Process for the manufacture of a functionalized polyolefin (FPO) composition, FPO obtained and article therefrom

Abstract

The present invention relates to a process for the manufacture of a functionalized polyolefin (FPO) composition, said process comprising the steps of: a) copolymerizing i) at least one olefin and ii) at least one protected functionalized olefin obtained or obtainable by protecting a functionalized olefin with a protecting agent, wherein said co- polymerizing is carried out in a solvent in the presence of a catalyst system comprising a catalyst, to obtain a solution comprising a copolymer containing repeating units from said at least one olefin and said at least one protected functionalized olefin, and said catalyst in said solvent, b) contacting the solution obtained in step a) with at least one alcohol, c) devolatilizing the solution obtained in step b) by to provide a concentrated solution, d) contacting the concentrated solution obtained in step c) with an aqueous composition to deprotect at least part, preferably all, of the protected functionalized olefin repeating units of the copolymer, to obtain a concentrated solution comprising a copolymer containing repeating units from said at least one olefin and said at least one functionalized olefin; said concentrated solution further comprising residues of the protecting agent, and e) devolatilizing the concentrated solution obtained in step d) to provide a stream comprising said functionalized polyolefin and a stream comprising solvent. In addition, the invention relates to a functionalized polyolefin composition and to an article.

Description

24POLY0062-WO-ORD 1TITLE PROCESS FOR THE MANUFACTURE OF A FUNCTIONALIZEDPOLYOLEFIN (FPO) COMPOSITION, FPO OBTAINED AND ARTICLE THEREFROMFIELD OF THE INVENTION

[0001] The present invention relates to a process for the manufacture of a functionalized polyolefin (FPO) composition, an FPO composition as well as an article therefrom. More in particular, the present invention relates to a process for the manufacture of a FPO that can be implemented on an industrial scale and can be carried out in a continuous or semi-continuous manner.

[0002] WO2022 / 106689 describes a process for solution copolymerization for the production of functionalized polyolefins (FPOs)

[0003] EP3034545 discloses a process for the preparation of a graft copolymer comprising a polyolefin main chain and one or multiple polymer side chains.

[0004] The process disclosed in EP3034545 is generally performed under slurry condition which has important drawbacks such as reactor fouling occurring when using homogeneous single-site catalysts at temperatures below the crystallization temperature of the polymer being formed, the precipitated polymer retains a large fraction of unreacted functional comonomer and deprotection is difficult once the polymer has precipitated.

[0005] Therefore, there is a need for a new process to produce functionalized polyolefins, in particular to an improved way of deactivating the catalyst and deprotection of the protected polymer. In particular, to indicate the appropriate deprotection agent, the appropriate amount of said agent, and the deprotection method that can be used in an industrial process preferably in a continuous or semi-continuous manner and that is economically viable.

[0006] More in particular, when preparing this functionalized polyolefin, there is a need for prevention or at least reduction of fouling of the reactor and / or other piping and equipment used in the industrial scale production of FPOs. Consequently, there is also a need for industrial procedures for the handling of deprotection byproducts.

[0007] It is an object of the present invention to provide an improved process for the manufacture of functionalized polyolefins. Specifically, an improved process for the solution copolymerization of functionalized polyolefins.

[0008] It is a further object of the present invention to provide a functionalized polyolefin composition obtainable by the improved process as described herein.24POLYOQ62-WO-ORD 2

[0009] Finally, it is an object of the present invention to provide an object comprising or consisting of the functionalized polyolefin composition as described herein.STATEMENT OF THE INVENTION

[0010] The objects cited above are met, at least in part by the process of the invention.

[0011] In a first aspect, the invention relates to a process for the manufacture of a functionalized polyolefin (FPO) composition, said process comprising the steps of: a) copolymerizing i) at least one olefin and ii) at least one protected functionalized olefin obtained or obtainable by protecting a functionalized olefin with a protecting agent, wherein said co-polymerizing is carried out in a solvent in the presence of a catalyst system comprising a catalyst, to obtain a solution comprising a copolymer containing repeating units from said at least one olefin and said at least one protected functionalized olefin, and said catalyst in said solvent, b) contacting the solution obtained in step a) with at least one alcohol, c) devolatilizing the solution obtained in step b) to provide a concentrated solution, d) contacting the concentrated solution obtained in step c) with an aqueous composition to deprotect at least part, preferably all, of the protected functionalized olefin repeating units of the copolymer, to obtain a concentrated solution comprising a copolymer containing repeating units from said at least one olefin and said at least one functionalized olefin; said concentrated solution further comprising residues of the protecting agent, and e) devolatilizing the concentrated solution obtained in step d) to provide a stream comprising said functionalized polyolefin and a stream comprising solvent.

[0012] In a second aspect, the invention relates to a functionalized polyolefin (FPO) composition obtainable by the process according to the first aspect of the invention.

[0013] In a third aspect, the invention relates to an article comprising or consisting of the functionalized polyolefin composition according to the second aspect of the invention.

[0014] Corresponding embodiments of the process are also applicable for the FPO compositions orthe article according to the present invention, unless specified otherwise.24POLYOQ62-WO-ORD 3

[0015] The present invention relates to a manufacturing process for an FPO composition that comprises a two-step catalyst deactivation and deprotection, that is suitable for industrial scale production.

[0016] The deactivation of the catalyst is important, in particular for an industrial scale operation, to avoid downstream (co)polymerization and therewith fouling of the reactor, pipes and equipment in the reactor system or the final product. Further, it is important that the copolymerization reaction is stopped, i.e. quenched, and does not continue outside of the reactor. Continued copolymerization outside of the reactor leads to uncontrolled polymer production which can affect, even in small quantities, the quality of the final product.

