Rare earth metal catalyst composition and method of making and using same

Abstract

The feed composition includes a main catalyst, a first alkyl metal reagent, and a polyene promoter, wherein the general structure of the main catalyst is LLnL 1 L 2 where the structure of L is [Formula 1] JPEG2025530143000013.jpg31134, and the general formula of the first alkylmetal reagent is MR 11 n The rare earth metal catalyst composition has a long duration of catalytic activity, a high catalytic efficiency, and good solubility in alkanes after the catalyst is activated.

Description

[Technical Field]

[0001] This application claims priority from a Chinese patent application filed with the China Patent Office on September 29, 2022, bearing application number 202211197805.0 and entitled "Rare earth metal catalyst composition and its manufacturing method and use," the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a rare earth metal catalyst composition for olefin polymerization, and more particularly to a rare earth metal catalyst composition for olefin polymerization improved with a polyene compound, which is suitable for producing high cis-conjugated diene rubber, and a method for producing the same. [Background technology]

[0003] Currently, industrially used rare earth catalysts are primarily multi-site Ziegler-Natta catalysts, such as ternary neodymium catalysts. In recent years, research has been actively conducted into single-site rare earth catalysts with specific structures, which, when used to catalyze the polymerization of conjugated dienes, are characterized by high activity and narrow molecular weight distributions. In particular, the PNP rare earth catalyst disclosed in US2008114136A1 offers optimal overall performance for the catalytic polymerization of butadiene and isoprene, maintaining good cis-1,4 selectivity even at high polymerization temperatures.

[0004] However, the current shortcomings of this type of catalyst are that after homogeneous single-site rare earth catalysts are cationized with borate reagents or methylaluminoxane (MAO), they lose activity quickly, the temperature rises too quickly, the active center has a short lifetime, and the catalyst has poor solubility in saturated alkanes.

[0005] In the preparation process of ternary neodymium-based rare earth catalysts, a certain proportion of conjugated diene (which may be the same as or different from the polymerization monomer) is usually added for prepolymerization to control the release of activity, but it is not often used in the production and use of single-site rare earth catalysts.However, considering the large difference in catalytic activity between ternary rare earth catalysts and single-site rare earth catalysts, the difficulty of controlling the release of activity and the activity retention time are both large differences, so they are not easily comparable.

[0006] Therefore, effective means to control the activity of single-site rare earth catalysts and improve the solubility of the catalysts are the key to whether these catalysts can be used industrially. Summary of the Invention [Problem to be solved by the invention]

[0007] In order to solve the above problems, the object of the present invention is to provide a rare earth metal catalyst composition having a long catalytic activity duration, high catalytic efficiency, and good solubility in alkanes after the catalyst is activated, as well as a method for preparing and using the same. [Means for solving the problem]

[0008] In order to achieve the above object, the present invention provides: The feed composition includes a main catalyst, a first alkyl metal reagent, and a polyene promoter; The primary catalyst is a rare earth metal complex having the structure shown in Formula I: LLnL 1 L 2 Formula I wherein L has the structure shown in Formula II:

[0009] [ka] Ln is a transition metal element of group IIIB, L 1 and L 2are the same or different and each independently selected from H, halogen, —R′, —SiR′3, —OR′, —SR′, —NR′2 and —PR′2, where R′ is C1-C 20 Alkyl groups, C2-C 20 Alkenyl groups, C3-C 20 Cycloalkyl groups of C6-C 30 Aryl groups and their derivatives, C6-C 30 Aralkyl groups and their derivatives, C1-C 30 Heteroatom-containing alkyl groups of Groups IIIA to VIIA and their derivatives, C1-C 30 Group IIIA to VIIA heteroatom-containing aryl groups and their derivatives, C1-C 30 is one selected from the group consisting of aralkyl groups containing heteroatoms of Group IIIA to Group VIIA elements and derivatives thereof; In Formula II, R 1 ~R 6 are the same or different and each independently represent H, halogen, C1-C 20 Alkyl groups, C2-C 20 Alkenyl groups, C3-C 20 Cycloalkyl groups of C6-C 30 Aryl groups and their derivatives, C7-C 30 Aralkyl groups and their derivatives, C7-C 30 Alkylaryl groups and their derivatives, C1-C 30 Heteroatom-containing alkyl groups of Groups IIIA to VIIA and their derivatives, C1-C 30 Group IIIA to VIIA heteroatom-containing aryl groups and their derivatives, C1-C 30 and aralkyl groups containing heteroatoms of Group IIIA to VIIA elements and derivatives thereof, -SiR"3, -OR", -SR", -NR"2, and -PR"2, wherein R" is C1-C 20 Alkyl groups, C2-C 20 Alkenyl groups, C3-C 20 Cycloalkyl groups of C6-C 30 Aryl groups and their derivatives, C6-C 30Aralkyl groups and their derivatives, C1-C 30 Heteroatom-containing alkyl groups of Groups IIIA to VIIA and their derivatives, C1-C 30 Group IIIA to VIIA heteroatom-containing aryl groups and their derivatives, C1-C 30 is one selected from the group consisting of aralkyl groups containing heteroatoms of Group IIIA to Group VIIA elements and derivatives thereof; The first alkylmetal reagent is selected from compounds of formula III: Formula III: MR 11 n , where M is Al, Zn, Mg, n=2 or 3, and R 11 are hydrogen, halogens, C1-C 20 is an alkyl group or a halogenated alkyl group of the formula the molar ratio of the first alkylmetal reagent to the main catalyst is 0.1:1 to 10000:1; The molar ratio of the polyene promoter to the main catalyst is 1:1 to 1000:1.

[0010] According to a specific embodiment of the present invention, preferably, when M in formula III is Mg or Zn, the molar ratio of the first alkylmetal reagent to the main catalyst is 0.1:1 to 10:1.

[0011] According to a specific embodiment of the present invention, preferably, when M in formula III is Al, the molar ratio of the first alkylmetal reagent to the main catalyst is 1:1 to 100:1.

[0012] According to a specific embodiment of the present invention, preferably, the feed composition further comprises a promoter.

[0013] According to a specific embodiment of the present invention, the co-catalyst is preferably selected from compounds of formula IV or V, Formula IV:[EH] + [BA] - , [E] + [BA] -or BA', where E is a nitrogen- or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, and A and A' are the same or different and each independently a C-C 20 Aryl or halogenated aryl groups, C1-C 20 is one selected from alkyl groups and halogenated alkyl groups, Formula V: [-Al(R 10 )O-] n , where R 10 is C1-C 20 and n is an integer of 2 or more, for example, an integer of 2 to 20.

[0014] According to a specific embodiment of the present invention, preferably, when the co-catalyst is selected from the compounds represented by Formula IV, the molar ratio of the co-catalyst to the main catalyst is 0.1:1 to 10:1; and when the co-catalyst is selected from the compounds represented by Formula V, the molar ratio of the co-catalyst to the main catalyst is 0.1:1 to 5000:1.

[0015] According to a specific embodiment of the present invention, preferably, when the co-catalyst is selected from the compounds represented by Formula IV, the molar ratio of the co-catalyst to the main catalyst is 0.5:1 to 2:1; and when the co-catalyst is selected from the compounds represented by Formula V, the molar ratio of the co-catalyst to the main catalyst is 10:1 to 500:1.

[0016] According to a specific embodiment of the present invention, preferably the polyene promoter is butadiene, C5-C 30 It is a type selected from hemiterpene, monoterpene, sesquiterpene, diterpene and triterpene compounds.

[0017] According to a specific embodiment of the present invention, the main catalyst preferably has a structure as shown in formula VI:

[0018] [ka] According to a specific embodiment of the present invention, Ln is preferably scandium, yttrium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium or lutetium.

[0019] According to a specific embodiment of the present invention, preferably, L 1 and L 2 are the same or different and each independently selected from hydrogen, halogen, 1,3-propenyl group, trimethylsilylmethyl group, di(trimethylsilyl)methyl group, tri(trimethylsilyl)methyl group, o-(N,N-dimethylamino)benzyl group, and N,N-di(trimethylsilyl)amino group.

