Amine-containing polymer compositions and uses thereof

Abstract

To provide amine-containing polymer compositions.SOLUTION: Disclosed herein is an amine-containing polymer composition based on the anionic polymerization of a monomer composition comprising an amine-derivatized alpha-methyl styrene (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 is an amine-containing polymer composition based on the anionic polymerization of difunctional monomers of these types having two polymerizable loci and / or two amine loci. Further disclosed herein are methods of using such polymer compositions.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] There are numerous documents that disclose nitrogen-containing (amine) groups pendant to the phenyl ring of styrenic monomers / polymers / copolymers. However, monomers and polymers having such pendant groups can be chemically difficult to synthesize reliably / repeatedly. Even if such synthesis could be achieved, whether alone or as a copolymer with other styrenic monomers, problems can arise with the propagation within the polymerization reaction containing such amine-functionalized styrenic monomers. Therefore, it is often possible to use post-polymerization chemical reactions to add amine groups to a small number of monomer repeat units. However, in post-polymerization chemical reactions, even if the propagation problem of amine-functionalized styrenic monomers can be avoided, often another problem can arise. Therefore, it is desirable to develop a different method from the conventional ones for functionalizing styrenic monomer prepolymers, particularly a method that is neutral with respect to propagation within the polymerization reaction or perhaps even enhances propagation. U.S. Patent Nos. 6,486,272, 9,364,825, 10,202,494, and 10,046,285 disclose polymers made from styrenic monomers having nitrogen-containing groups pendant to the phenyl ring, and all of these documents are hereby incorporated by reference in their entirety. British Patent No. 1,381,755 discloses amine-functional monomer compounds, but only those having acrylamide functionality. 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 International Publication No. WO 2021 / 127183 Pamphlet. All of these documents are hereby incorporated by reference in their entirety. In view of the difficulties in preparing and polymerizing styrenic monomers having nitrogen-containing groups pendant to the phenyl ring, Applicants have explored other potential structures for functional monomers that are both simpler to manufacture and further polymerize. Such functional monomer compositions, each containing an aromatic and / or conjugated (non-aromatic) structure containing at least one amine nitrogen, are described in co-owned related U.S. Patent Application No. 63 / 483,365, filed February 6, 2023, the contents of which are hereby incorporated by reference in their entirety. Both U.S. Patent No. 2,778,826 (the “’826 Schmidle Patent”) and the 1955 paper by Schmidle and Mansfield entitled “The Aminomethylation of Olefins. I. The Reaction of Secondary Amines, Formaldehyde, and Olefins” disclose various reactions in which 3-aryl-3-butenyl-1-amine is said to be formed. In such reactions, formaldehyde and a secondary amine form an iminium, which reacts with a styrenic olefin to form only the terminal (vinylidene) double bond type of the amine-functionalized styrenic material. The 1955 paper also disclosed the amine-functionalization of terpenoids such as α- and β-pinene, camphene, and limonene, but did not disclose isoprene or similar conjugated non-aromatic compounds.

[0003] The 1983 paper 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 cited in the ’826 Schmidle Patent in particular) further disclosed a mechanistic study of specific dimethyliminium compounds that react with styrenic and non-styrenic olefins. Notably, the 1983 paper states in the opening of the discussion section that there were errors in the ’826 Schmidle Patent (and the 1955 paper, which presumably included experiments and results very similar to it). Nevertheless, with respect to the aminomethylation of α-methylstyrene, the 1983 paper showed that the vinylidene-based product was formed with a significant vinylenic (not terminal double bond) content and a very significant (13% in the case of the dimethylamino type) saturated arylalkane-amine content. The monomer of the invention disclosed in U.S. Provisional Patent Application No. 63 / 483,365 has, to the applicant's knowledge, never been polymerized before.

[0004] In view of the above, there is a need to provide functional polymers based on alpha-substituted functional monomers, particularly functional polymers based on a functional monomer composition comprising aromatic and / or conjugated (non-aromatic) structures each containing at least one amine nitrogen, using anionic polymerization technique.

SUMMARY OF THE INVENTION

[0005] Accordingly, the present disclosure provides an inventive polymer composition based on anionic polymerization of addition polymerizable monomer compositions of structures (I) and (II) below, emphasizing that the vinylidene (terminal double bond or “exo”) type of structure (I) is the desired monomer. Other monomer by-products may be present in the monomer composition, determined by the various synthetic schemes by which the monomer is produced, as described in U.S. Provisional Patent Application No. 63 / 483,365 filed on February 6, 2023.

CHEMICAL FORMULA

CHEMICAL FORMULA

[0006] In one form, the present specification discloses a copolymer comprising (a) structure (V) [Chemical formula] (wherein k is an integer from 1 to 3, and R1 and R2 are each independently a hydrocarbyl group or hydrocarbon group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R1 and R2 are connected to form a moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, and R is hydrogen, a phenyl ring covalently bonded to the phenyl ring in the notation to form a naphthalene assembly at two adjacent ring carbon positions, a phenyl group bonded to a single carbon of the phenyl ring in the notation, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or structure (III) [Chemical formula] (wherein R’1 and R’2 are independently the same as or different from R1 and R2, but are identically defined) is a second amino functional group bonded via an asterisk) one or more amine-derivatized alpha-methylstyrene (ADAMS) repeat units; and (b) structures (VI), (VII a ), (VII b ) [Chemical Formula] (wherein R5 is hydrogen or a methyl group, and R’ is hydrogen, a phenyl ring covalently bonded to the phenyl ring shown and two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, and / or a combination thereof), or one or more repeat units by a combination thereof, a copolymer is disclosed.

[0007] In another form, herein is a polymer comprising (a) structure (V) [Chemical Formula] (wherein k is an integer from 1 to 3, and R1 and R2 are each independently a hydrocarbyl group or a hydrocarbon group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R1 and R2 are connected to form at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally, a moiety containing 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, and R is hydrogen, a phenyl ring covalently bonded to the phenyl ring shown and two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring shown, a C1-C4 hydrocarbyl group, a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or structure (III) [Chemical Formula] (wherein R'1 and R'2 are independently the same as or different from R1 and R2, but are identically defined) is a second amino functional group bonded via an asterisk), a polymer comprising three or more amine-derivatized alpha-methylstyrene (ADAMS) repeat units is disclosed.

