Functionalized polypropylene and / or polyethylene copolymers

Abstract

The invention relates to a functionalized copolymer comprising propylene and / or ethylene repeating units and ω-substituted α-olefin repeating units The invention also relates to polymer blends comprising the functionalized polymer and poly(propylene) and / or poly(ethylene) as well as methods for producing the same.

Description

[0001] SCG Chemicals Public Company Limited Functionalized polypropylene and / or polyethylene copolymers INTRODUCTION The invention relates to a functionalized copolymer comprising propylene and / or ethylene repeating units and ω-substituted α-olefin repeating units. The invention also relates to polymer blends comprising the functionalized polymer and poly(propylene) and / or poly(ethylene) as well as methods for producing the same. BACKGROUND OF THE INVENTION Poly(propylene) and poly(ethylene) are common polyolefins useful in a wide variety of applications. Commercially, polyolefins (PO), namely polypropylene (PP) and polyethylene (PE), are synthesized at scale to meet the needs of a broad array of applications. As an example, one possible application of functionalized POs is the use as hot melt adhesives capable of bonding diverse substrates, including metals and plastics, without the need for surface pre-treatment, thereby addressing challenges in multi-substrate adhesion for lightweight and environmentally friendly assembly methods. Desirable and tunable properties coupled with low production costs are amongst the driving forces behind their utility. Control of key polymeric characteristics such as branching, molecular weight (Mn, Mw), and dispersities (ĐM) are well studied both academically and industrially. However, there has been limited success industrially in deviating from the ubiquitous carbon and hydrogen backbone in a controlled manner; particularly, with respect to the incorporation of polar functionality. The copolymerization of olefins and polar comonomers is a well-documented pathway for incorporating functionality. A variety of polymeric architectures, principally block copolymers, with distinctly altered material properties have been synthesized in this way. However, widely employed early transition metal (groups III and IV) catalysts suffer from deactivation and significantly reduced activity due to ω-functional group (FG) coordination to the comonomer and backbiting oligomers to the electrophilic metal centers have limited the direct copolymerization of functional comonomers. Notably, Zr catalysts have exhibited tolerability towards ω-halo coordination. Increased separation, within the functional comonomer, between α-olefin and ω- FG or excess Lewis-acidic masking reagents like methylaluminoxane (MAO) or AlR3 have been utilized to aid comonomer enchainment. Late transition metal catalysts (Ni and Pd) have been utilized more extensively for the copolymerization of functional monomers with both propylene and ethylene due to their lower acidity and oxophilicity than early transition metal analogues. However, cost and toxicity hinder their large-scale application. Post-polymerization modification via C–H functionalization has been investigated to overcome low comonomer incorporation and polar monomer incompatibility. In principle, a multitude of covalent connections (C–C, C–N, C–O, C–B, C–S, and C–Halogen) are possible within poly-olefin systems, yet only chlorination and maleic anhydride grafting have been found to be industrially viable due to high cost, low efficiency, and the restrictions for dangerous solvents and reagents. Additionally, a variety of synthetic click chemistry pathways have been employed to further increase polar group content impacting molecular weight or polymeric morphologies. However, poly-olefin post-modification via traditional small molecule nucleophilic substitution chemistry presents solubility and purity complications and is subsequently less developed. Recently reported advances concerning improved end-group functionality have been achieved by quenching metal catalyzed polymerization in the presence of air, O2, I2, Br2, or S to yield PP-OH, PE-I (X = OH, I, and Br), and PE-S-PE. PP-OH were further modified via esterification to yield dye modified PP and PE-I / LDPE blends investigated for PE degradability through homolysis of the C-I bond. The latent reactivity, different to traditional vinylic end groups, enables the further synthesis of a wider array of modified PO. However, a potential limitation stemming from end- group post-modification is the limitation of one functional group per chain; lowering the impact of the functionality with increasing Mw. Circumventing the limited polar group incorporation level, synthesis of PO-polar block copolymers by a wide range of end group post-polymerization techniques has afforded materials able to span phase boundaries and improve immiscible polymer-polymer compatibility. Nevertheless, a need for poly(propylene)s and / or poly(ethylene)s with new and / or advanced properties remains. TECHNICAL OBJECT OF THE INVENTION Accordingly, it is an object of the present invention to provide functionalized poly(propylene)s and / or poly(ethylene)s having a significant amount of functional groups incorporated as well as a versatile and available preparation method applicable to industrial scales. The object is achieved by a copolymer comprising: propylene and / or ethylene repeating units A; and ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2- 20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6- 20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3- 20C)carbocyclyl, unsubstituted or substituted (2-20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. Surprisingly, a methodology for the preparation of a diverse range of functionalized poly(propylene)s and / or poly(ethylene)s has been found. In particular, poly(propylene)-co-(11- bromo-1-undecene) (PPBr) was employed as a tunable platform copolymer which can be readily functionalized. This allows the development of a series of covalent connections (C-O, C-N, C-S, C- P, and C-C) via a range of substitution pathways and reaction conditions yielding versatile PPs and PEs with properties suitable for an array of applications. SUMMARY OF THE INVENTION According to a first aspect of the invention there is provided a copolymer comprising: propylene and / or ethylene repeating units A; and ω-substituted α-olefin repeating units B, wherein the ω- substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, - CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2- 20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1- 20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2- 20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. According to a second aspect of the invention there is provided a method for the preparation of a copolymer, the method comprising the steps of: a) providing a precursor copolymer comprising: (i) propylene and / or ethylene repeating units A; and (ii) ω-substituted α-olefin repeating units B, wherein X is halogen; and b) post-modifying the precursor polymer provided in step a), such that the ω-substituted α- olefin repeating units B, wherein X is halogen, are converted into ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. Suitably, the method of the second aspect of the invention is a method for the preparation of a polymer of the first aspect of the invention. According to a third aspect of the invention there is provided a polymer obtained, directly obtained or obtainable by the method of the second aspect of the invention. According to a fourth aspect of the invention there is provided a polymer blend comprising: a polymer of the first or third aspect of the invention; and poly(propylene) and / or poly(ethylene). In this regard, the term “poly(propylene) and / or poly(ethylene)” shall be considered to encompass poly(propylene-ethylene)copolymers. According to a fifth aspect of the invention there is a provided a method for the preparation of a polymer blend, the method comprising the steps of: a) providing a precursor copolymer comprising: (i) propylene and / or ethylene repeating units A; and (ii) ω-substituted α-olefin repeating units B, wherein X is halogen; and b) post-modifying the precursor copolymer provided in step a), such that the ω-substituted α- olefin repeating units B, wherein X is halogen, are converted into ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms; and c) mixing the copolymer resulting from step b) with poly(propylene), poly(ethylene) or poly(propylene-ethylene)copolymer. Suitably, the process of the fifth aspect of the invention is a method for the preparation of a polymer blend of the fourth aspect of the invention. DETAILED DESCRIPTION OF THE INVENTION Definitions The term "(m-nC)" or "(m-nC) group" used alone or as a prefix, refers to any group having m to n carbon atoms. The term “together form” refers to a structural arrangement in which two substituents (e.g., R1 and R2) covalently link to each other to constitute a single chemical entity comprising a monocyclic or bicyclic ring system that includes the atom to which both substituents are attached. The ring system encompassed by the “together form” may be aromatic or non-aromatic, saturated or partially saturated, and may be carbocyclic or heterocyclic as defined herein. The ring system may be fused, bridged, or spiro bicyclic. The monocyclic rings suitably contain from 3 to 12 ring atoms, preferably from 3 to 7 ring atoms. Bicyclic rings suitably contain from 7 to 17 ring atoms, preferably from 7 to 12 ring atoms. The ring atoms are selected from carbon, nitrogen, oxygen, and sulfur. The ring system may be unsubstituted or substituted as defined in the specification.The term “alkyl” as used herein refers to straight or branched chain alkyl moieties, typically having 1, 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. Most suitably, an alkyl may have 1, 2, 3 or 4 carbon atoms. The term “alkylene” as used herein refers to a divalent equivalent of an alkyl group as described above. The term “alkenyl” as used herein refers to straight or branched chain alkenyl moieties, typically having 1, 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkenyl moieties containing 1, 2 or 3 carbon-carbon double bonds (C=C). This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl and hexenyl, as well as both the cis and trans isomers thereof. The term “alkenylene” as used herein refers to a divalent equivalent of an alkenyl group as described above. The term “alkynyl” as used herein refers to straight or branched chain alkynyl moieties, typically having 1, 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkynyl moieties containing 1, 2 or 3 carbon-carbon triple bonds (C≡C). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl and hexynyl. The term “alkynylene” as used herein refers to a divalent equivalent of an alkynyl group as described above. The term “alkoxy” as used herein refers to -O-alkyl, wherein alkyl is a straight or branched chain and comprises 1, 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1, 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like. The term "aryl" or “aromatic” as used herein means an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms. Aryl is often phenyl but may be a polycyclic ring system, having wo or more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like. The term “heteroaryl” or “heteroaromatic” means an aromatic mono-, bi-, or polycyclic ring incorporating one or more (for example 1-4, particularly 1, 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur. Examples of heteroaryl groups are monocyclic and bicyclic groups containing from five to twelve ring members, and more usually from five to ten ring members. The heteroaryl group can be, for example, a 5- or 6-membered monocyclic ring or a 9- or 10- membered bicyclic ring, for example a bicyclic structure formed from fused five and six membered rings or two fused six membered rings. Each ring may contain up to about four heteroatoms typically selected from nitrogen, sulfur and oxygen. Typically, the heteroaryl ring will contain up to 3 heteroatoms, more usually up to 2, for example a single heteroatom. The term “carbocyclyl”, “carbocyclic” or “carbocycle” means a non-aromatic saturated or partially saturated monocyclic, or a fused, bridged, or spiro bicyclic carbocyclic ring system(s). Monocyclic carbocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms. Bicyclic carbocycles contain from 7 to 17 carbon atoms in the rings, suitably 7 to 12 carbon atoms, in the rings. Bicyclic carbocyclic rings may be fused, spiro, or bridged ring systems. The term “heterocyclyl”, “heterocyclic” or “heterocycle” means a non-aromatic saturated or partially saturated monocyclic, fused, bridged, or spiro bicyclic heterocyclic ring system(s). Monocyclic heterocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms, with from 1 to 5 (suitably 1, 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur in the ring. Bicyclic heterocycles contain from 7 to 17 member atoms, suitably 7 to 12 member atoms, in the ring. Bicyclic heterocyclic(s) rings may be fused, spiro, or bridged ring systems. The term "halogen" or “halo” as used herein refers to F, Cl, Br or I. In particular, halogen may be F or Cl or Br, of which Cl and Br are more common. The term “haloalkyl” is used herein to refer to an alkyl group in which one or more hydrogen atoms have been replaced by halogen (e.g., fluorine) atoms. Often, haloalkyl is fluoroalkyl. Examples of haloalkyl groups include -CH2F, -CHF2 and -CF3. The term “substituted” as used herein in reference to a moiety means that one or more, especially up to 5 of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. Preferably, “substituted” as used herein in reference to a moiety means that 1, 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. Even more preferred, “substituted” as used herein in reference to a moiety means that 1 or 2, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. The term “optionally substituted” as used herein means substituted or unsubstituted. It will, of course, be understood that substituents are only at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible. As used herein, references to flame retardancy will be understood to embrace fire retardancy, and vice versa. Throughout the entirety of the description and claims of this specification, where subject matter is described herein using the term “comprise” (or “comprises” or “comprising”), the same subject matter instead described using the term “consist of” (or “consists of” or “consisting of”) or “consist essentially of” (or “consists essentially of” or “consisting essentially of”) is also contemplated. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise. Features described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and / or steps are mutually exclusive. The invention is not restricted to the details of any of the specific embodiments recited herein. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings) and / or all of the steps of any method or process so disclosed. Unless otherwise specified, where the quantity or concentration of a particular component of a given product is specified as a weight percentage (wt% or %w / w), said weight percentage refers to the percentage of said component by weight relative to the total weight of the product as a whole. It will be understood by those skilled in the art that the sum of weight percentages of all components of a product will total 100 wt%. However, where not all components are listed (e.g., where a product is said to “comprise” one or more particular components), the weight percentage balance may optionally be made up to 100 wt% by unspecified ingredients. Copolymers In a first aspect, the invention provides a copolymer comprising: propylene and / or ethylene repeating units A; and ω-substituted α-olefin repeating units B, wherein the ω-substituted α- olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2- 20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6- 20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3- 20C)carbocyclyl, unsubstituted or substituted (2-20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. Through extensive investigations, the inventors have devised new functionalized poly(propylene) and / or poly(ethylene) copolymers suitable for an array of applications. The term “propylene and / or ethylene repeating units” (repeating units A) refers to a propylenic (i.e., -CH2-CH(CH3)-) or ethylenic (i.e., -CH2-CH2-) unit of the polymer, wherein the polymer my comprise only propylenic (i.e., -CH2-CH(CH3)-) or only ethylenic (i.e., -CH2-CH2-) or both propylenic (i.e., -CH2-CH(CH3)-) and ethylenic (i.e., -CH2-CH2-) units. Thus, each propylene repeating unit has the structural formula: , and each ethylene repeating unit has the structural formula: . The repeating units A may be propylene repeating units, ethylene repeating units, or a combination of propylene and ethylene repeating units, and preferably are propylene repeating units. The copolymer may comprise 80-99.5 mol% of repeating units A. Suitably, the copolymer comprises 83.-99.0 mol% of repeating units A. The quantity of repeating units A in the copolymercan be calculated by integration of peaks recorded by 1H NMR in C2D2Cl4 at 130 °C. More suitably,the copolymer comprises 84.0-98.5 mol% of repeating units A. Even more suitably, the copolymer comprises 88.0-98.0 mol% of repeating units A. Yet even more suitably, the copolymer comprises 91.5-96.5 mol% of repeating units A. In embodiments, the copolymer comprises 92-96.25 mol% of repeating units A. Preferably, the repeating units A are propylene repeating units. The phrase “ω-substituted α-olefin repeating unit B” refers to an ethylenic (e.g., -CH2-CH2-) unit of the copolymer substituted with an alkyl chain having a moiety X in ω-position. Suitably, each ω-substituted α-olefin repeating unit B comprises independently one moiety X. The copolymer may comprise 0.5-20 mol% of ω-substituted α-olefin repeating units B. Suitably, the copolymer comprises 1.0-17.0 mol% of ω-substituted α-olefin repeating units B. The quantity of ω-substituted α-olefin repeating units B in the copolymer can be calculated by integration ofpeaks recorded by 1H NMR in C2D2Cl4 at 130 °C. More suitably, the copolymer comprises 1.5-16.0mol% of ω-substituted α-olefin repeating units B. Even more suitably, the copolymer comprises 2.0-12.0 mol% of ω-substituted α-olefin repeating units B. Yet even more suitably, the copolymer comprises 3.5-8.5 mol% of ω-substituted α-olefin repeating units B. In embodiments, the copolymer comprises 3.75-8 mol% of ω-substituted α-olefin repeating units B. In embodiments, the copolymer comprises: (i) 80-99.5 mol% of repeating units A, and (ii) 0.5-20 mol% of ω-substituted α-olefin repeating units B. Preferably, the repeating units A are propylene repeating units. In embodiments, the copolymer comprises: (i) 83.0-99.0 mol% of repeating units A, and (ii) 1.0- 17.0 mol% of ω-substituted α-olefin repeating units B. Preferably, the repeating units A are propylene repeating units. In embodiments, the copolymer comprises: (i) 84.0-98.5 mol% of repeating units A, and (ii) 1.5- 16.0 mol% of ω-substituted α-olefin repeating units B. Preferably, the repeating units A are propylene repeating units. In embodiments, the copolymer comprises: (i) 88.0-98.0 mol% of repeating units A, and (ii) 2.0- 12.0 mol% of ω-substituted α-olefin repeating units B. Preferably, the repeating units A are propylene repeating units. In embodiments, the copolymer comprises: (i) 91.5-96.5 mol% of repeating units A, and (ii) 3.5- 8.5 mol% of ω-substituted α-olefin repeating units B. Preferably, the repeating units A are propylene repeating units. In embodiments, the copolymer comprises: (i) 92-96.25 mol% of repeating units A, and (ii) 3.75- 8 mol% of ω-substituted α-olefin repeating units B. Preferably, the repeating units A are propylene repeating units. Each ω-substituted α-olefin repeating unit B, may independently have the structural formula B1: wherein Y is linking group connecting C1 to X; and X is selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2- 20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1- 20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2- 20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. Preferably, X may be selected from a group consisting of -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, - OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2- 20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1- 20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2- 20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. Preferably, R1 to R9 may be each independently selected from the group consisting of unsubstituted or substituted (1-12C)alkyl, unsubstituted or substituted (2-12C)alkenyl, unsubstituted or substituted (2-12C)alkynyl, unsubstituted or substituted (1-12C)alkoxy, unsubstituted or substituted (6-12C)aryl, unsubstituted or substituted (2-12C)heteroaryl, unsubstituted or substituted (3-12C)carbocyclyl, unsubstituted or substituted (2- 12C)heterocyclyl, unsubstituted or substituted (1-12C)haloalkyl, and unsubstituted or substituted (1-12C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 12 unsubstituted or substituted ring atoms. More preferably, R1 to R9 may be each independently selected from the group consisting of unsubstituted or substituted (1-10C)alkyl, unsubstituted or substituted (2-10C)alkenyl, unsubstituted or substituted (2-10C)alkynyl, unsubstituted or substituted (1-10C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-10C)heteroaryl, unsubstituted or substituted (3-10C)carbocyclyl, unsubstituted or substituted (2- 10C)heterocyclyl, unsubstituted or substituted (1-10C)haloalkyl, and unsubstituted or substituted(1-10C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated,partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 10 unsubstituted or substituted ring atoms. Even more preferably, R1 to R9 may be each independently selected from the group consisting of unsubstituted or substituted (1-6C)alkyl, unsubstituted or substituted (2-6C)alkenyl, unsubstituted or substituted (2-6C)alkynyl, unsubstituted or substituted (1-6C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (3-6C)carbocyclyl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-6C)haloalkyl, and unsubstituted or substituted (1-6C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partiallysaturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 6 unsubstituted or substituted ring atoms. Y may link C1 to X by 5-18 bridging atoms. The term “bridging atoms” refers to the fewest number of atoms directly connecting C1 to X. For example, when Y links C1 to X by 5 bridging atoms, this could mean that Y is a pentylene group (i.e., 5 carbons atoms directly connecting C1 to X). In this case, all other atoms not directly connecting C1 to X (e.g., H atoms) are not bridging atoms. Suitably, Y links C1 to X by 5-12 bridging atoms. More suitably, Y links C1 to X by 5-9 bridging atoms. In embodiments, Y links C1 to X by 5 bridging atoms. In a most preferred embodiment, Y links C1 to X by 9 bridging atoms. Y may be an alkylene, an alkenylene or an alkynylene group linking C1 to X. Suitably, Y is a (5- 18C)alkylene group, a (5-18C)alkenylene group, or a (5-18C)alkynylene group linking C1 to X. More suitably, Y is a (5-12C)alkylene group, a (5-12C)alkenylene group, or a (5-12C)alkynylene group linking C1 to X. Yet more suitably, Y is a (5-9C)alkylene group linking C1 to X. In embodiments, Y is a 5C alkylene group linking C1 to X. In a most preferred embodiment, Y is a 9C alkylene group linking C1 to X. In embodiments, Y is selected from: wherein denotes the point of attachment to C1; and denotes the point of attachment to X. Accordingly, each ω-substituted α-olefin repeating unit B may independently have the structural formula:

[0002] , wherein X is as defined herein. The distribution of repeating units A and B within the copolymer may be random (e.g., repeating units A and ω-substituted α-olefin repeating units B are present in any order in the copolymer). The ω-substituted α-olefin repeating units B may be randomly distributed along the length of the copolymer. It may be that the copolymer end groups are repeating units A, preferably it may be that the copolymer end groups are propylene repeating units. Preferably, the ω-substituted α- olefin repeating units B are randomly distributed along the length of the polymer and the polymer end groups are repeating units A, preferably the polymer end groups are propylene repeating units. The copolymer may have a -C-C- backbone (i.e., the polymer backbone consists of / consists essentially of carbon atoms). In embodiments of the invention defined herein, the copolymer may consist of / consist essentially of repeating units A, (preferably it may consist of / consist essentially of propylene repeating units) and ω-substituted α-olefin repeating units B. The copolymer may also be linear (e.g., units of the copolymer are arranged in a straight line) or branched (e.g., linear polymer chain substituted with one or more polymer chains along its length). Preferably, the copolymer may have monomodal molecular weight distribution as measured by SEC. The number average molecular weight Mnof the copolymer may be in the range from 1,000 to 400,000 g / mol, preferably 2,000 to 300,000 g / mol, more preferably 3,000 to 250,000 g / mol, most preferably 4,000 to 225,000 g / mol. In a specific embodiment, the number average molecular weight Mnof the copolymer may be 40,000 g / mol or more, preferably 50,000 g / mol or more, and / or 300,000 g / mol or less, preferably 250,000 g / mol or less. The weight average molecular weight Mwof the copolymer may be in the range from 5,000 to 600,000 g / mol, preferably 6,000 to 550,000 g / mol, more preferably 20,000 to 400,000 g / mol, most preferably 40,000 to 325,000 g / mol. In a specific embodiment, the weight average molecular weight Mwof the copolymer may be 40,000 g / mol or more, preferably 50,000 g / mol or more, and / or 600,000 g / mol or less, preferably 350,000 g / mol or less.The polydispersity Đm of the copolymer may be in the range from 1.3 to 6.0, preferably 1.5 to 4.9.In a preferred embodiment, the number average molecular weight Mnof the copolymer may be in the range from 3,000 to 15,000 g / mol and the polydispersity of the copolymer may be in the range from 1.5 to 2.5. In another preferred embodiment, the number average molecular weight Mn of the copolymer may be in the range from 20,000 to 225,000 g / mol and the polydispersity of the copolymer may be in the range from 2.0 to 4.9. The copolymer may be atactic, isotactic or syndiotactic. In embodiments, the copolymer may be atactic.In embodiments, the copolymer may be isotactic. Preferably, the copolymer may have mmmmpentads of 80% or more, more preferably 90% or more, even more preferably 95% or more, most preferably 98% or more.In embodiments, the copolymer may be syndiotactic. Preferably, the copolymer may have rrrrpentads of 50% or more, more preferably 60% or more, most preferably 70% or more. It is believed that the copolymer properties can be further tuned by adjusting Mn, W,Đm, tacticity and comonomer incorporation with respect to the targeted application. Post-polymerization modification According to the present invention, copolymers comprising: propylene and / or ethylene repeating units A; and ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2-20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms, can be obtained by a) providing a precursor copolymer comprising: (i) propylene and / or ethylene repeating units A; and (ii) ω-substituted α-olefin repeating units B, wherein X is halogen; and b) post-modifying the precursor polymer provided in step a), such that the ω-substituted α-olefin repeating units B, wherein X is halogen, are converted into ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2- 20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1- 20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2- 20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. A particularly preferred precursor copolymer is poly(propylene)-co-11-bromo-1-undecene (PPBr). Three straightforward and generally applicable synthetic routes using precursor copolymers, suchas PPBr, as a platform for the synthesis of modified copolymers are provided. These pathways formodification may be summarized into the following categories: Forcing conditions (A); high temperature, long reaction times, and large modifier. Mild nucleophilic substitutions; either base- mediated (B), or, by salt metathesis (C). Pathway (A) may require reaction temperatures of 150-180 °C and reaction times of 6 to 96 h. In general, reaction temperatures and reaction times may increase with increasing molecular weight of the precursor copolymer. Pathways (B) and (C) may require reaction temperatures of 60-120 °C and reaction times of 12 to 96 h. In general, reaction temperatures and reaction times may increase with increasing molecular weight of the precursor copolymer. Particularly preferably, the conversion may be quantitative. More preferably, the amount of residual moieties X, wherein X is halogen, may be less than 1.0 wt%, even more preferably less than 0.5 wt%, most preferably less than 0.3 wt% as measured by oxygen combustion flask technique. C-N modification In a first embodiment, the moiety X is -NR1R2. The moiety X being -NR1R2 may be obtained by reacting the precursor copolymer with secondary amines HNR1R2, such as HNEt2, HN(Et)(EtOH), HN(EtOH)2. Alternatively, the moiety X being -NR1R2 may be obtained by reacting the precursor copolymer with heterocyclic amines such as imidazole, N-substituted imidazoles, imidazolium, N-substituted imidazolium, pyrazole, triazole, benzimidazole, or N- alkylated derivatives thereof, preferably with imidazole, imidazolium, N-substituted imidazoles or N-substituted imidazoles, e.g. , wherein R is the ω-carbon atom of Y. R1 to R2 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2- 20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6- 20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3- 20C)carbocyclyl, unsubstituted or substituted (2-20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. Preferably, R1 to R2 may be each independently selected from the group consisting of unsubstituted or substituted (1-12C)alkyl, unsubstituted or substituted (2-12C)alkenyl, unsubstituted or substituted (2-12C)alkynyl, unsubstituted or substituted (1-12C)alkoxy, unsubstituted or substituted (6-12C)aryl, unsubstituted or substituted (2-12C)heteroaryl, unsubstituted or substituted (3-12C)carbocyclyl, unsubstituted or substituted (2- 12C)heterocyclyl, unsubstituted or substituted (1-12C)haloalkyl, and unsubstituted or substituted (1-12C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 12 unsubstituted or substituted ring atoms. More preferably, R1 to R2 may be each independently selected from the group consisting of unsubstituted or substituted (1-10C)alkyl, unsubstituted or substituted (2-10C)alkenyl, unsubstituted or substituted (2-10C)alkynyl, unsubstituted or substituted (1-10C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-10C)heteroaryl, unsubstituted or substituted (3-10C)carbocyclyl, unsubstituted or substituted (2- 10C)heterocyclyl, unsubstituted or substituted (1-10C)haloalkyl, and unsubstituted or substituted (1-10C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 10 unsubstituted or substituted ring atoms. Even more preferably, R1 to R2 may be each independently selected from the group consisting of unsubstituted or substituted (1-6C)alkyl, unsubstituted or substituted (2-6C)alkenyl, unsubstituted or substituted (2-6C)alkynyl, unsubstituted or substituted (1-6C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (3-6C)carbocyclyl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-6C)haloalkyl, and unsubstituted or substituted (1- 6C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 6 unsubstituted or substituted ring atoms. In particular embodiments R1 to R2 may be each independently selected from the group consisting of unsubstituted or substituted (1-6C)alkyl, or unsubstituted or substituted (1-6C)hydroxyalkyl, preferably (1-4C)alkyl, or unsubstituted or substituted (1-4C)hydroxyalkyl, more preferably (1- 3C)alkyl, or unsubstituted or substituted (1-3C)hydroxyalkyl, most preferably ethyl or ethyl-OH. The melting points of the amine-functionalized copolymers may be in the range from 80 to 140 °C, preferably 90 to 135 °C as measured by DSC. The amine amine-functionalized copolymers may have a lap shear strength for steel in the range from 1.5 to 15 MPa, preferably 1.6 to 5.5 MPa. The amine amine-functionalized copolymers may have a lap shear strength for aluminium in the range from 2.0 to 25 MPa, preferably 2.5 to 4.5 MPa. The copolymer according to the first embodiment may be used as a hot melt adhesive. C-P modification Post-polymerization modification with -P(=O)(OR3)2 provides new poly(propylene) and / or poly(ethylene) copolymers with enhanced flame retardancy and thermal stability, making them ideally suited for use in applications which require improved flame retardant properties and / or thermal stability. In particular, the presence of phosphonated α-olefin repeating units B has the effect of markedly improving the thermal degradation properties of the poly(propylene) and / or poly(ethylene) copolymer. Advantageously, the poly(propylene) and / or poly(ethylene) copolymers are devoid of the drawbacks associated with halogenated flame retardant polyolefins (e.g., high persistence and toxicity), and can be straightforwardly prepared using a two-step synthetic process. In a second embodiment, the moiety X is -P(=O)(OR3)2. Preferably, each R3 is independently selected from (1-6C)alkyl and aryl, wherein each R3 is optionally substituted. More preferably, each R3 is independently selected from (1-6C)alkyl and phenyl, wherein each R3 is optionally substituted. Even more preferably, each R3 is independently selected from methyl, propyl, butyl, pentyl, hexyl and phenyl, wherein each R3 is optionally substituted. Yet more preferably, each R3 is independently selected from iso-propyl and phenyl, wherein each R is optionally substituted. In embodiments wherein R3 is (1-6C)alkyl (or a subset thereof), each R3 may be substituted with one or more groups R’ independently selected from aryl, heteroaryl, carbocyclyl, heterocyclyl, halo, hydroxy, cyano and nitro. Suitably, each R’ is independently selected from phenyl, heteroaryl, halo and hydroxy. In embodiments wherein R3 is aryl (or a subset thereof), each R3 may be substituted with one or more groups R’’ independently selected from (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy, (1- 6C)alkenyl, (1-6C)alkynyl, aryl, heteroaryl, carbocyclyl, heterocyclyl, halo, hydroxy, cyano and nitro. Suitably, each R’’ is independently selected from (1-3C)alkyl, (1-3C)haloalkyl, (1-3C)alkoxy, phenyl, heteroaryl, halo and hydroxy. Each R3 may be unsubstituted. In embodiments, each R3 is independently selected from the group consisting of methyl, propyl, butyl, pentyl, hexyl and phenyl. In embodiments, each R3 is independently selected from iso-propyl and phenyl. Each R3 may be identical. In embodiments, each R3 is iso-propyl. In embodiments, each R3 is phenyl. In embodiments, each ω-substituted α-olefin repeating unit B is independently selected from: The copolymer may have a melting temperature (Tm) of 70-100 ⁰C. The melting temperature (Tm) of the copolymer can be determined by differential scanning calorimetry (DSC) within a temperature range of 30–180 °C at a rate of 20 °C min–1. Suitably, the copolymer has a melting temperature (Tm) of 75-97 °C. More suitably, the copolymer has a melting temperature (Tm) of 76- 95 °C. The copolymer according to the second embodiment may be used as a flame retardant. C-O modification In a third embodiment, the moiety X is -OC(=O)-R4. X being -OC(=O)-R4 may be obtained by reacting the precursor copolymer with organic acids HOC(=O)-R4 or esters ROC(=O)-R4, such as MeCO2H, PHCO2H, CH2CHCO2H, in presence of a non-nucleophilic organic base, such as 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU). R4 is unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl. Preferably, R4 may be unsubstituted or substituted (1-12C)alkyl, unsubstituted or substituted (2- 12C)alkenyl, unsubstituted or substituted (2-12C)alkynyl, unsubstituted or substituted (1- 12C)alkoxy, unsubstituted or substituted (6-12C)aryl, unsubstituted or substituted (2- 12C)heteroaryl, unsubstituted or substituted (3-12C)carbocyclyl, unsubstituted or substituted (2- 12C)heterocyclyl, unsubstituted or substituted (1-12C)haloalkyl, and unsubstituted or substituted (1-12C)hydroxyalkyl. More preferably, R4 may be unsubstituted or substituted (1-10C)alkyl, unsubstituted or substituted (2-10C)alkenyl, unsubstituted or substituted (2-10C)alkynyl, unsubstituted or substituted (1-10C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-10C)heteroaryl, unsubstituted or substituted (3-10C)carbocyclyl, unsubstituted or substituted (2-10C)heterocyclyl, unsubstituted or substituted (1-10C)haloalkyl, and unsubstituted or substituted (1-10C)hydroxyalkyl. Even more preferably, R4 may be unsubstituted or substituted (1-6C)alkyl, unsubstituted or substituted (2-6C)alkenyl, unsubstituted or substituted (2-6C)alkynyl, unsubstituted or substituted (1-6C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (3-6C)carbocyclyl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-6C)haloalkyl, and unsubstituted or substituted (1-6C)hydroxyalkyl. In particular embodiments R4 may be unsubstituted or substituted (1-6C)alkyl, or unsubstituted or substituted (1-6C)alkenyl, preferably (1-4C)alkyl, or unsubstituted or substituted (1- 4C)alkenyl, more preferably (1-3C)alkyl, or unsubstituted or substituted (1-3C)alkenyl, most preferably methyl, phenyl or vinyl. The melting points of the ester-functionalized copolymers may be in the range from 80 to 140 °C, preferably 90 to 135 °C as measured by DSC. In particular, ester-functionalized copolymers wherein R4 is alkenyl may be further crosslinked by thermal treatment or by vulcanization with sulfur. Furthermore, ester-functionalized copolymers wherein R4 is alkenyl may be used for thiol-ene click chemistry. The cross-linked copolymers according to the third embodiment may be used as a synthetic rubber. In a fourth embodiment, the moiety X is -OR5. X being -OR5 may be obtained by reacting the precursor copolymer with salts, such as Li+or K+salts, of organic compounds HOR5, such as phenol. R5 is unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl. Preferably, R5 may be unsubstituted or substituted (1-12C)alkyl, unsubstituted or substituted (2- 12C)alkenyl, unsubstituted or substituted (2-12C)alkynyl, unsubstituted or substituted (1- 12C)alkoxy, unsubstituted or substituted (6-12C)aryl, unsubstituted or substituted (2- 12C)heteroaryl, unsubstituted or substituted (3-12C)carbocyclyl, unsubstituted or substituted (2- 12C)heterocyclyl, unsubstituted or substituted (1-12C)haloalkyl, and unsubstituted or substituted (1-12C)hydroxyalkyl. More preferably, R5 may be unsubstituted or substituted (1-10C)alkyl, unsubstituted or substituted (2-10C)alkenyl, unsubstituted or substituted (2-10C)alkynyl, unsubstituted or substituted (1-10C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-10C)heteroaryl, unsubstituted or substituted (3-10C)carbocyclyl, unsubstituted or substituted (2-10C)heterocyclyl, unsubstituted or substituted (1-10C)haloalkyl, and unsubstituted or substituted (1-10C)hydroxyalkyl. Even more preferably, R5 may be unsubstituted or substituted (1-6C)alkyl, unsubstituted or substituted (2-6C)alkenyl, unsubstituted or substituted (2-6C)alkynyl, unsubstituted or substituted (1-6C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (3-6C)carbocyclyl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-6C)haloalkyl, and unsubstituted or substituted (1-6C)hydroxyalkyl. In particular embodiments R5 may be unsubstituted or substituted (6-10C)aryl, preferably unsubstituted or substituted (6C)aryl, most preferably phenyl. The melting points of the ether-functionalized copolymers may be in the range from 80 to 120 °C, preferably 90 to 110 °C as measured by DSC. C-S modification In a fifth embodiment, the moiety X is -SR6. X being -SR6 may be obtained by reacting the precursor copolymer with thiols HSR6, such as HSC12H24. R6 is unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl. Preferably, R6 may be unsubstituted or substituted (1-12C)alkyl, unsubstituted or substituted (2- 12C)alkenyl, unsubstituted or substituted (2-12C)alkynyl, unsubstituted or substituted (1- 12C)alkoxy, unsubstituted or substituted (6-12C)aryl, unsubstituted or substituted (2- 12C)heteroaryl, unsubstituted or substituted (3-12C)carbocyclyl, unsubstituted or substituted (2- 12C)heterocyclyl, unsubstituted or substituted (1-12C)haloalkyl, and unsubstituted or substituted (1-12C)hydroxyalkyl. More preferably, R6 may be unsubstituted or substituted (1-10C)alkyl, unsubstituted or substituted (2-10C)alkenyl, unsubstituted or substituted (2-10C)alkynyl, unsubstituted or substituted (1-10C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-10C)heteroaryl, unsubstituted or substituted (3-10C)carbocyclyl, unsubstituted or substituted (2-10C)heterocyclyl, unsubstituted or substituted (1-10C)haloalkyl, and unsubstituted or substituted (1-10C)hydroxyalkyl. Even more preferably, R6 may be unsubstituted or substituted (1-6C)alkyl, unsubstituted or substituted (2-6C)alkenyl, unsubstituted or substituted (2-6C)alkynyl, unsubstituted or substituted (1-6C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (3-6C)carbocyclyl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-6C)haloalkyl, and unsubstituted or substituted (1-6C)hydroxyalkyl. In particular embodiments R6 may be unsubstituted or substituted (1-16C)alkyl. The melting points of the thio-functionalized copolymers may be in the range from 80 to 120 °C, preferably 90 to 110 °C as measured by DSC. C-C modification In a sixth embodiment, the moiety X is -CR7(C(=O)OR8. X being -CR7(C(=O)OR8 may be obtained by reacting the precursor copolymer with salts, such as Li+or K+salts, of organic compounds HCR7(C(=O)OR8, such as diethylmethylmalonate. R7 to R8 are each independently unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2-20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl. Preferably, R7 to R8 may be each independently unsubstituted or substituted (1-12C)alkyl, unsubstituted or substituted (2-12C)alkenyl, unsubstituted or substituted (2-12C)alkynyl, unsubstituted or substituted (1-12C)alkoxy, unsubstituted or substituted (6-12C)aryl, unsubstituted or substituted (2-12C)heteroaryl, unsubstituted or substituted (3-12C)carbocyclyl, unsubstituted or substituted (2-12C)heterocyclyl, unsubstituted or substituted (1-12C)haloalkyl, and unsubstituted or substituted (1-12C)hydroxyalkyl. More preferably, R7 to R8 may be each independently unsubstituted or substituted (1-10C)alkyl, unsubstituted or substituted (2-10C)alkenyl, unsubstituted or substituted (2-10C)alkynyl, unsubstituted or substituted (1-10C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-10C)heteroaryl, unsubstituted or substituted (3-10C)carbocyclyl, unsubstituted or substituted (2-10C)heterocyclyl, unsubstituted or substituted (1-10C)haloalkyl, and unsubstituted or substituted (1-10C)hydroxyalkyl. Even more preferably, R7 to R8 may be each independently unsubstituted or substituted (1- 6C)alkyl, unsubstituted or substituted (2-6C)alkenyl, unsubstituted or substituted (2-6C)alkynyl, unsubstituted or substituted (1-6C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (3-6C)carbocyclyl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-6C)haloalkyl, and unsubstituted or substituted (1-6C)hydroxyalkyl. In particular embodiments R7 to R8 may be each independently unsubstituted or substituted (1- 4C)alkyl, unsubstituted or substituted (2-4C)alkenyl, unsubstituted or substituted (2-4C)alkynyl, unsubstituted or substituted (1-4C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-4C)haloalkyl, and unsubstituted or substituted (1- 4C)hydroxyalkyl. The melting points of the amine-functionalized copolymers may be in the range from 80 to 120 °C, preferably 90 to 110 °C as measured by DSC. In a seventh embodiment, the moiety X is -C≡C-R9. X being -C≡C-R9 may be obtained by reacting the precursor copolymer with salts, such as Li+or K+salts, of organic compounds H-C≡C-R9, such as phenylacetylene. R9 is unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl. Preferably, R9 may be unsubstituted or substituted (1-12C)alkyl, unsubstituted or substituted (2- 12C)alkenyl, unsubstituted or substituted (2-12C)alkynyl, unsubstituted or substituted (1- 12C)alkoxy, unsubstituted or substituted (6-12C)aryl, unsubstituted or substituted (2- 12C)heteroaryl, unsubstituted or substituted (3-12C)carbocyclyl, unsubstituted or substituted (2- 12C)heterocyclyl, unsubstituted or substituted (1-12C)haloalkyl, and unsubstituted or substituted (1-12C)hydroxyalkyl. More preferably, R9 may be unsubstituted or substituted (1-10C)alkyl, unsubstituted or substituted (2-10C)alkenyl, unsubstituted or substituted (2-10C)alkynyl, unsubstituted or substituted (1-10C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-10C)heteroaryl, unsubstituted or substituted (3-10C)carbocyclyl, unsubstituted or substituted (2-10C)heterocyclyl, unsubstituted or substituted (1-10C)haloalkyl, and unsubstituted or substituted (1-10C)hydroxyalkyl. Even more preferably, R9 may be unsubstituted or substituted (1-6C)alkyl, unsubstituted or substituted (2-6C)alkenyl, unsubstituted or substituted (2-6C)alkynyl, unsubstituted or substituted (1-6C)alkoxy, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (3-6C)carbocyclyl, unsubstituted or substituted (2-6C)heterocyclyl, unsubstituted or substituted (1-6C)haloalkyl, and unsubstituted or substituted (1-6C)hydroxyalkyl. In particular embodiments R9 may be unsubstituted or substituted (1-4C)alkyl, unsubstituted or substituted (6-10C)aryl, unsubstituted or substituted (2-6C)heteroaryl, unsubstituted or substituted (1-4C)haloalkyl, and unsubstituted or substituted (1-4C)hydroxyalkyl. The melting points of the alkyne-functionalized copolymers may be in the range from 80 to 120 °C, preferably 90 to 110 °C as measured by DSC. Furthermore alkyne-functionalized copolymers may be used for azido or thiol-yne click chemistry. Polymer blends In an aspect, the invention provides a polymer blend comprising: a copolymer of the first aspect of the invention; and poly(propylene) and / or poly(ethylene), preferably poly(propylene). In particular, through extensive investigations, the inventors have found that compounding the poly(propylene) and / or poly(ethylene) copolymer of the first aspect of the invention with poly(propylene) and / or poly(ethylene), when X is -P(=O)(OR3)2 results in an increase in thermal stability, as shown by higher T10%, T50% and Tmax values, when compared to virgin poly(propylene) and / or poly(ethylene). The polymer blend may comprise 0.1-30 wt% of the copolymer of the first aspect. The amount of copolymer and poly(propylene) and / or poly(ethylene) in the polymer blend can be determined by chromatographic methods, such as gel permeation chromatography (GPC), wherein the copolymer and poly(propylene) and / or poly(ethylene) can be distinguished by size and / or polarity. Suitably, the polymer blend comprises 1-20 wt% of the copolymer. In embodiments, the polymer blend comprises 1 wt%, 5 wt%, 10 wt% or 20 wt% of the copolymer. The polymer blend may comprise 70-99.9 wt% poly(propylene) and / or poly(ethylene), preferably poly(propylene). Suitably, the polymer blend comprises 80-99 wt% poly(propylene) and / or poly(ethylene), preferably poly(propylene). In embodiments, the polymer blend comprises 80 wt%, 90 wt%, 95 wt% or 99 wt% poly(propylene) and / or poly(ethylene), preferably poly(propylene). The polymer blend may comprise 0.1-30 wt% of the copolymer and 70-99.9 wt% poly(propylene) and / or poly(ethylene), preferably it comprises poly(propylene). Suitably, the polymer blend comprises 1-20 wt% of the copolymer and 80-99 wt% poly(propylene) and / or poly(ethylene), preferably it comprises 1-20 wt% of the copolymer and 80-99 wt% poly(propylene). In embodiments, the polymer blend comprises: a) 20 wt% of the copolymer and 80 wt% poly(propylene) and / or poly(ethylene), preferably it comprises poly(propylene); b) 10 wt% of the copolymer and 90 wt% poly(propylene) and / or poly(ethylene), preferably it comprises poly(propylene); c) 5 wt% of the copolymer and 95 wt% poly(propylene) and / or poly(ethylene), preferably it comprises poly(propylene); or d) 1 wt% of the polymer and 99 wt% poly(propylene) and / or poly(ethylene), preferably it comprises poly(propylene). Method for the preparation of a polymer and a polymer blend In an aspect of the invention there is a provided a method for the preparation of a copolymer, the method comprising the steps of: a) providing a precursor copolymer comprising: (i) propylene and / or ethylene repeating units A; and (ii) ω-substituted α-olefin repeating units B, wherein X is halogen; and b) post-modifying the precursor polymer provided in step a), such that the ω-substituted α- olefin repeating units B, wherein X is halogen, are converted into ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. In another aspect of the invention there is a provided a method for the preparation of a polymer blend, the method comprising the steps of: a) providing a precursor copolymer comprising: (i) propylene and / or ethylene repeating units A; and (ii) ω-substituted α-olefin repeating units B, wherein the substituent X is halogen; b) post-modifying the precursor copolymer provided in step a), such that the ω-substituted α- olefin repeating units B, wherein X is halogen, are converted into ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms; and c) mixing the copolymer resulting from step b) with poly(propylene) and / or poly(ethylene), preferably poly(propylene). In the precursor copolymer provided in step a), propylene and / or ethylene repeating units A may have any of the definitions discussed herein in relation to the first aspect. Furthermore, the ω- substituted α-olefin repeating units B, formed in step b), may have any of the definitions discussed herein in relation to the first aspect. When the substituent X of the ω-substituted α-olefin repeating units B in the precursor copolymer is halogen, halogen may be a leaving group which can be replaced with a moiety X selected from a group consisting of, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2-20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl, or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms. Preferably, X in the precursor copolymer may be bromo or iodo. More preferably, X in the precursor copolymer may be bromo. Accordingly, each ω-substituted α-olefin repeating unit B, wherein the substituent X is halogen, may independently