CN105061505A - Catalyst ligand, catalyst, and preparation methods and application thereof - Google Patents

Abstract

The invention provides a catalyst ligand, catalyst and its preparation method and application. The catalyst prepared by the ligand provided by the invention is applied to the polymerization of olefins, and not only has good activity for homopolymerization and copolymerization of olefins, but also can obtain The molecular weight of the polymer is high, and the proportion of the doped polar monomer is relatively high during the copolymerization. In addition, the catalyst provided by the invention can also catalyze the polymerization reaction at room temperature (20° C.).

Description

Catalyst ligand, catalyst and preparation method and application thereof

technical field

The catalyst field of the present invention particularly relates to a catalyst ligand, catalyst and its preparation method and application.

Background technique

Due to its excellent properties and relatively low price, polyolefin has become an indispensable material in modern social life. At present, the demand for polyolefin is very huge, and due to the particularity of its synthesis method, the research on the core catalyst in its synthesis has also attracted extensive attention of researchers.

Looking at the history of the development of the olefin polymerization industry, it can be found that technological progress is closely related to the discovery of new catalysts and the successful development of process technology. In the process of olefin polymerization, catalysts often determine the polymerization behavior of the entire olefin, the particle morphology of the resulting polymer, and the topology and properties of the polymer. The development of catalysts for olefin polymerization has made the polymerization of olefins more diverse and superior in performance, greatly broadening the practical application fields of polymers

Since the seminal discovery of Brookhart's α-diimine nickel and palladium catalysts and Grubbs' salicylaldimine nickel catalyst, late-transition metal-catalyzed olefin polymerization and copolymerization of polar monomers have attracted continuous attention. Recently, neutral palladium catalysts containing phosphine-sulfonic acid ligands were found to be used in the polymerization of ethylene to produce highly linear polyethylene. This class of catalysts also enables the copolymerization of ethylene with a surprising variety of polar vinyl monomers to give functionalized linear copolymers. The most notable feature of the ligands of this class of catalysts is the combination of a very strong σ-donating phosphine moiety with a very weak σ-donating moiety. It is widely believed that this electronically asymmetric coordination framework effectively suppresses the elimination of β-H(X), thus enabling the production of linear polymers and enabling the insertion of polar monomers during ethylene polymerization.

Due to these preliminary reports, various research groups have modified the existing coordination structures and conducted a large number of studies. Several anionic bidentate ligands with asymmetric frameworks and corresponding neutral palladium complexes have been designed and synthesized. For example, Nozaki et al. replaced the phosphine moiety with a stronger donor NHC (N-heterocyclic carbene) group for σ, and prepared a neutral NHC sulfonate palladium complex; Jordan et al. also synthesized a similar Arene-bridged NHC sulfonate palladium complexes. Unfortunately, these two complexes are not available for ethylene polymerization. Jordan and Piers independently reported a bidentate trifluoroboron-phosphine palladium complex, which was only able to dim polyvinyl butene and was less active. The catalyst diamine-substituted phosphine-sulfonate palladium (II) complexes synthesized by Mecking et al. cannot catalyze the copolymerization reaction of ethylene and methyl acrylate active monomers when they are applied to ethylene polymerization. Recently, the same group investigated the effect of some neutral phosphine-sulfonamide palladium(II) complexes on the polymerization behavior of ethylene. However, some of these palladium complexes can only catalyze the polymerization of ethylene to obtain low polyethylene, and even some catalysts have no activity on the polymerization of ethylene.

Relative to the above-mentioned anionic ligands, some exciting results arise from electronically asymmetric neutral ligands and corresponding cationic catalysts. For example, the research results of Nozaki et al. showed that cationic bisphosphine monooxide palladium complexes have high activity for ethylene homopolymerization. These complexes can also catalyze the copolymerization of ethylene with several challenging polar vinyl monomers to give highly linear functionalized polymers, but fail to catalyze the copolymerization of ethylene with the monomer methyl acrylate (MA); Jordan et al. Cationic palladium catalysts with phosphine-phospholipid ligands are highly active in the polymerization of ethylene. At the same time, these catalysts can not only catalyze the polymerization of ethylene, but also catalyze the copolymerization of ethylene, methyl acrylate and acrylic acid. However, when used for copolymerization, the proportion of doped polar monomers is low; and the catalytic activity is low, and the obtained polymer low molecular weight.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide a catalyst ligand, catalyst and its preparation method and application, the catalyst prepared by the ligand provided by the present invention is applied to the polymerization of olefins, not only can catalyze olefins and acrylic acid The copolymerization of the body, and the molecular weight of the obtained polymer is high.

The invention provides a catalyst ligand, which has a structure shown in formula (I),

Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents on the aryl groups in the substituted aryl groups are ^C1 ～C12 alkoxy groups;

R2 is selected from a C7 ^- C30 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C1-C12 alkoxy group;

^R3 is selected from C1～C15 alkyl or C6～C30 aryl;

R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

R ⁵ is selected from a C1-C15 alkyl group or a C6-C30 aryl group.

Preferably, the R ¹ is selected from a C9-C18 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C3-C8 alkoxy group;

R ² is selected from a C9-C18 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C3-C8 alkoxy group.

Preferably, the ^R3 is selected from a C3-C12 alkyl group or a C8-C20 aryl group;

R ⁴ is selected from C3～C12 alkyl or C8～C20 aryl;

R ⁵ is selected from a C3-C12 alkyl group or a C8-C20 aryl group.

Preferably, the R is selected from ² -methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4 -propoxyphenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxynaphthyl, 2 - Ethoxynaphthyl, 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl;

R is selected from ² -methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl Base, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthalene 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

The present invention also provides a preparation method of the catalyst ligand shown in formula (I), comprising:

1) reacting the compound shown in formula (I-1) with the compound shown in formula (I-2) to obtain the compound shown in formula (I-3),

in,

R ³ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30,

R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30,

R ⁵ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

2) reacting the compound shown in formula (I-3) with the compound shown in formula (I-4) to obtain the compound shown in formula (I),

Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents on the aryl groups in the substituted aryl groups are ^C1 ～C12 alkoxy groups;

R ² is selected from a C7-C30 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C1-C12 alkoxy group.

The present invention also provides a catalyst comprising the catalyst ligand represented by formula (I).

Preferably, the catalyst is a structure shown in formula (II) or a structure shown in formula (III),

Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents in the substituted aryl groups are ^C1 ～C12 alkoxy groups;

R2 is selected from a C7 ^- C30 substituted aryl group, and the substituent in the substituted aryl group is a C1-C12 alkoxy group;

^R3 is selected from C1～C15 alkyl or C6～C30 aryl;

R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

R ⁵ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

R ⁶ is selected from dimethyl sulfoxide, pyridine or 2,5-lutidine;

X is selected from fluorine, chlorine, bromine or iodine;

X ₁ is selected from tetrakis-(3,5-bistrifluoromethylphenyl)boryl or hexafluorotellurate.

