Solution process for producing 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 or zirconium complexes of polyvalent aryloxyethers and a cocatalyst selected from the group of MAO, MMAO, DMAO, SMAO or ammonium or triphenylmethyl salts of fluorinated tetraarylborates.

Description

Technical Field

[0001] This invention relates to a method for obtaining functionalized polyolefins, particularly hydroxyl-functionalized polyolefins, in solution processing, and the functionalized polyolefins thereof. Background Technology

[0002] Functionalized polyolefins are known in the art.

[0003] For example, EP3034545 discloses a method for preparing a graft copolymer comprising a polyolefin backbone and one or more polymer side chains, the method comprising the following steps:

[0004] A. Using a catalyst system to copolymerize at least one type I olefin monomer and at least one type II metal-pacified functionalized olefin monomer to obtain a polyolefin backbone having one or more metal-pacified functionalized short-chain branches, wherein the catalyst system comprises:

[0005] 1. Metal catalysts or metal catalyst precursors containing metals from Groups 3-10 of the IUPAC periodic table;

[0006] 2. Optional co-catalyst;

[0007] B. React the polyolefin backbone with one or more metal passivated functionalized short-chain branches obtained in step A) with at least one metal displacement agent to obtain a polyolefin backbone with one or more functionalized short-chain branches.

[0008] C. Forming one or more polymer side chains on the polyolefin backbone, wherein the functionalized short chain branches on the polyolefin backbone obtained in step B) are used as initiators to obtain graft copolymers.

[0009] However, this method is generally carried out under slurry conditions, which has a major drawback:

[0010] ■ Specific catalysts are required to highly blend functional comonomers;

[0011] ■ The solid content must be <15% by weight, especially when using homogeneous catalysts, otherwise statics will become a serious problem, resulting in a gel that retains a large amount of diluent.

[0012] ■ When a homogeneous unit point catalyst is used at a temperature below the crystallization temperature of the polymer formed, reactor scaling occurs;

[0013] ■ The precipitated polymer retains most of the unreacted functional comonomers;

[0014] ■Once the polymer has precipitated, it is difficult to remove the protection.

[0015] However, this method can also be implemented under solution conditions. But it presents the following drawbacks:

[0016] ■ The catalyst is thermally unstable, resulting in low catalyst yield;

[0017] ■ For polypropylene, only low-MW polymers with low isoregularity are produced.

[0018] Therefore, a method for producing functionalized polyolefins is needed to overcome at least one of these defects. Summary of the Invention

[0019] 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:

[0020] a) A copolymerization step of at least one olefin monomer and at least one protected functionalized olefin monomer in the presence of a catalyst system, 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 a hydrocarbon group having 1 to 6 carbon atoms.

[0021] The protected functionalized olefin monomer is the reaction product of the functionalized olefin monomer and the protecting agent during the protecting step, and the functionalized olefin monomer is represented by a structure according to formula (I):

[0022]

[0023] Where R 3 R 4 and R 5 Each group is independently selected from H and hydrocarbon groups having 1 to 16 carbon atoms.

[0024] 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

[0025] ● When n=1, X is selected from -O-, -S-, or -CO2-, and R 7 For H,

[0026] or

[0027] ● When n = 2, X is N, and at least one R 7 For H and other R 7Choose from the group consisting of H and hydrocarbon groups having 1 to 16 carbon atoms.

[0028] 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,

[0029] Where X is connected to R 6 The main chain and / or side chains,

[0030] Where R 4 and R 6 They can be formed together by one or more X-(R) 7 ) n Functionalized ring structures,

[0031] And the catalyst system includes:

[0032] ● Hafnium complexes of polyvalent aryloxy ethers selected from the following group: 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-pyrrolo-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), 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), dichloride bis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl) -1,4-Butanediylated Hafnium (IV), Dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-Butanediylated Hafnium (IV), Dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylated Hafnium (IV), Dibenzyl ...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)- 1,2-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), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV); or,

[0033] Zirconium complexes of polyvalent aryloxy ethers selected from the following group: dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyzirconium (IV), dichloride ((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-phenoxy)-1,3-propanediyzirconium (IV), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyzirconium (IV), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-1,3-propanediyzirconium (IV)), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy ...2,4-propanediyzirconium (IV)), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octa 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), dibenzylbis((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), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo))-1,3-propanedizirconium (IV)) (-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), dibenzylbis((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), 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-Pentanediyzirconium (IV), bis((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-(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), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-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-phenoxy)-2,4-pentanediyzirconium (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) -octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (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), 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)-methylenetrans-1,2-cyclohexanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanedizirconium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-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), dibenzylbis((2-oxy-3-(4-))-2-(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)-1,4-n-butylzirconium (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)-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); preferably dimethylbis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium (IV), dichloride bis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium (IV); and,

[0034] ●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

[0035] ●Optionally, a scavenger selected from the group consisting of: trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and

[0036] ●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 Independently selected from hydrogen or hydrocarbon groups,

[0037] b) Deprotection step, using water or Brønsted water. Treatment of the product obtained in step a) with an acid or alkali solution can extract residues from the protected functionalized olefin copolymer to obtain a functionalized polyolefin.

[0038] In the implementation scheme, after the deprotection step (b), a functionalized polyolefin recovery step (c) is carried out by a deashing step to separate the functionalized polyolefin from the residues such as aluminum oxides and hydroxides.

[0039] 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.

[0040] In the embodiments, at least one functionalized olefin monomer is selected from the group comprising: allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol, 5-hexen-1-ol, 5-hexen-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecen-1-ol, 5-norbornen-2-methanol, 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, 5-norbornen-2-carboxylic acid, 5-norbornen-2-carboxylic acid. En-2-acetic acid, 5-hexen-1-thiol, 10-undecen-1-thiol, N-propyl-5-hexen-1-amine, N-isopropyl-5-hexen-1-amine and N-cyclohexyl-5-hexen-1-amine, 4-penten-2-amine, 3-methyl-4-penten-2-amine, 3-buten-1-thiol, 5-hexen-1-thiol; preferably 3-buten-1-ol, 5-hexen-1-ol, 5-norbornen-2-methanol, 3-butenoic acid, 4-pentenoic acid, 5-norbornen-2-carboxylic acid.