[0017] A disadvantage of prior art processes that use water to deactivate the catalyst is that this will lead to at least partial deprotection of the functional groups will occur, which might lead to side reactions with the protecting agents causing fouling. The present invention solves this problem by first deactivating the catalyst and partially deprotecting the protection groups using an alcohol and later on removal of the protection groups by an appropriate deprotection agent, namely an aqueous composition. The present inventors have observed that the dual method according to the present invention solves this disadvantage.DETAILED DESCRIPTION

[0018] The present invention is elucidated below with a detailed description.

[0019] The following definitions are used in the present description and claims to define the stated subject matter. Other terms not cited below are meant to have the generally accepted meaning in the field.Brief description of drawings

[0020] The present invention is described hereinafter with reference to the accompanying drawings in which embodiments of the present invention are shown and in which like reference numbers indicate the same or similar elements.Figure 1 is a flow chart of an embodiment of the process according to the present invention.Figure 2 is a flow chart of another embodiment of the process according to the present invention wherein one or more optional features are shown.Figures 3 (3a, 3b, 3c) are overviews of the chemical deprotection reactions.24POLYOQ62-WO-ORD 4Figure 4 is a graph of the amount of alcohol required to remove a certain fraction of protecting groups of the repeating units from the protected functionalized olefin.First aspect - process

[0021] In a first aspect, the present invention relates to a process for the manufacture of a functionalized polyolefin (FPO) composition, said process comprising the steps a), b), c), d) and e), each disclosed below.

[0022] Figure 1 is a flowchart showing step a) to step e) according to the invention. The flowchart further shows the addition of a stream of at least one olefin (100) and a stream of protected functional comonomer (110) according to step a). A catalyst system comprising a catalyst is required during the copolymerization and may be already present in the reactor or may be added (not shown). Copolymerization of step a) results in a stream of a solution comprising a copolymer (113). A stream of alcohol (200) is added in step b) according to the invention at the reactor outlet, e.g. in the pipe connecting the reactor to a devolatilization vessel. Step c) of devolatilization is then performed to obtain a concentrated solution. Then, in step d), a stream of an aqueous composition (400) is added. In step e) the solution of step d) is devolatilized to provide a stream comprising the functionalized polyolefin (500);

[0023] Figure 2 is a flowchart of another embodiment of the process according to the present invention wherein one or more optional features are shown. Optionally, in step a) a stream of a first olefin (111) and a stream of a second olefin (112) is added. Further optionally, to step a) a stream (120) comprising a catalyst, and further a cocatalyst, a scavenger, a chain transfer agent, or combination thereof is added. Optionally in the devolatilization of step c), volatiles (301) are isolated and the heavies are removed resulting in a stream of volatiles without heavies (302) which may be provided in step a). Further optionally, after step e), step f) may be performed wherein the stream comprising the functionalized polyolefin (500) is cooled and converted into e.g. granules, pellets, powder or flakes (600).

[0024] The present invention is related to a solution polymerization process, not to a slurry process.Step a)24POLYOQ62-WO-ORD 5

[0025] Step a) comprises copolymerizing i) at least one olefin and ii) at least one protected functionalized olefin obtained or obtainable by protecting a functionalized olefin with a protecting agent, wherein said co-polymerizing is carried out in a solvent in the presence of a catalyst system comprising a catalyst, to obtain a solution comprising a copolymer containing repeating units from said at least one olefin and said at least one protected functionalized olefin, and said catalyst in said solvent.

[0026] In an embodiment, the at least one olefin is selected from the group consisting of C2-C10 alkene, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, and decene, preferably ethylene, propylene, butene, hexene, and octene.

[0027] In an embodiment, the at least one olefin comprises ethylene and at least an olefin selected from the group consisting of butene, hexene, and octene.

[0028] In an embodiment the at least one olefin comprises propylene and at least an olefin selected from the group consisting of ethylene, butene, hexene, and octene. In an embodiment, the process of step a) according to the invention is the same as the polymerization process described in WO2022 / 106689 page 2 to page 6 of the description, which are incorporated by reference herein.The at least one olefin

[0029] The olefin of step a) is represented by the formula CHR1 =CHR2, wherein R1 and R2 are each independently chosen from H or a hydrocarbyl group having 1 to 8 carbon atoms, optionally where R1 and R2 form a ring structure, preferably selected from the ethylene, propylene, 1-butene, 3-methyl-1 -butene, 1-pentene, 4-methyl-1-pentene, 1 -hexene, vinyl cyclohexane, 1 -octene, 1 -decene, norbornene, vinylidene-norbornene, ethylidene-norbornene, or a combination of thereof.

[0030] In another embodiment, the at least one olefin is propylene, in particular in an amount of at least 50 wt.%, preferably at least 60 wt.%, more preferably at least 70 wt.%, most preferably at least 80 wt.% with respect to the total weight of the olefins and the functionalized olefins.

[0031] In another embodiment, the at least one olefin is ethylene, in particular in an amount of at least 50 wt.%, preferably at least 60 wt.%, more preferably at least 70 wt.%, most preferably at least 80 wt.% with respect to the total weight of the olefins and the functionalized olefin.24POLYOQ62-WO-ORD 6

[0032] The polymerization step may use one type of olefin or two or more types of olefin, such as a first olefin and a second olefin. Each of these may be independently selected from the olefin of step a) cited above.

[0033] In another embodiment, the first and second olefin are different and the amount of the first olefin is from 10 mol% to 90 mol% and the amount of second olefin is from 90 mol% to 10 mol%, based on the total molar amount of first and second olefin.

