CN111620975B - Binuclear rare earth olefin polymerization catalyst and application thereof - Google Patents
Binuclear rare earth olefin polymerization catalyst and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明涉及一种双核稀土烯烃聚合催化剂及其应用，该双核稀土烯烃聚合催化剂由主催化剂、助催化剂、链转移试剂组成，该主催化剂为路易斯碱稳定的双核稀土络合物，由化学式[I]和化学式[II]表示：其中，Ln是元素周期表中第IIIB族的过渡金属元素。该双核稀土烯烃聚合催化剂适用于溶液聚合，其可以高活性地催化1,3‑丁二烯的聚合，聚合反应制得的聚丁二烯橡胶具有较高的顺式1,4‑含量以及较窄的分子量分布；与相应的单核稀土络合物相比，其具有活性和立体选择性的优势。The invention relates to a dual-nuclear rare earth olefin polymerization catalyst and application thereof. The dual-nuclear rare earth olefin polymerization catalyst is composed of a main catalyst, a co-catalyst and a chain transfer reagent. ] and formula [II] means: Among them, Ln is a transition metal element of group IIIB in the periodic table of elements. The dual-core rare earth olefin polymerization catalyst is suitable for solution polymerization, and can catalyze the polymerization of 1,3-butadiene with high activity. Narrow molecular weight distribution; offers advantages in activity and stereoselectivity compared to the corresponding mononuclear rare earth complexes.
Description
Technical Field
The invention relates to a catalyst for binuclear rare earth olefin polymerization, in particular to a catalyst for binuclear metallocene rare earth olefin polymerization with stable Lewis base and application thereof.
Background
The catalyst system for olefin rubber is a key to the production technology of olefin rubber, and currently used catalyst systems mainly include nickel (Ni) based, titanium (Ti) based, cobalt (Co) based, rare earth neodymium (Nd) based, and lithium (Li) based (zingiber officinale, et al, rare earth butadiene rubber, published by metallurgical industry, 2016, 39). Among them, the rare earth catalyst is the most distinctive and excellent in comprehensive performance, and the olefin rubber produced by using the rare earth catalyst has high cis-structure content, high linear structure regularity, high molecular weight and narrow distribution.
The Changchun acclimatization institute of Chinese academy of sciences in 1970 successfully developed a ternary catalytic system of rare earth carboxylate, alkylaluminum and alkylaluminum chloride for preparing high cis-polybutadiene rubber (rare earth catalytic synthetic rubber article [ C ]. scientific Press, 1980, 25). In the 80 s of the 20 th century, Bayer in Germany (At133rd meeting of the Rubber Division of ACS,1988,4, 19; At133rd meeting of the Rubber Division of ACS,1988,10,18) and Enichem in Italy (Kautschuk Gummi Kunststiffe,1993,6,458) successively realized the industrialization of rare earth polybutadiene Rubber. The rare earth catalysts currently used in industry are mainly ternary neodymium catalysts, and the core technology thereof is mainly mastered by Lanxess company in Germany (EP2311889, EP2363303, EP2676968, EP3057998, CN102574955, CN102762613, CN104395351 and CN107254008) and by the research groups of Changchun nationality institute (CN01128284, CN01128287, US7288611, CN01128289, CN03127180 and CN 200610016949).
Currently, the research on single-site rare earth metal catalysts with specific structures for the directional polymerization of conjugated dienes has been well developed, which catalyze diene polymerization reactions with characteristics of high activity and narrow molecular weight distribution (J.Organomet.chem.,2001,621,327; Macromol.chem.Phys.,2003,204,1747; Macromol.chem.Phys.,2004,205,737; Angel.chem., 2005,117,2649; Angel.chem.Int.Ed., 2005,44, 2593; Macromolecules 1999,32, 9078; Macromolecules 2001,34, 1539; Macromolecules 2003,36, 7923; romoles 2004,37, 5860; Macromolecules 2006,39, 1359; Dalton-, Trans 2008,2531; Angel.chem.Int.2007, 46,1909; Am 4984, 2008, 130.84, 2008).
Since rare earth elements are usually +3 valent, the cationic single-active-center rare earth catalyst for olefin polymerization is usually in a single-metallocene or non-metallocene structure, and the double-metallocene rare earth catalyst has no catalytic activity theoretically because no reaction site is inserted after cationization. The double Lewis base bridges 2 molecules of mononuclear double metallocene rare earth complex, hopefully, the aim of improving the catalytic activity is achieved by the synergistic action between double metals or the change of the coordination mode between metal and ligand. Some dinuclear or polynuclear rare earth metal complexes previously reported are usually bridged by sigma bond coordination of H or alkyl (Macromolecules 2004,37, 5860; Macromolecules 2006,39, 1359-.