[0020] According to a specific embodiment of the present invention, preferably, R 1 ~R 6 are the same or different and each independently represent a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or a C 11 -C 20 long-chain aliphatic alkyl groups, vinyl groups, propenyl groups, allyl groups, butenyl groups, pentenyl groups, octenyl groups, heptenyl groups, nonenyl groups, decenyl groups, C 11 -C 20Long-chain alkenyl groups, benzyl groups, biphenyl groups, naphthyl groups, phenanthryl groups, fluorenyl groups, phenyl groups, p-methylphenyl groups, o-methylphenyl groups, m-methylphenyl groups, o-dimethylphenyl groups, m-dimethylphenyl groups, mesityl groups, o-diisopropylphenyl groups, p-tert-butylphenyl groups, p-methoxyphenyl groups, p-chlorophenyl groups, m-chlorophenyl groups, o-chlorophenyl groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, chloroethyl groups, bromoethyl groups, iodoethyl groups, The group is one selected from the group consisting of trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, trimethylsilylmethyl group, dimethylamino group, diethylamino group, diisopropylamino group, methoxy group, ethoxy group, cyano group, nitro group, trifluoromethyl group, p-fluorophenyl group, p-chlorophenyl group, p-bromophenyl group, p-trifluoromethylphenyl group, p-methoxyphenyl group, p-cyanophenyl group, p-nitrophenyl group, and p-dimethylaminophenyl group.

[0021] According to a specific embodiment of the present invention, the compound represented by formula IV is preferably one of triphenyl(methyl)-tetra(pentafluorophenyl)boron salt, phenyl-dimethylamino-tetra(pentafluorophenyl)boron salt, phenyl-dimethylamino-tetraphenylboron salt, tri(pentafluorophenyl)boron, and triphenylboron.

[0022] According to a specific embodiment of the present invention, the compound represented by Formula V is preferably one of methylaluminoxane, ethyl-modified methylaluminoxane, n-propyl-modified methylaluminoxane, isobutyl-modified methylaluminoxane, n-hexyl-modified methylaluminoxane, and n-octyl-modified methylaluminoxane.

[0023] According to a specific embodiment of the present invention, the first alkylmetal reagent is preferably one or a combination of two or more of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, ethylp-tolylaluminum, diethylzinc, diisopropylzinc, dibutylzinc, diethylmagnesium, dibutylmagnesium, and n-butylethylmagnesium.

[0024] According to a specific embodiment of the present invention, the first alkylmetal reagent is preferably one or a combination of diethylzinc, diisopropylzinc, dibutylzinc, diethylmagnesium, dibutylmagnesium, n-butylethylmagnesium.

[0025] According to a specific embodiment of the present invention, the polyene accelerator is preferably one or a combination of isoprene, limonene, myrcene, ocimene, α-farnesene, β-farnesene, squalene.

[0026] According to a specific embodiment of the present invention, preferably the polyene enhancer is myrcene and / or β-farnesene.

[0027] According to a specific embodiment of the present invention, preferably, the molar ratio of the first alkylmetal reagent to the main catalyst is 10:1 to 100:1, and the molar ratio of the polyene promoter to the main catalyst is 1:1 to 200:1.

[0028] The present invention further provides a method for producing the above rare earth metal catalyst composition, which comprises the following steps:

[0029] (1) adding the polyene promoter to an alkane solvent and mixing to obtain a base mixture solution; (2) dissolving the main catalyst in an organic solvent, adding the basic mixed solution obtained in step (1), and mixing to obtain a mixed solution; (3) A step of aging the mixed solution obtained in step (2) (for example, aging at room temperature) to obtain the rare earth metal catalyst composition.

[0030] According to a specific embodiment of the present invention, preferably, step (1) or step (2) further comprises adding a first alkylmetal reagent to a saturated alkane solvent and mixing, and more preferably, the first alkylmetal reagent is added in step (1).

[0031] According to a specific embodiment of the present invention, preferably, step (2) further comprises dissolving a co-catalyst in an organic solvent and then adding the co-catalyst to the mixed solution.

[0032] According to a specific embodiment of the present invention, in step (1), the alkane solvent is preferably one or a combination of n-hexane, n-heptane, cyclopentane, and cyclohexane.

[0033] According to a specific embodiment of the present invention, in step (1), the mixing temperature is preferably 20°C to 40°C.

[0034] According to a specific embodiment of the present invention, in step (1), the mixing time is preferably 0.5 to 2 hours.

[0035] According to a specific embodiment of the present invention, in step (2), the organic solvent is preferably toluene and / or methylcyclohexane.

[0036] According to a specific embodiment of the present invention, in step (2), the mixing temperature is preferably 20°C to 40°C.

[0037] According to a specific embodiment of the present invention, in step (3), the aging time is preferably 0.5 hours to 5 hours, more preferably 1 hour to 2 hours, and the aging temperature is preferably 20°C to 40°C.