[0034] In another embodiment, the first olefin is ethylene and the second olefin is 1— octene. In another embodiment, the first olefin is ethylene and the second olefin is norbornene. In another embodiment, the first olefin is propylene and the second olefin is ethylene. In another embodiment, the first olefin is propylene and the second olefin is 1— butene. In another embodiment, the first olefin is propylene and the second olefin is 1— hexene.The least one functionalized olefin

[0035] The functionalized olefin monomer may the following structure according to formula (I)

[0036] In Formula I:R3, R4, and R5 are each independently selected from the group consisting of H and hydrocarbyl with 1 to 16 carbon atoms,R6-[X-(R7)n]m is a polar functional group containing m heteroatom-containing functionalities X-(R7)n,R6 is either -C(R8)(R9)- or a plurality of -C(R8)(R9)- groups, wherein R8, and R9 are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms and R6 comprises 1 to 10 carbon atoms, wherein X is attached to either the main chain and / or side chain of R6, wherein R4 and R6 may together form a ring structure that is functionalized with one or multiple X-(R7)n; n is 0, 1 or 2,24POLYOQ62-WO-ORD 7X is -O-, -S- or -C(=O)O- if n = 1 , X = N if n = 2, X = NH2if n = 0; preferably X is -O- or -C(=0)0-R7 is H if n =1 ; when n = 2 at least one R7 H and the other R7 is selected from the group consisting of H and a hydrocarbyl group with 1 to 16 carbon atoms;R11 is selected from the group consisting of methyl, ethyl, n— propyl, isopropyl, n— butyl, isobutyl, tert— butyl, and cyclohexyl,R12 is selected from the group consisting of ethyl, isobutyl, n— hexyl, and n— octyl, R13 is selected from the group consisting of H, methyl, ethyl, n— propyl, isopropyl, n— butyl, isobutyl, tert— butyl, and cyclohexyl, m is an integer between 1 and 10, preferably 1 or 2.Protecting agent

[0037] The hydrogen atoms directly bound to X in the functionalized olefin monomer has a Bronsted acidic nature poisonous to the highly reactive catalyst. A protecting agent is used, which can react with the acidic hydrogen and binds to the monomer comprising the polar group. This reaction will prevent a reaction of the acidic polar group (-X-H) with the catalyst and coordination of the polar group ( — X — ) to the catalyst.

[0038] Examples of protecting agents are silyl halides, trialkyl aluminum complexes, dialkyl aluminum alkoxide complexes, dialkyl magnesium complexes, dialkyl zinc complexes or trialkyl boron complexes.

[0039] The protecting agent may the following structure according to formula (II) or formula (llbis):AI(R13)3Formula (II)R11-O-AI(R12)2Formula (llbis)

[0040] In formula II R13 is selected from the group consisting of H, methyl, ethyl, n— propyl, isopropyl, n— butyl, isobutyl, tert— butyl, and cyclohexyl.

[0041] In formula llbis R11 is selected from the group consisting of methyl, ethyl, n— propyl, isopropyl, n— butyl, isobutyl, tert— butyl, cyclohexyl, and n— octyl and each R12 is independently selected from the group consisting of ethyl, isobutyl, n— hexyl, and n— octyl.24POLYOQ62-WO-ORD 8

[0042] In the process of the invention it is preferred that the protecting agent is selected from trialkyl aluminum complexes selected from the group comprising: triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, or with a dialkyl aluminum alkoxide, R11OAI(R12)2 where where R11 = methyl, ethyl, n— propyl, isopropyl, n— butyl, isobutyl, tert— butyl, cyclohexyl and R12= ethyl, isobutyl, n— hexyl, n— octyl, or a combination of a trialkyl aluminum and a dialkyl aluminum alkoxide. The most preferred protecting agent is triethyl aluminum.

[0043] Surprisingly, triethyl aluminum does not lead to severe chain transfer and does not inhibit the catalyst comprising the ligand-metal complex as describe above. This feature allows to use triethyl aluminum instead of tri— isobutyl aluminum, which is a great cost benefit.

[0044] In order to obtain the protected functionalized olefin monomer, a preliminary protection step is performed prior to the copolymerization step of the functionalized olefin monomer.

[0045] In an embodiment, the protection step in order to obtain a protected functionalized olefin monomer according to Formula (I) may be performed by an alumination reaction of a hydroxyl or carboxylic acid functionalized olefin monomer by reacting it with a trialkyl aluminum, for example triethyl aluminum, or a dialkyl aluminum alkoxide, for example diethyl aluminum ethoxide, or the combination of a trialkyl aluminum and dialkyl aluminum alkoxide, for example triethyl aluminum and diethyl aluminum ethoxide.

[0046] The molar amount of the protecting agent preferably is at least the same molar amount as the functional group in the functionalized olefin monomer. Preferably, the molar amount of protecting agent is at least 10 % higher than the amount of functionalized olefin monomer, or at least 20 % higher. Typically the amount of protecting agent is less than 250 % (equaling 2.5 molar equivalents) of functionalized olefin monomer. In some occasions higher amounts may be used or may be necessary.

[0047] In a preferred embodiment, the functionalized olefin monomer according to Formula I is a hydroxyl- or carboxylic acid-bearing alfa-olefin or hydroxyl- or carboxylic acid-functionalized ring-strained cyclic olefin monomer, preferably a hydroxyl, a dihydroxyl or carboxylic acid alfa-olefin monomer.

[0048] Hydroxyl-bearing functionalized alfa-olefin monomers may correspond for example to Formula I wherein R3, R4 and R5 are each H and wherein X is -O- and wherein R6 is either -C(R8)(R9)- or a plurality of -C(R8)(R9)- groups, wherein R8 and24POLYOQ62-WO-ORD 9R9 are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms. Examples of R6 groups are -(CH2)2-, -(CH2)4-, -(CH2)6-, -(CH2)8-, or -(CH2)9-.

