Solution process for producing halogen- or tertiary amine-functionalized polyolefins

Abstract

The present invention relates to a process for the solution copolymerization process for the production of functionalized polyolefins using a catalyst system comprising hafnium and zirconium complexes of polyvalent aryloxyethers and a cocatalyst selected from the group of ammonium or triphenylmethyl salts of MAO, DMAO, MMAO, SMAO and fluorinated tetraarylborates.

Description

Technical Field

[0001] This invention relates to a method for obtaining functionalized polyolefins, particularly halogenated and tertiary amine-functionalized polyolefins, by solution processing, and the functionalized polyolefins thereof. Background of the Invention

[0003] Polyolefins account for over 50% of the total polymer market and play a crucial role in our modern lives and the ongoing demand for new materials with low cost and customized properties. However, one of the drawbacks of polyolefins is their low adhesion to other materials such as inorganic fillers, metals, or other polymers. To overcome this problem, polyolefins must be functionalized. Introducing even a small fraction of functional groups into polyolefins can significantly improve surface properties, adhesion to other materials, and compatibility with other materials. Commercially, functionalized polyolefins are produced through post-polymerization treatments (chemical modification of non-functionalized polyolefins by reactive extrusion or corona / flame surface treatment of the processed portion). However, to obtain functionalized polyolefin products with well-defined molecular structures, uniform distribution, and / or relatively high concentrations of functional groups, copolymerization of olefin monomers with polar functionalized olefin comonomers is required. However, the combination of polar functional groups and highly electrophilic catalysts is significantly challenging, and often the functionalized comonomers must be passivated with masking agents, such as additionally added alkylaluminum. An example of this (1) protection, (2) copolymerization, (3) deprotection process is described, for instance, in Macromol. Chem. Phys. 1999, 200, 881-886, which discloses the production of hydroxyl-functionalized polyethylene by copolymerization of ethylene with TiBA-pretreated enol comonomers. This process is highly atomically inefficient and hampered by complex operating steps and large amounts of waste products. Alternatively, copolymerization of olefins with unmasked functionalized comonomers, such as tertiary amine-functionalized olefins, has been reported. However, this typically yields low molecular weight products, has low catalyst activity, and the copolymerization is generally carried out under slurry conditions at relatively low temperatures, which has significant drawbacks:

[0004] ■ Specific catalysts are required to highly blend functional comonomers;

[0005] ■ The solid content must be <15% by weight, especially when using homogeneous catalysts, otherwise statics will become a serious problem and a gel will be produced that retains a large amount of diluent.

[0006] ■ When a homogeneous unit point catalyst is used at a temperature below the crystallization temperature of the polymer formed, reactor scaling occurs;

[0007] ■ The precipitated polymer retains most of the unreacted functional comonomers;

[0008] ■Once the polymer has precipitated, it is difficult to remove the protection.

[0009] However, this process can also be achieved under solution conditions. But it presents the following drawbacks:

[0010] ■ The catalyst is thermally unstable, resulting in low catalyst yield;

[0011] ■ Functionalized polypropylene only produces low-MW polymers with low isoregularity.

[0012] Therefore, a method for producing functionalized polyolefins is needed to overcome at least one of these defects. Summary of the Invention

[0013] This objective is achieved through the present invention. Therefore, the present invention relates to a solution copolymerization method for obtaining functionalized polyolefins, comprising at least the following steps:

[0014] In the presence of a catalyst system, a copolymerization step of at least one olefin monomer and at least one functionalized olefin monomer is performed, wherein the olefin monomer is derived from CHR. 1 =CHR 2 It means that R 1 and R 2 Each is independently selected from hydrogen or alkyl groups having 1 to 6 carbon atoms, wherein R 1 and R 2 They can form a ring structure together.

[0015] The functionalized olefin monomers are represented by structures according to formula (I):

[0016]

[0017] Where R 3 R 4 and R 5 Each group is independently selected from H and hydrocarbon groups having 1 to 16 carbon atoms.

[0018] Where R 6 -[X-(R 7 ) n ] m It contains m heteroatom-containing functional groups X-(R) 7 ) n The polar functional group, where m is an integer from 1 to 10, preferably 1 or 2, wherein

[0019] ●When n=0 (therefore there is no R) 7 When X is selected from F, Cl, Br, and I,

[0020] or

[0021] ● When n = 2, X is N, and there are 2 R's. 7Each of them is independently selected from the group consisting of hydrocarbon groups having 1 to 16 carbon atoms.

[0022] Where R 6 For one or more -C(R) 8 (R) 9 )- group, wherein R 8 and R 9 Each is independently selected from the group consisting of H or hydrocarbon groups having 1 to 16 carbon atoms, and R 6 Contains 1 to 10 carbon atoms.

[0023] Where R 4 and R 6 They can be formed together by one or more X-(R) 7 ) n Functionalized ring structures,

[0024] Where X is connected to R 6 The main chain and / or side chains,

[0025] And the catalyst system includes:

[0026] ● Hafnium or zirconium complexes of polyvalent aryloxy ethers selected from the following group:

[0027] Dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl) (2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dibenzylbis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-but ... Hafnium(IV) of anthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium, dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dibenzylbis((2-oxy-3-) (Dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2,2-butanediylhafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2,4-Pentanediylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dichlorobis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl) (2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dibenzylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dimethylbis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzylbis((2-oxy- 3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzyl ...1-Dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl))-2-ethylhafnium ...)-2-ethylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-2-ethylhafnium)-2-ethylhafnium)-2-ethylhafnium (IV (2-O-( ... 4-Pentanedizirconium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene)) (-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-Octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dichloride bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), di bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium(IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium(IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium(IV), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2 4-Pentanedizirconium (IV), Dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV), Dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV), Dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanedizirconium (IV), Dichloride ...)-2-cyclohexanedizirconium (IV), Dichloride((2-oxy-3-(1,2,3,4,6,7,8)-2-cyclohexanedizirconium (IV), Dichloride((2-oxy-3-(1,2,3,4,6,7,8)-2-cyclohexanedizirconium (IV), Dichloride((2-oxy-3-(1,2,3, 9-Octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-Cyclohexanedizirconium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanedizirconium (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dimethyl ...dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenyl)-2-phenyl)-1,4-n-butylzirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrole-1-yl)phenyl)-2-phenyl)-2-phenyl)-2-phenyl)-2-butylzirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrole-1-yl)-2-phenyl)-2-phenyl)-2-phenyl)-2-phenyl)-2-phenyl)-2-phenyl)-2-phenyl)-2-phenyl)-2-butylzirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrole-1-yl) (2-O-(2-O-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylzirconium (IV), dibenzylbis((2-O-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylzirconium (IV), dimethylbis((2-O-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dibenzylbis((2-O-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dimethylbis((2-O-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), di Benzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (I) V), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), (OC-6-33)-[[2,2”'-[1,4-butanediylbis(oxy-κO)]bis[3”,5’,5”-tris(1,1-dimethylethyl)[1,1’:3’,1”-terphenyl]-2’-O-κO]](2-)]bis(phenylmethyl)hafnium, (OC-6-33)-[[2,2”'-[1,4-butanediylbis(oxy-κO)]bis[3”,5’,5”-tris(1,1-dimethylethyl)[1,1’:3’,1"-Triphenyl]-2'-O-κO]](2-)]bis(phenylmethyl)zirconium; preferably dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyrconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyrconium (IV); and,

[0028] ●A cocatalyst selected from the group consisting of: MAO, DMAO, MMAO, SMAO, or an ammonium salt or triphenylmethyl salt of a tetrafluoroarylborate; preferably MAO, MMAO, and

[0029] ●Optionally, a scavenger selected from the group consisting of: trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and

[0030] ●Optionally, chain transfer agents selected from the group consisting of dihydrogen or AlR 10 3, BR 10 3 or MgR 10 2 or ZnR 10 2, where each R 10 It is independently selected from hydrogen or hydrocarbon groups.

[0031] In the embodiments, at least one olefin monomer is selected from the group consisting of ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, 1-octene, norbornene, vinylidene norbornene, or at least one of the olefin monomers being propylene and / or 1-hexene.

[0032] In the embodiments, at least one functionalized olefin monomer is selected from the group comprising: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo-1-hexene, 6-chloro-1-hexene, 6-bromo- 1-Hexene, 6-Iodo-1-hexene, 5,6-Dichloro-1-hexene, 5,6-Dibromo-1-hexene, 5,6-Diiodo-1-hexene, 6,6-Dichloro-1-hexene, 6,6-Dibromo-1-hexene, 6,6-Diiodo-1-hexene, 5-Bromo-5-methyl-1-hexene, 5-Chloro-5-methyl-1-hexene, 7-Bromo-1-heptene, 7-Iodo-1-heptene, 6-Bromo-1-heptene, 6-Chloro-1-heptene, 6-Iodo-1-heptene, 6,7-Dichloro-1-heptene, 6, 7-Diiodo-1-heptene, 6-bromo-6-methyl-1-heptene, 6-chloro-6-methyl-1-heptene, 6-iodo-6-methyl-1-heptene, 8-bromo-1-octene, 8-chloro-1-octene, 8-iodo-1-octene, 7-bromo-1-octene, 7-chloro-1-octene, 7,8-dichloro-1-heptene, 7,8-diiodo-1-heptene, 11-bromo-1-undecene, 11-chloro-1-undecene, 11-iodo-1-undecene, 5-chloro-bicyclo(2.2.1)hept-2-ene, 5-Bromo-bicyclo(2.2.1)hept-2-ene, 5-Bromomethyl-bicyclo(2.2.1)hept-2-ene, 5-Chloromethyl-bicyclo(2.2.1)hept-2-ene, 5-Iodomethyl-bicyclo(2.2.1)hept-2-ene, 5-(2-Bromoethyl)-bicyclo(2.2.1)hept-2-ene, 5-(2-Chloroethyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-Bromopropyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-Bromopropyl)-bicyclo(2.2.1)hept-2-ene.1) Hepten-2-ene, N,N-diethyl-N-(butenyl)amine, N,N-di-n-propyl-N-(butenyl)amine, N,N-diisopropyl-N-(butenyl)amine, N,N-diethyl-N-(pentenyl)amine, N,N-di-n-propyl-N-(pentenyl)amine, N,N-diisopropyl-N-(pentenyl)amine, N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine, N,N-diethyl-N-(hexenyl)amine, N,N-diisopropyl-N-(hexenyl)amine, N,N-di-n-propyl-N-(hexenyl)amine, N,N-diethyl-N-(heptenyl)amine, N,N-diisopropyl- N-(heptenyl)amine, N,N-di-n-propyl-N-(heptenyl)amine, N,N-diethyl-N-(octenyl)amine, N,N-di-n-propyl-N-(octenyl)amine, N,N-diisopropyl-N-(octenyl)amine, N,N-diethyl-N-(undecenyl)amine, N,N-di-n-propyl-N-(undecenyl)amine, N,N-diisopropyl-N-(undecenyl)amine, 5-norbornen-2-N,N-diethylamine, 5-norbornen-2-N,N-(diethyl)methylamine, 5-norbornen-2-N,N-di(n-propyl)amine, 5-norbornen-2-N,N-(diisopropyl)methylamine.

[0033] Preferably, the functionalized olefin monomer is selected from the group consisting of: 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo-1-hexene, 6-chloro-1-hexene, 6-bromo-1-hexene, 6-iodo-1-hexene, 5,6-dichloro-1-hexene, 5,6-dibromo ... Iodo-1-hexene, 6,6-dichloro-1-hexene, 6,6-diiodo-1-hexene, 5-bromo-5-methyl-1-hexene, 5-chloro-5-methyl-1-hexene, 7-bromo-1-heptene, 7-iodo-1-heptene, 6-bromo-1-heptene, 6-chloro-1-heptene, 6-iodo-1-heptene, 6,7-dichloro-1-heptene, 6,7-diiodo-1-heptene, 6-bromo-6-methyl-1-heptene, 6-chloro-6-methyl-1-heptene, 6-iodo-6-methyl-1-heptene, 8-bromo-1-octene, 8-chloro-1-octene, 8-iodo-1-octene, 7- 1-Octenene, 7-Chloro-1-Octenene, 7,8-Dichloro-1-Octenene, 7,8-Diiodo-1-Octenene, 11-Bromo-1-Undecene, 5-Chloro-Bicyclo(2.2.1)Hept-2-ene, 5-Bromo-Bicyclo(2.2.1)Hept-2-ene, 5-Bromomethyl-Bicyclo(2.2.1)Hept-2-ene, 5-Chloromethyl-Bicyclo(2.2.1)Hept-2-ene, 5-Iodomethyl-Bicyclo(2.2.1)Hept-2-ene, 5-(2-Bromoethyl)-Bicyclo(2.2.1)Hept-2-ene, 5-(2-Chloroethyl)-Bicyclo(2.2.1)Hept-2 -ene, 5-(3-bromopropyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1)hept-2-ene, N,N-diethyl-N-(butenyl)amine, N,N-di-n-propyl-N-(butenyl)amine, N,N-diisopropyl-N-(butenyl)amine, N,N-diethyl-N-(pentenyl)amine, N,N-diisopropyl-N-(pentenyl)amine, N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine, N,N-diethyl-N-(hexenyl)amine, N,N-diethyl-N-(heptenyl)amine.

[0034] In the embodiment, the amount of functionalized olefin monomer in the functionalized polyolefin obtained by step b) is 0.01 to 20 mol% relative to the total molar amount of olefin monomer and functionalized olefin monomer in the functionalized polyolefin, preferably 0.02 to 15 mol% or 0.05 to 10 mol%, or 0.1 to 5 mol%, more preferably 0.02 to 2 mol%.

[0035] In the implementation scheme, the first and second olefin monomers are used to copolymerize with at least one functionalized olefin monomer, wherein the first and second olefin monomers are different, and wherein the amount of the first olefin monomer is 20 to 80 mol% and the amount of the second olefin monomer is 80 to 20 mol% based on the total molar amount of the first and second olefin monomers.