Disclosure of Invention
The invention aims to provide a binuclear rare earth olefin polymerization catalyst, in particular to a binuclear metallocene rare earth catalyst composition with stable Lewis base, which is particularly suitable for preparing high cis-conjugated diene rubber.
In order to achieve the purpose, the binuclear rare earth olefin polymerization catalyst provided by the invention consists of a main catalyst, a cocatalyst and a chain transfer reagent; the main catalyst is a binuclear rare earth complex with stable Lewis base, and is represented by chemical formulas [ I ] and [ II ]:
wherein Ln is a transition metal element of group IIIB;
x is selected from one of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, N-bis (trimethylsilyl) amino;
R1to R18Same or different, each independently selected from hydrogen, C1-C10At least one of saturated alkyl groups of (a);
the cocatalyst is selected from the group consisting of formula [ III]A compound shown as the formula (I); chemical formula [ III]Expressed as: [ EH]+[BA4]-、[E]+[BA4]-or BA3Wherein E is a nitrogen or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, and A is selected from C6-C30Aryl or haloaryl, C1-C10At least one of alkyl or haloalkyl.
The chain transfer agent is selected from the group consisting of formula [ IV]A compound shown as the formula (I); chemical formula [ IV]Expressed as: al (R)19)(R20)(R21) Wherein Al is aluminum element, R19To R21The same or different, each independently selected from hydrogen, halogen, C1-C10At least one of alkyl or haloalkyl.
In the dinuclear rare earth olefin polymerization catalyst of the present invention, Ln is at least one selected from scandium, yttrium, and lanthanoid rare earth metal elements, and Y and Gd are more preferable.
The binuclear rare earth olefin polymerization catalyst of the present invention comprises, in particular,
is a bis-lewis base compound linked by an aliphatic chain or an aromatic structural unit, and does not contain acidic hydrogen, and is at least one selected from pyridine, 2, 6-lutidine, 4 '-bipyridine, 4-dimethylaminopyridine, N' -tetramethylp-phenylenediamine, N '-tetramethylethylenediamine, p-dimethoxybenzene, 4' -dimethoxybiphenyl, but is not limited thereto; further preferred is 4,4' -bipyridine.
The dinuclear rare earth olefin polymerization catalyst of the present invention, wherein X is selected from one of, but not limited to, trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, N-bis (trimethylsilyl) amine; more preferably, o- (N, N-dimethylamino) benzyl is used.
The dinuclear rare earth olefin polymerization catalyst of the present invention is characterized in that R1To R18The same or different, each independently selected from hydrogen and C1-C10Saturated alkyl groups of (a); wherein, C1-C10Saturated alkane of (2)The group is preferably at least one selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl, but is not limited thereto; more preferably methyl.
The binuclear rare earth olefin polymerization catalyst of the present invention is synthesized by coordination reaction between a mononuclear rare earth complex and a bis-Lewis base compound, in which the binuclear rare earth complex represented by the chemical formula [ I ] and the chemical formula [ II ] is generated in situ, and is directly used in polymerization reaction.
In the dinuclear rare earth olefin polymerization catalyst, when the dinuclear rare earth complex is generated, the molar ratio of the double Lewis base to the mononuclear rare earth complex is 0.5/1.
In the dinuclear rare earth olefin polymerization catalyst of the present invention, the compound represented by the formula [ III ] is preferably at least one selected from the group consisting of a triphenyl (methyl) -tetrakis (pentafluorobenzene) boron salt, a phenyl-dimethylamino-tetraphenylboron salt, a tris (pentafluorobenzene) boron salt, and a triphenyl boron salt, and is more preferably a phenyl-dimethylamino-tetraphenylboron salt.
In the dinuclear rare earth olefin polymerization catalyst of the present invention, the compound represented by the formula [ IV ] is preferably at least one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, and ethyl-p-tolylaluminum, but is not limited thereto; further preferred is triisobutylaluminum.
The binuclear rare earth complexes of the present invention can be prepared according to scheme C:
(a)
(b)
as shown in the figure, the route (a) is the synthesis of the non-bridged binuclear rare earth complex, and the route (b) is the synthesis of the silicon-bridged binuclear rare earth complex. The mononuclear rare earth complex reacts with 0.5 equivalent of double Lewis base, the reaction solvent is toluene, the reaction temperature is 25 ℃, separation is not carried out after the reaction is finished, and the mononuclear rare earth complex is directly used for olefin polymerization after the reaction is reacted with a cocatalyst.