[0049] Further examples of the hydroxyl-functionalized alfa-olefin monomer include, but are not limited to allyl alcohol, 3-buten— 1-ol, 3-buten— 2-ol, 3-buten— 1 ,2-diol, 5— hexene- 1-ol, 5-hexene-1 ,2-diol, 7- octen— 1-ol, 7-octen— 1 ,2-diol, 9-decen— 1-ol, 10— undecene-1-ol, preferably 3-buten— 1-ol, 5-hexene- 1-ol.

[0050] Even further examples of functionalized olefin monomer include hydroxyl- functionalized ring strained cyclic olefins (also called internal olefins), which may be for example typically hydroxyl functionalized norbornenes, preferably 5-norbornene- 2— methanol. They correspond to Formula I wherein R3 and R5 are H and R4 and R6 together for a ring structure that is functionalized with XH, wherein X is -O-.

[0051] Carboxylic acid-bearing functionalized olefin monomers may for example correspond to Formula I wherein R3 and R5 are each H and wherein X is -C(=O)O- and wherein R6 is either -C(R8)(R9)- or a plurality of -C(R8)(R9)- groups, wherein R8 and R9 are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms. Example of an R6 group are -(CH2)2-, -(CH2)4-, -(CH2)6-, -(CH2)8-, or -(CH2)9-. Preferred acid functionalized olefin monomers may be selected from the group of 3-butenoic acid, 4-pentenoic acid, hexanoic acid, 5-norbornene-2-carboxylic acid, and 10-undecanoic acid.

[0052] Thiol-bearing functionalized olefin monomers may for example correspond to Formula I wherein R3 and R5 are each H and wherein X is -S- and wherein R6 is either -C(R8)(R9)- or a plurality of -C(R8)(R9)- groups, wherein R8 and R9 are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms. Examples of R6 groups are -(CH2)2-, -(CH2)4-, -(CH2)6-, -(CH2)8-, or -(CH2)9-. Preferred thiol functionalized olefin monomers may be selected from the group of 5- hexen— 1 -thiol, 10-undecen— 1 -thiol.

[0053] Amine-bearing functionalized olefin monomers may for example correspond to Formula I wherein R3 and R5 are each H and wherein X is -N(H)R7- and wherein Rs is either -C(R8)(R9)- or a plurality of -C(R8)(R9)- groups, wherein R8, and R9 are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms and wherein R7 is H or hydrocarbyl. Examples of an R6 group are-(CH2)2. -(CH2)4- -, -(CH2)6-, -(CH2)8-, or -(CH2)9-. Preferred amine functionalized olefin monomers may be selected from the group of N— methyl-5-hexen— 1 -amine, N— ethyl-5-hexen— 1 -amine,24POLYOQ62-WO-ORD 10N— propyl-5- hexen— 1 -amine, N— isopropyl-5-hexen— 1 -amine, N— cyclohexyl-5- hexen— 1 -amine.

[0054] In an embodiment 2 different monomers are used in order to obtain a copolymer, preferably a copolymer in which the first monomer is selected from the group comprising ethylene and propylene and the second monomer is selected from the group comprising 3-buten— 1-ol, 5-hexen— 1 -ol and 5-norbornene-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-norbornene-2-methanol).

[0055] In another embodiment 3 different monomers are used in order to obtain a terpolymer, preferably a terpolymer in which the first monomer is selected from the group comprising ethylene and propylene, the second monomer is selected from the group comprising propylene (in case the first monomer is ethylene), 1 -butene, 1 -hexene,1- octene and norbornene and the third monomer is selected from the group comprising3-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-buten— co-5-hexen— 1-ol), poly(propylene-co-1-octene-co-5— hexen— 1 -ol) , poly(propylene-co- 1 -hexene-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-hexene-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).The at least one protected functionalized olefin

[0056] The protected functionalized olefin monomer may the following structure according to Formula (III) or (I I Ibis) :24POLYOQ62-WO-ORD 1 1

[0057] In Formula III or lllbis:R3, R4, and R5 are each independently selected from the group consisting of H and hydrocarbyl with 1 to 16 carbon atoms,R6 is either -C(R8)(R9)- or a plurality of -C(R8)(R9)- groups, wherein R8 and R9 are each independently selected from the group consisting of H or hydrocarbyl with 1 to 16 carbon atoms. Examples of R6 groups are -(CH2)2-, -(CH2)4-, -(CH2)6-, -(CH2)8-, or -(CH2)9-; n is 1 or 2,X is -O-, -S- or -C(=O)O- or -NH- if n = 1 , X = N if n = 2,R1 1 is selected from the group consisting of methyl, ethyl, n— propyl, isopropyl, n— butyl, isobutyl, tert— butyl, and cyclohexyl,R12 is selected from the group consisting of ethyl, isobutyl, n— hexyl, and n— octyl, R13 is selected from the group consisting of H, methyl, ethyl, n— propyl, isopropyl, n— butyl, isobutyl, tert— butyl, and cyclohexyl, m is an integer between 1 and 10, preferably 1 or 2.