[0036] In the embodiments, at least one of the olefin monomers is propylene, used in an amount of at least 50% by weight, preferably at least 60% by weight, more preferably at least >70% by weight, and most preferably at least 80% by weight relative to the total weight of the olefin monomer and the functionalized olefin monomer.

[0037] In the implementation scheme, the first olefin is propylene or ethylene and the second olefin is 1-hexene, 1-octene or norbornene, or the first olefin is propylene and the second olefin is ethylene.

[0038] In an embodiment, a functionalized copolymer is obtained, preferably in which the first monomer is selected from the group consisting of ethylene and propylene, and the second monomer is a functionalized monomer selected from the group consisting of: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5- 1-Bromo-hexene, 5-Iodo-1-hexene, 6-Chloro-1-hexene, 6-Bromo-1-hexene, 6-Iodo-1-hexene, 5,6-Dichloro-1-hexene, 5,6-Dibromo-1-hexene, 5,6-Diiodo-1-hexene, 6,6-Dichloro-1-hexene, 6,6-Dibromo-1-hexene, 6,6-Diiodo-1-hexene, 5-Bromo-5-methyl-1-hexene, 5-Chloro-5-methyl-1-hexene, 7-Bromo-1-heptene, 7-Iodo-1-heptene, 6-Bromo-1-heptene, 6-Chloro-1-heptene, 6-Iodo- 1-Heptene, 6,7-Dichloro-1-heptene, 6,7-Diiodo-1-heptene, 6-Bromo-6-methyl-1-heptene, 6-Chloro-6-methyl-1-heptene, 6-Iodo-6-methyl-1-heptene, 8-Bromo-1-octene, 8-Chloro-1-octene, 8-Iodo-1-octene, 7-Bromo-1-octene, 7-Chloro-1-octene, 7,8-Dichloro-1-heptene, 7,8-Diiodo-1-heptene, 11-Bromo-1-undecene, 11-Chloro-1-undecene, 11-Iodo-1-undecene, 5-Chloro-bicyclo(2.2) .1) Hepta-2-ene, 5-bromo-bicyclo(2.2.1) hepta-2-ene, 5-bromomethyl-bicyclo(2.2.1) hepta-2-ene, 5-chloromethyl-bicyclo(2.2.1) hepta-2-ene, 5-iodomethyl-bicyclo(2.2.1) hepta-2-ene, 5-(2-bromoethyl)-bicyclo(2.2.1) hepta-2-ene, 5-(2-chloroethyl)-bicyclo(2.2.1) hepta-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1) hepta-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1) hepta-2-ene.1) Hepten-2-ene, N,N-diethyl-N-(butenyl)amine, N,N-di-n-propyl-N-(butenyl)amine, N,N-diisopropyl-N-(butenyl)amine, N,N-diethyl-N-(pentenyl)amine, N,N-di-n-propyl-N-(pentenyl)amine, N,N-diisopropyl-N-(pentenyl)amine, N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine, N,N-diethyl-N-(hexenyl)amine, N,N-diisopropyl-N-(hexenyl)amine, N,N-di-n-propyl-N-(hexenyl)amine, N,N-diethyl-N-(heptenyl)amine, N,N-diisopropyl- N-(heptenyl)amine, N,N-di-n-propyl-N-(heptenyl)amine, N,N-diethyl-N-(octenyl)amine, N,N-di-n-propyl-N-(octenyl)amine, N,N-diisopropyl-N-(octenyl)amine, N,N-diethyl-N-(undecenyl)amine, N,N-di-n-propyl-N-(undecenyl)amine, N,N-diisopropyl-N-(undecenyl)amine, 5-norbornen-2-N,N-diethylamine, 5-norbornen-2-N,N-(diethyl)methylamine, 5-norbornen-2-N,N-di(n-propyl)amine, 5-norbornen-2-N,N-(diisopropyl)methylamine;

[0039] More preferred functionalized copolymers are: poly(ethylene-co-4-bromo-1-butene), poly(ethylene-co-4-chloro-1-butene), poly(ethylene-co-4-iodo-1-butene), poly(ethylene-co-5-bromo-1-pentene), poly(ethylene-co-5-chloro-1-pentene), poly(ethylene-co-5-iodo-1-pentene), poly(ethylene-co-5-bromo-1-hexene), poly(ethylene-co-5-chloro-1-hexene), poly(ethylene-co-5-iodo-1-hexene), poly(ethylene-co-6-bromo-1-hexene), poly(ethylene-co-6-chloro-1-hexene), poly(ethylene-co-6-iodo-1-hexene), poly(ethylene-co-7-bromo-1-heptene), poly(ethylene-co-7-chloro-1-heptene). (Ethylene), poly(ethylene-co-7-iodo-1-heptene), poly(ethylene-co-8-bromo-1-octene), poly(ethylene-co-8-chloro-1-octene), poly(ethylene-co-8-iodo-1-octene), poly(ethylene-co-11-bromo-1-undecene), poly(ethylene-co-11-chloro-1-undecene), poly(ethylene-co-11-iodo-1-undecene), poly(ethylene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-11-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-11-N,N-diisopropyl-N-(pentenyl)amine) Propyl-N-(3-methyl-5-hexenyl)amine, poly(vinyl-co-N,N-diethyl-N-(hexenyl)amine), poly(vinyl-co-N,N-diethyl-N-(heptenyl)amine), poly(propylene-co-4-bromo-1-butene), poly(propylene-co-4-chloro-1-butene), poly(propylene-co-4-iodo-1-butene), poly(propylene-co-5-bromo-1-pentene), poly(propylene-co-5-chloro-1-pentene), poly(propylene-co-5-iodo-1-pentene), poly(propylene-co-5-bromo-1-hexene), poly(propylene-co-5-chloro-1-hexene), poly(propylene-co-6-bromo-1-hexene), poly(propylene-co-4-bromo-1-butene), poly(propylene-co-4-chloro-1-butene), poly(propylene-co-4-iodo-1-butene), poly(propylene-co-5-bromo-1-pentene), poly(propylene-co-5-bromo-1-hexene), poly(propylene-co-4-bromo-1-butene), poly(propylene-co-4-iodo-1-butene), poly(propylene-co-5-bromo-1-hexene), poly(propylene-co-4-bromo-1-but ... -6-chloro-1-hexene), poly(propylene-co-6-iodo-1-hexene), poly(propylene-co-7-bromo-1-heptene), poly(propylene-co-7-chloro-1-heptene), poly(propylene-co-7-iodo-1-heptene), poly(propylene-co-8-bromo-1-octene), poly(propylene-co-8-chloro-1-octene), poly(propylene-co-8-iodo-1-octene), poly(propylene-co-11-bromo-1-undecene), poly(propylene-co-11-chloro-1-undecene), poly(propylene-co-11-iodo-1-undecene), poly(propylene-co-N,N-diethyl-N-(butenyl)amine), poly(propylene-co-N,N-diisopropyl-N-(butenyl)amine), poly(propylene-co-N,N-Diethyl-N-(pentenyl)amine, poly(propylene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-N,N-diethyl-N-(hexenyl)amine), or poly(propylene-co-N,N-diethyl-N-(heptenyl)amine).

