Composition for preparing vinyl block copolymer

Abstract

Disclosed in the present invention is a composition for preparing a vinyl block copolymer, the composition comprising: a first monomer ethylene, a second monomer a C3-C20 α-olefin and at least one regulation monomer, the regulation monomer being an olefin or a substituted olefin with the C atom number greater than 3, or styrene / a styrene derivative, and in the same composition, the second monomer being different from the regulation monomer. The composition is catalyzed by a main catalyst and a co-catalyst to obtain the vinyl block copolymer, wherein the main catalyst is a complex L-MR1R2R3 that contains three substituents and that is formed by an IVB-group metal and a monoanionic ligand, and the co-catalyst includes alkyl aluminum, polymerized or oligomerized aluminoxane, a neutral Lewis acid, a non-polymer, a non-coordinated ionic compound, or a mixture of two or more described above. Provided in the present invention is a composition capable of obtaining a lower-olefin block copolymer, the composition can obtain a lower-olefin block copolymer without the need of replenishing monomers or adding a chain transfer reagent for polymerization during polymerization processes, so that a production process is simple and involves low cost.

Description

A composition for preparing a vinyl block copolymer TECHNICAL FIELD

[0001] The present invention relates to a composition for preparing a vinyl block copolymer, in particular a composition for preparing a vinyl block copolymer (OBC) comprising a lower alkene, a comonomer, a catalyst and other auxiliaries. BACKGROUND

[0002] Polyolefins have been widely used in human life due to their advantages of rich raw materials, low price and excellent performance. They are everywhere from daily necessities to national defense weapons. China is the world's largest producer and consumer of polyolefins, but there is a serious structural overcapacity problem in the domestic polyolefin industry. High-end polyolefin products rely on imports, and the self-sufficiency rate is only 44%. The largest production proportion in polyolefin products is polyethylene, and the largest production in polyethylene is LDPE, HDPE and LLDPE. Although they are all polyethylene, the performance difference is very large due to the different chain structures. LDPE is a highly branched polyethylene. The existence of branched chains inhibits the ordered arrangement of polymer chains, resulting in low crystallinity, which makes it have excellent flexibility and lower melting point. HDPE is opposite to LDPE, with short and few branched chains, so it has high crystallinity, high strength and high hardness. LLDPE is a linear structure with a large number of short branches, which has excellent flexibility and toughness. These three kinds of polyethylene each have their own characteristics, but also have their own shortcomings. In order to pursue polyolefin products with more excellent performance, people first used the method of blending modification to increase the flexibility of the blended polyolefin with LDPE. However, the melting point of the blended polymer is significantly reduced, which greatly limits the potential of using it as a thermoplastic elastomer. Later, people developed olefin block copolymer, which combined hard and soft from the microstructure level. The polyethylene segment with regular arrangement and easy crystallization acts as a hard segment to provide strength and hardness, and the highly branched segment acts as a soft segment to provide flexibility. The combination of soft and hard segments makes the product have the advantages of HDPE and LLDPE: excellent elasticity and high melting point. Excellent performance makes OBC applied in many fields, and the synthesis method of OBC (olefin block copolymer) has attracted the attention of researchers in industry and academia.

[0003] Currently, there are two main methods for the synthesis of OBCs: living polymerization and chain shuttling polymerization (coordination chain transfer polymerization). Living polymerization usually relies on active catalyst systems, and the polymerization of the first monomer (e.g., ethylene) is initiated first under strictly controlled reaction conditions (e.g., anhydrous and anaerobic environment, low temperature). Due to the effective inhibition of chain termination and chain transfer reactions during the living polymerization process, the polymer chain ends always retain active centers. After the first monomer is completely consumed, the active chain end can continue to initiate the polymerization of the second monomer (e.g., propylene, 1-octene, etc.) by adding the second monomer step by step. Thus, a clear AB diblock structure is formed. If the monomer is changed multiple times, a multi-block polymer can be obtained. However, the defects of living polymerization are quite significant. Living polymerization requires a large amount of catalyst, and the operation process is complex (e.g., adding monomers) and requires high equipment. Therefore, it is difficult to achieve industrial production. Chain shuttling polymerization achieves dynamic regulation in a single reactor by introducing a chain transfer agent (e.g., diethyl zinc) and two catalysts with different characteristics. The chain transfer agent reversibly "shuttles" the growing polymer chain from the active site of one catalyst to the active site of another catalyst, allowing the same polymer chain to alternate between different catalytic environments. Thus, a multi-block copolymer with alternating block structure is generated without the need for stepwise addition of monomers. However, the core problem of chain shuttling polymerization lies in the compatibility of the two catalysts (e.g., mutual interference or ligand competition of different metal centers) and the balance of chain transfer efficiency. If the chain transfer rate does not match the polymerization rate, it will lead to uneven block length distribution (e.g., formation of short blocks or random copolymers). In addition, the chain transfer agent may cause irreversible chain termination or catalyst deactivation (e.g., side reactions of alkyl aluminum with certain transition metal catalysts). Therefore, a chain transfer agent that can be used with the catalyst is required, two catalysts are required, and the chain transfer agent increases the cost of polymerization. These factors jointly restrict the application prospect of this method in the large-scale preparation of high-performance polyolefin materials.

[0004] Therefore, the present application is proposed. SUMMARY

[0005] The present application aims to provide a composition of ethylene-based block copolymer, which is polymerized without adding catalyst or chain transfer agent during the polymerization process, to obtain an ethylene-based block copolymer with a simple production process and low cost.

[0006] Another object of the present application is to provide an ethylene-based block copolymer, which is formed without relying on a chain shuttling agent. After a single catalyst is activated by a cocatalyst, the selectivity of the first monomer and the second monomer in the monomer adjustment system to the comonomer under the catalysis of the catalyst is adjusted to obtain an ethylene-based block copolymer.

[0007] Still another object of the present invention is to provide a method for preparing a vinyl block copolymer, which selectively polymerizes a comonomer under catalysis of a single catalyst to obtain a block copolymer.

[0008] A composition for preparing a vinyl block copolymer, comprising:

[0009] To achieve the above object, the present invention adopts the technical solution of:

[0010] A composition for preparing a vinyl block copolymer, comprising:

[0011] The first monomer is ethylene and the second monomer is C3-C 20 An α-olefin, and a modifying monomer; the modifying monomer is an olefin having more than 3 carbon atoms, a substituted olefin, or styrene / styrene derivative.

[0012] In the same composition, the second monomer and the modifying monomer are different;

[0013] The composition is catalyzed by a main catalyst and a cocatalyst to obtain a vinyl block copolymer;

[0014] The main catalyst is a complex of a trisubstituted Group IVB metal and a monanionic ligand;

[0015] The cocatalyst is an alkyl aluminum, a polymeric or oligomeric aluminoxane (also known as alkoxyl aluminum), a neutral Lewis acid, and a non-polymer, non-coordinating ionic form compound.

[0016] The modifying monomer is an olefin, a substituted olefin, or styrene / styrene derivative.

[0017] A main catalyst and a cocatalyst;

[0018] The main catalyst of the present invention is a compound of general formula (I);

[0019] wherein M is a Group IVB metal;

[0020] R 1 —R 3 each independently is selected from the group consisting of a halogen atom, a C1-C 20 hydrocarbon group, a C1-C 20 amino group, a C1-C 20 silane group-substituted hydrocarbon group, a (C6-C 40 ) aryl group-substituted hydrocarbon group, which is independently unsubstituted or substituted with one or more substituents R S ; here "the group" is a C1-C 20 hydrocarbon group, a C1-C 20 amino group, a C1-C 20silicon-substituted hydrocarbyl, (C6-C 40 ) aryl-substituted hydrocarbyl, wherein H in the (C1-C S ) hydrocarbyl group is unsubstituted or H is substituted by one or more substituents R

[0021] and

[0022] each R s is independently a halogen atom, polyfluoro, perfluoro, unsubstituted (C1-C 18 ) hydrocarbyl, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, RO-, RS-, RS(O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)-, RC(O)N(R)- or R2NC(O)-, wherein each R is independently unsubstituted (C1-C 18 ) hydrocarbyl;

[0023] L is a ligand selected from the group consisting of: phenoxyimine ligands, phenoxazoline ligands, pyridylamine ligands, imine amine ligands, amine quinoline ligands, amine tetrahydroquinoline ligands;

[0024] The amount of the second monomer in the block copolymer is in the range of 2 mol% to 30 mol%, preferably 5 mol% to 25 mol%, more preferably 5 mol% to 20 mol%, most preferably 5 mol% to 15 mol% of the total amount of each monomer in the polymer.

[0025] The amount of the second monomer in the block copolymer is in the range of 2 mol% to 30 mol%, preferably 5 mol% to 25 mol%, more preferably 5 mol% to 20 mol%, most preferably 5 mol% to 15 mol% of the total amount of each monomer in the polymer.

[0026] The amount of the second monomer in the block copolymer is in the range of 2 mol% to 30 mol%, preferably 5 mol% to 25 mol%, more preferably 5 mol% to 20 mol%, most preferably 5 mol% to 15 mol% of the total amount of each monomer in the polymer.

[0027] The amount of the second monomer in the block copolymer is in the range of 2 mol% to 30 mol%, preferably 5 mol% to 25 mol%, more preferably 5 mol% to 20 mol%, most preferably 5 mol% to 15 mol% of the total amount of each monomer in the polymer.

[0028] The amount of the second monomer in the block copolymer is in the range of 2 mol% to 30 mol%, preferably 5 mol% to 25 mol%, more preferably 5 mol% to 20 mol%, most preferably 5 mol% to 15 mol% of the total amount of each monomer in the polymer.

[0029] Co-catalyst: A co-catalyst is used to activate the metal-ligand complex catalyst by contacting or combining the metal-ligand complex catalyst with the co-catalyst to impart catalytic activity to the metal-ligand complex catalyst. The co-catalyst is also referred to as an activating co-catalyst in the present invention. Suitable co-catalysts for use in the present invention include neutral Lewis acids; including alkylaluminum, polymeric or oligomeric aluminoxanes (also known as aluminoxides), neutral Lewis acids, and non-polymeric, non-coordinating, ionic form compounds.

[0030] Neutral Lewis acid activators, i.e., cocatalysts, include Group 13 metal compounds containing from 1 to 3 of the (C1-C 40 ) hydrocarbyl substituents; in one embodiment, the Group 13 metal compound is a tri((C1-C 40 ) hydrocarbyl) substituted aluminum or a tri((C1-C 40 ) hydrocarbyl)-boron compound; in embodiments, the Group 13 metal compound is a tri(hydrocarbyl) substituted aluminum, a tri((C1-C 40 ) hydrocarbyl)-boron compound, a tri((C1-C 10 ) alkyl) aluminum, a tri((C6-C 18 ) aryl) boron compound, and halogenated (including perhalogenated) derivatives thereof; in further embodiments, the Group 13 metal compound is a tri(fluoro-substituted phenyl) borane, a tri(pentafluorophenyl) borane; in some embodiments, the activating cocatalyst is a tri((C1-C 40 ) hydrocarbyl borate (e.g., trityl tetra(pentafluorophyl) borate) or a tri((C1-C 40 ) hydrocarbyl) ammonium tetra((C1-C 40 ) hydrocarbyl) borate (e.g., bis(octadecyl)methylammonium tetra(pentafluorophyl) borate); the term "ammonium" means a nitrogen cation which is ((C1-C 40 ) hydrocarbyl)4N + , ((C1-C 40 ) hydrocarbyl)3N(H) + , ((C1-C 40 ) hydrocarbyl)2N(H)2 + , (C1-C 40 ) hydrocarbyl N(H)3 + , or N(H)4 + , where each of the two or more (C1-C 40 ) hydrocarbyl groups, when present, can be the same or different; combinations of neutral Lewis acid activators (cocatalysts) include mixtures comprising a tri((C1-C 10 ) alkyl) aluminum and a halogenated tri((C6-C 18 ) aryl) boron compound, especially a tri(pentafluorophenyl) borane; embodiments are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric aluminoxane and combinations of a single neutral Lewis acid, especially a tri(pentafluorophenyl) borane, with a polymeric or oligomeric aluminoxane; the ratio of (metal-ligand complex):(tri(pentafluoro-phenyl) borane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tri(pentafluoro-phenyl) borane):(aluminoxane)] moles is from 1:1:1 to 1:10:30, in other embodiments from 1:1:1.5 to 1:5:10;

[0031] Most preferred are triphenylcarbenium tetrakis(pentafluorophenyl)borate [Ph3C][B(C6F5)4] or N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate [PhNMe2H][B(C6F5)4] or tri((C1-C 40 )alkyl)ammonium tetrakis((C1-C 40 )alkyl)borates (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate) and B(C6F5)3; in certain specific polymerizations, oligomeric aluminoxanes are added to activate the catalyst or to scavenge impurities.