[0008] In yet another form, herein is a copolymer comprising (a) structure (VIII)

Chemical formula

Chemical formula

[0009] In yet another form, herein is a polymer comprising (a) structure (VIII)

Chemical formula

[0010] In yet another aspect, the present specification discloses a copolymer comprising (a) structure (I),

Chemical formula

Chemical formula

DETAILED DESCRIPTION OF THE INVENTION

[0011] All numerical values within the detailed description and claims of this specification are all modified by the indication that the indicated value is "about" or "approximately", taking into account experimental errors and variations that one of ordinary skill in the art would expect. The present disclosure provides novel polymers based on the anionic polymerization of functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring, or functionalized conjugated (non-aromatic) monomers containing nitrogen-containing moieties. Accordingly, in order to achieve nitrogen-containing functionality other than as a pendant to the phenyl ring of styrene units in alpha-substituted styrenic monomers, monomers of structure (I) were developed. This chemistry was also applied to the amine functionalization of alkyl-substituted conjugated (non-aromatic) monomers, such as isoprene. It should be noted that the prior art literature often describes functionalized styrenic monomers having nitrogen-containing groups pendant to the phenyl ring in general terms (e.g., "dimethylaminoethylstyrene"). This may be similar to the k = 2 monomer structure shown below, but the prior art does not teach or suggest the alpha-substituted functional monomers specifically disclosed herein.

[0012] The functional polymers of the present invention disclosed herein, which are based on functionalized styrene monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring or on functionalized conjugated (non-aromatic) monomers containing nitrogen-containing moieties, can be polymerized from an addition-polymerizable monomer composition comprising an amine-derivatized alpha-methylstyrene (ADAMS) monomer according to structure (I) and / or an aminated conjugated (non-aromatic) aliphatic methylated polyene (ACAMP) monomer according to structure (II).

Chemical formula

Chemical formula

Chemical formula

[0013] The functional polymers of the present invention disclosed herein, based on functionalized styrene monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, can be polymerized from exemplary ADAMS monomers according to Structure (I), and exemplary ADAMS monomers according to Structure (I) include, but are not limited to, the following: 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-quinolinyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N’-Bis(3-phenylbut-3-enyl)diazepane, N,N’-Bis(3-phenylbut-3-enyl)piperazine, N,N’-Bis(3-phenylbut-3-enyl)dihydrophenazine, N,N’-Bis(3-phenylbut-3-enyl)dihydrobenzoimidazole, N,N’-Bis(3-phenylbut-3-enyl)dihydropyrimidine, 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.

[0014] In some embodiments, the functional polymers of the present invention disclosed herein, based on functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring, can polymerize from exemplary ADAMS monomers of structure (I) and may exhibit exactly 2 k values.

[0015] For clarity, as used herein, the functional polymers of the present invention disclosed herein, based on functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to the phenyl ring, can polymerize from exemplary ADAMS monomers of structure (I) having a vinylidene bond, such as those derived from the olefin double bond of alpha-methylstyrene, which may be reflected in the phrase -3-ene / -3-enyl of the IUPAC nomenclature.