[0040] In the embodiments, a functionalized terpolymer is obtained, preferably in which the first monomer is selected from the group consisting of ethylene and propylene, the second monomer is selected from the group consisting of propylene, 1-hexene, 1-octene and norbornene, or ethylene when the first monomer is propylene, and propylene when the first monomer is ethylene, and the third monomer is selected from the terpolymer consisting of: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo- 1-Hexene, 6-Chloro-1-Hexene, 6-Bromo-1-Hexene, 6-Iodo-1-Hexene, 5,6-Dichloro-1-Hexene, 5,6-Dibromo-1-Hexene, 5,6-Diiodo-1-Hexene, 6,6-Dichloro-1-Hexene, 6,6-Dibromo-1-Hexene, 6,6-Diiodo-1-Hexene, 5-Bromo-5-methyl-1-Hexene, 5-Chloro-5-methyl 1-Hexene, 7-Bromo-1-Heptene, 7-Iodo-1-Heptene, 6-Bromo-1-Heptene, 6-Chloro-1-Heptene, 6-Iodo-1-Heptene, 6,7-Dichloro-1-Heptene, 6,7-Diiodo-1-Heptene, 6-Bromo-6-Methyl-1-Heptene, 6-Chloro-6-Methyl-1-Heptene, 6-Iodo-6-Methyl-1-Heptene, 8-Bromo-1-Octa Alkenes, 8-chloro-1-octene, 8-iodo-1-octene, 7-bromo-1-octene, 7-chloro-1-octene, 7,8-dichloro-1-heptene, 7,8-diiodo-1-heptene, 11-bromo-1-undecene, 11-chloro-1-undecene, 11-iodo-1-undecene, 5-chloro-bicyclo(2.2.1)hept-2-ene, 5-bromo-bicyclo(2.2.1)hept-2-ene, 5-bromomethyl-bicyclo(2.2.1)hept-2-ene, 5-chloromethyl-bicyclo(2.2.1)hept-2-ene, 5-iodomethyl-bicyclo(2.2.1)hept-2-ene, 5-(2-bromoethyl)-bicyclo(2.2.1)hept-2-ene, 5-( 3-Bromopropyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-Bromopropyl)-bicyclo(2.2.1)hept-2-ene, N,N-diethyl-N-(butenyl)amine, N,N-di-n-propyl-N-(butenyl)amine, N,N-diisopropyl-N-(butenyl)amine, N,N-diethyl-N-(pentenyl)amine, N,N-di-n-propyl -N-(pentenyl)amine, N,N-diisopropyl-N-(pentenyl)amine, N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine, N,N-diethyl-N-(hexenyl)amine, N,N-diisopropyl-N-(hexenyl)amine, N,N-di-n-propyl-N-(hexenyl)amine, N,N-diethyl-N-(heptenyl)amine, N,N-Diisopropyl-N-(heptenyl)amine, N,N-di-n-propyl-N-(heptenyl)amine, N,N-diethyl-N-(octenyl)amine, N,N-di-n-propyl-N-(octenyl)amine, N,N-diisopropyl-N-(octenyl)amine, N,N-diethyl-N-(undecenyl)amine, N,N-di-n-propyl-N-(undecenyl)amine, N,N-diisopropyl-N-(undecenyl)amine, 5-norbornen-2-N,N-diethylamine, 5-norbornen-2-N,N-(diethyl)methylamine, 5-norbornen-2-N,N-di(n-propyl)amine, 5-norbornen-2-N,N-(diisopropyl)methylamine; more preferably, the functionalized terpolymer is: poly(ethylene) -co-1-octene-co-4-bromo-1-butene), poly(ethylene-co-1-octene-co-4-chloro-1-butene), poly(ethylene-co-1-octene-co-4-iodo-1-butene), poly(ethylene-co-1-octene-co-5-bromo-1-pentene), poly(ethylene-co-1-octene-co-5-chloro-1-pentene), poly(ethylene-co-1-octene-co-5-iodo-1-pentene), poly(ethylene-co-1-octene-co-5-bromo-1-hexene), poly(ethylene-co-1-octene-co-5-chloro-1-hexene), poly(ethylene-co-1-octene-co-5-chloro-1-hexene), poly(ethylene-co-1-octene-co-6-bromo-1-hexene), poly(ethylene-co- -1-Octene-Co-6-Chloro-1-Hexene), Poly(Ethylene-Co-1-Octene-Co-6-Iodo-1-Hexene), Poly(Ethylene-Co-1-Octene-Co-7-Bromo-1-Heptene), Poly(Ethylene-Co-1-Octene-Co-7-Chloro-1-Heptene), Poly(Ethylene-Co-1-Octene-Co-7-Iodo-1-Heptene), Poly(Ethylene-Co-1-Octene-Co-8-Bromo-1-Octene), Poly(Ethylene-Co-1-Octene-Co-8-Chloro-1-Octene), Poly(Ethylene-Co-1-Octene-Co-8-Iodo-1-Octene), Poly(Ethylene-Co-1-Octene-Co-11-Bromo-1-Undecene), Poly(Ethylene-Co-1-Octene-Co-11-Chloro-1-Undecene), Poly(Ethylene-Co-1-Octene-Co-11-Chloro-1-Undecene), Poly(Ethylene-Co-1-Octene-Co-11-Chloro-1-Undecene) -co-1-octene-co-11-iodo-1-undecene), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-1-octene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-1-octene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-1-octene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-Diethyl-N-(heptenyl)amine), poly(ethylene-co-1-hexene-co-4-bromo-1-butene), poly(ethylene-co-1-hexene-co-4-chloro-1-butene), poly(ethylene-co-1-hexene-co-4-iodo-1-butene), poly(ethylene-co-1-hexene-co-5-bromo-1-pentene), poly(ethylene-co-1-hexene-co-5-chloro-1-pentene), poly(ethylene-co-1-hexene-co-5-iodo-1-pentene), poly(ethylene-co-1-hexene-co-5-bromo-1-hexene), poly( Ethylene-co-1-hexene-co-5-chloro-1-hexene), poly(ethylene-co-1-hexene-co-5-iodo-1-hexene), poly(ethylene-co-1-hexene-co-6-bromo-1-hexene), poly(ethylene-co-1-hexene-co-6-chloro-1-hexene), poly(ethylene-co-1-hexene-co-6-iodo-1-hexene), poly(ethylene-co-1-hexene-co-7-bromo-1-heptene), poly(ethylene-co-1-hexene-co-7-chloro-1-heptene), poly(ethylene-co-1-hexene-co-7-iodo-1-heptene) (ethylene), poly(ethylene-co-1-hexene-co-8-bromo-1-octene), poly(ethylene-co-1-hexene-co-8-chloro-1-octene), poly(ethylene-co-1-hexene-co-8-iodo-1-octene), poly(ethylene-co-1-hexene-co-11-bromo-1-undecene), poly(ethylene-co-1-hexene-co-11-chloro-1-undecene), poly(ethylene-co-1-hexene-co-11-iodo-1-undecene), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(butenyl)amine), poly( Ethylene-co-1-hexene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-1-hexene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-hexene-co-N,N-Diethyl-N-(heptenyl)amine), poly(propylene-co-1-octene-co-4-bromo-1-butene), poly(propylene-co-1-octene-co-4-chloro-1-butene), poly(propylene-co-1-octene-co-4-iodo-1-butene), poly(propylene-co-1-octene-co-5-bromo-1-pentene), poly(propylene-co-1-octene-co-5-chloro-1-pentene), poly(propylene-co-1-octene-co-5-iodo-1-pentene), poly(propylene-co-1-octene-co-5-bromo-1-hexene), poly( Propylene-co-1-octene-co-5-chloro-1-hexene), poly(propylene-co-1-octene-co-5-iodo-1-hexene), poly(propylene-co-1-octene-co-6-bromo-1-hexene), poly(propylene-co-1-octene-co-6-chloro-1-hexene), poly(propylene-co-1-octene-co-6-iodo-1-hexene), poly(propylene-co-1-octene-co-7-bromo-1-heptene), poly(propylene-co-1-octene-co-7-chloro-1-heptene), poly(propylene-co-1-octene-co-7-iodo-1-heptene) Poly(propylene-co-1-octene-co-8-bromo-1-octene), poly(propylene-co-1-octene-co-8-chloro-1-octene), poly(propylene-co-1-octene-co-8-iodo-1-octene), poly(propylene-co-1-octene-co-11-bromo-1-undecene), poly(propylene-co-1-octene-co-11-chloro-1-undecene), poly(propylene-co-1-octene-co-11-iodo-1-undecene), poly(propylene-co-1-octene-co-N,N-diethyl-N-(butenyl)amine), poly( Propylene-co-1-octene-co-N,N-diisopropyl-N-(butenyl)amine), poly(propylene-co-1-octene-co-N,N-diethyl-N-(pentenyl)amine), poly(propylene-co-1-octene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-1-octene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(propylene-co-1-octene-co-N,N-diisopropyl-N-(hexenyl)amine), poly(propylene-co-1-octene-co-N,N-Diethyl-N-(heptenyl)amine), poly(ethylene-co-norbornene-co-4-bromo-1-butene), poly(ethylene-co-norbornene-co-4-chloro-1-butene), poly(ethylene-co-norbornene-co-4-iodo-1-butene), poly(ethylene-co-norbornene-co-5-bromo-1-pentene), poly(ethylene-co-norbornene-co-5-chloro-1-pentene), poly(ethylene-co-norbornene-co-5-iodo-1-pentene), poly(ethylene-co-norbornene-co-5-bromo-1-hexene), poly( Ethylene-co-norbornene-co-5-chloro-1-hexene), poly(ethylene-co-norbornene-co-5-iodo-1-hexene), poly(ethylene-co-norbornene-co-6-bromo-1-hexene), poly(ethylene-co-norbornene-co-6-chloro-1-hexene), poly(ethylene-co-norbornene-co-6-iodo-1-hexene), poly(ethylene-co-norbornene-co-7-bromo-1-heptene), poly(ethylene-co-norbornene-co-7-chloro-1-heptene), poly(ethylene-co-norbornene-co-7-iodo-1-heptene) (Ethylene), poly(ethylene-co-norbornene-co-8-bromo-1-octene), poly(ethylene-co-norbornene-co-8-chloro-1-octene), poly(ethylene-co-norbornene-co-8-iodo-1-octene), poly(ethylene-co-norbornene-co-11-bromo-1-undecene), poly(ethylene-co-norbornene-co-11-chloro-1-undecene), poly(ethylene-co-norbornene-co-11-iodo-1-undecene), poly(ethylene-co-norbornene-co-N,N-diethyl-N-(butenyl)amine), poly( Ethylene-co-norbornene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-norbornene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-norbornene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-norbornene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-norbornene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-norbornene-co-N,N-diisopropyl-N-(hexenyl)amine), poly(ethylene-co-norbornene-co-N,N-Diethyl-N-(heptenyl)amine), poly(ethylene-co-propylene-co-4-bromo-1-butene), poly(ethylene-co-propylene-co-4-chloro-1-butene), poly(ethylene-co-propylene-co-4-iodo-1-butene), poly(ethylene-co-propylene-co-5-bromo-1-pentene), poly(ethylene-co-propylene-co-5-chloro-1-pentene), poly(ethylene-co-propylene-co-5-iodo-1-pentene), poly(ethylene-co-propylene-co-5-bromo-1-hexene), poly( Ethylene-co-propylene-co-5-chloro-1-hexene), poly(ethylene-co-propylene-co-5-iodo-1-hexene), poly(ethylene-co-propylene-co-6-bromo-1-hexene), poly(ethylene-co-propylene-co-6-chloro-1-hexene), poly(ethylene-co-propylene-co-6-iodo-1-hexene), poly(ethylene-co-propylene-co-7-bromo-1-heptene), poly(ethylene-co-propylene-co-7-chloro-1-heptene), poly(ethylene-co-propylene-co-7-iodo-1-heptene) Poly(ethylene-co-propylene-co-8-bromo-1-octene), poly(ethylene-co-propylene-co-8-chloro-1-octene), poly(ethylene-co-propylene-co-8-iodo-1-octene), poly(ethylene-co-propylene-co-11-bromo-1-undecene), poly(ethylene-co-propylene-co-11-chloro-1-undecene), poly(ethylene-co-propylene-co-11-iodo-1-undecene), poly(ethylene-co-propylene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(butenyl)amine) -co-propylene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-propylene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-propylene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-propylene-co-N,N-Diethyl-N-(heptenyl)amine), poly(propylene-co-1-hexene-co-4-bromo-1-butene), poly(propylene-co-1-hexene-co-4-chloro-1-butene), poly(propylene-co-1-hexene-co-4-iodo-1-butene), poly(propylene-co-1-hexene-co-5-bromo-1-pentene), poly(propylene-co-1-hexene-co-5-chloro-1-pentene), poly(propylene-co-1-hexene-co-5-iodo-1-pentene), poly(propylene-co-1-hexene-co-5-bromo-1-hexene), poly( Propylene-co-1-hexene-co-5-chloro-1-hexene), poly(propylene-co-1-hexene-co-5-iodo-1-hexene), poly(propylene-co-1-hexene-co-6-bromo-1-hexene), poly(propylene-co-1-hexene-co-6-chloro-1-hexene), poly(propylene-co-1-hexene-co-6-iodo-1-hexene), poly(propylene-co-1-hexene-co-7-bromo-1-heptene), poly(propylene-co-1-hexene-co-7-chloro-1-heptene), poly(propylene-co-1-hexene-co-7-iodo-1-heptene) Poly(propylene-co-1-hexene-co-8-bromo-1-octene), poly(propylene-co-1-hexene-co-8-chloro-1-octene), poly(propylene-co-1-hexene-co-8-iodo-1-octene), poly(propylene-co-1-hexene-co-11-bromo-1-undecene), poly(propylene-co-1-hexene-co-11-chloro-1-undecene), poly(propylene-co-1-hexene-co-11-iodo-1-undecene), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(butenyl)amine), poly( Propylene-co-1-hexene-co-N,N-diisopropyl-N-(butenyl)amine), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(pentenyl)amine), poly(propylene-co-1-hexene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-1-hexene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(propylene-co-1-hexene-co-N,N-Diethyl-N-(heptenyl)amine), poly(propylene-co-norbornene-co-4-bromo-1-butene), poly(propylene-co-norbornene-co-4-chloro-1-butene), poly(propylene-co-norbornene-co-4-iodo-1-butene), poly(propylene-co-norbornene-co-5-bromo-1-pentene), poly(propylene-co-norbornene-co-5-chloro-1-pentene), poly(propylene-co-norbornene-co-5-iodo-1-pentene), poly(propylene-co-norbornene-co-5-bromo-1-hexene), poly(propylene-co- Norbornene-co-5-chloro-1-hexene), poly(propylene-co-norbornene-co-5-iodo-1-hexene), poly(propylene-co-norbornene-co-6-bromo-1-hexene), poly(propylene-co-norbornene-co-6-chloro-1-hexene), poly(propylene-co-norbornene-co-6-iodo-1-hexene), poly(propylene-co-norbornene-co-7-bromo-1-heptene), poly(propylene-co-norbornene-co-7-chloro-1-heptene), poly(propylene-co-norbornene-co-7-iodo-1-heptene), poly(propylene-co-5-chloro-1-heptene) -norbornene-co-8-bromo-1-octene), poly(propylene-co-norbornene-co-8-chloro-1-octene), poly(propylene-co-norbornene-co-8-iodo-1-octene), poly(propylene-co-norbornene-co-11-bromo-1-undecene), poly(propylene-co-norbornene-co-11-chloro-1-undecene), poly(propylene-co-norbornene-co-11-iodo-1-undecene), poly(propylene-co-norbornene-co-N,N-diethyl-N-(butenyl)amine), poly(propylene-co-norbornene-co-N-N N-Diisopropyl-N-(Butenyl)amine, poly(propylene-co-norbornene-co-N,N-diethyl-N-(pentenyl)amine), poly(propylene-co-norbornene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-norbornene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-norbornene-co-N,N-diethyl-N-(hexenyl)amine), or poly(propylene-co-norbornene-co-N,N-diethyl-N-(heptenyl)amine).

[0041] A second aspect of the invention is that the functionalized polyolefin obtained by the method according to the invention is used in articles as a macromolecular initiator, compatibilizer, filler dispersant, melt flow improver, adhesive, adhesion improver in coatings or paints, shape memory film, self-healing film, antimicrobial or antiviral coating or film, or carrier for controlled drug release or fragrance release.

[0042] A third aspect of the invention is the use of a catalyst system comprising a hafnium complex of a polyvalent aryloxy ether and a co-catalyst selected from the group consisting of an ammonium salt or triphenylmethyl salt of MAO, DMAO, MMAO, SMAO and fluorinated tetraarylborates in a solution process to obtain functionalized polyolefins.

[0043] Finally, a last aspect of the invention is the functionalized olefins that can be obtained by the method of the invention, preferably:

[0044] ● Functionalized olefin copolymers, which have the following characteristics:

[0045] ○40 to 300 kg / mol M w scope,

[0046] ○M from 20 to 150 kg / mol n scope,

[0047] Crystallinity > 30%,

[0048] Melting point: 100-155℃

[0049] ○ Randomly distributed halogen or amine functional groups,

[0050] ○ 0.05-10 mol%, preferably 0.1-5 mol%, more preferably 0.02-2 mol% of functional comonomer content;

[0051] ● Functionalized olefin terpolymers, which have the following characteristics:

[0052] ○40 to 300 kg / mol M w scope,

[0053] ○M from 20 to 150 kg / mol n scope,

[0054] ○ Crystallinity range of 0-30%,

[0055] Melting point of 40-120℃

[0056] ○ Comonomer content of 0.5-20 mol%, preferably 2-18 mol%, more preferably 5-15 mol%,

[0057] ○ Randomly distributed halogen or amine functional groups,

[0058] ○ 0.05-10 mol%, preferably 0.1-5 mol%, more preferably 0.02-2 mol% of functional comonomer content. Invention Details

[0060] The copolymerization of at least one olefin monomer and at least one functionalized olefin monomer in the presence of the following components:

[0061] Olefin monomers

[0062] The olefin monomer is selected from the group consisting of ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, 1-octene, 1-decene, norbornene, vinylidene norbornene, ethylidene norbornene, or combinations thereof.

[0063] In another embodiment, at least one olefin monomer is propylene, and its amount is at least 50% by weight, preferably at least 60% by weight, more preferably at least >70% by weight, and most preferably at least 80% by weight, in particular relative to the total weight of the olefin monomer and the functionalized olefin monomer.

[0064] In another embodiment, at least one olefin monomer is ethylene, and its amount is at least 50% by weight, preferably at least 60% by weight, more preferably at least >70% by weight, and most preferably at least 80% by weight, in particular relative to the total weight of the olefin monomer and the functionalized olefin monomer.

[0065] The polymerization step may use one type of olefin monomer or two or more types of olefin monomers.

[0066] In another embodiment, the first and second olefin monomers are different, and based on the total molar amount of the first and second olefin monomers, the amount of the first olefin monomer is 20 to 80 mol% and the amount of the second olefin monomer is 80 to 20 mol%.

[0067] In another embodiment, the first olefin is ethylene and the second olefin is 1-octene.

[0068] In another embodiment, the first olefin is ethylene and the second olefin is norbornene.

[0069] In another embodiment, the first olefin is propylene and the second olefin is 1-hexene.

[0070] In another embodiment, the first olefin is propylene and the second olefin is ethylene.

[0071] Functionalized olefin monomers

[0072] Functionalized olefin monomers have the following structures according to formula (I):

[0073]

[0074] Where R 3 R 4 and R 5 Each group is independently selected from H and hydrocarbon groups having 1 to 16 carbon atoms.

[0075] Where R6 -[X-(R 7 ) n ] m It contains m heteroatom-containing functional groups X-(R) 7 ) n The polar functional group, where m is an integer from 1 to 10, preferably 1 or 2, wherein

[0076] ●When n=0 (therefore there is no R) 7 When X is selected from F, Cl, Br, I, or

[0077] ● When n = 2, X is N, and there are 2 R's. 7 Each of them is independently selected from the group consisting of hydrocarbon groups having 1 to 16 carbon atoms.

[0078] Where R 6 For one or more -C(R) 8 (R) 9 )- group, wherein R 8 and R 9 Each is independently selected from the group consisting of H or hydrocarbon groups having 1 to 16 carbon atoms, and R 6 Contains 1 to 10 carbon atoms.

