand for about 1h to separate the phases, the lower layer is the residual water phase, which is discharged from the lower port, and the upper organic phase is taken to obtain a vanadium compound saturated alkane solution. Sampling and analysis of the total vanadium concentration ∑[V] = 0.53mol / L, and the extraction rate is 78% by redox titration analysis.

[0039] The vanadium compound saturated alkane solution was placed in a flask, 0.20 mL of propionic acid was added, and the mixture was heated at 40°C for 3 h under nitrogen protection and vacuum distillation was performed to remove hexane to obtain a blue liquid, which was the vanadium catalyst composition V1. The vanadium catalyst composition V1 1 HNMR spectrum is attached Figure 1 .

[0040] Embodiment 2:

[0041] A method for preparing a vanadium catalyst composition comprises the following steps: adding 100 mL of pure water and 26.4 g of V2O5 into a 1000 mL beaker to prepare a slurry solution, diluting the solution to 400 mL with pure water, adding 12.0 g of NaOH to dissolve the V2O5 to generate a NaVO3 solution; adding 25 g of oxalic acid (H2C2O4·2H2O) in batches to the solution, stirring the solution at 95°C until the solid is dissolved, and then dripping 90 mL of a hydrochloric acid aqueous solution having a volume ratio of hydrochloric acid to water of 1:1; removing the solution and cooling it to room temperature, filtering the solution with a funnel to filter out insoluble matter, and adding deionized water to make the solution fixed to 500 mL to obtain an inorganic vanadium compound solution.

[0042] Take 26.2 mL of L507 extractant, add 0.45 g of electron donor dimethyl sulfoxide, and dilute to 60 mL with hexane to obtain an extractant dilution solution.

[0043] Add 60mL of the above extractant dilution and 10mL of 6mol / LNaOH solution to the separatory funnel, place the separatory funnel on a Conrad oscillator and shake for 5min, then add 50mL of the above inorganic vanadium compound solution, and shake the Conrad oscillator for 20min to fully mix the two phases. Then let it stand for 15min, release the water phase, and then add 20mL of the above inorganic vanadium compound solution, shake the Conrad oscillator for 20min, let it stand for about 1h to separate the phases, the lower layer is the residual water phase, which is released from the lower port, and the upper organic phase is taken to obtain a vanadium compound saturated alkane solution. Sampling and analysis of the total vanadium concentration ∑[V] = 0.57mol / L, and the extraction rate is 98% analyzed by redox titration.

[0044] The vanadium compound saturated alkane solution was placed in a flask, and 2.0 mL of propionic acid was added. Under nitrogen protection, the solution was heated at 40° C. and subjected to reduced pressure distillation for 3 h to remove hexane to obtain a blue liquid, which was the vanadium catalyst composition V2.

[0045] Embodiment 3:

[0046] A method for preparing a vanadium catalyst composition comprises the following steps: adding 14 ml of isooctyl alcohol extractant and 1.4 g of electron donor dimethyl sulfoxide to a separatory funnel, diluting the mixture to 60 ml with hexane to obtain an extractant dilution. Using 5 g of NaVO3 as an inorganic vanadium compound, the mixture is added to the extractant dilution, and then 25 ml of 37 wt% concentrated hydrochloric acid is added. The separatory funnel is placed on a Conrad oscillator and shaken for 15 min to fully mix the two phases. The mixture is then allowed to stand for about 1 hour for phase separation, and the lower layer is the residual water phase which is discharged from the lower port. The upper organic phase is taken to obtain a vanadium compound saturated alkane solution. Sampling and analysis of the total vanadium concentration ∑[V]=0.50 mol / L, and the extraction rate is 72% as analyzed by redox titration.

[0047] The vanadium compound saturated alkane solution was placed in a flask, and 1.0 mL of propionic acid was added. Under nitrogen protection, the solution was distilled under reduced pressure at 20° C. for 4 h to remove hexane to obtain an organic solution, which was the vanadium catalyst composition V3.

[0048] Embodiment 4:

[0049] A method for preparing a vanadium catalyst composition comprises the following steps: adding 14 ml of isooctyl alcohol extractant and 1.4 g of electron donor dimethyl sulfoxide to a separatory funnel, diluting the mixture to 60 ml with hexane to obtain an extractant dilution. 6 g of Ca2V2O7 is used as an inorganic vanadium compound, added to the extractant dilution, and then 21 ml of 37 wt% concentrated hydrochloric acid is added. The separatory funnel is placed on a Conrad oscillator and shaken for 15 min to fully mix the two phases. The mixture is then allowed to stand for about 1 hour for phase separation, and the lower layer is the residual water phase, which is discharged from the lower port. The upper organic phase is taken to obtain a vanadium compound saturated alkane solution. The total vanadium concentration ∑[V] is 0.50 mol / L when sampled and analyzed, and the extraction rate is 92% as analyzed by redox titration.