[0016] The functional polymers of the present invention disclosed herein, based on functionalized conjugated (non-aromatic) monomers containing nitrogen-containing moieties, can be polymerized from ACAMP monomers according to Structure (II), and examples of ACAMP monomers according to Structure (II) include, but are not limited to, the following: 1-dimethylamino-3-methylenepenta-4-ene, 1-diethylamino-3-methylenepenta-4-ene, 1-di-n-propylamino-3-methylenepenta-4-ene, 1-diisopropylamino-3-methylenepenta-4-ene, 1-di-2-propenylamino-3-methylenepenta-4-ene, 1-di-n-butylamino-3-methylenepenta-4-ene, 1-di-sec-butylamino-3-methylenepenta-4-ene, 1-diisobutylamino-3-methylenepenta-4-ene, 1-di-tert-butylamino-3-methylenepenta-4-ene, 1-cyclohexylmethylamino-3-methylenepenta-4-ene, 1-dicyclohexylamino-3-methylenepenta-4-ene, 1-di-(2-ethylhexyl)amino-3-methylenepenta-4-ene, 1-di-(methoxyethyl)amino-3-methylenepenta-4-ene, 1-di-(ethoxyethyl)amino-3-methylenepenta-4-ene, 1-di-(phenoxyethyl)amino-3-methylenepenta-4-ene, 1-di-(methylthioethyl)amino-3-methylenepenta-4-ene, 1-di-(ethylthioethyl)amino-3-methylenepenta-4-ene, 1-benzylmethylamino-3-methylenepenta-4-ene, 1-dibenzylamino-3-methylenepenta-4-ene, 1-benzylphenylamino-3-methylenepenta-4-ene, 1-diphenylamino-3-methylenepenta-4-ene, 1-dipyridylamino-3-methylenepenta-4-ene, 1-phenylmethylamino-3-methylenepenta-4-ene, 1-phenylmethoxyethylamino-3-methylenepenta-4-ene, 1-benzylmethoxyethylamino-3-methylenepenta-4-ene, 1-(N-morpholinyl)-3-methylenepenta-4-ene, 1-(N-thiomorpholinyl)-3-methylenepenta-4-ene, 1-(N-piperidinyl)-3-methylenepenta-4-ene, 1-(N-piperazinyl)-3-methylenepenta-4-ene,1-(N-diazepanyl)-3-methylenepenta-4-ene, 1-(N-pyrrolidinyl)-3-methylenepenta-4-ene, 1-(N-pyrrolyl)-3-methylenepenta-4-ene, 1-(1,2,3,4-tetrahydro-1-quinolinyl)-3-methylenepenta-4-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolinyl)-3-methylenepenta-4-ene, 1-(N-indolinyl)-3-methylenepenta-4-ene, 1-(N-indolyl)-3-methylenepenta-4-ene, 1-(N-carbazolyl)-3-methylenepenta-4-ene, 1-(N-phenothiazinyl)-3-methylenepenta-4-ene, 1-(N-phenothiazinyl-S-oxide)-3-methylenepenta-4-ene, 1-(N-phenothiazinyl-S,S-dioxide)-3-methylenepenta-4-ene, 1-(N-phenoxazinyl)-3-methylenepenta-4-ene, 1-(4-methyl-1-piperazinyl)-3-methylenepenta-4-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl)-3-methylenepenta-4-ene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-methylenepenta-4-ene, 1-(4-cyclopentyl-1-piperazinyl)-3-methylenepenta-4-ene, 1-(4-cyclopentadienyl-1-piperazinyl)-3-methylenepenta-4-ene, 1-(4-phenyl-1-piperazinyl)-3-methylenepenta-4-ene, 1-(4-(thiazolyl)-1-piperazinyl)-3-methylenepenta-4-ene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-methylenepenta-4-ene, 1-(4-(triazolyl)-1-piperazinyl)-3-methylenepenta-4-ene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-methylenepenta-4-ene, 1-(N’-methyl-N-diazepanyl)-3-methylenepenta-4-ene, 1-dimethylamino-3-methylenhepta-4,6-diene, 1-diethylamino-3-methylenhepta-4,6-diene, 1-di-n-propylamino-3-methylenhepta-4,6-diene, 1-diisopropylamino-3-methylenhepta-4,6-diene, 1-di-2-propenylamino-3-methylenhepta-4,6-diene1 - Di - n - butylamino - 3 - methylenehepta - 4,6 - diene, 1 - Di - sec - butylamino - 3 - methylenehepta - 4,6 - diene, 1 - Diisobutylamino - 3 - methylenehepta - 4,6 - diene, 1 - Di - tert - butylamino - 3 - methylenehepta - 4,6 - diene, 1 - Cyclohexylmethylamino - 3 - methylenehepta - 4,6 - diene, 1 - Dicyclohexylamino - 3 - methylenehepta - 4,6 - diene, 1 - Di - (2 - ethylhexyl)amino - 3 - methylenehepta - 4,6 - diene, 1 - Di - (methoxyethyl)amino - 3 - methylenehepta - 4,6 - diene, 1 - Di - (ethoxyethyl)amino - 3 - methylenehepta - 4,6 - diene, 1 - Di - (phenoxyethyl)amino - 3 - methylenehepta - 4,6 - diene, 1 - Di - (methylthioethyl)amino - 3 - methylenehepta - 4,6 - diene, 1 - Di - (ethylthioethyl)amino - 3 - methylenehepta - 4,6 - diene, 1 - Benzylmethylamino - 3 - methylenehepta - 4,6 - diene, 1 - Dibenzylamino - 3 - methylenehepta - 4,6 - diene, 1 - Benzylphenylamino - 3 - methylenehepta - 4,6 - diene, 1 - Diphenylamino - 3 - methylenehepta - 4,6 - diene, 1 - Dipyridylamino - 3 - methylenehepta - 4,6 - diene, 1 - Phenylmethylamino - 3 - methylenehepta - 4,6 - diene, 1 - Phenylmethoxyethylamino - 3 - methylenehepta - 4,6 - diene, 1 - Benzylmethoxyethylamino - 3 - methylenehepta - 4,6 - diene, 1 - (N - morpholinyl)-3 - methylenehepta - 4,6 - diene, 1 - (N - thiomorpholinyl)-3 - methylenehepta - 4,6 - diene, 1 - (N - piperidinyl)-3 - methylenehepta - 4,6 - diene, 1 - (N - piperazinyl)-3 - methylenehepta - 4,6 - diene, 1 - (N - diazepanyl)-3 - methylenehepta - 4,6 - diene, 1 - (N - pyrrolidinyl)-3 - methylenehepta - 4,6 - diene, 1 - (N - pyrrolyl)-3 - methylenehepta - 4,6 - diene, 1 - (1,2,3,4 - tetrahydro - 1 - quinolinyl)-3 - methylenehepta - 4,6 - diene, 1 - (1,2,3,4 - tetrahydro - 2 - isoquinolinyl)-3 - methylenehepta - 4,6 - diene, 1 - (N - indolinyl)-3 - methylenehepta - 4,6 - diene,1-(N-Indolyl)-3-methylenhepta-4,6-diene, 1-(N-carbazolyl)-3-methylenhepta-4,6-diene, 1-(N-phenothiazinyl)-3-methylenhepta-4,6-diene, 1-(N-phenothiazinyl-S-oxide)-3-methylenhepta-4,6-diene, 1-(N-phenothiazinyl-S,S-dioxide)-3-methylenhepta-4,6-diene, 1-(N-phenoxazinyl)-3-methylenhepta-4,6-diene, 1-(4-methyl-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(5-methyl-2,5-diazabicyclo[2.2.1]heptan-2-yl)-3-methylenhepta-4,6-diene, 1-(5-methyl-2,5-diazabicyclo[2.2.2]octan-2-yl)-3-methylenhepta-4,6-diene, 1-(4-cyclopentyl-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(4-cyclopentadienyl-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(4-phenyl-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(4-(thiazolyl)-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(4-(thiadiazolyl)-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(4-(triazolyl)-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(4-(1,2,3-benzotriazolyl)-1-piperazinyl)-3-methylenhepta-4,6-diene, 1-(N’-methyl-N-diazepanyl)-3-methylenhepta-4,6-diene, 1-dimethylamino-3,4-dimethylenhex-5-ene, 1-diethylamino-3,4-dimethylenhex-5-ene, 1-di-n-propylamino-3,4-dimethylenhex-5-ene, 1-diisopropylamino-3,4-dimethylenhex-5-ene, 1-di-2-propenylamino-3,4-dimethylenhex-5-ene, 1-di-n-butylamino-3,4-dimethylenhex-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-ene1-Cyclohexylmethylamino-3,4-dimethylenehex-5-ene, 1-Dicyclohexylamino-3,4-dimethylenehex-5-ene, 1-Di-(2-ethylhexyl)amino-3,4-dimethylenehex-5-ene, 1-Di-(methoxyethyl)amino-3,4-dimethylenehex-5-ene, 1-Di-(ethoxyethyl)amino-3,4-dimethylenehex-5-ene, 1-Di-(phenoxyethyl)amino-3,4-dimethylenehex-5-ene, 1-Di-(methylthioethyl)amino-3,4-dimethylenehex-5-ene, 1-Di-(ethylthioethyl)amino-3,4-dimethylenehex-5-ene, 1-Benzylmethylamino-3,4-dimethylenehex-5-ene, 1-Dibenzylamino-3,4-dimethylenehex-5-ene, 1-Benzylphenylamino-3,4-dimethylenehex-5-ene, 1-Diphenylamino-3,4-dimethylenehex-5-ene, 1-Dipyridylamino-3,4-dimethylenehex-5-ene, 1-Phenylmethylamino-3,4-dimethylenehex-5-ene, 1-Phenylmethoxyethylamino-3,4-dimethylenehex-5-ene, 1-Benzylmethoxyethylamino-3,4-dimethylenehex-5-ene, 1-(N-Morpholinyl)-3,4-dimethylenehex-5-ene, 1-(N-Thiomorpholinyl)-3,4-dimethylenehex-5-ene, 1-(N-Piperidinyl)-3,4-dimethylenehex-5-ene, 1-(N-Piperazinyl)-3,4-dimethylenehex-5-ene, 1-(N-Diazepanyl)-3,4-dimethylenehex-5-ene, 1-(N-Pyrrolidinyl)-3,4-dimethylenehex-5-ene, 1-(N-Pyrrolyl)-3,4-dimethylenehex-5-ene, 1-(1,2,3,4-Tetrahydro-1-quinolinyl)-3,4-dimethylenehex-5-ene, 1-(1,2,3,4-Tetrahydro-2-isoquinolinyl)-3,4-dimethylenehex-5-ene, 1-(N-Indolinyl)-3,4-dimethylenehex-5-ene, 1-(N-Indolyl)-3,4-dimethylenehex-5-ene, 1-(N-Carbazolyl)-3,4-dimethylenehex-5-ene, 1-(N-Phenothiazinyl)-3,4-dimethylenehex-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-cyclopentadienyl-1-piperazinyl)-3,4-dimethylenhex-5-ene,

