Amine-containing polymer compositions and uses thereof

Abstract

Disclosed herein are amine-containing polymer compositions based on anionic polymerization of a monomer composition comprising an amine-derivatized alpha-methylstyrene (ADAMS) monomer according to structure (I) and / or an aminated conjugated aliphatic methylated polyene (ACAMP) monomer according to structure (II) wherein k, R, R1, R2, R3 and R4 are as defined herein. Also provided are amine-containing polymer compositions based on anionic polymerization of these types of bifunctional monomers having two polymerizable sites and / or two amine sites. Further disclosed herein are methods of using such polymer compositions. # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to polymer compositions and methods of using such compositions, which may be derived from monomer compositions containing aromatic and / or conjugated (non-aromatic) structures, each of which contains at least one amine nitrogen. In particular, such functional monomers can be anionic polymerized to form the functional polymers disclosed herein. Background Art

[0002] Numerous documents have disclosed nitrogen-containing (amine) groups attached to the phenyl ring in styrene monomers / polymers / copolymers. However, monomers and polymers with such side groups are difficult to chemically synthesize reliably / repeatedly. Even when such syntheses can be accomplished, growth problems may exist in the polymerization reactions of monomers containing such amine-functionalized styrenes, either alone or as a copolymer with other styrene monomers.

[0003] Thus, post-polymerization chemical reactions are often used to add amine groups to a few monomer repeat units. However, post-polymerization chemistry may often be accompanied by different problems, even if it can avoid the growth problems of amine-functionalized styrene monomers.

[0004] Accordingly, it is desirable to develop an unconventional method for pre-polymerizing functionalized styrene monomers, particularly in a manner that is neutral to growth in the polymerization reaction or even enhances such growth.

[0005] U.S. Patent Nos. 6,486,272, 9,364,825, 10,202,494, and 10,046,285 disclose polymers prepared from styrene monomers having nitrogen-containing groups attached to the phenyl ring, all of which patents are hereby incorporated by reference in their entirety. GB Patent No. 1381755 discloses amine-functional monomer compounds, but only with acrylamide functional groups. Other examples of potentially relevant publications include but are not necessarily limited to U.S. Patent Nos. 7,790,661, 7,960,320, 8,778,854, and 10,414,999; and PCT Publication No. WO2021 / 127183, all of which documents are hereby incorporated by reference in their entirety.

[0006] Based on the difficulties in preparing and polymerizing styrene monomers having nitrogen-containing groups attached to the phenyl ring, the applicant has investigated other potential structures of functional monomers that are simpler to fabricate and polymerize. These functional monomer compositions containing aromatic and / or conjugated (non-aromatic) structures (each of which contains at least one amine nitrogen) are described in the related U.S. Provisional Application Serial No. 63 / 483,365, filed on February 6, 2023, the content of which is hereby incorporated by reference in its entirety.

[0007] U.S. Patent No. 2,778,826 (the “‘826 Schmidle patent”) and the 1955 article by Schmidle and Mansfield entitled “The Aminomethylation of Olefins. I. The Reaction of Secondary Amines, Formaldehyde, and Olefins” both disclose various reactions purported to form 3-aryl-3-butenyl-1-amines, in which formaldehyde and a secondary amine purportedly form an iminium, which reacts with styrenic olefins to form only the terminal (1,1-ethenylidene) double bond form of the amine-functionalized styrene. The 1955 article also discloses the aminofunctionalization of terpenes such as α- and β-pinene, camphene, and limonene, but does not disclose isoprene or similar conjugated non-aromatic compounds.

[0008] The 1983 article by Cohen and Onopchenko entitled “Competing Hydride Transfer and Ene Reactions in the Aminoalkylation of 1-Alkenes with N,N-Dimethylmethyleniminium Ions. A Literature Correction” (partially citing the ‘826 Schmidle patent) further discloses a mechanistic study of the reaction of specific dimethyliminium compounds with styrenic and non-styrenic olefins. Notably, at the beginning of the discussion section, the 1983 article argues that the ‘826 Schmidle patent is in error (and by inference the 1955 article containing very similar experiments and results). However, with respect to the aminomethylation of α-methylstyrene, the 1983 article notes the formation of 1,1-ethenylidene-based products, as well as a significant 1,2-ethenylidene (non-terminal double bond) content and a quite significant (13% in the case of the dimethylamino form) saturated arylalkane-amine content.

[0009] To the applicant's knowledge, the monomers of the present invention disclosed in U.S. Provisional Application Serial No. 63 / 483,365 have not been polymerized previously.

[0010] Based on the foregoing, there is a need to provide functional polymers based on α-substituted functional monomers, particularly functional polymers based on functional monomer compositions containing aromatic and / or conjugated (non-aromatic) structures, each structure containing at least one amine nitrogen, and the functional polymers utilize anionic polymerization processing techniques. SUMMARY OF THE INVENTION

[0011] Accordingly, the present disclosure provides a polymer composition of the present invention by anionic polymerization of an addition-polymerizable monomer composition based on the following structures (I) and (II), with the emphasis that the 1,1-ethenyl (terminal double bond, or "exo") form of structure (I) is the desired monomer. Other monomer by-product radicals may be present in the monomer composition, as shown in the various synthetic schemes for producing monomers described in U.S. Provisional Application Serial No. 63 / 483,365 filed on February 6, 2023. where k is an integer from 1 to 3, preferably 2; where R1 and R2 are each independently a hydrocarbon group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms such as O, N, S, P, Se and combinations thereof, or where R1 and R2 are joined to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 24 carbons, and optionally 1 to 6 additional heteroatoms (such as O, N, S, P, Se and combinations thereof); where in structure (I), R is hydrogen, a phenyl ring that is co-joined with the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group (such as methyl), a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms (such as O, N, S, P, Se and combinations thereof), or a second amino functional group having structure (III) connected via an asterisk where R'1 and R'2 are independently the same as or different from R1 and R2 but are defined the same; and where R3 and R4 in structure (II) are each independently hydrogen, methyl, or a second amino functional group having structure (III) connected via an asterisk (where R'1 and R'2 are independently the same as or different from R1 and R2 but are defined the same) or an alkenyl group having structure (IV) connected via an asterisk

[0012] However, in particular, they do not jointly combine with other (conjugated) olefins in structure (II) to achieve aromaticity, and the condition is that R3 and R4 are not both an alkenyl group having structure (IV) and not both methyl.

[0013] In one form, a copolymer is disclosed herein that comprises:

[0014] (a) one or more amine-derivatized α-methylstyrene (ADAMS) repeat units according to structure (V): wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) linked via an asterisk wherein R'1 and R'2 are independently the same as or different from but defined the same as R1 and R2; and (b) one or more repeating units according to structure (VI), (VII a ), (VII b ) or combinations thereof wherein: R5 is hydrogen or methyl; R' is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group and / or combinations thereof.

[0015] In another form, there is disclosed herein a polymer comprising: (a) three or more amine-derivatized α-methylstyrene (ADAMS) repeating units according to structure (V): wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) linked via an asterisk wherein R'1 and R'2 are independently the same as or different from but defined the same as R1 and R2; and (b) substantially no other repeating units.

[0016] In yet another form, a copolymer is disclosed herein that comprises: (a) one or more repeating units according to structure (VIII): wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbylaceous group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; and (b) one or more repeating units according to structure (VI), (VII a ), (VII b ) or combinations thereof wherein: R5 is hydrogen or methyl; R' is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, and / or combinations thereof.

[0017] In yet another form, a polymer is disclosed herein that comprises: (a) three or more repeating units according to structure (VIII) wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbylaceous group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; and (b) substantially no other repeating units.

[0018] In yet another form, a copolymer is disclosed herein that comprises: the reaction product of: (a) one or more monomers according to structure (I) Wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked together to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) linked via an asterisk wherein R'1 and R'2 are independently the same as or different from but defined the same as R1 and R2; (b) isoprene, 1,3-butadiene, styrene, or combinations thereof; and (c) an alkyllithium, alkylsodium, alkylpotassium initiator, or combinations thereof.

[0019] Other aspects of the present disclosure will become apparent from the detailed description and examples section below. Detailed Description

[0020] All numerical values in the detailed description and claims herein are modified by the terms "about" or "approximately" to indicate the value, and account is taken of experimental error and variations expected by a person of ordinary skill in the art.

[0021] The present disclosure provides novel polymers based on anionic polymerization of monomers including functionalized styrenic monomers having a nitrogen-containing structural moiety that is not side-bonded to the phenyl ring or functionalized conjugated (non-aromatic) monomers having a nitrogen-containing structural moiety. Thus, monomers of structure (I) were developed to obtain a nitrogen-containing functional group on an α-substituted styrenic monomer that is not side-bonded to the phenyl ring on the styrene unit. This chemistry was also applied to amine-functionalized alkyl-substituted conjugated (non-aromatic) monomers such as isoprene.

[0022] It should be noted that prior art literature generally describes functionalized styrenic monomers having a nitrogen-containing group side-bonded to the phenyl ring (e.g., "dimethylaminoethyl styrene"), which can be similar to the k = 2 monomer structure provided below. However, the prior art does not teach or suggest the α-substituted functional monomers specifically disclosed herein.

[0023] The functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be polymerized from an addition-polymerizable monomer composition comprising an amine-derived α-methylstyrene (ADAMS) monomer according to Structure (I) and / or an aminated conjugated (non-aromatic) aliphatic methylated polyene (ACAMP) monomer according to Structure (II). where k is an integer from 1 to 3, preferably 2; where R1 and R2 are each independently a hydrocarbyl group having 1 to 4 additional heteroatoms such as O, N, S, P, Se and combinations thereof, or where R1 and R2 are joined to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 24 carbons, and optionally 1 to 6 additional heteroatoms (such as O, N, S, P, Se and combinations thereof); where in Structure (I), R is hydrogen, a phenyl ring co-joined to the shown phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the shown phenyl ring, a C1-C4 hydrocarbyl group (such as methyl), a C1-C6 hydrocarbyl group having 1 to 4 additional heteroatoms (such as O, N, S, P, Se and combinations thereof), or a second amino functional group having Structure (III) attached via an asterisk where R’1 and R’2 are independently the same as or different from but defined the same as R1 and R2; and where in Structure (II), R3 and R4 are each independently hydrogen, methyl or a second amino functional group having Structure (III) attached via an asterisk, where R’1 and R’2 are independently the same as or different from but defined the same as R1 and R2, or an alkenyl group having Structure (IV) attached via an asterisk However, in particular, they do not jointly combine with other (conjugated) olefins in Structure (II) to achieve aromaticity, and provided that R3 and R4 are not both an alkenyl group having Structure (IV) and not both methyl.

[0024] The functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring can be polymerized from exemplary ADAMS monomers according to Structure (I), the monomers including but not limited to 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimino)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,(5-Diazabicyclo[2.2.1]heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopentenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-diazacycloheptyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)diazacycloheptane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropermidine, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoquinoline, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene, and combinations thereof.,

[0025] In some embodiments, the functional polymers of the present invention based on functionalized styrene monomers comprising nitrogenous structural moieties not flanked to the phenyl ring may be polymerized from the ADAMS monomers according to Structure (I) and may exhibit a k value of exactly 2.

[0026] For clarity and as used herein, the functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not ortho-fused to a phenyl ring can be polymerized from exemplary ADAMS monomers of structure (I) having a 1,1-ethenylidene bond, such as the vinylidene double bond in α-methylstyrene, which can be reflected, for example, in the -3-ene / -3-enyl language of IUPAC nomenclature.