[0032] The composition for the preparation of the ethylene block copolymer according to the present application further comprises at least one regulator monomer, said regulator monomer being selected from:

[0033] C3-C 20 terminal olefins or internal olefins; or

[0034] C4-C 20 conjugated dienes, said conjugated dienes being linear conjugated dienes, cyclic conjugated dienes or branched conjugated dienes; or

[0035] C5-C 20 non-conjugated dienes; or

[0036] C8-C 20 styrene and styrene derivatives, said olefins or styrene and styrene derivatives being independently unsubstituted or substituted by one or more substituents R S as defined before; S

[0037] Further, said regulator monomer is a C4-C 20 conjugated diene, said C4-C 20 conjugated diene being selected from linear conjugated dienes or cyclic conjugated dienes or branched conjugated dienes;

[0038] or said regulator monomer is selected from styrene or C8-C 20 styrene derivatives;

[0039] Preferably, said regulator monomer is a C4-C 10 conjugated diene or a C6-C 10 conjugated cyclic diene; or a C5-C 10 conjugated branched diene; or styrene or C8-C 10 styrene derivatives;

[0040] ​Further, the modulator monomer is selected from the group consisting of 1,3-butadiene, 1,3-hexadiene, cyclohexene, 1,4-cyclohexadiene, isoprene, 2,3-dimethyl-1,3-butadiene, norbornene, 4-phenyl-1-butene, dimethylphenylvinylsilane, 4-vinyl-1-cyclohexene, 1,7-octadiene, 1,9-decadiene, N,N-diphenylpentenamine, N,N-diphenylhexenamine, N,N-diphenyloctenamine, allylbenzene, trimethylvinylsilane, dimethylphenylvinylsilane, 2,3-dimethyl-1-butene, (S)-1-methyl-4-(propan-1-en-2-yl)cyclohex-1-ene, 3,3-dimethyl-1-butene, 5-vinylbicyclo[2.2.1]hept-2-ene, isobutylene, myrcene, ocimene, styrene, 2-methyl-vinylbenzene, α-methylstyrene, 2,4,6-trimethylstyrene, 1,2-dihydronaphthalene, 1,3-cyclohexadiene or 1,3-cyclooctadiene, triisopropyl(4-penten-1-yloxy)silane, dimethyl-tert-butyl(4-penten-1-yloxy)silane, triphenylvinylsilane or phenylsilane;

[0041] Preferably, the modulator monomer is selected from the group consisting of styrene, 2-methyl-vinylbenzene.

[0042] Further, in the catalyst, R 1 —R 3 are each independently selected from the group consisting of a halogen atom, a C1-C 15 hydrocarbon group, a C1-C 15 amine group, a C1-C 15 silane group, a (C6-C 20 ) aryl group, said groups being independently unsubstituted or substituted by one or more substituents R S ; wherein said groups, R S are as defined before.

[0043] The ligand L is selected from the group consisting of a phenoxyimine ligand or a phenoxyoxazoline ligand, the compounds having the following structure:

[0044] Phenoxyimine ligands

[0045] O, N and the metal form the ligand, and R 11 —R 16 may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocycle compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of them can combine with each other to form a ring. The groups are independently unsubstituted or substituted by one or more substituents R S ; here the groups, except for the halogen atom, can be substituted by one or more substituents R Ssubstitution, the target of substitution is H on the group, wherein R S as defined previously. R 11 -R 18 the number of carbon atoms in R

[0046] A halogen atom is fluorine, chlorine, bromine or iodine.

[0047] Examples of hydrocarbyl groups include straight or branched chain alkyl groups containing 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl and n-hexyl;

[0048] Examples of hydrocarbyl groups can also be straight or branched chain alkenyl groups containing 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethenyl, allyl and isopropenyl;

[0049] Examples of hydrocarbyl groups can also be straight or branched chain alkynyl groups containing 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl;

[0050] Examples of hydrocarbyl groups can also be cyclic saturated hydrocarbyl groups containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl;

[0051] Examples of hydrocarbyl groups can also be cyclic unsaturated hydrocarbyl groups containing 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, such as cyclopentadienyl, indenyl and fluorenyl;

[0052] Examples of hydrocarbyl groups can also be aryl groups containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl and terphenyl.

[0053] Hydrocarbyl groups can be substituted by halogens, such as trifluoromethyl, pentafluorophenyl and chlorophenyl.

[0054] In addition, the hydrocarbon group can have a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryl group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonato group, a hydroxyl group, a peroxy group, and a carboxylic anhydride group; a nitrogen-containing group such as an ammonium salt of an amino group, an imino group, an amide group, an imide group, a hydrazine group, a hydrazono group, a nitro group, a nitroso group, a fluoro group, an isocyano group, a cyanate group, an amidine group, and a diazo group; a boron-containing group such as a borandiyl group, a borantriyl group, and an ethylborane group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a sulfide group, a thiocyanate group, an isothiocyanate group, a sulfonester group, a sulfonamide group, a thio carboxyl group, a dithio carboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfoxy group; a phosphorus-containing group such as a phosphido group, a phospho group, a thiophospho group, and a phosphato group; a silicon-containing group; a germanium-containing group; and a tin-containing group.

[0055] Among them, straight-chain or branched alkyl groups having 1 to 30, preferably 1 to 20, carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms such as phenyl, benzyl, naphthyl, biphenyl, and terphenyl; and these aryl groups substituted with 1 to 5 substituents such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms, and an aryl group or an aryloxy group having 6 to 30, preferably 6 to 20, carbon atoms are particularly preferable.

[0056] The nitrogen-containing group, the boron-containing group, the sulfur-containing group, and the phosphorus-containing group are those exemplified above. Examples of the heterocyclic residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, residues of oxygen-containing compounds such as furan and pyran, and residues of sulfur-containing compounds such as thiophene, and groups formed by substituting these heterocyclic residues with substituents such as alkyl groups and alkoxy groups having 1 to 20 carbon atoms.

[0057] The silicon-containing group includes silyl groups, siloxy groups, and hydrocarbon-substituted silyl groups such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl-pentafluorophenylsilyl, with methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, and triphenylsilyl being preferable, and trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl being particularly preferable, and hydrocarbon-substituted siloxy groups such as trimethylsiloxy.

[0058] The germanium-containing group and the tin-containing group include the silicon-containing group described above in which the silicon is replaced by germanium and tin, respectively.

[0059] The R 11 The R 16 More specifically, the R

[0060] Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and t-butoxy.

[0061] Examples of the alkylthio group include methylthio and ethylthio.

[0062] Examples of the aryloxy group include phenoxy, 2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy.

[0063] Examples of the arylthio group include phenylthio, methylphenylthio and naphthylthio.

[0064] Examples of the acyl group include formyl, acetyl, benzoyl, p-chlorobenzoyl and p-methoxybenzoyl.

[0065] Examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.

[0066] Examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl and phenylthiocarbonyl.

[0067] Examples of the amido group include acetylamino, N-methylacetylamino and N-methylbenzoylamino.

[0068] Examples of the imido group include acetylimido and benzoylimido.

[0069] Examples of the amino group include dimethylamino, ethylmethylamino and diphenylamino.

[0070] Examples of the imino group include methylimino, ethylimino, propylimino, butylimino and phenylimino.

[0071] Examples of the sulfonato group include methylsulfonato, ethylsulfonato and phenylsulfonato.

[0072] Examples of the sulfonamido group include phenylsulfonamido, N-methylsulfonamido and N-methyl-p-toluenesulfonamido.

[0073] The R 16 The substituent other than hydrogen is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of them can be combined with each other to form a ring. 16Particularly preferred are halogen atoms, hydrocarbon groups, heterocyclic compound residues, hydrocarbon-substituted silyl groups, hydrocarbon-substituted silyloxy groups, alkoxy groups, alkylthio groups, aryloxy groups, arylthio groups, acyl groups, ester groups, thioester groups, amido groups, imido groups, amino groups, imino groups, sulfonate groups, sulfonamide groups, cyano groups, nitro groups or hydroxyl groups.

[0074] Preferred examples of R 16 include straight-chain or branched alkyl groups containing 1 to 30, preferably 1 to 20, carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl and n-hexyl; saturated cyclic hydrocarbon groups containing 3 to 30, preferably 3 to 20, carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; aryl groups containing 6 to 30, preferably 6 to 20, carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl and terphenyl; and groups formed by substituting these groups with substituents such as alkyl or alkoxy groups containing 1 to 30, preferably 1 to 20, carbon atoms, halogenated alkyl groups containing 1 to 30, preferably 1 to 20, carbon atoms, aryl or alkoxy groups containing 6 to 30, preferably 6 to 20, carbon atoms, halogen, cyano, nitro and hydroxyl groups.

[0075] Preferred examples of hydrocarbon-substituted silyl groups for R 16 include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl-pentafluorophenylsilyl. Particularly preferred are trimethylsilyl, triphenylsilyl, diphenylmethylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl-pentafluorophenylsilyl.

[0076] In the present application, R 16 is preferably selected from branched alkyl groups containing 3 to 30, preferably 3 to 20, carbon atoms (such as isopropyl, isobutyl, sec-butyl and t-butyl), groups formed by substituting these alkyl groups with aryl groups containing 6 to 30, preferably 6 to 20, carbon atoms (such as cumyl), and groups formed by substituting saturated cyclic hydrocarbon groups containing 3 to 30, preferably 3 to 20, carbon atoms (such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl). Preferred R 16 is also an aryl group containing 6 to 30, preferably 6 to 20, carbon atoms (such as phenyl, naphthyl, fluorenyl, anthryl or phenanthryl) or a hydrocarbon-substituted silyl group. R 16 is most preferably a tertiary carbon-containing group such as t-butyl or adamantyl. Two or more R 11 - R 16The groups (preferably, two groups adjacent to each other) can be linked together to form an alicyclic, aromatic or heterocyclic ring, and these rings can further have a substituent.

[0077] The ligand of the present application can also be a phenoxyoxazoline type ligand

[0078] The O and N in the above compound form a ligand with a metal, and R 11 -R 18 which can be the same or different, and each is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of these groups can be combined with each other to form a ring.

[0079] The halogen atom is fluorine, chlorine, bromine or iodine.

[0080] Examples of the hydrocarbon group include a straight-chain or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl and n-hexyl;

[0081] Examples of the hydrocarbon group can also be a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethenyl, allyl and isopropenyl;

[0082] Examples of the hydrocarbon group can also be a straight-chain or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl;

[0083] Examples of the hydrocarbon group can also be a cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl;

[0084] Examples of the hydrocarbon group can also be a cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, such as cyclopentadienyl, indenyl and fluorenyl;

[0085] Examples of the hydrocarbon group can also be an aromatic group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl and terphenyl.

[0086] The hydrocarbon group can be substituted with a halogen, such as trifluoromethyl, pentafluorophenyl and chlorophenyl.

[0087] In addition, the hydrocarbon group can have a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryl group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonato group, a hydroxyl group, a peroxy group, and a carboxylic anhydride group; a nitrogen-containing group such as an ammonium salt of an amino group, an imino group, an amide group, an imide group, a hydrazine group, a hydrazono group, a nitro group, a nitroso group, a fluoro group, an isocyano group, a cyanate group, an amidine group, and a diazo group; a boron-containing group such as a borandiyl group, a borantriyl group, and an ethylborane group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a sulfide group, a thiocyanate group, an isothiocyanate group, a sulfonester group, a sulfonamide group, a thio carboxyl group, a dithio carboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfoxy group; a phosphorus-containing group such as a phosphido group, a phospho group, a thiophospho group, and a phosphato group; a silicon-containing group; a germanium-containing group; and a tin-containing group.

[0088] Among them, straight-chain or branched alkyl groups having 1 to 30, preferably 1 to 20, carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms such as phenyl, benzyl, naphthyl, biphenyl, and terphenyl; and these aryl groups substituted with 1 to 5 substituents such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms, and an aryl group or an aryloxy group having 6 to 30, preferably 6 to 20, carbon atoms are particularly preferable.