The dinuclear rare earth olefin polymerization catalyst of the present invention is characterized in that the molar ratio of the compound represented by the formula [ III ] to the main catalyst is preferably 0.1/1 to 10/1, more preferably 1.0/1 to 2.0/1; the molar ratio of the compound represented by the formula [ IV ] to the main catalyst is preferably 1/1 to 10000/1, and more preferably 10/1 to 1000/1.
The invention also provides an application of the binuclear rare earth olefin polymerization catalyst in preparation of high cis-conjugated diene rubber.
In the binuclear rare earth olefin polymerization catalyst of the present invention, an alkylaluminum reagent represented by the chemical formula [ IV ] may be added in advance to a reaction system to be mixed with a polymerization monomer. The compound represented by the formula [ IV ] is mainly used as a polymer chain transfer agent, and the amount thereof has a large influence on the molecular weight of the polymer. In addition, the catalyst also serves as a main impurity removal reagent to react with impurities in the polymerized monomers for impurity removal. Therefore, when the molar ratio of the compound represented by the formula [ IV ] to the co-catalyst is in the above range, the problem of partial deactivation of the catalyst due to incomplete removal of impurities from the polymerized monomers can be avoided; further, the molecular weight distribution of the polymer can be controlled within a suitable range.
The binuclear rare earth olefin polymerization catalyst is used for preparing a conjugated diene polymer, the preparation process is homogeneous solution polymerization, a polymerization solvent is usually n-hexane, the binuclear rare earth olefin polymerization catalyst provided by the invention can catalyze the polymerization of 1, 3-butadiene with high activity, and polybutadiene rubber prepared by polymerization reaction has high cis-1, 4-content and narrow molecular weight distribution; compared with the corresponding mononuclear rare earth catalyst, the binuclear rare earth olefin polymerization catalyst has higher catalytic activity, and an olefin polymer generated by polymerization reaction has higher stereoregularity.
Drawings
FIG. 1 is a 1H-NMR spectrum of the compound shown in example 1;
FIG. 2 is a 1H-NMR spectrum of the compound shown in example 2;
FIG. 3 is a 1H-NMR spectrum of the compound shown in example 5.
Detailed Description
The present invention is described in detail by referring to the preferred examples below, and although the following examples are carried out on the premise of the technical scheme provided by the present invention, detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Wherein, part of the mononuclear rare earth complex can be synthesized by the reference (Journal of Organometallic Chemistry,322(1987) 321-329; Macromolecules 2004,37, 5860-5862; Organometallics,2005,24, 2269-2278).
In the following examples, the synthesis of the binuclear rare earth olefin polymerization catalyst and the catalytic olefin polymerization reaction are carried out under anhydrous and anaerobic conditions unless otherwise specified, and are realized by inert gas glove box or Schlenk technology, and the solvents used in the experiments are all subjected to anhydrous and anaerobic treatment; the invention is not so limited.
Furthermore, nuclear magnetic resonance of rare earth metal complexes1The H-NMR spectrum was tested by Bruker Ascend 600MHz, and part of the compounds could not be characterized by 1H-NMR due to paramagnetic properties. Cis-1, 4 selective passage of polymers13C-NMR spectrogram determination is carried out in an inverse gating decoupling mode; the molecular weight and molecular weight distribution of the polymer were measured by PL-GPC50 gel permeation chromatography.
Example 1
Preparation of mononuclear rare earth complex 1
Slowly dropwise adding n-butyllithium into the hexane solution of Cp at 0 ℃, then naturally raising the temperature to room temperature and stirringOvernight, a large amount of pale yellow precipitate was produced. And then, carrying out suction filtration in an inert gas glove box, washing the obtained solid with hexane for 2 times, and drying under vacuum to obtain light yellow powder solid, namely the CpLi compound. Slowly adding Cp Li in THF solution to YCl at room temperature3nTHF, followed by heating to reflux overnight. After the reaction, the THF solution was drained and extracted with toluene. Concentrating the toluene extract, and recrystallizing at-30 deg.C to obtain white solid, i.e. rare earth chloride Cp2YCl2Li(THF)2。
Slowly dropwise adding a toluene solution of ortho-dimethylaminobenzyllithium (AbzLi) to Cp at-30 DEG C2YCl2Li(THF)2Then the temperature is naturally raised to the room temperature, and the reaction is continued for 4 hours. Filtering with sand core funnel after reaction, vacuum drying filtrate to obtain yellow oily matter, washing with small amount of n-hexane to obtain light yellow powder, i.e. Cp2The YAbz product (compound 1).