[0041] In the implementation scheme, by reacting a functionalized olefin monomer with trialkylaluminum or dialkylalkoxyaluminum R 11 OAl(R 12 The protection step is carried out by reaction 2, wherein the trialkylaluminum is selected from the group consisting of: triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum; in R 11 OAl(R 12 )2 in R 11 =Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl and R 12 =Ethyl, isobutyl, n-hexyl, n-octyl.

[0042] 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%.

[0043] In the implementation scheme, the first olefin monomer and the second olefin monomer are used to copolymerize with at least one protected functionalized olefin monomer, wherein the first olefin monomer and the second olefin monomer 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 olefin monomer and the second olefin monomer.

[0044] 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.

[0045] 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.

[0046] In the implementation plan, water is used for the deprotection step.

[0047] In the implementation plan, the deprotection step is carried out using Brønsted acid, preferably HCl.

[0048] In the implementation plan, the deprotection step is carried out using an alkali, preferably a Brønsted base, and more preferably NaOH.

[0049] In the implementation plan, the de-ashing step can be performed after the deprotection step.

[0050] In the embodiments, 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 selected from the group consisting of 3-buten-1-ol, 5-hexen-1-ol and 5-norbornen-2-methanol, more preferably the functionalized copolymer is poly(propylene-co-5-hexen-1-ol), poly(ethylene-co-5-hexen-1-ol), poly(propylene-co-3-buten-1-ol), poly(ethylene-co-3-buten-1-ol) or poly(ethylene-co-5-norbornen-2-methanol).

[0051] 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, and the third monomer is selected from the group consisting of 3-buten-1-ol, 5-hexen-1-ol and 5-norbornene-2-methanol. More preferably, the functionalized terpolymer is poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-1-hexene-co-5-hexen-1-ol), or poly(propylene-co-1-hexene-co-5-hexene-1-ol). - alcohol), poly(ethylene-co-norbornene-co-5-hexen-1-ol), poly(ethylene-co-1-octen-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-3-buten-1-ol), poly(propylene-co-1-hexen-co-3-buten-1-ol), poly(ethylene-co-1-octen-co-3-buten-1-ol), poly(ethylene-co-norbornene-co-3-buten-1-ol) or poly(ethylene-co-norbornene-co-5-norbornene-2-methanol).

[0052] A second aspect of the invention is the use of functionalized polyolefins obtained by the method according to the invention as adhesive improvers, adhesives or compatibilizers in articles, coatings or paints.

[0053] A third aspect of the invention is the use of the functionalized polyolefin obtained by the method according to the invention in foam articles in which aluminum compounds, such as aluminum oxide hydroxides, have not been separated from the functionalized polyolefin.

[0054] A fourth 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.

[0055] Finally, a last aspect of the invention is the functionalized olefin that can be obtained by the method of the invention, preferably:

[0056] ● Functionalized olefin copolymers, which have the following characteristics:

[0057] ○40 to 300 kg / mol M w scope,

[0058] ○M from 20 to 150 kg / mol n scope,

[0059] Crystallinity > 30%,

[0060] Melting point between 100 and 155°C

[0061] ○ Randomly distributed hydroxyl, carboxylic acid, amine, or thiol functional groups.

[0062] ○ 0.05 to 10 mol%, preferably 0.1 to 5 mol%, more preferably 0.02 to 2 mol% of functional comonomer content;

[0063] ● Functionalized olefin terpolymers, which have the following characteristics:

[0064] ○40 to 300 kg / mol M w scope,

[0065] ○M from 20 to 150 kg / mol n scope,

[0066] ○ Crystallinity range of 0 to 30%,

[0067] Melting point between 40 and 120°C

[0068] ○ Comonomer content of 0.5 to 20 mol%, preferably 2 to 18 mol%, more preferably 5 to 15 mol%,

[0069] ○ Randomly distributed hydroxyl, carboxylic acid, amine, or thiol functional groups.

[0070] ○ 0.05 to 10 mol%, preferably 0.1 to 5 mol%, more preferably 0.02 to 2 mol% of functional comonomer content.

[0071] In the embodiments, the functionalized olefin comprises at least 0.1% by weight, more preferably at least 0.5% by weight and at most 5% by weight, aluminum. Detailed Implementation

[0072] The solution copolymerization method for obtaining functionalized polyolefins according to the present invention comprises at least the following two steps:

[0073] Step a)

[0074] A copolymerization step involving at least one olefin monomer and at least one protected functionalized olefin monomer in the presence of the following components:

[0075] Olefin monomers

[0076] 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, norbornene, vinylidene norbornene, ethylidene norbornene, or combinations thereof.

[0077] In another embodiment, at least one olefin monomer is propylene, particularly 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.

[0078] In another embodiment, at least one olefin monomer is ethylene, particularly 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.

[0079] The polymerization step may use one type of olefin monomer or two or more types of olefin monomers.

[0080] In another embodiment, the first olefin monomer and the second olefin monomer are different, and based on the total molar amount of the first olefin monomer and the second olefin monomer, 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%.

[0081] In another embodiment, the first olefin is ethylene and the second olefin is 1-octene.

[0082] In another embodiment, the first olefin is ethylene and the second olefin is norbornene.

[0083] In another embodiment, the first olefin is propylene and the second olefin is 1-hexene.

[0084] In another embodiment, the first olefin is propylene and the second olefin is ethylene.

[0085] Protected functionalized olefin monomers

[0086] The protected functionalized olefin monomers have the following structures according to formula (III) or (IIIbis):

[0087]

[0088] Where R 3 R 4 and R 5 Each group is independently selected from H and hydrocarbon groups having 1 to 16 carbon atoms.

[0089] Where n is 1 or 2

[0090] ● When n=1, X is selected from -O-, -S-, or -CO2-, and R 7 For H, or

[0091] ● When n = 2, X is N, and

[0092] Where R 11 =Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl

[0093] R 12 =Ethyl, isobutyl, n-hexyl, n-octyl, and

[0094] R 13 = Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl

[0095] Where m is an integer from 1 to 10, preferably 1 or 2.