[0027] The functional polymers of the present invention based on functionalized conjugated (non-aromatic) monomers including nitrogen-containing structural moieties can be polymerized from ACAMP monomers according to Structure (II). The monomers can include, but are not limited to, 1-dimethylamino-3-methylenepent-4-ene, 1-diethylamino-3-methylenepent-4-ene, 1-di-n-propylamino-3-methylenepent-4-ene, 1-diisopropylamino-3-methylenepent-4-ene, 1-di-2-propenylamino-3-methylenepent-4-ene, 1-di-n-butylamino-3-methylenepent-4-ene, 1-di-sec-butylamino-3-methylenepent-4-ene, 1-diisobutylamino-3-methylenepent-4-ene, 1-di-tert-butylamino-3-methylenepent-4-ene, 1-cyclohexylmethylamino-3-methylenepent-4-ene, 1-dicyclohexylamino-3-methylenepent-4-ene, 1-di-(2-ethylhexyl)amino-3-methylenepent-4-ene, 1-di-(methoxyethyl)amino-3-methylenepent-4-ene, 1-di-(ethoxyethyl)amino-3-methylenepent-4-ene, 1-di-(phenoxyethyl)amino-3-methylenepent-4-ene, 1-di-(methylthioethyl)amino-3-methylenepent-4-ene, 1-di-(ethylthioethyl)amino-3-methylenepent-4-ene, 1-benzylmethylamino-3-methylenepent-4-ene, 1-dibenzylamino-3-methylenepent-4-ene, 1-benzylphenylamino-3-methylenepent-4-ene, 1-diphenylamino-3-methylenepent-4-ene, 1-dipyridylamino-3-methylenepent-4-ene, 1-phenylmethylamino-3-methylenepent-4-ene, 1-phenylmethoxyethylamino-3-methylenepent-4-ene, 1-benzylmethoxyethylamino-3-methylenepent-4-ene, 1-(N-morpholinyl)-3-methylenepent-4-ene, 1-(N-thiomorpholinyl)-3-methylenepent-4-ene, 1-(N-piperidyl)-3-methylenepent-4-ene, 1-(N-piperazinyl)-3-methylenepent-4-ene, 1-(N-heptamethyleneimino)-3-methylenepent-4-ene, 1-(N-pyrrolidinyl)-3-methylenepent-4-ene, 1-(N-pyrrolyl)-3-methylenepent-4-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-methylenepent-4-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-methylenepent-4-ene, 1-(N-indolinyl)-3-methylenepent-4-ene, 1-(N-indolyl)-3-methylenepent-4-ene, 1-(N-carbazolyl)-3-methylenepent-4-ene, 1-(N-phenothiazinyl)-3-methylenepent-4-ene, 1-(N-phenothiazinyl-S-oxide)-3-methylenepent-4-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-methylenepent-4-ene, 1-(N-phenoxazinyl)-3-methylenepent-4-ene, 1-(4-methyl-1-piperazinyl)-3-methylenepent-4-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl)-3-methylenepent-4-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-methylenepent-4-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-methylenepent-4-ene, 1-(4-cyclopentenyl-1-piperazinyl)-3-methylenepent-4-ene, 1-(4-phenyl-1-piperazinyl)-3-methylenepent-4-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-methylenepent-4-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-methylenepent-4-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-methylenepent-4-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-methylenepent-4-ene, 1-(N'-methyl-N-diazacycloheptyl)-3-methylenepent-4-ene, 1-dimethylamino-3-methylenhept-4,6-diene, 1-diethylamino-3-methylenhept-4,6-diene, 1-di-n-propylamino-3-methylenhept-4,6-diene, 1-diisopropylamino-3-methylenhept-4,6-diene, 1-di-2-propenylamino-3-methylenhept-4,6-diene, 1-di-n-butylamino-3-methylenhept-4,6-diene, 1-di-sec-butylamino-3-methylenhept-4,6-diene, 1-diisobutylamino-3-methylenhept-4,6-diene, 1-di-tert-butylamino-3-methylenhept-4,6-diene, 1-cyclohexylmethylamino-3-methylenhept-4,6-diene, 1-dicyclohexylamino-3-methylenhept-4,6-diene, 1-di-(2-ethylhexyl)amino-3-methylenhept-4,6-diene, 1-di-(methoxyethyl)amino-3-methylenhept-4,6-diene, 1-di-(ethoxyethyl)amino-3-methylenhept-4,6-diene, 1-di-(phenoxyethyl)amino-3-methylenhept-4,6-diene, 1-di-(methylthioethyl)amino-3-methylenhept-4,6-diene, 1-di-(ethylthioethyl)amino-3-methylenhept-4,6-diene, 1-benzylmethylamino-3-methylenhept-4,6-diene, 1-dibenzylamino-3-methylenhept-4,6-diene, 1-benzylphenylamino-3-methylenhept-4,6-diene, 1-diphenylamino-3-methylenhept-4,6-diene, 1-dipyridylamino-3-methylenhept-4,6-diene, 1-phenylmethylamino-3-methylenhept-4,6-diene, 1-phenylmethoxyethylamino-3-methylenhept-4,6-diene, 1-benzylmethoxyethylamino-3-methylidenehepta-4,6-diene, 1-(N-morpholino)-3-methylidenehepta-4,6-diene, 1-(N-thiomorpholino)-3-methylidenehepta-4,6-diene, 1-(N-piperidino)-3-methylidenehepta-4,6-diene, 1-(N-piperazino)-3-methylidenehepta-4,6-diene, 1-(N-azepanyl)-3-methylidenehepta-4,6-diene, 1-(N-pyrrolidinyl)-3-methylidenehepta-4,6-diene, 1-(N-pyrrolyl)-3-methylidenehepta-4,6-diene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-methylidenehepta-4,6-diene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-methylidenehepta-4,6-diene, 1-(N-indolinyl)-3-methylidenehepta-4,6-diene, 1-(N-indolyl)-3-methylidenehepta-4,6-diene, 1-(N-carbazolyl)-3-methylidenehepta-4,6-diene, 1-(N-phenothiazinyl)-3-methylidenehepta-4,6-diene, 1-(N-phenothiazinyl-S-oxide)-3-methylidenehepta-4,6-diene, 1-(N-phenothiazinyl-S,S-dioxide)-3-methylidenehepta-4,6-diene, 1-(N-phenoxazinyl)-3-methylidenehepta-4,6-diene, 1-(4-methyl-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl)-3-methylidenehepta-4,6-diene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-methylidenehepta-4,6-diene, 1-(4-cyclopentyl-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(4-cyclopentenyl-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(4-phenyl-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(4-(thiazolyl)-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(4-(thiadiazolyl)-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(4-(triazolyl)-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazino)-3-methylidenehepta-4,6-diene, 1-(N'-methyl-N-azepanyl)-3-methylidenehepta-4,6-diene, 1-dimethylamino-3,4-dimethylidenehex-5-ene, 1-diethylamino-3,4-dimethylidenehex-5-ene, 1-di-n-propylamino-3,4-dimethylidenehex-5-ene, 1-diisopropylamino-3,4-dimethylidenehex-5-ene, 1-di-2-propenylamino-3,4-dimethylidenehex-5-ene, 1-di-n-butylamino-3,4-dimethylidenehex-5-ene, 1-di-sec-butylamino-3,4-Dimethylenhex-5-ene, 1-Diisobutylamino-3,4-dimethylenhex-5-ene, 1-Di-tert-butylamino-3,4-dimethylenhex-5-ene, 1-Cyclohexylmethylamino-3,4-dimethylenhex-5-ene, 1-Dicyclohexylamino-3,4-dimethylenhex-5-ene, 1-Di-(2-ethylhexyl)amino-3,4-dimethylenhex-5-ene, 1-Di-(methoxyethyl)amino-3,4-dimethylenhex-5-ene, 1-Di-(ethoxyethyl)amino-3,4-dimethylenhex-5-ene, 1-Di-(phenoxyethyl)amino-3,4-dimethylenhex-5-ene, 1-Di-(methylthioethyl)amino-3,4-dimethylenhex-5-ene, 1-Di-(ethylthioethyl)amino-3,4-dimethylenhex-5-ene, 1-Benzylmethylamino-3,4-dimethylenhex-5-ene, 1-Dibenzylamino-3,4-dimethylenhex-5-ene, 1-Benzylphenylamino-3,4-dimethylenhex-5-ene, 1-Diphenylamino-3,4-dimethylenhex-5-ene, 1-Dipyridylamino-3,4-dimethylenhex-5-ene, 1-Phenylmethylamino-3,4-dimethylenhex-5-ene, 1-Phenylmethoxyethylamino-3,4-dimethylenhex-5-ene, 1-Benzylmethoxyethylamino-3,4-dimethylenhex-5-ene, 1-(N-Morpholino)-3,4-dimethylenhex-5-ene, 1-(N-Thiomorpholino)-3,4-dimethylenhex-5-ene, 1-(N-Piperidyl)-3,4-dimethylenhex-5-ene, 1-(N-Piperazinyl)-3,4-dimethylenhex-5-ene, 1-(N-Homopiperazinyl)-3,4-dimethylenhex-5-ene, 1-(N-Pyrrolidinyl)-3,4-dimethylenhex-5-ene, 1-(N-Pyrrolyl)-3,4-dimethylenhex-5-ene, 1-(1,2,3,4-Tetrahydro-1-quinolyl)-3,4-dimethylenhex-5-ene, 1-(1,2,3,4-Tetrahydro-2-isoquinolyl)-3,4-dimethylenhex-5-ene, 1-(N-Indolinyl)-3,4-dimethylenhex-5-ene, 1-(N-Indolyl)-3,4-dimethylenhex-5-ene, 1-(N-Carbazolyl)-3,4-dimethylenhex-5-ene, 1-(N-Phenothiazinyl)-3,4-dimethylenhex-5-ene, 1-(N-Phenothiazinyl-S-oxide)-3,4-dimethylenhex-5-ene, 1-(N-Phenothiazinyl-S,S-dioxide)-3,4-dimethylenhex-5-ene, 1-(N-Phenoxazinyl)-3,4-dimethylenhex-5-ene, 1-(4-Methyl-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(5-Methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl)-3,4-dimethylenhex-5-ene, 1-(5-Methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3,4-dimethylenhex-5-ene, 1-(4-cyclopentyl-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(4-cyclopenta-1,3-dienyl-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(4-phenyl-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(4-(triazolyl)-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3,4-dimethylenhex-5-ene, 1-(N'-methyl-N-diazepanyl)-3,4-dimethylenhex-5-ene, N,N'-bis(3-methylenepent-4-enyl)diazepane, N,N'-bis(3-methylenepent-4-enyl)piperazine, N,N'-bis(3-methylenepent-4-enyl)dihydrophenazine, N,N'-bis(3-methylenepent-4-enyl)dihydrobenzindazole, N,N'-bis(3-methylenepent-4-enyl)dihydrophenanthroline, N,N'-bis(3-methylenepent-4-enyl)octahydropyridoquinoline, N,N'-bis(3-methylenepent-4-enyl)octahydropyridoisoquinoline, N,N'-bis(3-methylenepent-4-enyl)hexahydropyrroloquinoline, N,N'-bis(3-methylenepent-4-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-methylenepent-4-enyl)hexahydropyrroloisoindole, N,N'-bis(3-methylenepent-4-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-methylenepent-4-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-methylenepent-4-enyl)piperidin-4-yl)propane, N,N'-bis(3-methylenhept-4,6-dien-1-yl)diazepane, N,N'-bis(3-methylenhept-4,6-dien-1-yl)piperazine, N,N'-bis(3-methylenhept-4,6-dien-1-yl)dihydrophenazine, N,N'-bis(3-methylenhept-4,6-dien-1-yl)dihydrobenzindazole, N,N'-bis(3-methylenhept-4,6-dien-1-yl)dihydrophenanthroline, N,N'-bis(3-methylenhept-4,6-dien-1-yl)octahydropyridoquinoline, N,N'-bis(3-methylenhept-4,6-dien-1-yl)octahydropyridoisoquinoline, N,N'-bis(3-methylenhept-4,6-dien-1-yl)hexahydropyrroloquinoline, N,N'-bis(3-methylenhept-4,6-dien-1-yl)hexahydropyrroloisoquinoline, N,N'-bis(3-methylenhept-4,6-dien-1-yl)hexahydropyrroloisoindole, N,N'-Bis(3-methylidenhept-4,6-dien-1-yl)bicyclo[2.2.1]heptane, N,N'-bis(3-methylidenhept-4,6-dien-1-yl)bicyclo[2.2.2]octane, 1,3-bis(1-(3-methylidenhept-4,6-dienyl)piperidin-4-yl)propane, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)azepane, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)piperazine, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)dihydrophenazine, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)dihydrobenzindazole, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)dihydrophenanthroline, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)octahydropyridoquinoline, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)octahydropyridoisoquinoline, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)hexahydropyrroloquinoline, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)hexahydropyrroloisoquinoline, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)hexahydropyrroloisoindole, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)bicyclo[2.2.1]heptane, N,N'-bis(3,4-dimethylidenhex-5-en-1-yl)bicyclo[2.2.2]octane, 1,3-bis(1-(3,4-dimethylidenhex-5-enyl)piperidin-4-yl)propane, N,N,N'N'-tetramethyl-3,6-dimethylideneoct-4-ene-1,8-diamine, N,N,N'N'-tetrakis(2-methoxyethyl)-3,6-dimethylideneoct-4-ene-1,8-diamine, N,N'-dimethyl-N,N'-dibenzyl-3,6-dimethylideneoct-4-ene-1,8-diamine, N,N'-(3,6-dimethylideneoct-4-ene-1,8-diyl)bis(morpholine), N,N'-(3,6-dimethylideneoct-4-ene-1,8-diyl)bis(thiomorpholine), N,N'-(3,6-dimethylideneoct-4-ene-1,8-diyl)bis(piperidine), N,N'-(3,6-dimethylideneoct-4-ene-1,8-diyl)bis(pyrrolidine), 4,4'-(3,6-dimethylideneoct-4-ene-1,8-diyl)bis(1-methylpiperazine), N,N,N'N'-tetramethyl-3,4-dimethylidenehexane-1,6-diamine, N,N,N'N'-tetrakis(2-methoxyethyl)-3,4-dimethylidenehexane-1,6-diamine, N,N'-dimethyl-N,N'-dibenzyl-3,4-dimethylidenehexane-1,6-diamine, N,N'-(3,4-dimethylidenehexane-1,6-diyl)bis(morpholine), N,N'-(3,4-dimethylidenehexane-1,6 - bis(thiomorpholine), N,N'-(3,4 - dimethylenehexane - 1,6 - diyl)bis(piperidine), N,N'-(3,4 - dimethylenehexane - 1,6 - diyl)bis(pyrrolidine), 4,4'-(3,4 - dimethylenehexane - 1,6 - diyl)bis(1 - methylpiperazine), N,N,N'N'-tetramethyl - 3,4,5 - trimethylheptane - 1,7 - diamine, N,N,N'N'-tetrakis(2 - methoxyethyl)-3,4,5 - trimethylheptane - 1,7 - diamine, N,N'-dimethyl - N,N'-dibenzyl - 3,4,5 - trimethylheptane - 1,7 - diamine, N,N'-(3,4,5 - trimethylheptane - 1,7 - diyl)bis(thiomorpholine), N,N'-(3,4,5 - trimethylheptane - 1,7 - diyl)bis(piperidine), N,N'-(3,4,5 - trimethylheptane - 1,7 - diyl)bis(pyrrolidine), 4,4'-(3,4,5 - trimethylheptane - 1,7 - diyl)bis(1 - methylpiperazine), and combinations thereof.,

[0028] In some embodiments, the functional polymers of the present invention based on functionalized conjugated (non - aromatic) monomers comprising nitrogen - containing structural moieties can be based on ACAMP monomers according to Structure (II) and can exhibit a k value of exactly 2.

[0029] The polymer compositions disclosed herein may optionally contain residues of initiators and / or co - initiators used or usable in living or pseudo - living anionic polymerization. Non - limiting examples can include alkyl residues from sec - butyllithium, n - butyllithium, tert - butyllithium, etc., and combinations, reaction products, and / or degradation products thereof.

[0030] Alkyl residues from monofunctional initiators may optionally be present at one or more termini of the polymer backbone, while alkyl residues of bifunctional initiators may optionally be present near the center of the polymer backbone.

