CN111747891B

CN111747891B - SNN ligand based on quinoline skeleton, iron complex thereof, preparation method and application

Info

Publication number: CN111747891B
Application number: CN202010662265.3A
Authority: CN
Inventors: 黄正; 侯文君; 张丹; 刘桂霞
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2020-07-10
Filing date: 2020-07-10
Publication date: 2022-08-09
Anticipated expiration: 2040-07-10
Also published as: CN111747891A

Abstract

The invention discloses a quinoline skeleton-based SNN ligand, an iron complex thereof, a preparation method and application. The invention provides an SNN ligand based on a quinoline skeleton as shown in a formula I, wherein an iron complex of the SNN ligand has excellent catalytic activity on the polymerization reaction of an olefin-containing compound, the monomer insertion rate is high during copolymerization, and a polyolefin product in a wax or oil shape can be generated. And when the substrates are ethylene and non-conjugated diene, the catalytic reaction mainly generates a copolymer with a main chain containing unsaturated bonds, and various branched chains are less.

Description

SNN ligand based on quinoline skeleton, iron complex thereof, preparation method and application

Technical Field

The invention belongs to the field of olefin polymerization, and particularly relates to a quinoline skeleton-based SNN ligand, an iron complex thereof, a preparation method and application.

Background

Ziegler-Natta catalysts (K.Ziegler et al, Angew. chem.1995,67,424; K.Ziegler et al, Angew. chem.1995,67,541; N.Kashiwa et al, USP3642746,1968) discovered in the fifties of the twentieth century were widely used industrially to produce High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE), syndiotactic polypropylene (i-PP). Ziegler-Natta catalysts are heterogeneous, multi-site, and currently do not allow good control of polymer structure and properties by adjusting catalyst structure. The metallocene catalysts found in the eighties have better solved this problem and have enabled polymers of specific structure to be obtained by modifying the structure of the catalyst as required (W.Kaminsky et al. adv. organometamet. chem.1980,18, 99; W.Kaminsky et al. Angew. chem.int. Ed. Engl.1980,19,390; H.H.Brintzingger et al. Angew. chem.int. Ed. Engl.1995,34,1143). The metallocene catalyst has the advantages of single active center, capability of generating a polymer with highly uniform molecular structure and uniform components, capability of obtaining a polymer with narrow molecular weight distribution and the like, but because metallocene has strong electrophilicity, central metal ions are extremely easy to coordinate with polar functional groups to lose activity, and the polymerization or copolymerization of polar monomers is difficult to realize. Moreover, the metallocene catalyst has a large amount of the cocatalyst MAO, and the production cost is high.

In 1995, Brookhart et al reported that alpha-diimine nickel/palladium complexes catalyze ethylene polymerization and copolymerization with polar monomers (M.Brookhart et al, J.Am.chem.Soc.1995,117, 6414; M.Brookhart et al, J.Am.chem.Soc.1996,118,267.), which led to a great deal of research on late transition metal complexes. Late transition metals can tolerate polar monomers better because of their weaker oxophilicity. Part of the late transition catalyst can catalyze the copolymerization reaction of olefin and polar monomer, thereby providing possibility for producing novel polyolefin material.

Brookhart and Gibson et al, 1998, have also reported that iron pyridine diimine complexes catalyze olefin polymerization reactions which can catalyze the polymerization of ethylene to give high polymers or the oligomerization of ethylene to give statistically branched terminal olefins (M.Brookhart et al, J.am.Chem.Soc.1998,120, 4049; M.Brookhart et al, J.am.Chem.Soc.1998,120, 7143; V.C.Gibson et al, Chem.Commun.1998, 849). The iron metal complex attracts great interest of researchers due to the advantages of extremely high catalytic polymerization activity, abundant reserves, low price, environmental friendliness and the like. Since this time, many iron complexes of new ligands were designed, tridentate iron catalysts with one imine group on the ligand substituted for an amine group (v.c. gibson et al eur.j.inorg. chem.2001,2001,431), a carbonyl group (p.t. gos; m.m. marques et al polymer. int.2002,51,1301), a hydroxyl group (v.c. gibson; g.a. sol et al organometallics 2007,26,5119) were designed, but the activity was low. And at present, the SNN type tridentate coordination iron complex based on the quinoline skeleton is not reported to be used for catalyzing olefin polymerization.

NNN type tridentate coordination iron complexes based on a pyridinediimine framework have been reported to catalyze copolymerization of ethylene and alpha-olefins. Frd ric Peruch et al simply report that a small sterically hindered iron-2, 6- (2, 6-dimethylphenyl) diimine-pyridinium complex catalyzes the copolymerization of ethylene and 1-hexene with an insertion rate of 1-hexene of about 3.5%, the authors do not give the molecular weight of the polymer and its distribution, and that this complex is not capable of catalyzing the polymerization of 1-hexene (F.Peruch et al. C.R. Chimie 2002,5, 43.). The Kohtaro Osakada group studied the iron (cobalt) pyridine diimine complex catalyzed polymerization of 1, 6-heptadiene and copolymerization of 1, 6-heptadiene with ethylene (Kohtaro Osakada et al.J.am.chem.Soc.2007,129, 7002; Macromol.Rapid Commun.2008,29,1932; Dalton Transactions 2009,8955.). Wherein, the 2,6- (2, 6-dimethylphenyl) diimine pyridine iron complex is used for catalyzing 1, 6-heptadiene to carry out cyclopolymerization reaction, and a polymer containing a cis five-membered ring is obtained with high selectivity; in the catalytic copolymerization reaction of ethylene and 1, 6-heptadiene, five-membered rings are generated through cyclization, and no hexenyl branched chain exists in the polymer.

Therefore, the development of a high-efficiency olefin polymerization catalyst, which realizes the adjustable copolymerization of ethylene and alpha-olefin (such as 1-octene), realizes the non-cyclization copolymerization of ethylene and non-conjugated diene (such as 1, 7-octadiene), generates a copolymer with double bonds on the main chain, and provides possibility for post-functionalization (such as hydrosilylation, hydroboration, epoxidation and hydroxylation) (Kotohiro Nomura et al.J.Am.chem.Soc.2007,129,14170-14171), so that the properties of the polymer can be improved, is a technical problem which needs to be solved urgently at present.

Disclosure of Invention

The invention aims to solve the technical problem of providing a quinoline skeleton-based SNN ligand, an iron complex thereof, a preparation method and application which are completely different from the prior art. The iron complex of the SNN ligand based on the quinoline skeleton has excellent catalytic activity on the polymerization reaction of olefin-containing compounds, has high monomer insertion rate during copolymerization, and can generate a polyolefin product in a wax or oil shape. And when the substrates are ethylene and non-conjugated diene, the catalytic reaction mainly generates a copolymer with a main chain containing unsaturated bonds, and various branched chains are less.

The invention provides a compound shown as a formula I:

wherein:

r is a hydrogen atom, C substituted by one or more halogens or unsubstituted ₁ ～C ₁₀ Alkyl radical, C ₂ ～C ₁₀ Alkenyl radical, C ₂ ～C ₁₀ Alkynyl, C ₆ ～C ₁₄ Aryl radical, C ₃ ～C ₆ Cycloalkyl, diphenylmethyl or

R ¹ And R ⁵ Each independently is a hydrogen atom, a halogen, C substituted by one or more halogens or unsubstituted ₁ ～C ₁₀ Alkyl radical, C ₂ ～C ₁₀ Alkenyl radical, C ₂ ～C ₁₀ Alkynyl, C ₆ ～C ₁₄ Aryl or

R ² And R ⁴ Each independently is a hydrogen atom, a halogen, C substituted by one or more halogens or unsubstituted ₁ ～C ₁₀ Alkyl radical, C ₂ ～C ₁₀ Alkenyl radical, C ₂ ～C ₁₀ Alkynyl, C ₆ ～C ₁₄ Aryl or

R ³ Is hydrogen atom, halogen, C substituted by one or more halogens or unsubstituted ₁ ～C ₁₀ Alkyl radical, C ₂ ～C ₁₀ Alkenyl radical, C ₂ ～C ₁₀ Alkynyl, alkynyl,C ₆ ～C ₁₄ Aryl or

R ¹¹ Is hydrogen atom, halogen, C substituted by one or more halogens or unsubstituted ₁ ～C ₁₀ Alkyl of (C) ₂ ～C ₁₀ Alkenyl radical, C ₂ ～C ₁₀ Alkynyl, C ₆ ～C ₁₄ Aryl, diphenylmethyl or

R ¹² 、R ¹³ And R ¹⁴ Each independently is a hydrogen atom, C ₁ ～C ₆ Alkyl or C ₆ ～C ₁₀ An aryl group;

R ¹⁵ 、R ¹⁶ and R ¹⁷ Each independently is a hydrogen atom, C ₁ ～C ₆ Alkyl or C ₆ ～C ₁₀ An aryl group;

R ¹⁸ 、R ¹⁹ and R ²⁰ Each independently is a hydrogen atom, C ₁ ～C ₆ Alkyl or C ₆ ～C ₁₀ An aryl group;

R ²¹ 、R ²² and R ²³ Each independently is a hydrogen atom, C ₁ ～C ₆ Alkyl or C ₆ ～C ₁₀ An aryl group;

R ²⁴ 、R ²⁵ and R ²⁶ Each independently is a hydrogen atom, C ₁ ～C ₆ Alkyl or C ₆ ～C ₁₀ An aryl group;

or, R ¹ ～R ⁵ Any two adjacent groups in (a) have the definition as set forth in any one of the following:

(1)R ¹ and R ² Together with the atoms to which they are attached form a 5-7 membered cycloalkenyl group;

(2)R ² and R ³ Together with the atoms to which they are attached form a 5-7 membered cycloalkenyl group;

(3)R ³ and R ⁴ Together with the atoms to which they are attachedTo form a 5-7 membered cycloalkenyl group;

(4)R ⁴ and R ⁵ Together with the atoms to which they are attached form a 5-7 membered cycloalkenyl group.

In one embodiment, in the compounds of formula I, certain groups may be defined as follows, and the remaining groups may be defined as in any of the above embodiments: (hereinafter, abbreviated as "in a certain embodiment:")

When R is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl radicals such as C ₁ -C ₆ Alkyl radicals, e.g. C ₁ -C ₄ Alkyl, also for example methyl, ethyl, isopropyl or tert-butyl.