[0089] The nitrogen-containing group, the boron-containing group, the sulfur-containing group, and the phosphorus-containing group are those exemplified above. Examples of the heterocyclic residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, residues of oxygen-containing compounds such as furan and pyran, and residues of sulfur-containing compounds such as thiophene, and groups formed by substituting these heterocyclic residues with substituents such as alkyl groups and alkoxy groups having 1 to 20 carbon atoms.

[0090] The silicon-containing group includes silyl groups, siloxy groups, and hydrocarbon-substituted silyl groups such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl-pentafluorophenylsilyl, with methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, and triphenylsilyl being preferable, and trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl being particularly preferable, and hydrocarbon-substituted siloxy groups such as trimethylsiloxy.

[0091] The germanium-containing group and the tin-containing group include the silicon-containing group in which the silicon in the above-described silicon-containing group is replaced with germanium and tin, respectively.

[0092] The R 11 The R 18 The R

[0093] Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and t-butoxy.

[0094] Examples of the alkylthio group include methylthio and ethylthio.

[0095] Examples of the aryloxy group include phenoxy, 2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy.

[0096] Examples of the arylthio group include phenylthio, methylphenylthio and naphthylthio.

[0097] Examples of the acyl group include formyl, acetyl, benzoyl, p-chlorobenzoyl and p-methoxybenzoyl.

[0098] Examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.

[0099] Examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl and phenylthiocarbonyl.

[0100] Examples of the amido group include acetylamino, N-methylacetylamino and N-methylbenzoylamino.

[0101] Examples of the imido group include acetylimido and benzoylimido.

[0102] Examples of the amino group include dimethylamino, ethylmethylamino and diphenylamino.

[0103] Examples of the imino group include methylimino, ethylimino, propylimino, butylimino and phenylimino.

[0104] Examples of the sulfonato group include methylsulfonato, ethylsulfonato and phenylsulfonato.

[0105] Examples of the sulfonamido group include phenylsulfonamido, N-methylsulfonamido and N-methyl-p-toluenesulfonamido.

[0106] The R 16 It is preferably a substituent other than hydrogen, i.e., a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of them can be combined with each other to form a ring. 16Particularly preferred are halogen atoms, hydrocarbon groups, heterocyclic compound residues, hydrocarbon-substituted silyl groups, hydrocarbon-substituted silyloxy groups, alkoxy groups, alkylthio groups, aryloxy groups, arylthio groups, acyl groups, ester groups, thioester groups, amido groups, imido groups, amino groups, imino groups, sulfonate groups, sulfonamide groups, cyano groups, nitro groups or hydroxyl groups.

[0107] Preferred examples of R 16 include straight-chain or branched alkyl groups containing 1 to 30, preferably 1 to 20, carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl and n-hexyl; saturated cyclic hydrocarbon groups containing 3 to 30, preferably 3 to 20, carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; aryl groups containing 6 to 30, preferably 6 to 20, carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl and terphenyl; and groups formed by substituting these groups with substituents such as alkyl or alkoxy groups containing 1 to 30, preferably 1 to 20, carbon atoms, halogenated alkyl groups containing 1 to 30, preferably 1 to 20, carbon atoms, aryl or alkoxy groups containing 6 to 30, preferably 6 to 20, carbon atoms, halogen, cyano, nitro and hydroxyl groups.

[0108] Preferred examples of hydrocarbon-substituted silyl groups for R 16 include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl-pentafluorophenylsilyl. Particularly preferred are trimethylsilyl, triphenylsilyl, diphenylmethylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl-pentafluorophenylsilyl.

[0109] In the present application, R 16 is preferably selected from branched alkyl groups containing 3 to 30, preferably 3 to 20, carbon atoms (such as isopropyl, isobutyl, sec-butyl and t-butyl), groups formed by substituting these alkyl groups with aryl groups containing 6 to 30, preferably 6 to 20, carbon atoms (such as cumyl), and groups formed by substituting saturated cyclic hydrocarbon groups containing 3 to 30, preferably 3 to 20, carbon atoms (such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl). Preferred R 16 is also an aryl group containing 6 to 30, preferably 6 to 20, carbon atoms (such as phenyl, naphthyl, fluorenyl, anthryl or phenanthryl) or a hydrocarbon-substituted silyl group. R 16 Most preferred is a group containing a tertiary carbon, such as t-butyl or adamantyl. Two or more R 11 - R 18Groups (preferably two adjacent groups) can be linked together to form alicyclic, aromatic, or hydrocarbon rings containing heteroatoms (such as nitrogen atoms), and these rings may also have a substituent.

[0110] The ligands of this invention can also be pyridine amino ligands. in

[0111] pyridineamine ligand R 21 C is independent 1-40 Hydrocarbon groups, cycloalkyl groups, aryl groups, aralkyl groups, alkylaryl groups, heteroalkyl groups, heterocycloalkyl groups, heteroaryl groups, heteroaryl groups, heteroaryl groups, heteroalkylaryl groups, silyl groups, and those containing C 1-40 An inert-substituted derivative that does not include hydrogen atoms, wherein the group is independently unsubstituted or substituented by one or more substituents R. S Replace; where R S As defined above. Preferred are di- or o-alkyl-substituted aryl groups, with 2,6-diisopropylphenyl being the most preferred.

[0112] R 22 -R 23 In each case, it is independently hydrogen or C. 1-30 Hydroxyl, aryl, aralkyl, heteroalkyl, heteroaryl, or heteroaryl, provided that at least R 22 R 23 One of them is a C-ligand substituted at one or two adjacent positions by a secondary or tertiary alkyl- or cycloalkyl-ligand. 10-30 Aryl or heteroaryl; the group is independently unsubstituted or substituented by one or more R groups. S Replace; where R S As defined above. The optimal value R 22 R 23 One of them is hydrogen while the others are phenyl, pyridyl, naphthyl or anthracene substituted in one or two ortho positions (wherein possible) by isopropyl, tert-butyl, cyclopentyl or cyclohexyl;

[0113] R 24 -R 26 Is it hydrogen, halogen, or C? 1-20 Hydroxyl, aryl, aralkyl, cycloalkyl, or silyl, or up to 20 substituted alkyl, aryl, aralkyl, cycloalkyl, or silyl groups excluding hydrogen atoms, or adjacent R groups 14 -R 16 Groups can combine to form fused-ring derivatives. The groups are either independently unsubstituted or substituted with one or more substituents R. S Replace; where R S As defined above. Hydrogen or C is preferred. 1-4 alkyl.

[0114] R 27It is hydrogen, halogen, C 1-40 Hydrocarbon groups, cycloalkyl groups, heteroalkyl groups, heterocycloalkyl groups, silyl groups, and those containing C 1-40 Inertly substituted derivatives of hydrogen atoms or at least one ortho-substituted derivative with R are not considered. S Replacement C 8-40 Aryl or heteroaryl, wherein the group is independently unsubstituted or substituented by one or more substituents R. S Replace; where R S As defined above. Preferably hydrogen, C 1-10 Alkyl, cycloalkyl, heteroalkyl, cycloalkyl, silyl; or

[0115] In one embodiment, the ligand of the present invention may be an imine amino ligand:

[0116] Imine amino ligand 1 Imine amino ligand 2 Imine amino ligand 3 Imine amino ligand 4 Imine amino ligand 5 Imine amino ligand 6

[0117] imine amino ligand 1 middle,

[0118] Each R 31 Independently, it is H, (C1-C) 40 ) hydrocarbon group or (C1-C 40 Heterohydrocarbon groups; each R 32 Independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 ) hydrocarbon group O-, (C1-C 40 ) hydrocarbon group S-, (C1-C 40 )hydrocarbon group S(O)-, (C1-C 40 )hydrocarbon group S(O)2-, ((C1-C 40 )hydrocarbon group)2N-、((C1-C 40 )hydrocarbon group)2P- or (C1-C 40 Heterohydrocarbon groups; each R 33 Independently, it is H, (C1-C) 40 ) hydrocarbon group or (C1-C 40 Heteroalkyl group. The group is independently unsubstituted or substituted by one or more substituents R. S Replace; where R S As defined above. R 31 The preferred aryl group is di-ortho-alkyl substituted, with 2,6-diisopropylphenyl being the most preferred.

[0119] In the preferred case, imine amino ligand 1, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 40 )alkyl, (C3-C 40)cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 ) aryl or (C6-C 20 )aryl-(C1-C 20 Alkylene. More preferably, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 20 ) hydrocarbon groups, such as (C1-C 20 )alkyl, (C3-C 20 )cycloalkyl, (C3-C 10 )cycloalkyl-(C1-C 10 )alkylene, (C6-C 20 ) aryl or (C6-C 18 )aryl-(C1-C 10 )alkylene.

[0120] In a more preferred case, imine amino ligand 1, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 18 ) hydrocarbon groups, such as (C1-C 18 )alkyl, (C3-C 18 )cycloalkyl, (C3-C 12 )cycloalkyl-(C1-C6)alkylene, (C6-C 18 ) aryl or (C6-C 12 aryl-(C1-C6)alkylene. Preferably, any (C3-C6)alkylene group. 18 The cycloalkyl group is independently unsubstituted or substituted (C3-C4). 10 )cycloalkyl.

[0121] imine amino ligand 2 middle,

[0122] Each R 41 Independently, it is H, (C1-C) 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group; the group is independently unsubstituted or substituted by one or more substituents R S Replace; where R S As defined above. R 41 The preferred aryl group is di-ortho-alkyl substituted, with 2,6-diisopropylphenyl being the most preferred.

[0123] Each R 42 R 43 R 44 Independently is (C1-C 40 ) hydrocarbon group, (C1-C 40)hydrocarbon group O-, (C1-C 40 ) hydrocarbon group S-, (C1-C 40 )hydrocarbon group S(O)-, (C1-C 40 )hydrocarbon group S(O)2-, ((C1-C 40 )hydrocarbon group)2N-、((C1-C 40 )hydrocarbon group)2P- or (C1-C 40 heterohydrocarbon group; or

[0124] R 44 As defined above and R 42 With R 43 The passive form (R) 23 The bimolecular substitution (i.e., together forming the bimolecular): R 2A R 3A Independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 )hydrocarbon group O-, (C1-C 40 ) hydrocarbon group S-, (C1-C 40 )hydrocarbon group S(O)-, (C1-C 40 )hydrocarbon group S(O)2-, ((C1-C 40 )hydrocarbon group)2N-、((C1-C 40 )hydrocarbon group)2P- or (C1-C 40 Heteroalkyl group. The group is independently unsubstituted or substituted by one or more substituents R. S Replace; where R S As defined above.

[0125] Each R 45 Independently, it is H, (C1-C) 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group; the group is independently unsubstituted or substituted by one or more substituents R S Replace; where R S As defined above.

[0126] In the preferred case, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 ) aryl or (C6-C 20 )aryl-(C1-C 20 Alkylene. More preferably, (C1-C 40The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 20 ) hydrocarbon groups, such as (C1-C 20 )alkyl, (C3-C 20 )cycloalkyl, (C3-C 10 )cycloalkyl-(C1-C 10 )alkylene, (C6-C 20 ) aryl or (C6-C 18 )aryl-(C1-C 10 )alkylene.

[0127] In a more preferred case, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 18 ) hydrocarbon groups, such as (C1-C 18 )alkyl, (C3-C 18 )cycloalkyl, (C3-C 12 )cycloalkyl-(C1-C6)alkylene, (C6-C 18 ) aryl or (C6-C 12 aryl-(C1-C6)alkylene. Preferably, any (C3-C6)alkylene group. 18 The cycloalkyl group is independently unsubstituted or substituted (C3-C4). 10 )cycloalkyl.

[0128] imine amino ligand 3 middle,

[0129] Each R 41 Independently, it is H, (C1-C) 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group; the group is independently unsubstituted or substituted by one or more substituents R S Replace; where R S As defined above. R 41 The preferred aryl group is di-ortho-alkyl substituted, with 2,6-diisopropylphenyl being the most preferred.

