阅读说明：本技术 钳型稀土金属络合物及其制备方法、催化剂组合物和高顺式1,4-聚异戊二烯的制备方法 (Clamp-on rare earth metal complex, preparation method thereof, catalyst composition and preparation method of high cis-1, 4-polyisoprene ) 是由 王绍武 黄泽明 吴伟康 钟向阳 张军 于 2021-08-20 设计创作，主要内容包括：本发明公开了一种基于吲哚骨架的钳型稀土金属络合物及其制备方法、聚合催化剂组合物和高顺式1,4-聚异戊二烯的制备方法,该钳型稀土金属络合物的结构如式A、式B或式C所示；其中,在式A、式B和式C中,RE为稀土金属,X为卤素,R～(1)、R～(2)、R～(3)和R～(4)各自独立地选择氢原子或C1～C10的烃基,R～(5)为C25以内的烃基或取代烃基,L为配位溶剂,m、n为正整数；在式C中,G为H、C1-C15的烃基或取代烃基；在式A和式B中,G为C1-C15的烃基或取代烃基；该钳型稀土金属络合物对异戊二烯的聚合具有优异的顺式1,4-选择性,获得高分子量的聚合物。(The invention discloses a pincer-type rare earth metal complex based on an indole skeleton and a preparation method thereof, a polymerization catalyst composition and a preparation method of high cis-1, 4-polyisoprene, wherein the structure of the pincer-type rare earth metal complex is shown as a formula A, a formula B or a formula C; wherein, in the formula A, the formula B and the formula C, RE is rare earth metal, X is halogen, R 1 、R 2 、R 3 And R 4 Each independently selected from a hydrogen atom or a C1-C10 hydrocarbon group, R 5 Is alkyl or substituted alkyl within C25, L is coordination solvent, m and n are positive integers; in formula C, G is a hydrocarbyl or substituted hydrocarbyl group of H, C1-C15; in formula A and formula B, G is a C1-C15 hydrocarbyl or substituted hydrocarbyl group; the pincer-type rare earth metal complex has excellent effect on isoprene polymerizationCis-1, 4-selectivity, yielding high molecular weight polymers.)

1. A pincer-type rare earth metal complex based on an indole skeleton is characterized in that the structure of the pincer-type rare earth metal complex is shown as a formula A, a formula B or a formula C;

wherein, in the formula A, the formula B and the formula C, RE is rare earth metal, X is halogen, R¹、R²、R³And R⁴Each independently selected from a hydrogen atom or a C1-C10 hydrocarbon group, R⁵Is alkyl or substituted alkyl within C25, L is coordination solvent, m and n are positive integers; in formula C, G is a hydrocarbyl or substituted hydrocarbyl group of H, C1-C15; in formula A and formula B, G is a C1-C15 hydrocarbyl or substituted hydrocarbyl group.

2. The indole skeleton-based clamp rare earth metal complex according to claim 1, wherein G is hydrogen, a heteroatom-substituted aryl group of C1-C15, a heteroatom-substituted alkyl group, the heteroatom being selected from N, O, P or S, and in formula a and formula B, at least one heteroatom in G participates in the coordination of RE;

preferably, in formula A and formula B, G is selected from methoxy, tetrahydropyrrolyl, piperidinyl, dimethylamino, 2-tetrahydrofuranyl, 2-thienyl or morpholinyl; in formula C, G is selected from methoxy, tetrahydropyrrolyl, piperidinyl, dimethylamino, morpholinyl, hydrogen, or phenyl;

preferably, RE is selected from at least one of Sc, Y, Yb, Nd, Gd, Dy, Er, Ho and Tm; x is Cl, Br or I, and n is a positive integer of 1-3; r¹、R²、R³And R⁴Are all H, R⁵Is 2, 6-diisopropylphenyl, 2, 6-diethylphenyl, o-tert-butylphenyl, tert-butyl, adamantyl, 1-phenylethyl or 1-naphthylethyl; l is at least one of tetrahydrofuran, 2-methyltetrahydrofuran, pyran, substituted pyran, diethyl ether, ethylene glycol dimethyl ether, tetramethylethylenediamine and pyridine, and m is a positive integer of 1-2;

preferably, the structure of the pincer-type rare earth metal complex is shown as formula A-1, formula A-2, formula A-3, formula A-4, formula A-5, formula B-1, formula B-2, formula B-3, formula B-4 or formula C-1,

3. the method for preparing the indole skeleton-based clamp type rare earth metal complex according to claim 1, wherein the method comprises: in the presence of an alkali metal alkyl reagent, a ligand with a structure shown as a formula HL and REX₃Carrying out a coordination reaction with a coordination solvent L,

wherein RE is a rare earth metal, X is a halogen, R¹、R²、R³And R⁴Each independently selected from a hydrogen atom or a C1-C10 hydrocarbon group, R⁵Is a hydrocarbyl or substituted hydrocarbyl within C25, n is a positive integer; g is H, C1-C15 hydrocarbyl or substituted hydrocarbyl.

4. The process according to claim 3, wherein G is hydrogen, a C1-C15 hydrocarbyl group, a heteroatom-substituted aryl group, a heteroatom-substituted alkyl group, or a heteroatom-containing cyclic substituent selected from N, O, P or S, and in formula A and formula B, at least one heteroatom in G participates in the coordination of RE;

preferably, in formula A and formula B, G is selected from methoxy, tetrahydropyrrolyl, piperidinyl, dimethylamino, 2-tetrahydrofuranyl, 2-thienyl or morpholinyl; in formula C, G is selected from methoxy, tetrahydropyrrolyl, piperidinyl, morpholinyl, dimethylamino, 2-tetrahydrofuranyl, hydrogen, or phenyl;

preferably, RE is selected from at least one of Sc, Y, Yb, Nd, Gd, Dy, Er, Ho and Tm; x is Cl, Br or I, and n is a positive integer of 1-3; r¹、R²、R³And R⁴Are all H, R⁵Is 2, 6-diisopropylphenyl, 2, 6-diethylphenyl, o-tert-butylphenyl, tert-butyl, adamantyl, 1-phenylethyl or 1-naphthylethyl, and the alkali metal hydrocarbon-based reagent is at least one of N-butyllithium, trimethylsilylmethylenelithium, benzyllithium, o-N, N-dimethylaminobenzyllithium, methyllithium, tert-butyllithium, 2-pyridylmethylenelithium, trimethylsilylmethylenepotassium, benzylpotassium and 2-pyridylmethylenepotassium;

preferably, the ligand is selected from at least one of structural compounds represented by formula HL1, formula HL2, formula HL3, formula HL4, formula HL5, formula HL6, formula HL7, formula HL8, formula HL9, formula HL10, formula HL11 and formula HL12, and the REX is selected from the group consisting of₃Is selected from ScCl₃、NdCl₃、YCl₃、DyCl₃、GdCl₃、ErCl₃、HoCl₃、TmCl₃、ScBr₃、NdBr₃、YBr₃、DyBr₃、GdBr₃、ErBr₃、HoBr₃And TmBr₃(ii) the alkali metal hydrocarbyl reagent is n-butyllithium;

preferably, the coordinating solvent is selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, pyran, substituted pyran, diethyl ether, ethylene glycol dimethyl ether, tetramethylethylenediamine and pyridine;

more preferably, when the ligand is selected from the group consisting of formula HL1, formula HL2, formula HL3, formula HL4, formula HL5, formula HL6, formula HL7, formula HL8, formula HL9, and formula HL10, the structure of the pincer-type rare earth metal complex is as shown in formula a, formula B, or formula C due to the difference in the ionic radius of the rare earth metal, and when the ligand is selected from the group consisting of formula HL11 or HL12, the structure of the pincer-type rare earth metal complex is as shown in formula C;

5. the method of claim 3 or 4, wherein the ligand, REX₃And the dosage ratio of the alkali metal alkyl reagent to the coordination solvent is 1 mmol: 0.5-1.2 mmol: 0.8-1.2 mmol: 0.05-0.50 mol;

preferably, the coordination reaction satisfies the following condition: the reaction temperature is 15-35 ℃, and the reaction time is 6-18 h;

more preferably, the coordination reaction comprises: firstly, the ligand and an alkali metal alkyl reagent are subjected to a first reaction for 3-9h at the temperature of-20-35 ℃, and then a first reaction product, the tetrahydrofuran and the REX are subjected to a first reaction₃According to a molar ratio of 1: 1.0-1.2 or 2: 1.0-1.2, and carrying out the second reaction at 15-35 ℃ for 3-9 h.

6. A polymerization catalyst composition comprising an aluminum alkyl, a boron reagent, and the pincer-type rare earth metal complex of claim 1 or 2.

7. The polymerization catalyst composition of claim 6, wherein the molar ratio of the pincer-type rare earth metal complex, aluminum alkyl, boron reagent is 1: 2-20: 0.8 to 3;

preferably, the molar ratio of the pincer-type rare earth metal complex, the alkyl aluminum and the boron reagent is 1: 5-15: 0.8-1.2.