[0050] The vanadium compound saturated alkane solution was placed in a flask, and 1.0 mL of propionic acid was added. Under nitrogen protection, the solution was distilled under reduced pressure at 40° C. for 4 h to remove hexane to obtain an organic solution, which was the vanadium catalyst composition V4.

[0051] Embodiment 5~7:

[0052] Isoamyl alcohol, octadecyl alcohol, and N235 were used as extractants instead of isooctyl alcohol in Example 4, ethyl methyl sulfoxide, methyl phenyl sulfoxide, and n-propyl sulfoxide were used as electron donors instead of dimethyl sulfoxide in Example 4, and n-hexane, toluene, and heptane were used as diluents instead of hexane in Example 4, respectively. The extractants and electron donors were prepared into 60 ml of extractant diluent. The vanadium catalyst composition was prepared by the same method as in Example 4 to obtain vanadium catalyst compositions V5 to V7, respectively. The detailed process conditions and preparation results are listed in Table 1.

[0053] Table 1 Ratios of raw materials and extraction rates of Examples 3 to 7

[0054]

[0055] Embodiments 8 to 11

[0056] Install the reactor used for polymerization, keep it airtight, and replace it with nitrogen three times; add 0.025mmol of the vanadium catalyst composition (V1-V4) prepared in Examples 1 to 4, 0.4mmol of organic aluminum compound, 0.25g of ENB, and 50mL of hexane into the reactor respectively; introduce a mixed gas of ethylene and propylene with a molar ratio of 1:2, control the polymerization pressure at 0.4MPa, stir at 200r / min, and react at 20°C for 30min. After the polymerization is completed, add a 5% by mass hydrochloric acid-ethanol solution to the polymerization product to terminate the polymerization, wash the precipitate with ethanol, and then dry it at 40°C under vacuum to constant weight to obtain an EPDM rubber polymer. The specific experimental results and characterization data are shown in Table 2, and the DSC spectrum of the prepared EPDM rubber is shown in Figure 2 .

[0057] Table 2 Ratios of raw materials and structural parameters of EPDM rubber prepared in Examples 8 to 11

[0058]

[0059]

[0060] Embodiments 12 to 15

[0061] The reactor used for polymerization was installed, kept airtight, and replaced with nitrogen three times; 0.025mmol of the vanadium catalyst composition V4 prepared in Example 4, 0.5mmol of Al2(C2H5)3Cl3, 0.3g of the third monomer non-conjugated diene, and 50mL of hexane were added to the reactor respectively; ethylene and propylene mixed gas with a molar ratio of ethylene to propylene of 1:2 was introduced, the polymerization pressure was controlled at 0.4MPa, stirred at 200r / min, and reacted at 20°C for 30min. After the polymerization was completed, a 5% by mass hydrochloric acid-ethanol solution was added to the polymerization product to terminate the polymerization, washed and precipitated with ethanol, and then dried to constant weight at 40°C under vacuum to obtain ethylene propylene rubber polymer. The product ethylene propylene rubber was characterized, and the results are shown in Table 3.

[0062] The non-conjugated dienes used in Examples 12 to 15 are 5-vinyl-2-norbornene (VNB), dicyclopentadiene (DCPD), 4-ethylene-1-cyclohexene (VCH) and 1,4-hexadiene (HD), respectively.

[0063] Table 3 Structural parameters of EPDM rubber prepared in Examples 12 to 15

[0064]

[0065] Embodiments 16 to 19

[0066] The reactor used for polymerization was installed, kept airtight, and replaced with nitrogen three times; 0.075mmol of the vanadium catalyst composition (V4-V7) prepared in Examples 4 to 7, 1.5mmol of ethylaluminum dichloride (AlC2H5Cl2), and 50mL of hexane were added to the reactor respectively; a mixed gas of ethylene and propylene with a molar ratio of ethylene to propylene of 4:5 was introduced, the polymerization pressure was controlled at 0.5MPa, stirred at 200r / min, and reacted at different polymerization temperatures for 60min. After the polymerization was completed, a 5% by mass hydrochloric acid-ethanol solution was added to the polymerization product to terminate the polymerization, washed and precipitated with ethanol, and then dried to constant weight at 40°C under vacuum to obtain a diethylene glycol rubber polymer. The diethylene glycol rubber polymer was characterized, and the results are shown in Table 4.