The present invention also provides a kind of preparation method of catalyst described in the present invention, comprising:

The compound shown in formula (I) is reacted with the Pd precursor compound to obtain the compound shown in formula (II);

The compound shown in the formula (II) is reacted with the compound shown in NaX ₁ and R , to obtain the compound shown in the ^formula (III),

Wherein, R is selected from dimethyl sulfoxide, pyridine or 2,5 ^- lutidine;

X ₁ is selected from tetrakis-(3,5-bistrifluoromethylphenyl)boryl or hexafluorotellurate.

The present invention also provides the application of the catalyst described in the present invention as a catalyst for olefin polymerization.

Preferably, the olefin polymerization is olefin homopolymerization or olefin copolymerization;

The monomer copolymerized with olefin in the olefin copolymerization is methyl acrylate, vinyl ether, allyl acetate or allyl chloride.

Compared with the prior art, the catalyst prepared by the ligand provided by the present invention is applied to the polymerization of olefins, not only has good activity for homopolymerization and copolymerization of olefins, but also has a high molecular weight of the obtained polymer, and is mixed with The proportion of heterogeneous polar monomers is also relatively high. In addition, the catalyst provided by the invention can also catalyze the polymerization reaction at room temperature (20°C); the experimental results show that the catalyst provided by the invention is applied to the homopolymerization of ethylene, and can Make the molecular weight reach 10w or more, and apply it to the copolymerization of ethylene, the molecular weight can reach 20w or more.

Description of drawings

Figure 1 is a schematic diagram of the single crystal structure of the compound prepared in Example 2 of the present invention;

Fig. 2 is the hydrogen spectrum of the polyethylene that the embodiment of the present invention prepares;

Fig. 3 is the hydrogen spectrum of the ethylene copolymer prepared in the embodiment of the present invention.

Detailed ways

The invention provides a catalyst ligand, which has a structure shown in formula (I),

Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents on the aryl groups in the substituted aryl groups are ^C1 ～C12 alkoxy groups;

R2 is selected from a C7 ^- C30 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C1-C12 alkoxy group;

^R3 is selected from C1～C15 alkyl or C6～C30 aryl;

R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

R ⁵ is selected from a C1-C15 alkyl group or a C6-C30 aryl group.

According to the present invention, the R1 is preferably ^a C9-C18 substituted aryl group; wherein, the aryl group in the substituted aryl group is preferably phenyl or naphthyl; the substituent on the aryl group in the substituted aryl group is preferably C3-C8 alkoxy, more preferably C4-C6 alkoxy, most preferably methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutyl Baseoxy, tert-butyloxy, n-pentyloxy or n-octyloxy; the substituent in the substituted aryl group described in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or para-position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R is ² -methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4- Propoxyphenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl or 4-octyloxyphenyl.

The R2 is preferably a C9 ^- C18 substituted aryl group; wherein, the aryl group in the substituted aryl group is preferably phenyl or naphthyl; the substituent on the aryl group in the substituted aryl group is preferably C3-C8 Alkoxy, more preferably C4-C6 alkoxy, most preferably methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutyloxy, tert-butyloxy, n-pentyloxy or n-octyloxy; the substituent in the substituted aryl group described in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho or para position of the aryl group; In the present invention, there is no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R ² is 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4- Propoxyphenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octyloxyphenyl, 2-methoxynaphthyl, 2- Ethoxynaphthyl, 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

The ^R3 is preferably a C3-C12 alkyl group or a C8-C20 aryl group, wherein the alkyl group is a C3-C12 straight-chain alkyl group or a C3-C12 branched-chain alkyl group, more preferably a C4-C10 straight-chain alkyl group. Alkyl group or C4～C10 branched chain alkyl group; the aryl group is C8～C20 substituted aryl group or C8～C20 unsubstituted aryl group, more preferably C9～C15 substituted aryl group or C9～C15 Unsubstituted aryl; More specifically, the unsubstituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the substitution on the aryl in the substituted aryl The group is preferably a C3-C8 alkoxy group, more preferably a C4-C6 alkoxy group; in addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or para-position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the ^R3 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2- Isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octoxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2- Propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

^The R4 is preferably a C3-C12 alkyl group or a C8-C20 aryl group, wherein the alkyl group is a C3-C12 straight-chain alkyl group or a C3-C12 branched-chain alkyl group, more preferably a C4-C10 straight-chain alkyl group. Alkyl group or C4～C10 branched chain alkyl group; the aryl group is C8～C20 substituted aryl group or C8～C20 unsubstituted aryl group, more preferably C9～C15 substituted aryl group or C9～C15 Unsubstituted aryl; more specific unsubstituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the substituent on the aryl in the substituted aryl It is preferably a C3-C8 alkoxy group, more preferably a C4-C6 alkoxy group; in addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or Para position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R is methyl, ethyl, n ^- propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2- Isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octoxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2- Propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

The R ⁵ is preferably a C3-C12 alkyl group or a C8-C20 aryl group, wherein the alkyl group is a C3-C12 straight-chain alkyl group or a C3-C12 branched-chain alkyl group, more preferably a C4-C10 straight-chain alkyl group. Alkyl group or C4～C10 branched chain alkyl group; the aryl group is C8～C20 substituted aryl group or C8～C20 unsubstituted aryl group, more preferably C9～C15 substituted aryl group or C9～C15 Unsubstituted aryl; more specific unsubstituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the substituent on the aryl in the substituted aryl It is preferably a C3-C8 alkoxy group, more preferably a C4-C6 alkoxy group; in addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or Para position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R is methyl, ethyl, n ^- propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2- Isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octoxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2- Propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

The present invention also provides a preparation method of a catalyst ligand of structure shown in formula (I), comprising:

1) reacting the compound shown in formula (I-1) with the compound shown in formula (I-2) to obtain the compound shown in formula (I-3),

in,

R ³ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30,

R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30,

R ⁵ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

2) reacting the compound shown in formula (I-3) with the compound shown in formula (I-4) to obtain the compound shown in formula (I),

Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents on the aryl groups in the substituted aryl groups are ^C1 ～C12 alkoxy groups;

R ² is selected from a C7-C30 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C1-C12 alkoxy group.