8. The polymerization catalyst composition of claim 6, wherein the aluminum alkyl is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, tri-n-octylaluminum, triphenylaluminum, tribenzylaluminum, tri-p-tolylaluminum, and ethyldibenzylaluminum; preferably trimethylaluminum, triethylaluminum, triisobutylaluminum;

preferably, the boron reagent is selected from at least one of tris (pentafluorophenyl) boron, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

9. A method for preparing high molecular weight high cis-1, 4-polyisoprene, which comprises the following steps: polymerizing monomer isoprene in the presence of a catalyst, wherein the catalyst is the polymerization catalyst composition according to any one of claims 6 to 8.

10. The preparation method according to claim 6, wherein the monomer and the catalyst are used in a molar ratio of 8000 to 500: 1, preferably 2000 to 500: 1;

preferably, the polymerization reaction satisfies the following conditions: the polymerization temperature is-30 ℃ to 45 ℃, and the polymerization time is 5 minutes to 180 minutes;

preferably, the polymerization reaction satisfies the following conditions: the polymerization temperature is-20 ℃ to 45 ℃, and the polymerization time is 5 minutes to 150 minutes;

more preferably, the polymerization is carried out in a solvent selected from at least one of hexane, toluene, tetrahydrofuran and halogenated hydrocarbons, preferably chlorobenzene;

further preferably, the amount ratio of the monomer to the solvent is 5000 μmol: 2-5 mL.

Technical Field

The invention relates to a pincer-type rare earth metal complex, in particular to a pincer-type rare earth metal complex based on an indole skeleton and a preparation method thereof, a polymerization catalyst composition and a preparation method of high cis-1, 4-polyisoprene.

Background

The polymer obtained by polymerizing the isoprene monomer comprises the following four types of structural units, namely a 3, 4-bonding structural unit shown in a general formula (I), a 1, 2-bonding structural unit shown in a general formula (II), a 1, 4-cis bonding structural unit shown in a general formula (III) and a 1, 4-trans bonding structural unit shown in a general formula (IV).

The structure and performance of the high cis-polyisoprene rubber (isoprene rubber for short) are similar to those of natural rubber, the content of the 1, 4-cis bonding structural component has important influence on the performance of the high cis-polyisoprene rubber, and when the content of the 1, 4-cis bonding structural component in the synthetic isoprene rubber structure reaches 95 percent and the molecular weight reaches more than 30 ten thousand, the performance of the high cis-polyisoprene rubber can be comparable to that of the natural rubber.

The catalytic systems commonly used for the synthesis of isoprene rubber include lithium-based initiators, titanium-based catalysts and rare earth catalysts. The rare earth catalyst is superior to other catalytic systems in polymerization activity and 1, 4-cis bonding structure selectivity on isoprene, and the obtained isoprene rubber has excellent comprehensive performance, such as a plurality of characteristics of less gel, easy processing, wear resistance, tear resistance and the like.

Since the rare earth metal complex of the first invention in China in the last 60 th century can catalyze the polymerization of conjugated diene, a series of catalysts are developed by various rubber companies on the basis of the rare earth metal complex, however, the related formula of the catalysts is basically an improvement on rare earth carboxylate invented by Chinese scientists, and the change of the main catalyst component is very small. The catalyst can be divided into two types according to different types of the catalyst system: 1. the transition metal is a catalytic system of metal chlorides of Fe, Co, Cr and the like and methylaluminoxane. 2. A catalytic system consisting of rare earth metal chloride, alkyl aluminum and boron reagent.

For example, in patent document CN 108586641 a, the catalytic system consisting of pyridine imine iron chloride and Methylaluminoxane (MAO) applied by researchers at wang qing dynasty, and the catalytic system consisting of trivalent vanadium chloride/Methylaluminoxane (MAO) reported by researchers at Qingdao bioenergy and biological process technology institute biology base material focus laboratory in "polymers.2019, page 11,1122" all can catalyze the polymerization of isoprene, but cis-1, 4 and cis-3, 4 products are present in the polymerization product, and the ratio is high.

Catalytic systems of Co chlorination/alkylaluminium composition as reported by researchers at Ningbo university in the literature "Ind. Eng. chem. Res.2019,58, 2792-2800"; the catalytic system consisting of Co chloride/aluminum alkyl reported by researchers in the national institute of biological energy and bioprocess technology research institute of Qingdao in China academy of sciences in the literature "J.Polym.Sci., Part A: Polym.Chem.2019,57, 767-page 775"; catalytic systems of Co chloride/alkylaluminium composition reported by researchers at Manchester university in the literature "Ind. Eng. chem. Res.2019,58,2792 and 2800"; the catalytic system consisting of Fe or Co chloride/aluminum alkyl reported by researchers at the university of south Jiangnan in the literature "New J. chem.2020,44, 8076-page 8084"; the Co chloride/aluminum alkyl catalyst system reported by researchers at the university of MigJilin chemical college of the literature "Dalton Trans.2021,50, 5218-page 5225" all can catalyze the cis-1, 4 and cis-3, 4 polymerization of isoprene, but only obtain cis-1, 4 selectivity of about 80%.

The patent document of publication No. CN 101693754A discloses that the polymerization of conjugated diene can be catalyzed by a tridentate carbazolyl chelated rare earth complex/alkyl aluminum/organic boron reagent catalytic system applied by a Chimometer flos Pruni mume researcher in Changchun, and the cis-1, 4 poly-conjugated diene content of the obtained copolymer is 97-99.9%, but the use amount of alkyl aluminum is extremely high in the catalytic process and reaches 100 times of the molar amount of the rare earth complex.

Similarly, the pincer-type rare earth complex/alkyl aluminum/organoboron reagent catalytic system disclosed in the document "New J.chem.2020,44, 8076-page 8084", the beta-bisimine rare earth complex/alkyl aluminum/organoboron reagent catalytic system disclosed in the document "Organometallics 2010,29, 2987-page 2993", the 1, 3-bis (2-pyridinimino) isoindoline rare earth complex/alkyl aluminum/organoboron reagent catalytic system disclosed in the document "Organometallics 2017,36, 2446-page 2451", the bis (oxazolinyl) phenyl rare earth complex/alkyl aluminum/organoboron reagent catalytic system in the document "Inorg.chem.2013, 52, 2802-page 2808", has high cis-1, 4 selectivity to conjugated olefins, the polymerization reaction is carried out at 25 ℃ to obtain isoprene rubber with cis-1, 4 close to 99%, but the molar weight of the aluminum reagent used in the catalysis process is 10-20 times that of the rare earth complex. Too high an amount of aluminum reagent not only wastes the cocatalyst, but also has no significant effect on the molecular weight and molecular weight distribution of isoprene.

Disclosure of Invention

The invention aims to provide a pincer-type rare earth metal complex based on an indole skeleton, a preparation method thereof, a polymerization catalyst composition and a preparation method of high cis-1, 4-polyisoprene, wherein the pincer-type rare earth metal complex has excellent cis-1, 4-selectivity for polymerization of isoprene, the using amount of alkyl aluminum in the polymerization catalyst composition is low in the using process, and the preparation methods of the pincer-type rare earth metal complex and the 1, 4-polyisoprene have the advantages of simple process and mild conditions.

In order to achieve the aim, the invention provides a pincer-type rare earth metal complex based on an indole skeleton, wherein the structure of the pincer-type rare earth metal complex is shown as a formula A, a formula B or a formula C;

wherein, in the formula A, the formula B and the formula C, RE is rare earth metal, X is halogen, R¹、R²、R³And R⁴Each independently selected from a hydrogen atom or a C1-C10 hydrocarbon group, R⁵Is alkyl or substituted alkyl within C25, L is coordination solvent, m and n are positive integers; in formula C, G is a hydrocarbyl or substituted hydrocarbyl group of H, C1-C15; in formula A and formula B, G is a C1-C15 hydrocarbyl or substituted hydrocarbyl group.

The invention also provides a preparation method of the pincer-type rare earth metal complex based on the indole skeleton, which comprises the following steps: in the presence of an alkali metal alkyl reagent, a ligand with a structure shown as a formula HL and REX₃Carrying out a coordination reaction with a coordination solvent L,

wherein RE is a rare earth metal, X is a halogen, R¹、R²、R³And R⁴Each independently selected from a hydrogen atom or a C1-C10 hydrocarbon group, R⁵Is alkyl or substituted alkyl within C25, L is coordination solvent, n is positive integer; g is H, C1-C15 hydrocarbyl or substituted hydrocarbyl.

The invention also provides a polymerization catalyst composition comprising an aluminum alkyl, a boron reagent, and a pincer-type rare earth metal complex as described above.

The invention further provides a preparation method of the high molecular weight high cis-1, 4-polyisoprene, which comprises the following steps: and (2) carrying out polymerization reaction on monomer isoprene in the presence of a catalyst, wherein the catalyst is the polymerization catalyst composition.