[0096] Furthermore, during the protecting step, the following are the reaction products of the functionalized olefin monomer and the protecting agent:

[0097] ● Functionalized olefin monomers according to formula (I):

[0098]

[0099] Where R 3 R 4 and R 5 Each group is independently selected from H and hydrocarbon groups having 1 to 16 carbon atoms.

[0100] 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

[0101] ● When n=1, X is selected from -O-, -S-, or -CO2-, and R 7 For H, or

[0102] ● When n = 2, X is N, and at least one R 7 For H and other R 7 Choose from the group consisting of H and hydrocarbon groups having 1 to 16 carbon atoms.

[0103] 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.

[0104] Where X is connected to R 6 The main chain and / or side chains,

[0105] Where R 4 and R 6 They can be formed together by one or more X-(R) 7 )n Functionalized ring structure.

[0106] Preferably, X is selected from -O- or -CO2-.

[0107] and

[0108] ● Protective agent according to one of formula (II) or (IIbis):

[0109] AlR 13 3(II)

[0110] Where R 13 = Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl

[0111] R 11 OAl(R 12 )2(IIbis)

[0112] Where R 11 =Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, and R 12 =Ethyl, isobutyl, n-hexyl, n-octyl.

[0113] In a preferred embodiment, the functionalized olefin monomer according to Formula I is an α-olefin containing hydroxyl or carboxylic acid or a cyclic olefin monomer with hydroxyl or carboxylic acid functionalized ring strain, preferably a hydroxyl, dihydroxy, or carboxylic acid α-olefin monomer.

[0114] Hydroxyl-containing functionalized α-olefin monomers may, for example, correspond to formula I, where R 3 R 4 and R 5 Each is H, where X is -O- 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-.

[0115] Other examples of hydroxyl-functionalized α-olefin monomers include, but are not limited to, allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol, 5-hexen-1-ol, 5-hexen-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, and 10-undecen-1-ol; preferably 3-buten-1-ol and 5-hexen-1-ol.

[0116] Further examples of functionalized olefin monomers include hydroxylated cyclo-strained olefins (also known as internal olefins), which are typically, for example, hydroxylated norbornene, preferably 5-norbornene-2-methanol. 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 with XH, where X is -O-.

[0117] Carboxylic acid-containing functionalized olefin monomers may, for example, correspond to formula I, where R 3 and R 5 Each is H, where X is -CO2- 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)8-. Preferred acid-functionalized olefin monomers may be selected from the group consisting of 3-butenoic acid, 4-pentenoic acid, and 5-norbornene-2-carboxylic acid.

[0118] Thiol-containing functionalized olefin monomers may, for example, correspond to formula I, where R 3 and R 5 Each is H, where X is -S- 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 functional groups are -(CH2)9- and -(CH2)4-. Preferred thiol-functionalized olefin monomers may be selected from the group consisting of 5-hexene-1-thiol and 10-undecene-1-thiol.

[0119] Amine-containing functionalized olefin monomers may, for example, correspond to formula I, where R 3 and R 5 Each is H and X is -N(H)R 7 -and 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, wherein R 7 It is an H or hydrocarbon group. R 6Examples of the group are -(CH2)4-. Preferred amine-functionalized olefin monomers may be selected from the group consisting of N-methyl-5-hexen-1-amine, N-ethyl-5-hexen-1-amine, N-propyl-5-hexen-1-amine, N-isopropyl-5-hexen-1-amine, and N-cyclohexyl-5-hexen-1-amine.

[0120] 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 selected from the group consisting of 3-buten-1-ol, 5-hexen-1-ol and 5-norbornen-2-methanol. More preferably, the functionalized copolymer is poly(propylene-co-5-hexen-1-ol), poly(ethylene-co-5-hexen-1-ol), poly(propylene-co-3-buten-1-ol), poly(ethylene-co-3-buten-1-ol), or poly(ethylene-co-5-norbornen-2-methanol).

[0121] In another embodiment, three different monomers are used to obtain a terpolymer. Preferably, the first monomer in the terpolymer 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, and the third monomer is selected from the group consisting of 3-buten-1-ol, 5-hexen-1-ol, and 5-norbornene-2-methanol. More preferably, the functionalized terpolymer is poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-1-hexene-co-5-hexen-1-ol), or poly(propylene-co-1-hexen-co-5-hexen-1-ol). (-hexen-1-ol), poly(ethylene-co-norbornene-co-5-hexen-1-ol), poly(ethylene-co-1-octenene-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-3-buten-1-ol), poly(propylene-co-1-hexen-co-3-buten-1-ol), poly(ethylene-co-1-octenene-co-3-buten-1-ol), poly(ethylene-co-norbornene-co-3-buten-1-ol), or poly(ethylene-co-norbornene-co-5-norbornene-2-methanol).

[0122] Preferably, 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%.

[0123] Protectant

[0124] The hydrogen atom directly bonded to X in a functionalized olefin monomer exhibits Brønsted acid properties and is toxic to highly reactive catalysts. A protecting agent is used, which reacts with the acidic hydrogen and binds to the monomer containing the polar group. This reaction prevents the acidic polar group (-XH) from reacting with the catalyst and the polar group (-X-) from coordinating with the catalyst.

[0125] Examples of protective agents are silyl halides, trialkylaluminum complexes, dialkylalkoxyaluminum complexes, dialkylmagnesium complexes, dialkylzinc complexes, or trialkylboron complexes.

[0126] In the method of the present invention, the protective agent is preferably selected from trialkylaluminum complexes or dialkylalkoxyaluminum R. 11 OAl(R 12 )2 or a combination of trialkylaluminum and dialkylalkoxyaluminum, wherein the trialkylaluminum complex is selected from the group consisting of triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum; in R 11 OAl(R 12 )2 in R 11 =Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl and R 12 =Ethyl, isobutyl, n-hexyl, n-octyl. The most preferred protecting agent is triethylaluminum.

[0127] Preferably, the protective agent is according to one of formula (II) or (IIbis):

[0128] AlR 13 3(II)

[0129] Where R 13 = Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl

[0130] R 11 OAl(R 12 )2(IIbis)

[0131] Where R 11 =Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, and R 12 =Ethyl, isobutyl, n-hexyl, n-octyl.