According to the present invention, the compound represented by formula (I-1) is reacted with the compound represented by formula (I-2) to obtain the compound represented by formula (I-3); wherein, the compound represented by formula (I-1) R in the compound shown is preferably a C3 ^- C12 alkyl group or a C8-C20 aryl group, wherein the alkyl group is a C3-C12 straight-chain alkyl group or a C3-C12 branched-chain alkyl group, more preferably a C4 ~C10 straight-connected alkyl group or C4~C10 branched chain alkyl group; the aryl group is C8~C20 substituted aryl group or C8~C20 unsubstituted aryl group, more preferably C9~C15 substituted aryl group or C9 ~C15 unsubstituted aryl; more specific unsubstituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl The substituent is preferably a C3-C8 alkoxy group, more preferably a C4-C6 alkoxy group; in addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the position of the aryl group ortho-position or para-position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R is methyl, ethyl, n ^- propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2- Isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octoxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2- Propoxynaphthyl, 2-isopropoxynaphthyl or 2-octyloxynaphthyl; R ³ and R ⁴ in the compound represented by the formula (I-2) are independently preferably C3-C12 Alkyl or C8-C20 aryl, wherein the alkyl is C3-C12 straight-chain alkyl or C3-C12 branched-chain alkyl, more preferably C4-C10 straight-chain alkyl or C4-C10 branched-chain alkyl base; the aryl group is a C8-C20 substituted aryl group or a C8-C20 unsubstituted aryl group, more preferably a C9-C15 substituted aryl group or a C9-C15 unsubstituted aryl group; more specifically an unsubstituted The aryl in the substituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the substituent on the aryl in the substituted aryl is preferably a C3-C8 alkoxyl group, It is more preferably a C4～C6 alkoxy group; In addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho or para position of the aryl group; The number of substituents is not particularly limited, and is preferably 1, 2, 3 or 4. Specifically, the R ³ and R ⁴ are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl , 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxy phenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxynaphthyl, 2-ethoxy 2-propoxynaphthyl, 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octyloxynaphthyl. The molar ratio of the compound represented by the formula (I-1) to the compound represented by the formula (I-2) is preferably (1-1.2):1.

Specifically, the reaction of the present invention is as follows: the compound represented by the formula (I-1) and the compound represented by the formula (I-2) are first subjected to a substitution reaction, and then oxidized to obtain the compound represented by the formula (I-3) ; Wherein, the substitution reaction is carried out in the presence of an organic base, and the organic base is preferably a tertiary amine; the temperature of the reaction is preferably 10-120°C, more preferably 30-80°C; the oxidation reaction The oxidizing agent is preferably 30wt% hydrogen peroxide aqueous solution, and the temperature of the oxidation reaction is preferably -60--10°C.

According to the present invention, the present invention also reacts the compound shown in formula (I-3) with the compound shown in formula (I-4) to obtain the compound shown in formula (I), wherein, the compound shown in formula (I-4) R ¹ and R ² are independently preferably C9-C18 substituted aryl groups; wherein, the aryl group in the substituted aryl group is preferably phenyl or naphthyl; the substituent on the aryl group in the substituted aryl group is preferably C3-C8 alkoxy, more preferably C4-C6 alkoxy, most preferably methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutyl Baseoxy, tert-butyloxy, n-pentyloxy or n-octyloxy; the substituent in the substituted aryl group described in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or para-position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R ¹ and R ² are independently selected from 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxy phenyl, 4-propoxyphenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxy Basenaphthyl, 2-ethoxynaphthyl, 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octyloxynaphthyl; the compound shown in the formula (I-3) and The molar ratio of the compound shown in the formula (I-4) is preferably (1～1.2): 1; the base in the reaction is preferably an organic base and butyllithium, and the organic base is preferably tetramethylethyl Diamine (TMEDA); the temperature of the reaction is preferably -90 to -60°C; the solvent of the reaction is preferably one or both of toluene or tetrahydrofuran.

The present invention also provides a catalyst, comprising a ligand of the structure shown in formula (I), the catalyst preferably has the structure shown in formula (II) or the structure shown in formula (III),

Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents in the substituted aryl groups are ^C1 ～C12 alkoxy groups;

R2 is selected from a C7 ^- C30 substituted aryl group, and the substituent in the substituted aryl group is a C1-C12 alkoxy group;

^R3 is selected from C1～C15 alkyl or C6～C30 aryl;

R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

R ⁵ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30;

R ⁶ is selected from dimethyl sulfoxide, pyridine or 2,5-lutidine;

X is selected from fluorine, chlorine, bromine or iodine;

X ₁ is selected from tetrakis-(3,5-bistrifluoromethylphenyl) boron group or hexafluorotellurate (SbF ₆ ^— ).

According to the present invention, the R1 is preferably ^a C9-C18 substituted aryl group; wherein, the aryl group in the substituted aryl group is preferably phenyl or naphthyl; the substituent on the aryl group in the substituted aryl group is preferably C3-C8 alkoxy, more preferably C4-C6 alkoxy, most preferably methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutyl Baseoxy, tert-butyloxy, n-pentyloxy or n-octyloxy; the substituent in the substituted aryl group described in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or para-position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R is ² -methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4- Propoxyphenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl or 4-octyloxyphenyl.

The R2 is preferably a C9 ^- C18 substituted aryl group; wherein, the aryl group in the substituted aryl group is preferably phenyl or naphthyl; the substituent on the aryl group in the substituted aryl group is preferably C3-C8 Alkoxy, more preferably C4-C6 alkoxy, most preferably methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutyloxy, tert-butyloxy, n-pentyloxy or n-octyloxy; the substituent in the substituted aryl group described in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho or para position of the aryl group; In the present invention, there is no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R ² is 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4- Propoxyphenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octyloxyphenyl, 2-methoxynaphthyl, 2- Ethoxynaphthyl, 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

The ^R3 is preferably a C3-C12 alkyl group or a C8-C20 aryl group, wherein the alkyl group is a C3-C12 straight-chain alkyl group or a C3-C12 branched-chain alkyl group, more preferably a C4-C10 straight-chain alkyl group. Alkyl group or C4～C10 branched chain alkyl group; the aryl group is C8～C20 substituted aryl group or C8～C20 unsubstituted aryl group, more preferably C9～C15 substituted aryl group or C9～C15 Unsubstituted aryl; More specifically, the unsubstituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the substitution on the aryl in the substituted aryl The group is preferably a C3-C8 alkoxy group, more preferably a C4-C6 alkoxy group; in addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or para-position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the ^R3 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2- Isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octoxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2- Propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

^The R4 is preferably a C3-C12 alkyl group or a C8-C20 aryl group, wherein the alkyl group is a C3-C12 straight-chain alkyl group or a C3-C12 branched-chain alkyl group, more preferably a C4-C10 straight-chain alkyl group. Alkyl group or C4～C10 branched chain alkyl group; the aryl group is C8～C20 substituted aryl group or C8～C20 unsubstituted aryl group, more preferably C9～C15 substituted aryl group or C9～C15 Unsubstituted aryl; more specific unsubstituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the substituent on the aryl in the substituted aryl It is preferably a C3-C8 alkoxy group, more preferably a C4-C6 alkoxy group; in addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or Para position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R is methyl, ethyl, n ^- propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2- Isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octoxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2- Propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