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.86(s,30H,Cp-Me),2.14(s,6H,N-Me),2.28(br,2H,Y-CH2),6.71(d,J＝6Hz,1H),6.81(t,J＝6Hz,2H),7.05(t,J＝6Hz,2H),7.29(d,J＝6Hz,1H)。
example 2
Preparation of mononuclear rare earth complex 2
Alkyl lithium (TMSCH) was added at-30 deg.C2Li) was slowly added dropwise to Cp2YCl2Li(THF)2Then the temperature of the solution was naturally raised to room temperature, and the reaction was continued for 4 hours. Filtering with sand core funnel after reaction, vacuum drying filtrate to obtain yellow oily matter, washing with small amount of n-hexane to obtain light yellow powder, i.e. Cp2YACH2TMS product (compound 2).
Nuclear magnetic data:1H-NMR(600MHz,C6D6):0.00(s,2H,CH2TMS),0.44(s,9H,SiMe3),1.98(s,30H,Cp-Me)。
example 3
Preparation of mononuclear rare earth complex 3
Synthesis of Compound 3 referring to the synthesis of Compound 1, YCl in the starting Material3Replacement of nTHF to GdCl3nTHF, the experimental procedure was consistent and the product was obtained as a pale yellow powder solid. Due to the paramagnetic character of the + 3-valent Gd compound, NMR characterization was not possible, only on Cp-2GdCl2Li(THF)2X-ray single crystal diffraction characterization was performed.
Example 4
Preparation of mononuclear rare earth complex 4
Synthesis of Compound 4 referring to the synthesis of Compound 2, YCl in the starting Material3Replacement of nTHF to GdCl3nTHF, the experimental procedure was consistent and the product was obtained as a pale yellow powder solid. Due to the paramagnetic character of the +3 valent Gd compounds, NMR characterization was not possible, only Cp2GdCl2Li(THF)2X-ray single crystal diffraction characterization was performed.
Example 5
Preparation of mononuclear rare earth complex 5
N-butyllithium (2.4M in n-Hexane) was slowly added dropwise to dimethylsilyl Me at-30 deg.C2Adding Si-bridged bis (tetramethyl cyclopentadiene) ligand in ether solution, then heating to room temperature and continuing stirring for 2 hours, and keeping the reaction at the endAnd (4) drying the solvent in the air to obtain a light yellow solid, namely the dilithium salt of the ligand. Then the dilithium salt in THF was slowly added dropwise to YCl at-30 deg.C3(THF) n in THF suspension, after completion of the dropwise addition, the reaction solution was heated to reflux and the reaction was continued overnight. After the reaction is finished, pumping out THF under vacuum, adding toluene for extraction, filtering, pumping out the filtrate, and washing with a small amount of anhydrous hexane to obtain white solid powder, namely Si (CpMe)4)2YCl2Li(THF)2。
Slowly adding toluene suspension of benzyl lithium into toluene suspension of metallocene rare earth halide at-30 ℃, continuing to react overnight after the toluene suspension is heated to room temperature, filtering to remove generated LiCl after the reaction is finished, taking out the solvent from the filtrate in vacuum, and washing twice with a small amount of anhydrous n-hexane to obtain rare earth benzyl compound Si (CpMe)4)2YAbz (Compound 5).
Nuclear magnetic data:1H-NMR(600MHz,C6D6):0.94(s,3H,Si-Me),1.03(s,3H,Si-Me),1.39(s,2H,Y-CH2),1.45(s,6H,Cp-Me),1.76(s,6H,Cp-Me),2.00(s,6H,N-Me),2.07(d,12H,J＝6Hz,Cp-Me),6.56(m,1H,Ar-H),6.75(m,1H,Ar-H),7.02(m,1H,Ar-H),7.19(m,1H,Ar-H)。
example 6
Preparation of mononuclear rare earth complex 6
N-butyllithium (2.4M in n-Hexane) was slowly added dropwise to dimethylsilyl Me at-30 deg.C2And (3) adding the Si-bridged bis (tetramethylcyclopentadiene) ligand into an ether solution, then heating to room temperature, continuously stirring for 2 hours, and after the reaction is finished, pumping out the solvent in vacuum to obtain a light yellow solid, namely the dilithium salt of the ligand. Then the dilithium salt in THF was slowly added dropwise to YCl at-30 deg.C3(THF) n in THF suspension, after completion of the dropwise addition, the reaction solution was heated to reflux and the reaction was continued overnight. After the reaction is finished, pumping out THF in vacuum, adding toluene for extraction, filtering, pumping out the filtrate, and washing with a small amount of anhydrous hexane to obtain white solid powder, namely Si (CpMe)4)2YCl2Li(THF)2。
Reacting LiCH at-30 ℃2Si (CpMe) was added slowly to TMS in toluene4)2YCl2Li(THF)2Heating to room temperature, reacting overnight, filtering to remove generated LiCl, vacuum-removing solvent from filtrate, washing with small amount of anhydrous n-hexane twice to obtain rare earth benzyl compound Si (CpMe)4)2YCH2TMS (Compound 6). NMR characterization was not possible due to the paramagnetic nature of the +3 valent Gd compound.