In one aspect: when R is C substituted by one or more halogens ₁ -C ₁₀ Alkyl, said halogen is, for example, fluorine, chlorine, bromine or iodine, and further, for example, fluorine or chlorine.

In one aspect: when R is C substituted by more than one halogen ₁ -C ₁₀ When an alkyl group is used, the plural is two or three.

In one aspect: when R is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl radicals such as C ₂ ～C ₆ Alkenyl radicals, e.g. C ₂ ～C ₃ An alkenyl group.

In one aspect: when R is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl radicals such as C ₂ ～C ₆ Alkynyl, further for example C ₂ ～C ₃ Alkynyl.

In one aspect: when R is C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is, for example, phenyl or naphthyl, and further, phenyl.

In one aspect: when R is C ₃ ～C ₆ When there is a cycloalkyl group, said C ₃ ～C ₆ Cycloalkyl is cyclohexyl.

In one aspect: when R is ¹ And R ⁵ When each is independently a halogen, the halogen may be, for example, fluorine, chlorine,Bromine or iodine.

In one aspect: when R is ¹ And R ⁵ Each independently is C substituted or unsubstituted with one or more halogen ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl radicals such as C ₁ -C ₆ Alkyl radicals, e.g. C ₁ -C ₄ Alkyl, also for example methyl, ethyl, isopropyl or tert-butyl.

In one aspect: when R is ¹ And R ⁵ Each independently is C substituted by one or more halogen ₁ -C ₁₀ Alkyl, said halogen is, for example, fluorine, chlorine, bromine or iodine, and further, for example, fluorine or chlorine.

In one aspect: when R is ¹ And R ⁵ Each independently being C substituted by more than one halogen ₁ -C ₁₀ When an alkyl group is used, the plural is two or three.

In one aspect: when R is ¹ And R ⁵ Are each independently C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl radicals such as C ₂ ～C ₆ Alkenyl radicals, e.g. C ₂ ～C ₃ An alkenyl group.

In one aspect: when R is ¹ And R ⁵ Are each independently C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl radicals such as C ₂ ～C ₆ Alkynyl, further such as C ₂ ～C ₃ Alkynyl.

In one aspect: when R is ¹ And R ⁵ Are each independently C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl.

In one aspect: when R is ² And R ⁴ Each independently halogen, for example, fluorine, chlorine, bromine or iodine.

In one aspect: when R is ² And R ⁴ Each independently is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl radicals such as C ₁ -C ₆ Alkyl radicals, e.g. C ₁ -C ₄ Alkyl, also for example methyl, ethyl, isopropyl or tert-butyl.

In one aspect: when R is ² And R ⁴ Each independently is C substituted by one or more halogen ₁ -C ₁₀ Alkyl, said halogen is, for example, fluorine, chlorine, bromine or iodine, and further, for example, fluorine or chlorine.

In one aspect: when R is ² And R ⁴ Each independently being C substituted by more than one halogen ₁ -C ₁₀ When an alkyl group is used, the plural is two or three.

In one aspect: when R is ² And R ⁴ Are each independently C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl radicals such as C ₂ ～C ₆ Alkenyl radicals, e.g. C ₂ ～C ₃ An alkenyl group.

In one aspect: when R is ² And R ⁴ Are each independently C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl radicals such as C ₂ ～C ₆ Alkynyl, further for example C ₂ ～C ₃ Alkynyl.

In one aspect: when R is ² And R ⁴ Are each independently C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl.

In one aspect: when R is ³ In the case of halogen, the halogen is, for example, fluorine, chlorine, bromine or iodine.

In one aspect: when R is ³ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl radicals such as C ₁ -C ₆ Alkyl radicals, e.g. C ₁ -C ₄ Alkyl, also for example methyl, ethyl, isopropyl or tert-butyl.

In one aspect: when R is ³ Is C substituted by one or more halogens ₁ -C ₁₀ Alkyl, said halogen is, for example, fluorine, chlorine, bromine or iodine, and further, for example, fluorine or chlorine.

In one aspect: when R is ³ Is C substituted by more than one halogen ₁ -C ₁₀ When an alkyl group is used, the plural is two or three.

In one aspect: when R is ³ Is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl radicals such as C ₂ ～C ₆ Alkenyl radicals, e.g. C ₂ ～C ₃ An alkenyl group.

In one aspect: when R is ³ Is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl radicals such as C ₂ ～C ₆ Alkynyl, further for example C ₂ ～C ₃ Alkynyl.

In one aspect: when R is ³ Is C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl.

In one aspect: when R is ¹¹ In the case of halogen, the halogen is, for example, fluorine, chlorine, bromine or iodine.

In one aspect: when R is ¹¹ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl radicals such as C ₁ -C ₆ Alkyl radicals, e.g. C ₁ -C ₄ Alkyl, also for example methyl, ethyl, isopropyl or tert-butyl.

In one aspect: when R is ¹¹ Is C substituted by one or more halogens ₁ -C ₁₀ Alkyl, said halogen is, for example, fluorine, chlorine, bromine or iodine, and further, for example, fluorine or chlorine.

In one aspect: when R is ¹¹ Is C substituted by more than one halogen ₁ -C ₁₀ When an alkyl group is used, the plural is two or three.

In one aspect: when R is ¹¹ Is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl radicals such as C ₂ ～C ₆ Alkenyl radicals, e.g. C ₂ ～C ₃ An alkenyl group.

In a certain scheme: when R is ¹¹ Is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl radicals such as C ₂ ～C ₆ Alkynyl, further for example C ₂ ～C ₃ Alkynyl.

In one aspect: when R is ¹¹ Is C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl.

In one aspect: when R is ¹² 、R ¹³ And R ¹⁴ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl radicals such as C ₁ ～C ₃ Alkyl, for example methyl.

In one aspect: when R is ¹² 、R ¹³ And R ¹⁴ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl radicals are, for example, phenyl.

In one aspect: when R is ¹⁵ 、R ¹⁶ And R ¹⁷ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl radicals such as C ₁ ～C ₃ Alkyl, for example methyl.

In one aspect: when R is ¹⁵ 、R ¹⁶ And R ¹⁷ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl radicals are, for example, phenyl.

In one aspect: when R is ¹⁸ 、R ¹⁹ And R ²⁰ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl radicals such as C ₁ ～C ₃ Alkyl, for example methyl.

In one aspect: when R is ¹⁸ 、R ¹⁹ And R ²⁰ Are each independently C ₆ ～C ₁₀ Aryl, said C ₆ ～C ₁₀ Aryl radicals are, for example, phenyl.

In one aspect: when R is ²¹ 、R ²² And R ²³ Are each independently C ₁ ～C ₆ When alkyl is present, theC is ₁ ～C ₆ Alkyl radicals such as C ₁ ～C ₃ Alkyl, for example methyl.

In one aspect: when R is ²¹ 、R ²² And R ²³ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl radicals are, for example, phenyl.

In one aspect: when R is ²⁴ 、R ²⁵ And R ²⁶ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl radicals such as C ₁ ～C ₃ Alkyl, for example methyl.

In one aspect: when R is ²⁴ 、R ²⁵ And R ²⁶ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl radicals are, for example, phenyl.

In one aspect: r is C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ Alkyl radical, C ₆ ～C ₁₄ Aryl or C ₃ -C ₆ A cycloalkyl group.

In one aspect: r is C ₁ ～C ₁₀ Alkyl radical, C ₆ ～C ₁₄ Aryl or C ₃ -C ₆ A cycloalkyl group.

In one aspect: r is C ₁ ～C ₁₀ Alkyl or C ₃ -C ₆ A cycloalkyl group.

In one aspect: r ¹ And R ⁵ Each independently hydrogen or C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ An alkyl group.

In one aspect: r ¹ And R ⁵ Each independently is unsubstituted C ₁ ～C ₁₀ An alkyl group.

In one aspect: r ² And R ⁴ Each independently hydrogen.

In one aspect: r ³ Is hydrogen.

In one aspect: r ¹¹ Is C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ An alkyl group.

In one aspect: r is ¹¹ Is unsubstituted C ₁ ～C ₁₀ An alkyl group.

In one aspect:

r is C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ Alkyl radical, C ₆ ～C ₁₄ Aryl or C ₃ -C ₆ A cycloalkyl group;

R ¹ and R ⁵ Each independently hydrogen or C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ An alkyl group;

R ¹¹ is C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ An alkyl group.

In one aspect:

R ² and R ⁴ Each independently is hydrogen;

R ³ is hydrogen;

In one aspect:

r is C ₁ ～C ₁₀ Alkyl radical, C ₆ ～C ₁₄ Aryl or C ₃ -C ₆ A cycloalkyl group;

R ¹ and R ⁵ Each independently is unsubstituted C ₁ ～C ₁₀ An alkyl group;

R ² and R ⁴ Each independently is hydrogen;

R ³ is hydrogen;

R ¹¹ is unsubstituted C ₁ ～C ₁₀ Alkyl radical。

In one aspect:

r is C ₁ ～C ₁₀ Alkyl or C ₃ -C ₆ A cycloalkyl group;

R ² and R ⁴ Each independently is hydrogen;

R ³ is hydrogen;

R ¹¹ is unsubstituted C ₁ ～C ₁₀ An alkyl group.

In one aspect: the compound shown in the formula I is any one of the following compounds:

the invention also provides a compound shown as the formula II:

wherein X and Y are each independently halogen;

R、R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ and R ¹¹ Is as defined above.

In one embodiment, in the compounds of formula II, certain groups may be defined as follows, and the remaining groups may be defined as in any of the above embodiments:

the halogen is fluorine, chlorine or bromine, preferably chlorine.

a compound according to formula II any one of the following:

the invention also provides a preparation method of the compound shown as the formula II, which comprises the following steps: under the protection of inert gas, carrying out a complex reaction shown as the following between a compound shown as a formula I and FeXY in an organic solvent to obtain a compound shown as a formula II;

wherein, X, Y, R, R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ¹¹ Is as defined above.

In the complexing reaction, the inert gas may be an inert gas conventional in the art for such complexing reactions, preferably one or more of helium, argon, neon and nitrogen, more preferably argon.

In the complexation reaction, the organic solvent may be a solvent conventional in the complexation reaction in the field, preferably an ether solvent, and more preferably tetrahydrofuran.

In the complexation reaction, the volume-to-mass ratio of the organic solvent to the compound shown in formula I can be a ratio which is conventional in the complexation reaction in the field, preferably 10mL/g to 300mL/g, and further preferably 30mL/g to 150mL/g (for example, 82 mL/g).