[0079] Where X is connected to R 6 The main chain and / or side chains,

[0080] Where R 4 and R 6 They can be formed together by one or more X-(R) 7 ) n Functionalized ring structures,

[0081] Preferably, X is selected from Br, I, or N.

[0082] In a preferred embodiment, the functionalized olefin monomer according to Formula I is a halogenated α-olefin or a halogenated cyclo-strained olefin monomer.

[0083] Halogenated functionalized olefin monomers may, for example, correspond to formula I, where R 3 R 4 and R 5 Each is H, where X is F, Cl, Br or I, and R is... 6 For one or more -C(R) 8 (R) 9 )- group, wherein R 8 and R 9 Each group is independently selected from H or hydrocarbon groups having 1 to 16 carbon atoms. R 6 Examples of the groups are -(CH2)9- and -(CH2)4-.

[0084] Other examples of halogenated functionalized olefin monomers include, but are not limited to: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo-1-hexene, 6-chloro-1-hexene, 6-bromo-1-hexene, 6-iodo-1-hexene, 5,6-dichloro-1-hexene, 5,6-dibromo-1-hexene, 6,6-dichloro-1-hexene, 6,6-dibromo-1-hexene, 5-bromo-5-methyl-1-hexene, 8-chloro-1-octene, 8-bromo-1-octene, 8-iodo-1-octene, 11-chloro-1-undecene, 11-bromo-1-undecene, 11-iodo-1-undecene.

[0085] Further examples of halogenated olefin monomers include halogenated cyclo-strained cyclic olefins (also known as internal olefins), which can typically be, for example, halogenated norbornene, preferably 5-chloro-bicyclo(2.2.1)hept-2-ene, 5-chloromethyl-bicyclo(2.2.1)hept-2-ene, 5-bromo-bicyclo(2.2.1)hept-2-ene, and 5-bromomethyl-bicyclo(2.2.1)hept-2-ene. They correspond to Formula I, where R 3 and R 5 For H, and R 4 and R 6 Together they form a ring structure functionalized by X, where X is F, Cl, Br or I.

[0086] Functionalized olefin monomers containing tertiary amines may, for example, correspond to formula I, where R 3 R 4 and R 5 Each is H, where X is -N- and R is... 6 For one or more -C(R) 8 (R) 9 )- group, wherein R 8 and R 9 Each group is independently selected from H or hydrocarbon groups having 1 to 16 carbon atoms. R 6 An example of the group is -(CH2)6-.

[0087] Other examples of tertiary amine-functionalized olefin monomers include, but are not limited to: N,N-diethyl-N-(butenyl)amine, N,N-di-n-propyl-N-(butenyl)amine, N,N-diisopropyl-N-(butenyl)amine, N,N-diethyl-N-(hexenyl)amine, N,N-di-n-propyl-N-(hexenyl)amine, N,N-diisopropyl-N-(hexenyl)amine, N,N- Diethyl-N-(octenyl)amine, N,N-di-n-propyl-N-(octenyl)amine, N,N-diisopropyl-N-(octenyl)amine, 5-norbornen-2-N,N-di(ethyl)amine, 5-norbornen-2-N,N-(diethyl)methylamine, 5-norbornen-2-N,N-di(n-propyl)amine, 5-norbornen-2-N,N-(diisopropyl)methylamine.

[0088] Alkenes containing tertiary amine functions can be prepared and purified according to literature procedures, for example, those described by Agapie et al. (Journal of the American Chemical Society (2013), 135(10), 3784-3787) and Marks et al. (WO2019071102A1).

[0089] In the embodiments, two different monomers are used to obtain the copolymer. Preferably, the first monomer in the copolymer is selected from the group consisting of ethylene and propylene, and the second monomer is a functionalized monomer selected from the group consisting of: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo-1-hexene, 6-chloro-1-hexene, 6-bromo-1-hexene, 6-iodo-1-hexene, 5,6-dichloro-1-hexene, 5 6-Dibromo-1-hexene, 5,6-Diiodo-1-hexene, 6,6-Dichloro-1-hexene, 6,6-Dibromo-1-hexene, 6,6-Diiodo-1-hexene, 5-Bromo-5-methyl-1-hexene, 5-Chloro-5-methyl-1-hexene, 7-Bromo-1-heptene, 7-Iodo-1-heptene, 6-Bromo-1-heptene, 6-Chloro-1-heptene, 6-Iodo-1-heptene, 6,7-Dichloro-1-heptene, 6,7-Diiodo-1-heptene, 6-Bromo-6-methyl-1-heptene, 6-Chloro-6-methyl-1-heptene, 6-Iodo-6-methyl-1-heptene, 8-Bromo-1-octene, 8-Chloro-1-octene, 8-Iodo-1-octene, 7-Bromo-1-octene, 7-Chloro-1-octene, 7,8- Dichloro-1-heptene, 7,8-diiodo-1-heptene, 11-bromo-1-undecene, 11-chloro-1-undecene, 11-iodo-1-undecene, 5-chloro-bicyclo(2.2.1)hept-2-ene, 5-bromo-bicyclo(2.2.1)hept-2-ene, 5-bromomethyl-bicyclo(2.2.1)hept-2-ene, 5-chloromethyl-bicyclo(2.2.1)hept-2-ene, 5-iodomethyl-bicyclo(2.2.1)hept-2-ene, 5-(2-bromoethyl)-bicyclo(2.2.1)hept-2-ene, 5-(2-chloroethyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1)hept-2-ene. 1) Hepta-2-ene, N,N-diethyl-N-(butenyl)amine, N,N-di-n-propyl-N-(butenyl)amine, N,N-diisopropyl-N-(butenyl)amine, N,N-diethyl-N-(pentenyl)amine, N,N-di-n-propyl-N-(pentenyl)amine, N,N-diisopropyl-N-(pentenyl)amine, N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine, N,N-diethyl-N-(hexenyl)amine, N,N-diisopropyl-N-(hexenyl)amine, N,N-di-n-propyl-N-(hexenyl)amine, N,N-diethyl-N-(heptenyl)amine, N,N-diisopropyl-N-(heptenyl)amine, N,N-Diethyl-N-(octenyl)amine, N,N-di-n-propyl-N-(octenyl)amine, N,N-diisopropyl-N-(octenyl)amine, N,N-diethyl-N-(undecenyl)amine, N,N-di-n-propyl-N-(undecenyl)amine, N,N-diisopropyl-N-(undecenyl)amine, 5-norbornen-2-N,N-diethylamine, 5-norbornen-2-N,N-(diethyl)methylamine, 5-norbornen-2-N,N-di(n-propyl)amine, 5-norbornen-2-N,N-(diisopropyl)methylamine (Propyl)methylamine; more preferably, the functionalized copolymers are: poly(ethylene-co-4-bromo-1-butene), poly(ethylene-co-4-chloro-1-butene), poly(ethylene-co-4-iodo-1-butene), poly(ethylene-co-5-bromo-1-pentene), poly(ethylene-co-5-chloro-1-pentene), poly(ethylene-co-5-iodo-1-pentene), poly(ethylene-co-5-bromo-1-hexene), poly(ethylene-co-5-chloro-1-hexene), poly(ethylene-co-5-iodo-1-hexene), poly(ethylene-co-6-bromo-1-hexene) (Ethylene), poly(ethylene-co-6-chloro-1-hexene), poly(ethylene-co-6-iodo-1-hexene), poly(ethylene-co-7-bromo-1-heptene), poly(ethylene-co-7-chloro-1-heptene), poly(ethylene-co-7-iodo-1-heptene), poly(ethylene-co-8-bromo-1-octene), poly(ethylene-co-8-chloro-1-octene), poly(ethylene-co-8-iodo-1-octene), poly(ethylene-co-11-bromo-1-undecene), poly(ethylene-co-11-chloro-1-undecene), poly(ethylene-co-- 11-Iodo-1-undecene), poly(ethylene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-N,N-Diethyl-N-(heptenyl)amine), poly(propylene-co-4-bromo-1-butene), poly(propylene-co-4-chloro-1-butene), poly(propylene-co-4-iodo-1-butene), poly(propylene-co-5-bromo-1-pentene), poly(propylene-co-5-chloro-1-pentene), poly(propylene-co-5-iodo-1-pentene), poly(propylene-co-5-bromo-1-hexene), poly(propylene-co- 5-Chloro-1-hexene), poly(propylene-co-5-iodo-1-hexene), poly(propylene-co-6-bromo-1-hexene), poly(propylene-co-6-chloro-1-hexene), poly(propylene-co-6-iodo-1-hexene), poly(propylene-co-7-bromo-1-heptene), poly(propylene-co-7-chloro-1-heptene), poly(propylene-co-7-iodo-1-heptene), poly(propylene-co-8-bromo-1- Octene), poly(propylene-co-8-chloro-1-octene), poly(propylene-co-8-iodo-1-octene), poly(propylene-co-11-bromo-1-undecene), poly(propylene-co-11-chloro-1-undecene), poly(propylene-co-11-iodo-1-undecene), poly(propylene-co-N,N-diethyl-N-(butenyl)amine), poly(propylene-co-N,N-diisopropyl-N-(butenyl)amine) Poly(propylene-co-N,N-diethyl-N-(pentenyl)amine), poly(propylene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-N,N-diethyl-N-(hexenyl)amine), or poly(propylene-co-N,N-diethyl-N-(heptenyl)amine).