In the technical scheme, the clamp-type rare earth metal complex with the structure shown as the formula A, the formula B or the formula C, the alkyl aluminum and the boron reagent form the polymerization catalyst composition, the polymerization catalyst composition has high selectivity (stereoselectivity and regioselectivity) in the polymerization process of isoprene, a high cis-1, 4-isoprene polymer can be obtained, the monomer conversion rate can reach 95-100%, and the content of a 1, 4-cis bonded structural unit can reach 99.2 mol%.

More importantly, in the polymerization catalyst composition, the using amount of the alkyl aluminum is very low, and the molar ratio of the pincer-type rare earth metal complex to the alkyl aluminum can be as low as 1: 2, thereby overcoming the defect of excessive use of the alkyl aluminum in the prior art.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is an X-ray single crystal diffractogram of formula B1;

FIG. 2 is an X-ray single crystal diffractogram of formula A4;

FIG. 3 is an X-ray single crystal diffractogram of formula C1;

FIG. 4 is a nuclear magnetic hydrogen spectrum of the product of example 1;

FIG. 5 is a nuclear magnetic carbon spectrum of the product of example 1.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The invention provides a pincer-type rare earth metal complex based on an indole skeleton, which has a structure shown as a formula A, a formula B or a formula C;

wherein, in the formula A, the formula B and the formula C, RE is rare earth metal, X is halogen, R¹、R²、R³And R⁴Each independently selected from a hydrogen atom or a C1-C10 hydrocarbon group, R⁵Is alkyl or substituted alkyl within C25, L is coordination solvent, m and n are positive integers; in the formula C, G is a hydrocarbon group of H, C1-C15 orA substituted hydrocarbyl group; in formula A and formula B, G is a C1-C15 hydrocarbyl or substituted hydrocarbyl group.

Wherein G is a substituent which can be heteroatom or not, wherein the heteroatom can be nitrogen, oxygen or phosphine for electron donor; in addition, G may be a linear substituent or a cyclic substituent, and the present invention is not limited thereto.

In the present invention, the specific kind of RE is not particularly limited, but for the convenience of the preparation of the jaw-type rare earth metal complex, it is preferable that RE is at least one selected from Sc, Y, Yb, Nd, Gd, Dy, Er, Ho, and Tm; more preferably at least one of Y, Gd, Dy and Er. Herein, the valence of RE participating in coordination is also not specifically limited in the present invention, but from the viewpoint of structural stability, it is more preferable that RE be + 3.

In the present invention, the specific kind of X is not particularly limited, but for the convenience of the preparation of the clip-type rare earth metal complex, it is preferable that X is Cl, Br or I.

In the present invention, the value of n is not particularly limited, but for the convenience of the preparation of the clip-type rare earth metal complex, it is preferable that n is a positive integer of 1 to 3; more preferably, n is 1 or 2.

In the present invention, the value of m is not particularly limited, but for the convenience of the preparation of the pincer-type rare earth metal complex, it is preferable that m is a positive integer of 1 to 2.

In the present invention, for R¹、R²、R³、R⁴And R⁵Is not particularly limited, but for the convenience of preparation of the clip-type rare earth metal complex, preferably, R is¹、R²、R³And R⁴Are all H, R⁵Is 2, 6-diisopropylphenyl, 2, 6-diethylphenyl, o-tert-butylphenyl, tert-butyl, adamantyl, 1-phenylethyl or 1-naphthylethyl.

In the present invention, the specific kind of G is not particularly limited, and in the formula C, G is a hydrocarbon group or a substituted hydrocarbon group of H, C1 to C15, and in the formula A and the formula B, G is a hydrocarbon group or a substituted hydrocarbon group of C1 to C15; however, from the viewpoint of yield, it is preferable that G is hydrogen, a heteroatom-substituted aryl group of C1 to C15, a heteroatom-substituted alkyl group, the heteroatom being selected from N, O, P or S, and in the formulae A and B, at least one heteroatom in G participates in the coordination of RE; more preferably, in formula a and formula B, G is selected from methoxy, tetrahydropyrrole, piperidinyl, dimethylamino, 2-tetrahydrofuranyl, 2-thienyl or morpholinyl; in formula C, G is selected from methoxy, tetrahydropyrrolyl, piperidinyl, morpholinyl, dimethylamino, 2-tetrahydrofuranyl, hydrogen, or phenyl.

G may be a substituent containing a hetero atom which may be nitrogen, oxygen or phosphine which can donate electrons; in addition, G may be a linear substituent or a cyclic substituent, and the present invention is not limited thereto.

In the present invention, the specific kind of L is not particularly limited, but L is preferably selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, pyran, substituted pyran, diethyl ether, ethylene glycol dimethyl ether, tetramethylethylenediamine and pyridine in order to facilitate the preparation of the pincer-type rare earth metal complex.

On the basis of the above embodiments, in order to further facilitate the preparation of the complex, it is preferable that the structure of the pincer-type rare earth metal complex is represented by formula A-1, formula A-2, formula A-3, formula A-4, formula A-5, formula B-1, formula B-2, formula B-3, formula B-4 or formula C-1,

the invention also provides a preparation method of the pincer-type rare earth metal complex based on the indole skeleton, which comprises the following steps: in the presence of an alkali metal alkyl reagent, a ligand with a structure shown as a formula HL and REX₃And a coordinating solvent L, whereinThe alkali metal alkyl reagent plays a role in removing H in HL, and further activates HL;

wherein RE is a rare earth metal, X is a halogen, R¹、R²、R³And R⁴Each independently selected from a hydrogen atom or a C1-C10 hydrocarbon group, R⁵Is alkyl or substituted alkyl within C25, L is coordination solvent, n is positive integer; g is H, C1-C15 hydrocarbyl or substituted hydrocarbyl.

In the above production method, the specific kind of RE is not particularly limited, but from the viewpoint of yield, it is preferable that RE is selected from at least one of Sc, Y, Yb, Nd, Gd, Dy, Er, Ho, and Tm; more preferably at least one of Y, Gd, Dy and Er. Wherein, the valence state of RE participating in coordination is not specifically limited in the present invention, but from the viewpoint of structural stability, it is more preferable that RE is + 3; further preferably, the REX₃Is selected from ScCl₃、NdCl₃、 YCl₃、DyCl₃、GdCl₃、ErCl₃、HoCl₃、TmCl₃、ScBr₃、NdBr₃、YBr₃、DyBr₃、GdBr₃、ErBr₃、 HoBr₃And TmBr₃At least one of (1).

In the above production method, the specific kind of X is not particularly limited, but X is Cl, Br or I in view of the yield.

In the above production method, specific kind of L is not particularly limited, but in view of stability of the product, preferably, L is a heteroatom-containing solvent selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, pyran, substituted pyran, diethyl ether, ethylene glycol dimethyl ether, tetramethylethylenediamine and pyridine; but more preferably, the coordinating solvent is tetrahydrofuran, from the viewpoint of yield and ease of laboratory access.

In the above production method, the value of n is not particularly limited, but preferably, n is a positive integer of 1 to 3 from the viewpoint of yield; more preferably, n is 1 or 2.

In the above preparation process, for R¹、R²、R³、R⁴And R⁵Is not particularly limited, but preferably R is selected from the viewpoint of yield¹、R²、R³And R⁴Are all H, R⁵Is 2, 6-diisopropylphenyl, 2, 6-diethylphenyl, o-tert-butylphenyl, tert-butyl, adamantyl, 1-phenylethyl or 1-naphthylethyl.

In the above production method, the specific kind of G is not particularly limited, and in the formula C, G is a hydrocarbon group or a substituted hydrocarbon group of H, C1 to C15, and in the formula A and the formula B, G is a hydrocarbon group or a substituted hydrocarbon group of C1 to C15; however, from the viewpoint of yield, it is preferable that G is hydrogen, a heteroatom-substituted aryl group of C1 to C15, a heteroatom-substituted alkyl group, the heteroatom being selected from N, O, P or S, and in the formulae A and B, at least one heteroatom in G participates in the coordination of RE; more preferably, in formula a and formula B, G is selected from methoxy, tetrahydropyrrole, piperidinyl, dimethylamino, 2-tetrahydrofuranyl, 2-thienyl or morpholinyl; in formula C, G is selected from methoxy, tetrahydropyrrolyl, piperidinyl, morpholinyl, dimethylamino, 2-tetrahydrofuranyl, hydrogen, or phenyl.

In formula A and formula B, G is selected from methoxy, tetrahydropyrrole, piperidinyl, dimethylamino, 2-tetrahydrofuranyl, 2-thienyl or morpholinyl; in formula C, G is selected from methoxy, tetrahydropyrrolyl, piperidinyl, morpholinyl, dimethylamino, 2-tetrahydrofuranyl, hydrogen, or phenyl.

G may be a substituent containing a hetero atom which may be nitrogen, oxygen or phosphine which can donate electrons; in addition, G may be a linear substituent or a cyclic substituent, and the present invention is not limited thereto.