The R ⁵ is preferably a C3-C12 alkyl group or a C8-C20 aryl group, wherein the alkyl group is a C3-C12 straight-chain alkyl group or a C3-C12 branched-chain alkyl group, more preferably a C4-C10 straight-chain alkyl group. Alkyl group or C4～C10 branched chain alkyl group; the aryl group is C8～C20 substituted aryl group or C8～C20 unsubstituted aryl group, more preferably C9～C15 substituted aryl group or C9～C15 Unsubstituted aryl; more specific unsubstituted aryl is preferably phenyl or naphthyl; the aryl in the substituted aryl is preferably phenyl or naphthyl; the substituent on the aryl in the substituted aryl It is preferably a C3-C8 alkoxy group, more preferably a C4-C6 alkoxy group; in addition, the substituent in the substituted aryl group in the present invention can be at any position of the aryl group, preferably the substituent is located at the ortho position of the aryl group or Para position; the present invention has no special limitation on the number of substituents in the substituted aryl group, preferably 1, 2, 3 or 4. Specifically, the R is methyl, ethyl, n ^- propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-octyl, phenyl, 1-naphthyl, 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2- Isopropoxyphenyl, 4-isopropoxyphenyl, 2-octoxyphenyl, 4-octoxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2- Propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl.

R ⁶ is preferably dimethylsulfoxide.

Said X is preferably chlorine, bromine or iodine.

The present invention also provides a preparation method of catalyst, comprising:

The compound shown in formula (I) is reacted with the Pd precursor compound to obtain the compound shown in formula (II);

The compound shown in the formula (II) is reacted with the compound shown in NaX ₁ and R , to obtain the compound shown in the ^formula (III),

Wherein, R is selected from dimethyl sulfoxide, pyridine or 2,5 ^- lutidine;

X ₁ is selected from tetrakis-(3,5-bistrifluoromethylphenyl)boryl or hexafluorotellurate ions.

According to the present invention, the present invention reacts the compound shown in the formula (I) with the Pd precursor compound to obtain the compound shown in the formula (II); the Pd precursor compound is preferably Pd(COD)MeCl or Pd(COD)MeBr, Wherein, the COD is cyclooctadiene; the present invention has no special limitation on the reaction conditions, and any preparation method known in the art can be used.

According to the present invention, the compound shown in the formula (II) is reacted with the compound shown in NaX ₁ and R ⁶ to obtain the compound shown in the formula (III), the X is preferably chlorine, bromine or iodine ^; the R is preferably Dimethyl sulfoxide. The present invention has no special limitation on the reaction conditions, and any preparation method known in the art can be used.

The catalyst prepared by the ligand provided by the invention is applied to the polymerization of olefins, showing high thermal stability and activity; not only has good activity for homopolymerization and copolymerization of olefins, but also has a high molecular weight of the obtained polymer, and The proportion of doped polar monomers during the copolymerization is also relatively high. In addition, the catalyst provided by the invention can also catalyze the polymerization reaction at room temperature (20° C.).

The present invention also provides the use of a catalyst represented by formula (II) or formula (III) as a catalyst for olefin polymerization. In the present invention, the olefin is preferably one or more of ethylene, propylene, and butene, more preferably ethylene; the olefin polymerization includes olefin homopolymerization and olefin copolymerization, and the monomers copolymerized with olefin in the olefin copolymerization The solid is preferably methyl acrylate, vinyl ether, allyl acetate or allyl chloride.

When the olefin polymerization method provided by the invention is used for the homopolymerization of olefins, the obtained polymer not only has a large molecular weight, but also has a low degree of branching, and the polymerization reaction can be carried out at room temperature with high reactivity. When used for the copolymerization of olefins and active molecules, not only the molecular weight of the obtained polymer is high, but also the doping ratio of active molecules is high, and the polymerization reaction can also be carried out at room temperature.

A clear and complete description will be made below in conjunction with the technical solutions of the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

In the present invention, all substances sensitive to water and air are stored in a glove box, all solvents are dried to remove water, ethylene gas is purified by water and oxygen removal columns, and methyl acrylate is purified by water and oxygen removal vacuum distillation. Without special instructions, all the raw materials were purchased and used directly. The raw materials and reagents in the experiment were purchased from Anaiji, Bailingwei and Aladdin.

200-300 mesh silica gel is used for silica gel column separation, and Bruker 400MHz NMR instrument is used for nuclear magnetic detection. Elemental analysis was determined by the Physics and Chemistry Center of University of Science and Technology of China. Molecular weights and molecular weight distributions were determined by high temperature GPC. Mass spectra were determined with ThermoLTQ OrbitrapXL (ESI+) or P-SIMS-GlyofBrukerDaltonicsInc (EI+). Single crystal X-ray diffraction analysis uses OxfordDiffractionGeminiSUltraCCD single crystal diffraction instrument, CuKα Radiation at room temperature.

Example 1

p-(2-(bis(2-methoxyphenyl)phosphino)phenyl)-N,N-diisopropyl P-phenylimide

Diphenylphosphorous chloride (16.3 ml, 0.09 mol) was added to a solution containing the appropriate dialkylamine (0.09 mol, 1.0 eq, R: isopropyl, ethyl) and triethylamine (0.18 mol, 2.0 eq) In toluene (250 mL), the mixture was stirred at 0°C for 8 hours at room temperature, after which it was cooled to -10°C and 30% H ₂ O ₂ (15 mL) was added or 4.475 g of sulfur was added to the solution. The mixture was stirred for another 12 hours. The solvent was evaporated and the product was extracted with dichloromethane. After washing with diethyl ether, the white solid was collected to obtain the pure desired phosphinamide N,N-diisopropyldiphenylphosphonamide as a white solid with a yield of 80%.

A solution of n-butyllithium (1.0 mL, 2.4 molar solution in n-hexane, 2.4 mmol), keeping the solution at –80oC during the addition. One hour later, a toluene solution of diarylphosphine chloride (aryl: o-methoxyphenyl, 2.54 mmol) was injected into the above reaction solution. The reaction was stirred at room temperature for 2 hours, then poured into ice water, extracted with dichloromethane (3 x 15 mL), washed with sodium thiosulfate (2 x 15 mL), dried over anhydrous sodium sulfate and vacuum Drying gave a light yellow solid. Purified by column chromatography, using a silica gel column of 200-300 mesh silica gel for separation, wherein a 1:1 mixture of petroleum ether and ethyl acetate was used as the mobile phase to obtain a white solid that is the compound shown in formula (I). Yield: 0.71 g, 60% yield.