[0038] The present invention further provides the use of the above rare earth metal catalyst composition in olefin polymerization.

[0039] According to a specific embodiment of the present invention, preferably, the olefin is 1,3-butadiene or isoprene.

[0040] According to a specific embodiment of the present invention, preferably, the olefin polymerization comprises the following steps: In a protective gas atmosphere (e.g., nitrogen gas), a polymerization solvent, a polymerization monomer, and a second alkyl metal reagent are added and stirred at 20 to 50°C for 0.5 to 2 hours, and then the rare earth metal catalyst composition is added, followed by a polymerization reaction at 20 to 100°C for 0.1 to 4 hours. After the reaction is complete, the gum solution is added to an alcohol solution (e.g., ethanol) containing an antioxidant to cause coagulation, and the solvent is removed with hot steam, followed by drying on an open roll to obtain an olefin polymer. wherein the molar ratio of the polymerization monomer to the rare earth metal catalyst composition is 1,000 to 10,000,000:1; the molar ratio of the second alkylmetal reagent to the rare earth metal catalyst composition is 10 to 10,000:1; The second alkylmetal reagent is selected from compounds of formula III and may be the same as or different from the first alkylmetal reagent.

[0041] According to a specific embodiment of the present invention, the second alkylmetal reagent is preferably one or a combination of triisobutylaluminum, diisobutylaluminum hydride, triethylaluminum, diethylzinc, diethylmagnesium, and dibutylmagnesium.

[0042] According to a specific embodiment of the present invention, the polymerization solvent is preferably n-hexane and / or C6 extracted oil. [Effects of the Invention]

[0043] The present invention has the following beneficial effects: (1) The catalytic activity of the catalyst can be maintained for a long time. Polyene promoters have many double bonds, which can form weak coordination with the rare earth active center, providing good protection for the rare earth center. Furthermore, because of their weak coordination, they do not significantly affect the catalytic activity. (2) The catalyst releases its catalytic activity more slowly. Polyene accelerators have many double bonds, which can form weak coordination with the rare earth active center, which can inhibit the coordination between the monomer molecules and the rare earth center to some extent, slowing down the release of activity and further reducing the heat generated by polymerization, which is advantageous for industrial production control. (3) Higher catalytic efficiency of the catalyst. Polyene promoters can prolong the catalytic system's activity and maximize the conversion of polymerization monomers. (4) After the catalyst is activated, it has better solubility in saturated alkanes. The polyene promoter and the rare earth active center can form a weak coordination interaction, which reduces the polarity of the entire active species and makes it more soluble in saturated alkane solvents. [Brief explanation of the drawings]

[0044] [Figure 1] 1 is a graph showing the polymerization temperature-time of Polymerization Example 5 and Comparative Polymerization Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0045] In order to make the technical features, objectives and beneficial effects of the present invention more clearly understood, the technical solutions of the present invention are described in detail below, but should not be understood to limit the scope of the present invention.

[0046] In the following examples, experimental methods for which no specific conditions are specified are carried out according to normal conditions, and in the examples, all operations for preparing catalysts are carried out under the protection of high-purity nitrogen gas.

[0047] In the chemical formulae according to the present invention, "-" indicates that groups are linked together, and does not particularly mean a single bond. For example, the linkage between groups may be a single bond linkage, a coordinate linkage, or the like, or may be a combination of a single bond linkage and a coordinate linkage. [Example]

[0048] Example 1 This example provides a rare earth metal catalyst composition obtained by the following steps. (1) β-Farnesene (0.531 g, 2.6 mmol) and triisobutylaluminum (1 M, 0.52 mL, 0.52 mmol) were added to n-hexane (50 mL), mixed, and stirred at 25°C for 1 hour to obtain a basic mixed solution. (2) Compound a1 (52 μmol) was dissolved in 10 mL of toluene, and then the basic mixed solution obtained in step (1) was added and mixed to obtain mixed solution A. (3) A solution of modified methylaluminoxane (MMAO) in n-heptane (1.98 M, 5.25 mL, 2.65 mmol) was added to the mixed solution A obtained in step (2) and mixed to obtain a mixed solution B. (4) The mixed solution B obtained in step (3) was aged at 25°C for 1 hour, and then a rare earth metal catalyst composition A1 was obtained. Here, the synthesis of compound a1, the main catalyst, was carried out with reference to the literature (Zhang Lixin, Suzuki Toshiaki, Luo Yi, Nishiura Masayoshi, Hou Zhaomin. Cationic alkyl rare-earth metal complexes bearing an ancillary bis(phosphinophenyl)amide ligand: a catalytic system for living cis-1,4-polymerization and copolymerization of isoprene and butadiene. [J]. Angewandte Chemie (International ed. in English), 2007, 46(11): 1909-1913). The structure of compound a1 is as follows:

[0049] [ka] Example 2-22 Examples 2-22 provide rare earth metal catalyst compositions, respectively, the preparation methods of which are the same as those of Example 1, except that compound a1 is replaced with compounds a2-a14 having corresponding substituents, the structural information of compounds a2-a14 is shown in Table 1, and the promoter, alkyl metal reagent and polyene compound are replaced with corresponding raw materials, the raw material compositions of the catalyst compositions are shown in Table 2, to obtain rare earth metal catalyst compositions A2-A22.

[0050] Comparative Examples 1-5 Comparative Examples 1-5 provide catalyst compositions D1-D5, the raw material compositions of which are shown in Table 2, and the preparation methods are the same as those of Examples 1-5, except that no polyene promoter is added.

[0051] [Table 1]

[0052] Note: Cy = cyclohexyl group, i-Pr = isopropyl group, t-Bu = tert-butyl group.

[0053] [Table 2]

[0054] Comparative Examples 6-10 Catalysts D6-D10 provided by Comparative Examples 6-10 and their polymerization experiment results (shown in Tables 3 and 4) are derived from EP3705499A1 and are conventional ternary neodymium-based rare earth catalysts, the compositions of which are shown in Table 3 below.

[0055] Catalyst composition D6 is Example 1 in EP 3705499 A1, Catalyst composition D7 is example 2 in EP 3705499 A1, Catalyst composition D8 is example 3 in EP 3705499 A1, Catalyst composition D9 is example 4 in EP 3705499 A1, Catalyst composition D10 is example 5 in EP 3705499 A1.

[0056] [Table 3]

[0057] Note: DIBAH is diisobutylaluminum hydride and DEAC is diethylaluminum chloride.

[0058] The above catalyst composition was mixed at 20° C. for 10 minutes, and then 1,3-butadiene was added in an amount 10 times the neodymium carboxylate (molar ratio), and prepolymerized to form a catalyst.

[0059] Polymerization Example 1 After replacing the atmosphere with nitrogen gas, 5 kg of hexane, 900 g of 1,3-butadiene, and a 1 M n-hexane solution of triisobutylaluminum (57.2 mL, 57.2 mmol) were sequentially placed in a 15 L polymerization vessel and stirred at 40°C for 1 hour. The aged catalyst composition A1 (all rare earth metal catalyst composition A1 obtained in Example 1) was then added. After polymerization for 2 hours, the gum solution was coagulated by adding it to an ethanol solution (200 mL) containing 9 g of BHT antioxidant. The solvent was removed with hot steam, and the mixture was dried on an open roll to obtain a butadiene polymer. The results are shown in Table 4.

[0060] Polymerization Example 2-22 The polymerization method was the same as in Polymerization Example 1, except that catalyst compositions A2-A22 were used to catalyze the polymerization reaction, and the results are shown in Table 4. The polymerization temperature-time curve of Polymerization Example 5 is shown in Figure 1.

[0061] Comparative Polymerization Examples 1-5 The polymerization method was the same as in Polymerization Example 1, except that catalyst compositions D1-D5 were used to catalyze the polymerization reaction, and the results are shown in Table 4. The polymerization temperature-time curve of Polymerization Comparative Example 5 is shown in Figure 1.

[0062] Comparative Polymerization Examples 6-10 Polymerization Comparative Examples 6-10 polymerization results were derived from butadiene polymerization data in EP 3705499 A1 and used catalyst compositions D6-D10.

[0063] [Table 4-1]

[0064] [Table 4-2]

[0065] Note: The cis-1,4 selectivities for Comparative Examples 6-10 were 96.7%, 96.8%, 96.7%, 96.6%, and 96.7%, respectively, and the references do not indicate the maximum temperature or time to reach the maximum temperature during the polymerization process.