In the above-mentioned production method, the specific kind of the alkali metal hydrocarbon-based reagent is not particularly limited, but from the viewpoint of the reaction effect, it is preferable that the alkali metal hydrocarbon-based reagent is at least one of N-butyllithium, trimethylsilylmethylium, benzyllithium, o-N, N-dimethylaminobenzyllithium, methyllithium, t-butyllithium, 2-pyridylmethylium, trimethylsilylmethylenepotassium, benzylpotassium, and 2-pyridylmethylenepotassium; further preferably, the alkali metal hydrocarbyl reagent is n-butyllithium.

In order to further improve the yield based on the above embodiment, preferably, the ligand is at least one selected from structural compounds represented by formula HL1, formula HL2, formula HL3, formula HL4, formula HL5, formula HL6, formula HL7, formula HL8, formula HL9, formula HL10, formula HL11, and formula HL 12; wherein, when the formula is HL1, HL2, HL3, HL4, HL5, HL6, HL7, HL8, HL9 or HL10, the structure of the pincer-type rare earth metal complex is shown as formula A, B or C due to the difference of the ion radius of the rare earth metal, and when the ligand is selected from the formula HL11 or HL12, the structure of the pincer-type rare earth metal complex is shown as formula C;

in the above-mentioned production method, the amount of each material to be used is also not specifically limited, but in order to further improve the yield, it is preferable that the ligand, REX, is used₃The ratio of the amount of the alkali metal hydrocarbyl reagent to the amount of tetrahydrofuran is 1 mmol: 0.5-1.2 mmol: 0.8-1.2 mmol: 0.05-0.50 mol.

In the above production method, the reaction conditions are also not particularly limited, but in order to further improve the yield, it is preferable that the coordination reaction satisfies the following conditions: the reaction temperature is 15-35 ℃, and the reaction time is 6-18 h. More preferably, the coordination reaction comprises: firstly, the ligand and an alkali metal alkyl reagent are subjected to a first reaction for 3-9h at the temperature of-20-35 ℃ (for activating the ligand), and then a first reaction product, the tetrahydrofuran and the REX are subjected to a first reaction₃According to a molar ratio of 1: 1.0-1.2 or 2: 1.0-1.2 at 15-35 deg.CAnd carrying out a second reaction for 3-9h, wherein the second reaction is a coordination reaction.

In the first reaction and the second reaction, in order to improve the yield, preferably, a solvent is used in both the first reaction and the second reaction, wherein the kind of the solvent is not particularly limited, such as tetrahydrofuran, n-hexane, toluene or n-pentane, but in the second reaction, in consideration of the difficulty of the later purification, tetrahydrofuran is preferred, and the tetrahydrofuran plays a role of the solvent and directly participates in the coordination reaction, so that the difficulty of the later purification is reduced, and the yield is further ensured.

Further, in the above method, REX₃And tetrahydrofuran can also be provided in a variety of ways, and REX can be provided₃And tetrahydrofuran as reactants, respectively, but REX may be used₃Tetrahydrofuran, as a direct donor, e.g. REX₃(THF)_m(m is 1 to 4 and may be a decimal fraction).

The invention also provides a polymerization catalyst composition comprising an aluminum alkyl, a boron reagent, and a pincer-type rare earth metal complex as described above.

In the above polymerization catalyst composition, the content of each component is also not particularly limited, but in order to further improve the catalytic ability of the polymerization catalyst composition, it is preferable that the molar ratio of the pincer-type rare earth metal complex, the alkylaluminum, and the boron reagent is 1: 2-20: 0.8 to 3; more preferably, the molar ratio of the clamp type rare earth metal complex, the alkyl aluminum and the boron reagent is 1: 5-15: 0.8-1.2.

In the above polymerization catalyst composition, the kind of the aluminum alkyl is also not particularly limited, but in order to further improve the catalytic ability of the polymerization catalyst composition, preferably, the aluminum alkyl is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, tri-n-octylaluminum, triphenylaluminum, tribenzylaluminum, tri-p-tolylaluminum, and ethyldibenzylaluminum; trimethylaluminum, triethylaluminum, triisobutylaluminum are preferred.

In the above polymerization catalyst composition, the kind of the boron reagent is also not particularly limited, but in order to further improve the catalytic ability of the polymerization catalyst composition, it is preferable that the boron reagent is selected from at least one of tris (pentafluorophenyl) boron, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, and N, N-dimethylaniline tetrakis (pentafluorophenyl) borate.

The invention further provides a preparation method of the high molecular weight high cis-1, 4-polyisoprene, which comprises the following steps: and (2) carrying out polymerization reaction on monomer isoprene in the presence of a catalyst, wherein the catalyst is the polymerization catalyst composition.

In the above preparation method, the amount of the catalyst is also not particularly limited, but in order to further improve the conversion rate and selectivity of the monomer, the monomer and the catalyst are preferably used in a molar ratio of 8000 to 500: 1, preferably 2000 to 500: 1.

In the above production method, the conditions of the polymerization reaction are also not particularly limited, but in order to further improve the conversion rate and selectivity of the monomer, it is preferable that the polymerization reaction satisfies the following conditions: the polymerization temperature is-30 ℃ to 45 ℃, and the polymerization time is 5 minutes to 180 minutes; more preferably, the polymerization reaction satisfies the following conditions: the polymerization temperature is-20 to 45 ℃ and the polymerization time is 5 to 150 minutes.

In the above production method, in order to further improve the conversion rate and selectivity of the monomer, more preferably, the polymerization is carried out in a solvent selected from at least one of hexane, toluene, tetrahydrofuran and halogenated hydrocarbon, preferably chlorobenzene.

In the above embodiment, the amount of the solvent is also not particularly limited, and in order to further improve the conversion rate and selectivity of the monomer, it is more preferable that the polymerization is carried out in the solvent, and it is preferable that the monomer and the solvent are used in a ratio of 5000 μmol: 2-5 mL.

Preferably, the high molecular weight high cis-1, 4-polyisoprene satisfies the following condition: the cis-1, 4 polymerized isoprene has a content of 90 mol% to 99.6 mol% and a number average molecular weight of 20 ten thousand to 180 ten thousand.

The present invention will be described in detail below by way of examples. In the following examples, the percentage of cis 1,4 structural unit content refers to the molar weight percentage.

Preparation example 1

Preparation of ligand HL 1:

3- (2, 6-diisopropylphenyl) imino-indole (3.04g,10mmol) and anhydrous potassium carbonate (4.14g,30mmol) were dissolved in 10mL anhydrous DMF, after completion N- (2-chloroethyl) pyrrolidine hydrochloride (2.04g,12mmol) was added, reaction was carried out at 50 ℃ for 12 hours, 100mL cold water was added after the reaction was completed, 50mL ethyl acetate was added for extraction, the brown yellow solid after removal of the solvent under reduced pressure was recrystallized from ethyl acetate and petroleum ether to give pale yellow crystals, 3.82g was weighed, yield 95%.

The characterization data for the product are: m.p:122 ℃ IR (KBr pellets, cm)^-1):ν2957,2864,2793,1621,1538, 1467,1392,1362,1161,1049,853,747.¹H NMR(500MHz,C₆D₆,298K):δ9.00(d,J＝8.0Hz, 1H,PhH),8.34(s,1H,CH＝N),7.28(d,J＝7.5Hz,1H,PhH),7.25-7.23(m,2H,PhH), 7.18-7.09(m,5H,PhH),6.92(s,1H,2-C_indolyl-H),3.61(t,J＝7.0Hz,2H,NCH₂),3.42(hept,J＝ 7.0Hz,CHMe₂),2.33(t,J＝7.0Hz,NCH₂),2.14-2.12(m,4H,CH₂),1.47-1.44(m,4H,CH₂), 1.25(d,J＝7.0Hz,12H,CH₃).¹³C{¹H}NMR(125MHz,C₆D₆,298K):δ156.2(CH＝N),151.7, 138.4,137.9,134.0,127.0,124.0,123.7(2-C_indolyl),123.5,123.4,122.1,115.6,109.8,55.5,54.3, 45.9,28.6(CH),23.9(CH₂),23.9(CH₃).HR-MS(APCI)m/z calcd.for C₂₇H₃₆N₃[M+H]⁺: 402.2904；found:402.2905.

Preparation example 2

Preparation of ligand HL 2:

3- (2, 6-diisopropylphenyl) imino-indole (3.04g,10mmol) and anhydrous potassium carbonate (4.14g,30mmol) were dissolved in 10mL anhydrous DMF, after completion 1- (2-chloroethyl) piperidine hydrochloride (2.21g,12mmol) was added, reaction was carried out at 25 ℃ for 12 hours, after completion of the reaction 100mL cold water was added and 50mL ethyl acetate was added for extraction, the brown yellow solid after removal of the solvent under reduced pressure was recrystallized from ethyl acetate and petroleum ether to give white crystals, weighing 3.74g, yield 90%. (reference paper: Wuweikang. Synthesis, characterization of 1- (2-piperidinylethyl) -3-iminoindole ligand-containing rare earth metal hydrocarbyl complexes and NCN Pincer type rare earth metal dichlorides and study of their catalytic properties [ D ]. university of Anhui university, 2020).