[0067] The polymerization temperatures of Examples 16 to 19 were 70°C, 0°C, 30°C and 50°C, respectively.

[0068] Table 4 Structural parameters of EPDM rubber prepared in Examples 16 to 19

[0069]

[0070] Embodiment 20

[0071] The reactor used for polymerization was installed, kept airtight, and replaced with nitrogen three times; 0.025mmol of the vanadium catalyst composition (V4) prepared in Example 4, 0.5mmol of trichlorotriethylaluminum (Al2(C2H3)3Cl3), and 50mL of hexane were added to the reactor respectively; a mixed gas of ethylene and propylene with a molar ratio of ethylene to propylene of 1:2 was introduced, the polymerization pressure was controlled at 0.4MPa, stirred at 200r / min, and reacted at 20°C for 30min. After the polymerization was completed, a 5% by mass hydrochloric acid-ethanol solution was added to the polymerization product to terminate the polymerization, washed and precipitated with ethanol, and then dried to constant weight at 40°C under vacuum to obtain a diethylene glycol rubber polymer. The diethylene glycol rubber polymer was characterized, and the results are shown in Table 5.

[0072] Comparative Example 1

[0073] (1) Replace the air in a sealed 0.1 L reactor with nitrogen three times;

[0074] (2) 0.025 mmol of vanadium catalyst (VOCl3), 0.5 mmol of triethylaluminum trichloride (Al2(C2H3)3Cl3) and 0.3 g of VNB were added in sequence;

[0075] (3) Add 50 ml of hexane solvent, then introduce a mixed gas of ethylene and propylene with a molar ratio of ethylene to propylene of 1:2, and react at a pressure of 0.4 MPa, stirring at 200 r / min, and a temperature of 20°C for 30 min;

[0076] (4) The polymerization product was terminated with a 5% by mass hydrochloric acid-ethanol solution, washed with ethanol, and vacuum dried at 40° C. to a constant weight to obtain 1.5 g of EPDM rubber.

[0077] Comparative Example 2

[0078] (1) Replace the air in a sealed 0.1 L reactor with nitrogen three times;

[0079] (2) adding 0.025 mmol of vanadium catalyst (VOCl3) and 0.5 mmol of triethylaluminum trichloride (Al2(C2H3)3Cl3) in sequence;

[0080] (3) Add 50 ml of hexane solvent, then introduce a mixed gas of ethylene and propylene with a molar ratio of ethylene to propylene of 1:2, and react at a pressure of 0.4 MPa, stirring at 200 r / min, and a temperature of 20°C for 30 min;

[0081] (4) The polymerization product was terminated with a 5% by mass hydrochloric acid-ethanol solution, washed with ethanol, and vacuum dried at 40° C. to a constant weight to obtain 1.7 g of EPDM rubber.

[0082] The vanadium catalyst composition containing an extractant and an electron donor prepared in Example 4 of the present invention was compared with the VOCl3 catalyst used in the industrial production of ethylene propylene rubber to carry out polymerization experiments of preparing ethylene propylene rubber with VNB as the third monomer or without adding the third monomer. The results are shown in Table 5 below, and Figure 3 and Figure 4 .

[0083] Table 5 Comparison of structural parameters of EPDM rubber prepared using different catalysts

[0084]

[0085]

[0086] Note: “ / ” means that such substances are not added.

[0087] The polymerization results in Table 5 show that: (1) the catalytic efficiency of preparing EPDM rubber using the vanadium catalyst composition V4 prepared in Example 4 of the present invention is 1.9 times that of the industrial catalyst VOCl3 (see Example 12 and Comparative Example 1 for specific experimental conditions), and high value-added EPDM rubber with a branched structure can be prepared, see Figure 3 (2) The catalytic efficiency of preparing EPDM rubber using the vanadium catalyst composition V4 prepared in Example 4 of the present invention is 2.05 times that of the industrial catalyst VOCl3 (for specific experimental conditions, see Example 20 and Comparative Example 2). Figure 4 This is the temperature change curve of the polymerization reaction.

[0088] The EPDM rubber prepared using the vanadium catalyst composition of the present invention was analyzed by DSC, NMR and high-temperature GPC. The results showed that the vanadium catalyst composition of the present invention can be used to develop different types of EPDM rubbers and to prepare EPDM terpolymer with a branched structure, which is beneficial for post-processing.