Examples 7 to 10
Introducing a toluene solution of 4,4' -bipyridyl into a toluene solution of a mononuclear rare earth complex 1-4 at room temperature, immediately changing the solution from light yellow to dark yellow, and then continuously stirring for 15min at room temperature to obtain a dark brown solution, namely the in-situ prepared binuclear rare earth complex 7-10 (compound 7-10) which is directly used for a polymerization experiment.
Examples 11 to 12
Methods for the synthesis of binuclear rare earth complexes corresponding to examples 11-12 reference compounds 7-10, prepared in situ and used directly in polymerization experiments.
Example 13
Evaluation of catalyst polymerization:
in an inert gas glove box, 14.4g (2.16g,40mmol) of a hexane solution (mass fraction 15%) of 1, 3-butadiene was weighed in a 100mL round-bottomed flask, 0.2mL (1M,0.2mmol) of a hexane solution of triisobutylaluminum was added, and stirred at room temperature for 30min, to the polymerization solution were added a toluene solution of the binuclear rare earth complex (0.02mmol) of example 7 and [ PhNHMe2][B(C6F5)4]Toluene (D) ofAnd (4) suspending the solution. After polymerization for 30min at room temperature, the polymerization system became viscous and the polymerization monomers were completely consumed. After the polymerization was completed, the reaction flask was taken out of the inert gas glove box, anhydrous methanol was slowly added with stirring until the polymer was completely precipitated, 0.02g of BHT antioxidant (1% of the polymer mass) was added, the polymer was washed with anhydrous methanol 3 times, placed in a vacuum oven to dry at 70 ℃ for 5 hours, and weighed.
The polymerization results are shown in Table 1.
Examples 14 to 16
Evaluation of catalyst polymerization:
butadiene polymerization was performed according to the same method as in example 13, except that the dinuclear rare earth complexes of examples 8 to 10 were sequentially used.
The polymerization results are shown in Table 1.
Examples 17 to 18
Evaluation of catalyst polymerization:
butadiene polymerization was performed according to the same method as in example 13 using the binuclear rare earth complex of example 6 except that the molar ratios of butadiene and rare earth were 10000 and 20000, respectively.
The polymerization results are shown in Table 1.
TABLE 1 examples 13-18
Description of the drawings: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4],[B]N/[Ln]＝1.2
As can be seen from the data in the table, the catalytic activity is higher when the central metal is Y, but the cis-1, 4 selectivity is lower than 90%; and when the central metal is Gd, the catalytic activity is lower, but the cis-1, 4 selectivity can reach 99 percent.
Comparative examples 1 to 4
Butadiene polymerization was performed according to the same method as in example 13, except that the mononuclear rare earth complexes of examples 1 to 4 were sequentially used.
The polymerization results are shown in Table 2.
TABLE 2 COMPARATIVE EXAMPLES 1 to 4
Description of the invention: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4],[B]N/[Ln]＝1.2
By comparison (example 13, comparative example 1, example 15 and comparative example 3), it can be seen that the use of the mononuclear rare earth metal complex as the cocatalyst results in a much lower degree of both the catalyst activity and the stereoregularity of the polymerization product than the binuclear rare earth metal complex under the same polymerization experimental conditions.