[0132] 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.

[0133] To obtain protected functionalized olefin monomers, a pre-protection step is performed before the copolymerization step of the functionalized olefin monomers.

[0134] In an embodiment, the protection step of obtaining the protected functionalized olefin monomer according to formula (I) can be carried out by an aluminum reaction of a hydroxyl or carboxylic acid functionalized olefin monomer, wherein the hydroxyl or carboxylic acid functionalized olefin monomer is reacted with, for example, a trialkylaluminum of triethylaluminum or a dialkylalkoxyaluminum of, for example, a dialkylalkoxyaluminum of, or a combination of, for example, trialkylaluminum and dialkylalkoxyaluminum of, triethylaluminum and diethylethoxyaluminum.

[0135] The molar amount of the protecting agent is preferably at least the same as the molar amount of the functional groups in the functionalized olefin monomer. Preferably, the molar amount of the protecting agent is at least 10 mol% higher than the amount of the functionalized olefin monomer, or at least 20 mol% higher. The amount of the protecting agent is typically less than 250 mol% of the functionalized olefin monomer. In some cases, a higher amount may be used or may be necessary.

[0136] Catalyst systems suitable for the method according to the invention

[0137] The method according to the invention is carried out in the presence of a suitable catalyst system comprising at least the following:

[0138] ●Catalyst,

[0139] ● Co-catalyst,

[0140] ●Optional, cleaning agent

[0141] ●Optional, chain transfer agent.

[0142] catalyst

[0143] The catalyst is a ligand-metal complex with a bridged 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 bridged bis(diaryl) structure.

[0144] The metal-ligand complex used in this invention can be characterized by the general formula (4,O)MLn'(VI), where (4,O) is a dianionic ligand having at least four oxygen atoms chelated to metal M at four coordination sites, wherein both oxygen atoms in the oxygen-metal bond are covalent and both oxygen atoms in the bond are coordinate; M is a metal selected from Group 4 of the periodic table, more specifically Hf or Zr, 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, carboxyl ester / radix, 1,3-dionate / radix, oxalate / radix, carbonate / radix, nitrate / radix, sulfate / 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.

[0145] Metallic precursors can be monomers, dimers, or higher forms. Specific examples of suitable hafnium and zirconium precursors include, but are not limited to:

[0146] 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;

[0147] 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.

[0148] Lewis base adducts of these examples are also suitable as metal precursors, such as ethers, amines, thioethers, phosphines and the like, which are suitable as Lewis bases.

[0149] In other embodiments, the metal-ligand complexes of the present invention can be characterized by the following general formula:

[0150]

[0151] in

[0152] ●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 R 28 and R 29 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 (not counting hydrogen atoms) in the ring.

[0153] ●M is a metal, either Hf or Zr.

[0154] ●L is the structural part that forms a covalent, coordinate, or ionic bond with M; and n' is 1, 2, 3, or 4.

[0155] ●X, X', Y 2 and Y 3 It is an oxygen atom.

[0156] ●B is a bridging group having 1 to 50 atoms (excluding hydrogen atoms), more preferably B is a propane bridge.

[0157] In a preferred embodiment, the ligand-metal complex must be a hafnium or zirconium complex of a polyvalent aryloxy ether, selected from the group consisting of at least the following:

[0158] 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-(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), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV);

[0159] Dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV), dimethylbis((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), dimethylbis((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), dichlorobis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium (IV), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3- Propanediylzirconium (IV), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium (IV), dichloride bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium (IV), dibenzylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium (IV), dimethylbis((2-oxy-3-(dibenzo-1H-pyrrole-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), 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), dichloride7,8,9-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-cyclohexane) Dizirconium (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-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (IV), dichloride ... Zirconium dizirconia (IV) containing 1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanedizirconia, and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanedizirconia (IV), dimethylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconia (IV), dibenzylbis((2-oxy-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butylzirconia (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)-1,2-ethyl ...ethylzirconium (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).

[0160] co-catalyst

[0161] The cocatalyst is selected from the group consisting of: ammonium salts or triphenylmethyl salts of MAO, DMAO, MMAO, SMAO, or tetrafluoroarylborates; 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 in Bochmann Organometallics 2010, 29, 4711-4740 and Chen and Marks Chem. Rev. 2000, 100, 1391-1434.

[0162] 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.

[0163] As used in this specification, loaded methylaluminoxane or SMAO may mean: methylaluminoxane bound to a solid support.

[0164] As used in this specification, depleted methylaluminoxane or DMAO may mean: methylaluminoxane from which free trimethylaluminum has been removed.

[0165] As used in this specification, modified methylaluminoxane or MMAO may mean: modified methylaluminoxane, i.e., the product obtained by partial hydrolysis of trimethylaluminum with the addition of another trialkylaluminum such as triisobutylaluminum or tri-n-octylaluminum.

[0166] As used in this specification, fluorinated aryl borates may refer to: borate compounds having four fluorinated (preferably perfluorinated) aryl ligands.

[0167] Optional cleaning agents

[0168] 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.

[0169] 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.

[0170] Optional chain transfer agent

[0171] 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.

[0172] Aggregation conditions

[0173] The polymerization according to the invention is carried out in solution using the catalyst system described above.

[0174] 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.

[0175] 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, cocatalysts, and / or protectants. This can help increase the molecular weight and / or comonomer blending.

[0176] 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%.

[0177] This invention may involve the addition of other additives, such as processing stabilizers (primary antioxidants), such as Irganox 1010.

[0178] Step b)

[0179] Following polymerization step a), a deprotection step b) is performed, wherein the product obtained from step a) is processed to extract residues from the protective agent from the protected functionalized olefin copolymer, thereby obtaining the functionalized polyolefin.

[0180] In the implementation scheme, the protected functionalized olefin copolymer is treated with Brønsted acid, preferably HCl.

[0181] In another embodiment, the protected functionalized olefin copolymer is treated with an alkaline solution, preferably a Brønsted base, and more preferably NaOH.

[0182] In another embodiment, the protected functionalized olefin copolymer is treated with water.