[0017] 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)dihydrobenzoindazole, N,N’-bis(3-methylenepent-4-enyl)dihydropelmidine, 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)dihydrobenzoindazole, N,N’-bis(3-methylenhept-4,6-dien-1-yl)dihydropelmidine, N,N’-bis(3-methylenhept-4,6-dien-1-yl)octahydropyridoquinoline, N,N'-Bis(3-methylenhepta-4,6-dien-1-yl)octahydropyridoisoquinoline, N,N'-bis(3-methylenhepta-4,6-dien-1-yl)hexahydropyrroloquinoline, N,N'-bis(3-methylenhepta-4,6-dien-1-yl)hexahydropyrroloisoquinoline, N,N'-bis(3-methylenhepta-4,6-dien-1-yl)hexahydropyrroloisoindole, N,N'-bis(3-methylenhepta-4,6-dien-1-yl)diazabicyclo[2.2.1]heptane, N,N'-bis(3-methylenhepta-4,6-dien-1-yl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3-methylenhepta-4,6-dienyl)piperidin-4-yl)propane, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)diazepane, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)piperazine, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)dihydrophenazine, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)dihydrobenzoimidazole, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)dihydropelmidine, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)octahydropyridoquinoline, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)octahydropyridoisoquinoline, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)hexahydropyrroloquinoline, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)hexahydropyrroloisoquinoline, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)hexahydropyrroloisoindole, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)diazabicyclo[2.2.1]heptane, N,N'-bis(3,4-dimethylenhexa-5-en-1-yl)diazabicyclo[2.2.2]octane, 1,3-bis(1-(3,4-dimethylenhexa-5-enyl)piperidin-4-yl)propane, N,N,N'N'-tetramethyl-3,6-dimethylenocta-4-ene-1,8-diamine, N,N,N'N'-tetrakis(2-methoxyethyl)-3,6-dimethylenocta-4-ene-1,8-diamine, N,N'-dimethyl-N,N'-dibenzyl-3,6-dimethylenooct-4-ene-1,8-diamine, N,N'-(3,6-dimethylenooct-4-ene-1,8-diyl)bis(morpholine), N,N'-(3,6-dimethylenooct-4-ene-1,8-diyl)bis(thiomorpholine), N,N'-(3,6-dimethylenooct-4-ene-1,8-diyl)bis(piperidine), N,N'-(3,6-dimethylenooct-4-ene-1,8-diyl)bis(pyrrolidine), 4,4'-(3,6-dimethylenooct-4-ene-1,8-diyl)bis(1-methylpiperazine), N,N,N'N'-tetramethyl-3,4-dimethylenhexane-1,6-diamine, N,N,N'N'-tetrakis(2-methoxyethyl)-3,4-dimethylenhexane-1,6-diamine, N,N'-dimethyl-N,N'-dibenzyl-3,4-dimethylenhexane-1,6-diamine, N,N'-(3,4-dimethylenhexane-1,6-diyl)bis(morpholine), N,N'-(3,4-dimethylenhexane-1,6-diyl)bis(thiomorpholine), N,N'-(3,4-dimethylenhexane-1,6-diyl)bis(piperidine), N,N'-(3,4-dimethylenhexane-1,6-diyl)bis(pyrrolidine), 4,4'-(3,4-dimethylenhexane-1,6-diyl)bis(1-methylpiperazine), N,N,N'N'-tetramethyl-3,4,5-trimethylenheptane-1,7-diamine, N,N,N'N'-tetrakis(2-methoxyethyl)-3,4,5-trimethylenheptane-1,7-diamine, N,N'-dimethyl-N,N'-dibenzyl-3,4,5-trimethylenheptane-1,7-diamine, N,N'-(3,4,5-trimethylenheptane-1,7-diyl)bis(morpholine), N,N'-(3,4,5-trimethylenheptane-1,7-diyl)bis(thiomorpholine), N,N'-(3,4,5-trimethylenheptane-1,7-diyl)bis(piperidine), N,N'-(3,4,5-trimethylenheptane-1,7-diyl)bis(pyrrolidine), 4,4'-(3,4,5-trimethylenheptane-1,7-diyl)bis(1-methylpiperazine), and combinations thereof.,

[0018] In some embodiments, the functional polymers of the invention disclosed herein based on functionalized conjugated (non-aromatic) monomers containing nitrogen-containing moieties may be based on ACAMP monomers with a structure (II) that may exhibit an exact k value of 2. The polymer compositions disclosed herein may optionally contain residues of initiators and / or co-initiators that are used or can be used in living or pseudo-living anionic polymerization reactions. Non-limiting examples include alkyl residues derived from sec-butyllithium, n-butyllithium, tert-butyllithium, etc., and combinations, reaction products, and / or decomposition products thereof.