[0058] In an embodiment, the at least one protected functionalized olefin is selected from the group consisting of allyl alcohol, 3-buten— 1-ol, 3-buten— 2-ol, 3-buten— 1 ,2-diol, 5-hexene-1-ol, 5-hexene-1 ,2-diol, 7-octen— 1-ol, 7-octen— 1 ,2-diol, 9-decen— 1-ol, 10— undecene-1-ol, 5-norbornene-2- methanol, 3-butenoic acid, 4-pentenoic acid, 10— undecenoic acid, 5-norbornene-2-carboxylic acid, 5-norbornene-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-butene-1-thiol, 5-hexene-1-thiol, preferably 3-buten— 1-ol,24POLYOQ62-WO-ORD 125— hexene- 1-ol, 5-norbornene-2-methanol, 3-butenoic acid, 4-pentenoic acid, 5— norbornene-2-carboxylic acid.The catalyst system

[0059] In an embodiment, the catalyst system further comprises a co-catalyst, optionally a scavenger, and optionally a chain transfer agent.

[0060] In an embodiment, the catalyst is a ligand-metal complex having a bridged bis-bi-aryl structure. In particular, the ligands are dianionic chelating ligands that can occupy up to four coordination sites of a metal precursor atom and more specifically have a bridged-bis-bi-aryl structure.

[0061] The metal-ligand complexes can be characterized by the general formula: (4,O)MLn’ (VI) where (4,0) is a dianionic ligand having at least 4 atoms that are oxygen and chelating to the metal M at 4 coordination sites through oxygen atoms with two of the bonds between the oxygen and the metal being covalent in nature and two of the bonds being dative in nature; M is a metal selected from the group consisting of group 4 of the Periodic Table of Elements, more specifically, from Hf or Zr, preferentially Hf; L is independently selected from the group consisting of halide (F, Cl, Br, I), substituted or non— substituted alkyl, for example methyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl (e.g. benzyl), heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphine, amino, alkylthio, arylthio, nitro, hydrido, borohydride, allyl, diene, phosphine, carboxylates, 1 ,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers 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.

[0062] In still other embodiments, the metal-ligand complexes of this invention may be characterized by the general formula as depicted in, and as described in WO2022 / 106689 page 18 of the description, which is incorporated by reference herein

[0063] In an embodiment the ligand-metal complex is a hafnium or zirconium complex of a polyvalent aryloxyether selected from the group as described in WO2022 / 106689 page 18 to page 21 of the description, which are incorporated by reference herein

[0064] Methylaluminoxane or MAO as used in the present description may mean: a compound derived from the partial hydrolysis of trimethyl aluminum that serves as a cocatalyst for catalytic olefin polymerization.24POLYOQ62-WO-ORD 13

[0065] Supported methylaluminoxane or SMAO as used in the present description may mean: a methylaluminoxane bound to a solid support.

[0066] Depleted methylaluminoxane or DMAO as used in the present description may mean: a methylaluminoxane from which the free trimethyl aluminum has been removed.

[0067] Modified methylaluminoxane or MMAO as used in the present description may mean: modified methylaluminoxane, viz. the product obtained after partial hydrolysis of trimethyl aluminum plus another trialkyl aluminum such as tri(isobutyl) aluminum ortri- n— octyl aluminum.

[0068] Fluorinated aryl borates as used in the present description may mean: a borate compound having four fluorinated (preferably perfluorinated) aryl ligands.

[0069] In an embodiment, a scavenger is present. A scavenger can optionally be added to the catalyst system in order to react with impurities that are present in the polymerization reactor, and / or in the solvent and / or monomer feed. This scavenger prevents poisoning of the catalyst during the olefin polymerization process. The optional scavenger is selected from the group: trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, preferably triethyl aluminum.

[0070] In an embodiment, a chain transfer agent is optionally present, preferably selected from the group consisting of dihydrogen or AIR103, BR103or ZnR102, where each R10 is independently selected from H or hydrocarbyl.

[0071] In an embodiment, the solvent for the polymerization reaction is selected from the group consisting of, Isopar™ E (an isoparaffinic hydrocarbon fluid marketed by ExxonMobil), aliphatic or alicyclic solvents such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C4— C10 alkanes. Small quantities of aromatic hydrocarbons such as toluene, ethyl benzene or xylene may be included. The solvent is preferably methylcyclohexane (MCH) or Isopar™ E .The solution obtained in step a) may further comprise any unreacted monomer, namely one or more olefins and / or one or more protected functionalized olefin as well as other reaction products.

[0072] The polymerization of step a) is a solution process, using a catalyst system as described above.

[0073] The polymerization temperature of step a) is in the range from 100 to 250 °C, preferably 110 to 210 °C, more preferably 130 to 180 °C.24POLYOQ62-WO-ORD 14

[0074] The polymerization time of step a) is in the range of from 10 seconds to 20 hours, preferably from 1 minute to 2 hours, preferably 2 minutes to 1 hour, more preferably 5 to 30 minutes.

[0075] The molecular weight of the polymer can be controlled by adjusting the temperature and / or monomer concentration and / or use of hydrogen or other chain transfer agents. The polymerization may be conducted by a batch process, a semi- continuous process or a continuous process and may also be conducted in two or more steps of different polymerization conditions. The polyolefin produced is separated from the polymerization solvent and dried by methods known to a person skilled in the art.

[0076] The invention may involve a further addition of other additives such as a processing stabilizer (primary antioxidant) such as Irganox 1010, Igranox 1726, Irgafos 168 or mixture thereof. Optionally acid scavengers can be used such as calcium stearate or DHT4A.Step b)

[0077] Step b) comprises contacting the solution obtained in step a) with at least one alcohol.

[0078] In an embodiment, the alcohol used in step b) is selected from the group consisting of a C1-C6 alkyl alcohol, preferably a C2-C4 alkyl alcohol, more preferably ethanol, isopropyl alcohol, or butanol or a combination of two or more thereof.