In the complexation reaction, the molar ratio of the FeXY to the compound shown in the formula I is preferably 0.5-1, more preferably 0.8-1, and still more preferably 0.83-0.95.

In the complexing reaction, the temperature of the reaction can be the conventional temperature of the complexing reaction in the field, preferably 0-80 ℃, and further preferably 10-35 ℃.

In the complexing reaction, the progress of the reaction can be monitored by a conventional monitoring method (such as TLC, HPLC or NMR) of the complexing reaction in the art, and generally, the disappearance of the compound shown in formula I is taken as a reaction end point, and the reaction time is preferably 1 hour to 48 hours, more preferably 5 hours to 24 hours, and still more preferably 8 hours to 10 hours.

In the preparation method of the compound shown in the formula II, the complexation reaction may further include a post-treatment after the end of the complexation reaction, and the post-treatment preferably includes the following steps: after the complexation reaction is finished, filtering, washing with an alkane solvent, and drying to obtain a compound shown as a formula II; the alkane solvent is an alkane solvent which is conventional in the field, such as n-hexane or petroleum ether.

The preparation method of the compound shown in the formula II can further comprise the following steps: under the protection of inert gas, in an organic solvent and in the presence of a metal catalyst and in the presence of alkali, carrying out a coupling reaction between a compound A and a compound SRH as described below to generate a compound shown as a formula I;

wherein, R, R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ¹¹ Is as defined above.

In the coupling reaction, the inert gas may be an inert gas conventional in the art for such coupling reactions, preferably one or more of helium, argon, neon and nitrogen, more preferably argon.

In the coupling reaction, the organic solvent may be a solvent conventional in the art for such coupling reactions, preferably an aromatic hydrocarbon solvent, more preferably toluene.

In the coupling reaction, the metal catalyst may be a metal catalyst conventional in the art for such coupling reactions, preferably a late transition metal catalyst, preferably palladium-catalyzedAgents and/or cuprous catalysts, e.g. [1,1' -bis (diisopropylphosphine) ferrocene]Palladium dichloride, Pd (dba) ₂ 、Pd(OAc) ₂ Or CuI.

In the coupling reaction, the base may be a base conventional in the art for such coupling reactions, preferably NaO ^t Bu。

In the coupling reaction, the volume-to-mass ratio of the organic solvent to the compound A can be a ratio which is conventional in the coupling reaction in the field, and is preferably 1mL/g to 200mL/g, and more preferably 20mL/g to 49 mL/g.

In the coupling reaction, the molar ratio of the metal catalyst to the compound a may be a ratio conventionally used in such coupling reactions in the art, and is preferably 0.005 to 0.20, more preferably 0.01 to 0.11, and even more preferably 0.05 to 0.06.

In the coupling reaction, the molar ratio of the compound SRH to the compound a may be a ratio conventionally used in such coupling reactions in the art, and is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, and even more preferably 1.0 to 1.2.

In the coupling reaction, the molar ratio of the base to the compound 1 may be a molar ratio conventional in the art for such coupling reactions, and is preferably 2 to 1 (e.g., 1.2).

In the coupling reaction, the reaction temperature may be a temperature conventional in the art for such coupling reactions, preferably 50 ℃ to 200 ℃, more preferably 80 ℃ to 150 ℃, and still more preferably 110 ℃ to 120 ℃.

In the coupling reaction, the progress of the reaction can be monitored by a conventional monitoring method (e.g., TLC, HPLC, or NMR) in the art for such a coupling reaction, and the reaction time is preferably 2 hours to 48 hours, more preferably 10 hours to 36 hours, and still more preferably 20 hours to 24 hours (e.g., 12 hours).

After the coupling reaction is finished, the method can further comprise post-treatment, and the post-treatment preferably comprises the following steps: performing column chromatography and recrystallization to obtain the compound shown in the formula I.

The preparation method of the compound shown in the formula II can further comprise the following steps: in an organic solvent, in the presence of acid, carrying out condensation reaction on the compound B and the compound C as shown in the specification to obtain a compound A;

In the condensation reaction, the organic solvent may be a solvent conventionally used in such condensation reactions, preferably an aromatic hydrocarbon solvent, more preferably toluene.

In the condensation reaction, the acid may be an acid conventionally used in such condensation reactions, preferably a protic acid, more preferably p-toluenesulfonic acid and/or a monohydrate of p-toluenesulfonic acid.

In the condensation reaction, the volume-to-mass ratio of the organic solvent to the compound B can be the ratio which is conventional in the condensation reaction in the field, and is preferably 1mL/g to 100mL/g, and more preferably 10mL/g to 70 mL/g.

In the condensation reaction, the molar ratio of the compound C to the compound B may be a ratio conventionally used in such condensation reactions in the field, and is preferably 1-3, more preferably 1-1.5, and even more preferably 1-1.2.

In the condensation reaction, the molar ratio of the acid to the compound B may be a ratio conventionally used in such condensation reactions in the art, and is preferably 0.005 to 0.20, and more preferably 0.05 to 0.06.

In the condensation reaction, the reaction temperature may be a temperature conventional in the condensation reaction in the art, and is preferably 50 ℃ to 200 ℃, more preferably 100 ℃ to 180 ℃, and still more preferably 130 ℃ to 140 ℃.

In the condensation reaction, the progress of the reaction can be monitored by a conventional monitoring method (such as TLC, HPLC or NMR) in the art for such condensation reaction, and generally, the reaction time is preferably 12 hours to 96 hours, more preferably 24 hours to 60 hours, and still more preferably 24 hours to 60 hours (such as 48 hours) with the disappearance of the compound B as a reaction end point.

After the condensation reaction is finished, post-treatment can be further included, and the post-treatment preferably comprises the following steps: cooling, concentrating, and performing column chromatography to obtain compound A.

The invention also provides a preparation method of the compound shown in the formula I, which further comprises the following steps: under the protection of inert gas, in an organic solvent and in the presence of a metal catalyst and in the presence of alkali, carrying out a coupling reaction between a compound A and a compound SRH as described below to generate a compound shown as a formula I;

wherein, R, R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ¹¹ Is as defined above;

the reaction conditions and operation of the preparation method of the compound shown in the formula I are as described above.

The invention provides application of a compound shown as a formula II as a catalyst in olefin polymerization reaction.

In the olefin polymerization reaction, the olefin can be an olefin which is conventional in the polymerization reaction in the field, so as not to influence the polymerization reaction, and the olefin is one or more olefins.

When the olefin is an olefin, the olefin is preferably C ₂ -C ₁₀ Olefins, said C ₂ -C ₁₀ The olefin being ethylene or C ₃ -C ₁₀ An olefin; said C ₃ -C ₁₀ The olefin is preferably an alpha-olefin (e.g.propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 4-methyl-1-pentene). Said C ₃ -C ₁₀ The olefin is preferably C ₅ -C ₁₀ Non-conjugated dienes (e.g. 1, 4-pentadiene, 1, 5-hexadiene, 5, 7-dimethyl-1, 6-octadiene,1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene or 1, 9-decadiene).

In one embodiment, when the olefin is a plurality of olefins, the plurality is two.

In one embodiment, when the olefin is a plurality of olefins, the olefins are ethylene and C ₃ -C ₁₀ Olefins, said C ₃ -C ₁₀ The olefin is preferably an alpha-olefin, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 4-methyl-1-pentene.

In one embodiment, when the olefin is a plurality of olefins, the olefins are ethylene and C ₅ -C ₁₀ A non-conjugated diene, said C ₅ -C ₁₀ Non-conjugated dienes such as 1, 4-pentadiene, 1, 5-hexadiene, 5, 7-dimethyl-1, 6-octadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene or 1, 9-decadiene.

In one embodiment, the olefins are ethylene and 1, 7-octadiene.

In one embodiment, the olefins are ethylene and 1, 8-nonadiene.

In one embodiment, the olefins are ethylene and 1, 9-decadiene.

In one embodiment, the olefin is ethylene.

The invention provides a compound E, wherein the compound E is in a chain link

A polyolefin in a molar content higher than 2%,

is composed of

n is 1 to 5.

The invention provides a compound F, which is a compound F containing

And the polyolefin of G; wherein,

in a molar amount of more than 50%, G is

One or more of (a) or (b),

is composed of

n is 1 to 5.

In one embodiment, in compound F

The molar content of (b) is higher than 75%.

In one embodiment, in compound F

Is higher than 90%.

In one embodiment, compound E is in a mer

From 2% to 20% by mole of a polyolefin.

The invention also provides a preparation method of the polymer, which comprises the following steps: in a solvent, in the presence of a catalyst, carrying out copolymerization reaction on ethylene and a compound D to obtain a polymer; the catalyst is a compound shown in the formula II

Wherein n is 1-5.

The preparation method of the polymer can be a conventional method for carrying out the copolymerization reaction in the field, and the following reaction conditions are particularly preferred in the invention:

in the copolymerization reaction, the solvent is preferably one or more of an alkane solvent, a haloalkane solvent and an aromatic solvent, for example, one or more of n-heptane, dichloromethane and toluene.

In the copolymerization reaction, the concentration of ethylene in the solvent is preferably the saturation concentration of ethylene in the solvent.

In the copolymerization reaction, the concentration of the compound D in the solvent is preferably 3 to 8mol/L, more preferably 5.4 to 6.8 mol/L.

In the copolymerization, the molar ratio of the catalyst to the compound D is preferably 10 ^-3 :1～10 ^-5 1, more preferably 1.5X 10 ^-4 :1～1.9×10 ^-4 1, e.g. 1.7X 10 ^-4 :1。

In the copolymerization, the catalytic reaction is preferably carried out in the presence of a cocatalyst, and the cocatalyst is preferably MAO (methylaluminoxane), MMAO (modified methylaluminoxane), EAO (ethylaluminoxane), BAO (butylaluminoxane), LiR ', AlR' ₃ 、AlR’ _a X’ _3-a And boranes (e.g., B (C) ₆ F ₅ ) ₃ ) One or more of; further preferred are MAO (methylaluminoxane), MMAO (modified methylaluminoxane) and AlR' ₃ One or more of (a); wherein R' is C ₁ ～C ₄ Alkyl of said "C ₁ ～C ₄ Alkyl of (a) such as methyl, ethyl, isopropyl, tert-butyl or isobutyl; x' is halogen, such as fluorine, chlorine, bromine or iodine; a is 1 or 2.