Chemical formula

[0019] Alkyl residues derived from monofunctional initiators may optionally be present at one or more ends of the polymer backbone, and alkyl residues of difunctional initiators may optionally be present approximately in the middle of the polymer backbone.

[0020] Useful monofunctional initiators may generally be alkyl lithium compounds, alkyl sodium compounds, or alkyl potassium compounds in the range of C2 - C12. Alkyl lithium compounds, such as methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, iso-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-amyl lithium, iso-amyl lithium, sec-amyl lithium, tert-amyl lithium, hexyl lithium, or combinations thereof are preferred. Secondary alkyl lithium compounds, such as sec-butyl lithium, sec-amyl lithium, or combinations thereof are more preferred. sec-Butyl lithium is most preferred. Substituted alkyl lithium, such as aralkyl lithium compounds, such as benzyl lithium, 1-lithioethylbenzene, and 1-lithio-3-methylpentylbenzene can also be used.

[0021] The difunctional initiators that can be used are generally alkyldilithium compounds, alkyldisodium compounds, or alkyldipotassium compounds in the range of C2 - C12, such as 1,3 - propanediyl dilithium, 1,4 - butanediyl dilithium, 1,5 - pentanediyl dilithium, 1,6 - hexanedilyllithium, 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.

[0022] The functional polymers of the present invention disclosed herein based on functionalized styrenic monomers containing a nitrogen - containing moiety other than as a pendant to the phenyl ring or based on functionalized conjugated (non - aromatic) monomers containing a nitrogen - containing moiety can be preferentially polymerized by anionic polymerization. However, in addition or alternatively, the functional polymers of the present invention disclosed herein based on functionalized styrenic monomers containing a nitrogen - containing moiety other than as a pendant to the phenyl ring or based on functionalized conjugated (non - aromatic) monomers containing a nitrogen - containing moiety can optionally use initiators and / or co - initiators used in (free) radical polymerization reactions or can be used with them. Non - limiting examples include, but are not necessarily limited to, azobisisobutyronitrile (AIBN), di - tert - butyl peroxide, etc., and combinations, reaction products, and / or decomposition products thereof.

[0023] Disclosed herein are anionic polymerization polymers of the present invention derived from functionalized styrenic monomers containing a nitrogen - containing moiety other than as a pendant to the phenyl ring. More specifically, the functionalized styrenic monomers containing a nitrogen - containing moiety other than as a pendant to the phenyl ring have the basic structure

Chemical formula

[0024] Functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety can alternatively be copolymerized with isoprene, butadiene, styrene, and combinations thereof. Other non-limiting exemplary comonomers that may be copolymerized with a functionalized styrenic monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring or a functionalized conjugated (non-aromatic) monomer containing a nitrogen-containing 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, and 2-methyl-4-propylstyrene, etc.), vinylnaphthalene, vinylpyridine, piperylene, methylpentyl diene, or combinations thereof. In another form, a functionalized styrenic monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring or a functionalized conjugated (non-aromatic) monomer containing a nitrogen-containing moiety can be homopolymerized either as an isolable homopolymer or as a homopolymer block in a copolymer.

[0025] Depending on the reactivity ratios of the styrenic monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring and the other comonomers present in the polymerization reaction, in some cases, the repeat unit of structure (V) can form an alternating structure with the repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof. For example, in the following reaction, R1, R2, and R5 have the same meanings as those shown above.

Chemical formula

[0026] The repeat unit of structure (V) and the alternating structure formed as a combination of structure (VI), (VII a ), (VII b ), or a combination thereof will thereby form larger repeat units of structure (IX), (X a ), (X b ), or a combination thereof.

Chemical formula

Chemical formula

[0027] In addition, depending on the reactivity ratio of a styrene monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring and other comonomers present in the polymerization reaction, if one or more other comonomers are present in molar excess during the polymerization reaction, the polymer may, in some cases, have a structure (IX), (X a ), (X b ), or a repeat unit of a combination thereof, followed by a block of a repeat unit of structure (VI), (VII a ), (VII b ), or a combination thereof, and the repeat units of structure (IX), (X a ), (X b ) do not exist. For example, in the following reaction, R1, R2, and R5 have the same meanings as those shown above.

Chemical Formula

[0028] In some embodiments, different monomers or combinations thereof may optionally be sequentially added to the polymerization reaction. In such cases, the monomers added later in the reaction may form blocks of repeat units in the polymer having a composition different from the repeat units derived from the monomers earlier in the polymerization.

[0029] If, as a result of a difference in monomer reactivity ratios or as a result of sequentially adding monomers to a polymerization reaction, a polymer contains two blocks of repeat units of different compositions, the polymer is described as a "diblock". Similarly, if, as a result of a difference in monomer reactivity ratios or as a result of sequentially adding monomers to a polymerization reaction, a polymer contains three, four, five, or six blocks of repeat units of different compositions, the polymer is described as a "triblock", "tetrablock", "pentablock", or "hexablock", respectively.

[0030] In some embodiments, the polymer can be coupled using a polyfunctional coupling agent to form a polymer having a star architecture. Many suitable types of such polyfunctional compounds are 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 incorporated herein by reference in their entirety. The polyfunctional coupling agent can optionally be a halogen-substituted or alkoxy-substituted silane, including, for example, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, bis-trimethoxy-silylethane, bis-triethoxy-silylethane, hexachlorodisiloxane, bis-trichlorosilylethane, 1,6-bis(trichlorosilyl)-hexane, or combinations thereof.

[0031] 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. Generally, reference may be made to Canadian Patent No. 716,645, U.S. Patent No. 4,010,226, and No. 3,985,830. Such documents are hereby incorporated by reference in their entirety. A detailed description of various such coupling agents can be found in U.S. Patent No. 4,391,949, 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, and 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, etc., or combinations thereof.

[0032] When 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 crosslinked in the star architecture and means the mass percentage of the polymer of the star architecture relative to the total mass of the polymer in the sample. In some embodiments, the functional polymers of the present invention disclosed herein based on functionalized styrene monomers containing a nitrogen-containing moiety comprising a star polymer architecture may 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%.