[0090] In another embodiment, three different monomers are used to obtain a terpolymer, preferably in which the first monomer is selected from the group consisting of ethylene and propylene, the second monomer is selected from the group consisting of propylene, 1-hexene, 1-octene, norbornene, or ethylene when the first monomer is propylene, and the third monomer is selected from the terpolymer consisting of: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5 -Bromo-1-hexene, 5-iodo-1-hexene, 6-chloro-1-hexene, 6-bromo-1-hexene, 6-iodo-1-hexene, 5,6-dichloro-1-hexene, 5,6-dibromo-1-hexene, 5,6-diiodo-1-hexene, 6,6-dichloro-1-hexene, 6,6-dibromo-1-hexene, 5-bromo-5-methyl-1-hexene, 5-chloro-5-methyl-1-hexene, 7-bromo-1-heptene, 7-iodo-1-heptene, 6-bromo-1-heptene, 6-chloro-1-heptene, 6-iodo-1-heptene, 6,7-dichloro-1-heptene, 6,7-diiodo-1-heptene, 6-bromo-6-methyl-1-heptene, 6-chloro-6-methyl-1-heptene, 6-iodo-6-methyl 8-Bromo-1-octene, 8-Bromo-1-octene, 8-Chloro-1-octene, 8-Iodo-1-octene, 7-Bromo-1-octene, 7-Chloro-1-octene, 7,8-Dichloro-1-heptene, 7,8-Diiodo-1-heptene, 11-Bromo-1-undecene, 11-Chloro-1-undecene, 11-Iodo-1-undecene, 5-Chloro-bicyclo(2.2.1)hept-2-ene, 5-Bromo-bicyclo(2.2.1)hept-2-ene, 5-Bromomethyl-bicyclo(2.2.1)hept-2-ene, 5-Chloromethyl-bicyclo(2.2.1)hept-2-ene, 5-Iodomethyl-bicyclo(2.2.1)hept-2-ene, 5-(2-Bromoethyl)-bicyclo(2.2.1)hept-2-ene, 5-(2-Chloroethyl)-bicyclo( 2.2.1) Hepta-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1)hepta-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1)hepta-2-ene, N,N-diethyl-N-(butenyl)amine, N,N-di-n-propyl-N-(butenyl)amine, N,N-diisopropyl-N-(butenyl)amine, N,N-diethyl-N-(pentenyl)amine, N,N-di-n-propyl-N-(pentenyl)amine, N,N-diisopropyl-N-(pentenyl)amine, N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine, N,N-diethyl-N-(hexenyl)amine, N,N-diisopropyl-N-(hexenyl)amine, N,N-Diethyl-N-(heptenyl)amine, N,N-diisopropyl-N-(heptenyl)amine, N,N-di-n-propyl-N-(heptenyl)amine, N,N-diethyl-N-(octenyl)amine, N,N-di-n-propyl-N-(octenyl)amine, N,N-diisopropyl-N-(octenyl)amine, N,N-diethyl-N-(undecenyl)amine, N,N-di-n-propyl-N-(undecenyl)amine, N,N-diisopropyl-N-(undecenyl)amine, 5-norbornen-2-N,N-diethylamine, 5-norbornen-2-N,N-(diethyl)methylamine, 5-norbornen-2-N,N-di(n-propyl)amine, 5-norbornen-2-N,N-(diisopropyl)methylamine; more preferably, [missing information - likely a specific type of amino acid]. The terpolymers are: poly(ethylene-co-1-octene-co-4-bromo-1-butene), poly(ethylene-co-1-octene-co-4-chloro-1-butene), poly(ethylene-co-1-octene-co-4-iodo-1-butene), poly(ethylene-co-1-octene-co-5-bromo-1-pentene), poly(ethylene-co-1-octene-co-5-chloro-1-pentene), poly(ethylene-co-1-octene-co-5-iodo-1-pentene), poly(ethylene-co-1-octene-co-5-bromo-1-hexene), poly(ethylene-co-1-octene-co-5-chloro-1-hexene), poly(ethylene-co-1-octene-co-5-iodo-1-hexene), poly(ethylene-co-1-octene-co-5-iodo-1-hexene), poly(ethylene-co-1-octene-co-6-bromo-1-hexene). ), poly(ethylene-co-1-octene-co-6-chloro-1-hexene), poly(ethylene-co-1-octene-co-6-iodo-1-hexene), poly(ethylene-co-1-octene-co-7-bromo-1-heptene), poly(ethylene-co-1-octene-co-7-chloro-1-heptene), poly(ethylene-co-1-octene-co-7-iodo-1-heptene), poly(ethylene-co-1-octene-co-8-bromo-1-octene), poly(ethylene-co-1-octene-co-8-chloro-1-octene), poly(ethylene-co-1-octene-co-8-iodo-1-octene), poly(ethylene-co-1-octene-co-11-bromo-1-undecene), poly(ethylene-co-1-octene-co-11-chloro-1-undecene), Poly(ethylene-co-1-octene-co-11-iodo-1-undecene), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-1-octene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-1-octene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-1-octene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-octene-co-N,N-Diethyl-N-(heptenyl)amine), poly(ethylene-co-1-hexene-co-4-bromo-1-butene), poly(ethylene-co-1-hexene-co-4-chloro-1-butene), poly(ethylene-co-1-hexene-co-4-iodo-1-butene), poly(ethylene-co-1-hexene-co-5-bromo-1-pentene), poly(ethylene-co-1-hexene-co-5-chloro-1-pentene), poly(ethylene-co-1-hexene-co-5-iodo-1-pentene), poly(ethylene-co-1-hexene-co-5-bromo-1-hexene), poly( Ethylene-co-1-hexene-co-5-chloro-1-hexene), poly(ethylene-co-1-hexene-co-5-iodo-1-hexene), poly(ethylene-co-1-hexene-co-6-bromo-1-hexene), poly(ethylene-co-1-hexene-co-6-chloro-1-hexene), poly(ethylene-co-1-hexene-co-6-iodo-1-hexene), poly(ethylene-co-1-hexene-co-7-bromo-1-heptene), poly(ethylene-co-1-hexene-co-7-chloro-1-heptene), poly(ethylene-co-1-hexene-co-7-iodo-1-heptene) (ethylene), poly(ethylene-co-1-hexene-co-8-bromo-1-octene), poly(ethylene-co-1-hexene-co-8-chloro-1-octene), poly(ethylene-co-1-hexene-co-8-iodo-1-octene), poly(ethylene-co-1-hexene-co-11-bromo-1-undecene), poly(ethylene-co-1-hexene-co-11-chloro-1-undecene), poly(ethylene-co-1-hexene-co-11-iodo-1-undecene), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(butenyl)amine), poly( Ethylene-co-1-hexene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-1-hexene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-1-hexene-co-N,N-Diethyl-N-(heptenyl)amine), poly(propylene-co-1-octene-co-4-bromo-1-butene), poly(propylene-co-1-octene-co-4-chloro-1-butene), poly(propylene-co-1-octene-co-4-iodo-1-butene), poly(propylene-co-1-octene-co-5-bromo-1-pentene), poly(propylene-co-1-octene-co-5-chloro-1-pentene), poly(propylene-co-1-octene-co-5-iodo-1-pentene), poly(propylene-co-1-octene-co-5-bromo-1-hexene), poly( Propylene-co-1-octene-co-5-chloro-1-hexene), poly(propylene-co-1-octene-co-5-iodo-1-hexene), poly(propylene-co-1-octene-co-6-bromo-1-hexene), poly(propylene-co-1-octene-co-6-chloro-1-hexene), poly(propylene-co-1-octene-co-6-iodo-1-hexene), poly(propylene-co-1-octene-co-7-bromo-1-heptene), poly(propylene-co-1-octene-co-7-chloro-1-heptene), poly(propylene-co-1-octene-co-7-iodo-1-heptene) Poly(propylene-co-1-octene-co-8-bromo-1-octene), poly(propylene-co-1-octene-co-8-chloro-1-octene), poly(propylene-co-1-octene-co-8-iodo-1-octene), poly(propylene-co-1-octene-co-11-bromo-1-undecene), poly(propylene-co-1-octene-co-11-chloro-1-undecene), poly(propylene-co-1-octene-co-11-iodo-1-undecene), poly(propylene-co-1-octene-co-N,N-diethyl-N-(butenyl)amine), poly( Propylene-co-1-octene-co-N,N-diisopropyl-N-(butenyl)amine), poly(propylene-co-1-octene-co-N,N-diethyl-N-(pentenyl)amine), poly(propylene-co-1-octene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-1-octene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-1-octene-co-N,N-diethyl-N-(hexenyl)amine), poly(propylene-co-1-octene-co-N,N-diisopropyl-N-(hexenyl)amine), poly(propylene-co-1-octene-co-N,N-Diethyl-N-(heptenyl)amine), poly(ethylene-co-norbornene-co-4-bromo-1-butene), poly(ethylene-co-norbornene-co-4-chloro-1-butene), poly(ethylene-co-norbornene-co-4-iodo-1-butene), poly(ethylene-co-norbornene-co-5-bromo-1-pentene), poly(ethylene-co-norbornene-co-5-chloro-1-pentene), poly(ethylene-co-norbornene-co-5-iodo-1-pentene), poly(ethylene-co-norbornene-co-5-bromo-1-hexene), poly( Ethylene-co-norbornene-co-5-chloro-1-hexene), poly(ethylene-co-norbornene-co-5-iodo-1-hexene), poly(ethylene-co-norbornene-co-6-bromo-1-hexene), poly(ethylene-co-norbornene-co-6-chloro-1-hexene), poly(ethylene-co-norbornene-co-6-iodo-1-hexene), poly(ethylene-co-norbornene-co-7-bromo-1-heptene), poly(ethylene-co-norbornene-co-7-chloro-1-heptene), poly(ethylene-co-norbornene-co-7-iodo-1-heptene) (Ethylene), poly(ethylene-co-norbornene-co-8-bromo-1-octene), poly(ethylene-co-norbornene-co-8-chloro-1-octene), poly(ethylene-co-norbornene-co-8-iodo-1-octene), poly(ethylene-co-norbornene-co-11-bromo-1-undecene), poly(ethylene-co-norbornene-co-11-chloro-1-undecene), poly(ethylene-co-norbornene-co-11-iodo-1-undecene), poly(ethylene-co-norbornene-co-N,N-diethyl-N-(butenyl)amine), poly( Ethylene-co-norbornene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-norbornene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-norbornene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-norbornene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-norbornene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-norbornene-co-N,N-diisopropyl-N-(hexenyl)amine), poly(ethylene-co-norbornene-co-N,N-Diethyl-N-(heptenyl)amine), poly(ethylene-co-propylene-co-4-bromo-1-butene), poly(ethylene-co-propylene-co-4-chloro-1-butene), poly(ethylene-co-propylene-co-4-iodo-1-butene), poly(ethylene-co-propylene-co-5-bromo-1-pentene), poly(ethylene-co-propylene-co-5-chloro-1-pentene), poly(ethylene-co-propylene-co-5-iodo-1-pentene), poly(ethylene-co-propylene-co-5-bromo-1-hexene), poly( Ethylene-co-propylene-co-5-chloro-1-hexene), poly(ethylene-co-propylene-co-5-iodo-1-hexene), poly(ethylene-co-propylene-co-6-bromo-1-hexene), poly(ethylene-co-propylene-co-6-chloro-1-hexene), poly(ethylene-co-propylene-co-6-iodo-1-hexene), poly(ethylene-co-propylene-co-7-bromo-1-heptene), poly(ethylene-co-propylene-co-7-chloro-1-heptene), poly(ethylene-co-propylene-co-7-iodo-1-heptene) Poly(ethylene-co-propylene-co-8-bromo-1-octene), poly(ethylene-co-propylene-co-8-chloro-1-octene), poly(ethylene-co-propylene-co-8-iodo-1-octene), poly(ethylene-co-propylene-co-11-bromo-1-undecene), poly(ethylene-co-propylene-co-11-chloro-1-undecene), poly(ethylene-co-propylene-co-11-iodo-1-undecene), poly(ethylene-co-propylene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(butenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(butenyl)amine) -co-propylene-co-N,N-diisopropyl-N-(butenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(pentenyl)amine), poly(ethylene-co-propylene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(ethylene-co-propylene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(ethylene-co-propylene-co-N,N-diethyl-N-(hexenyl)amine), poly(ethylene-co-propylene-co-N,N-Diethyl-N-(heptenyl)amine), poly(propylene-co-1-hexene-co-4-bromo-1-butene), poly(propylene-co-1-hexene-co-4-chloro-1-butene), poly(propylene-co-1-hexene-co-4-iodo-1-butene), poly(propylene-co-1-hexene-co-5-bromo-1-pentene), poly(propylene-co-1-hexene-co-5-chloro-1-pentene), poly(propylene-co-1-hexene-co-5-iodo-1-pentene), poly(propylene-co-1-hexene-co-5-bromo-1-hexene), poly( Propylene-co-1-hexene-co-5-chloro-1-hexene), poly(propylene-co-1-hexene-co-5-iodo-1-hexene), poly(propylene-co-1-hexene-co-6-bromo-1-hexene), poly(propylene-co-1-hexene-co-6-chloro-1-hexene), poly(propylene-co-1-hexene-co-6-iodo-1-hexene), poly(propylene-co-1-hexene-co-7-bromo-1-heptene), poly(propylene-co-1-hexene-co-7-chloro-1-heptene), poly(propylene-co-1-hexene-co-7-iodo-1-heptene) Poly(propylene-co-1-hexene-co-8-bromo-1-octene), poly(propylene-co-1-hexene-co-8-chloro-1-octene), poly(propylene-co-1-hexene-co-8-iodo-1-octene), poly(propylene-co-1-hexene-co-11-bromo-1-undecene), poly(propylene-co-1-hexene-co-11-chloro-1-undecene), poly(propylene-co-1-hexene-co-11-iodo-1-undecene), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(butenyl)amine), poly( Propylene-co-1-hexene-co-N,N-diisopropyl-N-(butenyl)amine), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(pentenyl)amine), poly(propylene-co-1-hexene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-1-hexene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(propylene-co-1-hexene-co-N,N-diethyl-N-(hexenyl)amine), poly(propylene-co-1-hexene-co-N,N-Diethyl-N-(heptenyl)amine), poly(propylene-co-norbornene-co-4-bromo-1-butene), poly(propylene-co-norbornene-co-4-chloro-1-butene), poly(propylene-co-norbornene-co-4-iodo-1-butene), poly(propylene-co-norbornene-co-5-bromo-1-pentene), poly(propylene-co-norbornene-co-5-chloro-1-pentene), poly(propylene-co-norbornene-co-5-iodo-1-pentene), poly(propylene-co-norbornene-co-5-bromo-1-hexene), poly(propylene-co- Norbornene-co-5-chloro-1-hexene), poly(propylene-co-norbornene-co-5-iodo-1-hexene), poly(propylene-co-norbornene-co-6-bromo-1-hexene), poly(propylene-co-norbornene-co-6-chloro-1-hexene), poly(propylene-co-norbornene-co-6-iodo-1-hexene), poly(propylene-co-norbornene-co-7-bromo-1-heptene), poly(propylene-co-norbornene-co-7-chloro-1-heptene), poly(propylene-co-norbornene-co-7-iodo-1-heptene), poly(propylene-co-5-chloro-1-heptene) -norbornene-co-8-bromo-1-octene), poly(propylene-co-norbornene-co-8-chloro-1-octene), poly(propylene-co-norbornene-co-8-iodo-1-octene), poly(propylene-co-norbornene-co-11-bromo-1-undecene), poly(propylene-co-norbornene-co-11-chloro-1-undecene), poly(propylene-co-norbornene-co-11-iodo-1-undecene), poly(propylene-co-norbornene-co-N,N-diethyl-N-(butenyl)amine), poly(propylene-co-norbornene-co-N-N N-Diisopropyl-N-(Butenyl)amine, poly(propylene-co-norbornene-co-N,N-diethyl-N-(pentenyl)amine), poly(propylene-co-norbornene-co-N,N-diisopropyl-N-(pentenyl)amine), poly(propylene-co-norbornene-co-11-N,N-diisopropyl-N-(3-methyl-5-hexenyl)amine), poly(propylene-co-norbornene-co-N,N-diethyl-N-(hexenyl)amine), or poly(propylene-co-norbornene-co-N,N-diethyl-N-(heptenyl)amine).

[0091] The amount of functionalized olefin monomer in the preferred functionalized polyolefin is 0.01 to 20 mol% relative to the total molar amount of olefin monomer and functionalized olefin monomer in the functionalized polyolefin, preferably 0.02 to 15 mol%, or 0.05 to 10 mol%, or 0.1 to 5 mol%, more preferably 0.02 to 2 mol%.

[0092] Catalyst systems suitable for the method according to the invention

[0093] The method according to the invention is carried out in the presence of a suitable catalyst system comprising at least the following:

[0094] ●Catalyst,

[0095] ● Co-catalyst,

[0096] ●Optional, cleaning agent

[0097] ●Optional, chain transfer agent.

[0098] catalyst

[0099] The catalyst is a ligand-metal complex with a bridging bis(diaryl) structure. Specifically, the ligand is a dianionochelate ligand that can occupy up to four coordination sites on the metal precursor atom, and more specifically, has a bridging bis(diaryl) structure.

[0100] The metal-ligand complex used in this invention can be characterized by the general formula (4,O)MLn'(VI), wherein (4,O) is a dianionic ligand having at least four oxygen atoms chelated to metal M at four coordination sites via oxygen atoms, wherein two of the bonds between oxygen and the metal are covalent and the other two are coordinate; M is a metal selected from Group 4 of the periodic table, more specifically Hf or Zr, more preferably Hf; L is independently selected from the group consisting of halogens (F, CI, Br, I), optionally substituted. Alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, silyl, boronyl, phosphinyl, amino, alkylthio, arylthio, nitro, hydrido, borohydride, allyl, diene, phosphine, carboxylic acid group / radix, 1,3-dionate group / radix, oxalate group / radix, carbonate group / radix, nitrate group / radix, sulfate group / radix, ether, thioether and combinations thereof; and optionally two or more L groups may be linked together in a ring structure; n' is 1, 2, 3 or 4.