The obtained compound is carried out nuclear magnetic detection, the result is as follows:

¹ HNMR (400MHz, CDCl ₃ ): δ8.01(s, 1H, aryl-H), 7.68–7.60(m, 2H, aryl-H), 7.39(t, J=7.1Hz, 1H, aryl -H), 7.28 (dd, J=9.3, 3.2Hz, 1H, aryl-H), 7.22 (dd, J=11.4, 4.1Hz, 3H, aryl-H), 7.15 (td, J=7.5, 3.0Hz, 2H, aryl-H), 7.06–6.97 (m, 1H, aryl-H), 6.80–6.71 (m, 4H, aryl-H), 6.56 (ddd, J=7.4, 3.8, 1.5 Hz, 1H, aryl-H), 6.46(s, 1H, aryl-H), 3.65(dd, J=14.6, 7.5Hz, 2H, -CH(CH ₃ ) ₂ ), 3.57(d, J= 19.2Hz, 6H, -OCH ₃ ), 1.30 (d, J=6.7Hz, 6H, -CH(CH ₃ ) ₂ ), 1.26 (d, J=6.8Hz, 6H, -CH(CH ₃ ) ₂ ).

³¹ PNMR (162MHz, CDCl ₃ ): δ32.74 (d, J=3.7Hz), -27.95 (s).

¹³ CNMR (101MHz, CDCl ₃ ): δ160.87(t, J=16.2Hz), 136.95(s), 135.70(d, J=1.7Hz), 135.57(d, J=12.5Hz), 134.08(d, J=13.6Hz), 133.66(dd, J=10.7, 7.3Hz), 132.43(dd, J=10.0, 2.3Hz), 130.78(d, J=2.6Hz), 130.42(d, J=2.8Hz), 129.45(d, J=10.2Hz), 127.54(d, J=11.9Hz), 127.21(d, J=12.6Hz), 126.46(d, J=17.2Hz), 120.65(d, J=3.8Hz), 110.45(s), 109.76(s), 55.60(s, -OCH ₃ ), 55.14(s, -OCH ₃ ), 47.41(d, J=3.8Hz, -CH(CH ₃ ) ₂ ), 23.70(d, J = 2.0 Hz, -CH(CH ₃ ) ₂ ).

The obtained compound was detected by mass spectrometry, and the results showed: HRMS (m/z): calculated C ₃₂ H ₃₇ NO ₃ P ₂ : 545.2249, measured 546.2312 [M+H]+.

In addition: the synthesis method of complexes with different substituents of R ¹ , R ² , R ³ and R ⁴ is the same as this method, and the following compounds are also synthesized by this method:

Example 2

Synthesis of [o-((o-OMePh) ₂ P)C ₆ H ₄ (P(O)(N(iPr) ₂ )Ph)]Pd(Me)(Cl) Palladium Complexes

The ligand of formula (I) (1 mole) and (COD)PdMeCl (252 mg, 0.96 mmol) were weighed into a vial placed on the bench top. Dichloromethane (5 mL) was added to the solid, and the mixture was stirred at room temperature for 1 hr. After passing through diatomaceous earth, spread n-hexane on the filtrate and let it stand. After several hours, a pale yellow crystalline solid had formed, which was collected by filtration, washed with hexane (3 x 2 mL), and dried under vacuum to give a pale yellow solid as the compound of formula (II-1). The yield was 78%.

The obtained compound is carried out nuclear magnetic detection, the result is as follows:

¹ HNMR (400MHz, CDCl ₃ ): δ7.94(s, 1H, aryl-H), 7.52–7.35(m, 4H, aryl-H), 7.27(d, J=6.3Hz, 4H, aryl -H), 7.12 (s, 3H, aryl-H), 6.90–6.76 (m, 4H, aryl-H), 6.65 (s, 1H, aryl-H), 3.58 (d, J=39.3Hz , 8H), 1.25 (t, J = 14.0 Hz, 12H, -CH(CH ₃ ) ₂ ), 0.37 (s, 3H, Pd-CH ₃ ).

¹³ CNMR (101MHz, CDCl ₃ ): δ160.67(s), 160.29(d, J=4.9Hz), 135-137(br), 133-135(br), 133.05(d, J=9.0Hz), 132.55(s), 131.61(d, J=2.5Hz), 131.15(s), 129-131(br), 128.82(d, J=11.6Hz), 127.91(d, J=12.8Hz), 120.67(d ,J=9.0Hz),116.16(d,J=52.4Hz),111.07(s),110.88(d,J=4.8Hz),55.53(s,-OCH ₃ ),48.44(d,J=3.2Hz, -CH(CH ₃ ) ₂ ), 23.81(d, J=3.0Hz, -CH(CH ₃ ) ₂ ), 23.61(s, -CH(CH ₃ ) ₂ ), -1.65(s, Pd-CH ₃ ) .

³¹ PNMR (162 MHz, CDCl ₃ ): δ 32.98 (d, J=192.9 Hz), 27.54 (s), 19.36 (s).

Elemental analysis of the obtained compound: Calculated for C ₃₃ H ₄₀ ClNO ₃ P ₂ Pd: C, 56.42; H, 5.74; N, 1.99; Actual C, 56.47; H, 5.77; N, 2,21.

The compound obtained in Example 2 was subjected to single crystal diffraction, and the results are shown in FIG. 1 . FIG. 1 is a schematic diagram of the single crystal structure of the compound prepared in Example 2 of the present invention.

Comparative example 1

Synthesis of [o-(Cy ₂ P)C ₆ H ₄ (P(O)(N(iPr) ₂ )Ph)]Pd(Me)(Cl)palladium Complexes

Ligand of formula (I-d1) (1 mole) and (COD)PdMeCl (252 mg, 0.96 mmol) were weighed into a vial placed on the bench top. Dichloromethane (5 mL) was added to the solid, and the mixture was stirred at room temperature for 1 hr. After passing through diatomaceous earth, spread n-hexane on the filtrate and let it stand. After several hours, a pale yellow crystalline solid had formed which was collected by filtration, washed with hexane (3 x 2 mL), and dried under vacuum to give a pale yellow solid, the compound of formula (II-d1). The yield was 80%.

The obtained compound is carried out nuclear magnetic detection, the result is as follows:

¹ HNMR (400MHz, CDCl ₃ ): δ8.16–8.06(m, 2H, aryl-H), 8.03(ddd, J=13.0, 5.8, 3.4Hz, 1H, aryl-H), 7.80(s, 1H, aryl-H), 7.66 (d, J=4.4Hz, 2H, aryl-H), 7.56–7.42 (m, 3H, aryl-H), 3.43 (ddt, J=20.4, 13.5, 6.7 Hz, 2H, -CH(CH ₃ ) ₂ ), 2.23 (dd, J=24.1, 12.0Hz, 1H, cyclohexyl), 2.07 (ddd, J=12.5, 11.1, 4.6Hz, 1H, cyclohexyl), 1.95 (t, J = 12.2Hz, 1H, cyclohexyl), 1.81 (dd, J = 28.9, 12.7Hz, 4H, cyclohexyl), 1.68 (dd, J = 19.6, 10.9Hz, 4H, cyclohexyl), 1.52 ( d, J = 10.7Hz, 1H, cyclohexyl), 1.44–1.33 (m, 2H, cyclohexyl), 1.29 (dd, J = 11.8, 8.6Hz, 3H, cyclohexyl), 1.23 (d, J = 6.8Hz , 6H, -CH(CH ₃ ) ₂ ), 1.19 (d, J=6.7Hz, 6H, -CH(CH ₃ ) ₂ ), 1.10 (dd, J=20.5, 7.9Hz, 2H, cyclohexyl), 0.90 (dt, J=19.2, 13.0 Hz, 2H, cyclohexyl), 0.53 (d, J=2.1 Hz, 3H, Pd- _CH3 ), 0.12 (dt, J=21.4, 8.0 Hz, 1H, cyclohexyl).