[0031] The monofunctional initiators that can be used can be alkyl lithium, alkyl sodium, or alkyl potassium compounds, typically in the range of C2 to C12. Alkyl lithium compounds such as methyllithium, ethyllithium, n - propyllithium, isopropyllithium, n - butyllithium, isobutyllithium, sec - butyllithium, tert - butyllithium, n - pentyllithium, isopentyllithium, sec - pentyllithium, tert - pentyllithium, hexyllithium, or combinations thereof are preferred. Sec - alkyl lithium compounds, such as sec - butyllithium, sec - pentyllithium, or combinations thereof are more preferred. Most preferred is sec - butyllithium. Substituted alkyl lithium, such as aralkyl lithium compounds, e.g., benzyllithium, 1 - lithioethylbenzene, and 1 - lithio - 3 - methylpentylbenzene, can also be used.

[0032] The difunctional initiators that can be used can be alkyllithium, alkyldisodium or alkyldipotassium compounds, typically in the range of C2 to C12, such as 1,3-propanedilithium, 1,4-butanedilithium, 1,5-pentanedilithium, 1,6-hexanedilithium or combinations thereof. Additional difunctional initiators are disclosed in U.S. Patent No. 6,492,469, which is hereby incorporated by reference in its entirety.

[0033] The functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can preferably be polymerized via anionic polymerization. However, additionally or alternatively, the functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can optionally utilize initiators and / or co-initiators for or available for (free) radical polymerization reactions. Non-limiting examples can include but are not necessarily limited to azobisisobutyronitrile (AIBN), di-tert-butyl peroxide, etc., and combinations, reaction products, and / or degradation products thereof.

[0034] The present invention provides anionic polymerization polymers derived from functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring. More particularly, the functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring have the following general structure: wherein R1 and R2 are each independently a hydrocarbon group or a hydrocarbyl group having 1 to 4 additional heteroatoms such as O, N, S, P, Se and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 24 carbons, and optionally 1 to 6 additional heteroatoms (such as O, N, S, P, Se and combinations thereof). Due to the ease of synthesis of the monomers and their favorable reactivity in polymerization, monomers with k = 2 are preferred. Alternatively, monomers with k ≥ 3 can be used, but they are more complex to prepare and less commercially viable. Alternatively, monomers with k = 1 can be used, but they are difficult to polymerize via anionic polymerization.

[0035] A functionalized styrenic monomer comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or a functionalized conjugated (non-aromatic) monomer comprising a nitrogen-containing structural moiety may copolymerize with isoprene, butadiene, styrene, and combinations thereof. Other non-limiting exemplary comonomers that may copolymerize with a functionalized styrenic monomer comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or with a functionalized conjugated (non-aromatic) monomer comprising a nitrogen-containing structural moiety include various alkyl-substituted styrenes (i.e., 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-n-butylstyrene, 4-tert-butylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4-dipropylstyrene, 2-methyl-4-ethylstyrene, 2-methyl-4-propylstyrene, etc.), vinylnaphthalene, vinylpyridine, piperylene, methylpiperylene, or combinations thereof. In another form, a functionalized styrenic monomer comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or a functionalized conjugated (non-aromatic) monomer comprising a nitrogen-containing structural moiety may homopolymerize as an isolatable homopolymer or as a homopolymer block in a copolymer.

[0036] Depending on the reactivity ratios of the styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring and other comonomers present in the polymerization reaction, in some cases, the repeating units of structure (V) may form an alternating structure with the repeating units of structure (VI), (VII a ), (VII b ) or combinations thereof. For example, the following reaction, where R1, R2, and R5 have the same meanings as above.

[0037] As an alternating structure formed by the combination of the repeating units of structure (V) with the repeating units of structure (VI), (VII a ), (VII b ) or combinations thereof, a larger repeating unit of structure (IX), (X a ), (X b ) or combinations thereof will thus be formed.

[0038] where k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked together to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) linked via an asterisk

[0039] wherein R'1 and R'2 are independently the same as or different from but defined in the same manner as R1 and R2; R5 is hydrogen or methyl; R' is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, and / or combinations thereof.

[0040] Furthermore, depending on the reactivity ratios of styrenic monomers including nitrogen-containing structural moieties that are not side-linked to the phenyl ring and other comonomers present in the polymerization reaction, and if there is a molar excess of one or more other comonomers in the polymerization reaction, the polymer can in some cases form blocks of repeating units of structure (IX), (X a ), (X b ), or combinations thereof, followed by blocks of repeating units of structure (VI), (VII a ), (VII b ), or combinations thereof, without repeating units of structure (IX), (X a ), (X b ). For example, the following reaction, where R1, R2, and R5 have the same meanings as above.

[0041] In some embodiments, different monomers or combinations thereof can be optionally added to the polymerization reaction in sequence. In such cases, those monomers added later in the reaction can form blocks of repeating units within the polymer that have a different composition from those repeating units from the monomers earlier in the polymerization.

[0042] In the case where a polymer contains two blocks of repeating units having different compositions, the polymer is described as "diblock" due to differences in monomer reactivity ratios or due to the sequential addition of monomers to the polymerization reaction. Similarly, when a polymer contains three, four, five, or six blocks of repeating units of different compositions due to differences in monomer reactivity ratios or due to the sequential addition of monomers to the polymerization reaction, the polymer is described as "triblock", "tetrablock", "pentablock", or "hexablock", respectively.

[0043] In some embodiments, the polymers can be coupled using a polyfunctional coupling agent to form polymers having a star architecture. Many suitable types of these polyfunctional compounds have been described in U.S. Patent Nos. 3,595,941; 3,468,972; 3,135,716; 3,078,254 and 3,594,452, the disclosures of which are hereby incorporated by reference in their entireties. The polyfunctional coupling agent can optionally be a halogen-substituted or alkoxy-substituted silane, including tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, bis-trimethoxysilylethane, bis-triethoxysilylethane, hexachlorodisiloxane, bis-trichlorosilylethane, 1,6-bis(trichlorosilyl)-hexane, or combinations thereof.

[0044] Preferred coupling agents are polyalkenyl aromatic coupling agents. The most preferred coupling agent is divinylbenzene. Polyalkenyl aromatic coupling agents capable of forming star polymers are known in the art. See generally Canadian Patent No. 716,645 and U.S. Patent Nos. 4,010,226 and 3,985,830, the disclosures of which are hereby incorporated by reference in their entireties. A detailed description of various such coupling agents is found in U.S. Patent No. 4,391,949, the disclosure of which is hereby incorporated by reference in its entirety. Examples of suitable polyvinyl aromatic compounds are 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4'-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,5,6-trivinyl-3,7-diethylnaphthalene, 1,3-divinyl-4,5,6-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, and the like, or combinations thereof.

[0045] In the case of coupling polymers using a multifunctional coupling agent to form a polymer star architecture, the coupling ratio (CR) is used to refer to the amount of polymer that has been crosslinked into a star architecture, i.e., the weight percentage of the polymer in the star architecture relative to the total weight of the polymer in the sample. In some embodiments, the functional polymers of the present invention disclosed herein based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety and including a star polymer architecture can have a CR greater than 20%, or greater than 30%, or greater than 40%, or greater than 50%, or greater than 60%, or greater than 70%, or greater than 80%, or greater than 90%, or greater than 95%.

[0046] In some embodiments, the polymerization reaction can be terminated with an epoxide terminator such that the polymer will thereby contain one or more -OH functional groups at one or more ends of the polymer chain. Non-limiting examples of epoxide terminators include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, etc., or combinations thereof, with ethylene oxide and propylene oxide being preferred.

[0047] In some embodiments, the functional polymers of the present invention disclosed herein based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety that is not pendant to the phenyl ring or based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can have a number average molecular weight Mn greater than 500 Da, or greater than 1000 Da, or greater than 2000 Da, or greater than 5000 Da, or greater than 10,000 Da. Additionally or alternatively, the functional polymers of the present invention disclosed herein based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety that is not pendant to the phenyl ring or based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can have a number average molecular weight Mn less than 5,000,000 Da, or less than 3,000,000 Da, or less than 1,000,000 Da, or less than 500,000 Da, or less than 200,000 Da.

[0048] In some embodiments, the functional polymers of the present invention disclosed herein based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety that is not pendant to the phenyl ring can contain greater than 0.01 wt%, or greater than 0.05 wt%, or greater than 0.1 wt%, or greater than 0.5 wt%, or greater than 1.0 wt%, or greater than 5.0 wt%, or greater than 10 wt%, or greater than 15 wt%, or greater than 20 wt% of the repeating unit according to structure (V).

[0049] In some embodiments, the functional polymers of the present invention based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety may contain greater than 0.01 wt%, or greater than 0.05 wt%, or greater than 0.1 wt%, or greater than 0.5 wt%, or greater than 1.0 wt%, or greater than 5.0 wt%, or greater than 10 wt%, or greater than 15 wt%, or greater than 20 wt% of repeating units according to Structure (VIII).

[0050] In some embodiments, the functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not attached laterally to a phenyl ring may contain greater than 0.01 wt%, or greater than 0.05 wt%, or greater than 0.1 wt%, or greater than 0.5 wt%, or greater than 1.0 wt%, or greater than 5.0 wt%, or greater than 10 wt%, or greater than 15 wt%, or greater than 20 wt% of repeating units according to Structure (IX).

[0051] In some embodiments, the functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not attached laterally to a phenyl ring may contain greater than 0.01 wt%, or greater than 0.05 wt%, or greater than 0.1 wt%, or greater than 0.5 wt%, or greater than 1.0 wt%, or greater than 5.0 wt%, or greater than 10 wt%, or greater than 15 wt%, or greater than 20 wt% of repeating units according to Structure (X a )、Structure (X b ) or combinations thereof.

[0052] In some embodiments, the functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not attached laterally to a phenyl ring or based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety may optionally be further post-polymerization modified to modify their structure.

[0053] In some embodiments, the post-polymerization modification is hydrogenation. In the methods of the present disclosure, hydrogenation can be carried out by known catalytic systems, including heterogeneous systems and soluble systems. Soluble systems are disclosed in U.S. Patent No. 4,284,835, column 1, line 65 to column 9, line 16, and U.S. Patent No. 4,980,331, column 3, line 40 to column 6, line 28, both of which are incorporated herein by reference.

[0054] The above hydrogenated copolymer can be partially or substantially hydrogenated. In the context of the present disclosure, partial hydrogenation means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of the non-aromatic double bonds have been saturated. Substantially hydrogenated means that greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% of the non-aromatic bonds have been saturated.

[0055] Other teachings on hydrogenation can be found in Rachapudy et al., Journal of Polymer Science: Polymer Physics Edition, Vol. 17, 1211-1222 (1979), which is hereby incorporated by reference in its entirety. Table 1 of this article discloses several systems, including palladium on various supports (calcium carbonate, but it can also be barium sulfide). The article by Rachapudy et al. discloses the preparation of homogeneous and heterogeneous catalysts.

[0056] Other teachings on hydrogenation methods and catalysts are disclosed in U.S. Patent Nos. 4,284,835 and 4,980,331, both of which are hereby incorporated by reference in their entirety.

[0057] In some embodiments, the post-polymerization modification can be a deprotection reaction that removes a cleavable chemical protecting group from the repeating units of structure (V), (VIII), or a combination thereof. A cleavable chemical protecting group is a chemical group that is inert under polymerization reaction conditions but can be removed by a post-polymerization chemical reaction to produce a free -NH- or free -NH2 functional group on the ADAMS repeating unit. In one such form, a preferred cleavable chemical protecting group is benzyl and the deprotection reaction is a hydrogenation reaction.

[0058] In some embodiments, the post-polymerization modification is a protonation reaction, in which one or more amine functional groups within the repeating units of structure (V), (VIII), or a combination thereof are converted to their corresponding ammonium salts by treatment with a protonic acid. The protonic acid can be any acid strong enough to protonate the basic nitrogen atoms in the repeating units of structure (V), (VIII), or a combination thereof and thereby form an ammonium salt of the repeating unit with a counterion corresponding to the conjugate base of the protonic acid. Non-limiting examples of the protonic acid can include hydrochloric acid, hydrobromic acid, hydroiodic acid, various alkyl or aryl sulfonic acids (i.e., methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, n-butanesulfonic acid, tert-butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, etc.), sulfuric acid, phosphoric acid, formic acid, acetic acid, butyric acid, benzoic acid, trifluoromethanesulfonic acid, nitric acid, or a combination thereof, which will produce ammonium salts having chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions, or a combination thereof.

[0059] In some embodiments, the post-polymerization modification is an alkylation reaction, in which one or more amine functional groups within the repeating units of structure (V), (VIII), or a combination thereof are converted to their corresponding ammonium salts by treatment with an alkylating agent. Non-limiting examples of the alkylating agent can include various alkyl halides (i.e., methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, propyl bromide, propyl iodide, benzyl chloride, benzyl bromide, benzyl iodide, etc.), various alkyl sulfonates (i.e., methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, benzyl p-toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, benzyl methanesulfonate, etc.), various alkyl trifluoromethanesulfonates (i.e., methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, etc.), or a combination thereof, which will produce ammonium salts having counterions corresponding to the displaced leaving groups of the alkylating agent. Embodiments involving ADAMS copolymers

[0060] In one form of the invention disclosed herein, a copolymer composition based on amine-derivatized α-methylstyrene (ADAMS) monomers (also referred to as ADAMS copolymers) is polymerized via an anionic polymerization process. In particular, in one form, the ADAMS copolymer comprises the following: (a) one or more amine-derivatized α-methylstyrene (ADAMS) repeating units according to structure (V):

[0061] Wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) attached via an asterisk

[0062] Wherein R'1 and R'2 are independently the same as or different from R1 and R2 but are defined the same; and (b) one or more repeating units according to structure (VI), (VII a ), (VII b ) or combinations thereof

[0063] Wherein: R5 is hydrogen or methyl; R' is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group and / or combinations thereof. Regarding the polymeric repeating unit of the above structure (VII a ), it can be in the cis isomer form, the trans isomer form, or a combination thereof.

[0064] In an advantageous form, k of the above ADAMS copolymer is 2.

[0065] The above copolymers may include one or more ADAMS repeating units according to structure (V), which comprise the reacted forms of the following substances: 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimino)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1] (heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopenta-1,3-dienyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-azepanyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)azepane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoxaline, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof.