[0130] Each R 42 R 43 R 44、 R 46、 R 47 Independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 ) hydrocarbon group O-, (C1-C 40 ) hydrocarbon group S-, (C1-C 40 )hydrocarbon group S(O)-, (C1-C 40 )hydrocarbon group S(O)2-, ((C1-C 40 )hydrocarbon group)2N-、((C1-C 40)hydrocarbon group)2P- or (C1-C 40 heterohydrocarbon group; or

[0131] R 44 As defined above and R 42 With R 43 or R 46 With R 47 The passive form (R) 23 The bimolecular substitution (i.e., together forming the bimolecular): R 2A R 3A Independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 ) hydrocarbon group O-, (C1-C 40 ) hydrocarbon group S-, (C1-C 40 )hydrocarbon group S(O)-, (C1-C 40 )hydrocarbon group S(O)2-, ((C1-C 40 )hydrocarbon group)2N-、((C1-C 40 )hydrocarbon group)2P- or (C1-C 40 Heteroalkyl group. The group is independently unsubstituted or substituted by one or more substituents R. S Replace; where R S As defined above.

[0132] Each R 45 Independently, it is H, (C1-C) 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group; the group is independently unsubstituted or substituted by one or more substituents R S Replace; where R S As defined above.

[0133] In the preferred case, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 ) aryl or (C6-C 20 )aryl-(C1-C 20 Alkylene. More preferably, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 20 ) hydrocarbon groups, such as (C1-C 20 )alkyl, (C3-C 20 )cycloalkyl, (C3-C 10 )cycloalkyl-(C1-C10 alkylene, (C6-C 20 aryl or (C6-C 18 aryl-(C1-C 10 alkylene.

[0134] More preferably, each (C1-C 40 hydrocarbyl group is independently unsubstituted or substituted (C1-C 18 hydrocarbyl group, for example (C1-C 18 alkyl, (C3-C 18 cycloalkyl, (C3-C 12 cycloalkyl-(C1-C6)alkylene, (C6-C 18 aryl or (C6-C 12 aryl-(C1-C6)alkylene. Preferably, any (C3-C 18 cycloalkyl group is independently unsubstituted or substituted (C3-C 10 cycloalkyl.

[0135] Imine amine ligand 4 Imine amine ligand 5 and imine amine ligand 6 in which,

[0136] each R 51 , R 61 , R 71 is independently H, (C1-C 40 hydrocarbyl or (C1-C 40 heterohydrocarbyl; each R 52 , R 62 , R 72 , R 53 , R 63 , R 73 is independently (C1-C 40 hydrocarbyl, (C1-C 40 hydrocarbylO-, (C1-C 40 hydrocarbylS-, (C1-C 40 hydrocarbylS(O)-, (C1-C 40 hydrocarbylS(O)2-, ((C1-C 40 hydrocarbyl)2N-, ((C1-C 40 hydrocarbyl)2P- or (C1-C 40 heterohydrocarbyl. Said groups are independently unsubstituted or substituted by one or more substituents R S ; wherein R S is as previously defined. Each T is independently C(T1)2, O, S, S(O), S(O)2, N(R n ), Si(Re )2, or P(R p ), wherein each T1is independently H or C1-C 20 hydrocarbyl, and each R N , R e and R p are independently C1-C 20 hydrocarbyl, which groups are independently unsubstituted or substituted by one or more substituents R S ; wherein R S is as defined before. R 51 , R 61 , R 71 are preferably di-ortho alkyl substituted aryl, most preferably 2,6-diisopropylphenyl.

[0137] The imine amine ligands 3, 4, 5 are in a preferred case (C1-C 40 )hydrocarbyl is independently unsubstituted or substituted (C1-C 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 )aryl or (C6-C 20 )aryl-(C1-C 20 )alkylene. More preferably (C1-C 40 )hydrocarbyl is independently unsubstituted or substituted (C1-C 20 )hydrocarbyl, such as (C1-C 20 )alkyl, (C3-C 20 )cycloalkyl, (C3-C 10 )cycloalkyl-(C1-C 10 )alkylene, (C6-C 20 )aryl or (C6-C 18 )aryl-(C1-C 10 )alkylene.

[0138] The imine amine ligands 3, 4, 5 are in a more preferred case (C1-C 40 )hydrocarbyl is independently unsubstituted or substituted (C1-C 18 )hydrocarbyl, such as (C1-C 18 )alkyl, (C3-C 18 )cycloalkyl, (C3-C 12 )cycloalkyl-(C1-C6)alkylene, (C6-C 18 )aryl or (C6-C 12 )aryl-(C1-C6)alkylene. Preferably any (C3-C 18The cycloalkyl group is independently unsubstituted or substituted (C3-C4). 10 )cycloalkyl.

[0139] In the aminoquinoline ligands or aminotetrahydroquinoline ligands of the present invention,

[0140] Aminoquinoline ligands

[0141] Each R 81 To R 87 It is independently a hydrogen atom, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heterohydrocarbon group, (C1-C 40 ) hydrocarbon group -O- or halogen atom; R 87 Independently is (C1-C 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group, wherein the group is independently unsubstituted or substituted by one or more substituents R S Replace; where R S As defined above; R 87 The preferred aryl group is di-ortho-alkyl substituted, with 2,6-dimethylphenyl being the most preferred.

[0142] The term "(C1-C)" 40 "(C1-C4) hydrocarbon group" refers to a hydrocarbon group with 1 to 40 carbon atoms. 40 "Hydroalkyl group" refers to a hydrocarbon group with 1 to 40 carbon atoms, wherein each hydrocarbon group and hydrocarbon diester is independently aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic, or a combination of two or more thereof; and each hydrocarbon group and hydrocarbon diester is identical or different from the other hydrocarbon group and hydrocarbon diester, and is independently unsubstituted or substituted by one or more R groups. s Replace, R s As mentioned above.

[0143] In the preferred case, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 ) aryl or (C6-C 20 )aryl-(C1-C 20 )alkylene.

[0144] In a more preferred case, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2).20 ) hydrocarbon groups, such as (C1-C 20 )alkyl, (C3-C 20 )cycloalkyl, (C3-C 10 )cycloalkyl-(C1-C 10 )alkylene, (C6-C 20 ) aryl or (C6-C 18 )aryl-(C1-C 10 )alkylene.

[0145] In a more preferred case, (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 18 ) hydrocarbon groups, such as (C1-C 18) Alkyl, (C3-C) 18 )cycloalkyl, (C3-C 12 )cycloalkyl-(C1-C6)alkylene, (C6-C 18 ) aryl or (C6-C 12 aryl-(C1-C6)alkylene. Preferably, any (C3-C6)alkylene group. 18 The cycloalkyl group is independently unsubstituted or substituted (C3-C4). 10 )cycloalkyl.

[0146] Aminotetrahydroquinoline ligands

[0147] Each R 91 To R 99 It is independently a hydrogen atom, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heterohydrocarbon group, (C1-C 40 The group is a hydrocarbon group (-O-) or a halogen atom, wherein the group is independently unsubstituted or substituted by one or more R groups. S Replace; where R S As defined above; R 100 Independently is (C1-C 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group, wherein the group is independently unsubstituted or substituted by one or more substituents R S Replace; where R S As defined above. R 100 The preferred aryl group is di-ortho-alkyl substituted, with 2,6-diisopropylphenyl being the most preferred.

[0148] The term "(C1-C)" in aminotetrahydroquinoline ligands 40 "(C1-C4) hydrocarbon group" refers to a hydrocarbon group with 1 to 40 carbon atoms. 40"Hydroalkyl group" refers to a hydrocarbon diemer with 1 to 40 carbon atoms, wherein each hydrocarbon group and hydrocarbon diemer is independently aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic, or a combination of two or more thereof; and each hydrocarbon group and hydrocarbon diemer is the same as or different from the other hydrocarbon group and hydrocarbon diemer, and is independently unsubstituted or substituted by one or more Rs.

[0149] In preferred cases, aminotetrahydroquinoline ligands (C1-C) 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 ) aryl or (C6-C 20 )aryl-(C1-C 20 )alkylene.

[0150] In a more preferred case, aminotetrahydroquinoline ligands (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 20 ) hydrocarbon groups, such as (C1-C 20 )alkyl, (C3-C 20 )cycloalkyl, (C3-C 10 )cycloalkyl-(C1-C 10 )alkylene, (C6-C 20 ) aryl or (C6-C 18 )aryl-(C1-C 10 )alkylene.

[0151] In a more preferred case, aminotetrahydroquinoline ligands (C1-C 40 The hydrocarbon group is independently unsubstituted or substituted (C1-C2). 18 ) hydrocarbon groups, such as (C1-C 18 )alkyl, (C3-C 18 )cycloalkyl, (C3-C 12 )cycloalkyl-(C1-C6)alkylene, (C6-C 18 ) aryl or (C6-C 12 aryl-(C1-C6)alkylene. Preferably, any (C3-C6)alkylene group. 18 The cycloalkyl group is independently unsubstituted or substituted (C3-C4). 10 )cycloalkyl.

[0152] The preferred ligands of the present invention are the BY compounds shown below.

[0153] The vinyl block copolymer is prepared with the monomers in the following proportions:

[0154] The molar ratio refers to the ratio of the moles of a component to the total moles of all components and can be expressed in terms of mole percent, mole parts per thousand, or mole parts per ten thousand.

[0155] The amount of the second monomer in the polymer is in the range of 2-30 mole percent, preferably 5-25 mole percent, more preferably 5-20 mole percent, and most preferably 5-15 mole percent, of the total amount of monomers in the polymer.

[0156] 2 mole percent to 30 mole percent, preferably 5 mole percent to 25 mole percent, more preferably 5 mole percent to 20 mole percent, and most preferably 5 mole percent to 15 mole percent.

[0157] The amount of the regulating monomer in the polymer is in the range of 0.1 parts per ten thousand moles to 5 mole percent, preferably 0.5 parts per thousand moles to 4 mole percent, more preferably 0.5 parts per thousand moles to 3 mole percent, and most preferably 0.8 parts per thousand moles to 3 mole percent.

[0158] The amount of the regulating monomer in the polymer is in the range of 0.1 parts per ten thousand moles to 5 mole percent, preferably 0.5 parts per thousand moles to 4 mole percent, more preferably 0.5 parts per thousand moles to 3 mole percent, and most preferably 0.8 parts per thousand moles to 3 mole percent.

[0159] In a preferred embodiment, the amount of the second monomer and the regulating monomer in the polymer is in the range of:

[0160] 2 mole percent to 30 mole percent of the second monomer and 0.1 parts per ten thousand moles to 5 mole percent of the regulating monomer;

[0161] 5 mole percent to 25 mole percent of the second monomer and 0.5 parts per thousand moles to 4 mole percent of the regulating monomer;

[0162] 5 mole percent to 20 mole percent of the second monomer and 0.5 parts per thousand moles to 3 mole percent of the regulating monomer;

[0163] 5 mole percent to 15 mole percent of the second monomer and 0.8 parts per thousand moles to 3 mole percent of the regulating monomer.

[0164] The block copolymer of the present application has a second monomer insertion rate of 2 mole percent to 30 mole percent, preferably a second monomer insertion rate of 5 mole percent to 25 mole percent, more preferably a second monomer insertion rate of 5 mole percent to 20 mole percent, and most preferably a second monomer insertion rate of 5 mole percent to 15 mole percent. The DSC melting point is 65°C to 130°C, preferably the DSC melting point is 90°C to 130°C, and more preferably the DSC melting point is 95°C to 130°C.

[0165] The present application also relates to a method for preparing a vinyl block copolymer using the above composition, comprising:

[0166] S1, adding ethylene, second monomer, regulating monomer and solvent into a reaction vessel to obtain a mixture;

[0167] S2, adding catalyst and cocatalyst mixed solvent into the mixture to carry out polymerization reaction to obtain a polymer;

[0168] S3, separating solvent and polymer after termination of polymerization

[0169] Preferably, the temperature is raised to the polymerization temperature between steps S1 and S2;

[0170] The term "solvent" refers to a liquid which is compatible with the process of the present application, preferably a non-protic liquid. Suitable solvents include aliphatic and aromatic hydrocarbons, especially branched hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, as well as higher alkanes and mixtures thereof, benzene and (C1-C5)alkyl-substituted benzenes such as toluene and xylenes, other alkylbenzenes, and mixtures of the above.

[0171] The present application also relates to a vinyl block copolymer, which is obtained by polymerization of the composition, the block copolymer having a second monomer insertion rate of 2-30 mol%, a melting point of 65-130°C, a number average molecular weight of 10 to 210 Kg / mol, a weight average molecular weight of 20-800 Kg / mol, and a molecular weight distribution of 1.2-8.