¹³ CNMR (101MHz, CDCl ₃ ): δ140.54(d, J=12.4Hz), 139.30(d, J=12.4Hz), 134.75(d, J=9.9Hz), 134.28(t, J=11.6Hz) ,134.03–133.61(m),132.53(s),132.31(d,J=2.7Hz),131.31(s),130.93(s),129.43(d,J=11.4Hz),128.03(d,J=13.1 Hz), 48.39(d, J=4.2Hz, -CH(CH ₃ ) ₂ ), 37.59(d, J=24.9Hz, Cy), 34.37(d, J=24.3Hz, Cy), 29.59–29.01(m ,Cy),28.13(d,J=6.1Hz,Cy),27.62–26.66(m,Cy),25.94(d,J=15.6Hz,Cy),24.03(d,J=1.5Hz,-CH(CH ₃ ) ₂ ), 22.99 (d, J=2.9 Hz, -CH(CH ₃ ) ₂ ), -6.05 (s, Pd-CH ₃ ).

³¹ PNMR (162 MHz, CDCl ₃ ): δ 38.73 (d, J=12.7 Hz), 33.44 (d, J=12.7 Hz).

Elemental analysis of the obtained compound showed that calculated C ₃₁ H ₄₈ ClNOP ₂ Pd: C, 56.89; H, 7.39; N, 2.14; actual C, 57.03; H, 7.38; N, 2.31.

Comparative example 2:

Synthesis of [o-(Ph ₂ P)C ₆ H ₄ (P(S)(N(iPr) ₂ )Ph)]Pd(Me)(Cl)palladium Complexes

Add n Butyllithium solution (0.89 ml of 1.6M n-hexane solution, 1.42 mmol). After 2 hours of reaction at 0° C., 1.5 equivalents of chlorodiphenylphosphine (1.42 mmol) were added. The reaction mixture was stirred at 0 °C for 2 hours, then quenched with methanol. The reaction mixture was poured into water and extracted with dichloromethane (2 x 15 mL). The organic layer was dried over sodium sulfate and concentrated in vacuo. The crude mixture was subjected to column chromatography (silica gel, ethyl acetate/PE, 1:1) to obtain a white powder, which was the sulfur-containing ligand.

The resulting sulfur-containing ligand (1 mole) and (COD)PdMeCl (252 mg, 0.96 mmol) were weighed into a vial placed on the bench top. Dichloromethane (5 mL) was added to the solid, and the mixture was stirred at room temperature for 1 hr. After passing through diatomaceous earth, spread n-hexane on the filtrate and let it stand. After several hours, a pale yellow crystalline solid had formed which was collected by filtration, washed with hexane (3 x 2 mL), and dried under vacuum to give a pale yellow solid, the compound of formula (II-d2), The yield was 79%.

The obtained compound is carried out nuclear magnetic detection, the result is as follows:

¹ HNMR (400MHz, CDCl3): δ8.36–8.13 (m, 1H, aryl-H), 7.66 (dd, J = 13.7, 7.6Hz, 3H, aryl-H), 7.55 (t, J = 7.4 Hz, 1H, aryl-H), 7.43–7.18(m, 8H, aryl-H), 7.04(dd, J=9.2, 5.3Hz, 6H, aryl-H), 3.79–3.54(m, 2H ,-CH(CH3)2),1.27(d,J=6.7Hz,6H,-CH(CH3)2),1.11(d,J=6.7Hz,6H,-CH(CH3)2),0.49(d , J=2.9Hz, 3H, Pd-CH3).

¹³ CNMR (101MHz, CDCl3): δ138.67(d, J=13.4Hz), 138.09(d, J=12.0Hz), 137.77(t, J=12.5Hz), 137.43(d, J=11.4Hz), 134.90(d, J=13.6Hz), 134.27(d, J=11.9Hz), 133.36(s), 132.93(d, J=11.8Hz), 132.82(s), 132.69(d, J=2.9Hz), 132.54(d, J=7.8Hz), 131.55(dd, J=6.2, 2.4Hz), 130.95(s), 130.31(d, J=2.1Hz), 129.97(s), 129.59(d, J=9.4Hz ), 128.31(t, J=11.4Hz), 127.94(d, J=13.3Hz), 127.77(s), 49.67(d, J=4.1Hz, -CH(CH3)2), 23.45(d, J= 2.5Hz, -CH(CH3)2), 23.31(d, J=1.7Hz, -CH(CH3)2), 11.39(s, Pd-CH3).

³¹ PNMR (162MHz, CDCl3): δ61.99 (d, J=26.4Hz), 31.01 (d, J=26.4Hz).

The obtained compound was subjected to elemental analysis, and the results showed that: elemental analysis calculated C ₃₁ H ₃₆ ClNP ₂ PdS: C, 56.54; H, 5.51; N, 2.13; actual C, 56.85; H, 5.43; N, 2.17.

Example 3

Synthesis of {[o-((o-OMePh)2P)C6H4(P(O)(N(iPr)2)Ph)]Pd(Me)(DMSO)}+BAF-Palladium Cation Complex

A vial was charged with the complex represented by formula (II-1) (0.25 mmol), NaBAF (0.25 mmol), dimethyl sulfoxide (0.25 mmol), and then dichloromethane (2 ml) was added. The resulting yellow solution was stirred vigorously after 40 min at room temperature. Filtration through celite gave a clear yellow solution. The solvent was removed under vacuum to obtain a light yellow solid, which is the compound represented by formula (III-1). The yield was 62%.

The obtained compound is carried out nuclear magnetic detection, the result is as follows:

¹ HNMR (400MHz, CDCl3): δ8.02–7.92(m, 1H, aryl-H), 7.71(s, 8H, aryl-H), 7.59(d, J=7.5Hz, 2H, aryl-H H), 7.52 (s, 5H, aryl-H), 7.45 (d, J=7.4Hz, 2H, aryl-H), 7.38–7.27 (m, 4H, aryl-H), 7.18 (s, 3H, aryl-H), 6.95(dd, J=13.3, 7.6Hz, 3H, aryl-H), 6.60(s, 3H, aryl-H), 3.69(s, 3H), 3.47(s, 5H), 2.76(s, 6H, DMSO), 1.20(d, J=6.6Hz, 12H, -CH(CH ₃ ) ₂ ), 0.18(s, 3H, Pd-CH ₃ ).