Preparation example 3

Preparation of ligand HL 3:

a solution of 3- (2, 6-diisopropylphenyl) imino-indole (3.04g,10mmol) in DMF was added dropwise to a solution of sodium hydride (0.5g,20mmol) in tetrahydrofuran and chloroethyl methyl ether (1.13g,12mmol) was added and the reaction was carried out at 70 ℃ for 12 hours, after the reaction was completed, 100mL of cold water was added and 50mL of ethyl acetate was added for extraction, the brown yellow solid after removal of the solvent under reduced pressure was recrystallized from ethyl acetate and petroleum ether to give pale yellow crystals, 3.26g was weighed and the yield was 90%.

The characterization data for the product are: mp 94 ℃ IR (KBr pellets, cm)^-1):ν3020(w),2956(s),2862(m), 2359(m),2341(m),1903(m),1845(m),1790(m),1705(m),1676(m),1636(s),1604(m), 1543(m),1458(m),1437(m),1360(m),1251(m),1170(s),1117(s),1072(m),1011(m),976 (w),932(m),883(m),853(m),802(m),786(m),750(s).¹H NMR(500MHz,CDCl₃):δ8.54 (d,J＝5.0Hz,1H),8.33(s,1H),7.58(s,1H),7.41(d,J＝5.0Hz,1H),7.36-7.28(m,2H),7.17 (d,J＝5.0Hz,2H),7.10-7.07(m,1H),4.35(t,J＝5.0Hz,2H),3.78(t,J＝5.0Hz,2H),3.37(s, 3H),3.14(hept,J＝7.5Hz,2H),1.19(d,J＝7.5Hz,12H)ppm.¹³C NMR(125MHz,CDCl₃):δ 156.3,151.2,138.6,137.8,134.5,126.7,123.9,123.8,123.4,123.3,122.1,115.5,110.1,77.9, 77.6,77.4,71.6,59.6,47.1,28.5,24.1ppm.HRMS(ESI)m/z calcd.for C₂₄H₃₀N₂O(M+H⁺): 363.2431,found:363.2426.

Preparation example 4

Preparation of ligand HL 4:

dissolving 3- (2, 6-diisopropylphenyl) imino-indole (3.04g,10mmol) and 4- (2-chloroethyl) morpholine hydrochloride (2.04g,11mmol) in 15mL tetrahydrofuran, stirring for 30min, adding potassium hydroxide (100mmol,5.7g) in an ice-water bath, heating and refluxing for 12h after the reaction is recovered to 25 ℃, filtering after the reaction is finished, collecting the filtrate and spin-drying to obtain a crude product, recrystallizing with ethyl acetate and petroleum ether to obtain white crystals, weighing 3.83g, and obtaining the yield of 92%.

The characterization data for the product are: m.p:214 ℃ IR (KBr pellets, cm)^-1):ν3051(m),2862(m),2812(m), 1845(m),2361(m),1790(m),1705(m),1624(s),1587(m),1571(m),1537(m),1170(s),1117 (s),1072(m),1011(m),1469(m),854(m),750(m),731(m).¹H NMR(500MHz,CDCl₃)δ 8.55(d,J＝7.8Hz,1H),8.37(s,1H),7.62(s,1H),7.51–7.02(m,6H),4.32(t,J＝6.8Hz,2H), 3.76-3.73(m,4H),3.19–3.13(hept,J＝6.9Hz,2H),2.84(t,J＝6.8Hz,2H),2.2.56-2.50(m, 4H),1.23(d,J＝6.9Hz,12H).¹³C NMR(125MHz,CDCl₃,ppm):δ156.1,151.1,138.5,137.6, 133.9,126.6,123.8,123.7,123.3,123.0,122.0,115.3,109.9,67.3,58.3,54.2,44.7,28.3,24.0. HRMS(ESI)m/z calcd for C₂₇H₃₆N₃O(M+H⁺):418.2853,found:418.2860.

Preparation example 5

Preparation of ligand HL 5:

dissolving 1- (2-methylene thiophene) -3-indole formaldehyde (4.84g,20mmol) and 2, 6-diisopropylaniline (3.56g,20mmol) in 20mL of absolute ethyl alcohol, adding 0.01mmol of p-toluenesulfonic acid after the reaction is finished, heating and refluxing for 12 hours to react, wherein the solution is dark and is red clear and transparent. Cooling, separating out white solid, washing with hexane, vacuum filtering to obtain light red solid, removing pigment by column chromatography or active carbon, recrystallizing to obtain light yellow crystal, i.e. 1- (2-thienylmethylene) -3- (2, 6-diisopropylphenylimino) indole, weighing 6.82g, yield 85%.

The characterization data for the product are: IR (KBr pellets, cm)^-1):ν2959,2926,2862,1626,1587,1572,1541, 1464,1437,853,793,750,712cm^-1.¹H NMR(300MHz,CDCl₃,ppm):δ8.51(d,1H,-CH＝N-), 8.27(m,1H,indole-Ar-H),7.52(d,1H),7.42(d,1H),7.29(m,3H),7.14,(s,1H),7.12(s,1H), 7.06(m,1H),7.01(s,1H),6.95(s,1H),5.49(d,2H,-CH₂),3.08(m,2H,-CHMe),1.14(d,12H, -CHMe).¹³C NMR(75MHz,CDCl₃,ppm):δ155.71,155.66,150.65,138.59,138.16,137.23, 132.78,132.73,127.24,126.84,126.46,126.05,123.61,123.54,122.97,121.93,115.62,109.88, 45.37,28.01,23.45.HRMS(ESI)m/z calcd for C₂₆H₂₉N₂S(M+H⁺):401.2046,found:401.2052.

Preparation example 6

Preparation of ligand HL 6:

dissolving 1- (N, N-dimethylaminoethyl) -3-indole carbaldehyde (10.5g,50mmol) and 2, 6-diisopropylaniline (10.6g, 60mmol) in 20mL of absolute ethanol, adding 0.01mmol of p-toluenesulfonic acid after the reaction is finished, heating and refluxing for 24h, cooling to separate out white powder, filtering, washing and drying to obtain a white solid, weighing 14.08g, and obtaining the yield of 75%.

The characterization data for the product are: IR (KBr pellets, cm)^-1):ν3123(m),3053(m),3022(w),2960(s),2862 (m),2821(m),2785(m),2769(m),1951(w),1909(w),1857(w),1705(w),1624(s),1539(s), 1467(s),1458(s),1438(s),1392(s),1352(m),1257(m),1240(m),1163(s),1153(s),1097 (w),1028(w),985(m),952(w),935(w),853(s),817(w),748(s),719(w),526(m),511(w), 426(m)cm^-1.¹H NMR(CDCl₃,500MHz,ppm):δ9.13(d,J＝10Hz,1H,CH＝N),8.47(s,1H, 2-H_indole),7.38-7.07(m,7H),3.64(t,J＝10Hz,2H),3.56(m,J＝10Hz,2H),2.22(t,J＝5Hz,2H), 1.97(s,6H),1.38(d,J＝5Hz,12H).¹³C NMR(C₆D₆,75MHz,ppm)δ:155.95,151.46,138.16, 137.59,133.85,126.69,123.80,123.40,123.29,123.13,121.87,115.31,109.50,58.50,45.22, 44.46,28.33,23.62.HRMS(ESI)m/z calcd.for C₂₅H₃₄N₃(M+H)⁺:376.2747,found:376.2738.

Preparation example 7

Preparation of ligand HL 7:

respectively dissolving (4.8g,25mmol) and 1-chloroethyl-3- (2, 6-diisopropylphenyl) iminoindole (9.17g,25mmol) in 10mL of tetrahydrofuran, then leading the tetrahydrofuran solution of diphenyl lithium phosphide into the 1-chloroethyl-3- (2, 6-diisopropylphenyl) iminoindole solution, stirring for reaction for 24 hours, removing the solvent under reduced pressure after the reaction is finished, dissolving the residual solid with ethyl acetate, washing with saturated saline solution (3X 50mL), and then spin-drying the solvent to obtain pure white powdery solid, weighing 12.9g and obtaining the yield of 100%.