[0172] The block copolymer of the present application has a second monomer insertion rate of 2 mol% to 30 mol%, and a melting point of 65°C to 130°C as determined by DSC; preferably, the melting point is 90°C to 130°C as determined by DSC, and more preferably, the melting point is 95°C to 130°C as determined by DSC.

[0173] The present application proposes a new method for synthesizing olefin block copolymer based on a single catalyst and by adding a regulating monomer in one step. A complex formed by a group IVB metal with three substituents and a monoanionic ligand is used as the catalyst, and the selectivity of the catalyst to ethylene is regulated by the insertion of the regulating monomer. During the polymerization process, when the active center of the catalyst is inserted by the regulating monomer, the catalyst preferentially inserts ethylene to form a high-crystalline "hard segment"; when the catalyst is not inserted by the regulating monomer, the catalyst switches to a high-efficiency α-olefin copolymerization state to generate a "soft segment" rich in comonomer. This method does not require chain shuttling agents, stepwise feeding or adjustment of reaction conditions, and the hard / soft segment ratio can be regulated by adding the regulating monomer, and the melting point of the product can exceed 120°C. Compared with traditional systems, this method has the advantages of simplified operation, reduced cost and high safety. This description only provides a possible explanation for the generation of block polymers, and does not represent that the polymerization mechanism is completely in accordance with this description.

[0174] The catalyst composition of the present application uses a metal tri-substituted compound containing a ligand to catalyze the synthesis of polymers with different chain structures by using a regulating monomer, which can affect the metal center of the catalyst through its electronic effect or steric effect, change the chemical environment around the metal center, change the performance of the catalyst, and make the catalyst capable of catalyzing the synthesis of olefin multi-block copolymers. The regulating monomer (single-component monomer or multi-component monomer) of the present application has low cost, good effect, good controllability, and large selection range.

[0175] The amount of the regulating monomer (single-component monomer or multi-component monomer) monomer added is small, and it only acts as a regulator of the catalyst, and there is no polymerization fragment of a large amount of the regulating monomer (single-component monomer or multi-component monomer).

[0176] The composition of the present application has strong polymer regulating ability, and the second olefin monomer insertion rate can be adjusted by adjusting the concentration of the regulating monomer (single-component monomer or multi-component monomer).

[0177] Compared with the prior art, the present application does not need a chain transfer agent, uses a single catalyst, only needs to add the regulating monomer (single-component monomer or multi-component monomer) once in the system for polymerization, has a simple process, has low requirements for equipment, and does not need to upgrade the equipment and complex production process.

[0178] The polymer obtained by the composition of the present application has excellent performance, and can be used to produce olefin block polymers, which have excellent mechanical properties such as elasticity, and high melting point, thereby expanding the use temperature range.

[0179] The specific embodiments of the present application will be further described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0180] The drawings are part of the present application, which are used to provide a further understanding of the present application, and the schematic embodiments of the present application and their descriptions are used to explain the present application, but do not constitute an improper limitation on the present application. Obviously, the drawings described below are only some embodiments, and other drawings can be obtained by those skilled in the art without creative labor. In the drawings:

[0181] FIG. 1 is a GPC result graph of the sample prepared in Example 1;

[0182] FIG. 2 is a DSC result graph of the sample prepared in Example 1;

[0183] FIG. 3 is a TREF result graph of the sample prepared in Example 1;

[0184] FIG. 4 is a GPC result graph of the sample prepared in Example 3;

[0185] Figure 5 is a graph of DSC results for samples prepared in Example 3;

[0186] Figure 6 is a graph of TREF results for samples prepared in Example 3;

[0187] Figure 7 is a graph of GPC results for samples prepared in Example 49;

[0188] Figure 8 is a graph of DSC results for samples prepared in Example 49;

[0189] Figure 9 is a graph of GPC results for samples prepared in Example 50;

[0190] Figure 10 is a graph of DSC results for samples prepared in Example 50;

[0191] Figure 11 is a graph of GPC results for samples prepared in Example 51;

[0192] Figure 12 is a graph of DSC results for samples prepared in Example 51;

[0193] Figure 13 is a graph of GPC results for samples prepared in Example 52;

[0194] Figure 14 is a graph of DSC results for samples prepared in Example 52;

[0195] Figure 15 is a graph of GPC results for samples prepared in Example 53;

[0196] Figure 16 is a graph of DSC results for samples prepared in Example 53;

[0197] Figure 17 is a graph of GPC results for samples prepared in Example 54;

[0198] Figure 18 is a graph of DSC results for samples prepared in Example 54;

[0199] Figure 19 is a graph of GPC results for samples prepared in Example 55;

[0200] Figure 20 is a graph of DSC results for samples prepared in Example 55;

[0201] Figure 21 is a graph of GPC results for samples prepared in Example 56;

[0202] Figure 22 is a graph of DSC results for samples prepared in Example 56;

[0203] Figure 23 is a graph of stress-strain curve results for samples prepared in Example 85;

[0204] Figure 24 is a graph of dynamic mechanical analysis results for samples prepared in Example 89;

[0205] Figure 25 is a chart of the nuclear magnetic hydrogen spectrum results of a sample prepared in Example 85.

[0206] Figure 26 is a chart of the nuclear magnetic hydrogen spectrum results of a sample prepared in Example 86.

[0207] It should be noted that the drawings and detailed description are not intended to limit the scope of the present application in any way, but rather to illustrate the concept of the present application to those skilled in the art by reference to specific embodiments. DETAILED DESCRIPTION

[0208] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments will be described clearly and completely below with reference to the drawings in the embodiments of the present application. The following embodiments are used to illustrate the present application, but are not used to limit the scope of the present application.

[0209] Comparative Example 1 (Catalyst A)

[0210] Catalyst A:

[0211] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene were added to a polymerization bottle, which was sealed and transferred out of the glove box, connected to the polymerization line, and the polymerization line was replaced with nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, the polymerization bottle valve was opened and the polymerization bottle was degassed for 10 minutes using vacuum, ethylene was added to positive pressure (1 atm), the temperature was raised to the experimental temperature of 40℃, and the temperature was maintained for 5 minutes. In the glove box, 3.6 mg of catalyst pyridine amine hafnium catalyst A and 6.6 mg of cocatalyst tetra(pentafluorophenyl)borate were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed evenly, 5 mL of solution was drawn into a syringe, transferred out of the glove box, and injected into the polymerization bottle, polymerized for 1 minute, 5 mL of methanol was added to quench, and after drying, 2.58 g of polymer was obtained, with an activity of 30960 (kg / mol·M·h·atm), GPC showed Mn = 382 Kg / mol, Mw = 770 Kg / mol, and the molecular weight distribution was 2.0, high temperature nuclear magnetic resonance showed that the 1-octene insertion rate was 21.0%, and DSC testing showed no melting point. The melting point is similar to that of the random copolymer with 1-octene insertion rate, and the melting point limits the upper use temperature of the polymer.

[0212] Example 1

[0213] Catalyst B:

[0214] Cocatalyst: [HNMe2Ph][B(C6F5)4]

[0215] Procedure: In a glovebox, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization vial, which was sealed and transferred out of the glovebox, connected into the polymerization line, the polymerization line was purged with nitrogen to ensure no air, the polymerization vial was frozen at low temperature (-10°C to -70°C) for 10 minutes, the polymerization vial valve was opened and the vial was degassed with vacuum for 10 minutes, ethylene was charged to positive pressure (1 atm), the temperature was raised to the experimental temperature 40°C, and kept for 5 minutes. In the glovebox, catalyst pyridyl amido hafnium catalyst B 3.7 mg and cocatalyst N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate 10 mg were weighed into an 8 mL sample vial, 6 mL of toluene was added and mixed well, 5 mL of the solution was drawn into a syringe, transferred out of the glovebox, and injected into the polymerization vial, polymerized for 1 minute, 5 mL of methanol was added to quench, and after drying, 0.97 g of polymer was obtained, with an activity of 11640 (kg / mol M h atm), GPC showed Mn = 120 Kg / mol, Mw = 299 Kg / mol, and the molecular weight distribution was 2.5, high temperature NMR showed that the 1-octene insertion rate was 4.6%, and DSC test showed that the melting point was 121.0°C. The 1-octene insertion rate of this example is significantly higher than that of the comparative example, and the melting point of this comparative example is significantly higher than that of the comparative example, and the high melting point brings higher upper limit use temperature to the polymer.

[0216] Example 2

[0217] Procedure: In a glovebox, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization vial, which was sealed and transferred out of the glovebox, connected into the polymerization line, the polymerization line was purged with nitrogen to ensure no air, the polymerization vial was frozen at low temperature (-10°C to -70°C) for 10 minutes, the polymerization vial valve was opened and the vial was degassed with vacuum for 10 minutes, ethylene was charged to positive pressure (1 atm), the temperature was raised to the experimental temperature 40°C, and kept for 5 minutes. In the glovebox, catalyst pyridyl amido hafnium catalyst C 7.6 mg and cocatalyst N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate 10 mg were weighed into an 8 mL sample vial, 6 mL of toluene was added and mixed well, 5 mL of the solution was drawn into a syringe, transferred out of the glovebox, and injected into the polymerization vial, polymerized for 1 minute, 5 mL of methanol was added to quench, and after drying, 1.22 g of polymer was obtained, with an activity of 7320 (kg / mol h atm), GPC showed Mn = 44 Kg / mol, Mw = 148 Kg / mol, and the molecular weight distribution was 3.4, high temperature NMR showed that the 1-octene insertion rate was 11.7%, and DSC test showed that the melting point was 98.2°C. The 1-octene insertion rate of this example is significantly higher than that of the comparative example, and the melting point of this comparative example is significantly higher than that of the comparative example, and the high melting point brings higher upper limit use temperature to the polymer.

[0218] Example 3

[0219] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, which was sealed and then transferred out of the glove box, connected into the polymerization line, the polymerization line was purged with nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10°C to -70°C) for 10 minutes, the valve of the polymerization bottle was opened and the bottle was degassed with vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40°C and kept for 5 minutes. In the glove box, the catalyst FI catalyst D 8.7 mg and the cocatalyst N,N-dimethyl anilinium tetrakis(pentafluorophenyl)borate 10 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed well, 5 mL of the solution was drawn into a syringe, transferred out of the glove box, and injected into the polymerization bottle, polymerized for 1 minute, 5 mL of methanol was added to quench, and after drying, 0.71 g of polymer was obtained, with an activity of 4260 (kg / mol M h atm), GPC showed Mn = 33 Kg / mol, Mw = 86 Kg / mol, and the molecular weight distribution was 2.6, high temperature NMR showed that the 1-octene insertion rate was 11.2%, and DSC test showed that the melting point was 119.37°C. The 1-octene insertion rate of this example is similar to that of the comparative example, but the melting point is significantly higher than that of the comparative example, and the high melting point brings a higher upper limit use temperature to the polymer.

[0220] Example 4

[0221] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, which was sealed and then transferred out of the glove box, connected into the polymerization line, the polymerization line was purged with nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10°C to -70°C) for 10 minutes, the valve of the polymerization bottle was opened and the bottle was degassed with vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40°C and kept for 5 minutes. In the glove box, the catalyst FI catalyst D 8.7 mg and the cocatalyst N,N-dimethyl anilinium tetrakis(pentafluorophenyl)borate 10 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed well, 5 mL of the solution was drawn into a syringe, transferred out of the glove box, and injected into the polymerization bottle, polymerized for 1 minute, 5 mL of methanol was added to quench, and after drying, 0.71 g of polymer was obtained, with an activity of 4260 (kg / mol M h atm), GPC showed Mn = 33 Kg / mol, Mw = 86 Kg / mol, and the molecular weight distribution was 2.6, high temperature NMR showed that the 1-octene insertion rate was 11.2%, and DSC test showed that the melting point was 119.37°C. The 1-octene insertion rate of this example is similar to that of the comparative example, but the melting point is significantly higher than that of the comparative example, and the high melting point brings a higher upper limit use temperature to the polymer.

[0222] Example 5

[0223] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, which was sealed and then transferred out of the glove box, connected into the polymerization line, and the polymerization line was replaced by nitrogen to ensure no air. The polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, and then the valve of the polymerization bottle was opened and the bottle was degassed by vacuum for 10 minutes. Ethylene was added to positive pressure (1 atm), and the temperature was raised to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, the pyridyl amido hafnium catalyst F 10 mg and the cocatalyst N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate 10 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of the solution was extracted by a syringe, and then transferred out of the glove box and injected into the polymerization bottle. The polymerization was carried out for 1 minute, 5 mL of methanol was added to quench the reaction, and the polymer was dried to obtain 0.94 g of polymer with an activity of 5640 (kg / mol·M·h·atm). GPC measurement showed that Mn was 51 Kg / mol, Mw was 72 Kg / mol, and the molecular weight distribution was 1.4. High temperature NMR measurement showed that the 1-octene insertion rate was 16.0%, and DSC test showed that the melting point was 66.8℃.