[0066] In another form, the above-mentioned ADAMS copolymer can be a copolymer in which one or more of the repeating units according to structure (VI) include a reacted form of styrene, and one or more of the repeating units according to structure (VII a ) and (VII b) The repeating units include the reacted forms of isoprene, 1,3-butadiene, or a combination thereof. Regarding the polymeric repeating units of structure (VII a ), they can be in the form of a cis isomer, a trans isomer, or a combination thereof.

[0067] Alternatively, the ADAMS copolymer can further include alkyl residues from monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiators present at one or more ends of the polymer backbone; or alkyl residues from bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiators near the center of the polymer backbone. For alkyl residues from monofunctional initiators, such alkyl residues can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or a combination thereof. For alkyl residues from such bifunctional initiators, they can include propyl, butyl, pentyl, hexyl, 1,4-diphenylbutyl, or a combination thereof.

[0068] Alternatively, the above ADAMS copolymer can be partially or substantially hydrogenated. Partially hydrogenated means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of the non-aromatic double bonds are saturated. Substantially hydrogenated means that greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% of the non-aromatic bonds are saturated.

[0069] Alternatively, the above ADAMS copolymer can be a copolymer in which the repeating units of one or more of structure (V) are dispersed within at least one polymer block containing repeating units of one or more of structure (VI), (VII a ), (VII b ), or a combination thereof. Alternatively, the above ADAMS copolymer can be a copolymer in which the repeating units of one or more of structure (V) can be partially or substantially alternating with the repeating units of one or more of structure (VI), (VII a ), (VII b ), or a combination thereof, thereby forming one or more repeating units corresponding to structure (IX), (X a ), (X b ), or a combination thereof:

[0070] Partially alternating means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of the repeating units of one or more of structure (V) are alternating with the repeating units of one or more of structure (VI), (VII a ), (VII b) or an alternating repetition unit of a combination thereof. Substantially alternating means that the repetition unit of one or more of the structures (V) is greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% and the repetition unit of one or more of the structures (VI), (VII a ), (VII b ) or an alternating repetition unit of a combination thereof. Regarding the polymeric repeating unit of structure (X a ), it can be in the form of a cis isomer, a trans isomer or a combination thereof.

[0071] In yet another form, the above-mentioned ADAMS copolymer may include one or more polymer blocks, and the block contains one or more repeating units of the structures (VI), (VII a ), (VII b ) or a combination thereof and does not contain one or more repeating units according to structure (V). In such a form, the one or more polymer blocks of the copolymer may form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture or a combination thereof. The distributed polymer architecture means that the repeating units of structure (V) are randomly or uniformly widely distributed in the block of larger non-ADAMS repeating units, which means that there are more than 3, or more than 5, or more than 10, or more than 15, or more than 20 repeating units of non-ADAMS monomers connected between the ADAMS repeating units.

[0072] In yet another form, the above-mentioned ADAMS copolymer may be a copolymer in which, in structure (V), R1, R2, R'1, R'2 or a combination thereof is a cleavable chemical protecting group. A cleavable chemical protecting group refers to a chemical group that is inert under the polymerization reaction conditions but can be removed by a post-polymerization chemical reaction to generate a free -NH- or free -NH2 functional group on the ADAMS repeating unit. In one such form, the at least one cleavable chemical protecting group is benzyl.

[0073] In yet another form, the above-mentioned ADAMS copolymer may further include one or more -OH, -NH- or -NH2 functional groups or a combination thereof at one or more ends of the copolymer backbone.

[0074] In yet another form, the above ADAMS copolymer can be a copolymer in which the amino groups in the repeating units of one or more structures (V) are protonated or alkylated to their corresponding ammonium salts. In such forms, the protonated or alkylated ammonium salts can include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions, or combinations thereof.

[0075] In particular, in one form of the ADAMS copolymer disclosed herein, the ADAMS copolymer comprises the following: (a) a copolymer that is a reaction product of: (a) one or more monomers according to structure (I)

[0076] wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are joined to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) attached via an asterisk

[0077] wherein R'1 and R'2 are independently the same as or different from R1 and R2 but are defined the same; (b) isoprene, 1,3-butadiene, styrene, or combinations thereof; and (c) an alkyllithium, alkylsodium, alkylpotassium initiator, or combinations thereof.

[0078] The above copolymers may include one or more monomers, which include 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimine)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopentadienyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-heptazepinyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)heptazepine, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoline, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof. Embodiments related to ADAMS homopolymers

[0079] In another form of the invention disclosed herein, a polymer is provided that comprises: (a) three or more amine-derivatized α-methylstyrene (ADAMS) repeat units according to structure (V):

[0080] wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) linked via an asterisk

[0081] wherein R'1 and R'2 are independently the same as or different from but defined the same as R1 and R2; and (b) substantially no other repeating units are present. In an advantageous form, k of the above-mentioned ADAMS homopolymer is 2.

[0082] The above-mentioned homopolymer may include three or more ADAMS repeating units according to structure (V), which include the reacted forms of the following substances: 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimine)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1-(heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopenta-1,3-dienyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-azepanyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)azepane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoxaline, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof.

[0083] Alternatively, the ADAMS homopolymer can further include alkyl residues from monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiators present at one or more ends of the polymer backbone; or alkyl residues from bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiators near the center of the polymer backbone. For alkyl residues from monofunctional initiators, such alkyl residues can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or combinations thereof. For alkyl residues from such bifunctional initiators, it can include propyl, butyl, pentyl, hexyl, 1,4-diphenylbutyl, or combinations thereof.

[0084] Alternatively, the above ADAMS homopolymer can be partially or substantially hydrogenated. Partially hydrogenated means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of the non-aromatic double bonds are saturated. Substantially hydrogenated means that greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% of the non-aromatic bonds are saturated.

[0085] In yet another form, the above ADAMS homopolymer can be a homopolymer in which, in structure (V), R1, R2, R'1, R'2, or combinations thereof are cleavable chemical protecting groups. A cleavable chemical protecting group is a chemical group that is inert under polymerization reaction conditions but can be removed by post-polymerization chemical reactions to generate free -NH- or free -NH2 functional groups on the ADAMS repeating unit. In one such form, the at least one cleavable chemical protecting group is benzyl.

[0086] In yet another form, the above ADAMS homopolymer can further include one or more -OH, -NH-, or -NH2 functional groups or combinations thereof at one or more ends of the polymer backbone.

[0087] In still another form, the above ADAMS homopolymer can be a homopolymer in which the amino groups in one or more repeating units of structure (V) are protonated or alkylated to their corresponding ammonium salts. In such forms, the protonated or alkylated ammonium salts can include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions, or combinations thereof. Embodiments relating to ACAMP copolymers

[0088] In yet another form of the invention disclosed herein, there is provided a copolymer comprising: (a) one or more repeating units according to structure (VIII):

[0089] Wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbylene group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; and (b) one or more repeating units according to structure (VI), (VII a ), (VII b ) or combinations thereof

[0090] Wherein: R5 is hydrogen or methyl; R' is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, and / or combinations thereof.

[0091] Regarding the polymeric repeating unit of structure (VII a ), which can be in the cis isomer form, the trans isomer form, or a combination thereof.

[0092] In an advantageous form, k = 2 for the above ACAMP copolymer.

[0093] The above copolymer can include one or more ACAMP repeating units according to structure (VI) (which contains the reacted form of styrene), and one or more repeating units according to structure (VII a ) and (VII b ) (which contains the reacted form of isoprene, 1,3-butadiene, or combinations thereof).

[0094] Alternatively, the ACAMP copolymer can further include alkyl residues from monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiators present at one or more ends of the polymer backbone; or alkyl residues from bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiators near the center of the polymer backbone. For alkyl residues from monofunctional initiators, such alkyl residues can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or combinations thereof. For alkyl residues from such bifunctional initiators, it can include propyl, butyl, pentyl, hexyl, 1,4-diphenylbutyl, or combinations thereof.

[0095] Alternatively, the above ACAMP copolymer may be partially or substantially hydrogenated. Partial hydrogenation means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of the non-aromatic double bonds are saturated. Substantially hydrogenated means that greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% of the non-aromatic bonds are saturated.

[0096] Alternatively, the above ACAMP copolymer may be a copolymer in which the repeating units of one or more structures (VIII) are dispersed within at least one polymer block containing the repeating units of one or more structures (VI), (VII a ), (VII b ), or a combination thereof. Alternatively, the above ACAMP copolymer may be a copolymer in which the repeating units of one or more structures (VIII) may be partially or substantially alternating with the repeating units of one or more structures (VI), (VII a ), (VII b ), or a combination thereof, thereby forming one or more repeating units corresponding to structures (XII), (XII a ), (XII b ), or a combination thereof:

[0097] Partial alternation means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of the repeating units of one or more structures (VIII) alternate with the repeating units of one or more structures (VI), (VII a ), (VII b ), or a combination thereof. Substantially alternating means that greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% of the repeating units of one or more structures (VIII) alternate with the repeating units of one or more structures (VI), (VII a ), (VII b ), or a combination thereof.

[0098] In yet another form, the above ACAMP copolymer may include one or more polymer blocks that contain one or more structures (VI), (VII a ), (VII b) or repeating units of combinations thereof and does not contain one or more repeating units according to structure (VIII). In such forms, one or more polymer blocks of the copolymer can form a distributed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture or combinations thereof. A distributed polymer architecture means that the repeating units of structure (VIII) are randomly or uniformly widely distributed in a block of larger non-ACAMP repeating units, which means that there are more than 3, or more than 5, or more than 10, or more than 15, or more than 20 repeating units of non-ACAMP monomers connected between ACAMP repeating units.

[0099] In yet another form, the above ACAMP copolymer can be a copolymer in which, in structure (VIII), R1, R2, R'1, R'2 or combinations thereof are cleavable chemical protecting groups. A cleavable chemical protecting group is a chemical group that is inert under polymerization reaction conditions but can be removed by a post-polymerization chemical reaction to generate a free -NH- or free -NH2 functional group on the ACAMP repeating unit. In one such form, the at least one cleavable chemical protecting group is benzyl.

[0100] In yet another form, the above ACAMP copolymer can further include one or more -OH, -NH- or -NH2 functional groups or combinations thereof at one or more ends of the copolymer backbone.

[0101] In yet another form, the above ACAMP copolymer can be a copolymer in which the amino groups in one or more repeating units of structure (VIII) are protonated or alkylated to their corresponding ammonium salts. In such forms, the protonated or alkylated ammonium salts can include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions or combinations thereof. Embodiments related to ACAMP homopolymers

[0102] In yet another form of the invention disclosed herein, a polymer is provided that comprises: (a) three or more repeating units according to structure (VIII):

[0103] Wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are joined to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; and (b) substantially no other repeating units are present. In an advantageous form, k of the above ACAMP homopolymer is 2.

[0104] Alternatively, the ACAMP homopolymer may further include alkyl residues from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more ends of the polymer backbone; or alkyl residues from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator near the center of the polymer backbone. For alkyl residues from monofunctional initiators, such alkyl residues may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or combinations thereof. For alkyl residues from such difunctional initiators, they may include propyl, butyl, pentyl, hexyl, 1,4-diphenylbutyl, or combinations thereof.

[0105] Alternatively, the above ACAMP homopolymer may be partially or substantially hydrogenated. Partially hydrogenated means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of the non-aromatic double bonds are saturated. Substantially hydrogenated means that greater than 90%, or greater than 92%, or greater than 94%, or greater than 96%, or greater than 98%, or greater than 99%, or greater than 99.5%, or greater than 99.9% of the non-aromatic bonds are saturated.

[0106] In yet another form, the above ACAMP homopolymer may be a homopolymer wherein in structure (VIII), R1, R2, R'1, R'2, or combinations thereof are cleavable chemical protecting groups. Cleavable chemical protecting groups are chemical groups that are inert under polymerization reaction conditions but can be removed by post-polymerization chemical reactions to generate free -NH- or free -NH2 functional groups on the ACAMP repeating units. In one such form, the at least one cleavable chemical protecting group is benzyl.

[0107] In yet another form, the above ACAMP homopolymer may further include one or more -OH, -NH-, or -NH2 functional groups or combinations thereof at one or more ends of the polymer backbone.

[0108] In yet another form, the above ACAMP homopolymers can be homopolymers in which the amino groups in the repeating units of one or more structures (VIII) are protonated or alkylated to their corresponding ammonium salts. In such forms, the protonated or alkylated ammonium salts can include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions or combinations thereof. Methods of using ADAMS and ACAMPS copolymers and homopolymers

[0109] Novel polymers based on anionic polymerization of functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be used in a range of different applications. In particular, the functional polymers of the present invention based on functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to a phenyl ring or based on functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be polymerized from an addition-polymerizable monomer composition comprising an amine-derived α-methylstyrene (ADAMS) monomer according to the following structure (I) and / or an aminated conjugated (non-aromatic) aliphatic methylated polyene (ACAMP) monomer according to the following structure (II):

[0110] wherein k is an integer from 1 to 3, preferably 2; wherein R1 and R2 are each independently a hydrocarbon group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms such as O, N, S, P, Se and combinations thereof, or wherein R1 and R2 are joined to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 24 carbons, and optionally 1 to 6 additional heteroatoms (such as O, N, S, P, Se and combinations thereof); wherein in structure (I), R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group (such as methyl), a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms (such as O, N, S, P, Se and combinations thereof), or a second amino functional group having structure (III)

[0111] wherein R'1 and R'2 are independently the same as or different from R1 and R2 but are defined the same; and wherein in structure (II), R3 and R4 are each independently hydrogen, methyl or a second amino functional group having structure (III) attached via an asterisk, wherein R'1 and R'2 are independently the same as or different from R1 and R2 but are defined the same, or an alkenyl group having structure (IV) attached via an asterisk

[0112] However, in particular, they do not jointly achieve aromaticity in combination with other (conjugated) olefins in Structure (II), and provided that R3 and R4 are not both alkenyl groups having Structure (IV) and are not both methyl, they can be used in a variety of applications.