The characterization data for the product are:¹H NMR(500MHz,CDCl₃,ppm)δ8.47-8.45(m,1H),8.28-8.27(m, 1H),7.47-7.42(m,5H),7.37-7.34(m,6H),7.31-7.27(m,2H),7.21-7.19(m,1H),7.17-7.15(m, 2H),7.10-7.07(m,1H),4.30-4.25(m,2H),3.14-3.08(m,2H),2.67-2.63(m,2H),1.19-1.17(m, 12H).¹³C NMR(125MHz,CDCl₃,ppm)δ155.7,150.7,138.2,137.2,137.1,136.9,132.8(d, J_P-C＝25Hz),132.6,129.3,128.9(d,²J_P-C＝12.5Hz),126.4,123.5(d,²J_P-C＝12.5Hz),123.0, 122.8,121.7,115.2,109.6,44.1(d,J_P-C＝25Hz),29.5(d,²J_P-C＝12.5Hz),28.0,23.7.³¹P NMR (202MHz,CDCl₃,ppm)δ-21.5.

preparation example 8

Preparation of ligand HL 8:

3- (2, 6-diisopropylphenyl) imino-indole (15.22g,50mmol) and anhydrous potassium carbonate (13.8g,100mmol) were dissolved in 10mL anhydrous DMF, after completion 2-chloromethyl tetrahydrofuran (6.0g,50mmol) was added and reacted at 120 ℃ for 48 hours, after completion of the reaction, extracted with water and ethyl acetate, dried, filtered and recrystallized from ethyl acetate and petroleum ether to give colorless crystals, weighing 17.5g, yield 90%. (reference paper: Wangru, synthesis and performance research of novel NCO Pincer type rare earth metal organic complex containing electron-rich indole skeleton [ D ]. university of Anhui, 2019).

Preparation example 9

Preparation of ligand HL 9:

dissolving 1- (2-pyrrolylethyl) -3-indolecarboxaldehyde (4.8g,20mmol) and 1-amantadine (3.0g,20mmol) in 20mL of absolute ethanol, adding 0.01mmol of p-toluenesulfonic acid after the reaction is finished, heating and refluxing for 2 days, after the reaction is finished, performing spin drying, and recrystallizing by using ethyl acetate and petroleum ether to obtain 1- (2-pyrrolylethyl) -3-adamantylimindole, wherein the weight is 6.0g, and the yield is 80%.

The characterization data for the product are: mp is 150 ℃.¹H NMR(C₆D₆,500MHz,ppm):δ9.06(d,J＝10.0Hz, 1H),8.60(s,1H),7.36-7.33(m,1H),7.30-7.26(m,1H),7.17-7.14(m,3H),3.70(t,J＝10Hz, 2H),2.44(t,J＝5Hz,2H),2.20-2.17(m,4H),2.12(s,3H),1.99(d,J＝5Hz,6H),1.70(t,J＝5 Hz,6H),1.51-1.45(m,4H).¹³C NMR(C₆D₆,125MHz,ppm):δ148.7,137.7,131.8,127.3, 123.8,123.0,121.2,116.5,109.5,57.2,55.7,54.3,45.8,44.0,37.2,30.3,23.9.IR(KBr pellets, cm^-1):ν3039(w),2901(s),2847(s),2803(m),1631(m),1534(m),1459(s),1387(m),1345 (w),1301(w),1172(w),1101(w),1083(w),810(s),747(s).HR-MS(ESI)m/z Calcd for C₂₅H₃₄N₃(M+H⁺):376.2747,Found:376.2748.

Preparation example 10

Preparation of ligand HL 10:

3- (2-tert-butylphenyl) iminoindole (13.8g,50mmol) and anhydrous potassium carbonate (20.7g,150mmol) were dissolved in 10mL of anhydrous DMF, after completion, 2-chloromethyltetrahydrofuran (6.6g,55mmol) was added and reacted at 120 ℃ for 48 hours, after completion of the reaction, the product was extracted with ethyl acetate, extracted with water and ethyl acetate, dried, filtered, and recrystallized from ethyl acetate and petroleum ether to give white crystals, which were weighed 14.4g, in 80% yield.

The characterization data for the product are:¹H NMR(500MHz,CDCl₃,ppm):δ8.56(d,J＝7.5Hz,1H, 4-indol-H),8.45(s,1H,CH＝N),7.64(s,1H,Ar-H),7.40(t,J＝7.5Hz,2H,Ar-H),7.35-7.27(m, 2H,Ar-H),7.23(t,J＝7.5Hz,1H,Ar-H),7.12(t,J＝7.5Hz,1H,Ar-H),6.86(d,J＝7.5Hz, 1H,Ar-H),4.33-4.27(m,2H,NCH2),4.20(dd,J＝15.4,7.0Hz,1H,THF-H),3.87(dt,J＝8.2, 6.8Hz,1H,THF-H),3.82-3.76(m,1H,THF-H),2.07-2.00(m,1H,THF-H),1.93-1.78(m,2H, THF-H),1.65-1.58(m,1H,THF-H),1.51(s,9H,CMe3).¹³C NMR(125MHz,C₆D₆,ppm):δ 154.2,153.1,143.0 138.4,135.2,127.5,126.5,126.3,125.0,123.5,123.2,122.1,120.5,116.7, 110.1,77.8,68.1,49.9,36.0,31.0,28.9,25.8.IR(KBr pellets,cm^-1):ν3044(w),2955(s), 2897(m),1602(w),1578(m),1503(w),1469(m),1432(m),1384(w),1306(w),1285(w), 1248(s),1200(w),1057(m),1020(w),992(m),955(w),859(s),774(w),757(m),737(s). HRMS(ESI)m/z calcd for C₂₄H₂₈N₂O(M+H⁺):361.2274,found:361.2276.

preparation example 11

Preparation of ligand HL 11:

dissolving N-methyl-3-indole carbaldehyde (1.59g,10mmol) and 2, 6-diisopropylaniline (1.77g,10.0mmol) in 20mL of absolute ethyl alcohol, adding 0.01mmol of p-toluenesulfonic acid after the reaction is finished, heating and refluxing for 12 hours, cooling to separate out white powder, filtering, washing and drying to obtain a white solid, weighing 1.71g and obtaining the yield of 54%. (reference paper: synthesis, structure and performance studies of Guoliping.1, 3-disubstituted-2-indolyl and neutral pyrrolyl metal complexes [ D ]. university of Anhui, 2015).

Preparation example 12

Preparation of ligand HL 12:

dissolving N-benzyl-3-indole carbaldehyde (2.35g,10.0mmol) and 2, 6-diisopropylaniline (1.77g,10.0mmol) in 20mL of absolute ethanol, adding 0.01mmol of p-toluenesulfonic acid after the reaction is finished, heating and refluxing for 12 hours, cooling to separate out white powder, filtering, washing and drying to obtain a white solid, weighing 2.64g, and obtaining the yield of 67%. (reference paper: synthesis, structure and performance studies of Guoliping.1, 3-disubstituted-2-indolyl and neutral pyrrolyl metal complexes [ D ]. university of Anhui, 2015).

Example 1

Preparation of Complex B-1:

dropwise adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium and 0.625mL) into n-hexane solution (10mL and containing 1.0mmol of HL1) containing ligand HL1 at-20 deg.C, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, and collecting solid with tetrahydrofuranPyran (5mL) solution was added dropwise to YCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of YCl)₃) Reacting at 25 deg.C for 6 hr, removing solvent under reduced pressure, extracting the rest solid n-hexane and toluene (volume ratio 1:1) mixed solvent (20mL), and standing the concentrated solution at 25 deg.C to obtain yellow crystal 0.669g with yield of 95%.

The characterization data for the product are: m.p. 201 ℃ IR (KBr pellets, cm)^-1):v 3050,2968,2868,1629,1580, 1559,1462,1357,1323,1204,1118,1006,913,854,740.¹H NMR(500MHz,C₆D₆,298K):δ 8.56(s,1H,CH＝N),8.55(s,1H,CH＝N),7.59-7.22(m,14H,PhH),3.97-0.84(m,68H, C_saturatedH).¹³C NMR(125MHz,C₆D₆,298K):δ199.6(d,J_Y-C50Hz, CH ═ N),169.4,156.2, 151.7,143.4,141.1,138.4,133.9,129.3,128.6,126.2,125.6,124.0,123.8,123.6,123.5,123.4, 122.1,121.9,121.3,117.6,110.4,109.8,71.3,55.5,55.3,54.2,45.9,44.8,32.0,28.6,28.4,26.2, 25.3,23.9,23.8,23.7,23.3,23.1,21.4,14.3, results of elemental analysis (%): calculated value (C)₆₂H₈₄Cl₄N₆O₂Y₂)(C₇H₈)_2.8C, 64.35; h, 7.04; n,5.52, found C, 64.48; h, 7.28; and N,5.17.