In the copolymerization reaction, the molar ratio of the catalyst to the co-catalyst is preferably 100:1 to 300:1, for example 200: 1.

In the copolymerization reaction, the progress of the reaction can be determined by conventional test methods in the art (such as nuclear magnetic resonance, infrared spectroscopy, spectrophotometry or mass spectrometry, HPLC or TLC), with disappearance of compound IV as the end point of the reaction, and the reaction time is preferably 0.5h to 15h, for example 10 h.

The copolymerization reaction may further comprise a post-treatment after the end of the copolymerization reaction, and the post-treatment preferably comprises the following steps: quenching the reaction to obtain a mixture, stirring the mixture in an acidic alcohol solution, filtering, washing with the acidic alcohol solution, and drying to obtain a polyolefin material; the acidic alcohol solution is preferably an acidic ethanol solution, more preferably an ethanol hydrochloride solution, and even more preferably an ethanol hydrochloride solution containing 10% by mass of the acidic alcohol solution.

In one embodiment, the catalyst is any one of the following compounds:

in the compound F

The molar content of (a) is higher than 75%.

In one embodiment, the catalyst is any one of the following compounds:

in the compound F

Is higher than 90%.

A polymer prepared according to the method of making a polymer as described above.

Unless otherwise indicated, the following terms appearing in the specification and claims of the invention have the following meanings:

term C ₁ ～C ₁₀ Alkyl means a straight or branched chain hydrocarbon radical having 1 to 10 carbon atoms, preferably C ₁ ～C ₆ Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

Term C ₂ ～C ₁₀ Alkenyl means a straight or branched chain hydrocarbon radical having 2 to 10 carbon atoms comprising at least one double bond, preferably C ₂ ～C ₆ Alkenyl radicals, such as the vinyl radical,

Term C ₃ -C ₁₀ By olefin is meant a straight or branched chain olefin having 3 to 10 carbon atoms comprising at least one double bond. In one embodiment, C ₃ -C ₁₀ The olefin is an alpha-olefin (i.e., an olefin having an alkenyl group in the alpha position). In one embodiment, C ₃ -C ₁₀ The olefin being C ₅ -C ₁₀ Non-conjugated dienes, such as one or more of 1, 4-pentadiene, 1, 5-hexadiene, 5, 7-dimethyl-1, 6-octadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene and 1, 9-decadiene.

Term C ₂ ～C ₁₀ Alkynyl means a straight or branched chain hydrocarbon radical having 2 to 10 carbon atoms comprising at least one triple bond, preferably C ₂ ～C ₆ Alkynyl radicals, such as the ethynyl radical,

Term C ₆ ～C ₁₄ Aryl means a hydrocarbon radical having 6 to 14 carbon atoms comprising one or more aromatic rings, preferably C ₆ ～C ₁₀ Aryl, preferably phenyl or β -naphthyl.

The term "cycloalkenyl" includes any stable cyclic alkenyl group containing one or more unsaturated carbon-carbon double bonds at any position in the group, but any ring of the system is non-aromatic. In some embodiments, the cycloalkenyl group is a 5-7 membered cycloalkenyl group. Examples of such cycloalkenyl groups include, but are not limited to, cyclopentenyl, cyclohexenyl, and the like.

The term C substituted by one or more halogens ₁ ～C ₁₀ Halogen in the alkyl group is preferably fluorine, chlorine or bromine, and when a plurality of halogen atoms are present, the halogen atoms may be the same or different; said "C substituted by one or more halogens ₁ ～C ₁₀ Alkyl "described for" C ₁ ～C ₁₀ Alkyl "preferably C ₁ ～C ₆ Alkyl, said "C ₁ ～C ₆ Alkyl "may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl. Said "C substituted by one or more halogens ₁ ～C ₁₀ Alkyl is "preferably" C substituted by one or more of fluorine, chlorine and bromine atoms ₁ ～C ₆ Alkyl group ", said" C substituted by one or more of fluorine, chlorine and bromine atoms ₁ ～C ₆ Alkyl "preferably" methyl group substituted by one or more of fluorine, chlorine and bromine atoms "," ethyl group substituted by one or more of fluorine, chlorine and bromine atoms "," propyl group substituted by one or more of fluorine, chlorine and bromine atoms "," isopropyl group substituted by one or more of fluorine, chlorine and bromine atoms "," butyl group substituted by one or more of fluorine, chlorine and bromine atoms "," isobutyl group substituted by one or more of fluorine, chlorine and bromine atoms "or" tert-butyl group substituted by one or more of fluorine, chlorine and bromine atoms "; said "fluorine atom-substituted methyl group" is preferably a trifluoromethyl group, and said "bromine atom-substituted methyl group" is preferably a bromine atom-substituted methyl group

The term "cycloalkyl" includes stable monocyclic cyclic alkyl groups. In one embodiment, cycloalkyl is C ₃ -C ₆ Cycloalkyl groups, examples of which include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows:

(1) the iron complex of the SNN ligand based on the quinoline skeleton has excellent catalytic activity for catalyzing the polymerization reaction of an olefin-containing compound, has high monomer insertion rate during copolymerization, and can generate a polyolefin product in a wax or oil shape;

(2) when the substrates are ethylene and non-conjugated diene, the catalytic reaction mainly generates a copolymer with an unsaturated bond in the main chain, and various branched chains are less;

(3) the obtained polymer product has the characteristics of lower molecular weight, narrower molecular weight distribution and the like, and is particularly suitable for preparing high-quality polyethylene wax and high-quality lubricating oil;

(4) in the polymerization reaction, the insertion rate of the olefin-containing compound can be regulated and controlled by changing the electronic property and the steric hindrance of the ligand.

Drawings

FIG. 1 is an exemplary hydrogen spectrum

FIG. 2 is a graph of the products of entry 1 of Table 2 ¹ H NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 3 shows the hydrogenated compounds of item 1 in Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 4 is a graph of the products of entry 2 of Table 2 ¹ H NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 5 shows the hydrogenated compounds of item 2 in Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 6 is a graph of the products of entry 3 of Table 2 ¹ H NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 7 shows the hydrogenated compounds of item 3 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 8 is a graph of the products in entry 4 of Table 2 ¹ H NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 9 shows the hydrogenated compounds of item 4 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 10 is a graph of the products of entry 5 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 11 shows the hydrogenated compounds of item 5 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 12 is a graph of the products in entry 6 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 13 shows the hydrogenated compounds of item 6 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 14 is a graph of the products of entry 7 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 15 shows the hydrogenated compounds of item 7 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 16 is a graph of the products in entry 8 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 17 shows the hydrogenated compounds of item 8 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 18 is a graph of the products in entry 9 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 19 shows hydrogenated compounds of item 9 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 20 is a graph of the products in entry 10 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 21 shows hydrogenated compounds of item 10 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 22 is a graph of the products of entry 11 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 23 shows the hydrogenated compounds of item 11 in Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

FIG. 24 is a graph of the products in item 12 of Table 2 ¹ H NMR(400MHz,CDCl ₃ )

FIG. 25 shows hydrogenated compounds of the products of item 12 of Table 2 ¹³ C NMR(600MHz,C ₂ D ₂ Cl ₄ )

Detailed Description

The features mentioned above with reference to the invention, or the features mentioned with reference to the embodiments, can be combined arbitrarily. All the features disclosed in this specification may be combined in any combination, and each feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the appended claims of the present application.

Example 1: preparation of SNN ligands

Compound 2a to a 100mL three-necked flask was added 2-acetyl-8-bromoquinoline (0.50g, 2mmol), 2, 6-dimethylaniline (0.24g, 2mmol), p-toluenesulfonic acid monohydrate (19mg,0.1mmol), and toluene as a solvent 35mL, charged to a reflux apparatus, and the reaction was heated to reflux for 48 h. Cooled to room temperature, concentrated in vacuo and purified by flash column chromatography (ethyl acetate: petroleum ether: 1:200) to give a yellow solid (0.65g, 92%). ¹ H NMR(400MHz,CDCl3)δ8.61(d,J＝8.8Hz,1H),8.23(d,J＝8.8Hz,1H),8.09(dd,J＝7.6Hz,1H),7.84(dd,J＝8.0Hz,1H),7.45(t,J＝8.0Hz,1H),7.10(d,J＝7.6Hz,2H),6.98(t,J＝7.6Hz,1H),2.41(s,3H),2.07(s,6H). ¹³ C NMR(101MHz,CDCl3)δ167.55,156.48,136.63,133.15,136.76,129.99,127.89,127.80,127.37,125.87,125.15,123.12,119.37,17.95,16.29.

Compound 2b the synthesis of this compound was the same as the synthesis procedure of 2a, giving a yield of 2b of 97%. Yellow solid (0.67g, 88%) was obtained. ¹ H NMR(400MHz,CDCl3)δ8.59(d,J＝8.7Hz,1H),8.23(d,J＝8.6Hz,1H),8.09(d,J＝7.5Hz,1H),7.85(d,J＝8.1Hz,1H),7.45(t,J＝7.8Hz,1H),7.14(d,J＝7.5Hz,2H),7.10–7.01(m,1H),2.49–2.29(m,7H),1.14(t,J＝7.5Hz,6H). ¹³ C NMR(101MHz,CDCl3)δ167.39,156.59,147.92,144.38,136.76,133.25,131.01,130.08,127.88,127.47,126.08,125.99,123.57,119.45,24.74,16.76,13.83.

Compound 2c the synthesis of this compound was the same as the synthesis procedure of 2a, giving a yield of 98% for 2 c. ¹ H NMR(400MHz,CDCl3)δ8.60(d,J＝8.4Hz,1H),8.24(d,J＝8.8Hz,1H),8.10(d,J＝7.2Hz,1H),7.85(d,J＝8.0Hz,1H),7.45(t,J＝8.0Hz,1H),7.19(d,J＝7.2Hz,2H),7.15-7.09(m,1H),2.77(p,J＝6.8Hz,2H),2.43(s,3H),1.16(dd,J＝6.8Hz,12H). ¹³ C NMR(101MHz,CDCl3)δ167.31,156.50,136.66,135.52,133.15,130.02,127.79,127.38,123.69,122.99,119.40,28.30,23.20,22.84,16.95.