¹³ CNMR (101MHz, CDCl ₃ ): δ162.61(s), 162.12(s), 161.62(s), 161.13(s), 160.31(s), 159.95(s), 136.02(s), 134.96(s) ,134.17(s),133.78(s),133.05(s),132.28(d,J=9.9Hz),131.38(s),130.02(d,J=13.8Hz),129.53(s),129.22(s) ,128.71(dd,J=27.0,14.6Hz),126.06(s),123.35(s),121.19(t,J=13.0Hz),120.64(s),117.62(s),111.39(d,J=31.6 Hz),55.56(s,-OCH ₃ ),54.87(s,-OCH ₃ ),48.66(s,-CH(CH ₃ ) ₂ ),40.05(s,DMSO),23.86(s,-CH(CH ₃ ) ₂ ),22.98(s,-CH(CH ₃ ) ₂ ),3.50(s,Pd-CH ₃ ).

³¹ PNMR (162MHz, CDCl ₃ ): δ40.80, 29.95.

Mass analysis was performed on the obtained compound, and the results are as follows: ESI-mass spectrum: (CH ₃ CN, positive ion scan): 666.1512 ([M-DMSO-BAF ^- ] ⁺ ).

The obtained compound was subjected to elemental analysis, and the results are as follows: elemental analysis calculation C ₆₇ H ₅₈ BF ₂₄ NO ₄ P ₂ PdS: C, 50.03; H, 3.63; N, 0.87; actual C, 50.22; H, 3.55; N, 0.96 .

Comparative example 3

Synthesis of {[o-(Cy2P)C6H4(P(O)(N(iPr) ₂ )Ph)]Pd(Me)(DMSO)} ⁺ BAF ^- Palladium Cationic Complex

A vial was charged with a compound represented by formula (II-d1) (0.25 mmol), NaBAF (0.25 mmol), dimethyl sulfoxide (0.25 mmol), and then dichloromethane (2 ml) was added. The resulting yellow solution was stirred vigorously after 40 min at room temperature. Filtration through celite gave a clear yellow solution. The solvent was removed under vacuum to obtain a pale white solid, which is the compound represented by formula (III-d1). The yield is 67%;

The obtained compound is carried out nuclear magnetic detection, the result is as follows:

¹ HNMR (400MHz, CDCl ₃ ): δ8.09(s, 1H, aryl-H), 7.73(s, 11H, aryl-H), 7.66(s, 2H, aryl-H), 7.54(s , 5H, aryl-H), 7.48 (d, J=4.4Hz, 2H, aryl-H), 3.53–3.34 (m, 2H, -CH(CH ₃ ) ₂ ), 2.85 (s, 6H, DMSO ),2.39–2.17(m,2H,cyclohexyl),1.99(s,1H,cyclohexyl),1.89–1.70(m,8H,cyclohexyl),1.48(s,4H,cyclohexyl),1.28(d, J＝9.9Hz, 3H, cyclohexyl), 1.18–1.11 (m, 12H, -CH(CH ₃ ) ₂ ), 0.89 (dd, J＝21.4, 11.1Hz, 4H, cyclohexyl), 0.37 (s, 3H , Pd—CH ₃ ).

¹³ CNMR (101MHz, CDCl ₃ ): δ162.47(s), 161.98(s), 161.48(s), 160.99(s), 134.81(s), 134.44–133.90(m), 133.17(d, J＝11.0 Hz), 132.04(m), 131.85(d, J=21.8Hz), 130.94–130.23(m), 129.38(s), 128.77(dd, J=30.7, 23.7Hz), 125.92(s), 123.21(s ),120.51(s),117.47(s),48.65(s,-CH(CH ₃ ) ₂ ),39.78(s,DMSO),37.90(s,Cy),37.61(s,Cy),35.72(s, Cy),35.45(s,Cy),30.03(s,Cy),29.76(d,J=50.7Hz,Cy),29.07(s,Cy),27.97(d,J=6.4Hz,Cy),26.78( dd,J=25.4,14.2Hz,Cy),25.94(s,Cy),25.63(s,Cy),23.64(s,-CH(CH ₃ ) ₂ ),22.85(s,-CH(CH ₃ ) ₂ ), -1.18(s, Pd—CH ₃ ).

³¹ PNMR (162 MHz, CDCl ₃ ) δ 44.44 (s), 41.45 (d, J=9.5 Hz).

The obtained compound was analyzed by mass spectrometry, and the results showed that ESI-mass spectrum: (CH ₃ CN, positive ion scan): 618.2228 ([M-DMSO-BAF ⁻ ] ⁺ ).

The obtained compound was subjected to elemental analysis, and the results showed that elemental analysis calculated C ₆₅ H ₆₆ BF ₂₄ NO ₂ P ₂ PdS: C, 50.03; H, 4.26; N, 0.90; actual C, 50.37; H, 4.16; N, 1.09 .

Example 4

Application of Catalyzed Ethylene Polymerization

In a glove box, 20-300 mL of toluene was added to a 350 mL autoclave (with magnetic stirring device, oil bath heating device and thermometer) under nitrogen atmosphere. Then liquid nitrogen is refrigerated and evacuated, filled with ethylene back and forth three times, the reaction temperature is adjusted to 20-100°C, and a certain amount of palladium catalyst prepared in the examples of the present invention or comparative examples is injected into it to dissolve it in 2 milliliters of dichloro solution in methane. Close the valve, adjust the ethylene pressure to 9 atmospheres, and react for 30 minutes. Stop the reaction, open the reactor, add methanolic hydrochloric acid (95:5) solution to precipitate the solid, filter under reduced pressure to obtain crude polyethylene, wash with pure methanol three times, and air dry. Obtain 3 grams of white polyethylene;

By detecting the melting point and molecular weight of the obtained polyethylene, the results are shown in Table 1. Table 1 shows the performance test results of the polyethylene obtained by catalyzing the homopolymerization of ethylene with the catalysts provided in the examples and comparative examples of the present invention under different conditions.

Table 1 is the performance test results of the polyethylene obtained by catalyzing ethylene homopolymerization under different conditions for the catalysts provided by the examples of the present invention and comparative examples

Wherein, a is the polymerization condition: 48mL toluene, 2mL dichloromethane, 9 atmospheres. b Activity unit 10 ⁵ grams per mole per hour. c Determined using universally calibrated GPC. d Determined by differential scanning calorimetry, second heating. e Add 1.2 equivalents of AgSbF ₆ . f Significant polymer precipitation was observed. g Add 1.2 equivalents of NaBAF.

The structure of PO-Pd is

Analyze the polyethylene obtained by catalyzing ethylene polymerization with the catalysts described in 4-5 in Table 1 and the reaction conditions by using NMR, the results are shown in Fig. 2, and Fig. 2 is the hydrogen spectrum of the polyethylene prepared by the embodiment of the present invention, from Fig. It can be seen from the figure that the degree of branching of the polyethylene prepared by the present invention is less than 10.