Example 2

Preparation of Complex B-2:

at-20 deg.C, dropwise adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium, 0.625mL) into n-hexane solution (10mL, containing 1.0mmol of HL2) containing ligand HL2, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, dissolving solid with tetrahydrofuran (5mL), and dropwise adding into YCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of YCl)₃) Reacting at 25 deg.C for 6 hr, removing solvent under reduced pressure, extracting with mixed solvent of solid n-hexane and toluene (volume ratio 1:1) (20mL), and standing at 25 deg.C to obtain yellow crystal 0.216g with yield of 30%. (reference paper: Wuweikang containing 1- (2-piperacillin)Synthesis, characterization and catalytic performance study of pyridylethyl) -3-iminoindole ligand rare earth metal hydrocarbyl complex and NCN Pincer type rare earth metal dichloride [ D]. University of Anhui, 2020),

example 3

Preparation of Complex B-3:

at-20 deg.C, dropwise adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium, 0.625mL) into n-hexane solution (10mL, containing 1.0mmol of HL2) containing ligand HL2, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, dissolving solid with tetrahydrofuran (5mL), and dropwise adding into DyCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of DyCl)₃) Reacting at 25 deg.C for 6 hr, removing solvent under reduced pressure, extracting the rest solid n-hexane and toluene (volume ratio 1:1) mixed solvent (20mL), and standing the concentrated solution at 25 deg.C to obtain yellow crystal 0.436g with yield of 55%. (reference paper: Wuweikang, Synthesis, characterization and catalytic Properties of rare earth Metal hydrocarbyl Complex containing 1- (2-Piperidinylethyl) -3-iminoindole ligand and NCN Pincer type rare earth Metal dichloride [ D]. University of Anhui, 2020),

example 4

Preparation of Complex B-4:

dropwise adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium and 0.625mL) into n-hexane solution (10mL and containing 1.0mmol of HL2) containing ligand HL2 at-20 deg.C, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, dissolving solid with tetrahydrofuran (5mL), and dropwise adding into GdCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of GdCl₃) Reacting at 25 deg.C for 6 hr, removing solvent under reduced pressure, extracting the rest solid n-hexane and toluene (volume ratio of 1:1) mixed solvent (20mL), concentrating at 25 deg.CStanding to obtain 0.393g of yellow crystals with 50% yield. (reference paper: Wuweikang, Synthesis, characterization and catalytic Properties of rare earth Metal hydrocarbyl Complex containing 1- (2-Piperidinylethyl) -3-iminoindole ligand and NCN Pincer type rare earth Metal dichloride [ D]. University of Anhui, 2020),

example 5

Preparation of Complex A-1:

at-20 deg.C, dropwise adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium, 0.625mL) into n-hexane solution (10mL, containing 1.0mmol of HL3) containing ligand HL3, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, dissolving solid with tetrahydrofuran (5mL), and dropwise adding into YCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of YCl)₃) Reacting at 25 deg.C for 6 hr, removing solvent under reduced pressure, extracting the rest solid n-hexane and toluene (volume ratio 1:1) mixed solvent (20mL), and standing the concentrated solution at 25 deg.C to obtain yellow crystal 0.366g with yield of 55%.

The characterization data for the product are: m.p. 176 ℃ IR (KBr pellets, cm)^-1):v 3089(w),2948(m),2867(m), 1707(w),1630(s),1588(m),1577(m),1540(m),1470(m),1395(m),1360(m),1333(m), 1255(m),1170(m),1078(m),1009(m),936(w),855(w),788(m),744(s).¹H NMR(500MHz, C₆D₆):δ8.98(d,J＝8.0Hz,1H),8.60(s,2H,PhH),8.31(s,1H,PhH),7.59-7.22(m,4H,PhH), 3.79-0.84(m,37H,C_saturatedH).¹³C NMR(125MHz,C₆D₆Ppm). delta 199.7,168.9,156.1,151.7, 151.0,142.9,141.1,138.4,137.9,134.2,129.3,128.6,126.9,125.4,123.4,122.8,122.1,121.5, 120.8,117.2,115.8,109.8,73.9,71.1,59.6,58.5,46.3,42.5,32.0,28.6,28.3,26.0,25.8,23.8, 23.0,21.4,14.3. results of elemental analysis (%): calculated value C₃₂H₄₅N₂O₃Cl₂Y(C₇H₈) C, 58.43; h, 6.86; n,4.12, found C, 58.73; h, 6.92; and N,3.91.

Example 6

Preparation of Complex A-2:

at-20 ℃, dropwise adding n-hexane solution (containing 1.0mmol of n-butyllithium and 0.625mL) of n-butyllithium into n-hexane solution (10mL and containing 1.0mmol of HL3) containing ligand HL3, heating to 25 ℃, reacting at 25 ℃ for 6 hours, vacuumizing the solvent, dissolving the solid with tetrahydrofuran (5mL), and dropwise adding the solid into ErCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of ErCl)₃) And reacting at 25 ℃ for 6 hours, removing the solvent under reduced pressure, extracting the rest solid n-hexane and toluene (volume ratio is 1:1) mixed solvent (20mL), and standing the concentrated solution at 25 ℃ to obtain yellow crystals 0.372g with the yield of 50%.

The characterization data for the product are: m.p. 180 ℃ IR (KBr pellets, cm)^-1) V 3099(w),2958(m),2906(m), 2827(w),1701(w),1627(s),1573(m),1544(m),1467(m),1442(m),1398(m),1354(m), 1333(m),1261(m),1169(m),1075(m),1011(m),934w,854(w),788(m),749(s). elemental analysis results (%): calculated value C₃₂H₄₅N₂O₃Cl₂Er(C₇H₈) C, 53.98; h, 6.25; n,3.55, found C, 54.18; h, 6.44; and N,3.59.

Example 7

Preparation of Complex A-3:

at-20 deg.C, dropwise adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium, 0.625mL) into n-hexane solution (10mL, containing 1.0mmol of HL3) containing ligand HL3, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, dissolving solid with tetrahydrofuran (5mL), and dropwise adding into DyCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of DyCl)₃) At 25 deg.C for 6 hr, removing solvent under reduced pressure, and mixing the rest solid n-hexane and toluene (volume ratio 1:1) to obtain mixed solvent (20mL)) Extracting, and standing the concentrated solution at 25 deg.C to obtain yellow crystal 0.443g with yield of 60%.

The characterization data for the product are: m.p. 170 ℃ IR (KBr pellets, cm)^-1) V 3066(w),2965(m),2870(m), 1632(s),1544(m),1465(m),1444(m),1400(m),1351(m),1333(m),1200(w),1166(s), 1117(s), 1017(m),931(w),880(m),855(m),800(m),746(s) elemental analysis results (%): calculated value C₃₂H₄₅N₂O₃Cl₂Dy(C₇H₈) C, 52.96; h, 6.20; n,3.70, found C, 52.74; h, 6.21; and N,3.45.

Example 8

Preparation of Complex A-4:

adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium and 0.625mL) into n-hexane solution (10mL and containing 1.0mmol of HL3) containing ligand HL3 at-20 deg.C, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, removing solvent under vacuum, dissolving solid with tetrahydrofuran (5mL), and adding GdCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of GdCl₃) Reacting at 25 deg.C for 6 hr, removing solvent under reduced pressure, extracting the rest solid n-hexane and toluene (volume ratio 1:1) mixed solvent (20mL), and standing the concentrated solution at 25 deg.C to obtain yellow crystal 0.550g with yield of 75%.

The characterization data for the product are: m.p. 172 ℃ IR (KBr pellets, cm)^-1) V 3104(w),2940(m),2900(m), 1629(s),1568(m),1551(m),1463(m),1446(m),1400(m),1350(m),1333(m),1263(m), 1171(m),1120(m),1060(m),937(w),854(w),786(m),749(s) elemental analysis results (%): calculated value C₃₂H₄₅N₂O₃Cl₂Gd(C₇H₈) C, 53.78; h, 6.27; n,3.68, found C, 53.61; h, 6.31; n,3.51.

Example 9

Preparation of Complex A-5:

dropwise adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium and 0.625mL) into n-hexane solution (10mL and containing 1.0mmol of HL4) containing ligand HL4 at-20 deg.C, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, dissolving solid with tetrahydrofuran (5mL), and dropwise adding into GdCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of GdCl₃) Reacting at 25 deg.C for 6 hr, removing solvent under reduced pressure, extracting with mixed solvent of solid n-hexane and toluene (volume ratio 1:1) (20mL), and standing at 25 deg.C to obtain yellow crystal 0.203g with yield of 28%.

The characterization data for the product are: m.p. 244 ℃ IR (KBr pellets, cm)^-1) V 3063(m),2955(m),2683(w), 2461(w),2370(w),1810(w),1720(w),1665(w),1630(s),1585(w)1465(m),1444(m),1357 (m),1328(m),1163(w),1114(w),929(w),855(m),749(m). elemental analysis results (%): c₃₁H₄₂Cl₂GdN₃O₂C, 51.94; h, 5.91; n, 5.86; measured value C, 51.77; h, 6.06; and N,5.47.

Example 10

Preparation of Complex C-1:

adding n-hexane solution of n-butyllithium (containing 1.0mmol of n-butyllithium and 0.625mL) into n-hexane solution (10mL and containing 1.0mmol of HL4) containing ligand HL4 at-20 deg.C, heating to 25 deg.C, reacting at 25 deg.C for 6 hr, vacuum removing solvent, dissolving solid with tetrahydrofuran (5mL), and adding into YCl₃In tetrahydrofuran solution (10mL, containing 1.0mmol of YCl)₃) And reacting at 25 ℃ for 6 hours, removing the solvent under reduced pressure, extracting the remaining solid with a mixed solvent (12mL) of n-hexane and tetrahydrofuran (volume ratio 5:1), condensing, and standing to obtain yellow crystals (0.361 g) with a yield of 63%.