[0101] Metallic precursors can be monomers, dimers, or higher forms. Specific examples of suitable hafnium and zirconium precursors include, but are not limited to:

[0102] HfCl4, Hf(CH2Ph)4, Hf(CH2CMe3)4, Hf(CH2SiMe3)4, Hf(CH2Ph)3Cl, Hf(CH2CMe3)3Cl, Hf(CH2SiMe3)3Cl , Hf(CH2Ph)2Cl2, Hf(CH2CMe3)2Cl2, Hf(CH2SiMe3)2Cl2, Hf(NMe2)4, Hf(NEt2)4, and Hf(N(SiMe3)2)2Cl2;

[0103] ZrCl4, Zr(CH2Ph)4, Zr(CH2CMe3)4, Zr(CH2SiMe3)4, Zr(CH2Ph)3Cl, Zr(CH2CMe3)3Cl, Zr(CH2SiMe3)3Cl, Zr(CH2Ph)2Cl 2. Zr(CH2CMe3)2Cl2, Zr(CH2SiMe3)2Cl2, Zr(NMe2)4, Zr(NEt2)4, Zr(NMe2)2Cl2, Zr(NEt2)2Cl2, and Zr(N(SiMe3)2)2Cl2.

[0104] Lewis base adducts of these examples are also suitable as metal precursors; for example, ethers, amines, thioethers, phosphines, and the like are suitable as Lewis bases.

[0105] In other embodiments, the metal-ligand complexes of the present invention can be characterized by the following general formula:

[0106]

[0107] in

[0108] ●R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 and R 28 The R group is independently selected from the group consisting of: hydrogen groups, halogen groups, and optionally substituted hydrocarbon groups, heteroatom-containing hydrocarbon groups, alkoxy groups, aryloxy groups, silyl groups, boron groups, phosphin groups, amino groups, alkylthio groups, arylthio groups, thiooxy groups, selenyl groups, nitro groups, and combinations thereof; optionally, two or more R groups can be combined to form a ring structure, wherein such ring structures have 3 to 100 atoms in the ring, not counting hydrogen atoms.

[0109] ●M is a metal, either Hf or Zr.

[0110] ●L is the structural part that forms a covalent, coordinate, or ionic bond with M; and n' is 1, 2, 3, or 4.

[0111] ●X, X', Y 2 and Y 3 It is an oxygen atom.

[0112] ●B is a bridging group having 1 to 50 atoms with an uncounted number of hydrogen atoms, more preferably B is a propane bridge.

[0113] In a preferred embodiment, the ligand-metal complex must be a hafnium or zirconium complex of a polyaryloxy ether, selected from the group comprising at least the following: dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium (IV), dichlorobis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl) Hafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium Hafnium(IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-butanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-butanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-butanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-butanediylhafnium(IV)) Hafnium di(IV)-1,4-butanediylhafnium (2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pent ...9-Octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV), dimethylbis((2-oxy-3-(1,2,3,4,6) ,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl) (-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl) -2-phenoxy)-1,4-n-butylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-Butylhafnium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-Butylhafnium (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-Butylhafnium (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-Butylhafnium (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-Butylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), Dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV); preferably dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dichlorobis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-2-ethyl ... (2-O-( ... 2,3,4,6,7,8,9-Octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dichloride bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl) (2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dibenzylbis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV), dimethylbis((2-Oxy-3-(1,2) ... ,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyzirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyzirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyzirconium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2- Phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dichloride bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-Cyclohexanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)-2- ... (2-O-(2-O-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylzirconium (IV), dibenzylbis((2-O- ... H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)- 2-Phenoxy)-1,4-n-Butylzirconium (IV), Dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-Butylzirconium (IV), (OC-6-33)-[[2,2”'-[1,4-butanediylbis(oxy-κO)]bis[3”,5’,5”-tris(1,1-dimethylethyl)[1,1’:3’,1”-terphenyl]-2’-O-κO]](2-)]bis(phenylmethyl)hafnium, (OC-6-33)-[[2,2”'-[1,4-butanediylbis(oxy-κO)]bis[3”,5’,5”-tris(1,1-dimethylethyl)[1,1’:3’,1"-Triphenyl]-2'-O-κO]](2-)]bis(phenylmethyl)zirconium; preferably dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyrconium (IV) or dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyrconium (IV).

[0114] co-catalyst

[0115] The cocatalyst is selected from the group consisting of MAO, DMAO, MMAO, SMAO, or ammonium salts or triphenylmethyl salts of tetrafluoroarylborates or arylboranes; preferably MAO, MMAO, dimethylphenylammonium triphenylmethyltetra(pentafluorophenyl)borate or tri(alkyl)ammonium tetra(pentafluorophenyl)borate, such as tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, methyl di(alkyl)ammonium tetra(pentafluorophenyl)borate. Further examples can be found in the review articles Bochmann Organometallics 2010, 29, 4711-4740 and Chen and Marks Chem. Rev. 2000, 100, 1391-1434.

[0116] As used in this specification, methylaluminoxane or MAO may refer to compounds derived from the partial hydrolysis of trimethylaluminum that act as co-catalysts for the polymerization of olefins.

[0117] As used in this specification, loaded methylaluminoxane or SMAO may mean: methylaluminoxane bound to a solid support.

[0118] As used in this specification, depleted methylaluminoxane or DMAO may mean: methylaluminoxane from which free trimethylaluminum has been removed.

[0119] As used in this specification, modified methylaluminoxane or MMAO may mean: modified methylaluminoxane, i.e., the product obtained by partial hydrolysis of trimethylaluminum with another trialkylaluminum such as triisobutylaluminum or tri-n-octylaluminum.

[0120] As used in this specification, fluorinated arylborates or fluorinated arylboranes may mean: borate compounds having three or four fluorinated (preferably perfluorinated) aryl ligands or borane compounds having three fluorinated (preferably perfluorinated) aryl ligands.

[0121] Optional cleaning agents

[0122] Optionally, a scavenger can be added to the catalyst system to react with impurities present in the polymerization reactor and / or in the solvent and / or monomer feed. This scavenger prevents catalyst poisoning during olefin polymerization. Optional scavengers are selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum; preferably triethylaluminum.

[0123] Surprisingly, triethylaluminum does not cause significant chain transfer and does not inhibit catalysts containing ligand-metal complexes as described above. This characteristic allows for the use of triethylaluminum instead of triisobutylaluminum, which is a significant cost benefit.

[0124] Optional chain transfer agent

[0125] The optional chain transfer agent is selected from the group consisting of dihydrogen or AlR. 10 3, BR 10 3 or ZnR 10 2, where each R 10 It is independently selected from hydrogen or hydrocarbon groups.

[0126] Aggregation conditions

[0127] The polymerization according to the invention is carried out in solution using the catalyst system described above.

[0128] In this process, polymerization conditions such as temperature, time, pressure, and monomer concentration can be selected within a wide range. The polymerization temperature is 100 to 250°C, preferably 110 to 210°C, more preferably 130 to 180°C. The polymerization time is 10 seconds to 20 hours, preferably 1 minute to 2 hours, more preferably 2 minutes to 1 hour, and more preferably 5 to 30 minutes. The molecular weight of the polymer can be controlled by using hydrogen or other chain transfer agents. Polymerization can be carried out by batch, semi-continuous, or continuous processes, and can also be carried out in two or more steps under different polymerization conditions. The resulting polyolefin is separated from the polymerization solvent and dried by methods known to those skilled in the art.

[0129] In the implementation scheme, hindered phenols such as butylated hydroxytoluene (BHT) may be added during the polymerization process, particularly in amounts of one or more group metal compounds, for example, from 0.1 to 5 molar equivalents, which act as scavengers and / or cocatalysts. This can help increase the molecular weight and / or comonomer blending.

[0130] Preferably, in step a), the amount of functionalized olefin monomer is 0.01 to 20 mol% relative to the total molar amount of olefin monomer and functionalized olefin monomer, preferably 0.02 to 15 mol% or 0.05 to 10 mol%, or 0.1 to 5 mol%, more preferably 0.02 to 2 mol%.

[0131] The present invention may include the addition of other additives, such as processing stabilizers (primary antioxidants), such as Irganox 1010.

[0132] The polymerization is quenched by treating the polymer solution obtained after the polymerization process with a quenching agent. Typical examples of quenching agents are carbon monoxide, carbon dioxide, oxygen, water, alcohol, or acidification or alkalization of water or alcohol.

[0133] Optionally, a deashing step may be performed after the polymerization step to separate water-insoluble aluminum-based residues derived from co-catalysts and scavengers, such as aluminum oxides and aluminum hydroxides, for example Al(O)OH, Al(OH)3 and Al2O3, from the polymer by means of flocculation and sedimentation, filtration, including membrane separation, centrifugation or adsorption.

[0134] It should be noted that this invention relates to all possible combinations of the features described herein, preferably, in particular, those combinations of the features presented in the claims. Specifically, it should be noted that the preferred materials or preferred amounts of materials disclosed in the case of the method according to the invention are equally applicable to functionalized olefin copolymers and / or functionalized olefin copolymer compositions.

[0135] It should be further noted that the terms 'comprising,' 'including,' and 'containing' do not exclude the presence of other elements. However, it should also be understood that descriptions of products / compositions comprising certain components also disclose products / compositions composed of those components. Products / compositions composed of these components may be advantageous because they provide a simpler and more economical method for preparing the product / composition. Similarly, it should be understood that descriptions of methods including certain steps also disclose methods composed of those steps. Methods composed of these steps may be advantageous because they provide a simpler and more economical method.

[0136] When a value is mentioned for the lower and upper limits of a parameter, it is also understood to mean that the range of combinations of the lower and upper limits is disclosed. Example

[0137] The invention is now illustrated by means of the following non-limiting embodiments.

[0138] 1 HNMR characterization

[0139] The percentage of functionalization was determined by 1H NMR analysis on a Varian Mercury spectrometer operating at 400 MHz, using tetrachloroethane deuterated (TCE-D2) as solvent at 130 °C, and recorded in 5 mm tubes. Chemical shifts were reported as ppm relative to tetramethylsilane and determined by reference to residual solvent protons.

[0140] High-Temperature Size Exclusion Chromatography (HT-SEC)

[0141] Molecular weight and PDI, reported in kg / mol, were determined by high-temperature size exclusion chromatography (HMS) at 150 °C in a GPC-IR system (PolymerChar, Valencia, Spain) equipped with an IR4 detector and a carbonyl sensor. Column settings: three Polymer Laboratories 13 μm PLgel Olexis columns, 300 × 7.5 mm. 1,2-Dichlorobenzene (o-DCB) was used as the eluent at a flow rate of 1 mL / min. Molecular weight and corresponding PDI were calculated relative to narrow-band polystyrene standards (PSS, Mainz, Germany) from HT SEC analysis.

[0142] Differential scanning calorimetry (DSC)

[0143] Thermal analysis was performed on a TA Instruments DSC Q100 at a heating rate of 5 °C / min. First and second runs were recorded after cooling to approximately -40 °C. As determined by DSC, all copolymers were found to be amorphous.

[0144] According to embodiments of the present invention

[0145] Use stainless steel filled with 0.15L of pentamethylheptane (PMH) solvent. The copolymerization experiment was conducted in a 0.3 L reactor using a stirring speed of 500 rpm. Catalyst and comonomer solutions were prepared in a glove box. For example, for Item 3 in Table 1, the reactor was first heated to 40 °C, followed by the addition of TiBA (1.0 M solution in toluene, 0.5 mL) and 11-bromo-1-undecene (1.0 M solution in toluene, 4 mmol). The reactor was loaded with gaseous propylene (25 g) at 40 °C and heated to the desired polymerization temperature of 130 °C, resulting in a propylene partial pressure of 15 bar. Once the set temperature is reached, polymerization is initiated by injecting a pre-activated catalyst precursor, dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV) [CAS 958665-18-4], also known as [[2',2”'-[(1,3-dimethyl-1,3-propanediyl)bis(oxy-κO)]bis[3-(9H-carbazole-9-yl)-5-methyl[1,1'-biphenyl]-2-O-κO]](2-)]dimethyl]hafnium (Hf-O4, 0.25 mg, 0.25 μmol), into MAO (30 wt% solution in toluene, 4.5 mmol). The polymer solution is then poured into a solution containing acidified isopropanol (2.5% v / v HCl, 500 mL) and Irganox. The reaction was stopped using an Erlenmeyer flask containing 1010 (1.0 M, 0.5 mmol). The resulting suspension was stirred for about 4 h, filtered, washed with demineralized water / iPrOH (50 wt%, 2 × 500 mL), and dried in a vacuum oven at 80 °C. Irganox 1010 was then added as an antioxidant to obtain poly(propylene-co-1-bromo-undecene) (2.9 g).

[0146] Table 1. Copolymerization of propylene with 11-bromo-1-undecene using Hf-O4 and Zr-O4 catalysts

[0147]

[0148] condition:

[0149] The reaction is The experiment was conducted in a reactor (0.3 L) using either dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) (Hf-O4 = 0.25 μmol) or dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium(IV) (Zr-O4 = 0.1 μmol), propylene partial pressure approximately 15 bar, pentamethylheptane = 0.15 L, MAO (30 wt% solution in toluene) = 4.5 mmol, with an additional amount of TiBA (1.0 M solution in toluene, 0.5 mL) added as a scavenger.

[0150] Yield was determined by weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 80°C.

[0151] na = Not applicable

[0152] Comparative Examples

[0153] The following comparative examples were conducted without utilizing the hafnium or zirconium complex catalysts of the polyvalent aryloxy ethers according to the present invention:

[0154] ●rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst (Zr-metallocene)

[0155] ●rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2 catalyst (Hf-metallocene)

[0156] Table 2. Copolymerization of propylene with 11-bromo-1-undecene using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst (A) and rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2 catalyst (B)

[0157]

[0158] Conditions: The reaction was carried out in a BUCHI reactor (0.3 L) using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2(A) = 3.2 μmol and rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2(B) = 5.5 μmol, propylene partial pressure approximately 15 bar, pentamethylheptane = 0.15 L, MAO (30 wt% solution in toluene) = 4.5 mmol, with an additional amount of TiBA (1.0 M solution in toluene, 0.5 mL) added as a scavenger.