^iPr SNN ^iPr (ligand 3a) Compound 2c (0.2047g, 0.5mmol), Pd (OAc) were weighed in an argon glove box ₂ (0.0056g，0.025mmol)，DiPPF(0.0176g，0.030mmol)，NaO ^t Bu (0.0577g, 0.6mmol), placed in a 50mL stopcock and dissolved by addition of toluene (10 mL). After stirring at room temperature for 1h, iPrSH (0.0381g, 0.5mmol) was added. Heating in oil bath at 120 deg.C for 12 hr. Column chromatography and ethanol recrystallization afforded 3a as a yellow solid (0.1900g, 94%). ¹ H NMR(400MHz,CDCl3)δ8.59(d,J＝8.6Hz,1H),8.21(d,J＝8.6Hz,1H),7.63(d,J＝7.8Hz,1H),7.60–7.49(m,2H),7.20(d,J＝7.7Hz,2H),7.16–7.11(m,1H),3.77(p,J＝6.6Hz,1H),2.78(p,J＝6.8Hz,2H),2.42(s,3H),1.52(d,J＝6.7Hz,6H),1.16(d,J＝6.9Hz,12H). ¹³ C NMR (101MHz, CDCl3) delta 167.48,139.18,136.68,135.76,129.14,127.61,125.50,123.91,123.72,123.10,119.17,34.30,28.40,23.34,23.14,23.02,17.15 HRMS (ESI +): Calcd C ₂₅ H ₃₀ N ₂ S[M+H] ⁺ 405.2359, measurement 405.2364.

^Et SNN ^iPr (ligand 3b) the ligand was synthesized in the same manner as in the synthesis of 3a, giving a yield of 83% for 3 b. ¹ H NMR(400MHz,CDCl3)δ8.60(d,J＝8.6Hz,1H),8.21(d,J＝8.6Hz,1H),7.62(dd,J＝7.8,1.6Hz,1H),7.57–7.46(m,2H),7.20(s,2H),7.15(d,J＝6.8Hz,1H),3.13(q,J＝7.4Hz,2H),2.80(p,J＝6.8Hz,2H),2.44(s,3H),1.54(d,J＝7.4Hz,3H),1.17(d,J＝6.9Hz,12H). ¹³ C NMR (101MHz, CDCl3) delta 167.45,154.57,136.60,135.76,128.95,127.66,123.73,123.64,123.42,123.10,123.10,119.21,28.40,24.82,23.34,23.01,17.12,13.67 HRMS (ESI +): MeterCalculation of C ₂₅ H ₃₀ N ₂ S[M+H] ⁺ 391.2202, measurement 391.2215.

^Ph SNN ^iPr (ligand 3c) the synthesis of the ligand was the same as the synthesis procedure of 3a, giving a yield of 83% for 3 c. Yellow solid (135mg, 62%). ¹ H NMR(400MHz,CDCl3)δ8.56(d,J＝8.5Hz,1H),8.25(d,J＝8.5Hz,1H),8.08(d,J＝7.2Hz,1H),7.86(d,J＝8.1Hz,1H),7.56(t,J＝7.7Hz,1H),7.21(d,J＝7.5Hz,2H),7.17–7.11(m,1H),2.79(p,J＝6.8Hz,2H),2.44(s,3H),1.44(s,9H),1.17(d,J＝6.8Hz,12H). ¹³ C NMR (101MHz, CDCl3) delta 167.98,155.95,138.24,136.89,135.75,135.09,129.59,128.52,127.06,123.74,123.11,118.98,47.15,31.64,28.42,23.36,23.01,17.39 HRMS (ESI +): Calcd C ₂₇ H ₃₄ N ₂ S[M+H] ⁺ 419.2515, measurement 419.2515.

^Ph SNN ^iPr (ligand 3d) the ligand was synthesized in the same manner as in the synthesis of 3a, giving a yield of 62% for 3 d. ¹ H NMR(400MHz,CDCl3)δ8.63(d,J＝8.6Hz,1H),8.23(d,J＝8.7Hz,1H),7.70(d,J＝5.1Hz,2H),7.62(d,J＝8.1Hz,1H),7.49(d,J＝5.6Hz,3H),7.37(t,J＝7.8Hz,1H),7.22(d,J＝7.5Hz,2H),7.15(d,J＝15.2Hz,1H),7.03(d,J＝7.5Hz,1H),2.81(p,J＝6.8Hz,2H),2.44(s,3H),1.19(d,J＝7.0Hz,12H). ¹³ C NMR (101MHz, CDCl3) delta 167.44,154.79,146.66,143.59,141.24,136.57,135.83,135.76,131.85,129.88,129.14,128.91,127.72,125.28,124.13,123.78,123.12,119.39,28.43,23.36,23.04,17.11 HRMS (ESI +): Calcd C ₂₉ H ₃₀ N ₂ S[M+H] ⁺ 439.2202, measurement 439.2203.

^Ph SNN ^Me (ligand 3e) the ligand was synthesized in the same manner as in the synthesis of 3a, giving a yield of 68% for 3 e. ¹ H NMR(400MHz,CDCl3)δ8.62(d,J＝8.6Hz,1H),8.23(d,J＝8.6Hz,1H),7.71(d,J＝7.7Hz,2H),7.61(d,J＝9.3Hz,1H),7.48(d,J＝7.2Hz,3H),7.36(t,J＝7.8Hz,1H),7.12(d,J＝7.5Hz,2H),7.04(d,J＝7.5Hz,1H),6.99(t,J＝7.5Hz,1H),2.40(s,3H),2.09(s,6H). ¹³ C NMR (101MHz, CDCl3) delta 167.61,154.72,148.89,143.49,141.15,136.47,135.70,131.84,131.05,129.78,129.21,129.03,128.81,127.94,127.64,125.29,124.07,123.13,119.26,18.02,16.35 HRMS (EI +): calculated C ₂₅ H ₂₂ N ₂ S382.1504, measurement 382.1513.

^Ph SNN ^Et (ligand 3f) the synthesis of the ligand was the same as the synthesis of 3a, giving a yield of 77% for 3 f. ¹ H NMR(400MHz,CDCl3)δ8.61(d,J＝8.6Hz,1H),8.23(d,J＝8.6Hz,1H),7.70(dd,J＝7.2,2.3Hz,2H),7.61(d,J＝8.4Hz,1H),7.48(dd,J＝5.1,2.0Hz,3H),7.36(t,J＝7.8Hz,1H),7.16(d,J＝7.5Hz,2H),7.08(d,J＝6.5Hz,1H),7.06–7.01(m,1H),2.49–2.35(m,7H),1.17(t,J＝7.5Hz,6H). ¹³ C NMR (101MHz, CDCl3) delta 167.39,154.84,148.00,143.58,141.24,136.57,135.80,131.91,131.14,129.87,129.12,128.89,127.71,126.07,125.32,124.14,123.50,119.32,24.75,16.78,13.85,23.04,17.11 HRMS (ESI +): calculated C ₂₇ H ₂₆ N ₂ S[M+H] ⁺ 411.1889, measurement 411.1884.

^Et SNN ^Me (ligand 3g) the synthesis of the ligand was the same as the synthesis procedure of 3a, giving a yield of 68% for 3 g. ¹ H NMR(400MHz,CDCl3)δ8.59(d,J＝8.6Hz,1H),8.20(d,J＝8.6Hz,1H),7.61(dd,J＝7.8,1.6Hz,1H),7.55–7.46(m,2H),7.11(d,J＝7.5Hz,2H),7.00–6.95(m,1H),3.13(q,J＝7.4Hz,2H),2.40(s,3H),2.07(s,6H),1.52(t,J＝7.4Hz,3H). ¹³ C NMR (101MHz, CDCl3) delta 167.67,154.54,148.96,144.38,139.92,136.56,128.91,127.98,127.64,125.35,123.66,123.40,123.13,119.14,24.80,18.08,16.43,13.65 HRMS (ESI +): Calcd C ₂₁ H ₂₂ N ₂ S[M+H] ⁺ 335.1576, measurement 335.1570.

^Et SNN ^Et (ligand 3h) the ligand synthesis was the same as the synthesis procedure of 3a, giving a 3h yield of 73%. ¹ H NMR(400MHz,CDCl3)δ8.56(d,J＝8.7Hz,1H),8.20(d,J＝8.6Hz,1H),7.61(d,J＝9.2Hz,1H),7.55–7.46(m,2H),7.13(d,J＝7.6Hz,2H),7.08–7.02(m,1H),3.12(q,J＝7.4Hz,2H),2.38(dp,J＝22.3,7.3Hz,7H),1.51(t,J＝7.4Hz,3H),1.13(t,J＝7.5Hz,6H). ¹³ C NMR (101MHz, CDCl3) delta 167.32,154.51,147.94,144.33,139.87,136.53,131.05,128.85,127.58,125.97,123.57,123.37,123.34,119.05,24.72,24.66,16.72,13.76,13.58 HRMS (EI +): calcd for C ₂₃ H ₂₆ N ₂ S[M+H] ⁺ 363.1879, measurement 363.1889.

^iPr SNN ^Me (ligand 3i) the synthesis of this ligand was the same as the synthesis procedure of 3a, giving a yield of 68% for 3 i. ¹ H NMR(400MHz,CDCl3)δ8.58(d,J＝8.6Hz,1H),8.20(d,J＝8.6Hz,1H),7.63(dd,J＝7.9,1.5Hz,1H),7.60–7.56(m,1H),7.52(t,J＝7.7Hz,1H),7.10(d,J＝7.5Hz,2H),7.00–6.94(m,1H),3.77(p,J＝6.7Hz,1H),2.39(s,3H),2.06(s,6H),1.51(d,J＝6.7Hz,6H). ¹³ C NMR (101MHz, CDCl3) delta 167.32,154.51,147.94,144.33,139.87,136.53,131.05,128.85,127.58,125.97,123.57,123.37,123.34,119.05,24.72,24.66,16.72,13.76,13.58 HRMS (EI +): calcd for C ₂₂ H ₂₄ N ₂ S 348.1660, measurement 348.1659.