The characterization data for the product are: m.p. 214 ℃ IR (KBr pellets, cm)^-1):v 2955(m),2814(m),1665 (w),1630(s),1544(m),1465(m),1427(m),1397(s),1357(m),1325(w)1178(w),1115(m), 932(m),857(s),748(s),695(w).¹H NMR(500MHz,C₆D₆):δ8.97(d,J＝10.0Hz,1H),8.37 (s,1H),7.29-7.21(m,4H),7.05(d,J＝10.0Hz,1H),6.92(s,1H),3.54(d,J＝5.0Hz,2H), 3.47-3.40(m,8H),2.03(t,J＝7.5Hz,2H),1.89(t,J＝5.0Hz,4H),1.38(t,J＝5.0Hz,2H), 1.26(d,J＝10.0Hz,12H).¹³C NMR(125MHz,C₆D₆Ppm). delta 156.1,151.7,138.4,137.7, 133.9,127.0,124.1,123.6,123.5,123.4,122.2,115.6,109.7,67.8,67.0,57.8,53.9,44.0,31.9, 28.6,23.8. results of elemental analysis (%): calculated value C₆₂H₈₄Cl₂LiN₆O₄Y is C, 65.09; h, 7.40; n,7.35, found C, 64.73; h, 7.53; and N,7.47.

Application example 1

In a glove box, 10. mu. mol of the rare earth complex B-1 was weighed into a 25mL polymerization flask, 2mL of chlorobenzene was weighed and added thereto, 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate and 100. mu. mol of triisobutylaluminum were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 15 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight to give 0.34g of a product with a conversion of 100%.

Molecular weight Mn of the polymer by GPC analysis was 20.3 ten thousand; PDI 2.67, and nmr spectroscopy showed 98.8% cis 1,4 structure content.

Application example 2

In a glove box, 10. mu. mol of the rare earth complex B-1 was weighed and placed in a 25mL polymerization flask, 8mL of chlorobenzene was weighed and added thereto, 10. mu. mol of triphenylcarbenium tetrakis (pentafluorophenyl) borate and 100. mu. mol of triisobutylaluminum were sequentially added, and the resulting solution was stirred for 1 minute and then 20000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 180 minutes, and 40mL of a methanol solution (containing 0.4mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight to give 1.36g of a product with a conversion of 100%.

The molecular weight Mn of the polymer by GPC analysis was 87.6 ten thousand; PDI is 1.36. The cis-1, 4 structure content was 99.1% by NMR spectroscopy.

Application example 3

In a glove box, 10. mu. mol of the rare earth complex B-2 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 50. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 10 minutes, 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, i.e., 0.34g of product, with 100% conversion.

Molecular weight Mn of the polymer by GPC analysis is 30.2 ten thousand; PDI 3.35, and content of cis-1, 4 structure 99.2% by nmr spectroscopy.

Application example 4

In a glove box, 10. mu. mol of the rare earth complex B-3 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 50. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 5 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight to give 0.34g of a product with a conversion of 100%.

Molecular weight Mn of the polymer by GPC analysis was 26.9 ten thousand; PDI 2.45. The content of cis-1, 4 structure was 98.8% by NMR spectroscopy.

Application example 5

In a glove box, 10. mu. mol of the rare earth complex B-4 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 100. mu. mol of triisobutylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 8 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight to give 0.34g of a product with a conversion of 100%.

The molecular weight Mn of the polymer by GPC analysis was 19.7 ten thousand; PDI 2.76. The content of cis-1, 4 structure was 98.8% by NMR spectroscopy.

Application example 6

In a glove box, 10. mu. mol of the rare earth complex A-1 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 50. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 10 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis is 29.0 ten thousand; PDI 2.39. The cis-1, 4 structure content was 99.1% by NMR spectroscopy.

Application example 7

In a glove box, 10. mu. mol of the rare earth complex A-2 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 50. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 10 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis was 14.1 ten thousand; PDI 2.19. The cis-1, 4 structure content was 99.2% by NMR spectroscopy.

Application example 8

In a glove box, 10. mu. mol of the rare earth complex A-3 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 50. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 8 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis was 21.8 ten thousand; PDI 2.64. The content of cis-1, 4 structure was 98.9% by NMR spectroscopy.

Application example 9

In a glove box, 10. mu. mol of the rare earth complex A-4 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 50. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 5 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

The molecular weight Mn of the polymer by GPC analysis was 65.4 ten thousand; PDI is 1.89. The content of cis-1, 4 structure was 98.8% by NMR spectroscopy.

Application example 10

In a glove box, 10. mu. mol of the rare earth complex A-4 was weighed and placed in a 50mL polymerization flask, 10mL of chlorobenzene was weighed and added thereto, 50. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 20000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 8 minutes, and 40mL of a methanol solution (containing 0.4mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 1.36g, and the conversion was 100%.

The molecular weight Mn of the polymer by GPC analysis was 36.9 ten thousand; PDI is 2.63. The content of cis-1, 4 structure was 97.6% by NMR spectroscopy.

Application example 11

In a glove box, 10. mu. mol of the rare earth complex A-4 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 100. mu. mol of triethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 5 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis was 45.1 ten thousand; PDI is 1.61. The content of cis-1, 4 structure was 98.7% by NMR spectroscopy.

Application example 12

In a glove box, 10. mu. mol of the rare earth complex A-4 was weighed into a 50mL polymerization flask, 20mL of chlorobenzene was weighed and added thereto, 100. mu. mol of triethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and 40000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 90 minutes, and 80mL of a methanol solution (containing 0.8mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 2.58g, and the conversion was 95%.

Molecular weight Mn of the polymer by GPC analysis 36.4 ten thousand; PDI 2.28. The content of cis-1, 4 structure was 98.0% by NMR spectroscopy.

Application example 13

In a glove box, 10. mu. mol of the rare earth complex A-4 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 100. mu. mol of triisobutylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 10 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis 23.4 ten thousand; PDI 2.97. The content of cis-1, 4 structure was 98.8% by NMR spectroscopy.

Application example 14

In a glove box, 10. mu. mol of the rare earth complex A-4 was weighed and placed in a 25mL polymerization flask, 10mL of chlorobenzene was weighed and added thereto, 100. mu. mol of triisobutylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 20000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 20 minutes, and 40mL of a methanol solution (containing 0.4mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into pieces, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 1.36g, and the conversion was 100%.

The molecular weight Mn of the polymer by GPC analysis was 36.3 ten thousand; PDI is 1.81. The content of cis-1, 4 structure was 98.9% by NMR spectroscopy.

Application example 15

In a glove box, 10. mu. mol of rare earth complex A-5 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate and 100. mu. mol of triethylaluminum were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 0 ℃ for 20 minutes, 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into pieces, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis was 48.4 ten thousand; PDI is 1.92. The cis-1, 4 structure content was 99.5% by NMR spectroscopy.

Application example 16

In a glove box, 10. mu. mol of the rare earth complex C-1 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 100. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 15 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis was 17.6 ten thousand; PDI is 1.79. The content of cis-1, 4 structure was 94.4% by NMR spectroscopy.

Application example 17

In a glove box, 10. mu. mol of the rare earth complex A-4 was weighed into a 25mL polymerization flask, 5mL of chlorobenzene was weighed and added thereto, 100. mu. mol of trimethylaluminum and 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were sequentially added, and then 5000. mu. mol of isoprene monomer was added at 0 ℃. The reaction was carried out at 0 ℃ for 20 minutes, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to terminate the reaction, and the resulting white polymer was washed with methanol, cut into chips, and dried in a vacuum oven to a constant weight, wherein the weight of the product was 0.34g and the conversion was 100%.

Molecular weight Mn of the polymer by GPC analysis was 115.5 ten thousand; PDI 2.04. The content of cis-1, 4 structure was 99.0% by NMR spectroscopy.

Comparative example 1

In a glove box, 10. mu. mol of rare earth complex B-1 was weighed into a 25mL polymerization flask, 2.5mL of chlorobenzene was weighed and added thereto, 100. mu. mol of triisobutylaluminum was added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for 2 hours, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to obtain no polymer.

Comparative example 2

In a glove box, 10. mu. mol of the rare earth complex B-1 was weighed into a 25mL polymerization flask, 2.5mL of chlorobenzene was added thereto, 10. mu. mol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate was added, and the resulting solution was stirred for 1 minute and then 5000. mu. mol of isoprene monomer was added. The reaction was carried out at 20 ℃ for two hours, and 10mL of a methanol solution (containing 0.1mL of hydrochloric acid) was added to obtain no polymer.

The reaction conditions and the results of the product analyses of examples 1-17 are summarized in Table 1, wherein the conversion refers to the monomer conversion.

TABLE 1

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.