[0033] In some embodiments, the polymerization reaction can be terminated with an epoxide terminator, so that the polymer will 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, and phenyl glycidyl ether, etc., or combinations thereof, among which ethylene oxide and propylene oxide are preferred.

[0034] In some embodiments, the functional polymers of the present invention disclosed herein, based on functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or based on functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety, may have a number average molecular weight Mn greater than 500 Da, greater than 1000 Da, greater than 2000 Da, 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 containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or based on functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety, may 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.

[0035] In some embodiments, the functional polymers of the present invention disclosed herein, based on functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, may contain repeat units according to structure (V) in an amount greater than 0.01% by weight, or greater than 0.05% by weight, or greater than 0.1% by weight, or greater than 0.5% by weight, or greater than 1.0% by weight, or greater than 5.0% by weight, or greater than 10% by weight, or greater than 15% by weight, or greater than 20% by weight. In some embodiments, the functional polymers of the present invention disclosed herein, based on functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety, may contain more than 0.01 wt%, or more than 0.05 wt%, or more than 0.1 wt%, or more than 0.5 wt%, or more than 1.0 wt%, or more than 5.0 wt%, or more than 10 wt%, or more than 15 wt%, or more than 20 wt% of repeat units according to Structure (VIII). In some embodiments, the functional polymers of the present invention disclosed herein, based on functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, may contain more than 0.01 wt%, or more than 0.05 wt%, or more than 0.1 wt%, or more than 0.5 wt%, or more than 1.0 wt%, or more than 5.0 wt%, or more than 10 wt%, or more than 15 wt%, or more than 20 wt% of repeat units according to Structure (IX).

[0036] In some embodiments, the functional polymers of the present invention disclosed herein, based on functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, contain more than 0.01 wt%, or more than 0.05 wt%, or more than 0.1 wt%, or more than 0.5 wt%, or more than 1.0 wt%, or more than 5.0 wt%, or more than 10 wt%, or more than 15 wt%, or more than 20 wt% of a Structure (X b ), Structure (X ), or a combination thereof. In some embodiments, the post-polymerization modification is hydrogenation. In the methods of the present disclosure, hydrogenation can be carried out with known catalyst systems including heterogeneous and soluble systems. The soluble system is disclosed in column 1, line 65 to column 9, line 16 of U.S. Patent No. 4,284,835 and column 3, line 40 to column 6, line 28 of U.S. Patent No. 4,980,331, both of which are incorporated herein by reference.

[0037] The hydrogenated copolymers described above may be partially or substantially hydrogenated. In the context of the present disclosure, being 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. Being substantially hydrogenated means that more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of the non-aromatic bonds are saturated. Additional teachings regarding hydrogenation can be found in Rachapudy et al., Journal of Polymer Science: Polymer Physics Edition, Vol. 17, pp. 1211 - 1222 (1979), which is incorporated herein by reference in its entirety. Table 1 of this paper discloses several systems containing palladium on various supports (including not only calcium carbonate but also barium sulfide). The paper by Rachapudy et al. discloses the preparation of homogeneous and heterogeneous catalysts.

[0038] Additional teachings regarding hydrogenation methods and catalysts are disclosed in U.S. Patent Nos. 4,284,835 and 4,980,331, both of which are incorporated herein by reference in their entireties. In some embodiments, the post-polymerization modification may be a deprotection reaction that removes a cleavable chemical protecting group from a repeat unit of structure (V), (VIII), or a combination thereof. A cleavable chemical protecting group means a chemical group that is inert under the polymerization reaction conditions but can be removed by a chemical reaction after polymerization to yield a free -NH- functional group or a free -NH₂ functional group in the ADAMS repeat unit. In one such form, a preferred cleavable chemical protecting group is a benzyl group and the deprotection reaction is a hydrogenation reaction. In some embodiments, the post-polymerization modification is a protonation reaction, and one or more amine functional groups within a repeat unit of structure (V), (VIII), or a combination thereof are converted to the corresponding ammonium salts by treatment with a protic acid. The protic acid may be any acid strong enough to protonate the basic nitrogen atoms within the repeat unit of structure (V), (VIII), or a combination thereof, thereby forming an ammonium salt of the repeat unit with a counterion corresponding to the conjugate base of the protic acid. Non-limiting examples of protic acids include hydrochloric acid, hydrobromic acid, hydroiodic acid, various alkyl or aryl sulfonic acids (i.e., methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, n-butylsulfonic acid, tert-butylsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and p-dodecylbenzenesulfonic acid, etc.), sulfuric acid, phosphoric acid, formic acid, acetic acid, butyric acid, benzoic acid, trifluoromethanesulfonic acid, nitric acid, or combinations thereof, each yielding an ammonium salt with a chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, nitrate counterion, or combinations thereof.

[0039] In some embodiments, the post-polymerization modification is an alkylation reaction, and one or more amine functional groups within the repeat units of structure (V), (VIII), or a combination thereof are converted to the corresponding ammonium salts by treatment with an alkylating agent. Non-limiting examples of alkylating agents include various alkyl halides (i.e., bromomethane, iodomethane, bromoethane, iodoethane, bromopropane, iodopropane, benzyl chloride, benzyl bromide, and benzyl iodide, etc.), various alkyl sulfonates (i.e., methyl tosylate, ethyl tosylate, propyl tosylate, benzyl tosylate, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, and benzyl methanesulfonate, etc.), various alkyl triflates (i.e., methyl triflate, ethyl triflate, and propyl triflate, etc.), or combinations thereof, which will produce ammonium salts with counterions corresponding to the substitution leaving groups of the alkylating agent.