[0113] In particular, polymer compositions based on anionic polymerization of functionalized styrene monomers comprising a nitrogen-containing structural moiety not attached to the phenyl ring or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be used in a variety of applications, including but not limited to lithium-ion battery additives, plastic additives, drag reducers, magnetorheological fluids, electrochlorination additives, industrial coating additives, adhesive additives, asphaltene and wax inhibitors, refinery antifoulants, industrial or household surfactants, agrochemical additives, ceramic capacitor or indicator additives, emulsion explosive additives, antibacterial coatings, crude oil transportation and refining additives, and carbon capture additives. Method for manufacturing ADAMS and ACAMPS copolymers and homopolymers

[0114] Novel polymers comprising functionalized styrene monomers comprising a nitrogen-containing structural moiety not attached to the phenyl ring or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be prepared by an anionic polymerization method.

[0115] Anionic polymerization methods in the absence of functionalized styrene monomers comprising a nitrogen-containing structural moiety not attached to the phenyl ring or in the absence of functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety are well known in the art and are described, for example, in U.S. Patent Nos. 5,736,612, 5,773,521, 8,604,136, and 9,809,671, which are hereby incorporated by reference in their entireties. Anionic polymerization methods generally include at least the following steps: (a) polymerizing one or more monomers in an inert hydrocarbon solvent in the presence of an alkyllithium initiator until substantially complete conversion; (b) optionally adding one or more monomers having the same or different compositions in one or more sequential additions, and allowing each sequential addition of the monomers to polymerize until substantially complete conversion; (c) optionally adding a multifunctional coupling agent to couple some or all of the polymers or copolymers; (d) adding a terminator.

[0116] Anionic polymerization is usually initiated with an alkyllithium reagent, most commonly sec-butyllithium, although other mono- and di-functional alkyllithium initiators can also be used [Lintsell et al., Synthesis and characterization of α,ω- and α-functionalized hydrogenated polybutadienes: telechelic and semi-telechelic amine and phosophite terminated polymers, Polymer, Vol. 38, No. 11, 2835 (1997)].

[0117] The mono-functional initiators that can be used can be alkyllithium, alkylsodium or alkylpotassium compounds, usually in the range of C2 to C12. Alkyllithium compounds such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, isopentyllithium, sec-pentyllithium, tert-pentyllithium, hexyllithium or combinations thereof are preferred. Sec-alkyllithium compounds such as sec-butyllithium, sec-pentyllithium or combinations thereof are more preferred. Sec-butyllithium is most preferred. Substituted alkyllithiums such as aralkyllithium compounds, for example benzyllithium, 1-lithioethylbenzene and 1-lithio-3-methylpentylbenzene, can also be used.

[0118] The di-functional initiators that can be used can be alkyldilithium, alkyldisodium or alkyldipotassium compounds, usually in the range of C2 to C12, such as 1,3-propanediyldilithium, 1,4-butanediyldilithium, 1,5-pentanediyldilithium, 1,6-hexanediyldilithium or combinations thereof. Additional di-functional initiators are disclosed in U.S. Patent No. 6,492,469, which is hereby incorporated by reference in its entirety.

[0119] Functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to the phenyl ring or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be copolymerized with isoprene, butadiene, styrene, and combinations thereof. Other non-limiting exemplary comonomers that can be copolymerized with functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to the phenyl ring or with functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety include various alkyl-substituted styrenes (i.e., 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-n-butylstyrene, 4-tert-butylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4-dipropylstyrene, 2-methyl-4-ethylstyrene, 2-methyl-4-propylstyrene, etc.), vinylnaphthalene, vinylpyridine, piperylene, methylpiperylene. In another form, functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to the phenyl ring or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be homopolymerized as isolatable homopolymers or as homopolymer blocks in copolymers.

[0120] Novel polymers comprising functionalized styrenic monomers comprising a nitrogen-containing structural moiety not side-bonded to the phenyl ring or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety can be prepared via an anionic polymerization process, wherein the monomer or combination thereof is solution polymerized in an inert hydrocarbon solvent in the presence of an alkyllithium initiator. The inert hydrocarbon solvent can be any hydrocarbon, typically having 5 to 8 carbons, or a mixture thereof, which does not react with the alkyllithium initiator or the "living" anionic chain ends of the polymer backbone and provides suitable solubility for the resulting polymer. Non-limiting examples of suitable solvents are cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, all of which are relatively non-polar. Other suitable solvents are known to those skilled in the art and can be selected to effectuate the polymerization efficiently under the given process conditions, where the polymerization temperature is one of the main factors to be considered.

[0121] The polymerization is preferably carried out in the presence of a polar additive that reduces the association between ions at the reactive "living" anionic chain ends of the polymer backbone and thereby promotes the polymerization. Non-limiting examples of polar additives can include various ethers (i.e., dimethyl ether, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, anisole, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxybenzene, 1-methoxy-2-(2-methoxyethoxy)ethane, etc.), various amines (i.e., trimethylamine, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, etc.), or combinations thereof. Among the above polar additives, ethers are preferred.

[0122] The polymerization reaction conditions for preparing novel polymers comprising a nitrogen-containing structural moiety that is not side-bonded to a phenyl ring, or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety, are generally similar to those commonly used for anionic polymerization. Depending on the monomer and the reaction solvent, the polymerization reaction can be carried out at a temperature of about -80 °C to about 200 °C, or about -40 °C to about 150 °C, preferably about 0 °C to about 100 °C, more preferably about 20 °C to about 90 °C. In some instances, the polymerization of the functionalized monomer and the copolymerization with other monomers and blocks can be carried out at room temperature, or at 15 to 70 °C, or 20 to 60 °C, or 25 to 50 °C, or a combination of these aforementioned temperatures, or at individual temperatures within such ranges.

[0123] The polymerization reaction is carried out in a dry inert atmosphere, preferably nitrogen, and can also be carried out at a pressure of about 0 bar to about 10 bar.

[0124] After the polymerization reaction is completed, a terminator can be added to stop the reaction and quench the reactive "living" anionic chain ends of the polymer backbone. The polymerization terminator can be various primary or secondary alcohols or epoxide terminators. Non-limiting examples of various primary or secondary alcohols include methanol, ethanol, isopropyl alcohol, 2-ethyl-1-hexanol, etc., or combinations thereof. Non-limiting examples of epoxide terminators include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, etc., or combinations thereof. Among the polymerization terminators, methanol or isopropyl alcohol is preferred, unless one or more -OH functional groups are required at one or more ends of the polymer chain, in which case ethylene oxide or propylene oxide is preferred.

[0125] Novel polymers comprising a nitrogen-containing structural moiety that is not side-bonded to a phenyl ring, or functionalized conjugated (non-aromatic) monomers comprising a nitrogen-containing structural moiety, can optionally be separated or purified according to various general polymer separation or purification techniques known in the art. For example, the polymerization reaction solution can be poured into a poor solvent for the polymer (such as methanol) to solidify the polymer, or the polymerization reaction solution can be poured into hot water together with steam to remove the solvent by azeotropic distillation (stripping) and dry the resulting product.

[0126] Due to the difficulty in preparing and polymerizing these monomers, the applicant has studied other potential structures of the functional monomers, which are simpler to manufacture and polymerize. These functional monomer compositions containing aromatic and / or conjugated (non-aromatic) structures (each of which contains at least one amine nitrogen) are described in the related U.S. Provisional Application Serial No. 63 / 483,365, jointly owned and filed on February 6, 2023, the content of which is hereby incorporated by reference in its entirety.

[0127] To the applicant's knowledge, the monomers of the present invention disclosed in U.S. Provisional Application Serial No. 63 / 483,365 have not been polymerized previously. Additional Embodiments / EP Projects

[0128] Additionally or alternatively, the present disclosure may include one or more of the following embodiments.

[0129] 1. A copolymer comprising: (a) one or more amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (V):

[0130] wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbylene group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are joined to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having Structure (III) attached via an asterisk

[0131] wherein R’1 and R’2 are independently the same as or different from but defined the same as R1 and R2; and (b) one or more repeat units according to Structure (VI), (VII a )、(VII b ) or combinations thereof

[0132] wherein: R5 is hydrogen or methyl; R’ is hydrogen, a phenyl ring co-joined to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring attached at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, and / or combinations thereof.

[0133] 2. The copolymer of item 1, wherein k = 2.

[0134] 3. A copolymer of item 1 or 2, wherein said one or more ADAMS repeating units according to structure (V) comprise the reacted forms of the following substances: 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimine)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1-(heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopenta-1,3-dien-1-yl-piperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-heptazacycloheptyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)heptazacycloheptane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoxaline, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof.

[0135] 4. The copolymer of items 1-3, wherein said one or more repeating units according to structure (VI) comprise a reacted form of styrene, and said one or more according to structure (VII a ) and (VII b) The repeating units include the reacted forms of isoprene, 1,3 - butadiene, or combinations thereof.

[0136] 5. The copolymer of Items 1 - 4, further comprising: an alkyl residue from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more ends of the polymer backbone; or an alkyl residue from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator near the center of the polymer backbone.

[0137] 6. The copolymer of Item 5, wherein the alkyl residue from the monofunctional initiator includes methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, sec - butyl, tert - butyl, n - pentyl, isopentyl, sec - pentyl, tert - pentyl, hexyl, or combinations thereof, or wherein the alkyl residue from the difunctional initiator includes propyl, butyl, pentyl, hexyl, 1,4 - diphenylbutyl, or combinations thereof.

[0138] 7. The copolymer of Items 1 - 6, wherein the copolymer is partially or substantially hydrogenated.

[0139] 8. The copolymer of Items 1 - 7, wherein the repeating units of one or more structures (V) are dispersed within at least one polymer block that contains the repeating units of one or more structures (VI), (VII a )), (VII b )), or combinations thereof.

[0140] 9. The copolymer of Item 8, wherein the repeating units of one or more structures (V) may be partially or substantially alternating with the repeating units of one or more structures (VI), (VII a )), (VII b )), or combinations thereof, thereby forming one or more repeating units corresponding to structures (IX), (X a )), (X b )), or combinations thereof:

[0141] 10. The copolymer of Item 9, wherein the copolymer comprises one or more polymer blocks that contain the repeating units of one or more structures (VI), (VII a )), (VII b )), or combinations thereof and do not contain the repeating units of one or more structures according to (V).

[0142] 11. The copolymer of Item 10, wherein the one or more polymer blocks of the copolymer form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof.

[0143] 12. A copolymer of Items 1-11, wherein in Structure (V), R1, R2, R'1, R'2, or a combination thereof is a cleavable chemical protecting group.

[0144] 13. The copolymer of Item 12, wherein at least one cleavable chemical protecting group is benzyl.

[0145] 14. The copolymer of Items 1-13, wherein the copolymer further comprises one or more -OH, -NH-, or -NH2 functional groups or a combination thereof at one or more termini of the copolymer backbone.

[0146] 15. The copolymer of Items 1-14, wherein the amino groups in the repeating units of one or more Structures (V) are protonated or alkylated to their corresponding ammonium salts.

[0147] 16. The copolymer of Item 15, wherein the protonated or alkylated ammonium salt comprises chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions, or a combination thereof.

[0148] 17. A polymer comprising: (a) three or more amine-derivatized α-methylstyrene (ADAMS) repeating units according to Structure (V):

[0149] wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring that is linked to a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbon group, a C1-C6 hydrocarbon group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having Structure (III) linked via an asterisk

[0150] wherein R'1 and R'2 are independently the same as or different from R1 and R2 but are defined the same; and (b) substantially no other repeating units.

[0151] 18. The polymer of Item 17, wherein k = 2.

[0152] 19. A polymer according to item 17 or 18, wherein said three or more ADAMS repeating units according to structure (V) comprise the reacted forms of the following substances: 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-azepanyl)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1-(heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopenta-1,3-dien-1-ylpiperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-azepanyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)azepane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoxaline, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof.

[0153] The polymer of items 17 - 19, further comprising: an alkyl residue from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at the end of the polymer chain; or an alkyl residue from a bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator near the center of the polymer chain.

[0154] 21. The polymer of item 20, wherein the alkyl residue from the monofunctional initiator comprises methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or a combination thereof, or wherein the alkyl residue from the bifunctional initiator comprises propyl, butyl, pentyl, hexyl, 1,4-diphenylbutyl, or a combination thereof.

[0155] 22. The polymer of items 17 - 21, wherein in structure (V), R1, R2, R’1, R’2, or a combination thereof is a cleavable chemical protecting group.

[0156] 23. The polymer of item 22, wherein at least one cleavable chemical protecting group is benzyl.

[0157] 24. The polymer of items 17 - 23, further comprising one or more -OH, -NH-, or -NH2 functional groups or a combination thereof at one or more ends of the polymer backbone.

[0158] 25. The polymer of items 17 - 24, wherein the amino group in one or more repeating units of structure (V) is protonated or alkylated to their corresponding ammonium salts.

[0159] 26. The polymer of item 25, wherein the protonated or alkylated ammonium salt comprises chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions, or a combination thereof.

[0160] 27. A copolymer comprising: (a) one or more repeating units according to structure (VIII):

[0161] wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbyl group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are connected to form a structural moiety containing at least one 5 - to 12 - membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; and (b) one or more repeating units according to structure (VI), (VII a )、(VII b ) or a combination thereof

[0162] wherein: R5 is hydrogen or methyl; R’ is hydrogen, a phenyl ring co - connected to the shown phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring connected at a single carbon of the shown phenyl ring, a C1 - C4 hydrocarbon group, and / or a combination thereof.

[0163] 28. The copolymer of item 27, wherein k = 2.

[0164] 29. The copolymer of item 27 or 28, wherein said one or more repeating units according to structure (VI) comprise a reacted form of styrene, and said one or more repeating units according to structure (VII a ) and (VII b ) comprise a reacted form of isoprene, 1,3-butadiene, or a combination thereof.

[0165] 30. The copolymer of items 27 - 29, further comprising: an alkyl residue from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more ends of the polymer backbone; or an alkyl residue from a bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator near the center of the polymer backbone.

[0166] 31. The copolymer of item 30, wherein the alkyl residue from the monofunctional initiator comprises methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or a combination thereof, or wherein the alkyl residue from the bifunctional initiator comprises propyl, butyl, pentyl, hexyl, 1,4-diphenylbutyl, or a combination thereof.