^iPr SNN ^Et (ligand 3j) the synthesis of this ligand was the same as the synthesis procedure of 3a, giving a yield of 3j of 79%. ¹ H NMR(400MHz,CDCl3)δ8.58(d,J＝8.6Hz,1H),8.20(d,J＝8.6Hz,1H),7.63(dd,J＝7.9,1.5Hz,1H),7.60–7.56(m,1H),7.52(t,J＝7.7Hz,1H),7.10(d,J＝7.5Hz,2H),7.00–6.94(m,1H),3.77(p,J＝6.7Hz,1H),2.39(s,3H),2.06(s,6H),1.51(d,J＝6.7Hz,6H). ¹³ C NMR (101MHz, CDCl3) delta 167.32,154.51,147.94,144.33,139.87,136.53,131.05,128.85,127.58,125.97,123.57,123.37,123.34,119.05,24.72,24.66,16.72,13.76,13.58 HRMS (ESI +): calculated C ₂₄ H ₂₈ N ₂ S[M+H] ⁺ 377.2046, measurement 377.2040.

^Cy SNN ^Me (ligand 3k) the ligand was synthesized in the same manner as in the synthesis of 3a, giving a 3k yield of 94%. ¹ H NMR(400MHz,CDCl3)δ8.62(d,J＝8.6Hz,1H),8.23(d,J＝8.6Hz,1H),7.71(d,J＝7.7Hz,2H),7.61(d,J＝9.3Hz,1H),7.48(d,J＝7.2Hz,3H),7.36(t,J＝7.8Hz,1H),7.12(d,J＝7.5Hz,2H),7.04(d,J＝7.5Hz,1H),6.99(t,J＝7.5Hz,1H),2.40(s,3H),2.09(s,6H). ¹³ C NMR (101MHz, CDCl3) delta 167.61,154.72,148.89,143.49,141.15,136.47,135.70,131.84,131.05,129.78,129.21,129.03,128.81,127.94,127.64,125.29,124.07,123.13,119.26,18.02,16.35 HRMS (EI +): calculated C ₂₅ H ₂₈ N ₂ S[M+H] ⁺ 389.2046, measurement 389.2039.

^Cy SNN ^Et (ligand 3l) Synthesis of the ligand andthe synthesis procedure for 3a was the same, giving a yield of 77% 3 l. ¹ H NMR(400MHz,CDCl3)δ8.56(d,J＝8.6Hz,1H),8.20(d,J＝8.6Hz,1H),7.62(d,J＝7.9Hz,1H),7.58(d,J＝7.7Hz,1H),7.50(t,J＝7.7Hz,1H),7.14(d,J＝7.5Hz,2H),7.05(dd,J＝8.4,6.6Hz,1H),3.52(tt,J＝10.9,3.6Hz,1H),2.47–2.31(m,7H),2.26–2.17(m,2H),1.88(dt,J＝12.8,3.8Hz,2H),1.72(dt,J＝12.5,3.9Hz,1H),1.64–1.25(m,6H),1.14(t,J＝7.5Hz,6H). ¹³ C NMR (101MHz, CDCl3) delta 167.50,154.71,148.05,138.75,136.70,131.16,129.21,127.57,126.06,125.63,123.97,123.44,119.09,42.90,33.36,26.50,26.04,24.74,16.87,13.84 HRMS (EI +): Calcd C ₂₇ H ₃₂ N ₂ S[M+H] ⁺ 417.2359, measurement 417.2352.

Example 2: preparation of SNN-type iron complexes

( ^iPr SNN ^iPr )FeCl ₂ (Complex 4 a): ligand 3a (0.1214g,0.3mmol) was added slowly to FeCl in an Ar glove box ₂ A clear solution (0.0317g,0.25mmol) in THF (10mL) immediately precipitated a dark green solid. The reaction was stirred at room temperature for 10h, filtered, washed with n-hexane and dried under vacuum to give a green solid (111.6mg, 84%). Calculated value of elemental analysis C ₂₆ H ₃₂ Cl ₂ FeN ₂ S, C, 58.77; h, 6.07; n,5.27 measured C, 58.26; h, 6.35; n,5.31.

( ^Et SNN ^iPr )FeCl ₂ (Complex 4 b): the synthesis of the complex was identical to that of 4a, giving a yield of 71% for 4 b. Calculated value of elemental analysis C ₂₅ H ₃₀ Cl ₂ FeN ₂ S, C, 58.04; h, 5.85; n,5.42, measurement C, 57.63; h, 5.85; and N,5.50.

( ^tBu SNN ^iPr )FeCl ₂ (Complex 4 c): the synthesis of the complex was the same as that of 4a, giving a yield of 89% for 4 c. Calculated value of elemental analysis C ₂₇ H ₃₄ Cl ₂ FeN ₂ S, C, 59.46; h, 6.28; n,4.89, measurement C, 60.02; h, 6.76; and N,4.76.

( ^Ph SNN ^iPr )FeCl ₂ (complex 4 d): the synthesis of the complex was identical to the synthesis procedure of 4a, giving a yield of 92% for 4 d. Calculated value of elemental analysis C ₂₉ H ₃₀ Cl ₂ FeN ₂ S, C, 61.61; h, 5.35; n,4.95, measurement C, 60.00; h, 5.52; and N,4.48.

( ^Ph SNN ^Me )FeCl ₂ (complex 4 e): the synthesis of the complex was the same as that of 4a, giving a yield of 81% of 4 e. Calculated value of elemental analysis C ₂₅ H ₂₂ Cl ₂ FeN ₂ S, C, 58.96; h, 4.35; n,5.50, measurement C, 58.63; h, 4.48; n,5.53.

( ^Ph SNN ^Et )FeCl ₂ (Complex 4 f): the synthesis of the complex was the same as that of 4a, giving a yield of 86% for 4 f. Calculated value of elemental analysis C ₂₇ H ₂₆ Cl ₂ FeN ₂ S is C, 60.35; h, 4.88; n,5.21, measurement C, 60.14; h, 4.87; and N,5.24.

( ^Et SNN ^Me )FeCl ₂ (Complex 4 g): the synthesis of the complex was identical to the synthesis procedure of 4a, giving a yield of 57% of 4 g. Calculated value of elemental analysis C ₂₁ H ₂₂ Cl ₂ FeN ₂ S, C, 54.69; h, 4.81; n,6.07, measurement C, 53.78; h, 4.74; and N,6.10.

( ^Et SNN ^Et )FeCl ₂ (Complex 4 h): the synthesis of the complex was identical to that of 4a, giving a yield of 68% over 4 h. Calculated value of elemental analysis C ₂₃ H ₂₆ Cl ₂ FeN ₂ S, C, 56.46; h, 5.36; n,5.73, measurement C, 55.51; h, 5.75; and N,5.16.

( ^iPr SNN ^Me )FeCl ₂ (Complex 4 i): the synthesis of the complex was the same as that of 4a, giving a yield of 84% for 4 i. Calculated value of elemental analysis C ₂₂ H ₂₄ Cl ₂ FeN ₂ S, C, 55.60; h, 5.09; n,5.89, measurement C, 55.16; h, 5.16; n,5.77.

( ^iPr SNN ^Et )FeCl ₂ (complex 4 j): the synthesis of the complex was identical to the synthesis procedure of 4a, giving a yield of 82% for 4 j. Calculated value of elemental analysis C ₂₄ H ₂₈ Cl ₂ FeN ₂ S is C, 57.27; h, 5.61; n,5.57, measurement C, 57.05; h, 5.64; n,5.54.

( ^Cy SNN ^Me )FeCl ₂ (Complex 4 k): the synthesis of the complex was identical to the synthesis procedure of 4a, giving a 4k yield of 81%. Calculated value of elemental analysis C ₂₅ H ₂₈ Cl ₂ FeN ₂ S is C, 58.27; h, 5.48; n,5.44, measurement C, 57.77; h, 5.53; n,5.41.

( ^Cy SNN ^Et )FeCl ₂ (Complex 4 l): the synthesis of the complex was identical to that of 4a, giving a yield of 77% of 4 l. Calculated value of elemental analysis C ₂₇ H ₃₂ Cl ₂ FeN ₂ S is C, 59.68; h, 5.94; n,5.16, measurement C, 59.72; h, 6.09; and N,5.07.

Example 3: experiment on catalytic Activity of Complex for ethylene polymerization

(Table 1, item 1) the freshly dried autoclave was assembled under an ethylene atmosphere of 300psi and the ethylene gas was replaced three times. The autoclave was placed in an oil bath, the temperature of the oil bath was controlled at 120 ℃ and dried under vacuum with an oil pump for 2 hours. The oil bath temperature was lowered to 20 ℃, and after the kettle also reached the predetermined temperature, 100mL of toluene solvent was added under ethylene gas flow, and stirred for 10 minutes to reach the predetermined temperature and to saturate ethylene in toluene. A certain amount of cocatalyst (MMAO,600eq) was added and stirred for 2 minutes. The catalyst complex 4a solution was added while adjusting the pressure of ethylene gas to 300psi, and the reaction was started for 15 minutes. After the polymerization was completed, the ethylene gas flow was rapidly cut off, the cock was opened to release the ethylene gas pressure, and 10% ethanol hydrochloride solution (5mL) was added to quench the polymerization reaction. The reaction mixture was poured into a large amount of 10% ethanol hydrochloride solution and stirred at normal temperature for 1 hour. Filtering, washing with 10% hydrochloric acid ethanol solution and ethanol in sequence, collecting polymer, and vacuum drying at 70 deg.C for 24 hr to constant weight to obtain polyethylene 6.10 g. The catalytic activity was 4.88X 10 ⁶ g PE(mol Fe) ^-1 h ^-1 . The molecular weight Mw of the resulting polymer was 1417, with a molecular weight distribution of 1.61.

Catalytic activity-product yield/molar amount of catalyst/reaction time

The other experimental procedures were essentially the same, and the conditions and results are shown in Table 1.

TABLE 1 ethylene polymerization results

[a] The experimental conditions are as follows: 5 mu mol of catalyst, 100mL of toluene, 20 ℃, reacting for 15min, and taking the average value of the two experiments.

[b] Pressure unit: psi. [ c ] 2. mu. mol of catalyst 4 a. The other conditions are the same [ d ] units: g PE/mol Fe. h.

[e] The molecular weight is distributed in a bimodal manner. [f] A wider melting transition.

The SNN iron complex based on the quinoline skeleton disclosed by the invention has excellent catalytic activity even at a higher reaction temperature, and the maximum catalytic activity can reach 10 ⁷ g PE(mol Fe) ^-1 h ^-1 The low molecular weight and high linear polyethylene material is produced, the molecular weight distribution of the polymer is narrow, and the polyethylene product can be applied to high-quality polyethylene wax.