[0040] Embodiments related to ADAMS copolymers In one aspect of the invention disclosed herein, a copolymer composition based on an amine-derivatized alpha-methylstyrene (ADAMS) monomer (also referred to as an ADAMS copolymer) is polymerized by an anionic polymerization method. In particular, in one aspect, the ADAMS copolymer comprises the following: (a) structure (V)

Chemical formula

[0041] In an advantageous form, for the ADAMS copolymer described above, k = 2. The above copolymer may contain one or more ADAMS repeat units of structure (V) including the reaction forms of the following: 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-quinolinyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N’-bis(3-phenylbut-3-enyl)diazepane, N,N’-bis(3-phenylbut-3-enyl)piperazine, N,N’-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N’-bis(3-phenylbut-3-enyl)dihydrobenzoindazole, N,N’-bis(3-phenylbut-3-enyl)dihydropelmidine, 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, or a combination thereof.,

[0042] In another form, the ADAMS copolymer described above includes one or more repeat units of structure (VI) that contain a reactive form of styrene, and structure (VII a ) and one or more repeat units of (VII b ) may contain a reactive form of isoprene, 1,3-butadiene, or a combination thereof. In the case of the polymeric repeating unit of structure (VII a ), it may be in the cis isomeric form, the trans isomeric form, or a combination thereof.,

[0043] Alternatively, the ADAMS copolymer may further include an alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone, or an alkyl residue derived from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the center of the polymer backbone. In the case of an alkyl residue derived from a monofunctional initiator, examples of such an alkyl residue include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof. Examples of such an alkyl residue derived from a difunctional initiator include a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof.

[0044] Alternatively, the ADAMS copolymer described above may be partially or substantially hydrogenated. Being 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. Being substantially hydrogenated means that more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of the non-aromatic bonds are saturated.

[0045] Alternatively, in the ADAMS copolymer described above, one or more repeat units of structure (V) may be dispersed within at least one polymer block containing one or more repeat units of structure (VI), (VII a )、(VII b )、or a combination thereof. Further alternatively, in the ADAMS copolymer described above, one or more repeat units of structure (V) may be dispersed within at least one polymer block containing one or more repeat units of structure (VI), (VII a )、(VII b) or one or more repeat units of these combinations, partially or substantially alternating therewith, whereby a structure (IX), (X a )、(X b )、or one or more repeat units corresponding to these combinations may be formed.

Chemical formula

[0046] Partially alternating means that 10% - 90%, or 20% - 80%, or 30% - 70%, or 40% - 60% of one or more repeat units of structure (V) are alternating with one or more repeat units of structure (VI), (VII a )、(VII b )、or these combinations. Substantially alternating means more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of one or more repeat units of structure (V) are alternating with one or more repeat units of structure (VI), (VII a )、(VII b )、or these combinations. In the case of the polymeric repeat unit of structure (X a ), it may be in the cis isomeric form, the trans isomeric form, or a combination thereof.

[0047] In yet another form, the ADAMS copolymer described above is of structure (VI), (VII a )、(VII b) may include one or more repeat units of these or combinations thereof, and may include one or more polymer blocks that do not include one or more repeat units of structure (V). In such a form, one or more polymer blocks of the copolymer can form a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or a combination thereof. The dispersed polymer architecture means that the repeat units of structure (V) are dispersed either randomly or uniformly over a larger block of non-ADAMS repeat units, which means that more than 3, or more than 5, or more than 10, or more than 15, or more than 20 repeat units of non-ADAMS monomers are joined between the ADAMS repeat units.

[0048] In yet another form, the ADAMS copolymer described above may be one in which R1, R2, R'1, R'2, or a combination thereof in structure (V) is a cleavable chemical protecting group. A cleavable chemical protecting group means a chemical group that is inert under the polymerization reaction conditions but can be removed by a chemical reaction after polymerization to produce a free -NH- or free -NH2 functional group of the ADAMS repeat unit. In one such form, at least one cleavable chemical protecting group is a benzyl group.

[0049] In yet another form, the ADAMS copolymer described above may further include one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or a combination thereof at one or more terminals of the copolymer backbone.

[0050] In yet another embodiment, in the ADAMS copolymer described above, one or more amino groups of the repeat unit of structure (V) may be protonated or alkylated to the corresponding ammonium salt. In such an embodiment, examples of the protonated or alkylated ammonium salt include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, triflate, nitrate counterion, or a combination thereof.

[0051] In particular, in one form of the ADAMS copolymer disclosed herein, the ADAMS copolymer comprises the following: (a) structure (I)

Chemical formula

Chemical formula

[0052] The above copolymer may contain one or more monomers including the following: 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-quinolinyl)-3-phenylbut-3-ene, 1-(1,2,3,1-(4-Tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N’-bis(3-phenylbut-3-enyl)diazepane, N,N’-bis(3-phenylbut-3-enyl)piperazine, N,N’-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N’-bis(3-phenylbut-3-enyl)dihydrobenzoimidazole, N,N’-bis(3-phenylbut-3-enyl)dihydropyrimidine, 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, or a combination thereof.,

[0053] Embodiments relating to ADAMS homopolymers In another form of the invention disclosed herein, a polymer comprising (a) Structure (V)

Chemical formula

[0054] The above homopolymer may contain three or more ADAMS repeat units according to structure (V), including the reaction forms of the following: 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-3-phenylbut-3-ene, 1-(N-pyrrolidinyl)-3-phenylbut-3-ene, 1-(N-pyrrolyl)-3-phenylbut-3-ene, 1-(1,2,3,1-(1,2,3,4-Tetrahydro-1-quinolinyl)-3-phenylbut-3-ene, 1-(1,2,3,4-tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N’-bis(3-phenylbut-3-enyl)diazepane, N,N’-bis(3-phenylbut-3-enyl)piperazine, N,N’-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N’-bis(3-phenylbut-3-enyl)dihydrobenzoindazole, N,N’-bis(3-phenylbut-3-enyl)dihydropelmidine, 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, or a combination thereof.,

[0055] Alternatively, the ADAMS homopolymer may further include an alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone, or an alkyl residue derived from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the center of the polymer backbone. In the case of an alkyl residue derived from a monofunctional initiator, such alkyl residues can include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof. Such alkyl residues derived from a difunctional initiator can include a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof.

[0056] Alternatively, the ADAMS homopolymer described above 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 more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of the non-aromatic bonds are saturated. In yet another form, the ADAMS homopolymer described above may be such that in structure (V), R1, R2, R'1, R'2, or a combination thereof is a cleavable chemical protecting group. A cleavable chemical protecting group means a chemical group that is inert under polymerization reaction conditions but can be removed by a chemical reaction after polymerization to produce a free -NH- functional group or a free -NH2 functional group of the ADAMS repeat unit. In one such form, at least one cleavable chemical protecting group is a benzyl group.