[0159] ● The yield was determined by the weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 80°C.

[0160] ●CE1 is a reference propylene polymerization using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst.

[0161] ●CE3 is a reference propylene polymerization using rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2 catalyst.

Claims

1. A method for obtaining functionalized polyolefins by solution copolymerization, comprising at least the following steps: A copolymerization step involving at least one olefin monomer and at least one functionalized olefin monomer in the presence of a catalyst system, wherein the polymerization temperature is between 100 and 250 °C. The olefin monomers therefrom are CHR 1 =CHR 2 It means that R 1 and R 2 Each is independently hydrogen or an alkyl group having 1 to 6 carbon atoms, wherein R 1 and R 2 They can form a ring structure together. The functionalized olefin monomers described herein are represented by structures according to formula (I): Where R 3 R 4 and R 5 Each group is independently selected from H and hydrocarbon groups having 1 to 16 carbon atoms. Where R 6 -[X-(R 7 ) n ] m It contains m heteroatom-containing functional groups X-(R) 7 ) n The polar functional groups, where m is an integer from 1 to 10, where n=0, meaning there is no R. 7 X is selected from F, Cl, Br, and I. Where R 6 For one or more -C(R) 8 (R) 9 )- group, wherein R 8 and R 9 Each is independently selected from the group consisting of H or hydrocarbon groups having 1 to 16 carbon atoms, and R 6 Contains 1 to 10 carbon atoms, Where R 4 and R 6 They can be formed together by one or more X-(R) 7 ) n Functionalized ring structures, Where X is connected to R 6 The main chain or side chain, And the catalyst system described herein comprises: ● Hafnium or zirconium complexes of polyvalent aryloxy ethers selected from the following groups: Dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl) (2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dibenzylbis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-but ... Hafnium(IV) of anthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium, dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dibenzylbis((2-oxy-3-) (Dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2,2-butanediylhafnium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2,4-Pentanediylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dichlorobis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl) (2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dibenzylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dimethylbis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzylbis((2-oxy- 3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzyl ...1-Dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)- 2-Phenoxy)-1,2-Ethylhafnium (IV), Dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV); Dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyrzirconium (IV), Dichloride ((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyrzirconium (IV), Dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3- Propanediylzirconium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-propanediylzirconium (IV), dimethyl ... (-phenoxy)-1,3-propanedizirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanedizirconium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dibenzyl ...9-Octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanedizirconium (IV), dimethylbis((2-oxy-3-(1,2,3-) ... 4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl) Zirconium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylzirconium (IV), dichloride bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylzirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylzirconium (IV), dimethylbis((2- oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-Butylzirconium (IV), Dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-Butylzirconium (IV), Dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-Ethylzirconium (IV), Dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-Ethylzirconium (IV), Dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl) (-2-phenoxy)-1,3-propylzirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9 H-Carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylzirconium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium Hafnium(IV), (OC-6-33)-[[2,2”'-[1,4-butanediylbis(oxy-κO)]bis[3”,5’,5”-tris(1,1-dimethylethyl)[1,1’:3’,1”-terphenyl]-2’-O-κO]](2-)]bis(phenylmethyl)zafnium, (OC-6-33)-[[2,2”'-[1,4-butanediylbis(oxy-κO)]bis[3”,5’,5”-tris(1,1-dimethylethyl)[1,1’:3’,1”-terphenyl]-2’-O-κO]](2-)]bis(phenylmethyl)zafnium; and, ●A cocatalyst selected from the following group: MAO, DMAO, MMAO, SMAO, or an ammonium salt or triphenylmethyl salt of a tetrafluoroarylborate; and ●Optionally, a scavenger selected from the group consisting of: trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and ●Optionally, chain transfer agents selected from the following group: AlR 10 3, BR 10 3 or MgR 10 2 or ZnR 10 2, where each R 10 It can be a hydrogen or hydrocarbon group independently.

2. The method of claim 1, wherein a deashing step is performed after the polymerization step to separate aluminum-based residues from the functionalized polyolefin derived from the co-catalyst and the scavenger.

3. The method according to claim 1 or 2, wherein the at least one olefin monomer is selected from the group consisting of ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, 1-octene, norbornene, or ethylidene norbornene.

4. The method according to claim 1 or 2, wherein the at least one functionalized olefin monomer is selected from the group comprising: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo-1-hexene, 6-chloro-1-... 5-Hexene, 6-Bromo-1-hexene, 6-Iodo-1-hexene, 5,6-Dichloro-1-hexene, 5,6-Dibromo-1-hexene, 5,6-Diiodo-1-hexene, 6,6-Dichloro-1-hexene, 6,6-Dibromo-1-hexene, 6,6-Diiodo-1-hexene, 5-Bromo-5-methyl-1-hexene, 5-Chloro-5-methyl-1-hexene, 7-Bromo-1-heptene, 7-Iodo-1-heptene, 6-Bromo-1-heptene, 6-Chloro-1-heptene, 6-Iodo-1-heptene, 6,7-Dichloro-1-heptene 6,7-Diiodo-1-heptene, 6-bromo-6-methyl-1-heptene, 6-chloro-6-methyl-1-heptene, 6-iodo-6-methyl-1-heptene, 8-bromo-1-octene, 8-chloro-1-octene, 8-iodo-1-octene, 7-bromo-1-octene, 7-chloro-1-octene, 7,8-dichloro-1-heptene, 7,8-diiodo-1-heptene, 11-bromo-1-undecene, 11-chloro-1-undecene, 11-iodo-1-undecene, 5-chloro-bicyclo(2.2.1)hept-2-ene, 5-bromo- Bicyclo(2.2.1)hept-2-ene, 5-bromomethyl-bicyclo(2.2.1)hept-2-ene, 5-chloromethyl-bicyclo(2.2.1)hept-2-ene, 5-iodomethyl-bicyclo(2.2.1)hept-2-ene, 5-(2-bromoethyl)-bicyclo(2.2.1)hept-2-ene, 5-(2-chloroethyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1)hept-2-ene, or 5-(3-bromopropyl)-bicyclo(2.2.1)hept-2-ene.

5. The method according to claim 1 or 2, wherein the amount of the functionalized olefin monomer in the functionalized polyolefin obtained by step b) is 0.01 to 20 moles relative to the total molar amount of the olefin monomer and the functionalized olefin monomer in the functionalized polyolefin.

6. The method according to claim 1 or 2, wherein the first and second olefin monomers are used to copolymerize with the at least one functionalized olefin monomer, wherein the first and second olefin monomers are different, and wherein the amount of the first olefin monomer is 20 to 80 mol% and the amount of the second olefin monomer is 80 to 20 mol% based on the total molar amount of the first and second olefin monomers.

7. The method according to claim 1 or 2, wherein at least one of the olefin monomers is propylene, and is used in an amount of at least 50% by weight relative to the total weight of the olefin monomer and the functionalized olefin monomer.

8. The method according to claim 1 or 2, wherein at least one of the olefin monomers is ethylene, used in an amount of at least 50% by weight relative to the total weight of the olefin monomer and the functionalized olefin monomer.

9. The method of claim 6, wherein the first olefin is propylene or ethylene and the second olefin is 1-hexene, 1-octene or norbornene, or the first olefin is propylene and the second olefin is ethylene.

10. The method according to claim 1 or 2, wherein the functionalized polyolefin is obtained, wherein the first monomer is selected from the group comprising ethylene and propylene, and the second monomer is a functionalized monomer selected from the group comprising: allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 5-iodo-1-pentene, 5-chloro-1-hexene, 5- 1-Bromo-hexene, 5-Iodo-1-hexene, 6-Chloro-1-hexene, 6-Bromo-1-hexene, 6-Iodo-1-hexene, 5,6-Dichloro-1-hexene, 5,6-Dibromo-1-hexene, 5,6-Diiodo-1-hexene, 6,6-Dichloro-1-hexene, 6,6-Dibromo-1-hexene, 6,6-Diiodo-1-hexene, 5-Bromo-5-methyl-1-hexene, 5-Chloro-5-methyl-1-hexene, 7-Bromo-1-heptene, 7-Iodo-1-heptene, 6-Bromo-1-heptene, 6-Chloro-1-heptene, 6-Iodo-1-heptene Alkenes, 6,7-dichloro-1-heptene, 6,7-diiodo-1-heptene, 6-bromo-6-methyl-1-heptene, 6-chloro-6-methyl-1-heptene, 6-iodo-6-methyl-1-heptene, 8-bromo-1-octene, 8-chloro-1-octene, 8-iodo-1-octene, 7-bromo-1-octene, 7-chloro-1-octene, 7,8-dichloro-1-heptene, 7,8-diiodo-1-heptene, 11-bromo-1-undecene, 11-chloro-1-undecene, 11-iodo-1-undecene, 5-chloro-bicyclo(2.2.1)hept-2 5-Bromo-bicyclo(2.2.1)hept-2-ene, 5-Bromomethyl-bicyclo(2.2.1)hept-2-ene, 5-Chloromethyl-bicyclo(2.2.1)hept-2-ene, 5-Iodomethyl-bicyclo(2.2.1)hept-2-ene, 5-(2-Bromoethyl)-bicyclo(2.2.1)hept-2-ene, 5-(2-Chloroethyl)-bicyclo(2.2.1)hept-2-ene, 5-(3-Bromopropyl)-bicyclo(2.2.1)hept-2-ene, or 5-(3-Bromopropyl)-bicyclo(2.2.1)hept-2-ene.

11. The method according to claim 10, wherein the functionalized polyolefin is: poly(ethylene-co-4-bromo-1-butene), poly(ethylene-co-4-chloro-1-butene), poly(ethylene-co-4-iodo-1-butene), poly(ethylene-co-5-bromo-1-pentene), poly(ethylene-co-5-chloro-1-pentene), poly(ethylene-co-5-iodo-1-pentene), poly(ethylene-co-5-bromo-1-hexene), poly(ethylene-co-5-chloro-1-hexene), poly(ethylene-co-5-iodo-1-hexene), poly(ethylene-co-4-bromo ... 6-Bromo-1-hexene), poly(ethylene-co-6-chloro-1-hexene), poly(ethylene-co-6-iodo-1-hexene), poly(ethylene-co-7-bromo-1-heptene), poly(ethylene-co-7-chloro-1-heptene), poly(ethylene-co-7-iodo-1-heptene), poly(ethylene-co-8-bromo-1-octene), poly(ethylene-co-8-chloro-1-octene), poly(ethylene-co-8-iodo-1-octene), poly(ethylene-co-11-bromo-1-undecene), poly(ethylene-co-11-chloro-1-undecene), poly(ethylene- Co-11-iodo-1-undecene), poly(propylene-co-4-bromo-1-butene), poly(propylene-co-4-chloro-1-butene), poly(propylene-co-4-iodo-1-butene), poly(propylene-co-5-bromo-1-pentene), poly(propylene-co-5-chloro-1-pentene), poly(propylene-co-5-iodo-1-pentene), poly(propylene-co-5-bromo-1-hexene), poly(propylene-co-5-chloro-1-hexene), poly(propylene-co-5-iodo-1-hexene), poly(propylene-co-6-bromo-1-hexene), poly(propylene- Co-6-chloro-1-hexene), poly(propylene-co-6-iodo-1-hexene), poly(propylene-co-7-bromo-1-heptene), poly(propylene-co-7-chloro-1-heptene), poly(propylene-co-7-iodo-1-heptene), poly(propylene-co-8-bromo-1-octene), poly(propylene-co-8-chloro-1-octene), poly(propylene-co-8-iodo-1-octene), poly(propylene-co-11-bromo-1-undecene), poly(propylene-co-11-chloro-1-undecene), or poly(propylene-co-11-iodo-1-undecene).

12. The method according to claim 1 or 2, wherein a functionalized terpolymer is obtained.

13. The method of claim 12, wherein the terpolymer is obtained by means of a first monomer selected from the group consisting of ethylene and propylene, a second monomer selected from the group consisting of propylene, 1-hexene, 1-octene, and norbornene, and a third monomer being a functionalized monomer selected from the group consisting of allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene, 3-bromo-3-methyl-1-butene, 3-chloro-3-methyl-1-butene, 3-iodo-3-methyl-1-butene, 5-bromo-1-pentene, and 5-chloro-1-pentene. 5-Iodo-1-pentene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo-1-hexene, 6-chloro-1-hexene, 6-bromo-1-hexene, 6-iodo-1-hexene, 5,6-dichloro-1-hexene, 5,6-dibromo-1-hexene, 5,6-diiodo-1-hexene, 6,6-dichloro-1-hexene, 6,6-dibromo-1-hexene, 5-bromo-5-methyl-1-hexene, 5-chloro-5-methyl-1-hexene, 7-bromo-1-heptene, 7-iodo-1-heptene, 6-bromo-1-heptene, 6- Chloro-1-heptene, 6-iodo-1-heptene, 6,7-dichloro-1-heptene, 6,7-diiodo-1-heptene, 6-bromo-6-methyl-1-heptene, 6-chloro-6-methyl-1-heptene, 6-iodo-6-methyl-1-heptene, 8-bromo-1-octene, 8-chloro-1-octene, 8-iodo-1-octene, 7-bromo-1-octene, 7-chloro-1-octene, 7,8-dichloro-1-heptene, 7,8-diiodo-1-heptene, 11-bromo-1-undecene, 11-chloro-1-undecene, 11-iodo-1-undecene, 5-chloro-bicyclo(2). 2.1) Hepta-2-ene, 5-bromo-bicyclo(2.2.1) hepta-2-ene, 5-bromomethyl-bicyclo(2.2.1) hepta-2-ene, 5-chloromethyl-bicyclo(2.2.1) hepta-2-ene, 5-iodomethyl-bicyclo(2.2.1) hepta-2-ene, 5-(2-bromoethyl)-bicyclo(2.2.1) hepta-2-ene, 5-(2-chloroethyl)-bicyclo(2.2.1) hepta-2-ene, 5-(3-bromopropyl)-bicyclo(2.2.1) hepta-2-ene, or 5-(3-bromopropyl)-bicyclo(2.2.1) hepta-2-ene.