[0079] In an embodiment, the alcohol during step b) will advantageously ensure that i) at least part, preferably all, of the catalyst will be deactivated; and ii) at least part, preferably all, of the protecting groups of the repeating units from the protected functionalized olefin and / or the protection groups of any unreacted protected functionalized olefin will be modified, i.e. at least partially deprotecting the protected functionalized olefin. As exemplified in Figure 3a, preferably the protecting group of the protected functionalized olefin is an di-alkyl aluminum group of formula AIR2wherein preferably R = ethyl or isobutyl. The addition of a preferably stoichiometric amount of ethanol (EtOH) partially deprotects the di-alkyl aluminum group resulting in a di-alkoxy aluminum group (as shown in Figure 3a). Figure 3b shows the reaction of the resulting di-alkoxy aluminum group with ethanol leading to hexenol (5-hexen-1-ol) and a tri-alkoxy aluminum. Tri-alkoxy aluminum can further form multimeric species (not shown). Figure24POLYOQ62-WO-ORD 153c shows the reaction of an di-alkyl aluminum group with water leading to hexenol and tri-hydroxy-aluminum.

[0080] Advantageously, step b) of the present invention does not involve contacting the solution comprising protected functionalized olefin with water or oxygen. Water or oxygen can be used to partially, or fully deprotect the protected functionalized olefin. However, whilst deprotection with water at the reactor outlet is chemically possible, it is industrially impractical because deprotection with water produces insoluble AI(OH)3as a deprotection byproduct. The presence of insoluble AI(OH)3at the reactor would cause critical fouling in equipment downstream. Deprotection with oxygen at the reactor outlet is also chemically possible, but industrially risky because oxygen and the flammable hydrocarbon solvent used in the process can form an explosive mixture. With “reactor outlet” in the present description is meant that this is not inside of the polymerization reactor, but for example in a pipe that is connecting the reactor to downstream processing equipment, such as in the pipe connecting reactor outlet to the downstream heat exchanger.

[0081] In an embodiment, in step b) alcohol is added in such an amount that the molar ratio of alcohol to the amount of protected functionalized olefin added during step a) is at least 10.0, preferably at least 5.0, more preferably from 2.0 - 4.0

[0082] In an embodiment, in step b) alcohol is added in such an amount that the molar ratio of alcohol to the amount of protected functionalized olefin added during step a), and hence as present in the copolymer and as unreacted olefin, is at least 2.0, preferably at least 4.0, more preferably at least 5.0, or even 10.0 or higher.

[0083] In an embodiment, a stoichiometric amount, or stoichiometric ratio of alcohol to protected functionalized olefin present in the copolymer is used in step b).

[0084] Advantageously, according to the step b) of the invention, no large excess of alcohol relative to the protected functionalized olefin is required, thus avoiding subsequent purification or scavenging reactions to remove excess alcohol from the reaction.

[0085] It is understood that the partial deprotection in step b) will occur for the both protected functionalized olefin comprised in the copolymer as well as any unreacted, i.e. not-polymerized, protected functionalized olefin coming out of the reactor

[0086] In an embodiment, the amount of copolymer in the solution obtained in step b) is at least 10 wt.%, preferably from 15 wt.% to 25 wt.%, based on the weight of the solution.24POLYOQ62-WO-ORD 16

[0087] In an embodiment, the amount of water during step b) is less than 2 molar equivalent to catalyst metal, preferably less than 1 molar equivalent. The present inventors have found, without wishing to be bound to a particular theory that by deactivating (quenching) of the catalyst in step b) with an alcohol, in the absence of water this avoids the creation of insoluble matter due to side reactions with the protecting agent, which insoluble matter creates fouling which is undesirable.

[0088] In an embodiment, the copolymerizing of step a) is carried out in at least one reactor and the contacting of step b) is not carried out in said at least one reactor, preferably the contacting of step b) is carried out in the reactor outlet.

[0089] In an embodiment, the contacting temperature of step b) is in the range from 100 to 250 °C, preferably 110 to 210 °C, more preferably 130 to 180 °C.

[0090] In an embodiment, the contacting time of step b) is in the range of 1 second to 2 hours, preferably 5 seconds to 1 minute.

[0091] The alcohol is added to the solution obtained in step a) preferably in such a mannerthatthe addition, causes mixing of the alcohol and the solution and thus provides good contact between the solution comprising the protected functionalized olefin and alcohol. For example, the alcohol is added at such a flow rate and volume that it fully mixes with the solution obtained in step a). In an embodiment, the alcohol is actively mixed with the solution obtained in step a) using a stirred vessel or more preferably a static mixer.Step c)

[0092] Step c) comprises devolatilizing the solution obtained in step b) to provide a concentrated solution.

[0093] During step c) the solution obtained in step b) will be subjected to one or more devolatilization steps, preferably in one or more devolatilization vessels.

[0094] During this devolatilization part of the solvent will be removed from the solution. In addition, preferably at least part of any unreacted olefin and at least part of any unreacted protected functionalized olefin (or modified protected functionalized olefin) will also be removed from the solution.

[0095] In an embodiment, the one or more devolatilization vessels are operated under a vacuum, at atmospheric pressure, above atmospheric pressure, or a combination thereof. For example, the first devolatilization vessel is operated above atmospheric pressure and the second devolatilization vessel is operated under vacuum.24POLYOQ62-WO-ORD 17

[0096] This step c) of devolatilization prior to step d) will allow the recovery of solvent and possibly starting materials, such as unreacted olefins of step a), a-i), a-ii) or (partially or fully deprotected) functionalized olefin, for recycling into the reaction without fouling of the solvent and other materials due to the reaction with water in step d). Advantageously, recovery and re-use of solvents and possibly starting materials increases efficiency and is cost effective, especially in large scale operations.