[0224] Example 6

[0225] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, which was sealed and then transferred out of the glove box, connected into the polymerization line, and the polymerization line was replaced by nitrogen to ensure no air. The polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, and then the valve of the polymerization bottle was opened and the bottle was degassed by vacuum for 10 minutes. Ethylene was added to positive pressure (1 atm), and the temperature was raised to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, the pyridyl amido hafnium catalyst F 10 mg and the cocatalyst N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate 10 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of the solution was extracted by a syringe, and then transferred out of the glove box and injected into the polymerization bottle. The polymerization was carried out for 1 minute, 5 mL of methanol was added to quench the reaction, and the polymer was dried to obtain 0.94 g of polymer with an activity of 5640 (kg / mol·M·h·atm). GPC measurement showed that Mn was 51 Kg / mol, Mw was 72 Kg / mol, and the molecular weight distribution was 1.4. High temperature NMR measurement showed that the 1-octene insertion rate was 16.0%, and DSC test showed that the melting point was 66.8℃.

[0226] Example 7

[0227] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, after sealing the cap, it was transferred out of the glove box, connected into the polymerization line, the polymerization line was replaced by vacuum and nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, the valve of the polymerization bottle was opened and the polymerization bottle was degassed by vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, 7.3 mg of pyridyl amido hafnium catalyst B and 13.2 mg of co-catalyst tetra(pentafluorophenyl)borate were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of solution was extracted using a syringe, transferred out of the glove box, and injected into the polymerization bottle, polymerized for 1 minute, 5 mL of methanol was added to quench, and after drying, 1.66 g of polymer was obtained, with an activity of 9960 (kg / mol·M·h·atm), GPC showed Mn = 32 Kg / mol, Mw = 139 Kg / mol, and the molecular weight distribution was 4.3, high temperature NMR showed that the 1-octene insertion rate was 18.9%, and DSC test showed that the melting point was 101.3℃.

[0228] Example 8

[0229] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, after sealing the cap, it was transferred out of the glove box, connected into the polymerization line, the polymerization line was replaced by vacuum and nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, the valve of the polymerization bottle was opened and the polymerization bottle was degassed by vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, 7.3 mg of pyridyl amido hafnium catalyst B and 13.2 mg of co-catalyst tetra(pentafluorophenyl)borate were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of solution was extracted using a syringe, transferred out of the glove box, and injected into the polymerization bottle, polymerized for 1 minute, 5 mL of methanol was added to quench, and after drying, 1.66 g of polymer was obtained, with an activity of 9960 (kg / mol·M·h·atm), GPC showed Mn = 32 Kg / mol, Mw = 139 Kg / mol, and the molecular weight distribution was 4.3, high temperature NMR showed that the 1-octene insertion rate was 18.9%, and DSC test showed that the melting point was 101.3℃.

[0230] Example 9

[0231] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, which was sealed and then transferred out of the glove box, connected into the polymerization line, the polymerization line was replaced by vacuum and nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, the valve of the polymerization bottle was opened and the polymerization bottle was degassed by vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, pyridyl amido hafnium catalyst B 7.3 mg and co-catalyst tris(pentafluorophenyl)borane 6.1 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of the solution was extracted using a syringe, transferred out of the glove box, and injected into the polymerization bottle, polymerized for 5 minutes, 5 mL of a stearic acid toluene solution was added to quench, and after drying, 0.51 g of polymer was obtained, with an activity of 3060 (kg / mol·M·h·atm), GPC showed Mn = 90 Kg / mol, Mw = 310 Kg / mol, and the molecular weight distribution was 3.5, high temperature NMR showed that the 1-octene insertion rate was 13.6%, and DSC test showed that the melting point was 117.2℃.

[0232] Example 10

[0233] Procedure: In a glove box, 42 mL of toluene, 2.24 g of 1-octene, 52 mg of styrene were added into a polymerization bottle, which was sealed and then transferred out of the glove box, connected into the polymerization line, the polymerization line was replaced by vacuum and nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, the valve of the polymerization bottle was opened and the polymerization bottle was degassed by vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, pyridyl amido hafnium catalyst B 7.3 mg and co-catalyst tris(pentafluorophenyl)borane 6.1 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of the solution was extracted using a syringe, transferred out of the glove box, and injected into the polymerization bottle, polymerized for 5 minutes, 5 mL of a stearic acid toluene solution was added to quench, and after drying, 0.51 g of polymer was obtained, with an activity of 3060 (kg / mol·M·h·atm), GPC showed Mn = 90 Kg / mol, Mw = 310 Kg / mol, and the molecular weight distribution was 3.5, high temperature NMR showed that the 1-octene insertion rate was 13.6%, and DSC test showed that the melting point was 117.2℃.

[0234] Example 11

[0235] Procedure: 42 mL of toluene, 2.24 g of 1-octene, 41 mg of 1,4-cyclohexadiene were added into a polymerization bottle in a glove box, after sealing the cap, it was transferred out of the glove box and connected into the polymerization line, the polymerization line was replaced by vacuum and nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, the valve of the polymerization bottle was opened and the polymerization bottle was degassed by vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, pyridyl amido hafnium catalyst B 7.3 mg and cocatalyst N,N-dimethyl anilinium tetrakis(pentafluorophenyl)borate 10 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of the solution was extracted by a syringe, transferred out of the glove box and injected into the polymerization bottle, polymerized for 1 minute, 5 mL of methanol was added for quenching, after drying, 1.05 g of polymer was obtained, the activity was 6300 (kg / mol·M·h·atm), GPC showed that Mn was 27 Kg / mol, Mw was 85 Kg / mol, the molecular weight distribution was 3.1, high temperature NMR showed that the 1-octene insertion rate was 19.6%, and DSC test showed that the melting point was 104.1℃.

[0236] Example 12

[0237] Procedure: 42 mL of toluene, 2.24 g of 1-octene, 41 mg of 1,4-cyclohexadiene were added into a polymerization bottle in a glove box, after sealing the cap, it was transferred out of the glove box and connected into the polymerization line, the polymerization line was replaced by vacuum and nitrogen to ensure no air, the polymerization bottle was frozen at low temperature (-10℃ to -70℃) for 10 minutes, the valve of the polymerization bottle was opened and the polymerization bottle was degassed by vacuum for 10 minutes, ethylene was added to positive pressure (1 atm), the temperature was increased to the experimental temperature 40℃ and kept for 5 minutes. In the glove box, pyridyl amido hafnium catalyst B 7.3 mg and cocatalyst N,N-dimethyl anilinium tetrakis(pentafluorophenyl)borate 10 mg were weighed into an 8 mL sample bottle, 6 mL of toluene was added and mixed uniformly, 5 mL of the solution was extracted by a syringe, transferred out of the glove box and injected into the polymerization bottle, polymerized for 1 minute, 5 mL of methanol was added for quenching, after drying, 1.05 g of polymer was obtained, the activity was 6300 (kg / mol·M·h·atm), GPC showed that Mn was 27 Kg / mol, Mw was 85 Kg / mol, the molecular weight distribution was 3.1, high temperature NMR showed that the 1-octene insertion rate was 19.6%, and DSC test showed that the melting point was 104.1℃.

[0238] In the above Comparative Example 1 and Examples 1-12, the units of Mn and Mw are Kg / mol

[0239] Examples 13-90

[0240] The procedure and conditions are the same as Examples 1-12. For details, refer to Example 12.

[0241] For comparison, the main components and conditions of Examples 1-90 are listed in Table 1 below.

[0242] Table 1

[0243] The detection results of Examples 1-90 are shown in Table 2 below.

[0244] Table 2

[0245] The results show that the addition of the regulating monomer (the third monomer) can effectively improve the melting point of the polymer and expand the use temperature of the polymer.

[0246] From the CEF data, it can be seen that the components flowed out at high elution temperature contain a relatively high 1-octene insertion rate, which is significantly higher than the 1-octene insertion rate of the random copolymer at the same elution temperature.

[0247] It should be noted that in the present application, the preparation method of each catalyst is as follows:

[0248] 1. Preparation example of catalyst E

[0249] Pyridine amine ligand 1 (0.19 g, 0.5 mmol, 1.0 eq) and Hf(CH2TMS)4 (0.26 g, 0.5 mmol, 1.0 eq.) were each prepared into a pentane solution (10 mL) and mixed. After stirring for 1 min, all volatiles were removed under vacuum and concentrated, and recrystallized at low temperature. The product E was a white solid, which was dried under vacuum (0.24 g, yield 59%).

[0250] 1H NMR (600 MHz, C6D6, 25 °C) δ 8.61 (d, J = 4.8 Hz, 1H), 7.16-7.17 (m, 1H), 7.05-7.08 (m, 2H), 7.00 - 6.95 (m, 3H), 6.91-6.93 (m, 1H), 6.66 (td, J = 7.7, 1.6 Hz, 1H), 6.56 (d, J = 8.0 Hz, 1H), 6.48 (t, J = 5.9 Hz, 1H), 6.34 (s, 1H), 3.66 (hept, J = 6.9 Hz, 1H), 3.51 (hept, J = 6.8 Hz, 1H), 2.78 (hept, J = 6.9 Hz, 1H), 1.44-1.47 (m, 6H), 1.40 (d, J = 6.8 Hz, 3H), 1.10 (d, J = 6.9 Hz, 3H), 0.60 (d, J = 6.7 Hz, 3H), 0.57 - 0.46 (m, 6H), 0.23 (s, 27H), 0.15 (d, J = 6.6 Hz, 3H)

[0251] 2. Catalyst F Preparation Example

[0252] Pyridyl amine ligand 1 (0.19 g, 0.5 mmol, 1.0 eq) and Hf(Bn)4(0.27 g, 0.5 mmol, 1.0 eq.) were each dissolved in toluene (10 mL) and mixed at room temperature. After stirring for 6 h, all volatiles were removed under vacuum and the resulting solid was washed with n-pentane (3 x 2 mL). The product F was then collected and dried under vacuum. Yellow solid, 0.32 g, 77% yield, 97.1% purity.

[0253] 1H NMR (600 MHz, C6D6, 25 °C) δ 7.44 (d, J = 5.6 Hz, 1H), 7.19-7.16 (m, 2H), 7.16–7.09 (m, 7H), 7.04 (dd, J = 7.5, 1.9 Hz, 1H), 6.97–6.92 (m, 2H), 6.89–6.79 (m, 9H), 6.55 (td, J = 7.7, 1.6 Hz, 1H), 6.38 (d, J = 8.0 Hz, 1H), 6.32 (s, 1H), 6.29 (dd, J = 8.0, 1.3 Hz, 1H), 6.16 (t, J = 7.2 Hz, 1H), 3.59 (hept, J = 6.7 Hz, 1H), 3.34 (hept, J = 6.8 Hz, 1H), 2.80 (hept, J = 6.9 Hz, 1H), 2.70-2.18 (m, 6H), 1.45 (d, J = 6.8 Hz, 3H), 1.40 (d, J = 6.8 Hz, 3H), 1.32 (d, J = 6.7 Hz, 3H), 1.09 (d, J = 7.0 Hz, 3H), 0.59 (d, J = 6.7 Hz, 3H), 0.07 (d, J = 6.6 Hz, 3H).

[0254] 3. Catalyst G Preparation Example

[0255] Pyridyl amine ligand 1 (0.19 g, 0.5 mmol, 1.0 eq) and Zr(Bn)4(0.27 g, 0.5 mmol, 1.0 eq.) were each dissolved in toluene (10 mL) and mixed at room temperature. After stirring for 6 h, all volatiles were removed under vacuum and the resulting solid was washed with n-pentane (3 x 2 mL). The product F was then collected and dried under vacuum. Yellow solid, 0.25 g, 66% yield.