[0167] 32. The copolymer of items 27 - 31, wherein the copolymer is partially or substantially hydrogenated.

[0168] 33. The copolymer of items 27 - 32, wherein said one or more repeating units of structure (VIII) are dispersed within at least one polymer block that comprises one or more repeating units of structure (VI), (VII a ), (VII b ) or a combination thereof.

[0169] 34. The copolymer of item 33, wherein said one or more repeating units of structure (VIII) may be partially or substantially alternating with said one or more repeating units of structure (VI), (VII a ), (VII b ) or a combination thereof, thereby forming one or more repeating units corresponding to structure (XII), (XII a ), (XII b ) or a combination thereof:

[0170] 35. The copolymer of item 34, wherein the copolymer comprises one or more polymer blocks that comprise one or more repeating units of structure (VI), (VII a ), (VIIb ) or repeating units of combinations thereof and not containing one or more repeating units according to structure (VIII).

[0171] 36. The copolymer of item 35, wherein one or more polymer blocks of the copolymer form a distributed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture or combinations thereof.

[0172] 37. The copolymer of items 27 - 36, wherein in structure (VIII), R1, R2, R'1, R'2 or combinations thereof are cleavable chemical protecting groups.

[0173] 38. The copolymer of item 37, wherein at least one cleavable chemical protecting group is benzyl.

[0174] 39. The copolymer of items 27 - 38, further comprising one or more -OH, -NH- or -NH2 functional groups or combinations thereof at one or more ends of the copolymer backbone.

[0175] 40. The copolymer of items 27 - 39, wherein the amino groups in the one or more repeating units of structure (VIII) are protonated or alkylated to their corresponding ammonium salts.

[0176] 41. The copolymer of item 40, wherein the protonated or alkylated ammonium salts comprise chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions or combinations thereof.

[0177] 42. A polymer comprising: (a) three or more repeating units according to structure (VIII):

[0178] wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbon group or a hydrocarbonaceous group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se and combinations thereof, or wherein R1 and R2 are joined to form a structural moiety containing at least one 5 - to 12 - membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se and combinations thereof; and (b) substantially no other repeating units.

[0179] 43. The polymer of item 42, wherein k = 2.

[0180] 44. The polymer of item 42 or 43, further comprising: an alkyl residue from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more ends of the polymer backbone; or an alkyl residue from a bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator near the center of the polymer backbone.

[0181] 45. The polymer of item 44, wherein the alkyl residue from the monofunctional initiator comprises methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, or a combination thereof, or wherein the alkyl residue from the bifunctional initiator comprises propyl, butyl, pentyl, hexyl, 1,4-diphenylbutyl, or a combination thereof.

[0182] 46. The polymer of items 42-45, wherein the polymer is partially or substantially hydrogenated.

[0183] 47. The polymer of items 42-46, wherein in structure (VIII), R1, R2, R'1, R'2, or a combination thereof is a cleavable chemical protecting group.

[0184] 48. The polymer of item 47, wherein at least one cleavable chemical protecting group is benzyl.

[0185] 49. The polymer of items 42-48, further comprising one or more -OH, -NH-, or -NH2 functional groups or a combination thereof at one or more ends of the polymer backbone.

[0186] 50. The polymer of items 42-49, wherein the amino group in the repeating unit of the one or more structures (VIII) is protonated or alkylated to their corresponding ammonium salts.

[0187] 51. The polymer of item 50, wherein the protonated or alkylated ammonium salt comprises chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, trifluoromethanesulfonate, nitrate counterions, or a combination thereof.

[0188] 52. A copolymer comprising the reaction product of: (a) one or more monomers according to structure (I)

[0189] Wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) linked via an asterisk

[0190] wherein R'1 and R'2 are independently the same as or different from but defined in the same manner as R1 and R2; (b) isoprene, 1,3-butadiene, styrene, or combinations thereof; and (c) an alkyllithium, alkylsodium, alkylpotassium initiator, or combinations thereof.

[0191] 53. The copolymer of item 52, wherein the one or more monomers comprise 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimino)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2-(Octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopenta-1,3-dienyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-heptazolinyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)heptazoline, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoxaline, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof.

[0192] 54. A method of using a copolymer, comprising: providing a copolymer according to items 1-53, or an additive mixture comprising a copolymer according to items 1-53, and using the copolymer or the additive mixture comprising the copolymer in an application selected from: lithium-ion battery additives, plastic additives, drag reducers, magnetorheological fluids, electrochlorination additives, industrial coating additives, adhesive additives, asphaltene and wax inhibitors, refinery antifoulants, industrial or household surfactants, agrochemical additives, ceramic capacitor or indicator additives, emulsion explosive additives, antibacterial coatings, crude oil transportation and refining additives, and carbon capture additives.

[0193] The present invention will now be described only by way of non-limiting examples. Examples

[0194] Unless otherwise stated, all reactions were carried out in a glass reactor of appropriate size equipped with magnetic stirring and were run inside a VAC OMNI-LAM inert atmosphere (e.g., N2) glove box. The atmosphere in the glove box was maintained below 10 ppm oxygen and 0.2 ppm moisture.

[0195] All monomers used in anionic polymerization were purified by methods familiar to those of ordinary skill in the art to remove added stabilizers or adventitious moisture; by distilling the monomers, filtering the monomers through basic alumina, or a combination of both.

[0196] During the polymerization reactions described below, a small amount of the initiator solution was slowly added dropwise to the reaction before the major portion of the initiator solution. This “extra” initiator was immediately consumed by residual stabilizers or adventitious moisture in the solvent or reactants, and the exact volume varied based on the efficacy of the above monomer purification. The ADAMS-derived “active” anion responsible for the polymerization was a strong orange-red color. Once enough initiator was added such that a light yellow color persisted in the reaction mixture (indicating the very slight presence of the “active” anion), the reaction was judged to be free of inhibitors / moisture and the target volume of the initiator solution could be added.

[0197] Samples of each polymer were purified for analysis by polymer separation techniques familiar to those skilled in the art, typically by slowly pouring a solution of the crude polymer into a poor solvent for the polymer such as methanol to solidify the polymer, followed by thorough drying under vacuum.

[0198] Gel permeation chromatography (GPC) samples were prepared on a 3.0 - 5.0 ml scale by dissolving samples of the crude reaction mixture or the isolated polymer product in stabilized tetrahydrofuran (THF) targeting a final sample concentration of 1.0 - 5.0 g polymer / ml THF. Before analysis, the samples were filtered through a PALL ACRODISC 0.45 μm PTFE filter.

[0199] The GPC was run on an AGILENT 1260 INFINITY II system equipped with an AGILENT 1260 refractive index detector and three AGILENT PLGEL 10μm Mixed-B chromatographic columns. The columns were maintained at 35 °C by a GPC column heater. Samples were run with a 50 μL injection volume, using stabilized THF (1.0 ml / min, isocratic solvent) as the mobile phase, and a 45.0 min experimental run time.

[0200] GPC data analysis was performed using AGILENT CIRUS GPC / SEC software, version 3.4.2.

[0201] The GPC was calibrated using a WATERS ACQUITY APC polystyrene (PS) test kit standard with Mn = 266 - 1,760,000 Da. Unless otherwise stated, all polymer Mn, Mw, and Mz values are reported relative to the PS standard.

[0202] To prepare the NMR sample, ~50 - 100 mg of the crude reaction mixture was added to a vial, followed by 400 μL of benzene-d6. The vial was sealed and mixed thoroughly until the sample was completely dissolved, and then transferred to an NMR tube. 1 1H NMR spectra (16 scans) were recorded on a Bruker AVANCE TM -300 instrument at 300 MHz. Samples were prepared in benzene-d6, and the chemical shift (δ) was expressed in parts per million (ppm). Referring to TMS contained in the NMR solvent, or preferably referring to the benzene-d6 solvent peak, the solvent singlet was calibrated to 7.16 ppm. Example 1

[0203] Anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added to a 50 ml reactor, followed by 1-(pyrrolidin-1-yl)-3-phenylbut-3-ene (2.0 ml, 9.7 mmol) and isoprene (4.0 ml, 39.9 mmol). The solution was stirred for ~1 minute, and then a 1.4 M solution of sec-butyllithium (0.20 ml, 0.28 mmol) was added in one portion to obtain a bright orange solution.

[0204] The reaction was allowed to stir at room temperature, and ~0.1 ml aliquots of the reaction mixture were taken for 1 1H NMR to monitor the reaction periodically. After ~6 hours, the reaction was judged to be substantially complete, and isopropanol (0.2 ml, 2.6 mmol) was added to quench the reaction. Example 2

[0205] To a 50 ml reactor was added anhydrous cyclohexane (15.0 ml) and anhydrous unstabilized THF (0.5 ml), followed by 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene (1.5 ml, 6.4 mmol) and a 15 wt% solution of 1,3-butadiene in hexane (10.0 ml, 18.9 mmol). The solution was stirred for ~1 minute, then a solution of 1.4 M sec-butyllithium (0.60 ml, 0.84 mmol) was added in one portion to obtain a bright orange solution.

[0206] The reaction was stirred at room temperature and ~0.1 ml aliquots of the reaction mixture were taken for 1 1H NMR to monitor the reaction periodically. After ~2 hours, the reaction was judged to be substantially complete, and propylene oxide (0.065 ml, 0.93 mmol) was added to the reaction, which gradually turned colorless. The reaction was stirred at ambient temperature for 1 hour, after which 1 1H NMR indicated that the reaction was complete. Example 3

[0207] To a 50 ml reactor was added anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml), followed by 1-(dibenzylamino)-3-phenylbut-3-ene (1.0 ml, 4.1 mmol) and isoprene (0.5 ml, 5.0 mmol). The solution was stirred for ~1 minute, then a 1.4 M sec-butyllithium solution (0.40 ml, 0.56 mmol) was added in one portion to obtain a bright orange solution.

[0208] The reaction was stirred at room temperature and the reaction was monitored periodically by 1 1H NMR (as above), and additional amounts of isoprene (0.5 ml each time, 5.0 mmol each time) were added every 30 min until 3.5 hours had passed (a total of 4.0 ml of isoprene). Once the addition was complete, the reaction was stirred at room temperature for an additional 1.5 hours, then the reaction was judged to be substantially complete by 1 1H NMR and isopropyl alcohol (0.4 ml, 5.2 mmol) was added to quench the reaction. Example 4

[0209] To a 50 ml reactor was added anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml), followed by styrene (3.0 ml, 26.2 mmol). The solution was stirred for ~1 minute, then a 1.4 M sec-butyllithium solution (0.40 ml, 0.56 mmol) was added in one portion to obtain a bright orange solution.

[0210] The reaction was stirred at room temperature and aliquots of ~0.1 ml of the reaction mixture were taken for 1 1H NMR to monitor the reaction periodically. After ~1 h, the reaction was judged to be substantially complete and then 1-(1,2,3,4-tetrahydro-2-isoquinolinyl)-3-phenylbut-3-ene (1.0 ml, 4.1 mmol) and styrene (4.0 ml, 34.99 mmol) were added. The reaction was allowed to mix at room temperature for a further ~3 h and once 1 1H NMR showed that the monomers were substantially completely consumed, an additional amount of 1-(1,2,3,4-tetrahydro-2-isoquinolinyl)-3-phenylbut-3-ene (1.0 ml, 4.1 mmol) and styrene (4.0 ml, 34.99 mmol) was added. The reaction was mixed for a further ~3 h and then 1 1H NMR again showed that the monomers were substantially completely consumed and isopropyl alcohol (0.4 ml, 5.2 mmol) was added to quench the reaction. Example 5

[0211] Anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added to a 50 ml reactor, followed by 1-(N-thiomorpholinyl)-3-phenylbut-3-ene (1.0 ml, 4.2 mmol). The solution was stirred for ~1 min and then 1.4 M sec-butyllithium solution was added dropwise until a very pale orange color from the lithium anion persisted (~0.012 ml), and then styrene (0.50 ml, 4.4 mmol) and a subsequent second amount of 1.4 M sec-butyllithium (0.10 ml, 0.14 mmol) were added all at once to give a bright orange solution.

[0212] The reaction was stirred at room temperature and monitored periodically by 1 1H NMR (as above), and additional amounts of styrene (0.5 ml each time, 4.4 mmol each time) (a total of 3.0 ml of isoprene over 3 h, a total of 26.2 mmol) were added according to the time limits in Table 1 below. Once the addition was complete, the reaction was stirred at room temperature for a further 1 h and then 1 1H NMR showed that the remaining monomers were substantially completely consumed.

[0213] Isoprene (4.0 ml, 39.9 mmol) was added to the reaction and the mixture was further mixed at room temperature for 2 h and then 11H NMR showed that isoprene was almost completely consumed. Additional amounts of styrene (0.5 ml each time, 4.4 mmol each time) were added according to the time limits in Table 1 below (a total of 3.0 ml of additional isoprene over 3 hours, a total of 26.2 mmol). Once the addition was complete, the reaction was stirred overnight at room temperature and quenched with isopropanol (0.10 ml, 1.31 mmol).

[0214] Table 1 Example 6

[0215] Anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added to a 50 ml reactor, followed by 1-(N-morpholino)-3-phenylbut-3-ene (3.0 ml, 13.5 mmol) and isoprene (3.0 ml, 30.0 mmol). The solution was stirred for ~1 min, then 1.4 M sec-butyllithium solution was added dropwise until a very pale orange color from the lithium anion persisted (~0.1 ml), and then a second amount of 1.4 M sec-butyllithium (0.10 ml, 0.14 mmol) was added in one portion to give a bright orange solution.

[0216] The reaction was stirred at room temperature and ~0.1 ml aliquots of the reaction mixture were withdrawn for 1 1H NMR to monitor the reaction periodically. After ~6 hours, the reaction was judged to be essentially complete, and then divinylbenzene [technical grade, 80%] (0.10 ml, 0.56 mmol) was added to the reaction to give a dark red solution. The reaction was allowed to mix for another 2 hours at room temperature, and then 1 1H NMR detected no residual divinylbenzene. Isopropanol (0.1 ml, 1.31 mmol) was added to quench the reaction. Example 7

[0217] Anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added to a 50 ml reactor, followed by isoprene (3.0 ml, 30.0 mmol). The solution was stirred for ~1 minute, and then 1.4 M sec-butyllithium solution (0.050 ml, 0.070 mmol) was added in one portion to give a bright orange solution.