[0066] "Catalytic efficiency (Kg BR / gM)" means kilograms of rare earth metal catalyzed polybutadiene product per gram of polybutadiene product.

[0067] Polymerization Examples 23-27 The polymerization method was the same as in Polymerization Example 5, except that different proportions of polyene promoter were used. The β-farnesene / rare earth metal molar ratios used in Polymerization Examples 23-27 are shown in Table 5 below.

[0068] [Table 5]

[0069] Comparison of Polymerization Example 1-22 with Comparative Polymerization Example 1-5 shows that after adding polyene accelerator, the polymerization activity is significantly improved, the polymerization temperature is significantly higher, and the time to reach the maximum temperature is longer, so the survival time of catalytic active species is longer and the release of activity is slower, which is advantageous for industrial production. Comparative Polymerization Example 6-10 is the data in EP3705499A1, and the activity is significantly lower, but the temperature data is not shown, so it cannot be compared.

[0070] Furthermore, the catalyst prepared with the addition of a polyene promoter can always maintain clarity, whereas the catalyst without the addition of a polyene promoter may show obvious precipitation or oily substance after standing for a certain period of time, indicating partial deactivation of the catalyst.

Claims

1. The feed composition includes a main catalyst, a first alkyl metal reagent, and a polyene promoter; The primary catalyst is a rare earth metal complex having the structure shown in Formula I: LLnL 1 L 2 ・・・ Formula I wherein L has the structure shown in Formula II: 【Chemical 1】 Ln is a transition metal element of group IIIB, L 1 and L 2 are the same or different and each independently represent H, halogen, -R', or -SiR' 3 , -OR', -SR', -NR' 2 and -PR' 2 wherein R' is selected from C 1 -C 20 Alkyl groups of C 2 -C 20 Alkenyl groups of C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups and their derivatives, C 6 -C 30 Aralkyl groups and their derivatives, C 1 -C 30 Heteroatom-containing alkyl groups of Groups IIIA to VIIA and their derivatives, 1 -C 30 Group IIIA to VIIA heteroatom-containing aryl groups and their derivatives, C 1 -C 30 is one selected from the group consisting of aralkyl groups containing heteroatoms of Group IIIA to Group VIIA elements and derivatives thereof; In Formula II, R 1 ~R 6 are the same or different and each independently represent H, halogen, C 1 -C 20 Alkyl groups of C 2 -C 20 Alkenyl groups of C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups and their derivatives, C 7 -C 30 Aralkyl groups and their derivatives, C 7 -C 30 Alkylaryl groups and their derivatives, C 1 -C 30 Heteroatom-containing alkyl groups of Groups IIIA to VIIA and their derivatives, 1 -C 30 Group IIIA to VIIA heteroatom-containing aryl groups and their derivatives, C 1 -C 30 Aralkyl groups containing heteroatoms of Groups IIIA to VIIA elements and derivatives thereof, -SiR'' 3 , -OR'', -SR'', -NR'' 2 ,-PR'' 2 wherein R″ is C 1 -C 20 Alkyl groups of C 2 -C 20 Alkenyl groups of C 3 -C 20 cycloalkyl groups, C 6 -C 30 aryl groups and their derivatives, C 6 -C 30 Aralkyl groups and their derivatives, C 1 -C 30 Heteroatom-containing alkyl groups of Groups IIIA to VIIA and their derivatives, 1 -C 30 Group IIIA to VIIA heteroatom-containing aryl groups and their derivatives, C 1 -C 30 is one selected from the group consisting of aralkyl groups containing heteroatoms of Group IIIA to Group VIIA elements and derivatives thereof; the first alkylmetal reagent is selected from compounds of formula III: Formula III: MR 11 n , where M is Al, Zn, Mg, n=2 or 3, and R 11 is hydrogen, halogen, C 1 -C 20 is an alkyl group or a halogenated alkyl group of the formula the molar ratio of the first alkylmetal reagent to the main catalyst is 0.1:1 to 10,000:1; the molar ratio of the polyene promoter to the main catalyst is 1:1 to 1000:1; Rare earth metal catalyst compositions.

2. 2. The rare earth metal catalyst composition of claim 1, wherein when M in Formula III is Mg or Zn, the molar ratio of the first alkylmetal reagent to the main catalyst is 0.1:1 to 10:

1.

3. 10. The rare earth metal catalyst composition of claim 1, wherein when M is Al in Formula III, the molar ratio of the first alkylmetal reagent to the main catalyst is from 1:1 to 100:

1.