Example 4: experiment of catalytic Activity of Complex for copolymerization of ethylene and alpha-olefin

A freshly dried 100mL Schlenk flask was purged with ethylene three times under an ethylene atmosphere of 1 atm. 10mL of toluene and 10mL of 1, 7-octadiene, a non-conjugated diene, were added under a stream of ethylene gas, and the solution was brought to the predetermined temperature and saturated with ethylene by stirring for 10 minutes in a 20 ℃ water bath outside the Schlenk flask. The cocatalyst (MMAO,200eq) was added and stirred for 2 minutes. A solution of the complex in 1, 7-octadiene was added (Table 2, entries 4-6) and the timer was started. After 10 hours of polymerization, the ethylene flow was rapidly cut off and the polymerization was quenched by addition of 10% ethanolic hydrochloric acid solution (5 mL). The reaction mixture was poured into a large amount of 10% ethanol hydrochloride solution and stirred at normal temperature overnight. Filtering, washing with 10% hydrochloric acid ethanol solution and ethanol in sequence, collecting the polymer, and vacuum drying at 50 deg.C for 24 hr to constant weight to obtain copolymerization product with main chain containing unsaturated bond copolymer and less branched chains. The results are shown in Table 2.

The comonomer insertion rate in Table 2 below is chain Link: (

n is 1-5) the molar content in the polymer;

the linear selectivity in Table 2 below is the monomer at the time of polymerization

In units formed in the polymer

(n is 1 to 5) mole content.

TABLE 2 results of copolymerization of ethylene with non-conjugated diene

[a]The experimental conditions are as follows: 10 μmol catalyst, 10mL 1, 7-octadiene, 10mL toluene, 20 ℃, 10h,1atm ethylene pressure. [ b ] A]The experimental conditions are as follows: 10 μmol catalyst, 10mL 1, 8-nonadiene, 10mL toluene, 20 ℃, 0.5h,1atm ethylene pressure. [ c ] is]The experimental conditions are as follows: 10 μmol catalyst, 10mL 1, 9-decadiene, 10mL toluene, 20 ℃, 0.5h,1atm ethylene pressure. [ d]Unit: g polymer/mol Fe. h. [ e ]]A wider melting transition. [ f ] of]According to ¹ H NMR measurement. [ g ]]According to ¹³ C NMR measurement.

The SNN iron complex based on the quinoline skeleton catalyzes the copolymerization reaction of ethylene and non-conjugated diene (such as 1, 7-octadiene), has excellent catalytic activity, and can generate a polyolefin product in a wax or oil shape. The polymer product has the characteristics of low molecular weight, narrow molecular weight distribution and the like. The copolymer mainly containing unsaturated bonds in the main chain is generated structurally, and various branched chains are few. In addition, the insertion rate and the linear chain selectivity of the non-conjugated diene (such as 1, 7-octadiene) can be regulated and controlled by changing the electronic property and the steric hindrance of the ligand.

Comonomer insertion and linear selectivity were calculated from figures 1-25 and the following equations, as follows:

taking the inserted 1, 7-octadiene as an example, the nuclear magnetic hydrogen spectrum of the copolymer is shown in fig. 1, in which we can assign various hydrogens in the copolymer and calculate the comonomer insertion rate:

P1：0.81-0.92＝1s+A+Me

P2：1.14-1.41＝δ ⁺ δ ⁺ +4s+3s+2s+a+b+g+α′+β′+γ′+αCy+βCy+6′+5′+4′+c′+b′+D+C+MCy+M′+M+B

P3：1.92-2.09＝1a+a′

P4：4.90-5.04＝1′+1u

P5：5.75-5.89＝u′

P6：5.75-5.89＝2u+2′

the following quantities of 1, 7-octadiene with respect to the ethylene inserted and the different structures inserted into the main chain can be obtained from the stoichiometry:

M(ethylene)＝[(δ ⁺ δ ⁺ +4s+3s+2s+α′/2+β′+γ′+βcy/2+D)/2+(1u+1′)/2+(2u+2′)+1s/3]/2

＝[(P2-α-β-γ-α′/2-αCy-βCy/2-6′-5′-4′-c′-b′-C-MCy-M′-M-B)/2+P4/2+P6+1s/3]/2

＝[(P2-4M(MB)*3-2M(PH)-8M(McH)-4M(McH)-2M(PH)*3-8M(1inear)-2M(iBu)

-M(PH)-2M(MCH)-M(MB)-M(iBu))/2+P4/2+P6+(P1-6M(iBu)-3M(MB)-3M(PH))/3]/2

＝[P2/2+P4/2+P6+P1/3-13M(MB)/2-9M(PH)/2-7M(MCH)-4M(1inear)-3M(iBu)/2-2M(iBu)-M(MB)-M(PH)]/2

＝P2/4+P4/4+P6/2+P1/6-15M(MB)/4-11M(PH)/4-7M(McH)/2-2M(linear)-7M(iBu)/4

M(1inear)＝u′/2＝P5/2＝b′/4＝c′/4＝a′/4

M(MB)＝1/3＝M＝α/4＝β/4＝γ/4

M(MCH)＝M/2＝αCy/8＝β/8

M(PH)＝M＝1′/2＝2′＝3′/2＝4′/2＝5′/2＝6′/2＝α′/4

we can therefore calculate the insertion rate of the linear inserted 1, 7-octadiene (i.e. comonomer insertion rate in table 2):

in the nuclear magnetic carbon spectrum of the hydrogenated copolymer, we can also assign carbons at different positions, and the structures and their shifts that may occur in the copolymer are summarized in the following figure and the following table:

TABLE 3 chemical shifts of carbons at different positions of different structures

Note: each of β Cy, α Cy and MCy

The beta, alpha and M carbons in the compound.

We can obtain molar expressions of different structures:

M(linear)*8+M(ethylene)*2＝(δ ⁺ δ ⁺ +4s+3s+2s+1s+D+α′/2+β′+γ′+βCy+β/2)

M(linear)/[M(ethylene)+M(linear)]＝i.r.(Linear)(mol％)

M(PH)＝M′

from this the selectivity of comonomer insertion can be calculated: (M (linear) is linear selectivity in Table 2):

Claims

1. a compound of formula I:

wherein:

R ³ Is hydrogen atom, halogen, C substituted by one or more halogens or unsubstituted ₁ ～C ₁₀ Alkyl radical, C ₂ ～C ₁₀ Alkenyl radical, C ₂ ～C ₁₀ Alkynyl, C ₆ ～C ₁₄ Aryl or

R ¹¹ Is hydrogen atom, halogen, C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ Alkyl of (C) ₂ ～C ₁₀ Alkenyl radical, C ₂ ～C ₁₀ Alkynyl, C ₆ ～C ₁₄ Aryl, diphenylmethyl or

(3)R ³ and R ⁴ Together with the atoms to which they are attached form a 5-7 membered cycloalkenyl group;

2. A compound of formula I according to claim 1, wherein when R is C substituted or unsubstituted with one or more halogen ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₆ An alkyl group;

and/or, when R is C substituted by one or more halogens ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine, chlorine, bromine or iodine;

and/or, when R is C substituted by multiple halogens ₁ -C ₁₀ When alkyl, said plurality is two or three;

and/or, when R is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₆ An alkenyl group;

and/or, when R is C ₂ ～C ₁₀ Alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₆ Alkynyl;

and/or, when R is C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl;

and/or, when R is C ₃ ～C ₆ When there is a cycloalkyl group, said C ₃ ～C ₆ Cycloalkyl is cyclohexyl;

and/or when R ¹ And R ⁵ When each is independently halogen, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ¹ And R ⁵ Each independently is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₆ An alkyl group;

and/or when R ¹ And R ⁵ Each independently is C substituted by one or more halogen ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ¹ And R ⁵ Each independently being substituted by more than one halogenC of (A) ₁ -C ₁₀ When alkyl, said plurality is two or three;

and/or when R ¹ And R ⁵ Are each independently C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₆ An alkenyl group;

and/or when R ¹ And R ⁵ Are each independently C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₆ An alkynyl group;

and/or when R ¹ And R ⁵ Are each independently C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl;

and/or when R ² And R ⁴ When each is independently halogen, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ² And R ⁴ Each independently is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₆ An alkyl group;

and/or when R ² And R ⁴ Each independently is C substituted by one or more halogen ₁ -C ₁₀ When the alkyl is substituted, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ² And R ⁴ Each independently being C substituted by more than one halogen ₁ -C ₁₀ When alkyl, said plurality is two or three;

and/or when R ² And R ⁴ Are each independently C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₆ An alkenyl group;

and/or when R ² And R ⁴ Are each independently C ₂ ～C ₁₀ Alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₆ An alkynyl group;

and/or when R ² And R ⁴ Are each independently C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl;

and/or when R ³ When the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ³ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₆ An alkyl group;

and/or when R ³ Is C substituted by one or more halogens ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ³ Is C substituted by more than one halogen ₁ -C ₁₀ When alkyl, said plurality is two or three;

and/or when R ³ Is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₆ An alkenyl group;

and/or when R ³ Is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₆ An alkynyl group;

and/or when R ³ Is C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl;

and/or when R ¹¹ When the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ¹¹ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₆ An alkyl group;

and/or when R ¹¹ Is C substituted by one or more halogens ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R ¹¹ Is C substituted by more than one halogen ₁ -C ₁₀ When there is alkyl, theA plurality is two or three;

and/or when R ¹¹ Is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₆ An alkenyl group;

and/or when R ¹¹ Is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₆ An alkynyl group;

and/or when R ¹¹ Is C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl or naphthyl;

and/or when R ¹² 、R ¹³ And R ¹⁴ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is C ₁ ～C ₃ An alkyl group;

and/or when R ¹² 、R ¹³ And R ¹⁴ Are each independently C ₆ ～C ₁₀ Aryl, said C ₆ ～C ₁₀ Aryl is phenyl;

and/or when R ¹⁵ 、R ¹⁶ And R ¹⁷ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is C ₁ ～C ₃ An alkyl group;

and/or when R ¹⁵ 、R ¹⁶ And R ¹⁷ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl is phenyl;

and/or when R ¹⁸ 、R ¹⁹ And R ²⁰ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is C ₁ ～C ₃ An alkyl group;

and/or when R ¹⁸ 、R ¹⁹ And R ²⁰ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl is phenyl;

and/or when R ²¹ 、R ²² And R ²³ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is C ₁ ～C ₃ An alkyl group;

and/or when R ²¹ 、R ²² And R ²³ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl is phenyl;

and/or when R ²⁴ 、R ²⁵ And R ²⁶ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is C ₁ ～C ₃ An alkyl group;

and/or when R ²⁴ 、R ²⁵ And R ²⁶ Are each independently C ₆ ～C ₁₀ Aryl radical, said C ₆ ～C ₁₀ Aryl is phenyl.