[0183] To prevent corrosion of the polymerization reactor, the deprotection step can be carried out in a tank coated with PE, PTFE or PFA, and the base material is stainless steel when using alkali or carbon steel when using acid.

[0184] Optionally, a deashing step may be performed after the deprotection step to separate the polymer from water-insoluble aluminum compounds, such as aluminum oxides and hydroxides, for example, Al(O)OH, Al(OH)3 and Al2O3, by means of flocculation and sedimentation, including membrane separation, centrifugation or adsorption, filtration.

[0185] However, this deashing step can be skipped, especially when the functionalized polyolefin obtained by the method according to the invention is used in foamed products. In this embodiment, aluminum compounds such as aluminum oxide hydroxide will help form the foam.

[0186] Optionally, when an acid is used during the deprotection step, a sodium hydroxide solution can be used to neutralize the aqueous phase containing aluminum compounds such as aluminum oxide hydroxides; and when an alkali is used during the deprotection step, a sulfuric acid solution or CO2 gas can be used for neutralization.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] The invention is now illustrated by means of the following non-limiting embodiments.

[0191] Example

[0192] 1 HNMR characterization

[0193] The percentage of functionalization is through 1¹H NMR analysis was performed on a Varian Mercury spectrometer operating at 400 MHz, using tetrachloroethane deuterated (TCE-D2) as the solvent at 130 °C, and recorded in 5 mm tubes. Chemical shifts compared to tetramethylsilane were reported in ppm and determined by reference to residual solvent protons.

[0194] High-Temperature Size Exclusion Chromatography (HT-SEC)

[0195] Molecular weight and PDI, reported in kg / mol, were determined by high-temperature size exclusion chromatography at 150 °C in a GPC-IR system (PolymerChar, Valencia, Spain) equipped with an IR4 detector and a carbonyl sensor. Column assembly: three Polymer Laboratories 13 μm PLgel Olexis columns, 300 × 7.5 mm. 1,2-Dichlorobenzene (o-DCB) was used as eluent at a flow rate of 1 mL / min. Molecular weight and corresponding PDI were calculated from HTSEC analysis relative to narrow-band polystyrene standards (PSS, Mainz, Germany).

[0196] Differential scanning calorimetry (DSC)

[0197] 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.

[0198] Inductively Coupled Plasma Mass Spectrometry (ICP-MS)

[0199] Aluminum content (wt%) was determined using ICP-MS: 100–200 mg of sample was digested in 6 mL of concentrated nitric acid (trace metal grade) using an AntonPaar Multiwave PRO equipped with a sealed high-pressure quartz digestion vessel via microwave-assisted acid digestion. After the microwave digestion run, the acid was analytically transferred to a pre-cleaned plastic centrifuge tube containing 1 mL of internal standard solution and diluted to 50 mL with Milli-Q water. Aluminum in the sample was quantified using Inorganic Ventures multi-element calibration standards. Aluminum was detected and measured using an Agilent 8900 ICP-MS system by measuring aluminum at 27 m / z isotopes in (high-energy) helium collision mode.

[0200] Example 1

[0201] Use stainless steel filled with pentamethylheptane (PMH) solvent (1L). The copolymerization experiment was conducted in a 2L reactor using a stirring speed of 600 rpm. Catalyst and comonomer solutions were prepared in a glove box. For example, for Item 2 in Table 1, the reactor was first heated to 40°C, followed by the addition of TiBA (1.0M solution in toluene, 2 mL) and TiBA-passivated 10-undecen-1-ol (TiBA:10-undecen-1-ol = 1:0, 1.0M solution in toluene, 20 mmol). The reactor was loaded with gaseous propylene (100 g) at 40°C and heated to the desired polymerization temperature of 130°C, resulting in a propylene partial pressure of approximately 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by injecting the 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, 11.3 mmol). The polymer solution was then poured into a solution containing acidified isopropanol (2.5% v / v HCl, 500 mL) and Irganox. The reaction was stopped using a conical flask containing 1010 (1.0 M, 0.5 mmol). The resulting suspension was stirred for 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. A white powder of poly(propylene-co-1-undecenol) (20.9 g) was obtained.

[0202] Table 1a. Copolymerization of propylene with TiBA or TEA-protected 10-undecenol, 5-hexen-1-ol and 3-buten-1-ol using Hf-O4 catalyst

[0203]

[0204]

[0205] condition:

[0206] The reaction in 2L The experiment was conducted in a reactor using dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) (HfO4 = 0.24 μmol) [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), at the polymerization temperature, propylene partial pressure = 15 bar, pentamethylheptane = 1 L, MAO (30% wt% solution in toluene) = 11.3 mmol, TiBA or TEA passivated enol (C11OH is 10-undecen-1-ol, C6OH is 5-hexen-1-ol, C4OH is 3-buten-1-ol), TiBA or TEA:enol (molar ratio) = 1, with an additional amount of TiBA (1.0M solution in toluene, 2 mL) added as a scavenger.

[0207] TiBA:10-Undecenoic acid (molar ratio) = 2.

[0208] Yield was determined by weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 80°C.

[0209] na = Not applicable, ns = Insoluble, nd = Not measured.

[0210] Table 1b. Copolymerization of propylene with TEA-protected 10-undecenol and 5-hexen-1-ol using Zr-O4 catalyst

[0211]

[0212] condition:

[0213] The reaction occurred in 0.3L The experiment was conducted in a reactor using dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanedizirconium (IV) (Zr-O4, 0.1 μmol) [CAS: 1407984-39-7], 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]zirconium, partial pressure of propylene = 15 bar, pentamethylheptane = 0.15 L, MAO (30% wt% solution in toluene) = 4.5 mmol, TEA passivated enol (C11OH is 10-undecen-1-ol, C6OH is 5-hexen-1-ol), TEA:enol (molar ratio) = 1, with additional TiBA (1.0 M solution in toluene, 1 mL) added as a scavenger.

[0214] Yield was determined by weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 80°C.