be a halogenated ethylene repeating unit. Suitably, each ω-substituted α- olefin repeating unit B, wherein the substituent X is halogen, is a brominated ethylene repeating unit. The precursor copolymer provided in step a) may comprise 80-99.5 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units. Suitably, the precursor copolymer provided in step a) comprises 83.0-99.0 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units. More suitably, the precursor copolymer comprises 84.0-98.5 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units. Even more suitably, the precursor copolymer comprises 88.0-98.0 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units. Yet even more suitably, the precursor copolymer comprises 91.5-96.5 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units. In embodiments, the precursor copolymer comprises 92- 96.25 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units. The precursor copolymer provided in step a) may comprise 0.5-20 mol% ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. Suitably, the precursor copolymer provided in step a) comprises 1.0-17.0 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. More suitably, the precursor copolymer comprises 1.5-16.0 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. Even more suitably, the precursor copolymer comprises 2.0-12.0 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. Yet even more suitably, the precursor copolymer comprises 3.5-8.5 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. In embodiments, the precursor copolymer comprises 3.75-8 mol% of ω-substituted α- olefin repeating units B, wherein the substituent X is halogen. In such embodiments, X may be suitably bromo or iodo, more suitably bromo. In embodiments, the precursor copolymer provided in step a) comprises: (i) 80-99.5 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units and (ii) 0.5-20 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. In embodiments, the precursor copolymer provided in step a) comprises: (i) 83.0-99.0 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units, and (ii) 1.0- 17.0 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. In embodiments, the precursor copolymer provided in step a) comprises: (i) 84.0-98.5 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units, and (ii) 1.5- 16.0 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. In embodiments, the precursor copolymer provided in step a) comprises: (i) 88.0-98.0 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units, and (ii) 2.0- 12.0 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. In embodiments, the precursor copolymer provided in step a) comprises: (i) 91.5-96.5 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units, and (ii) 3.5- 8.5 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. In embodiments, the precursor copolymer provided in step a) comprises: (i) 92-96.25 mol% of propylene and / or ethylene repeating units A, preferably propylene repeating units, and (ii) 3.75- 8 mol% of ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. The distribution of repeating units A and B within the precursor copolymer may be random (e.g., propylene and / or ethylene repeating units A, and ω-substituted α-olefin repeating units B, wherein the substituent X is halogen, are present in any order in the precursor copolymer). The ω-substituted α-olefin repeating units B, wherein the substituent X is halogen, may be randomly distributed along the length of the copolymer. It may be that the copolymer end groups are propylene and / or ethylene repeating units A, preferably they are propylene repeating units. Suitably, the ω-substituted α-olefin repeating units B, wherein the substituent X is halogen, are randomly distributed along the length of the copolymer and the copolymer end groups are propylene and / or ethylene repeating units A, preferably they are propylene repeating units. In embodiments, the precursor copolymer may consist of / consist essentially of propylene and / or ethylene repeating units A, preferably the precursor copolymer may consist of / consist essentially of propylene repeating units, and ω-substituted α-olefin repeating units B, wherein the substituent X is halogen. The precursor copolymer may be linear or branched. The precursor polymer may be prepared by polymerizing propylene and / or ethylene monomers, A’, and ω-substituted α-olefin monomers B’, wherein the substituent X is halogen. Suitably, each propylene monomer has the structural formula: , and each ethylene monomer has the structural formula: Each ω-substituted α-olefin monomer B’, wherein the substituent X is halogen, may independently have the structural formula B’1: wherein Y is as defined herein and X is halogen. In preferred embodiments, each ω-substituted α-olefin monomer B’, wherein the substituent X is halogen, independently has the structural formula: wherein X is halogen. Preferably, each ω-substituted α-olefin monomer B’ may be an ω-bromo-α-alkene. In preferred embodiments, each ω-substituted α-olefin monomer B’ may be 11-bromo-1-undecene. Accordingly, the precursor copolymer provided in step a) may be poly(propylene)-co-11-bromo- 1-undecene. In embodiments wherein the precursor copolymer provided in step a) is prepared by polymerizing propylene and / or ethylene monomers A’ (preferably the precursor copolymer is prepared by polymerizing propylene monomers) and ω-substituted α-olefin monomers B’, wherein the substituent X is halogen, said polymerization may be conducted in the presence of an olefinpolymerization catalyst. Suitably, the olefin polymerization catalyst is a metallocene, ansa-metallocene, half-metallocene or ansa-half-metallocene, examples of which will be readilyfamiliar to one of skill in the art. The olefin polymerization catalyst may have a structure according to formula (D1): (L1)(L2)M1(Y1)(Y2) (D1) wherein M1is zirconium, hafnium or titanium; L1and L2are each independently a ligand comprising a cyclopentadienyl moiety, said cyclopentadienyl moiety being η5bound to M1, wherein L1and L2are optionally linked to one another; and Y1and Y2are each independently a ligand selected from hydride, halo and (1-3C)alkyl. In embodiments, L1and L2may be each independently an optionally-substituted cyclopentadienyl group that is η5bound to M1, an optionally-substituted indenyl group that is η5bound to M1, or an optionally-substituted fluorenyl group that is η5bound to M1, wherein L1and L2are optionally linked to one another. More suitably, L1and L2are each independently an optionally-substituted cyclopentadienyl group that is η5bound to M1or an optionally-substituted indenyl group that is η5bound to M1, wherein L1and L2are optionally linked to one another. In embodiments, L1and L2are each independently an optionally-substituted indenyl group that is η5bound to M1, wherein L1and L2are optionally linked to one another. In embodiments, L1and L2may optionally linked to one another by an alkylene or a silylene linking group. In embodiments, L1and L2may be optionally linked to one another by an ethylene group. In embodiments, M1may be zirconium. In embodiments, Y1and Y2may be each independently selected from hydride, chloro and methyl. In embodiments, Y1and Y2may be each chloro. It will be understood that the optional substituents present in L1and L2may be selected from (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl (e.g., phenyl), aryl(1-2C)alkyl (e.g., benzyl), aryloxy (e.g., phenoxy) and heteroaryl. Particularly suitable optional substituents are selected from (1-4C)alkyl, (1-4C)alkoxy and phenyl.In particular embodiments, the olefin polymerization catalyst may be a bis-indenyl zirconocenecompound. In a preferred embodiment, the olefin polymerization catalyst may be selected from the group consisting of: In a catalyst may be a C2-symmetric ansa- prepare highly isotactic polypropyleneiPP, preferably having mmmm pentads of 98% or more. Preferably, the olefin polymerizationcatalyst may be In a further particularly preferred polymerization catalyst may be a Cs-symmetric ansa-zirconocene be suitable to prepare syndiotacticpolypropylene sPP, preferably Preferably, the olefin polymerizationcatalyst may be . In another particularly preferred embodiment, the olefin polymerization catalyst may be C1-symmetric ansa-bridged titanium post metallocene catalyst. Such catalyst may be suitable toprepare atactic polypropylene aPP. Preferably, the olefin polymerization catalyst may be. The olefin polymerization catalyst may be used together with one or more suitable activators. Suitable activators are well known in the art and include organo aluminium compounds (e.g., alkyl aluminium compounds). Particularly suitable activators include aluminoxanes (e.g., methylaluminoxane (MAO)), triisobutylaluminium (TIBA), diethylaluminium (DEAC) and triethylaluminium (TEA). In embodiments, the olefin polymerization catalyst is used together with MAO, TIBA, DEAC and / or TEA. In step b), the precursor copolymer may be functionalized by contacting the precursor copolymer with a nucleophilic reagent. The nucleophilic reagent may be selected from compounds providing the structures of the moieties X as defined herein. Suitable compounds that can be used as nucleophilic reagents are well known in the art. In step b), the precursor copolymer provided in step a) may be functionalized such that 50% of the ω-substituted α-olefin repeating units B, wherein X is halogen, are converted. Suitably, the precursor copolymer provided in step a) is functionalized such that 60% of the ω ω-substituted α-olefin repeating units B, wherein X is halogen, are converted. More suitably, the precursor copolymer provided in step a) is functionalized such that 70% of the ω-substituted α-olefin repeating units B, wherein X is halogen, are converted. Yet more suitably, the precursor copolymer provided in step a) is functionalized such that 80% of the ω-substituted α-olefin repeating units B, wherein X is halogen, are converted. Even more suitably, the precursor copolymer provided in step a) is functionalized such that 90% of the ω-substituted α-olefin repeating units B, wherein X is halogen, are converted. In preferred embodiments, the precursor copolymer provided in step a) is functionalized such that greater than 95% of the ω-substituted α-olefin repeating units B, wherein X is halogen, are converted into. In embodiments, the precursor copolymer provided in step a) is functionalized such that all (or substantially all) of the ω-substituted α-olefin repeating units B, wherein X is halogen are converted. As discussed herein, an aspect of the invention provides a method for the preparation of a polymer blend, the method comprising the steps of: a) providing a precursor copolymer comprising: (i) propylene and / or ethylene repeating units A; and (ii) ω-substituted α-olefin repeating units B, wherein X is halogen; and b) post-modifying the precursor copolymer provided in step a), such that the ω-substituted α- olefin repeating units B, wherein X is halogen, are converted into ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from a group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2-20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1- 20C)hydroxyalkyl or R1 and R2 together form a substituted or unsubstituted saturated, partially saturated, or aromatic heterocyclic or heteroaryl ring consisting of 3 to 6 unsubstituted or substituted ring atoms; and c) mixing the copolymer resulting from step b) with poly(propylene) and / or poly(ethylene). Suitably, steps a) and b) are as defined herein. Polymer blends are known in the art and refer to a mixture in which two or more polymers are combined to create a new material. In an aspect, the present invention provides a copolymer obtained, directly obtained or obtainable by a method of the third aspect of the invention. In an aspect, the present invention provides a polymer blend obtained, directly obtained or obtainable by a method of the fifth aspect of the invention. All combinations of preferred ranges and / or embodiments are particularly preferred. Further features and advantages of the invention will emerge from the following detailed description of exemplary embodiments. EXAMPLES One or more examples of the invention will now be described, for the purpose of illustration only, with reference to the accompanying figures:Fig. 1. is a 1H NMR spectrum (600 MHz, C2D2Cl4, 393 K) of poly(propylene) (PP).Fig. 2 is a 1H NMR spectrum (600 MHz, C2D2Cl4, 393 K) of poly(propylene)-co-11-bromo-1-undecene (PPBr).Fig. 3 is a 1H NMR spectrum (600 MHz, C2D2Cl4, 393 K) of poly(propylene)-co-11-bromo-1-undecene (PPBr) exemplifying PPBr mol% incorporation calculation.Fig 4. shows (left) SEC traces and (right) DSC curves of PP and PPBr synthesized by M1-4.Fig. 5 shows DSC thermograms for PPAA / S / MBT vulcanization at a heating rate of 20 °C min–1under and inert atmosphere.Fig. 6 is a DOSY 1H NMR spectra (500 MHz, C2D2Cl4, 393 K) of PPBr.Fig. 7 shows (left) SEC traces and (right) DSC curves of PP and PPBr synthesized at 2.96, 4.78,and 9.10 mol% incorporation.Fig. 8 shows FT-IR spectra of PP, PPBr, PPDEA, PPEAE, and PPDEOA at 2.96, 4.78, and 9.10 mol%incorporation between 3050–3900 cm–1.Fig. 9 shows lap shear strength tests with low Mw inventive functionalalized polymers as theadhesive interlayers, with error bars representing standard deviation and compared to poly(propylene). Fig. 10 shows lap shear strength test results with inventive functionalized polymers as the adhesive interlayers between steel, with error bars representing standard deviation and compared to poly(propylene).Fig. 