[0218] The reaction was stirred at room temperature and ~0.1 ml aliquots of the reaction mixture were withdrawn for 1 1H NMR to monitor the reaction periodically. After ~1 hour, 11H NMR showed that isoprene was almost completely consumed. At this time, 1-benzylmethylamino-3-phenylbut-3-ene (1.0 ml, 3.9 mmol) and an additional amount of isoprene (2.0 ml, 20.0 mmol) were added to the reaction. The reaction was allowed to mix for an additional 4 hours at room temperature, after which 1 1H NMR showed that the remaining monomer was almost completely consumed. Divinylbenzene [technical grade, 55%] (0.055 ml, 0.21 mmol) was added to the reaction to give a dark red solution. The reaction was allowed to mix for an additional 2 hours at room temperature, and then 1 1H NMR detected no residual divinylbenzene. Isopropyl alcohol (0.050 ml, 0.65 mmol) was added to quench the reaction. Example 8

[0219] 200 ml of anhydrous cyclohexane and 4.0 ml of anhydrous tetrahydrofuran were added to a 250 ml dry glass jar equipped with magnetic stirring. Then, 1.0 ml of 1-(N-morpholino)-3-phenylbut-3-ene (4.5 mmol) and 36.0 ml of isoprene (359.5 mmol) were added. The solution was stirred for ~1 minute, and a 0.1 ml aliquot of the solution was taken for 1 1H NMR. A small amount (usually 0.05 to 0.20 ml) of a 1.12 M solution of sec-butyllithium in cyclohexane was slowly added dropwise to the reaction mixture until the solution turned a persistent light yellow color, and then an additional 0.45 ml of the 1.12 M sec-butyllithium solution (0.50 mmol) was added all at once.

[0220] The reaction was stirred at room temperature, and the reaction was monitored periodically by taking ~0.1 ml aliquots of the reaction mixture for 1 1H NMR. When the reaction was judged to be substantially complete by 1 1H NMR, 0.45 ml of isopropyl alcohol (5.9 mmol) was added to quench the reaction. Example 9

[0221] The reaction was carried out according to the procedure of Polymer Example 8, except that 2.0 ml of 1-(N-morpholino)-3-phenylbut-3-ene (9.0 mmol) and 35.0 ml of isoprene (349.5 mmol) were added instead. Example 10

[0222] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.0 ml of 1-(N-morpholino)-3-phenylbut-3-ene (18.0 mmol) and 32.0 ml of isoprene (319.5 mmol) were added instead. Example 11

[0223] The reaction was carried out according to the procedure of Polymer Example 8, except that 1.0 ml of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene (4.3 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene. Example 12

[0224] The reaction was carried out according to the procedure of Polymer Example 8, except that 2.0 ml of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene (8.6 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 34.0 ml of isoprene (339.5 mmol) was added instead. Example 13

[0225] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.0 ml of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene (17.1 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 32.0 ml of isoprene (319.5 mmol) was added instead. Example 14

[0226] The reaction was carried out according to the procedure of Polymer Example 8, except that 1.0 ml of 1-benzylmethylamino-3-phenylbut-3-ene (3.9 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 35.0 ml of isoprene (349.5 mmol) was added instead. Example 15

[0227] The reaction was carried out according to the procedure of Polymer Example 8, except that 2.0 ml of 1-benzylmethylamino-3-phenylbut-3-ene (7.8 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 35.0 ml of isoprene (349.5 mmol) was added instead. Example 16

[0228] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.2 ml of 1-benzylmethylamino-3-phenylbut-3-ene (16.4 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 30.0 ml of isoprene (299.6 mmol) was added instead. Example 17

[0229] The reaction was carried out according to the procedure of Polymer Example 8, except that 1.0 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (4.6 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 36.0 ml of isoprene (359.5 mmol) was added instead. Example 18

[0230] The reaction was carried out according to the procedure of Polymer Example 8, except that 2.0 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (9.1 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 34.0 ml of isoprene (339.5 mmol) was added instead. Example 19

[0231] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.0 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (18.2 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 32.0 ml of isoprene (319.5 mmol) was added instead. Example 20

[0232] The reaction was carried out according to the procedure of Polymer Example 8, except that 2.0 ml of 1-(N-morpholinyl)-3-phenylbut-3-ene (9.0 mmol), 16.0 ml of isoprene (319.5 mmol) and 2.4 ml of 1.12 M sec-butyllithium (2.7 mmol) were added instead. The reaction was quenched with 2.4 ml of isopropanol (31.4 mmol). Example 21

[0233] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.0 ml of 1-(N-morpholinyl)-3-phenylbut-3-ene (18.0 mmol), 32.0 ml of isoprene (319.5 mmol) and 0.15 ml of 1.12 M sec-butyllithium (0.17 mmol) were added instead. The reaction was quenched with 2.4 ml of isopropanol (2.0 mmol). Example 22

[0234] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.0 ml of 1-(N-morpholinyl)-3-phenylbut-3-ene (18.0 mmol), 32.0 ml of isoprene (319.5 mmol) and 0.05 ml of 1.12 M sec-butyllithium (0.06 mmol) were added instead. The reaction was quenched with 2.4 ml of isopropanol (0.7 mmol). Example 23

[0235] The reaction was carried out according to the procedure of Polymer Example 8, except that 8.0 ml of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene (34.2 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 26.0 ml of isoprene (259.6 mmol) was added instead. Example 24

[0236] The reaction was carried out according to the procedure of Polymer Example 8, except that 12.0 ml of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene (51.3 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 20.0 ml of isoprene (199.7 mmol) was added instead. Example 25

[0237] The reaction was carried out according to the procedure of Polymer Example 8, except that 16.0 ml of 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene (68.4 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene; 14.0 ml of isoprene (139.8 mmol) and 0.56 ml of 1.12 M sec-butyllithium (0.62 mmol) were used instead. Example 26

[0238] The reaction was carried out according to the procedure of Polymer Example 8, except that 2.0 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (9.1 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 16.0 ml of isoprene (159.8 mmol) was added instead. Once the initial reaction was determined to be substantially complete by 1 1H NMR, an additional portion of 2.0 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (9.1 mmol) and 16.0 ml of isoprene (159.8 mmol) was added, and the reaction was continued until the second stage of the reaction was determined to be complete by 1 1H NMR. Example 27

[0239] The reaction was carried out according to the procedure of Polymer Example 8, except that 1.4 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (6.4 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 11.0 ml of isoprene (109.8 mmol) was added instead. Once the reaction was determined to be substantially complete by1 The initial reaction was judged to be basically completed by \(^1H\) NMR. 1.4 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (6.4 mmol) and 11.0 ml of isoprene (109.8 mmol) of the additional part were added, and the reaction continued. Once by 1 \(^1H\) NMR judged that the second-stage reaction was basically completed, and 1.4 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (6.4 mmol) and 11.0 ml of isoprene (109.8 mmol) of the additional part were further added, and the reaction continued until by 1 \(^1H\) NMR judged that the third stage of the reaction was completed. Example 28

[0240] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.0 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (18.2 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 32.0 ml of isoprene (319.5 mmol) was added instead. Once by 1 \(^1H\) NMR judged that the initial reaction was basically completed, 0.45 ml of technical grade divinylbenzene (55%, 1.7 mmol) was added, the reaction was continued for another 1 hour, and then it was quenched. Example 29

[0241] 100 ml of anhydrous cyclohexane and 4.0 ml of anhydrous tetrahydrofuran were added to a 250 ml dry glass jar equipped with magnetic stirring. Then 2.1 ml of 1-benzylmethylamino-3-phenylbut-3-ene (8.2 mmol) and 100 ml of a 15% hexane solution of 1,3-butadiene (189.1 mmol) were added. The solution was stirred for about 1 minute, and a 0.1 ml aliquot of the solution was taken for 1 \(^1H\) NMR. A small amount (usually 0.5 to 1.5 ml) of 1.12 M sec-butyllithium cyclohexane solution was slowly added dropwise to the reaction mixture until the solution turned into a persistent light yellow color, and then an additional 1.0 ml of 1.12 M sec-butyllithium solution (1.1 mmol) was added in one portion.

[0242] The reaction was allowed to stir at room temperature, and the reaction was monitored regularly by taking about 0.1 ml aliquots of the reaction mixture for 1 \(^1H\) NMR. When the reaction was judged to be basically completed by 1 \(^1H\) NMR, 1.0 ml of isopropanol (13.1 mmol) was added to quench the reaction. Example 30

[0243] The reaction was carried out according to the procedure of Polymer Example 8, except that 4.0 ml of 1-benzylmethylamino-3-phenylbut-3-ene (156.6 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, 26.0 ml of styrene (227.1 mmol) was used instead of isoprene, and 1.0 ml of 1.12 M sec-butyllithium (1.1 mmol) was added instead. Example 31

[0244] The reaction was carried out according to the procedure of Example 8, except that 4.0 ml of 1-benzylmethylamino-3-phenylbut-3-ene (15.6 mmol) was used instead of 1-(N-morpholinyl)-3-phenylbut-3-ene, and 18.0 ml of isoprene (179.7 mmol) was added instead. Once the initial reaction was judged to be substantially complete by 1 1H NMR, 10.0 ml of styrene (87.3 mmol) of the additional portion was added, and the reaction was continued until the second stage of the reaction was judged to be complete by 1 1H NMR. Example 32

[0245] In a 250 ml round-bottom flask equipped with a magnetic stirrer and a water-cooled condenser, under a N2 atmosphere, 6.0 g of the isolated polymer from Example 17 (roughly 3.9 wt% ADAMS repeat units) was dissolved in 80 ml of stabilized tetrahydrofuran. 0.14 ml of benzyl bromide (1.2 mmol, 1.1 mol equivalent vs. ADAMS repeat units) was added to this solution, and then the solution was heated to 65 °C for 3 hours. The reaction was allowed to cool, and the polymer solution was used directly in the emulsification step without further purification. A small aliquot of the solution was evaporated under reduced pressure for GPC analysis. Example 33

[0246] Samples were prepared according to the procedure in Example 38, except that the isolated polymer from Example 18 (roughly 7.8 wt% ADAMS repeat units) was used instead of the isolated polymer from Example 17, and 0.29 ml of benzyl bromide (2.4 mmol, 1.1 mol equivalent vs. ADAMS repeat units) was added instead. Example 34

[0247] Samples were prepared according to the procedure in Example 38, except that the isolated polymer from Example 19 (roughly 15.3 wt% ADAMS repeat units) was used instead of the isolated polymer from Example 17, and 0.56 ml of benzyl bromide (4.7 mmol, 1.1 mol equivalent vs. ADAMS repeat units) was added instead. Example 35

[0248] At ambient temperature, anhydrous THF (20 ml), a sample of poly(isoprene-co-1-(pyrrolidin-1-yl)-3-phenylbut-3-ene) from Example 1 (0.467 g), and benzyl bromide (0.13 g, 0.77 mmol) were added to a reactor equipped with a water-cooled reflux condenser. The mixture was heated to reflux (∼66 °C) for 3 h. The mixture was cooled to ambient temperature and the solvent was removed under reduced pressure to give a dry solid powder that was poorly soluble in THF at ambient temperature (and thus could not be analyzed under standard GPC conditions). 1H NMR analysis in methanol-d4 showed the presence of a polymer with a sharp peak at ∼3.74 ppm (presumably corresponding to the benzyl CH2 protons adjacent to the quaternary ammonium salt). 1 1H NMR analysis showed an 85% reduction in the olefinic C-H bonds between 4.0 - 6.0 ppm, compared to the morpholino pattern CH2-O peak at ∼3.8 ppm. Example 36

[0249] In a pressure reactor, 1.1 g of the isolated polymer from Example 8 was dissolved in 100 ml of cyclohexane, followed by the addition of 0.2 g of tris(triphenylphosphine)rhodium(I) chloride. The reactor was then sealed and first purged with N2 gas, followed by hydrogen. The reaction solution was heated to 140 °C at 425 psi hydrogen pressure for 4 h, then cooled and the reactor was opened. The residual catalyst was removed by filtering the product solution through a charcoal pad (NORIT AS5) and CELITE 545, and then the polymer solution filtrate was concentrated under reduced pressure. 1 1H NMR analysis showed an 85% reduction in the olefinic C-H bonds between 4.0 - 6.0 ppm, compared to the morpholino pattern CH2-O peak at ∼3.8 ppm. Example 37 (Predictive Example)

[0250] Under an inert atmosphere, a sample of 3.0 g of poly(isoprene-co-1-(dibenzylamino)-3-phenylbut-3-ene) from Example 3 was dissolved in 20 ml of cyclohexane, followed by the addition of 1.0 ml of cobalt neodecanoate-triethylaluminum (0.0962 mol / L cyclohexane solution) as a hydrogenation catalyst. The atmosphere in the reactor was purged with hydrogen, and the hydrogenation reaction was carried out at a hydrogen pressure of up to 2 MPa and up to 150 °C until the hydrogen consumption (monitored by the pressure difference in the reactor) stopped. After cooling and depressurizing, an aqueous phosphoric acid solution was added under an air atmosphere. The solution was washed with an excess of aqueous potassium hydroxide solution, followed by washing with water. The polymer solution was then concentrated under reduced pressure to obtain the hydrogenated block copolymer. Example 38 (Predictive Example)

[0251] Under an inert atmosphere, 3.0 g of the poly(isoprene-co-1-benzylmethylamino-3-phenylbut-3-ene) sample from Example 7 was dissolved in 20 ml of cyclohexane, and then 1.0 ml of cobalt neodecanoate-triethylaluminum (0.0962 mol / L cyclohexane solution) was added as a hydrogenation catalyst. The atmosphere in the reactor was purged with hydrogen, and the hydrogenation reaction was carried out at a hydrogen pressure of up to 2 MPa and up to 150 °C until the hydrogen consumption (monitored by the pressure difference in the reactor) stopped. After cooling and depressurization, an aqueous phosphoric acid solution was added under an air atmosphere. The solution was washed with an excess of aqueous potassium hydroxide solution and then with water. Subsequently, the polymer solution was concentrated under reduced pressure to obtain the hydrogenated block copolymer. Explanation of the data in Table 2:

[0252] The amine functional groups present in the functional monomers used in Examples 1-31 are known or reasonably believed to interact with the stationary phase in the standard GPC column, thereby altering the polymer retention time measured by the chromatographic system. Thus, there may be a significant source of error introduced into the molecular weight values reported by GPC (which are based on the retention time within the GPC column). The magnitude of this error can depend on the individual ADAMS monomer structure, the weight % content of the ADAMS repeating unit in the copolymer, the distribution of the ADAMS repeating unit within the polymer backbone, or a combination thereof.