[0215] Results in Tables 1a and 1b

[0216] The results presented in Tables 1a and 1b show that, compared to when metallocenes are used as catalysts under the same conditions (see comparative examples described in Tables 4a, 4b, and 5), the copolymers based on propylene and protected enols produced by the method according to the invention using hafnium or zirconium complexes of polyvalent aryloxy ethers as catalysts exhibit significantly higher M values. w M n and T m .

[0217] Example 2

[0218] The same polymerization procedure as described in Example 1 was used to produce poly(propylene-co-1-hexene-co-5-hexen-1-ol) (Item 21 in Table 2), using a dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) (Hf-O4) catalyst (0.75 μmol), 1-hexene (5 mL, 40 mmol), along with TiBA scavenger (1.0 M solution in toluene, 2 mL) and a TEA-passivated 5-hexen-1-ol comonomer solution (TEA:5-hexen-1-ol (molar ratio) = 1, 10 mM). The resulting hydroxyl-functionalized poly(propylene-co-1-hexene-co-1-hexen-1-ol) (11.7 g) was analyzed to determine the molecular weight by HT-SEC, the melting temperature by DSC, and... 1 Functionality was determined by 1H NMR.

[0219] Table 2. Copolymerization of propylene with 1-hexene and TEA-protected 5-hexen-1-ol using Hf-O4 catalyst

[0220]

[0221] condition:

[0222] The reaction in 2L The experiment was conducted in a reactor using Hf-O4 = 0.72 μmol, propylene partial pressure = 15 bar, pentamethylheptane = 1 L, MAO (30% wt% solution in toluene) = 11.3 mmol, a TEA passivated 5-hexen-1-ol comonomer solution, TEA:5-hexen-1-ol (molar ratio) = 1, and an additional amount of TiBA (1.0 M solution in toluene, 2 mL) was added as a scavenger.

[0223] Yield was determined by weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 60°C.

[0224] Results in Table 2

[0225] The results presented in Table 2 show that, using hafnium complexes of polyvalent aryloxy ethers as catalysts, terpolymers based on propylene, 1-hexene, and protected enols produced by the method according to the invention exhibit similar high M values ​​as found for the copolymers (Table 1a). w M n and T m .

[0226] In addition, Table 2 shows that Hf-O4 formation has high T m High M w The high capacity of terpolymers, and T m The amount of 1-hexene in the feed can be adjusted.

[0227] Example 3

[0228] Trimerization experiments of ethylene, 1-octene, and 5-hexen-1-ol or 3-buten-1-ol using Hf-O4 catalysts were conducted in a parallel pressure reactor platform (PPR) apparatus, integrally embedded within a triple MBraun LabMaster glove box, characterized by 48 reactors (“units”) arranged in six modules of eight units each. Each unit, with a working volume of 5.0 mL liquid phase, was individually controlled using online monitoring of temperature and pressure. Prior to experimental execution, the PPR modules underwent an overnight conditioning period (8 h using intermittent dry N2 flow at 90–140 °C). After cooling to glove box temperature, the 48 units were assembled using disposable 10 mL glass inserts and disposable polyetheretherketone (PEEK) stirrers. For example, for item 28 in Table 3, the module was loaded with toluene (5.0 mL), MAO (30 wt% solution in toluene, 13 μmol) as a scavenger, 1-octene (0.25 mL, 5 vol%), and a TiBA-passivated 5-hexen-1-ol comonomer solution (TiBA:5-hexen-1-ol = 1:1, 0.2 μmol). The module was kept at the desired temperature (130 °C) and brought to the predetermined operating ethylene pressure (9 bar). At this point, Hf-O4 catalyst (2.0 nmol) pre-activated with MAO (30 wt% solution in toluene, 2 μmol, MAO / catalyst = 1000) was injected into the target unit, thus initiating the reaction. The total liquid phase volume of 5.0 mL was allocated as follows: 4.0 mL during solvent / scavenger addition and 1.0 mL during the catalyst injection sequence. The polymerization was continued for the required time under constant ethylene pressure with stirring (800 rpm), and quenched by overpressure of the unit with an O2 / N2 mixture of 3.5 bar (O2, 0.5 v%). Once the unit was quenched, the module was cooled to glove box temperature and vented, the stir top was removed, the glass insert containing the reaction phase was removed and transferred to a Genevac centrifugal drying rack, where the polymer sample was thoroughly dried under vacuum overnight.

[0229] Table 3. Trimerization of ethylene, 1-octene, and TiBA-protected 5-hexen-1-ol or TiBA-protected 3-buten-1-ol using Hf-O4 catalyst

[0230]

[0231] condition:

[0232] The reaction was carried out on a parallel pressure reactor platform (PPR) using 2 nmol Hf-O4, ethylene pressure of 9 bar, and a time of 10 minutes. The total toluene volume including reagents was 5 mL, MAO (30% by weight solution in toluene) was 15 μmol, and TiBA-passivated enol (C6OH was 5-hexen-1-ol and C4OH was 3-buten-1-ol) was used. The TiBA:enol molar ratio was 1. For more experimental details, see Experimental Procedure Example 3.

[0233] Results in Table 3

[0234] The results presented in Table 3 show that, using hafnium complexes of polyvalent aryloxy ethers as catalysts, the terpolymers based on ethylene, 1-octene, and TiBA-protected enols produced by the method according to the present invention exhibit high Mg. w and M n However, due to the high affinity of Hf-O4 for enols and 1-octene, the ethylene-based terpolymers obtained under the applied polymerization conditions were amorphous and did not yield T... m .

[0235] Comparative Examples

[0236] The following comparative examples were conducted without using the hafnium or zirconium complex catalysts of the polyvalent aryloxy ethers according to the present invention:

[0237] ●rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst,

[0238] ●rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2 catalyst,

[0239] ●TiCl4 / MgCl2 Ziegler-Natta catalyst.

[0240] Table 4a. Copolymerization of propylene with TiBA-protected 10-undecen-1-ol and TiBA-protected 3-buten-1-ol using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst

[0241]

[0242] condition:

[0243] The reaction was carried out on a parallel pressure reactor platform (PPR) using 20 nmol of rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst, 6 bar of propylene pressure, 5 mL of toluene, 15 μmol of MAO (30 wt% solution in toluene), TiBA-passivated enols (C11OH for 10-undecen-1-ol, C4OH for 3-buten-1-ol), and a TiBA:enol molar ratio of 1.