[0097] In an embodiment, the recovered solution comprising solvent and possibly starting materials are transferred to a solvent conditioning unit for removal of impurities (e.g. water or alcohol residues) from the solution.

[0098] In an embodiment, the amount of copolymer in the concentrated solution obtained in step c) is at least 25 wt.%, preferably from 30 wt.% to 80 wt.%, based on the weight of the concentrated solution.Step d)

[0099] Step d) comprises contacting the concentrated solution obtained in step c) with an aqueous composition (comprising water) to deprotect at least part, preferably all, of the protected functionalized olefin repeating units of the copolymer, to obtain a concentrated solution comprising a copolymer containing repeating units from said at least one olefin and said at least one functionalized olefin; said concentrated solution further comprising residues of the protecting agent.

[0100] In an embodiment, the aqueous composition used in step d) comprises water, and further an alcohol and / or an acid.

[0101] The alcohol may selected from the group consisting of a C1-C6 alkyl alcohol, preferably a C2-C4 alkyl alcohol, more preferably ethanol, isopropyl alcohol, or butanol or a combination of two or more thereof.

[0102] The aqueous composition may have a pH of between 1 and 7, such as between 3 and 4.

[0103] The acid may be selected from the group consisting of acetic acid, carbonic acid (formed from carbon dioxide and water), hydrochloric acid, fatty acids, phosphoric acid, nitric acid, and sulphuric acid.

[0104] Examples of fatty acids are heptanoic acid, lauric acid, hexanoic acid, dodecanoic acid, and 2-methylhexanoic acid.

[0105] The acid may be present in an amount of between 0.1 and 10 wt.% in water, such as between 0.2 and 2.0 wt. %, for example 2.5 wt.% in water.24POLYOQ62-WO-ORD 18

[0106] In an embodiment, the alcohol used in step b) is the same as the alcohol used in step d).

[0107] In an embodiment, the alcohol used in step b) is the same as the alcohol used in the mixture of water and alcohol used in step d).

[0108] In another embodiment, the alcohol used in step d) is an aliphatic alcohol, preferably methanol, ethanol or isopropanol.

[0109] In another embodiment, aqueous composition used in step d) is a combination of an aliphatic alcohol and / or water and / or a Bransted acid or a Bransted base.

[0110] In order to prevent the corrosion of the polymerization reactor, the step d) may be carried out in a tank coated with PE, PTFE or PFA, and the base material is stainless steel when a base is used or carbon steel when an acid is used

[0111] In case a mixture of water and one or more alcohol is used in step d), a skilled person can determine the ratio between water and the one or more alcohol. In an embodiment, the volume ratio between water and alcohol in the aqueous composition is between 1 : 10 and 10 : 1.

[0112] In an embodiment, in step d) the molar ratio of water to the functional groups incorporated in the polymer or present as unreacted protected functionalized olefin is between 3 and 60, preferably between 3 and 30, more preferably between 3 and 20.

[0113] In an embodiment, in step d) the molar ratio of -OH moieties to the functional groups incorporated in the polymer or present as unreacted protected functionalized olefin is between 3 and 60, preferably between 3 and 30, more preferably between 3 and 20.Step e)

[0114] Step e) comprises devolatilizing the concentrated solution obtained in step d) to provide a stream comprising said functionalized polyolefin and a stream comprising solvent.

[0115] During this devolatilization of step e) part of the solvent and aqueous composition added in step d) will be removed from the solution, preferably in one or more devolatilization vessels. In addition, preferably at least part of any unreacted olefin and at least part of any unreacted protected functionalized olefin (or modified protected functionalized olefin) will also be removed from the solution.24POLYOQ62-WO-ORD 19

[0116] In an embodiment, the one or more devolatilization vessels are operated under a vacuum, at atmospheric pressure, above atmospheric pressure, or a combination thereof. For example, the first devolatilization vessel the devolatilization is operated above atmospheric pressure and the second devolatilization vessel is operated under vacuum.

[0117] In an embodiment, the amount of copolymer in the polymer stream obtained in step e) is at least 90 wt.%, preferably from 95 wt.% to 100 wt.%, based on the weight of the polymer.

[0118] The solvent stream obtained in step e) may comprise in addition to the solvent, water from the aqueous solution and optionally other components thereof, any remaining unreacted monomers and optionally other components. Possibly, residues of the protecting agent are also in that stream. The polymer stream may also comprise residues of the protecting agent depending on the volatility thereof and of the temperature of the step of devolatilization.

[0119] In an embodiment, said process is continuous.

[0120] In an embodiment, the process further comprises a step of separating at least part of the residues of the protecting agent from the concentrated solution obtained in step d) and / or the functional polymer stream obtained in step e) and / or the solvent stream obtained in step e).

[0121] In an embodiment, the process further comprises a step f) of combining the polymer stream obtained in step e) with further components. The further components may be the additives, fillers, other polymers, that are known to a person skilled in the art.

[0122] In an embodiment, the polymer stream obtained in step e) or step f) is cooled and converted into granules, pellets, powder or flakes, preferably pellets.

[0123] Complete deprotection of the protecting groups of the repeating units from the protected functionalized olefin is an equilibrium limited reaction. The graph in Figure 4 illustrates the amount of alcohol (y-axis) required to completely deprotect a certain fraction (x-axis) of the protecting groups of the repeating units from the protected functionalized olefin, and optionally unreacted protected functionalized olefin. For example, to achieve 99% of deprotection of the functional groups we require an alcohol / functional group molar ratio of 98 as compared to alcohol / functional group molar ratio of 2 to achieve partial deprotection.24POLYOQ62-WO-ORD 20Second aspect - FPO

[0124] In a second aspect, the present invention relates to a functionalized polyolefin composition obtainable by the process according to the first aspect.Third aspect - article

[0125] In a third aspect, the present invention relates to an article comprising or consisting of the functionalized polyolefin composition according to the second aspect.