[0089] The present invention reduces the consumption of alkyl aluminum compounds while ensuring polymerization activity, selects a vanadium catalyst composition containing an oxidizing electron donor, and carries out copolymerization of ethylene, propylene, or ethylene, propylene, and non-conjugated dienes, thereby increasing the stability of vanadium metal active centers, increasing the catalytic activity of the vanadium catalyst, and increasing the insertion rate of the third monomer; at the same time, the amount of the co-catalyst organic aluminum compound is reduced, which is conducive to replacing the industrial catalyst VOCl3 in industrial devices and being used as a vanadium catalyst for the production of ethylene-propylene rubber; the vanadium catalyst composition of the present invention is stable, has a simple preparation method, is safe to use, and has mild reaction conditions, thereby overcoming many disadvantages of the existing industrial catalyst VOCl3 in the preparation and use processes.

[0090] The above-described embodiments are only preferred solutions of the present invention and are not intended to limit the present invention in any form. Other variations and modifications are possible without exceeding the technical solutions described in the claims.

Claims

1. A vanadium catalyst composition, characterized in that: The vanadium catalyst composition is composed of a vanadium complex and an electron donor, wherein the ligand of the vanadium complex is one of fatty alcohols, amines and phosphates, and the structural formula of the electron donor is shown in formula (I): In the electron donor, R is selected from one of C1-C3 alkyl, aryl, and C1-C3 alkyl-substituted aryl; R' is selected from one of C1-C3 alkyl and aromatic alkyl. The preparation method of the vanadium catalyst composition adopts an aqueous phase one-step preparation method, comprising the following steps: (1) mixing an extractant, an electron donor and a diluent to obtain an extractant dilution solution; the diluent is a C6-C8 saturated alkane or toluene, and the extractant is a ligand of a vanadium complex; (2) mixing the extractant dilution prepared in step (1) with an inorganic vanadium compound or an aqueous solution of an inorganic vanadium compound, performing extraction and phase separation, and obtaining a dilute solution of a vanadium catalyst composition; the inorganic vanadium compound is selected from one or two of vanadium pentoxide, sodium metavanadate, ammonium metavanadate, calcium pyrovanadate, calcium orthovanadate, and sodium hexavanadate.

2. The vanadium catalyst composition according to claim 1, characterized in that: The fatty alcohols are C5~C 18 The fatty alcohol; the phosphate ester is selected from one of di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate 2-ethylhexyl ester, and di(2-ethylhexyl)phosphonic acid; the amine is selected from N 235 、N 1923 , one of tri-n-octylamine.

3. The vanadium catalyst composition according to claim 1, characterized in that: The method further comprises the step (3) of subjecting the dilute solution of the vanadium catalyst composition prepared in the step (2) to reduced pressure distillation under the protection of a stabilizer to remove the diluent, thereby obtaining the vanadium catalyst composition.

4. The vanadium catalyst composition according to claim 1, characterized in that: The molar ratio of the extractant to the electron donor in step (1) is 1:(0.2-2.0).

5. The vanadium catalyst composition according to claim 1, characterized in that: In step (2), the aqueous solution of the inorganic vanadium compound is adjusted to a pH value of 1 to 10 using an acid-base solution, the concentration of vanadium in the aqueous solution of the inorganic vanadium compound is 0.4 to 1.5 mol / L, and the molar ratio of the extractant to the inorganic vanadium compound or the vanadium in the aqueous solution of the inorganic vanadium compound is (1 to 3.0):

1.

6. The vanadium catalyst composition according to claim 1, characterized in that: In step (2), before extraction and phase separation, the volume ratio of the total aqueous phase to the total organic phase is 1:(1-3).

7. The vanadium catalyst composition according to claim 3, characterized in that: In step (3), the stabilizer is a C2-C4 fatty acid with a mass concentration of less than 1%; the temperature of the vacuum distillation is 20-70° C., and the time of the vacuum distillation is 0.5-4 hours.

8. Use of the vanadium catalyst composition according to claim 1 or 2, characterized in that: The applications include use in the synthesis of ethylene propylene rubber.

9. The use according to claim 8, characterized in that: In an organic solvent, the vanadium catalyst composition and the co-catalyst organoaluminum compound are used to carry out copolymerization of ethylene and propylene to prepare EPDM rubber; in an organic solvent, the vanadium catalyst composition and the co-catalyst organoaluminum compound are used to carry out copolymerization of ethylene, propylene and non-conjugated diene to prepare EPDM rubber.

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