[0244] CE1 is a reference propylene polymerization using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst.

[0245] Table 4b. Copolymerization of propylene with TEA and TiBA-protected 5-hexen-1-ol using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst

[0246]

[0247] condition:

[0248] The reaction was carried out in a 2 L Buchi reactor using 3.2 μmol of rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2, a partial pressure of propylene of 15 bar, 1.0 L of pentamethylheptane, 11.3 mmol of MAO (30 wt% solution in toluene), passivated C6OH (5-hexen-1-ol) with TiBA or TEA, and a molar ratio of TiBA or TEA:5-hexen-1-ol of 1. An additional amount of TiBA (2 mL of 1.0 M solution in toluene) was added as a scavenger.

[0249] Yield was determined by weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 80°C.

[0250] CE4 is a reference propylene polymerization using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 catalyst.

[0251] nd = Not measured.

[0252] Table 5. Copolymerization of propylene with TiBA-protected 10-undecen-1-ol using rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2 catalyst

[0253]

[0254] condition:

[0255] The reaction occurred in 0.6L The experiment was conducted in a reactor using rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2 catalyst = 0.3 μmol, propylene partial pressure = 15 bar, toluene = 200 mL, MAO (30 wt% solution in toluene) = 1 mmol, TiBA passivated 10-undecen-1-ol (C11OH) molar ratio = 1, and an additional amount of TiBA (1.0 M solution in toluene, 1 mL) was added as a scavenger.

[0256] Yield was determined by weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 80°C.

[0257] CE8 is a reference propylene polymerization using rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2 catalyst.

[0258] The results presented in Tables 4a, 4b, and 5 show that polymers produced under the solution processing conditions according to the invention (Table 1a) but using other zirconium and hafnium complexes that are outside the range of polyvalent aryloxy ethers defined above have very low M. w and M n and T m Value. Furthermore, it is almost entirely unfunctionalized.

[0259] Table 6. Copolymerization of propylene and TiBA-protected 10-undecen-1-ol using Ziegler-Natta catalyst TiCl4 / MgCl2 / di-n-butyl phthalate-TEA / diisobutyldimethoxysilane

[0260]

[0261] Conditions: The reaction takes place in 2L of water. The reaction was carried out in a reactor using 10 mg TiCl4 / MgCl2Z-N catalyst, 15 bar propylene partial pressure, 1 L pentamethylheptane, 0.3 mmol 1.2 mL diisobutyldimethoxysilane (DiBMS), and 1.5 mmol TEA (1.0 M solution in toluene). An additional 2 mL of TiBA (1.0 M solution in toluene) was added as a scavenging agent to a TiBA passivated 10-undecen-1-ol comonomer solution (molar ratio = 1).

[0262] Yield was determined by weight of the polymer obtained after filtration and drying overnight in a vacuum oven at 60°C.

[0263] The results presented in Table 6 show that, under the solution-based conditions according to the present invention, using the TiCl4 / MgCl2 Ziegler-Natta catalyst, no functionalization occurs, as shown by... 1 Revealed by H NMR analysis.

Claims

1. A method for solution copolymerization to obtain functionalized polyolefins, the method comprising at least the following steps: a) A copolymerization step of at least one olefin monomer and at least one protected functionalized olefin monomer in the presence of a catalyst system, wherein the polymerization temperature is 100 to 250 °C. The olefin monomers therefrom are CHR 1 =CHR 2 It means that R 1 and R 2 Each can be independently hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. The protected functionalized olefin monomer is the reaction product of the functionalized olefin monomer and the protecting agent during the protecting step, and the functionalized olefin monomer is represented by a structure 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, X is selected from -O- or -CO2-, n is 1, and R 7 For H, 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 X is connected to R 6 The main chain and / or side chains, Where R 4 and R 6 They can be formed together by one or more X-(R) 7 ) n Functionalized ring structures, And the catalyst system mentioned above comprises: ● Hafnium complexes of polyvalent aryloxy ethers selected from the following group: 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-pyrrolo-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), 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), dichloride bis((2-Oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl) -1,4-Butanediylated Hafnium (IV), Dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-Butanediylated Hafnium (IV), Dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylated Hafnium (IV), Dibenzyl ...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-(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), and dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV); or, Zirconium complexes of polyvalent aryloxy ethers selected from the following group: dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyzirconium (IV), dichloride ((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-phenoxy)-1,3-propanediyzirconium (IV), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyzirconium (IV), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-1,3-propanediyzirconium (IV)), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxy ...2,4-propanediyzirconium (IV)), dichloride ((2-oxy-3-(1,2,3,4,6,7,8,9-octa 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), dibenzylbis((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), dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo))-1,3-propanedizirconium (IV)) (-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), dibenzylbis((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), 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-Pentanediyzirconium (IV), bis((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-(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), dimethylbis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracene-5-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-phenoxy)-2,4-pentanediyzirconium (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) -octahydroanthracene-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanedizirconium (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), 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)-methylenetrans-1,2-cyclohexanedizirconium (IV), dichloride bis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanedizirconium (IV), and dibenzylbis((2-oxy-3-(dibenzo-1H-pyrrolo-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), dibenzylbis((2-oxy-3-(4-))-2-(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)-1,4-n-butylzirconium (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)-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), and dibenzylbis((2-Oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butylzirconium (IV); 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 ZnR 10 2, where each R 10 Independently, it can be a hydrogen or hydrocarbon group. b) A deprotection step, wherein treatment of the product obtained in step a) with water or a Brønsted acid or alkaline solution enables the extraction of residues from the protected functionalized olefin copolymer derived from the protective agent to obtain the functionalized polyolefin.

2. The method according to claim 1, wherein the at least one olefin monomer is replaced by 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 ethylidene norbornene.

3. The method according to claim 1, wherein after the deprotection step (b), a recovery step (c) of the functionalized polyolefin is performed by a deashing step to separate the functionalized polyolefin from the residue of the protective agent.