4. 10. The rare earth metal catalyst composition of claim 1, wherein the feed composition further comprises a promoter.

5. 5. The rare earth metal catalyst composition of claim 4, wherein the co-catalyst is selected from compounds of formula IV or formula V: Formula IV: [EH] + [BA] - , [E] + [BA] - or BA', where E is a nitrogen- or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, A and A' are the same or different and each independently represent C 6 -C 20 Aryl group or halogenated aryl group, C 1 -C 20 is one selected from alkyl groups and halogenated alkyl groups, Formula V: [-Al(R 10 )O-] n , where R 10 is C 1 -C 20 and n is an integer of 2 to 20.

6. 6. The rare earth metal catalyst composition of claim 5, wherein when the co-catalyst is selected from the compound represented by Formula IV, the molar ratio of the co-catalyst to the main catalyst is 0.1:1 to 10:1, and when the co-catalyst is selected from the compound represented by Formula V, the molar ratio of the co-catalyst to the main catalyst is 0.1:1 to 5000:

1.

7. 6. The rare earth metal catalyst composition of claim 5, wherein when the co-catalyst is selected from the compound represented by Formula IV, the molar ratio of the co-catalyst to the main catalyst is 0.5:1 to 2:1, and when the co-catalyst is selected from the compound represented by Formula V, the molar ratio of the co-catalyst to the main catalyst is 10:1 to 500:

1.

8. The polyene accelerator may be butadiene, C 5 -C 30 2. The rare earth metal catalyst composition according to claim 1, wherein the compound is one selected from the group consisting of hemiterpene, monoterpene, sesquiterpene, diterpene and triterpene compounds.

9. 10. The rare earth metal catalyst composition of claim 1, wherein the main catalyst has the structure shown in Formula VI: 【Chemistry 2】

10. 2. The rare earth metal catalyst composition of claim 1, wherein Ln is scandium, yttrium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, or lutetium.

11. L 1 and L 2 are the same or different and each independently represent one selected from the group consisting of hydrogen, halogen, 1,3-propenyl, trimethylsilylmethyl, di(trimethylsilyl)methyl, tri(trimethylsilyl)methyl, o-(N,N-dimethylamino)benzyl, and N,N-di(trimethylsilyl)amino.

12. R 1 ~R 6 are the same or different and each independently represent a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or a C 11 -C 20 long-chain aliphatic alkyl groups, vinyl groups, propenyl groups, allyl groups, butenyl groups, pentenyl groups, octenyl groups, heptenyl groups, nonenyl groups, decenyl groups, C 11 -C 20 Long-chain alkenyl groups, benzyl groups, biphenyl groups, naphthyl groups, phenanthryl groups, fluorenyl groups, phenyl groups, p-methylphenyl groups, o-methylphenyl groups, m-methylphenyl groups, o-dimethylphenyl groups, m-dimethylphenyl groups, mesityl groups, o-diisopropylphenyl groups, p-tert-butylphenyl groups, p-methoxyphenyl groups, p-chlorophenyl groups, m-chlorophenyl groups, o-chlorophenyl groups, chloromethyl groups, bromomethyl groups, iodomethyl groups, chloroethyl groups, bromoethyl groups, iodoethyl groups, trimethylsilyl groups, trimethylsilyl groups, 2. The rare earth metal catalyst composition according to claim 1, wherein the aryl group is one selected from the group consisting of a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a methoxy group, an ethoxy group, a cyano group, a nitro group, a trifluoromethyl group, a p-fluorophenyl group, a p-chlorophenyl group, a p-bromophenyl group, a p-trifluoromethylphenyl group, a p-methoxyphenyl group, a p-cyanophenyl group, a p-nitrophenyl group, and a p-dimethylaminophenyl group.

13. 6. The rare earth metal catalyst composition of claim 5, wherein the compound represented by formula IV is one of triphenyl(methyl)-tetra(pentafluorophenyl)boron salt, phenyl-dimethylamino-tetra(pentafluorophenyl)boron salt, phenyl-dimethylamino-tetraphenylboron salt, tri(pentafluorophenyl)boron, and triphenylboron.