[0256] 1H NMR (600 MHz, Benzene-d6) δ 7.27 (d, J = 5.7 Hz, 1H), 7.19 (d, J = 7.7 Hz, 1H), 7.15 - 7.09 (m, 8H), 7.05 (t, J = 7.1 Hz, 2H), 7.01 (d, J = 7.6 Hz, 1H), 6.98 (d, J = 6.4 Hz, 1H), 6.95 (d, J = 6.9 Hz, 1H), 6.89 (t, J = 7.4 Hz, 3H), 6.84 (d, J = 7.7 Hz, 6H), 6.58 - 6.54 (m, 1H), 6.43 (m, 2H), 6.32 (s, 1H), 6.17 (t, J = 6.5 Hz, 1H), 3.59 (hept, J = 6.8 Hz, 1H), 3.45 (hept, J = 6.7 Hz, 1H), 2.84 (hept, J = 6.8 Hz, 1H), 2.68 - 2.56 (m, 6H), 1.42 (dd, J = 6.8, 5.4 Hz, 6H), 1.31 (d, J = 6.7 Hz, 3H), 1.10 (d, J = 6.9 Hz, 3H), 0.61 (d, J = 6.7 Hz, 3H), 0.11 (d, J = 6.6 Hz, 3H).

[0257] 4. Catalyst H Preparation Example

[0258] Class FI Ligand 5 (0.28 g, 1 mmol, 1.0 eq) and Hf(CH2TMS)4(0.53 g, 1 mmol, 1.0 eq.) were each dissolved in pentane (10 mL) and mixed at room temperature. After stirring for 1 min, all volatiles were removed under vacuum, concentrated under vacuum, and recrystallized at -30 °C. The product was a white solid, 0.42 g, 59% yield.

[0259] 1H NMR (600 MHz, Benzene-d6) δ 8.09 (d, J = 2.6 Hz, 1H), 7.78 (d, J = 2.6 Hz, 1H), 3.72 - 3.56 (m, 4H), 1.67 (s, 9H), 1.21 (s, 9H), 0.58 (s, 6H), 0.20 (s, 27H).

[0260] 5. Catalyst I Preparation Example

[0261] Class FI Ligand 5 (0.28 g, 1 mmol, 1.0 eq) and Zr(CH2TMS)4(0.44 g, 1 mmol, 1.0 eq.) were each dissolved in pentane (10 mL) and mixed at room temperature. After stirring for 1 min, all volatiles were removed under vacuum, concentrated under vacuum, and recrystallized at -30 °C. The product was a white solid, 0.32 g, 51% yield.

[0262] 1H NMR (600 MHz, Benzene-d6) δ 8.13 - 8.06 (m, 1H), 7.76 (q, J = 2.4 Hz, 1H), 3.71 - 3.56 (m, 4H), 1.68 (s, 9H), 1.22 (s, 9H), 1.15 (s, 6H), 0.20 (s, 27H).

[0263] 6. Catalyst J preparation example

[0264] FI class ligand 7 (0.29 g, 1 mmol, 1.0 eq) and Zr(CH2TMS)4(0.53 g, 1 mmol, 1.0 eq.) were each dissolved in pentane (10 mL) and mixed at room temperature. After stirring for 1 min, all volatiles were removed under vacuum, concentrated under vacuum, and recrystallized at -30 °C to yield the product as a white solid, 0.36 g, 56% yield.1H NMR (600 MHz, Benzene-d6) δ 8.10 (d, J = 2.5 Hz, 1H), 7.77 (d, J = 2.6 Hz, 1H), 4.32 (dt, J = 8.9, 6.3 Hz, 1H), 3.74 (t, J = 8.7 Hz, 1H), 3.34 (dd, J = 8.4, 5.7 Hz, 1H), 1.68 (s, 9H), 1.29 - 1.22 (m, 15H), 0.98 (d, J = 6.6 Hz, 3H), 0.24 (s, 27H).

[0265] 7. The remaining catalysts were synthesized according to the literature, for example:

[0266] Catalyst A reference: K. A. Frazier, R. D. Froese, Y. He, J. Klosin, C. N. Theriault, P. C. Vosejpka, Z. Zhou, K. A. Abboud, Pyridylamido Hafnium and Zirconium Complexes: Synthesis, Dynamic Behavior, and Ethylene / 1-Octene and Propylene Polymerization Reactions. Organometallics 30, 3318-3329 (2011). doi:10.1021 / om200167h

[0267] Catalyst B-C reference: J. Zhang, A. H. Mason, A. Motta, L. G. Cesar, Y. Kratish, T. L. Lohr, J. T. Miller, Y. Gao, T. J. Marks, Surface vs Homogeneous Organo-Hafnium Catalyst Ion-Pairing and Ligand Effects on Ethylene Homo- and Copolymerizations. ACS Catal. 11, 3239-3250 (2021). doi:10.1021 / acscatal.0c04678

[0268] Catalyst D reference: C. Meng, L. Lu, C. Guo, D. Zhao, Y. Wang, Mono(phenoxy-imine) Group 4 Trialkyl Complexes: A Family of Olefin Polymerization Catalysts. Macromolecules 57, 2697-2705 (2024). doi:10.1021 / acs.macromol.4c00048

[0269] Catalyst K-N reference: B. Han, Y. Liu, C. Feng, S. Liu, Z. Li, Development of Group 4 Metal Complexes Bearing Fused-Ring Amido-Trihydroquinoline Ligands with Improved High-Temperature Catalytic Performance toward Olefin (Co)polymerization. Organometallics 40, 242-252 (2021). doi:10.1021 / acs.organomet.0c00739

[0270] Catalyst O-Q reference: P. P. Fontaine, S. Ueligger, J. Klosin, A. Hazari, J. Daller, J. Hou, Development of Improved Amidoquinoline Polyolefin Catalysts with Ultrahigh Molecular Weight Capacity. Organometallics 34, 1354-1363 (2015). doi:10.1021 / acs.organomet.5b00053

[0271] Catalyst R-U reference: P. P. Fontaine, R. Figueroa, S. D. McCann, D. Mort, J. Klosin, Synthesis and Scale-up of Imino-Enamido Hafnium and Zirconium Olefin Polymerization Catalysts. Organometallics 32, 2963-2972 (2013). doi:10.1021 / om400189w

[0272] Catalyst V reference: Yang, X. H.; Liu, C. R.; Wang, C.; Sun, X. L.; Guo, Y. H.; Wang, X. K.; Wang, Z.; Xie, Z.; Tang, Y. [O-NSR]TiCl3-Catalyzed Copolymerization of Ethylene with Functionalized Olefins. Angew. Chem. Int. Ed. 2009, 48, 8099-8102.

[0273] Catalyst W reference: Zhang, J.; Mason, A. H.; Wang, Y.; Motta, A.; Kobayashi, T.; Pruski, M.; Gao, Y.; Marks, T. J. Beyond the Active Site. Cp*ZrMe3 / Sulfated Alumina-Catalyzed Olefin Polymerization Tacticity via Catalyst…Surface Ion-Pairing. ChemCatChem. 2021, 13, 2564-2569.

[0274] Catalyst X reference: Fang, X.-Y.; Qin, L.; Liu, J.; Shi, H.; Sun, X.-L.; Kuang, X.; Gao, Y.; Tang, Y. Synthesis and characterization of oxazoline-amine zirconium complexes for ethylene homo- and co-polymerization catalysis. Molecular Catalysis. 2023, 541, 113108.

[0275] Catalyst Y reference: patent WO2020243241A1

[0276] The above description is only the preferred embodiment of the present application, not any form of limitation on the present application, although the present application has been disclosed as above with the preferred embodiment, however, it is not intended to limit the present application, any skilled person familiar with the present application can make some changes or modifications within the scope of the technical scheme of the present application by using the above-mentioned technical content as a hint to make equivalent embodiments with equivalent changes, but as long as it does not deviate from the content of the technical scheme of the present application, any simple modification, equivalent change and modification made on the above embodiments according to the technical essence of the present application, all still belong to the scope of the present application.

Claims

1. A composition for the preparation of an ethylene-based block copolymer, comprising: first monomer ethylene, second monomer C3-C 20 alpha-olefin and at least one modifying monomer; said modifying monomer is an olefin, substituted olefin, or styrene / styrene derivative having a C-atom number greater than 3; said second monomer and modifying monomer are different in the same composition; said composition yields an ethylene-based block copolymer under catalysis of a procatalyst and a cocatalyst; said procatalyst is a complex of a trisubstituted Group IVB metal and a monoanionic ligand; said cocatalyst is selected from the group consisting of alkylaluminum, polymeric or oligomeric aluminoxane (also known as alkoxyl aluminum), neutral Lewis acid, and non-polymeric, non-coordinating ionic form compound.

2. The composition for preparing a vinyl block copolymer according to claim 1, wherein the main catalyst is a compound of general formula (I); wherein M is a Group IVB metal, R 1 —R 3 are each independently selected from the group consisting of halogen atoms, C1-C 20 hydrocarbon groups, C1-C 20 amine groups, C1-C 20 silane groups, (C6-C 40 ) aryl groups, the hydrogen atoms in the non-halogen atom groups being independently unsubstituted or substituted by one or more substituents R S ; and Each R s Independently, it is a halogen atom, polyfluorine, perfluorine, unsubstituted (C1-C) 18 ) hydrocarbon group, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, RO-, RS-, RS(O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)-, RC(O)N(R)- or R2NC(O)-, where each R is independently unsubstituted (C1-C 18 ) hydrocarbon group; L is a ligand selected from the group consisting of phenoxyimine ligand, phenoxyoxazoline ligand, pyridyl amido ligand, imine amido ligand, amido quinoline ligand, amido tetrahydroquinoline ligand; said second monomer is present in the block copolymer in an amount in the range of: 2 mol% to 30 mol%, preferably 5 mol% to 25 mol%, more preferably 5 mol% to 20 mol%, and most preferably 5 mol% to 15 mol% of the total amount of monomers in the polymer; said modifying monomer is present in the block copolymer in an amount in the range of: 0.1 molar percent to 5 mol%, preferably 0.5 molar percent to 4 mol%, more preferably 0.5 molar percent to 3 mol%, and most preferably 0.8 molar percent to 3 mol% of the total amount of monomers in the polymer.

3. The composition for the preparation of an ethylene-based block copolymer according to claim 1 or 2, wherein said modifying monomer is selected from the group consisting of: C3-C 20 terminal or internal olefin; or C4-C 20 a conjugated diene, which is a linear conjugated diene, a cyclic conjugated diene or a branched conjugated diene; or C5-C 20 non-conjugated diene; or C8-C 20 styrene and styrene derivatives, the olefins or styrene and styrene derivatives being independently unsubstituted or substituted by one or more substituents R S substituted.

4. A composition for the preparation of an ethylene block copolymer according to claim 3, said modifying monomer being a C4-C 20 conjugated diene, said C4-C 20 conjugated diene being selected from a linear conjugated diene or a cyclic conjugated diene or a branched conjugated diene; or said modifying monomer being selected from styrene or a C8-C 20 styrene derivative, said olefin or styrene and styrene derivative independently being unsubstituted or substituted by one or more substituents R S substituents; Preferably, the monomers are C4-C 10 conjugated dienes or C6-C 10 conjugated cyclic dienes; or C5-C 10 conjugated branched dienes; or styrene or C8-C 10 styrene derivatives, the olefins or styrenes and styrene derivatives being independently unsubstituted or substituted by one or more substituents R S substituted.

5. The composition for the preparation of an ethylene-based block copolymer according to claim 3, wherein said modifying monomer is selected from the group consisting of 1,3-butadiene, 1,3-hexadiene, cyclohexene, 1,4-cyclohexadiene, isoprene, 2,3-dimethyl-1,3-butadiene, norbornene, 4-phenyl-1-butene, dimethylphenylvinylsilane, 4-vinyl-1-cyclohexene, 1,7-octadiene, 1,9-decadiene, N,N-diphenylpentenamine, N,N-diphenylhexenamine, N,N-diphenyloctenamine, allylbenzene, trimethylvinylsilane, bismethylphenylvinylsilane, 2,3-dimethyl-1-butene, (S)-1-methyl-4-(propan-1-en-2-yl)cyclohex-1-ene, 3,3-dimethyl-1-butene, 5-vinylbicyclo[2.2.1]hept-2-ene, isobutylene, myrcene, ocimene, styrene, 2-methyl-vinylbenzene, α-methylstyrene, 2,4,6-trimethylstyrene, 1,2-dihydronaphthalene, 1,3-cyclohexadiene, or 1,3-cyclooctadiene, triisopropyl(4-penten-1-yloxy)silane, bismethyl-tert-butyl(4-penten-1-yloxy)silane, triphenylvinylsilane, or phenylsilane. Preferably, said modifying monomer is selected from the group consisting of styrene and 2-methyl-vinylbenzene.