11 shows lap shear strength tests with inventive functionalized polymers as the adhesiveinterlayers between steel and commercial polypropylene, with error bars representing standard deviation and compared to poly(propylene).Fig. 12 shows lap shear strength samples evidencing failure modes: Triangle with apex orientedupward = Adhesive (steel), rotated quadrilateral = Stock break, and triangle with apex oriented downward = Adhesive (plastic). Materials and methods Materials 11-Bromo-1-undecene (11-Br, Sigma Aldrich) was dried over pre-activated 3 Å molecular sieves, filtered and freeze-pump-thaw degassed before use. Propylene (N2.5) was supplied by BOC Ltd. and was used as received. MAO was supplied by Chemtura Corporation as a slurry in toluenewhich was dried under vacuum before use. Rac-ethylenebis(indenyl)zirconium dichloride wasused as supplied by SGC Chemicals PLC. Triphenyl phosphite, triisopropyl phosphite, xylene, 1,1,2,2 tetrachloroethane d2, triisobutylaluminium, were used as received from Sigma Aldrich. Aluminium (A23.5, smooth mill finish, Q-Panel) and steel (QD23.5, smooth mill finish, Q-Panel) were employed as surfaces for adhesive experiments from Q-LAB. Methods Air- and moisture-sensitive compounds were manipulated under an inert atmosphere of nitrogen, using standard Schlenk line techniques on a dual manifold vacuum / nitrogen line or in an MBraun Labmaster 100 glovebox. Hexanes and toluene were dried using an MBraun SPS 800 solvent purification system, stored over a potassium mirror, and degassed under partial vacuum before use. Solution NMR spectroscopy NMR spectra were recorded on a Bruker NEO 600 (14.1 T, 600.4 MHz) with a broadband heliumcryoprobe. Spectra were recorded at 393 K and referenced internally to the residual protio solventresonance. Chemical shifts, δ, are reported in parts per million (ppm) relative to tetramethylsilane(δ = 0 ppm). Quantitative 13C NMR spectroscopy was performed using an inverse-gated 1Hdecoupling pulse sequence, a relaxation delay of 60 s, and 2.8 mg mL–1 Cr(acac)3 as a T1 relaxationagent. Limited solubility of iPP, sPP, and functionalised derivates incorporation observed poorsignal-noise ratio in 13C{1H} NMR spectra due to high Mn and low mol% incorporation, hencesome known peaks, observed in HSQC or HMBC, were not observed 13C{1H} NMR spectra.DOSY 1H NMR spectra (Fig. 6) were recorded on a Bruker AVD 500 MHz. Spectra were recordedat 393 K and referenced internally to the residual protio solvent resonance (C2D2Cl4). Chemicalshifts, δ, are reported in parts per million (ppm) relative to tetramethylsilane (δ = 0 ppm). Convection compensated diffusion experiment was carried out using Bruker pulse program “dstebpgp3s” on a Bruker AVD 500 MHz, C2D2Cl4, 393 K. Gel permeation chromatography Gel permeation chromatography (GPC) was performed on a high temperature gel permeation chromatograph with an IR5 infrared detector (GPC-IR5). Samples were prepared by dissolution in 1,2,4-trichlorobenzene (TCB) containing 300 ppm of 3,5-di-tert-buty-4-hydroxytoluene (BHT) at 160 °C for 90 minutes and then filtered with a 10 µm SS filter before being passed through the GPC column. The samples were run under a flow rate of 0.5 mL min−1using TCB containing 300 ppm of BHT as mobile phase with 1 mg mL−1BHT added as a flow rate marker. The GPC column and detector temperature were set at 145 and 160 °C respectively. Differential scanning calorimetry Differential scanning calorimetry was performed on a Perkin Elmer DSC 4000 System, unless otherwise stated, within a temperature range of 30-200 °C at a rate of 20 K min-1. Polymer samples were sealed in 50 μL aluminium crucibles. An empty crucible was used as a reference, and the DSC was calibrated using indium and zinc. Vulcanization: polymer, sulfur, and MBT were combined in agitated hot toluene prior to vacuum drying. Vulcanizations were performed in 50 μL DSC pans, and the reactions were followed by dynamic DSC protocols. Samples were heated at a constant rate (2.5–20 °C min–1) to 300 °C, then cooled to ambient temperature at the same rate. A second cycle was performed to obtain the baseline for the experiment. Thermogravimetric analysis Thermogravimetric analysis was performed on a Perkin Elmer TGA 8000 thermogravimetric analyzer within a temperature range of 50-800 °C. Polymer samples were loaded into pre- weighed ceramic pans and heated at a rate of 20 K min–1unless otherwise stated. A purge gas of either dry nitrogen or synthetic air (20% O2 in N2) was used. Fourier-Transform Infrared spectroscopy Fourier-Transform Infrared Spectroscopy spectra were collected on a Bruker VERTEX 80 FT-IR spectrometer fitted with a DuraSamplIR Diamond ATR. Before the sample scans, 128 scans were taken as a background over the range 4000-400 cm–1. Transmittance was recorded at a resolution of 4 cm–1over the range 4000-400 cm–1for 128 scans. Quantitative bromine analysis Quantitative bromine analysis was performed in accordance with bromine method covered by ISO 17025 UKAS. An accurately weighed sample containing greater than 2 mg bromine is combusted in an oxygen flask over sodium meta-bisulphite solution. This process yields the sample into a gaseous form which is then immersed into the absorbent. The solution is acidified and boiled to dispel any chlorine fumes and titrated with silver nitrate. The end point of the titration is measured at the inflection point of the titration curve with an analytical uncertainty of 0.3% absolute. Lap shear strengthFor the data related to Table 2, samples were prepared via vacuum compression-molding thepolymer. Propylene-based copolymers were loaded between the substrates: Steel QD35 and Aluminum A35 with overlap of 12.5 mm (312.5 mm2bonding area). Then, the compression- heating cycle was applied: (i) heating to 130 °C (ii) stabilizing for 5 min with no force applied, (iii) applying for 5 min with 100 kN (2 MPa) normal force and cooling down to 40 °C under 100 kN (0.6 MPa) normal force. Before measurements, samples were conditioned for 7 days at room temperature. The measurements were performed using an Instron 5582 tensile tester equipped with a 5 kN load cell. The tests were performed on specimens (51 cm × 12.7 cm) with surface overlapping 10 mm at room temperature. A grip-to-grip separation of 140 mm was used. The samples were pre-stressed to 3 N, then loaded with a constant cross-head speed 100 mm / min. To calculate the lap shear strength the reported force value divided by the bonding surface (127 mm2) of the specimens. The reported values are an average of at least 4 measurements of each composition.For the data related to Table 3, samples were prepared via vacuum compression-molding thepolymer. Propylene-based copolymers were loaded between the substrates: Steel QD35 and Plastic with overlap of 10 mm (127 mm2bonding area). Then, the compression-heating cycle was applied: (i) heating to 180 °C (ii) stabilizing for 5 min with no force applied, (iii) applying for 5 min with 25 kN normal force and cooling down to 40 °C under 25 kN normal force. Before measurements, samples were conditioned for 7 days at room temperature. The measurements were performed using an Instron 5582 tensile tester equipped with a 5 kN load cell. The tests were performed on specimens (51 cm × 12.7 cm) with surface overlapping 10 mm at room temperature. A grip-to-grip separation of 140 mm was used. The samples were pre-stressed to 3 N, then loaded with a constant cross-head speed 100 mm / min. To calculate the lap shear strength the reported force value divided by the bonding surface (127 mm2) of the specimens. The reported values are an average of at least 4 measurements of each composition. Dynamic Rheology Rheology was performed on a TA Instruments Discovery HR-2 hybrid rheometer using a temperature controlled stainless steel Peltier plate and a flat parallel plate geometry (20 mmdiameter) with a working gap of 1000 μm. Approximately 180 mg PPAA / S / MBT were pressedusing a pellet press under 10 tons of pressure which was then placed on the rheometer plate at 25 °C. Under continuous oscillation (ω = 1 rad s–1; 0.2% strain), the temperature was raised to 200 °C at a heating rate of 20 °C min–1and held for 6 hours. Experimental General procedure for the solution-phase polymerization of propylene with a series of bromoalkenesA catalyst stock solution of M1-4 (24 μmol) in toluene (10 mL) was prepared. Prescribedquantities of catalyst stock solutions were added into an ampoule containing a hexane solution of cocatalyst MAO and magnetic stirrer bar. In the ampoule side arm, n- bromoalkene, TIBA and hexane were added. The polymerization ampoule was then stirred in a preheated oil bath and evacuated before simultaneous additions of the n-bromoalkene and TIBA solution, and exposure to propylene (2 bar) for the duration of the polymerization. After the above procedure, the reaction mixture was degassed and themixture was precipitated in acidified methanol (2 wt% HCl) before being collected byfiltration, washed with methanol (20 mL), then acetone (2 x 20 mL), and dried in vacuo at40 °C to a constant mass. Comonomer incorporation (mol%) and conversion calculatedaccording to Figure 3. PPBr (3.99 mol%). 1H NMR (600 MHz, C2D2Cl4, 393 K): δ 4.84(0.14H, s, H15), 4.77 (0.14H, s, H15), 3.49 (2H, t, 3JHH = 6.8 Hz, H1), 1.97 (2H, p, 3JHH = 6.9 Hz, H2),1.75-1.58 ppm (25H, br m, H13), 1.58-1.50 (4H, m, H3and Ha), 1.50-1.06 (46H, m, Ha, H4, and H12(anti)), 1.05-0.84 ppm (95H, br d, H14 and H12 (syn)). 13C{1H} NMR (151 MHz, C2D2Cl4, 393 K):δ 120.54, 99.91, 45.82 (1C, s, C10), 45.43 (C13), 42.94 (2C, s, C11), 35.14 (1C, s, C9), 32.87 (1C, s, Ca),32.81 (1C, s, C1), 32.37 (1C, s, C2), 29.45 (1C, s, Ca), 28.87 (1C, s, Ca), 28.77 (1C, s, Ca), 28.13 (1C, s, C4), 27.90 (C12), 27.64 (1C, s, C3), 26.11 (1C, s), 21.80-19.65 (26.5C, C14, mmmm = 83%b).aResonances corresponding to C5-8. bAssigned according to literature.3 FTIR: ν (cm-1) = 2950,2867, and 1456 (ν (C-H, CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 2917, 2838, and 1377 (ν (CH2)), 721 (ν (CBr)).Table 1: (Co)polymerisation data of propylene (and 11-Br) using M1-4.Cata 11- Acti- Prod Yield Incor- MWeĐmeTmfCryst Major -lyst Br vitybuc- poration al- pentaddtivity d linity En- c f try (g (MX) (mM)(g) (mol%)(°C) (%)mol-1) 1M1 4932 15.7 3.92 30100 2.3 131 54 mmmm 2M1 45.5 3575 11.4 2.84 2.01 28500 2.2 116 303 M2 10 32.898 mmmm 328 8.21 000 4.7 141 78(98.4%) 4M2 45.5 7254 23.1 5.77 1.64 152200 3.6 142 545 M3 4491 14.3 3.19 318rrrr 800 3.2 126 23 6M3 45.5 2192 7.6 1.69 3.95 271600 2.3 104 167 M4 4419 15.3 3.51 3.08 M4 45.5 1879 6.5 1.49 15.48 2.4aConditions: M1-4 (0.024 mM, 1 mg mL-1toluene), MAO used as a cocatalyst and scavenger with [Al]0:[MX]0 = 1000:1. Molar ratio of [TIBA]0:[11-Br]0 = 1:10, 0.50–0.75 mL toluene, 49.25–49.50 mL hexanes, propylene 2 bar, Tp = 50 °C, 20 min-1. Polymerization and analysis were performedin duplicate and mean values are reported. bkgPP mol[MX]–1 h–1 bar–1.ckgPP g[MX] –1 h.dDetermined by 1H NMR.eDetermined by SEC.fDetermined by DSC. It would be evident to the skilled person that the general polymerization procedure described herein for propylene is applicable, with routine modifications, to the copolymerization of ethylene with 11-bromo-1-undecene, thereby yielding the corresponding poly(ethylene-co-11-bromo-1- undecene) (PEBr) copolymer.Synthesis and characterization of functional polypropylenes Post-modification of poly(propylene)-co-(11-bromo-1-undecene) with triisopropylphosphite. Triisopropyl phosphite (P(OiPr)3, 50 equiv.) was added to poly(propylene)-co-(11-bromo-1-undecene) (0.5 g). The reaction mixture was heated and stirred at 180 °C for6 h in an ampoule. Aliquots were taken periodically and dried in vacuo at 40 °C. The finalpolymer was precipitated in acidified methanol (2 wt% HCl) before being collected byfiltration, washed with methanol (20 mL), then acetone (2 x 20 mL), and dried in vacuo at40 °C to a constant mass. PPPPr (3.99 mol%). 1H NMR (600 MHz, C2D2Cl4, 393 K): δ4.80-4.68 ppm (2H, m, H15), 1.77-1.51 (27H, br m, H13), 1.55-1.45 (4H, m, Ha) 1.44-1.06 (54H, m,Ha, H12 (anti) and H16), 1.05-0.84 ppm (80H, br m, H14 and H12 (syn)). 13C{1H} NMR (151 MHz,C2D2Cl4, 393 K): 120.53, 99.89, 69.61 (2C, d, 2JCP = 6.9 Hz, C15), 46.21 (C13), 35.88 (1C, s, Ca),30.59 (1C, d, 3JCP = 15.2 Hz, C3), 30.20 (1C, s, Ca), 29.66 (1C, s, Ca), 29.50 (1C, s, Ca), 29.18 (1C, s,Ca), 28.58 (C12), 27.38 (1C, d, 1JCP = 141.5 Hz, C1), 24.09 (2C, dd, 3JCP = 7.8, 3.62 Hz, C16), 22.70(1C, d, 2JCP = 5.5 Hz, C2), 21.64 (C14). aResonances corresponding to unassigned CH2. 31P{1H}NMR (243 MHz, C2D2Cl4, 393 K): 28.80 ppm (s, O=P(OiPr)2). FTIR: ν (cm-1) = 2950, 2867,and 1456 (ν (C-H, CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 1245 (ν (P=O)), 1006 and 981 (ν (P-O-C)). Post-modification of poly(propylene)-co-(11-bromo-1-undecene) with triphenyl phosphite. Triphenyl phosphite (P(OPh)3, 50 equiv.) were added to poly(propylene)-co- (11-bromo-1-undecene) (0.5 g) heated and stirred at 180 °C for 48 h in an ampoule.Aliquots were taken periodically and dried in vacuo at 40 °C. The final polymer wasprecipitated in acidified methanol (2 wt% HCl) before being collected by filtration, washedwith methanol (20 mL), then acetone (2 x 20 mL), and dried in vacuo at 40 °C to aconstant mass. PPPPh (3.99 mol%). 1H NMR (600 MHz, C2D2Cl4, 393 K): δ 7.39 (4H, t,3JHH 7.7 Hz, H17), 7.27 (4H, d, 3JHH = 7.8 Hz, H16), 7.23 (2H, t, 3JHH = 7.4 Hz, H18), 2.19-2.09 (2H,br m, H1), 1.92-1.82 (2H, br m, H2), 1.75-1.60 (20H, br m, H13), 1.59-1.06 (44H, m, Haand H12(anti)), 1.04-0.84 ppm (78H, br m, Ha, H14 and H12 (syn)). 