[0126] Other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed invention, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The scope of the present invention is defined by the appended claims. One or more of the objects of the invention are achieved by the appended claims.LIST OF REFERENCE NUMBERS

[0127] The following reference numbers are used in the description and the drawings:100 stream of at least one olefin according to step a-i)110 stream of protected functional comonomer according to step a-ii)111 stream of first olefin112 stream of second olefin113 stream of solution comprising a copolymer120 stream of catalyst, co-catalyst and / or scavenger and / or chain transfer agent 200 stream of alcohol301 volatiles302 volatiles without heavies400 stream of aqueous composition500 FPO melt stream

Claims

24POLY0062-EPA 21CLAIMS1. A process for the manufacture of a functionalized polyolefin (FPO) composition, said process comprising the steps of: a) copolymerizing i) at least one olefin represented by the formula CHR1=CHR2, wherein R1 and R2 are each independently chosen from H or a hydrocarbyl group having 1 to 8 carbon atoms and ii) at least one protected functionalized olefin according to Formula (III) or (lllbis), obtained or obtainable by protecting a functionalized olefin with a protecting agent, wherein said copolymerizing is carried out in a solvent in the presence of a catalyst system comprising a catalyst comprising a ligand-metal complex, to obtain a solution comprising a copolymer containing repeating units from said at least one olefin and said at least one protected functionalized olefin, and said catalyst in said solvent, b) contacting the solution obtained in step a) with at least one alcohol, c) devolatilizing the solution obtained in step b) to provide a concentrated solution, d) contacting the concentrated solution obtained in step c) with an aqueous composition to deprotect at least part, preferably all, of the protected functionalized olefin repeating units of the copolymer, to obtain a concentrated solution comprising a copolymer containing repeating units from said at least one olefin and said at least one functionalized olefin; said concentrated solution further comprising residues of the protecting agent, and e) devolatilizing the concentrated solution obtained in step d) to provide a stream comprising said functionalized polyolefin and a stream comprising solvent, wherein the amount of water during step b) is less than 2 molar equivalent to catalyst metal, preferably less than 1 molar equivalent more preferably no water has been used in step b).

2. The process according to claim 1 , wherein the at least one olefin comprises propylene and at least an olefin selected from the group consisting of ethylene, butene, hexene, and octene.24POLY0062-EPA 223. The process according to claim 1 or claim 2, wherein the catalyst system further comprises a co-catalyst, optionally a scavenger, and optionally a chain transfer agent.

4. The process according to any one of the preceding claims, wherein the alcohol used in step b) is selected from the group consisting of a C1-C6 alkyl alcohol, preferably a C2-C4 alkyl alcohol, more preferably ethanol, isopropyl alcohol, or butanol or a combination of two or more thereof.

5. The process according to any one of the preceding claims, wherein in step b) alcohol is added in such an amount that the molar ratio of alcohol to the amount of protected functionalized olefin added during step a) is at least 2.0, preferably at least 4.0, more preferably at least 5.0.

6. The process according to any one of the preceding claims, wherein the copolymerizing of step a) is carried out in at least one reactor and the contacting of step b) is not carried out in said at least one reactor, preferably the contacting of step b) is carried out in the reactor outlet.

7. The process according to any one of the preceding claims, wherein the amount of copolymer in the concentrated solution obtained in step c) is at least 25 wt.%, preferably from 30 wt.% to 80 wt.%, based on the weight of the concentrated solution.

8. The process according to any one of the preceding claims, wherein the aqueous composition used in step d) comprises water, and further comprises an alcohol and / or an acid, preferably wherein the alcohol is selected from the group consisting of a C1- C6 alkyl alcohol, preferably a C2-C4 alkyl alcohol, more preferably ethanol, isopropyl alcohol, or butanol or a combination of two or more thereof, and / or preferably wherein the acid is selected from the group consisting of acetic acid, carbonic acid, hydrochloric acid, fatty acids, phosphoric acid, nitric acid, and sulphuric acid, preferably wherein the fatty acids are selected from the group consisting of heptanoic acid, lauric acid, hexanoic acid, dodecanoic acid, and 2-methylhexanoic acid, and a combination of two or more thereof; and / or24POLY0062-EPA 23 preferably wherein the aqueous composition has a pH of between 1 and 7, such as between 3 and 4.

9. The process according to any one of the preceding claims, wherein in step d) the molar ratio of water to the functional groups incorporated in the polymer and / or present as unreacted protected functionalized olefin is between 3 and 60, preferably between 3 and 30, more preferably between 3 and 20; and / or the ratio of alcohol to the functional groups incorporated in the polymer and / or present as unreacted protected functionalized olefin is between 3 and 60, preferably between 3 and 30, more preferably between 3 and 20.

10. The process according to any one of the preceding claims, wherein said process is continuous.11 . The process according to any one of the preceding claims, further comprising a step of separating at least part of the residues of the protecting agent from the concentrated solution obtained in step d) and / or the functional polymer stream obtained in step e) and / or the solvent stream obtained in step e).

12. The process according to any one of the preceding claims, further comprising a step f) of combining the polymer stream obtained in step e) with further components.

13. The process according to any one of the preceding claims, wherein the polymer stream obtained in step e) or step f) is cooled and converted into granules, pellets, powder or flakes, preferably pellets.

14. Functionalized polyolefin composition obtainable by the process of any one or more of claims 1 to 13.

15. An article comprising or consisting of the functionalized polyolefin composition of claim 14.

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