6. A composition for the preparation of ethylene block copolymers according to any one of claims 1 to 5, wherein in the catalyst R 1 — R 3 each independently is selected from the group consisting of halogen atoms, C1-C 15 hydrocarbon radicals, C1-C 15 amine radicals, C1-C 15 silane radicals, (C6-C 20 ) aryl radicals, said radicals being independently unsubstituted or substituted by one or more substituents R S ; wherein R S are as defined before; L is a ligand selected from the group consisting of: Phenoxyimine ligands Phenoxyoxazoline ligands R 11 -R 18 may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these groups can be combined with each other to form a ring; the groups are independently unsubstituted or substituted with one or more substituents R S ; the number of carbon atoms in R 11 -R 18 is less than 40; R 16 is most preferably a tertiary carbon-containing group such as a tert-butyl group, an adamantyl group; or Pyridinamine ligands pyridinylamino ligand R 21 independently C 1-40 hydrocarbyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroalkyl, heterocycloalkyl, heteroaryl, heteroaralkyl, heteroalkaryl, silyl, and inertly substituted derivatives thereof, said groups being independently unsubstituted or substituted with one or more substituents R 1-40 independently C S substituted; preferably di-ortho-alkyl substituted aryl, most preferably 2,6-diisopropylphenyl; R 22 -R 23 independently in each occurrence is hydrogen or C 1-30 hydrocarbyl, aryl, aralkyl, heteroalkyl, heteroaryl, or heteroaralkyl, provided that at least one of R 22 , R 23 is C 10-30 aryl or heteroaryl; said groups are independently unsubstituted or substituted by one or more substituents R S ; most preferably one of R 22 , R 23 is hydrogen and the other is phenyl, pyridyl, naphthyl or anthracyl substituted in one or both ortho positions (where possible) by isopropyl, t-butyl, cyclopentyl, or cyclohexyl; R 24 -R 26 is hydrogen, halogen, or C 1-20 hydrocarbyl, aryl, aralkyl, cycloalkyl, or silyl, or a substituted alkyl, aryl, aralkyl, cycloalkyl, or silyl of up to 20 atoms not counting hydrogen, or adjacent R 14 -R 16 groups can be joined together thereby forming a fused ring derivative; preferably hydrogen or C 1-4 alkyl; R 27 is hydrogen, halogen, C 1-40 hydrocarbyl, cycloalkyl, heteroalkyl, heterocycloalkyl, silyl, and groups comprising C 1-40 atoms other than hydrogen or at least one ortho position is substituted with R S substituted C 8-40 aryl or heteroaryl, which groups are independently unsubstituted or substituted with one or more substituents R S ; preferably hydrogen, C 1-10 alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, silyl; or One of the imine amine ligands: wherein each R 31 independently is H, (C1-C 40 )alkyl or (C1-C 40 )heteroalkyl; each R 32 independently is (C1-C 40 )alkyl, (C1-C 40 )alkylO-, (C1-C 40 )alkylS-, (C1-C 40 )alkylS(O)-, (C1-C 40 )alkylS(O)2-, ((C1-C 40 )alkyl)2N-, ((C1-C 40 )alkyl)2P- or (C1-C 40 )heteroalkyl; each R 33 independently is H, (C1-C 40 )alkyl or (C1-C 40 )heteroalkyl; said groups are independently unsubstituted or substituted with one or more substituents R S ; R 31 is preferably di-ortho alkyl substituted aryl, most preferably 2,6-diisopropylphenyl; each R 41 independently H, (C1-C 40 )alkyl or (C1-C 40 )heteroalkyl; said groups are independently unsubstituted or substituted with one or more substituents R S ; R 41 is preferably di-ortho alkyl substituted aryl, most preferably 2,6-diisopropylphenyl; each R 42 , R 43 , R 44、 R 46、 R 47 is independently (C1-C 40 )alkyl, (C1-C 40 )alkylO-, (C1-C 40 )alkylS-, (C1-C 40 )alkylS(O)-, (C1-C 40 )alkylS(O)2-, ((C1-C 40 )alkyl)2N-, ((C1-C 40 )alkyl)2P- or (C1-C 40 )heteroalkyl; or R 44 As defined above and R 42 With R 43 or R 46 With R 47 The passive form (R) 23 The bimolecular substitution (i.e., together forming the bimolecular): R 2A R 3A Independently is (C1-C 40 ) hydrocarbon group, (C1-C 40 )hydrocarbon group O-, (C1-C 40 ) hydrocarbon group S-, (C1-C 40 )hydrocarbon group S(O)-, (C1-C 40 )hydrocarbon group S(O)2-, ((C1-C 40 )hydrocarbon group)2N-、((C1-C 40 )hydrocarbon group)2P- or (C1-C 40 ( ) heteroalkyl group; the group is independently unsubstituted or substituted by one or more substituents R S Replace; where R S As defined above; each R 45 independently H, (C1-C 40 )alkyl or (C1-C 40 )heteroalkyl; said groups are independently unsubstituted or substituted with one or more substituents R S as previously defined; and n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. S as previously defined; and n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. each R 51 , R 61 , R 71 , independently is H, (C1-C 40 )hydrocarbyl or (C1-C 40 )heterohydrocarbyl; each R 52 , R 62 , R 72 , R 53 , R 63 , R 73 independently is (C1-C 40 )hydrocarbyl, (C1-C 40 )hydrocarbylO-, (C1-C 40 )hydrocarbylS-, (C1-C 40 )hydrocarbylS(O)-, (C1-C 40 )hydrocarbylS(O)2-, ((C1-C 40 )hydrocarbyl)2N-, ((C1-C 40 )hydrocarbyl)2P- or (C1-C 40 )heterohydrocarbyl; said groups independently are unsubstituted or substituted with one or more substituents R S ; wherein R S is as previously defined; each T independently is C(T1)2, O, S, S(O), S(O)2, N(R n ), Si(R e )2, or P(R p ), wherein each T1 independently is H or C1-C 20 hydrocarbyl, and each R N , R e and R p independently is C1-C 20 hydrocarbyl, said groups independently are unsubstituted or substituted with one or more substituents R S ; R 51 , R 61 , R 71 is preferably di-ortho alkyl substituted aryl, most preferably 2,6-diisopropylphenyl; or Aminoquinoline-based ligands Each R 81 To R 87 It is independently a hydrogen atom, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heterohydrocarbon group, (C1-C 40 ) hydrocarbon group -O- or halogen atom; R 87 Independently is (C1-C 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group, wherein the group is independently unsubstituted or substituted by one or more substituents R S Replace; R 87 Preferred aryl groups are di- or o-alkyl substituted, with 2,6-diisopropylphenyl being the most preferred; or Amino tetrahydroquinoline ligands Each R 91 To R 99 It is independently a hydrogen atom, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heterohydrocarbon group, (C1-C 40 The group is a hydrocarbon group (-O-) or a halogen atom, wherein the group is independently unsubstituted or substituted by one or more R groups. S Replace; where R S As defined above; R 100 Independently is (C1-C 40 ) hydrocarbon group or (C1-C 40 ( ) heteroalkyl group, wherein the group is independently unsubstituted or substituted by one or more substituents R S Replace; R 100 The preferred aryl group is di-ortho-alkyl substituted, with 2,6-diisopropylphenyl being the most preferred.

7. The composition for the preparation of an ethylene-based block copolymer according to claim 5, wherein said metal in said procatalyst is selected from the group consisting of titanium, zirconium, and hafnium. The ligand is selected from the group consisting of monoanionic ligands, preferably phenoxyimine ligands, phenoxyoxazoline ligands, pyridylamine ligands, imine amine ligands, amine quinoline ligands or amine tetrahydroquinoline ligands; The co-catalyst is selected from the group consisting of alkylaluminums, polymeric or oligomeric aluminoxanes (also known as alkoxyaluminums), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds; the alkylaluminum refers to monoalkylaluminum dihydrides or dihalides, dialuminum alkyls or halides, or trialkylaluminums; examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane; Neutral Lewis acid activators, i.e., cocatalysts, include Group 13 metal compounds containing from 1 to 3 of the (C1-C 40 ) hydrocarbyl substituents; in one embodiment, the Group 13 metal compound is a tri((C1-C 40 ) hydrocarbyl) substituted aluminum or a tri((C1-C 40 ) hydrocarbyl)-boron compound; in embodiments, the Group 13 metal compound is a tri(hydrocarbyl) substituted aluminum, a tri((C1-C 40 ) hydrocarbyl)-boron compound, a tri((C1-C 10 ) alkyl) aluminum, a tri((C6-C 18 ) aryl) boron compound, and halogenated (including perhalogenated) derivatives thereof; in further embodiments, the Group 13 metal compound is a tri(fluoro-substituted phenyl) borane, a tri(pentafluorophenyl) borane; in some embodiments, the activating cocatalyst is a tri((C1-C 40 ) hydrocarbyl borate (e.g., trityl tetra(pentafluorophyl) borate) or a tri((C1-C 40 ) hydrocarbyl) ammonium tetra((C1-C 40 ) hydrocarbyl) borate (e.g., bis(octadecyl)methylammonium tetra(pentafluorophyl) borate); the term "ammonium" means a nitrogen cation which is ((C1-C 40 ) hydrocarbyl)4N + , ((C1-C 40 ) hydrocarbyl)3N(H) + , ((C1-C 40 ) hydrocarbyl)2N(H)2 + , (C1-C 40 ) hydrocarbyl N(H)3 + , or N(H)4 + , where each of the two or more (C1-C 40 ) hydrocarbyl groups, when present, can be the same or different; combinations of neutral Lewis acid activators (cocatalysts) include mixtures comprising a tri((C1-C 10 ) alkyl) aluminum and a halogenated tri((C6-C 18 ) aryl) boron compound, especially a tri(pentafluorophenyl) borane; embodiments are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric aluminoxane and combinations of a single neutral Lewis acid, especially a tri(pentafluorophenyl) borane, with a polymeric or oligomeric aluminoxane; the ratio of (metal-ligand complex):(tri(pentafluoro-phenyl) borane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tri(pentafluoro-phenyl) borane):(aluminoxane)] moles is from 1:1:1 to 1:10:30, in other embodiments from 1:1:1.5 to 1:5:10; Most preferred are triphenylcarbenium tetrakis(pentafluorophenyl)borate [Ph3C][B(C6F5)4] or N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate [PhNMe2H][B(C6F5)4] or tri((C1-C 40 )alkyl)ammonium tetrakis((C1-C 40 )alkyl)borates (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate) and B(C6F5)3; in certain specific polymerizations, oligomeric aluminoxanes are added to activate the catalyst or to scavenge impurities.

8. A composition for the preparation of ethylene block copolymer according to claim 6, wherein R in the catalyst is 1 —R 3 each independently is: methyl - Me, benzyl - CH2Ph or methylene trimethylsilyl - CH2TMS; The second monomer is 1-hexene, propylene, 1-butene or 1-octene; The modulating monomer is selected from the group consisting of styrene or 2-methyl-vinylbenzene.

9. A composition for the preparation of ethylene block copolymers according to claim 1, wherein said catalyst is selected from one of the following structural compounds:

10. A vinyl block copolymer, said block copolymer being obtained by polymerization of the composition according to any one of claims 1 to 8, said second monomer being incorporated in an amount of 2 to 30 mol%, and having a melting point of 65 to 130°C as determined by DSC, preferably a melting point of 90 to 130°C as determined by DSC, more preferably a melting point of 95 to 130°C as determined by DSC.

11. A process for the preparation of a vinyl block copolymer using the composition according to any one of claims 1 to 9, comprising: S1. introducing ethylene, the second monomer, the modulating monomer and a solvent into a reaction vessel to obtain a mixture; S2. adding the catalyst and the co-catalyst in a solvent to the mixture and carrying out a polymerization reaction to obtain a mixture of the polymer and the solvent; S3. terminating the polymerization reaction and separating the polymer from the solvent; Preferably, the temperature is raised to the polymerization temperature between steps S1 and S2. The solvent is a liquid compatible with the process, preferably an aprotic liquid; suitable solvents include aliphatic and aromatic hydrocarbons, especially branched hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, as well as higher carbon alkanes and mixtures thereof, benzene and (C1-C5)alkyl-substituted benzenes such as toluene and xylenes, other alkylbenzenes, and mixtures of the foregoing.

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