13C{1H} NMR (151 MHz, C2D2Cl4,393 K): 150.99 (2C, d, 2JCP = 8.7, C15), 129.70 (4C, s, C17), 124.94 (2C, s, C18), 120.62 (4C, d, 3JCP= 4.4 Hz, C16), 99.89, 46.21 (C13), 43.64 (2C, s Cb), 35.90 (1C, s, Ca), 33.60 (1C, s, Ca), 30.44 (1C,d, 3JCP = 15.8 Hz, C3), 30.19 (1C, s, Ca), 29.63 (1C, s, Ca), 29.44 (1C, s, Ca), 29.09 (1C, s, Ca), 28.58(C12), 26.84 (1C, s, Ca), 26.57 (1C, d, 1JCP = 139.8 Hz, C1), 22.45 (1C, d, 2JCP = 5.5 Hz, C2), 21.64(C14). aPeaks corresponding to unassigned CH2. 31P{1H} NMR (243 MHz, C2D2Cl4, 393 K):24.52 ppm (s, O=P(OPh)2). FTIR: ν (cm-1) = 2950, 2867, and 1456 (ν (C-H, CH3)), 2917, 2838,and 1377 (ν (C-H, CH2)), 1274 (ν (P=O)), 1191, 927, 900 (ν (P-O-Ph)), 762 (ν (C=CAr)), and 681(ν (C-HAr)). Synthesis of N-ethylethanamine (DEA) modified PPBr, PPDEA. DEA (50 equiv.) wereadded to PPBr (0.5 g) heated and stirred at 150 °C for 24 h in an ampoule. The final polymer wasprecipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, then acetone, and dried in vacuo at 60 °C to aconstant weight. PPDEA (3.99 mol%). 1H NMR (600 MHz, C2D2Cl4, 393 K): 3.12 (4H, br s,H15)a, 2.99 (2H, br s, H1)a, 1.89 (2H, br s, H2)a, 1.75-1.58 (19H, br m, H13), 1.57-1.06 (49H, br m,Hb, H12 (anti) and H16)a, 1.05-0.84 ppm (70H, br m, Hb, H12 (syn), and H14). 13C{1H} NMR (151MHz, C2D2Cl4, 393 K): 123.92, 120.52, 52.03 (1C, s, C1)a, 47.39 (2C, s, C15)a, 46.19 (C13), 43.63(1C, s, Cb), 35.91 (1C, s, Cb), 33.63 (1C, s, Cb), 30.16 (1C, s, Cb), 29.55 (1C, s, Cb), 29.48 (1C, s, Cb), 29.11 (1C, s, Cb), 28.56 (C12), 27.23 (1C, s, Cb), 26.84 (1C, s, Cb), 23.66 (1C, s, C2)a, 21.63 (C14), 9.11(2C, s, C16)a. aNitrogen adjacent 1H and 13C NMR peaks appear broad. This observation ispotentially explained by an increase in the relaxation rate caused by quadrupolar Nitrogen. A lack of HMBC cross-peaks whilst still evidencing HSQC cross-peaks support this. Experimentally, HSQC equivalent delays were optimised for 145 Hz (3 ms delay) whereas HMBC experiments were optimised for a 125 ms delay, giving the nuclei sufficient time to relax and preventing the appearance of any cross-peak to carbons adjacent to nitrogen.bPeaks corresponding tounassigned CH2. FTIR: ν (cm−1) = 2950, 2867, and 1456 (ν (C-H, CH3)), 2917, 2838, and 1377 (ν(C-H, CH2)), 1203 (ν (CN)). Synthesis of 2,2'-iminodiethanol (EAE) modified PPBr, PPEAE. EAE (50 equiv.) wereadded to PPBr (0.5 g) heated and stirred at 180 °C for 48 h in an ampoule. The final polymer wasprecipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glasssintered frit (porosity 3), washed with methanol, then acetone, and dried in vacuo at 60 °C to aconstant weight. PPEAE (3.99 mol%).1H NMR (600 MHz, C2D2Cl4, 393 K): 4.05 (2H, br s,H16)a, 3.27 (2H, br s, H15)a, 3.18 (2H, br s, H18)a, 3.13 (2H, br s, H1)a, 1.92 (2H, br s, H2)a, 1.75-1.62 (33H, br m, H13), 1.55-1.06 (72H, br m, Hb, H3-4, H12 (anti), and H19), 1.05-0.84 ppm (135H, br m,H14 and H12 (syn)). 13C{1H} NMR (151 MHz, C2D2Cl4, 393 K): 144.85, 123.93, 111.22, 99.88,57.49 (1C, br s, C18)a, 56.75 (1C, s, C16), 54.13 (1C, s, C1), 49.40 (1C, s, C15), 46.51 (1C, s, C10), 46.21 (C13), 43.65 (1C, s, Ca), 39.53 (1C, s, Ca), 35.93 (1C, s, Ca), 33.66 (1C, s, Ca), 30.16 (1C, s, Ca), 29.09 (1C, s, Ca), 28.57 (C12), 27.05, 26.85, 23.47 (1C, s, C2)a, 21.64 (C14), 20.85, 19.67, 8.81 (1C, s, C19).FT-IR: ν (cm−1) = 2950, 2867, and 1456 (ν (CH, CH3)), 2917, 2838, and 1377 (ν (CH, CH2)), 1110-1014 (ν (CN)). aNitrogen adjacent 1H and 13C NMR peaks appear broad. This observation ispotentially explained by an increase in the relaxation rate caused by quadrupolar Nitrogen. A lack of HMBC cross-peaks whilst still evidencing HSQC cross-peaks support this. Experimentally, HSQC equivalent delays were optimised for 145 Hz (3 ms delay) whereas HMBC experiments were optimised for a 125 ms delay, giving the nuclei sufficient time to relax and preventing theappearance of any cross-peak to carbons adjacent to nitrogen. bPeaks corresponding tounassigned CH2. Synthesis of 2,2'-iminodiethanol (DEOA) modified PPBr, PPDEOA. DEOA (50 equiv.)were added to PPBr (0.5 g) heated and stirred at 180 °C for 48 h in an ampoule. The final polymerwas precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, then acetone, and dried in vacuo at 60 °C to aconstant weight. PPDEOA (3.99 mol%). 1H NMR (600 MHz, C2D2Cl4, 393 K): 4.13 (4H, br s,H16)a, 3.37 (4H, br s, H15)a, 3.25 (2H, br s, H1)a, 1.93 (2H, br s, H2)a, 1.75-1.62 (40H, br m, H13),1.55-1.06 (78H, br m, Hb, H3-4 and H12 (anti)), 1.05-0.84 ppm (162H, br m, H14 and H12 (syn)).13C{1H}NMR (151 MHz, C2D2Cl4, 393 K): 123.93, 120.53, 116.47, 111.23, 99.88, 58.72 (2C, br s, C15)a,56.90 (2C, br s, C16)a, 55.54 (1C, br s, C1)a, 46.21 (C13), 45.83, 45.38 (1C, s, C4), 43.66, 39.52, 35.96,33.68, 28.58 (C12), 26.99, 23.67 (1C, br s, C2)a, 22.45, 21.64 (C14), 19.66, 14.32. aNitrogen adjacent1H and 13C NMR peaks appear broad. This observation is potentially explained by an increase inthe relaxation rate caused by quadrupolar Nitrogen. A lack of HMBC cross-peaks whilst still evidencing HSQC cross-peaks support this. Experimentally, HSQC equivalent delays were optimised for 145 Hz (3 ms delay) whereas HMBC experiments were optimised for a 125 ms delay, giving the nuclei sufficient time to relax and preventing the appearance of any cross-peak tocarbons adjacent to nitrogen. bPeaks corresponding to unassigned CH2. FTIR: ν (cm−1) = 3506-3182 (ν (OH)), 2950, 2867, and 1456 (ν (C-H, CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 1080- 1045 (ν (CN)). Synthesis of ethanoic acid modified PPBr, PPAc. 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (DBU, 2 equiv.) were added to a THF (1 ml) solution of ethanoic acid (2 equiv.) and PPBr (0.25 g) in an ampoule before being heated and stirred at 77 °C for 24 h. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, then acetone, and dried in vacuo at 60 °C to aconstant weight. PPAc (3.99 mol%). 1H NMR (600 MHz, C2D2Cl4, 393 K): 4.15 (2H, t, 3JHH =6.7 Hz, H1), 2.09 (3H, s, H16), 1.74-1.58 (25H, br m, H13), 1.58-1.06 (45H, br m, Ha, H2and H12(anti)), 1.05-0.84 ppm (67H, br m, H14 and H12 (syn)).13C{1H} NMR (151 MHz, C2D2Cl4, 393 K):170.60 (1C, s, C15), 120.53, 99.89, 64.59 (1C, s, C1), 46.21 (C13), 43.63 (1C, s, Ca), 35.85 (1C, s, Ca), 33.57 (1C, s, Ca), 30.17 (1C, s, Ca), 29.68 (1C, s, Ca), 29.59 (1C, s, Ca), 29.54 (1C, s, Ca), 29.28 (1C, s, C3), 28.88 (1C, s, C2), 28.58 (C12), 26.81 (1C, s, Ca), 26.04 (1C, s, C4), 21.64 (C14), 20.76 (1C, s,C16). aPeaks corresponding to unassigned CH2. FTIR: ν (cm−1) = 2950, 2867, and 1456 (ν (C-H,CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 1745 (ν (C=O)), 1433 (ν (C-O)). Synthesis of benzoic acid modified PPBr, PPBn. DBU (2 equiv.) were added to a THF (1 ml)solution of benzoic acid (2 equiv.) and PPBr (0.25 g) in an ampoule before being heated and stirredat 77 °C for 24 h. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, thenacetone, and dried in vacuo at 60 °C to a constant weight. PPBn (3.99 mol%). 1H NMR (500MHz, C2D2Cl4, 393 K): 8.11 (2H, d, 3JHH = 7.4 Hz, H17), 7.61 (1H, t, 3JHH = 6.7 Hz, H19), 7.50(2H, t, 3JHH = 7.5 Hz, H18), 4.41 (2H, t, 3JHH = 6.6 Hz, H1), 1.87 (2H, m, H2), 1.75-1.58 (23H, br m,H13), 1.58-1.06 (52H, br m, Ha, H2, and H12 (anti)), 1.04-0.93 ppm (88H, br m, H14and H12 (syn)).13C{1H} NMR (151 MHz, C2D2Cl4, 393 K): 166.54 (1C, s, C15), 132.61 (1C, s, C16), 131.21 (1C, s,C19), 129.60 (2C, s, C18), 128.33 (2C, s, C17), 120.54, 99.89, 65.21 (1C, s, C1), 46.21 (C13), 43.63 (1C, s, Ca), 39.54 (1C, s, Ca), 35.87 (1C, s, Ca), 33.59 (1C, s, Ca), 30.18 (1C, s, Ca), 29.62 (1C, s, Ca), 29.58 (1C, s, Ca), 29.33 (1C, s, C3), 28.98 (1C, s, C2), 28.58 (C12), 26.82 (1C, s, Ca), 26.16 (1C, s, C4), 21.64(C14). aPeaks corresponding to unassigned CH2. FTIR: ν (cm−1) = 2950, 2867, and 1456 (ν (C-H,CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 1724 (ν (C=O)), 1272 (ν (CAl-O)), 1113 (ν (CAr-O)), and 709 (ν (C=CAr)).Synthesis of acrylic acid modified PPBr, PPAA. DBU (2 equiv.) were added to a THF (5 ml)solution of propenoic acid (2 equiv.) and PPBr (0.25 g) in an ampoule, sparged with N2 for 15minutes before being heated and stirred at 77 °C for 96 h. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, then acetone, and dried in vacuo at 60 °C to a constant weight. PPAA(3.99 mol%).1H NMR (600 MHz, C2D2Cl4, 393 K): 6.43 (1H, d, 3JHH = 17.3 Hz, H17 (cis)), 6.20(1H, dd, 3JHH = 17.3 and 10.3 Hz, H16), 5.84 (1H, d, 3JHH = 10.3 Hz, H17 (trans)), 4.25 (2H, t, 3JHH =6.6 Hz, H1), 1.76 (2H, m, H2), 1.75-1.58 (30H, br m, H13), 1.48-1.32 (68H, br m, Haand H12 (anti)),1.04-0.93 ppm (110H, br m, H14 and H12 (syn)). 13C{1H} NMR (151 MHz, C2D2Cl4, 393 K):166.04 (1C, s, C15), 129.51 (1C, s, C17), 129.13 (1C, s, C16), 64.72 (1C, s, C1), 46.21 (C13), 43.62 (2C, s, Ca), 35.85 (1C, s, Ca), 33.57 (1C, s, Ca), 30.16 (1C, s, Ca), 29.67-29.53 (3C, m, Ca), 29.28 (1C, s, C3),28.86 (1C, s, C2), 28.58 (C12), 26.81 (1C, s, Ca), 26.05 (1C, s, C4), 21.64 (C14). aPeaks correspondingto unassigned CH2. FTIR: ν (cm−1) = 2950, 2867, and 1456 (ν (C-H, CH3)), 2917, 2838, and 1377(ν (C-H, CH2)), 1729 (ν (C=O)), 1637 (ν (C=C)), 1407, 1296, and 1267 (ν (CH=)), 1189 (ν (C-O)). Synthesis of 1-dodecanethiol modified PPBr, PPS. DBU (50 equiv.) were added to a THF (5ml) solution of 1-dodecanethiol (50 equiv.) and PPBr (0.5 g) in an ampoule before being heatedand stirred at 77 °C for 24 h. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol,then acetone, and dried in vacuo at 60 °C to a constant weight. PPS (3.99 mol%).1H NMR (600MHz, C2D2Cl4, 393 K): 2.59 (4H, t, 3JHH = 7.2 Hz, H1 and H15), 1.75-1.58 (27H, br m, H2, H13,and H16), 1.55-1.46 (8H, br m, H3and Ha), 1.46-1.06 (66H, br m, Haand H12 (anti)), 1.05-0.84 ppm(87H, br m, H18, H14 and H12 (syn)). 13C{1H} NMR (151 MHz, C2D2Cl4, 393 K): 120.54, 99.90,46.21 (C13), 43.63 (2C, s, Ca), 35.87 (1C, s, Ca), 33.58 (1C, s, Ca), 32.68 (2C, s, C1and C15), 31.91 (1C, s, Ca), 30.30-29.98 (4C, m, Ca), 29.78-29.42 (8C, m, Ca, C2and C16), 29.4-29.12 (4C, m, Ca), 29.02 (2C, s, C3and Ca), 28.58 (C12), 26.83 (1C, s, Ca), 22.60 (2C, s, Ca), 21.64 (C14), 13.92 (1C, s, C18).aPeaks corresponding to unassigned CH2. FTIR: ν (cm−1) = 2950, 2867, and 1456 (ν (C-H, CH3)),2917, 2838, and 1377 (ν (C-H, CH2)). Synthesis of potassium phenoxide (KOPh) modified PPBr, PPOPh. KOPh (2 equiv.) wereadded under an inert atmosphere to a THF (4 ml) solution of PPBr (0.2 g) in an ampoule beforebeing heated and stirred at 77 °C for 24 h. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed withmethanol, then acetone, and dried in vacuo at 60 °C to a constant weight. PPOPh (3.99 mol%).1HNMR (600 MHz, C2D2Cl4, 393 K): 7.33 (2H, t, 3JHH = 7.4 Hz, H17), 6.99 (3H, m, H16 and H18),4.06 (2H, t, 3JHH = 6.3 Hz, H1), 1.86 (2H, m, H2), 1.75-1.58 (br m, H13), 1.58-1.06 (50H, br m, Haand H12 (anti)), 1.05-0.84 ppm (88H, br m, H14 and H12 (syn)). 13C{1H} NMR (151 MHz, C2D2Cl4,393 K): 159.62 (1C, s, C15), 129.40 (2C, s, C17), 120.70 (2C, s, C16), 115.31 (2C, s, C18), 159.62, 129.40, 120.74, 115.31, 99.89, 68.59 (1C, s, C1), 46.21 (C13), 43.63 (1C, s, Ca), 35.85 (1C, s, Ca), 33.57 (1C, s, Ca), 30.19 (1C, s, Ca), 29.62 (2C, s, Ca), 29.54 (1C, s, Ca), 29.44 (1C, s, Ca), 29.62 (C2), 28.58 (C12), 26.82 (1C, s, Ca), 26.18 (1C, s, C3), 21.64 (C14).aPeaks corresponding to unassigned CH2.FTIR: ν (cm−1) = 2950, 2867, and 1456 (ν (C-H, CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 1601and 1497 (ν (C=C)), 1244 (ν (CAl-O)), 1080 (ν (CAr-O)), and 752 (ν (C=CAr)), and 690 (ν (C-HAr)). Synthesis of potassium 1,3-diethoxy-2-methyl-1,3-dioxopropan-2-ide (KDEMM)modified PPBr, PPM. KDEMM (2 equiv.) was added under an inert atmosphere to a THF (4 ml)solution of PPBr (0.2 g) in an ampoule before being heated and stirred at 77 °C for 24 h. The finalpolymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, then acetone, and dried in vacuo at 60 °Cto a constant weight. PPM (3.99 mol%). 1H NMR (600 MHz, C2D2Cl4, 393 K): 4.26 (4H, q,3JHH = 7.0 Hz, H18), 1.94 (2H, m, H1), 1.75-1.58 (22H, br m, H13), 1.58-1.29 (63H, br m, Ha, H2,H19, and H12 (anti)), 1.05-0.84 ppm (83H, br m, H14 and H12 (syn)). 13C{1H} NMR (151 MHz,C2D2Cl4, 393 K): 172.31 (2C, s, C17), 120.54, 99.89, 60.93 (2C, s, C18), 54,14 (1C, s, C15), 46.21(C13), 43.63 (1C, s, Ca), 35.93 (1C, s, C1), 30.23 (1C, s, Ca), 30.03 (1C, s, Ca), 29.67 (1C, s, Ca), 29.63 (1C, s, Ca), 29.42 (1C, s, Ca), 28.58 (C12), 26.58 (1C, s, C2), 24.45 (1C, s, Ca), 21.64 (C14), 20.05 (1C,s, C16), 14.06 (2C, s, C19). aPeaks corresponding to unassigned CH2. FTIR: ν (cm−1) = 2950, 2867,and 1456 (ν (C-H, CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 1736 (ν (C=O)), 1253 and 1115 (ν (C-O)). Synthesis of lithium phenylacetylide (LiPA) modified PPBr, PPPA. LiPA (2 equiv.) wasadded under an inert atmosphere to a THF (4 ml) solution of PPBr (0.2 g) in an ampoule beforebeing heated and stirred at 77 °C for 24 h. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed withmethanol, then acetone, and dried in vacuo at 60 °C to a constant weight. PPPA (3.99 mol%).1HNMR (600 MHz, C2D2Cl4, 393 K): 7.47 (2H, d, 3JHH = 6.5 Hz, H17), 7.32 (3H, m, H18 and H19),2.49 (2H, t, 3JHH = 6.8 Hz, H2), 1.75-1.63 (24H, br m, H3 and H13), 1.63-1.05 (57H br m, Ha, andH12 (anti)), 1.05-0.84 (89H, br m, H14 and H12 (syn)). 13C{1H} NMR (151 MHz, C2D2Cl4, 393 K):131.72 (2C, s, C17), 128.15 (2C, s, C18), 127.37 (1C, s, C19), 124.69 (1C, s, C16), 90.83 (1C, s, C1), 80.96 (1C, s, C15), 46.21 (C13), 33.57 (1C, s, Ca), 30.20 (1C, s, Ca), 29.67 (1C, s, Ca), 29.59 (1C, s, Ca), 29.20 (1C, s, Ca), 29.02 (1C, s, Ca), 29.01 (1C, s, Ca), 28.58 (C12), 26.83 (1C, s, Ca), 21.64 (C14), 19.55 (1C,s, C2). aPeaks corresponding to unassigned CH2.FTIR: ν (cm−1) = 2950, 2867, and 1456 (ν (C-H,CH3)), 2917, 2838, and 1377 (ν (C-H, CH2)), 1598 and 1491 (ν (C=C)), 754 (ν (C=CAr)), and 690 (ν (C-HAr)). Synthesis of DEA modified iPPBr and sPPBr, iPPDEA and sPPDEA. DEA, (50 equiv.) and PPBr(200 mg) were added to an ampoule. The reaction mixture was heated at 150 °C and agitated for 48 hrs. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, then acetone,and dried in vacuo at 60 °C to a constant weight. Polymer isolated: 178 mg iPPDEA (2.42 mol%)and 183 mg sPPDEA (1.88 mol%). iPPDEA: 1H NMR (600 MHz, C2D2Cl4, 393 K): δ 3.13 (4H,br s, H15)b, 3.00 (2H, br s, H1)b, 2.30, 2.13, 1.91 (2H, br s, H2)b, 1.75-1.63 (48.5H, br m, H13), 1.63- 1.23 (93H, br m, H3, H12(anti), H16and Ha)b, 1.20-0.81 (196H, br m, H12 (syn), H14).13C{1H} NMR (151 MHz, C2D2Cl4, 393 K): δ 123.94, 120.54, 99.89, 51.88 (C1), 47.36 (C15), 47.04 (C15), 46.20 (C12), 43.63, 42.75, 35.92, 29.55, 29.49, 28.56 (C13), 27.21, 23.52 (C2), 21.64(C14), 8.85 (C16). FTIR: ν (cm−1) = 2951, 2868 and 1456 (ν (C-H, CH3)), 2918, 2839 and 1376 (ν(C-H, CH2)), 1228 (ν (C-N)). sPPDEA: 1H NMR (600 MHz, C2D2Cl4, 393 K): δ 3.13 (4H, br s,H15)b, 3.01 (2H, br s, H1)b, 2.30, 2.13, 1.91 (2H, br s, H2)b, 1.75-1.63 (53H, br m, H13), 1.63-1.26 (64H, br m, H3, H16and Ha)b, 1.26-1.03 (103H, br m, H12and Ha), 1.03-0.82 (155H, br m, H14).13C{1H} NMR (151 MHz, C2D2Cl4, 393 K): δ 120.53, 99.88, 51.55 (C1), 47.04 (C15), 46.93 (C12),28.14 (C13), 23.19 (C2), 20.09 (C14), 8.69 (C16). FTIR: ν (cm−1) = 2956, 2868 and 1462 (ν (C-H,CH3)), 2914, 2839 and 1377 (ν (C-H, CH2)), 1232 (ν (C-N)). aResonances corresponding tounassigned CH2. b Peaks refer to 1H atoms adjacent to the Nitrogen which appear broad, this couldbe attributed to the effect of the quadrupolar 14N on the relaxation rate. Synthesis of P(OiPr)3 modified iPPBr and sPPBr, iPPPPr and sPPPPr. P(OiPr)3 (50 equiv.)and PPBr (200 mg) were added to an ampoule. The reaction mixture was heated at 150 °C andagitated for 96 hrs. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity 3), washed with methanol, thenacetone, and dried in vacuo at 60 °C to a constant weight. Polymer isolated: 172 mg of iPPPPr(2.42 mol%) and 193 mg of sPPPPr (1.88 mol%). iPPPPr: 1H NMR (600 MHz, C2D2Cl4,393 K): δ 4.73 (2H, m, H15), 2.90, 2.12, 1.84-1.63 (66H, br m, H1, H13and Ha), 1.63-1.24 (105H,br m, H12 (anti), H16 and Ha), 1.24-0.83 (252H, br m, H12 (syn) and H14). 13C{1H} NMR (151 MHz,C2D2Cl4, 393 K): δ 120.54, 99.89, 69.58 (C15), 46.21 (C12), 43.64(Ca), 35.88(Ca), 33.59(Ca), 32.50 (Ca), 29.66 (Ca), 29.51 (Ca), 29.19 (Ca), 28.58 (C13), 26.90 (Ca), 26.84 (Ca), 24.63 (Ca), 24.11(Ca),24.09 (Ca), 23.84 (C16), 21.64 (C14). 31P{1H} NMR (243 MHz, C2D2Cl4, 393 K): δ 29.49.FTIR: ν (cm−1) 2951, 2868 and 1458 (ν (C-H, CH3)), 2920, 2838 and 1377 (ν (C-H, CH2)), 1250(ν (P=O)), 1109 (ν (C-O)), 982 (ν (P-O-C)). sPPPPr:1H NMR (600 MHz, C2D2Cl4, 393 K): δ4.74 (2H, h, H15), 2.30, 2.12, 1.86-1.62 (68H, br m, H13, H1and Ha), 1.62-1.26 (59H, br m, H16andHa), 1.26- 1.03 (126H, br m, H12 and Ha), 1.03-0.75 (190H, br m, H14). 13C{1H} NMR (151 MHz,C2D2Cl4, 393 K): δ 120.54, 99.90, 69.28 (C15), 46.93 (C12), 46.29, 46.16, 44.15, 28.14 (C13), 24.09,23.84 (C16), 20.81, 20.62, 20.46, 20.09(C14). 31P{1H} NMR (243 MHz, C2D2Cl4, 393 K): δ29.63. FTIR: ν (cm−1) 2956, 2868 and 1464 (ν (C-H, CH3)), 2914, 2839 and 1377 (ν (C-H, CH2)),1246 (ν (P=O)), 1109 (ν (C-O)), 982 (ν (P-O-C)). aPeaks corresponding to unassigned CH2. Synthesis of Bn modified iPPBr and sPPBr, iPPBn and sPPBn. Bn (2 equiv.) and DBU (2equiv.) were added to an ampoule containing PPBr (200 mg) and THF (5 mL). The reactionmixture was heated at 95 °C and agitated for 96 hrs. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected by filtration on a glass sintered frit (porosity3), washed with methanol, then acetone, and dried in vacuo at 60 °C to a constant weight.Polymer isolated:163 mg of iPPBn and 205 mg of sPPBn. iPPBn: 1H NMR (600 MHz, C2D2Cl4,393 K): δ 8.11 (2H, d, 3JHH = 7.4 Hz, H17), 7.62 (1H, t, 3JHH = 7.4 Hz, H19), 7.51 (2H, t,3JHH = 7.4 Hz, H18), 4.42 (2H, t, 3JHH = 6.6 Hz, H1), 1.88 (2H, p, 3JHH = 7.2 Hz, H2), 1.75-1.64 (54H,br m, H13),1.58-1.33 (81H, br m, H3, H4, H12 (anti)and Ha), 1.07-0.92 (213H, br m, H12 (syn), H14).13C{1H} (151 MHz, C2D2Cl4, 393 K): δ 166.53 (C15) 132.60 (C19), 131.21 (C16) 129.60 (C17), 128.32 (C18), 120.54, 99.89, 65.21 (C1), 46.21 (C12), 43.62(Ca), 38.23(Ca), 33.58(Ca), 30.18(Ca),29.62(Ca), 29.57(Ca), 29.33 (C4) 28.98 (C2), 28.57 (C13), 26.83 (Ca), 26.16 (C3), 21.64 (C14). FTIR:ν (cm-1) = 2950, 2867 and 1456 (ν (C-H, CH3)), 2917, 2839 and 1376 (ν (C-H, CH2)), 1726 (ν(C=O)), 1272 (ν (CAlk-O)), 1111 (ν (CAr-O)). sPPBn: 1H NMR (600 MHz, C2D2Cl4, 393 K): δ 8.11(2H, d, 3JHH = 7.5 Hz, H17), 7.62 (1H, t, 3JHH = 7.4 Hz, H19), 7.51 (2H, t, 3JHH = 7.6 Hz, H18), 4.42(2H, t, 3JHH = 6.6 Hz, H1), 1.88 (2H, p, 3JHH = 6.8 Hz, H2), 1.78-1.63 (25H, br m, H13), 1.63-1.26(20H, br m, H3, H4and Ha), 1.26-1.03 (49H, br m, H12and Ha), 1.03-0.83 (75H, br m, H14).13C{1H} NMR (151 MHz, C2D2Cl4, 393 K): δ 165.93 (C15), 132.61 (C19), 131.21 (C16), 129.60 (C17), 128.32 (C18), 120.54, 99.89, 65.21 (C1), 46.92 (C12), 44.15, 38.95, 32.68, 32.24, 29.56, 28.97(C2), 28.14 (C13), 27.54, 25.93 (C3), 20.62, 20.09 (C14). FTIR: ν (cm-1) = 2956, 2868 and 1464 (ν(C-H, CH3)), 2915, 2841 and 1377 (ν (C-H, CH2)), 1726 (ν (C=O)), 1273 (ν (CAlk-O)), 1111 (ν (CAr-O)). aPeaks corresponding to unassigned CH2. Synthesis of KOPh modified iPPBr and sPPBr, iPPOPh and sPPOPh. Under an inert nitrogenatmosphere, pre-prepared KOPh (2 equiv.), PPBr (200 mg) and THF (5 mL) were added to anampoule and sealed with a Teflon tap. The reaction mixture was heated at 95 °C and agitated for 96 hrs. The polymer formed was worked up with the relevant procedure, yielding 187 mg ofiPPOPh and 179 mg of sPPOPh. iPPOPh: 1H NMR (600 MHz, C2D2Cl4,393 K): δ 7.33 (2H, t,3JHH = 7.6 Hz, H17), 6.99 (3H, dd, 3JHH = 12.8, 7.4 Hz, H16 and H18), 4.07 (2H, t, 3JHH = 7.6 Hz, H1),2.30, 2.12, 1.87 (2H, p, 3JHH = 6.8 Hz, H2), 1.83-1.62 (59H, br m, H13), 1.63-1.21 (91H, br m, H3,H4, H12(anti) and Ha) 1.21-0.74 (240H, br m, H12 (syn) and H14). 13C{1H } (151 MHz, C2D2Cl4,393 K): δ 159.61 (C15), 129.41 (C17), 120.70 (C18), 116.94 (C16), 99.89, 68.59 (C1), 47.73, 46.21 (C12),43.63, 35.85, 34.96, 34.24, 33.93, 33.91, 29.62, 29.5428.66, 28.57 (C13), 21.89, 21.65 (C14). FTIR:ν (cm−1) = 2951, 2868 and 1456 (ν (C-H, CH3)), 2918, 2839 and 1377 (ν (C-H, CH2)), 1601 and1497 (ν (C=C)), 1246 (ν (CAlk-O)), 1043 (ν (CAr-O)). sPPOPh: 1H NMR (600 MHz, C2D2Cl4,393 K): δ 7.33 (2H, t, 3JHH = 7.7 Hz, H17), 6.99 (3H, dd, 3JHH = 12.6, 7.4 Hz, H16 and H18), 4.07(2H, t, 3JHH = 6.5 Hz, H1), 2.30, 2.13, 1.88 (2H, p, 3JHH = 6.8 Hz, H2), 1.77-1.62 (53H, br m, H13),1.62-1.26 (30H, br m, H3and Ha), 1.26-1.03 (107H, br m, H12and Ha), 1.03-0.8 (165H, br m, H14).13C{1H} (151 MHz, C2D2Cl4, 393 K): δ 159.62 (C15), 129.40 (C17), 120.70 (C18), 120.54, 115.31 (C16), 99.89, 68.59 (C1), 46.93 (C12), 46.30, 46.16, 44.16 (Ca), 43.47 (Ca), 34.77 (Ca), 29.61 (C2), 29.54 (Ca), 29.43 (Ca), 28.14 (C13), 26.27 (Ca), 26.17 (Ca), 20.82 (Ca), 20.63, 20.48 (Ca), 20.09(C14). FTIR: ν (cm−1) = 2954, 2868 and 1462 (ν (C-H, CH3)), 2914, 2839 and 1377 (ν (C-H, CH2)),1602 and 1497 (ν (C=C)), 1244 (ν (CAlk-O)), 1038 (ν (CAr-O)). aPeaks corresponding to unassignedCH2. Synthesis of KDEMM modified iPPBr and sPPBr, iPPM and sPPM. Under an inert nitrogenatmosphere, KDEMM salt (2 equiv.), PPBr (200 mg) and THF (5 mL) were added to an ampouleand sealed with a Teflon tap. The reaction mixture was heated at 95 °C and agitated for 96 hrs. The final polymer was precipitated in acidified methanol (2wt% HCl) before being collected byfiltration on a glass sintered frit (porosity 3), washed with methanol, then acetone, and dried invacuo at 60 °C to a constant weight. Polymer isolated: 173 mg of iPPM and 210 mg of sPPM. iPPM:1H NMR (600 MHz, C2D2Cl4, 393 K): δ 4.26 (4H, q, 3JHH = 7.0 Hz, H18), 2.30, 2.13, 1.95 (2H,m, H1), 1.90-1.63 (67H, br m, H13), 1.63-1.24 (90H, br m, H2, H12(anti), H15, H19and Ha), 1.24-0.86(225H, br m, H12(syn) and H14).13C{1H} (151 MHz, C2D2Cl4, 393 K): δ 172.30 (C17), 99.89, 60.93(C18), 54.14 (C15), 46.21 (C12), 43.63 (Ca), 35.93 (C1), 30.22 (Ca), 30.03 (Ca), 29.68 (Ca), 26.63 (Ca), 29.41 (Ca), 28.57 (C13), 26.85 (Ca), 25.64 (Ca), 24.45 (C2), 21.64 (C14), 20.05 (C16), 15.81, 14.06(C19). FTIR: ν (cm−1) = 2951, 2868 and 1458 (ν (C-H, CH3)), 2918, 2839, and 1377 (ν (C-H, CH2)),1735 (ν (C=O)), 1255 and 1113 (ν (C-O)). sPPM: 1H NMR (600 MHz, C2D2Cl4, 393 K): δ 4.26(4H, q, 3JHH = 7.0 Hz, H18), 2.30. 2.13, 1.95 (2H, m, H1), 1.89-1.63 (56H, br m, H13), 1.63-1.26(52H, br m, H2, H15, H19and Ha), 1.26-1.03 (109H, br m, H12and Ha), 1.03-0.82 (165H, br m, H14).13C{1H} (151 MHz, C2D2Cl4, 393 K): δ 172.30 (C17), 120.54, 99.89, 60.93 (C18), 54.14 (C15), 46.92 (C12), 46.29, 42.37, 29.66, 28.14 (C13), 24.44 (C2), 20.82, 20.62, 20.46, 20.09 (C14), 19.65(C16), 14.06 (C19). FTIR: ν (cm−1) = 2956, 2868 and 1468 (ν (C-H, CH3)), 2914, 2839 and 1377 (ν(C-H, CH2)), 1736 (ν (C=O)), 1246 and 1113 (ν (C-O)). aPeaks corresponding to unassigned CH2. It would be evident to the skilled person that the synthesis and characterization of functional polypropylenes, as described above starting from PPBr, are applicable, with routine modifications, to the synthesis and characterization of functional polyethylenes starting from PEBr. Synthesis of potassium 1,3-diethoxy-2-methyl-1,3-dioxopropan-2-ide (KDEMM).Potassium t-butoxide (1.2 g, 1 eq.) were dissolved in THF (12 ml) in a schlenk and diethyl methylmalonate (DEMM, 2 ml, 1.2 eq.) added dropwise via cannula transfer. After stirring for 16 hvolatiles were removed in vacuo and the solid washed with pentane (3 x 20 ml) and dried in vacuoto yield a yellow? solid (96.20 %), mp 164-166 °C. 1H NMR (500 MHz, THF-d8, 298 K): ^ = 3.89(q, 3J = 7.1 Hz, 4H, H5, 7), 1.67 (s, 3H, H4), 1.14 (t, 3J =7.1 Hz, 6H, H6, 8); 13C{1H} NMR (126 MHz,THF-d8, 298 K): ^ = 172.1 (C1,3), 61.0 (C2), 57.3 (C5,7), 15.7 (C4), 12.2 (C6,8). Synthesis of potassium phenolate (KOPh). Phenol (3 g, 1.5 eq.) were dissolved in THF (6ml) in a schlenk and added dropwise via cannula transfer to a schlenk containing a slurry ofpotassium hydride (0.85 g, 1 eq.) in THF (6 ml). After stirring for 16 h volatiles were removed invacuo and the solid washed with pentane (3 x 20 ml) and dried in vacuo to yield a white solid(96.16 %), mp 103-104 °C. 1H NMR (500 MHz, THF-d8, 298 K): ^ = 6.53 (m, 2H, o-C6H5), 6.51(dd, J = 8.4, 0.80 Hz, 2H, m-C6H5), 6.25 (tt, J = 7.2, 1.2 Hz, 1H, p-C6H5); 13C{1H} NMR (126 MHz,THF-d8, 298 K): ^ = 168.3 (C1), 130.0 (C3,5), 118.7 (C2,6), 113.0 (C4). Lap shear strength (LSS)Table 2: LSS measured adhesive forcesEntry Steel AluminiumPP 0.07983 (0.06995) 0.14622 (0.06299)PPBr 0.27859 (0.2268) 2.05613 (0.68799)PPDEA 0.38582 (0.18388) 1.76286 (0.69736)PPEAE 1.65481 (0.76366) 2.59508 (0.61809)PPDEOA 5.03594 (0.9856) 3.85552 (0.85359)Values reported in MPa. One standard deviation shown in brackets (σ).Hot melt adhesive performance of various functionalized polypropylenesPPBr copolymers incorporating 2.96, 4.78, and 9.10 mol% of 11-Br, as quantified by 1H-NMRspectroscopy and prepared according to the general procedure outlined above by varying the amount of present 11-Br, were isolated. Each copolymer was subsequently functionalized, following the general procedure described above, with one of the modifiers DEA, EAE, or DEOA. The functionalization of polypropylene (PP) with comonomers resulted in a surprisingly improved adhesive performance, as demonstrated by lap shear strength data in Table 3. The inventive functionalized copolymers exhibited significantly higher adhesion values on both steel and polypropylene substrates compared to unmodified polypropylene, which showed negligibleadhesion to plastic and only 0.1 MPa on steel. Notably, certain copolymers (e.g. PPEAE 4′′′ andPPDEOA 5′′′) achieved steel-steel adhesion strengths exceeding 16 MPa, while maintaining 5– 6 MPa adhesion on steel-plastic joints. The shift in failure mode from adhesive (PP, PPBr) to stock break (PPEAE, PPDEA) or plastic interfacial failure (PPDEOA) further highlights the improved interfacial bonding. This effect correlates with increased functional group incorporation and occurs despite a concurrent decrease in crystallinity. Without being bound to a particular theory, this emphasizes that the enhanced adhesion arises not from mechanical properties but from improved chemical interaction at the interface. The observed combination of high adhesion values, broad substrate compatibility, and altered failure mechanisms constitutes a clear andunexpected technical effect over unmodified PP, especially given the over 100-fold increase of themean adhesive force of PPDEOA and PPEAE vs PP.Table 3: Characterization and adhesive data for propylene (co)polymers.Entry Modifier IncorporationaTmbCrystallinitybSteel PlasticcSteel Steelc(mol%) (°C) (%) (MPa) (MPa)PP 0 139 73 d 0.1 ± 0.0PPBr 2′ 11-Br 2.96 120 33 0.8 ± 0.3e 3.6 ± 1.8PPBr 2′′ 4.78 104 17 3.4 ± 1.8 e 1.8 ± 1.0PPBr 2′′′ 9.10 96 5 0.7 ± 0.4 e 7.6 ± 3.7PPDEA 3′ DEA 2.96 121 27 5.6 ± 0.8f 1.5 ± 0.9PPDEA 3′′ 4.78 105 25 5.9 ± 0.7f 7.6 ± 3.1PPDEA 3′′′ 9.10 99 5 5.5 ± 0.6g 6.1 ± 2.9PPEAE 4′ EAE 2.96 119 30 5.8 ± 0.4f 6.7 ± 2.6PPEAE 4′′ 4.78 106 21 6.1 ± 0.4f 15.2 ± 2.2PPEAE 4′′′ 9.10 101 14 5.6 ± 0.6g 16.8 ± 0.9PPDEOA 5′ DEOA 2.96 116 29 3.4 ± 1.8g 9.1 ± 2.6PPDEOA 5′′ 4.78 101 11 6.0 ± 0.7g 15.3 ± 1.4PPDEOA 5′′′ 9.10 93 1 5.0 ± 0.3g 17.4 ± 1.6aDetermined by 1H NMR spectroscopy. bDetermined by DSC. cDetermined by lap shear strength,mean adhesion ± one standard deviation reported. dMeasurement not possible due to lack ofadhesion. eAdhesive failure to metal. fStock break failure. gAdhesive failure to plastic.