As described above, the dinuclear rare earth olefin polymerization catalyst containing the dinuclear double-metallocene rare earth metal complex connected by the Lewis base has the advantages of high activity, high stereoselectivity and the like compared with the corresponding mononuclear rare earth complex in the olefin polymerization reaction.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (19)
1. A dual-core rare-earth catalyst for polymerizing olefin is composed of main catalyst, cocatalyst and chain transfer reagent; the main catalyst is a binuclear rare earth complex with stable Lewis base and is represented by a chemical formula [ I ] and a chemical formula [ II ]:
wherein X is selected from one of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, and N, N-bis (trimethylsilyl) amine;
said R is1To R18Same or different and are selected from hydrogen and C1-C10At least one of saturated alkyl groups of (a);
the Ln is a transition metal element of a IIIB group;
the above-mentioned
Is 4,4' -bipyridine.
2. The dinuclear rare earth olefin polymerization catalyst according to claim 1,
the cocatalyst is selected from the chemical formula [ III]A compound shown in the specification; the chemical formula [ III]Is [ EH ]]+[BA4]-、[E]+[BA4]-or BA3Wherein E is a nitrogen or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, and A is selected from C6-C30Aryl or haloaryl of and C1-C10At least one of alkyl or haloalkyl;
the chain transfer agent is selected from the group consisting of formula [ IV]A compound shown as the formula (I); the chemical formula [ IV]Is Al (R)19)(R20)(R21) Wherein Al is aluminum element, R19To R21Same or different and are selected from hydrogen, halogen and C1-C10At least one of alkyl or haloalkyl.
3. The dinuclear rare earth olefin polymerization catalyst of claim 1, wherein Ln is at least one element selected from scandium, yttrium, and lanthanoid rare earth elements.
4. The dinuclear rare earth olefin polymerization catalyst of claim 3, wherein Ln is Y and Gd.
5. The dinuclear rare earth olefin polymerization catalyst according to claim 1, wherein X is o- (N, N-dimethylamino) benzyl.
6. The dinuclear rare earth olefin polymerization catalyst of claim 1, wherein R is1To R18Is selected from C1-C10Saturated alkyl of (a), said C1-C10The saturated alkyl group of (b) is at least one selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl.
7. The dinuclear rare earth olefin polymerization catalyst of claim 6, wherein said C is1-C10The saturated alkyl group of (2) is a methyl group.
8. The dinuclear rare earth olefin polymerization catalyst according to claim 1, wherein the dinuclear rare earth complex represented by the chemical formula [ I ] and the chemical formula [ II ] is generated in situ, synthesized by a coordination reaction between a mononuclear rare earth complex and a bis-lewis base compound, and directly used for polymerization.
9. The dinuclear rare earth olefin polymerization catalyst according to claim 8, wherein said dinuclear rare earth complex is formed according to the following route:
(a)
(b)
wherein, the route (a) is the synthesis of non-bridging binuclear rare earth complex, the route (b) is the synthesis of silicon bridging binuclear rare earth complex, the mononuclear rare earth complex reacts with the double Lewis base, the reaction solvent is toluene, the separation is not carried out after the reaction, and the catalyst is directly used for olefin polymerization after the reaction with a cocatalyst.
10. The dinuclear rare earth olefin polymerization catalyst according to claim 9, wherein the molar ratio of the bis-lewis base to the mononuclear rare earth complex is 0.5/1.
11. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the compound represented by the formula [ III ] is at least one selected from the group consisting of triphenyl (methyl) -tetrakis (pentafluorobenzene) boron salt, phenyl-dimethylamino-tetraphenylboron salt, tris (pentafluorobenzene) boron salt, and triphenylboron salt.
12. The dinuclear rare earth olefin polymerization catalyst according to claim 11, wherein said compound represented by the formula [ III ] is a phenyl-dimethylamino-tetraphenylboron salt.
13. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the molar ratio of the compound represented by the formula [ III ] to the procatalyst is 0.1/1 to 10/1.
14. The dinuclear rare earth olefin polymerization catalyst according to claim 13, wherein the molar ratio of the compound represented by the formula [ III ] to the procatalyst is 1.0/1 to 2.0/1.
15. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the compound represented by the formula [ IV ] is at least one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, and ethyl-p-tolylaluminum.
16. The dinuclear rare earth olefin polymerization catalyst according to claim 15, wherein said compound represented by the formula [ IV ] is triisobutylaluminum.
17. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the molar ratio of the compound represented by the formula [ IV ] to the main catalyst is 1/1 to 10000/1.
18. The dinuclear rare earth olefin polymerization catalyst according to claim 17, wherein the molar ratio of the compound represented by the formula [ IV ] to the procatalyst is from 10/1 to 1000/1.
19. Use of the dinuclear rare earth olefin polymerization catalyst according to any one of claims 1 to 18 in the preparation of a high cis-conjugated diene rubber.
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