[0253] Due to this potential source of error, the calculated target number-average molecular weight Mn of the polymers prepared in Examples 1-31 is included in Table 2 below. These calculated values are based on the molar ratio between the monomers used in the reaction and the alkyllithium initiator, according to Equation 1;

[0254] where, n 单体 is the molar amount of the monomers present in the reaction in mol, n 引发剂 is the molar amount of the alkyllithium initiator present in the reaction in mol, MW 单元 is the molecular weight of the polymerization repeating unit in Da (based on the monomers present in the reaction).

[0255] The calculated molecular weights in Table 2 were not corrected by comparison with polystyrene standards. In the case where 1 monitoring the reaction by 1The alternating ADAMS / comonomer polymer blocks are described as separate blocks from the polymer blocks containing the remaining comonomer (see above), as evidenced by the approximately 1:1 molar consumption rate of the two monomers monitored by H NMR, even though a large molar excess of comonomer may be present). In such cases, the repeating units within the ADAMS / comonomer blocks are considered to be combined alternating structures such as structures (IX), (X a ) and (X b ), there are no additional comonomer repeat units in the ADAMS / comonomer blocks. The GPC molecular weights reported in Table 2 are based on samples taken from the polymerization reaction, or samples taken between subsequent monomer additions, or samples taken in the final product polymer after separation. Therefore, the calculated and measured molecular weights reported in Table 2 are cumulative molecular weights, which show the total polymer molecular weight when each polymer block sampling is completed. In the case where the monomer reactivity ratio leads to the first polymerization of the ADAMS-containing block (such as 1 In the case of a second block of the remaining comonomer immediately polymerized following polymerization of the ADAMS-containing blocks, as evidenced by H NMR monitoring, the ADAMS-containing blocks could not be isolated independently and only the combined Mn of the two blocks was reported.

[0256] In Table 2, IP refers to isoprene, BD refers to 1,3-butadiene, STY refers to styrene, PDI refers to polydispersity index, and CR refers to star polymer coupling ratio.

[0257] For the alkylated ADAMS copolymers in Polymer Examples 32-35, no polymer peaks were visible by GPC due to their strong interaction with the stationary phase of the GPC column.

[0258] All documents described herein are hereby incorporated by reference to the extent that they are not inconsistent with the present disclosure, including any priority documents and / or test procedures. From the foregoing general description and specific embodiments, it will be apparent that, although the forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended to limit the invention hereby. The term "comprising" specifies the presence of the recited element, step, integer or component, but does not preclude the presence or addition of one or more other elements, steps, integers, components or combinations thereof. Thus, the term "comprising" is considered synonymous with the term "including". Similarly, whenever a composition, element or group of elements is preceded by the connective "comprising", it should be understood that the same composition or group of elements preceded by the connectives "consisting essentially of", "consisting of", "selected from" or "may be", "might be", "is" are contemplated, and vice versa. Except that the well-known term "comprising" means "including the matter recited thereafter and any other matter" [open] and "consisting of" means "including only the matter recited thereafter" [closed], the term "consisting essentially of" should be understood to be semi-inclusive and means, according to United States judicial interpretation, including the matter recited thereafter and other matters that do not materially affect the basic and novel properties.

[0259] The applicant has attempted to disclose all embodiments and applications of the disclosed subject matter that are reasonably foreseeable. However, there may be some unforeseeable, insubstantial modifications that still constitute equivalents. Although the invention has been described in connection with specific exemplary embodiments, it will be apparent that, in light of the foregoing description, many changes, modifications and variations will be apparent to those skilled in the art without departing from the spirit or scope of the present disclosure. Accordingly, the present disclosure is intended to embrace all such changes, modifications and variations as described in detail above.

[0260] All patents, test procedures and other documents cited herein, including priority documents, are hereby incorporated by reference in their entirety to the extent that such disclosure is not inconsistent with the present invention and in all jurisdictions where such incorporation is permitted.

[0261] When numerical lower and upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

1. A copolymer comprising: (a) one or more amine - derivatized α - methylstyrene (ADAMS) repeat units according to structure (V): Wherein: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbylene group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5 - to 12 - membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring co - linked to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbyl group, a C1 - C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino - functional group having structure (III) linked via an asterisk wherein R’1 and R’2 are independently the same as or different from R1 and R2 but are defined the same; and (b) one or more repeating units according to structure (VI), (VII a ), (VII b ) or combinations thereof Wherein: R5 is hydrogen or methyl; R’ is hydrogen, a phenyl ring co - linked to the indicated phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group linked at a single carbon of the indicated phenyl ring, a C1 - C4 hydrocarbyl group and / or combinations thereof.

2. The copolymer according to claim 1, wherein k = 2.

3. The copolymer according to claim 2, wherein the one or more ADAMS repeating units according to structure (V) comprise the reacted forms of the following substances: 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimino)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1-(heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopenta-1,3-dien-1-ylpiperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-azepanyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)azepane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoxaline, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof.

4. The copolymer according to claims 1-3, wherein said one or more repeating units according to structure (VI) comprise a reacted form of styrene, and said one or more repeating units according to structures (VII a ) and (VII b ) comprise a reacted form of isoprene, 1,3-butadiene, or a combination thereof.

5. The copolymer according to claims 1 - 4, further comprising: alkyl residues from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more termini of the polymer backbone; or alkyl residues from a bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator near the center of the polymer backbone.

6. The copolymer according to claim 5, wherein the alkyl residues from the monofunctional initiator include methyl, ethyl, n - propyl, isopropyl, n - butyl, isobutyl, sec - butyl, tert - butyl, n - pentyl, isopentyl, sec - pentyl, tert - pentyl, hexyl, or combinations thereof, or wherein the alkyl residues from the bifunctional initiator include propyl, butyl, pentyl, hexyl, 1,4 - diphenylbutyl, or combinations thereof.

7. The copolymer according to claims 1 - 6, wherein the copolymer is partially or substantially hydrogenated.

8. The copolymer according to any one of claims 1-7, wherein said one or more repeating units according to structure (V) are dispersed within at least one polymer block comprising said one or more repeating units according to structure (VI), (VII a ), (VII b ) or a combination thereof.

9. The copolymer according to claim 8, wherein the one or more repeating units according to structure (V) are partially or substantially alternating with the one or more repeating units according to structure (VI), (VII a ), (VII b ), or a combination thereof, thereby forming one or more repeating units corresponding to structure (IX), (X a ), (X b ), or a combination thereof:

10. The copolymer according to claim 9, wherein the copolymer comprises one or more polymer blocks, the block comprising one or more repeating units according to structure (VI), (VII a ), (VII b ) or a combination thereof and not comprising one or more repeating units according to structure (V).

11. The copolymer according to claim 10, wherein the one or more polymer blocks of the copolymer form a distributed polymer architecture, a diblock, a triblock, a tetrablock, a pentablock, a hexablock, a star polymer architecture, or combinations thereof.

12. The copolymer according to claims 1 - 11, wherein in structure (V), R1, R2, R’1, R’2, or combinations thereof are cleavable chemical protecting groups.

13. The copolymer according to claims 1 - 12, wherein the copolymer further comprises one or more - OH, - NH -, or - NH2 functional groups or combinations thereof at one or more termini of the copolymer backbone.

14. The copolymer according to claims 1 - 13, wherein the amino groups in one or more repeat units according to structure (V) are protonated or alkylated to their corresponding ammonium salts.

15. A polymer comprising: (a) Three or more amine-derivatized α-methylstyrene (ADAMS) repeat units according to Structure (V): Where: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring that is linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having Structure (III) linked via an asterisk Wherein R’1 and R’2 are independently the same as or different from R1 and R2 but are defined the same; and (b) Substantially no other repeat units.

16. A copolymer comprising: (a) One or more repeat units according to Structure (VIII): Where: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5 to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; and (b) one or more repeating units according to structure (VI), (VII a ), (VII b ) or combinations thereof Where: R5 is hydrogen or methyl; R’ is hydrogen, a phenyl ring that is co-linked to the indicated phenyl ring at two adjacent ring carbon positions to form a naphthalene assembly, a phenyl ring that is linked at a single carbon of the indicated phenyl ring, a C1-C4 hydrocarbyl group and / or combinations thereof.

17. A polymer comprising: (a) Three or more repeat units according to Structure (VIII): Where: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5 to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; and (b) Substantially no other repeat units.

18. A copolymer comprising the reaction product of: (a) One or more monomers according to Structure (I) Where: k is an integer from 1 to 3; R1 and R2 are each independently a hydrocarbyl group or a hydrocarbyl-like group having 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or wherein R1 and R2 are linked to form a structural moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof; R is hydrogen, a phenyl ring that is co - connected to the shown phenyl ring at two adjacent ring - carbon positions to form a naphthalene assembly, a phenyl group connected at a single carbon of the shown phenyl ring, a C1 - C4 hydrocarbyl group, a C1 - C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from O, N, S, P, Se, and combinations thereof, or a second amino functional group having structure (III) connected via an asterisk wherein R’1 and R’2 are independently the same as or different from R1 and R2 but are defined the same; (b) isoprene, 1,3 - butadiene, styrene, or a combination thereof; and (c) an alkyllithium, alkylsodium, alkylpotassium initiator, or a combination thereof.

19. The copolymer according to claim 18, wherein the one or more monomers include 1-dimethylamino-3-phenylbut-3-ene, 1-diethylamino-3-phenylbut-3-ene, 1-di-n-propylamino-3-phenylbut-3-ene, 1-diisopropylamino-3-phenylbut-3-ene, 1-di-2-propenylamino-3-phenylbut-3-ene, 1-di-n-butylamino-3-phenylbut-3-ene, 1-di-sec-butylamino-3-phenylbut-3-ene, 1-diisobutylamino-3-phenylbut-3-ene, 1-di-tert-butylamino-3-phenylbut-3-ene, 1-cyclohexylmethylamino-3-phenylbut-3-ene, 1-dicyclohexylamino-3-phenylbut-3-ene, 1-di-(2-ethylhexyl)amino-3-phenylbut-3-ene, 1-di-(methoxyethyl)amino-3-phenylbut-3-ene, 1-di-(ethoxyethyl)amino-3-phenylbut-3-ene, 1-di-(phenoxyethyl)amino-3-phenylbut-3-ene, 1-di-(methylthioethyl)amino-3-phenylbut-3-ene, 1-di-(ethylthioethyl)amino-3-phenylbut-3-ene, 1-benzylmethylamino-3-phenylbut-3-ene, 1-dibenzylamino-3-phenylbut-3-ene, 1-benzylphenylamino-3-phenylbut-3-ene, 1-diphenylamino-3-phenylbut-3-ene, 1-dipyridylamino-3-phenylbut-3-ene, 1-phenylmethylamino-3-phenylbut-3-ene, 1-phenylmethoxyethylamino-3-phenylbut-3-ene, 1-benzylmethoxyethylamino-3-phenylbut-3-ene, 1-(N-morpholinyl)-3-phenylbut-3-ene, 1-(N-thiomorpholinyl)-3-phenylbut-3-ene, 1-(N-piperidyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-heptamethyleneimino)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-1-quinolyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolyl)-3-phenylbut-3-ene, 1-(N-indolinyl)-3-phenylbut-3-ene, 1-(N-indolyl)-3-phenylbut-3-ene, 1-(N-carbazolyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S-oxide)-3-phenylbut-3-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-phenylbut-3-ene, 1-(N-phenoxazinyl)-3-phenylbut-3-ene, 1-(4-methyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1-(heptan-2-yl)-3-phenylbut-3-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-phenylbut-3-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-cyclopenta-1,3-dien-1-ylpiperazinyl)-3-phenylbut-3-ene, 1-(4-phenyl-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-phenylbut-3-ene, 1-(N'-methyl-N-azepanyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)azepane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropyridoquinoxaline, N,N'-bis(3-phenylbut-3-enyl)octahydropyridoisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoquinoline, N,N'-bis(3-phenylbut-3-enyl)hexahydropyrroloisoindole, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-phenylbut-3-enyl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-phenylbut-3-enyl)piperidin-4-yl)propane, bis(1-dimethylamino-3-phenylbut-3-enyl)benzene, bis(1-benzylmethylamino-3-phenylbut-3-enyl)benzene, bis(1-(N-morpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-thiomorpholinyl)-3-phenylbut-3-enyl)benzene, bis(1-(di-methoxyethyl)amino-3-phenylbut-3-enyl)benzene, bis(1-(N-piperidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(N-pyrrolidinyl)-3-phenylbut-3-enyl)benzene, bis(1-(4-methyl-1-piperazinyl))-3-phenylbut-3-enyl)benzene or a combination thereof.

20. A method of using a copolymer, comprising: providing the copolymer according to claim 18 or an additive mixture comprising the copolymer according to claim 18, and using the copolymer or the additive mixture comprising the copolymer in an application selected from: lithium - ion battery additives, plastic additives, drag - reducing agents, magnetorheological fluids, electro - chlorination additives, industrial coating additives, adhesive additives, asphaltene and wax inhibitors, refinery antifoulants, industrial or household surfactants, agrochemical additives, ceramic capacitor or indicator additives, emulsion explosive additives, antibacterial coatings, crude oil transportation and refining additives, and carbon capture additives.

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