Claims

Claims1. A copolymer comprising:propylene and / or ethylene repeating units A; and ω-substituted α-olefin repeating units B, wherein the ω-substituted α-olefin repeating units B are each independently substituted by a moiety X selected from a group consisting of halogen, -NR1R2, -P(=O)(OR3)2, -OC(=O)- R4, -OR5, -SR6, -CR7(C(=O)OR8, -C≡C-R9, wherein R1 to R9 are each independently selected from the group consisting of unsubstituted or substituted (1-20C)alkyl, unsubstituted or substituted (2-20C)alkenyl, unsubstituted or substituted (2-20C)alkynyl, unsubstituted or substituted (1-20C)alkoxy, unsubstituted or substituted (6-20C)aryl, unsubstituted or substituted (2-20C)heteroaryl, unsubstituted or substituted (3-20C)carbocyclyl, unsubstituted or substituted (2- 20C)heterocyclyl, unsubstituted or substituted (1-20C)haloalkyl, and unsubstituted or substituted (1-20C)hydroxyalkyl,2. or R¹ and R² together form a substituted or unsubstituted saturated, partially saturated, oraromatic heterocyclic or heteroaryl ring consisting of 3 to 17 unsubstituted or substituted ring atoms.The copolymer according to claim 1, wherein the moiety X is selected from a group consisting of -NR1R2, -P(=O)(OR3)2, -OC(=O)-R4, -OR5, -SR6, -CR7(C(=O)OR8, - C≡C-R9, wherein R1 to R9 are defined as above.

3. The copolymer according to claim 1 or 2, wherein the copolymer comprises 80-99.5 mol%of propylene and / or ethylene repeating units A, preferably propylene repeating units.

4. The copolymer according to any one of the preceding claims, wherein the copolymer comprises 0.5-20 mol% of ω-substituted α-olefin repeating units B.

5. The copolymer according to any one of the preceding claims, wherein the weight averagemolecular weight Mw is 40,000 g / mol or more as measured by GPC.

6. The copolymer according to any one of the preceding claims, wherein the copolymer is isotactic or syndiotactic.

7. The copolymer of any one of the preceding claims, wherein each ω-substituted α-olefinrepeating unit B, independently has the structural formula B1: [Formula B1]wherein Y is a linking group connecting C1 to X; andX is a moiety linked to Y as define above.

8. The copolymer of claim 7, wherein Y is a (6-12C)alkylene group linking C1 to X.

9. The copolymer of any one of the preceding claims, wherein each ω-substituted α-olefin repeating unit B, independently has the structural formula:wherein X is a moiety as define above.

10. The copolymer according to any of the preceding claims, wherein the moiety X is -NR1R2, wherein R1 and R2 are each independently (1-6C)alkyl or (1-6C)hydroxyalkyl.

11. The copolymer according to any of the preceding claims, wherein the moiety X is -P(=O)(OR3)2 wherein R3 is each independently selected from -OPh and -O(1-6C)alkyl).

12. The copolymer according to any of the preceding claims, wherein the moiety X is -OC(=O)- R4, wherein R4 is (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)hydroxyalkyl, (6-10C)aryl, or (2- 6C)alkenyl.

13. The copolymer according to any of the preceding claims, wherein the moiety X is selected from the following structures:, wherein R is the ω-carbon atom of Y.

14. The copolymer according to any of the preceding claims, wherein the moiety X iswherein R is the ω-carbon atom of Y, and wherein the polymer is further cross-linked by vulcanization.

15. The copolymer according to any of the preceding claims, wherein the moiety X is, wherein R is the ω-carbon atom of Y.

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