3. A compound of formula I according to claim 2, wherein when R is C substituted or unsubstituted with one or more halogen ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₄ An alkyl group;

and/or, when R is C substituted by one or more halogens ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine or chlorine;

and/or, when R is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₃ An alkenyl group;

and/or, when R is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₃ An alkynyl group;

and/or, when R is C ₆ ～C ₁₄ When aryl, said C ₆ ～C ₁₄ Aryl is phenyl;

and/or when R ¹ And R ⁵ Each independently is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₄ An alkyl group;

and/or when R ¹ And R ⁵ Each independently is C substituted by one or more halogen ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine or chlorine;

and/or when R ¹ And R ⁵ Are each independently C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₃ An alkenyl group;

and/or when R ¹ And R ⁵ Are each independently C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₃ An alkynyl group;

and/or when R ² And R ⁴ Each independently is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₄ An alkyl group;

and/or when R ² And R ⁴ Each independently is C substituted by one or more halogen ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine or chlorine;

and/or when R ² And R ⁴ Are each independently C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₃ An alkenyl group;

and/or when R ² And R ⁴ Are each independently C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₃ An alkynyl group;

and/or when R ³ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₄ An alkyl group;

and/or when R ³ Is C substituted by one or more halogens ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine or chlorine;

and/or when R ³ Is C ₂ ～C ₁₀ When the alkenyl group is used, the alkenyl group,said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₃ An alkenyl group;

and/or when R ³ Is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₃ An alkynyl group;

and/or when R ¹¹ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is C ₁ -C ₄ An alkyl group;

and/or when R ¹¹ Is C substituted by one or more halogens ₁ -C ₁₀ When the alkyl is selected, the halogen is fluorine or chlorine;

and/or when R ¹¹ Is C ₂ ～C ₁₀ When alkenyl, said C ₂ ～C ₁₀ Alkenyl is C ₂ ～C ₃ An alkenyl group;

and/or when R ¹¹ Is C ₂ ～C ₁₀ When it is alkynyl, said C ₂ ～C ₁₀ Alkynyl is C ₂ ～C ₃ An alkynyl group;

and/or when R ¹² 、R ¹³ And R ¹⁴ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is methyl;

and/or when R ¹⁵ 、R ¹⁶ And R ¹⁷ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is methyl;

and/or when R ¹⁸ 、R ¹⁹ And R ²⁰ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is methyl;

and/or when R ²¹ 、R ²² And R ²³ Are each independently C ₁ ～C ₆ When alkyl, said C ₁ ～C ₆ Alkyl is methyl;

and/or when R ²⁴ 、R ²⁵ And R ²⁶ Are each independently C ₁ ～C ₆ Alkyl radicalWhen, C is said ₁ ～C ₆ The alkyl group is a methyl group.

4. A compound of formula I according to claim 3, wherein when R is C substituted or unsubstituted with one or more halogen ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is methyl, ethyl, isopropyl or tert-butyl;

and/or when R ¹ And R ⁵ Each independently is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is methyl, ethyl, isopropyl or tert-butyl;

and/or when R ² And R ⁴ Each independently is C substituted or unsubstituted with one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is methyl, ethyl, isopropyl or tert-butyl;

and/or when R ³ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is methyl, ethyl, isopropyl or tert-butyl;

and/or when R ¹¹ Is C substituted or unsubstituted by one or more halogens ₁ -C ₁₀ When alkyl, said C ₁ -C ₁₀ Alkyl is methyl, ethyl, isopropyl or tert-butyl.

5. A compound of formula I according to claim 1, wherein R is C ₁ ～C ₁₀ Alkyl radical, C ₆ ～C ₁₄ Aryl or C ₃ -C ₆ A cycloalkyl group;

and/or, R ¹ And R ⁵ Each independently hydrogen or C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ An alkyl group;

and/or, R ² And R ⁴ Each independently is hydrogen;

and/or, R ³ Is hydrogen;

and/or, R ¹¹ Is C substituted or unsubstituted by one or more halogens ₁ ～C ₁₀ An alkyl group.

6. A compound of formula I according to claim 5, wherein R is C ₁ ～C ₁₀ Alkyl or C ₃ -C ₆ A cycloalkyl group;

and/or, R ¹ And R ⁵ Each independently is unsubstituted C ₁ ～C ₁₀ An alkyl group;

and/or, R ¹¹ Is unsubstituted C ₁ ～C ₁₀ An alkyl group.

7. The compound of formula I according to claim 1, wherein said compound of formula I is:

8. The compound of formula I according to claim 1, wherein said compound of formula I is:

R ² and R ⁴ Each independently is hydrogen;

R ³ is hydrogen;

9. The compound of formula I according to claim 1, wherein said compound of formula I is:

R ¹ and R ⁵ Each independently of the other is unsubstituted C ₁ ～C ₁₀ An alkyl group;

R ² and R ⁴ Each independently is hydrogen;

R ³ is hydrogen;

R ¹¹ is unsubstituted C ₁ ～C ₁₀ An alkyl group.

10. The compound of formula I according to claim 1, wherein said compound of formula I is:

r is C ₁ ～C ₁₀ Alkyl or C ₃ -C ₆ A cycloalkyl group;

R ² and R ⁴ Each independently is hydrogen;

R ³ is hydrogen;

R ¹¹ is unsubstituted C ₁ ～C ₁₀ An alkyl group.

11. The compound of formula I according to claim 1, wherein the compound of formula I is any one of the following compounds:

12. a compound of formula II:

wherein X and Y are each independently halogen;

R、R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ and R ¹¹ As defined in any one of claims 1 to 11;

when said X is halogen, said halogen is fluorine, chlorine or bromine;

when said Y is halogen, said halogen is fluorine, chlorine or bromine.

13. The compound of formula II according to claim 12,

when said X is halogen, said halogen is chlorine;

when Y is halogen, the halogen is chlorine.

14. The compound of formula II according to claim 12, wherein said compound of formula II is any one of the following compounds:

15. a process for the preparation of a compound of formula II as claimed in any one of claims 12 to 14, comprising the steps of: under the protection of inert gas, carrying out a complex reaction shown as the following between a compound shown as a formula I and FeXY in an organic solvent to obtain a compound shown as a formula II;

16. use of a compound of formula II according to any one of claims 12 to 14 as a catalyst in the polymerisation of olefins.

17. The use of claim 16, wherein the olefin is one or more olefins.

18. The use of claim 17 wherein when said olefin is an olefin, said olefin is C ₂ -C ₁₀ Olefins, said C ₂ -C ₁₀ The olefin being ethylene or C ₃ -C ₁₀ An olefin;

and/or, when the olefin is a plurality of olefins, the olefin is ethylene and C ₃ -C ₁₀ An olefin;

and/or, when the olefin is a plurality of olefins, the olefin is ethylene and C ₅ -C ₁₀ A non-conjugated diene.

19. The use according to claim 18,

when the olefin is an olefin, the olefin is C ₂ -C ₁₀ Olefins, said C ₂ -C ₁₀ The olefin being ethylene or C ₃ -C ₁₀ An olefin; said C ₃ -C ₁₀ The olefin being alpha-olefin or C ₅ -C ₁₀ A non-conjugated diene;

and/or, when the olefin is a plurality of olefins, the olefin is ethylene and C ₃ -C ₁₀ An olefin; said C ₃ -C ₁₀ The olefin is alpha-olefin;

and/or, when the olefin is a plurality of olefins, the olefins are ethylene and C ₅ -C ₁₀ A non-conjugated diene, said C ₅ -C ₁₀ The non-conjugated diene is 1, 4-pentadiene, 1, 5-hexadiene, 5, 7-dimethyl-1, 6-octadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene or 1, 9-decadiene.

20. The use according to claim 19,

when the olefin is an olefin, the olefin is C ₂ -C ₁₀ Olefins, said C ₂ -C ₁₀ The olefin being ethylene or C ₃ -C ₁₀ An olefin; said C ₃ -C ₁₀ The olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, or said C ₃ -C ₁₀ The olefin is 1, 4-pentadiene, 1, 5-hexadiene, 5, 7-dimethyl-1, 6-octadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene and 1, 9-decadiene;

and/or, when the olefin is a plurality of olefins, the olefin is ethylene and C ₃ -C ₁₀ An olefin; said C ₃ -C ₁₀ The olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 4-methyl-1-pentene.

21. A method of preparing a polymer comprising the steps of: in a solvent, in the presence of a catalyst, carrying out copolymerization reaction on ethylene and a compound D to obtain a polymer; the catalyst is a compound as described in any one of claims 12-14 as formula II;

wherein n is 1-5.

22. The method of claim 21, wherein the solvent is one or more of an alkane solvent, a haloalkane solvent and an aromatic hydrocarbon solvent;

and/or the concentration of the compound D in the solvent is 3-8 mol/L;

and/or the molar ratio of the catalyst to the compound D is 10 ^-5 :1～10 ^-3 :1；

And/or, the catalytic reaction is carried out in the presence of a cocatalyst;

and/or the molar ratio of the catalyst to the cocatalyst is 100: 1-300: 1;

and/or the reaction time is 0.5 to 15 hours;

and/or, the copolymerization reaction also comprises post treatment after the end of the copolymerization reaction.

23. The method of claim 22, wherein the solvent is one or more of n-heptane, dichloromethane, and toluene;

and/or the concentration of the compound D in the solvent is 5.4-6.8 mol/L;

and/or the molar ratio of the catalyst to the compound D is 1.5X 10 ^-4 :1～1.9×10 ^-4 :11；

And/or the cocatalyst is methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, butylaluminoxane, LiR 'and AlR' ₃ 、AlR’ _a X’ _3-a And borane; r' is C ₁ ～C ₄ Alkyl groups of (a); x' is halogen; a is 1 or 2;

and/or, the post-treatment comprises the following steps: and quenching the reaction to obtain a mixture, stirring the mixture in an acidic alcohol solution, filtering, washing with the acidic alcohol solution, and drying to obtain the polyolefin material.

24. A process for preparing a polymer as defined in claim 23 wherein R' is methyl, ethyl, isopropyl, tert-butyl or isobutyl; x' is fluorine, chlorine, bromine or iodine.