Example 5

Application of Catalytic Copolymerization of Ethylene and Polar Monomer

In a glove box, under a nitrogen atmosphere, add toluene, a polar monomer, to a 350 mL autoclave (with a magnetic stirring device, an oil bath heating device and a thermometer) so that the total volume of the solution is 50 mL. And inject a certain amount of the catalyst prepared in the embodiment of the present invention and the comparative example therein, make it dissolve in the solution in 5 milliliters of dichloromethane. Close the valve, adjust the ethylene pressure to 9 atmospheres, feed ethylene to react for 1 hour, and then add methanol to quench. The precipitated solid is obtained by filtration under reduced pressure, then hot toluene is dissolved, and passed through a silica gel column (using 200-300 mesh silica gel column separation while hot), wherein the mixture of sherwood oil and dichloromethane 1:1 is used as the mobile phase earlier, Then use pure dichloromethane to separate through the column again). The developer was collected and evaporated to dryness. Drain overnight at 40°C. Obtain 0.12 g of light yellow solid, which is ethylene copolymer;

By detecting the melting point and molecular weight of the obtained copolymer product, the results are shown in Table 2. Table 2 is the performance of the ethylene copolymer obtained by the catalyst provided by the examples of the present invention and the comparative examples under different conditions to catalyze the copolymerization of ethylene and polar monomers Test Results.

Table 2 The performance test results of the ethylene copolymer obtained by catalyzing the copolymerization of ethylene and polar monomers under different conditions using the catalysts provided by the examples of the present invention and comparative examples

Among them, a polymerization condition: total volume of toluene and polar vinyl monomer: 50 ml (200 mg 2,6-di-tert-butyl-p-cresol in methyl acrylate copolymerization, 30 microliters 2,6-di-tert- butylpyridine in n-butyl vinyl ether copolymerization), 20 micromole catalyst, 1 hour. b Determined by NMR spectroscopy. c activity is in unit 10 ³ grams per mole per hour. d Determined by GPC using universal calibration.

The polar monomer MA is methyl acrylate, BE is vinyl n-butyl ether, and AA is allyl acetate.

Analyze the ethylene copolymer obtained by catalyzing the polymerization of ethylene with the catalyst described in 5-2 in Table 2 and the reaction conditions by using NMR, the results are shown in Fig. 3, and Fig. 3 is the hydrogen spectrum of the ethylene copolymer prepared by the embodiment of the present invention, It can be seen from the figure that the insertion ratio of MA is 3.2%.

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (10)

1. A catalyst ligand having a structure shown in formula (I), Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents on the aryl groups in the substituted aryl groups are ^C1 ～C12 alkoxy groups; R2 is selected from a C7 ^- C30 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C1-C12 alkoxy group; ^R3 is selected from C1～C15 alkyl or C6～C30 aryl; R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30; R ⁵ is selected from a C1-C15 alkyl group or a C6-C30 aryl group. 2. catalyst ligand according to claim 1, is characterized in that, described R ¹ is selected from the substituted aryl group of C9～C18, and the substituting group on the aryl group in the described substituted aryl group is the alkoxy group of C3～C8 base; R ² is selected from a C9-C18 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C3-C8 alkoxy group. 3. catalyst ligand according to claim 1, is characterized in that, described R ³ is selected from the alkyl of C3～C12 or the aryl group of C8～C20; R ⁴ is selected from C3～C12 alkyl or C8～C20 aryl; R ⁵ is selected from a C3-C12 alkyl group or a C8-C20 aryl group. 4. preparation method according to claim ¹ , is characterized in that, described R is selected from 2-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxy phenyl, 2-propoxyphenyl, 4-propoxyphenyl, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl, 4-octyloxy phenyl, 2-methoxynaphthyl, 2-ethoxynaphthyl, 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl; R is selected from ² -methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 4-ethoxyphenyl, 2-propoxyphenyl, 4-propoxyphenyl Base, 2-isopropoxyphenyl, 4-isopropoxyphenyl, 2-octyloxyphenyl, 4-octyloxyphenyl, 2-methoxynaphthyl, 2-ethoxynaphthalene 2-propoxynaphthyl, 2-isopropoxynaphthyl or 2-octoxynaphthyl. 5. A method for preparing the catalyst ligand according to any one of claims 1 to 4, comprising: 1) reacting the compound shown in formula (I-1) with the compound shown in formula (I-2) to obtain the compound shown in formula (I-3), in, R ³ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30, R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30, R ⁵ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30; 2) reacting the compound shown in formula (I-3) with the compound shown in formula (I-4) to obtain the compound shown in formula (I), Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents on the aryl groups in the substituted aryl groups are ^C1 ～C12 alkoxy groups; R ² is selected from a C7-C30 substituted aryl group, and the substituent on the aryl group in the substituted aryl group is a C1-C12 alkoxy group. 6. A catalyst comprising the ligand according to any one of claims 1 to 4 or the ligand prepared by the preparation method according to claim 5. 7. catalyzer according to claim 6, is characterized in that, described catalyzer is structure shown in formula (II) or formula (III), Wherein, R is selected from C7～C30 substituted aryl groups, and the substituents in the substituted aryl groups are ^C1 ～C12 alkoxy groups; R2 is selected from a C7 ^- C30 substituted aryl group, and the substituent in the substituted aryl group is a C1-C12 alkoxy group; ^R3 is selected from C1～C15 alkyl or C6～C30 aryl; R ⁴ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30; R ⁵ is selected from the alkyl group of C1～C15 or the aryl group of C6～C30; R ⁶ is selected from dimethyl sulfoxide, pyridine or 2,5-lutidine; X is selected from fluorine, chlorine, bromine or iodine; X ₁ is selected from tetrakis-(3,5-bistrifluoromethylphenyl)boryl or hexafluorotellurate. 8. A preparation method of the catalyst according to any one of claims 6 to 7, comprising: The compound shown in formula (I) is reacted with the Pd precursor compound to obtain the compound shown in formula (II); The compound shown in the formula (II) is reacted with the compound shown in NaX ₁ and R , to obtain the compound shown in the ^formula (III), Wherein, R is selected from dimethyl sulfoxide, pyridine or 2,5 ^- lutidine; X ₁ is selected from tetrakis-(3,5-bistrifluoromethylphenyl)boryl or hexafluorotellurate. 9. The application of the catalyst according to any one of claims 6 to 7 or the catalyst prepared by the preparation method according to claim 8 as a catalyst for olefin polymerization. 10. The application according to claim 9, the olefin polymerization is olefin homopolymerization or olefin copolymerization; The monomer copolymerized with olefin in the olefin copolymerization is methyl acrylate, vinyl ether, allyl acetate or allyl chloride.