14. The method according to claim 13, wherein the functionalized terpolymer is: poly(ethylene-co-1-octene-co-4-bromo-1-butene), poly(ethylene-co-1-octene-co-4-chloro-1-butene), poly(ethylene-co-1-octene-co-4-iodo-1-butene), poly(ethylene-co-1-octene-co-5-bromo-1-pentene), poly(ethylene-co-1-octene-co-5-chloro-1-pentene), poly(ethylene-co-1-octene-co-5-iodo-1-pentene), poly(ethylene-co-1-octene-co-5-bromo-1-hexene), poly(ethylene-co-1-octene-co-5-chloro-1-hexene), poly(ethylene-co-1-octene-co-5-iodo-1-hexene), poly(ethylene-co-1-octene-co-5-iodo-1-hexene), poly(ethylene-co-1-octene-co-5-iodo-1-hexene), poly( Ethylene-co-1-octene-co-6-bromo-1-hexene), poly(ethylene-co-1-octene-co-6-chloro-1-hexene), poly(ethylene-co-1-octene-co-6-iodo-1-hexene), poly(ethylene-co-1-octene-co-7-bromo-1-heptene), poly(ethylene-co-1-octene-co-7-chloro-1-heptene), poly(ethylene-co-1-octene-co-7-iodo-1-heptene), poly(ethylene-co-1-octene-co-8-bromo-1-octene), poly(ethylene-co-1-octene-co-8-chloro-1-octene), poly(ethylene-co-1-octene-co-8-iodo-1-octene), poly(ethylene-co-1-octene-co-11-bromo-1-undecene), poly(ethylene-co-1-octene-co-11-bromo-1-undecene). Ethylene-co-11-chloro-1-undecene), poly(ethylene-co-1-octene-co-11-iodo-1-undecene), poly(ethylene-co-1-hexene-co-4-bromo-1-butene), poly(ethylene-co-1-hexene-co-4-chloro-1-butene), poly(ethylene-co-1-hexene-co-4-iodo-1-butene), poly(ethylene-co-1-hexene-co-5-bromo-1-pentene), poly(ethylene-co-1-hexene-co-5-chloro-1-pentene), poly(ethylene-co-1-hexene-co-5-iodo-1-pentene), poly(ethylene-co-1-hexene-co-5-bromo-1-hexene), poly(ethylene-co-1-hexene-co-5-chloro-1-hexene), poly(ethylene-co-1-hexene-co-5-chloro-1-hexene), poly(ethylene-co-1-hexene-co-5-chloro-1-hexene) Iodine-1-hexene), poly(ethylene-co-1-hexene-co-6-bromo-1-hexene), poly(ethylene-co-1-hexene-co-6-chloro-1-hexene), poly(ethylene-co-1-hexene-co-6-iodo-1-hexene), poly(ethylene-co-1-hexene-co-7-bromo-1-heptene), poly(ethylene-co-1-hexene-co-7-chloro-1-heptene), poly(ethylene-co-1-hexene-co-7-iodo-1-heptene), poly(ethylene-co-1-hexene-co-8-bromo-1-octene), poly(ethylene-co-1-hexene-co-8-chloro-1-octene), poly(ethylene-co-1-hexene-co-8-iodo-1-octene), poly(ethylene-co-1-hexene-co-11-bromo-1-undecene),Poly(ethylene-co-1-hexene-co-11-chloro-1-undecene), Poly(ethylene-co-1-hexene-co-11-iodo-1-undecene), Poly(propylene-co-1-octene-co-4-bromo-1-butene), Poly(propylene-co-1-octene-co-4-chloro-1-butene), Poly(propylene-co-1-octene-co-4-iodo-1-butene), Poly(propylene-co-1-octene-co-5-bromo-1-pentene), Poly(propylene-co-1-octene-co-5-chloro-1-pentene), Poly(propylene-co-1-octene-co-5-iodo-1-pentene), Poly(propylene-co-1-octene-co-5-bromo-1-hexene), Poly(propylene-co-1-octene-co-5-chloro-1-hexene), Poly(propylene -co-1-octene-co-5-iodo-1-hexene), poly(propylene-co-1-octene-co-6-bromo-1-hexene), poly(propylene-co-1-octene-co-6-chloro-1-hexene), poly(propylene-co-1-octene-co-6-iodo-1-hexene), poly(propylene-co-1-octene-co-7-bromo-1-heptene), poly(propylene-co-1-octene-co-7-chloro-1-heptene), poly(propylene-co-1-octene-co-7-iodo-1-heptene), poly(propylene-co-1-octene-co-8-bromo-1-octene), poly(propylene-co-1-octene-co-8-chloro-1-octene), poly(propylene-co-1-octene-co-8-iodo-1-octene), poly(propylene-co-1-octene-co-8-iodo-1-octene), poly(propylene-co-1-octene-co-8-iodo-1-octene), poly(propylene-co-1-octene-co-8-iodo-1-octene), poly(propylene-co-1-octene-co-6-bromo-1-octene) -11-bromo-1-undecene), poly(propylene-co-1-octene-co-11-chloro-1-undecene), poly(propylene-co-1-octene-co-11-iodo-1-undecene), poly(ethylene-co-norbornene-co-4-bromo-1-butene), poly(ethylene-co-norbornene-co-4-chloro-1-butene), poly(ethylene-co-norbornene-co-4-iodo-1-butene), poly(ethylene-co-norbornene-co-5-bromo-1-pentene), poly(ethylene-co-norbornene-co-5-chloro-1-pentene), poly(ethylene-co-norbornene-co-5-iodo-1-pentene), poly(ethylene-co-norbornene-co-5-bromo-1-hexene), poly(ethylene-co-norbornene-co-5-bromo-1-hexene), poly(ethylene-co-norbornene-co-5-bromo-1-hexene) 1-Chloro-hexene), poly(ethylene-co-norbornene-co-5-iodo-1-hexene), poly(ethylene-co-norbornene-co-6-bromo-1-hexene), poly(ethylene-co-norbornene-co-6-chloro-1-hexene), poly(ethylene-co-norbornene-co-6-iodo-1-hexene), poly(ethylene-co-norbornene-co-7-bromo-1-heptene), poly(ethylene-co-norbornene-co-7-chloro-1-heptene), poly(ethylene-co-norbornene-co-7-iodo-1-heptene), poly(ethylene-co-norbornene-co-8-bromo-1-octene), poly(ethylene-co-norbornene-co-8-chloro-1-octene), poly(ethylene-co-norbornene-co-8-iodo-1-octene),Poly(ethylene-co-norbornene-co-11-bromo-1-undecene), Poly(ethylene-co-norbornene-co-11-chloro-1-undecene), Poly(ethylene-co-norbornene-co-11-iodo-1-undecene), Poly(ethylene-co-propylene-co-4-bromo-1-butene), Poly(ethylene-co-propylene-co-4-chloro-1-butene), Poly(ethylene-co-propylene-co-4-iodo-1-butene), Poly(ethylene-co-propylene-co-5-bromo-1-pentene), Poly(ethylene-co-propylene-co-5-chloro-1-pentene), Poly(ethylene-co-propylene-co-5-iodo-1-pentene), Poly(ethylene-co-propylene-co-5-bromo-1-hexene), Poly(ethylene-co-propylene-co- 5-Chloro-1-hexene), poly(ethylene-co-propylene-co-5-iodo-1-hexene), poly(ethylene-co-propylene-co-6-bromo-1-hexene), poly(ethylene-co-propylene-co-6-chloro-1-hexene), poly(ethylene-co-propylene-co-6-iodo-1-hexene), poly(ethylene-co-propylene-co-7-bromo-1-heptene), poly(ethylene-co-propylene-co-7-chloro-1-heptene), poly(ethylene-co-propylene-co-7-iodo-1-heptene), poly(ethylene-co-propylene-co-8-bromo-1-octene), poly(ethylene-co-propylene-co-8-chloro-1-octene), poly(ethylene-co-propylene-co-8-iodo-1-octene), poly(ethylene-co-propylene-co-11- Bromo-1-undecene), poly(ethylene-co-propylene-co-11-chloro-1-undecene), poly(ethylene-co-propylene-co-11-iodo-1-undecene), poly(propylene-co-1-hexene-co-4-bromo-1-butene), poly(propylene-co-1-hexene-co-4-chloro-1-butene), poly(propylene-co-1-hexene-co-4-iodo-1-butene), poly(propylene-co-1-hexene-co-5-bromo-1-pentene), poly(propylene-co-1-hexene-co-5-chloro-1-pentene), poly(propylene-co-1-hexene-co-5-iodo-1-pentene), poly(propylene-co-1-hexene-co-5-bromo-1-hexene), poly(propylene-co-1-hexene-co-5-bromo-1-hexene), poly(propylene-co-1-hexene-co-5-bromo-1-hexene) Poly(propylene-co-1-hexene-co-5-iodo-1-hexene), poly(propylene-co-1-hexene-co-6-bromo-1-hexene), poly(propylene-co-1-hexene-co-6-chloro-1-hexene), poly(propylene-co-1-hexene-co-6-iodo-1-hexene), poly(propylene-co-1-hexene-co-7-bromo-1-heptene), poly(propylene-co-1-hexene-co-7-chloro-1-heptene), poly(propylene-co-1-hexene-co-7-iodo-1-heptene), poly(propylene-co-1-hexene-co-8-bromo-1-octene), poly(propylene-co-1-hexene-co-8-chloro-1-octene), poly(propylene-co-1-hexene-co-8-iodo-1-octene).Poly(propylene-co-1-hexene-co-11-bromo-1-undecene), poly(propylene-co-1-hexene-co-11-chloro-1-undecene), poly(propylene-co-1-hexene-co-11-iodo-1-undecene), poly(propylene-co-norbornene-co-4-bromo-1-butene), poly(propylene-co-norbornene-co-4-chloro-1-butene), poly(propylene-co-norbornene-co-4-iodo-1-butene) Poly(propylene-co-norbornene-co-5-bromo-1-pentene), poly(propylene-co-norbornene-co-5-chloro-1-pentene), poly(propylene-co-norbornene-co-5-iodo-1-pentene), poly(propylene-co-norbornene-co-5-bromo-1-hexene), poly(propylene-co-norbornene-co-5-chloro-1-hexene), poly(propylene-co-norbornene-co-5-iodo-1-hexene), Poly(propylene-co-norbornene-co-6-bromo-1-hexene), poly(propylene-co-norbornene-co-6-chloro-1-hexene), poly(propylene-co-norbornene-co-6-iodo-1-hexene), poly(propylene-co-norbornene-co-7-bromo-1-heptene), poly(propylene-co-norbornene-co-7-chloro-1-heptene), poly(propylene-co-norbornene-co-7-iodo-1-heptene), poly(propylene-co-norbornene-co-7-iodo-1-heptene) Propylene-co-norbornene-co-8-bromo-1-octene, poly(propylene-co-norbornene-co-8-chloro-1-octene), poly(propylene-co-norbornene-co-8-iodo-1-octene), poly(propylene-co-norbornene-co-11-bromo-1-undecene), poly(propylene-co-norbornene-co-11-chloro-1-undecene), or poly(propylene-co-norbornene-co-11-iodo-1-undecene).

15. A functionalized olefin polymer obtained by the method according to any one of claims 1-14.

16. A functionalized olefin copolymer obtained by the method according to any one of claims 1-14, comprising: M40 to 300 kg / mol was determined by high-temperature size exclusion chromatography. w scope, M from 20 to 150 kg / mol was determined by high-temperature size exclusion chromatography. n scope, Crystallinity >30% as determined by differential scanning calorimetry Melting point of 100-155℃ Randomly distributed halogenated functional groups The content of 0.05-10 mol% of halogenated functional comonomers, and olefin comonomers selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, 1-octene, norbornene or ethylidene norbornene.

17. A functionalized olefin terpolymer obtained by the method according to any one of claims 1-14, comprising: M40 to 300 kg / mol was determined by high-temperature size exclusion chromatography. w scope, M from 20 to 150 kg / mol was determined by high-temperature size exclusion chromatography. n scope, The crystallinity range of 0-30% was determined by differential scanning calorimetry. Melting point of 40-120℃ Randomly distributed halogenated functional groups The first olefin comonomer is selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, 1-octene, norbornene, or ethylidene norbornene; the second comonomer is present in a content of 0.5-20 mol%, which is different from the first olefin comonomer and is selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, 1-octene, norbornene, or ethylidene norbornene; and the content of 0.05-10 mol% of halogenated functional comonomers.

18. Use of a catalyst system comprising a hafnium complex containing a polyvalent aryloxy ether and a co-catalyst selected from the group consisting of an ammonium salt or triphenylmethyl salt of MAO, MMAO, DMAO, SMAO and fluorinated tetraarylborates, for obtaining halogenated functionalized polyolefins by solution copolymerization. The polymerization temperature ranges from 110 to 250°C. The hafnium complex of the polyaryloxy ethers mentioned above is selected from dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrole)) -1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), ... 6,7,8,9-Octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dibenzylbis((2- oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2,4-Pentanediylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dichlorobis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl) (2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dibenzylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dimethylbis((2-Oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dimethylbis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium(IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzylbis((2-oxy- 3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dibenzylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV), dimethylbis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium (IV), dibenzyl ...1-Dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium(IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylhafnium(IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyl Hafnium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,2-ethylhafnium (IV), or dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV).

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