14. 6. The rare earth metal catalyst composition according to claim 5, wherein the compound represented by formula V is one of methylaluminoxane, ethyl-modified methylaluminoxane, n-propyl-modified methylaluminoxane, isobutyl-modified methylaluminoxane, n-hexyl-modified methylaluminoxane, and n-octyl-modified methylaluminoxane.

15. 2. The rare earth metal catalyst composition according to claim 1, wherein the first alkylmetal reagent is one or a combination of two or more of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, ethylp-tolylaluminum, diethylzinc, diisopropylzinc, dibutylzinc, diethylmagnesium, dibutylmagnesium, and n-butylethylmagnesium.

16. 16. The rare earth metal catalyst composition of claim 15, wherein the first alkylmetal reagent is one or a combination of two or more of diethylzinc, diisopropylzinc, dibutylzinc, diethylmagnesium, dibutylmagnesium, n-butylethylmagnesium.

17. 2. The rare earth metal catalyst composition of claim 1, wherein the polyene promoter is one or a combination of two or more of isoprene, limonene, myrcene, ocimene, α-farnesene, β-farnesene, squalene.

18. 18. The rare earth metal catalyst composition of claim 17, wherein the polyene promoter is myrcene and / or β-farnesene.

19. 10. The rare earth metal catalyst composition of claim 1, wherein the molar ratio of the first alkylmetal reagent to the main catalyst is from 10:1 to 100:1, and the molar ratio of the polyene promoter to the main catalyst is from 1:1 to 200:

1.

20. 10. A method for preparing the rare earth metal catalyst composition of claim 1, comprising the steps of: (1) adding the polyene promoter to an alkane solvent and mixing to obtain a base mixed solution; (2) dissolving the main catalyst in an organic solvent, adding the basic mixed solution obtained in step (1) and mixing to obtain a mixed solution; (3) aging the mixed solution obtained in step (2) to obtain the rare earth metal catalyst composition; Step (1) or step (2) may further comprise placing and mixing the first alkylmetal reagent in a saturated alkane solvent.

21. 21. The method according to claim 20, wherein a first alkylmetal reagent is added in step (1).

22. The method according to claim 20, wherein in step (2), the co-catalyst is dissolved in an organic solvent and then added to the mixed solution.

23. 21. The method according to claim 20, wherein in step (1), the alkane solvent is one or a combination of n-hexane, n-heptane, cyclopentane, and cyclohexane.

24. The method according to claim 20, wherein in step (1), the mixing temperature is 20°C to 40°C.

25. The method according to claim 20, wherein in step (1), the mixing time is 0.5 to 2 hours.

26. 21. The method according to claim 20, wherein in step (2), the organic solvent is toluene and / or methylcyclohexane.

27. The method according to claim 20, wherein in step (2), the mixing temperature is 20°C to 40°C.

28. 21. The method according to claim 20, wherein in step (3), the aging time is 0.5 hours to 5 hours, and the aging temperature is 20°C to 40°C.

29. The method according to claim 20, wherein in step (3), the aging time is 1 hour to 2 hours.

30. 10. Use of the rare earth metal catalyst composition of claim 1 in olefin polymerization.

31. 31. The use according to claim 30, wherein the olefin is 1,3-butadiene or isoprene.

32. 31. The use according to claim 30, wherein the olefin polymerization comprises the steps of: In a protective gas atmosphere, a polymerization solvent, a polymerization monomer, and a second alkyl metal reagent are added and stirred at 20 to 50°C for 0.5 to 2 hours. After the rare earth metal catalyst composition is added, a polymerization reaction is carried out at 20 to 100°C for 0.1 to 4 hours. After the reaction is completed, the gum solution is added to an alcohol solution containing an antioxidant to cause coagulation. After the solvent is removed, the mixture is dried to obtain an olefin polymer. the molar ratio of the polymerization monomer to the rare earth metal catalyst composition is 1,000 to 10,000,000:1; the molar ratio of the second alkylmetal reagent to the rare earth metal catalyst composition is 10 to 10,000:1; The second alkylmetal reagent is selected from compounds of formula III and may be the same as or different from the first alkylmetal reagent.

33. 33. The use according to claim 32, wherein the second alkylmetal reagent is one or a combination of two or more of triisobutylaluminum, diisobutylaluminum hydride, triethylaluminum, diethylzinc, diethylmagnesium, and dibutylmagnesium.

34. 33. The use according to claim 32, wherein the polymerization solvent is n-hexane and / or C6 extracted oil.

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