4. The method according to claim 3, wherein the residue of the protective agent is aluminum oxide and hydroxide.

5. The method according to any one of claims 1-4, wherein the at least one olefin monomer is propylene and / or 1-hexene.

6. The method according to any one of claims 1-4, wherein the at least one functionalized olefin monomer is selected from the group comprising: allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-buten-1,2-diol, 5-hexen-1-ol, 5-hexen-1,2-diol, 7-octen-1-ol, 7-octen-1,2-diol, 9-decen-1-ol, 10-undecen-1-ol, 5-norbornen-2-methanol, 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, 5-norbornen-2-carboxylic acid, or 5-norbornen-2-acetic acid.

7. The method according to any one of claims 1-4, wherein the functionalized olefin monomer is reacted with trialkylaluminum or dialkylalkoxyaluminum R 11 OAl(R 12 The protection step is performed by reaction 2, wherein the trialkylaluminum is selected from the group consisting of: triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum; in the R 11 OAl(R 12 )2 in R 11 The derivatives are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and cyclohexyl, and R 12 It is ethyl, isobutyl, n-hexyl, or n-octyl.

8. The method according to any one of claims 1-4, 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.

9. The method according to any one of claims 1-4, wherein the first olefin monomer and the second olefin monomer are used to copolymerize with the at least one protected functionalized olefin monomer, wherein the first olefin monomer and the second olefin monomer are different, and wherein, based on the total molar amount of the first olefin monomer and the second olefin monomer, 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%.

10. The method according to any one of claims 1-4, 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.

11. The method according to any one of claims 1-4, 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.

12. The method of claim 9, 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.

13. The method according to any one of claims 2-4, wherein the deprotection step is performed using water.

14. The method according to any one of claims 2-4, wherein the deprotection step is carried out with Brønsted acid.

15. The method according to any one of claims 1-4, wherein the deprotection step is performed with HCl.

16. The method according to any one of claims 2-4, wherein the deprotection step is carried out with an alkali.

17. The method according to any one of claims 1-4, wherein the deprotection step is carried out with a Brønsted base.

18. The method according to any one of claims 1-4, wherein the deprotection step is carried out with NaOH.

19. The method of claim 13, wherein the de-ashing step is performed after the deprotection step.

20. The method according to any one of claims 1-4, wherein a functionalized terpolymer is obtained, wherein the first monomer is selected from the group consisting of ethylene and propylene, the second monomer is replaced by the group consisting of propylene, 1-hexene, 1-octene or norbornene, and the third monomer is selected from the group consisting of 3-buten-1-ol, 5-hexen-1-ol or 5-norbornene-2-methanol.

21. The method according to claim 20, wherein the functionalized terpolymer is poly(propylene-co-ethylene-co-5-hexen-1-ol), poly(propylene-co-1-hexen-co-5-hexen-1-ol), poly(ethylene-co-norbornene-co-5-hexen-1-ol), poly(ethylene-co-1-octene-co-5-hexen-1-ol), poly(propylene-co-ethylene-co-3-buten-1-ol), poly(propylene-co-1-hexen-co-3-buten-1-ol), poly(ethylene-co-1-octene-co-3-buten-1-ol), poly(ethylene-co-norbornene-co-3-buten-1-ol), or poly(ethylene-co-norbornene-co-5-norbornene-2-methanol).

22. The functionalized olefin copolymer obtained by the method of any one of claims 1-21.

23. The functionalized olefin copolymer obtained by the method of any one of claims 1-21, comprising: a. M 40 to 300 kg / mol determined by high temperature size exclusion chromatography (HT-SEC) w scope, b. M 20 to 150 kg / mol determined by high temperature size exclusion chromatography (HT-SEC) n scope, c. Crystallinity > 30%, as determined by differential scanning calorimetry (DSC). d. Melting point of 100 to 155°C e. Randomly distributed hydroxyl or carboxylic acid functional groups, f. 0.05 to 10 mol% of hydroxyl or carboxylic acid functional comonomer content, and olefin comonomers selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane or 1-octene.

24. The functionalized olefin copolymer of claim 23, wherein the olefin comonomer is replaced by the group consisting of norbornene, vinylidene norbornene or ethylidene norbornene.

25. A functionalized olefin terpolymer obtained by the method of any one of claims 1-21, comprising: a. M 40 to 300 kg / mol determined by high temperature size exclusion chromatography (HT-SEC) w scope, b. M 20 to 150 kg / mol determined by high temperature size exclusion chromatography (HT-SEC) n scope, c. Crystallinity range of 0% to 30%, determined by differential scanning calorimetry (DSC). d. Melting point of 40 to 120°C e. A first olefin comonomer selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, or 1-octene; a second comonomer, different from the first olefin comonomer and selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, or 1-octene, in a content of 0.5 to 20 mol%; and a third comonomer with hydroxyl or carboxylic acid functionality in a content of 0.05 to 10 mol%. f. Randomly distributed hydroxyl or carboxylic acid functional groups.

26. The functionalized olefin terpolymer according to claim 25, wherein the first olefin comonomer is replaced by the group consisting of norbornene, vinylidene norbornene or ethylidene norbornene, or the second comonomer is replaced by the group consisting of norbornene, vinylidene norbornene or ethylidene norbornene.

27. The functionalized olefin copolymer according to any one of claims 22-26, wherein the copolymer contains at least 0.1% by weight and at most 5% by weight of aluminum.

28. Use of the functionalized polyolefin obtained by the method of any one of claims 1-2, 5-21 or the functionalized olefin copolymer according to any one of claims 22-27, in a foam article wherein aluminum compounds have not been separated from the functionalized polyolefin.

29. Use of catalyst systems comprising hafnium complexes containing polyvalent aryloxy ethers and co-catalysts selected from the group consisting of ammonium salts or triphenylmethyl salts of MAO, MMAO, DMAO, SMAO and fluorinated tetraarylborates, for the purpose of obtaining hydroxyl- or carboxylic acid-functionalized polyolefins by solution copolymerization. The polymerization temperature is between 100 and 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), and dimethylbis((2-oxy-3-(dibenzo-1H-pyrrolo-1-yl)phenyl)-2-phenoxy)-1,3-propylhafnium (IV).

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