[0057] In yet another form, the ADAMS homopolymer described above may further include one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or combinations thereof, at one or more terminals of the polymer backbone. In yet another further form, the ADAMS homopolymer described above may be one in which the amino groups of one or more repeat units of structure (V) are protonated or alkylated to the corresponding ammonium salts. In such forms, examples of the protonated or alkylated ammonium salts include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, triflate, nitrate counterions, or combinations thereof.

[0058] Embodiments related to ACAMP copolymers In yet another form of the invention disclosed herein, a copolymer comprising (a) structure (VIII)

Chemical formula

Chemical formula

[0059] For the polymeric repeat unit of the above structure (VII a ), it may be in a cis isomeric form, a trans isomeric form, or a combination thereof. In an advantageous form, for the ACAMP copolymer described above, k = 2. The above copolymer contains one or more ACAMP repeat units according to structure (VI) including a reactive form of styrene, and one or more repeat units according to structure (VII a ) and (VII b ) contain a reactive form of isoprene, 1,3-butadiene, or a combination thereof. Alternatively, the ACAMP copolymer may further contain an alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone, or an alkyl residue derived from a bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the center of the polymer backbone. In the case of an alkyl residue derived from a monofunctional initiator, examples of such an alkyl residue include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof. Examples of such an alkyl residue derived from a bifunctional initiator include a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof.

[0060] Alternatively, the ACAMP copolymer described above 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 more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of the non-aromatic bonds are saturated.

[0061] Alternatively, in the ACAMP copolymer described above, one or more repeat units of structure (VIII) may be dispersed within at least one polymer block containing one or more repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof. Further alternatively, in the ACAMP copolymer described above, one or more repeat units of structure (VIII) may be partially or substantially alternating with one or more repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof, thereby forming one or more repeat units corresponding to structure (XII), (XII a ), (XII b ), or a combination thereof.

Chemical Structure

[0062] Partially alternating means that 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60% of one or more repeat positions of structure (VIII) are of structure (VI), (VII a ), (VII b) means alternating with one or more repeat units of these or combinations thereof. Substantially alternating means more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of one or more repeat units of structure (VIII) are with structure (VI), (VII a )、(VII b ) means alternating with one or more repeat units of these or combinations thereof.

[0063] In yet another form, the ACAMP copolymer described above comprises one or more polymer blocks that comprise one or more repeat units of structure (VI), (VII a )、(VII b ) or combinations thereof and do not comprise one or more repeat units according to structure (VIII). In such a form, one or more polymer blocks of the copolymer can form a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or combinations thereof. A dispersed polymer structure means that the repeat units of structure (VIII) are dispersed either randomly or uniformly over larger blocks of non-ACAMP repeat 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 repeat units of non-ACAMP monomers between ACAMP repeat units.

[0064] In yet another form, in the ACAMP copolymer described above, in structure (VIII), R1, R2, R'1, R'2, or a combination thereof may be a cleavable chemical protecting group. A cleavable chemical protecting group means a chemical group that is inert under the polymerization reaction conditions but can be removed by a chemical reaction after polymerization to produce a free -NH- functional group or a free -NH2 functional group in the ACAMP repeat unit. In one such form, at least one cleavable chemical protecting group is a benzyl group. In yet another form, the ACAMP copolymer described above may further include one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or a combination thereof, at one or more ends of the copolymer backbone. In yet another form, in the ACAMP copolymer described above, the amino groups of one or more repeat units of structure (VIII) may be protonated or alkylated to the corresponding ammonium salts. In such a form, examples of the protonated or alkylated ammonium salts include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, triflate, nitrate counterions, or a combination thereof.

[0065] Embodiments regarding ACAMP homopolymers In yet another form of the invention disclosed herein, a polymer comprising (a) structure (VIII)

Chemical formula

[0066] Alternatively, the ACAMP homopolymer may further contain an alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone, or an alkyl residue derived from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the middle of the polymer backbone. In the case of an alkyl residue derived from a monofunctional initiator, such alkyl residues can include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or combinations thereof. Such alkyl residues derived from a difunctional initiator can include a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or combinations thereof.

[0067] Alternatively, the ACAMP homopolymer described above may be partially or substantially hydrogenated. Partially hydrogenated means that 10% - 90%, or 20% - 80%, or 30% - 70%, or 40% - 60% of the non-aromatic double bonds are saturated. Substantially hydrogenated means that more than 90%, or more than 92%, or more than 94%, or more than 96%, or more than 98%, or more than 99%, or more than 99.5%, or more than 99.9% of the non-aromatic bonds are saturated.

[0068] In yet another form, in structure (VIII) of the ACAMP homopolymer described above, R1, R2, R’1, R’2, or a combination thereof may be a cleavable chemical protecting group. A cleavable chemical protecting group means a chemical group that is inert under the polymerization reaction conditions but can be removed by a chemical reaction after polymerization to produce a free -NH- functional group or a free -NH2 functional group in the ACAMP repeat unit. In one such form, at least one cleavable chemical protecting group is a benzyl group.

[0069] In yet another form, the ACAMP homopolymer described above may further include one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or a combination thereof at one or more terminals of the polymer backbone.

[0070] In still yet another form, in the ACAMP homopolymer described above, the amino group of one or more repeat units of structure (VIII) may be protonated or alkylated to the corresponding ammonium salt. In such a form, examples of the protonated or alkylated ammonium salt include chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, triflate, nitrate counterions, or a combination thereof.

[0071] Methods for Using ADAMS and ACAMPS Copolymers and Homopolymers Novel polymers based on the anionic polymerization of functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to phenyl rings, or functionalized conjugated (non-aromatic) monomers containing nitrogen-containing moieties, can be used in a wide variety of applications. In particular, the functional polymers of the present invention disclosed herein, based on functionalized styrenic monomers containing nitrogen-containing moieties other than as pendants to phenyl rings, or based on functionalized conjugated (non-aromatic) monomers containing nitrogen-containing moieties, can be polymerized from an addition-polymerizable monomer composition comprising an amine-derivatized alpha-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).

Chemical formula

Chemical formula

[0072] In particular, polymer compositions based on the anionic polymerization of functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to a phenyl ring, or based on functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety, include, but are not limited to, lithium ion battery additives, plastic additives, resistance reducers, magnetorheological fluids, electrochlorination additives, industrial coating additives, adhesive additives, asphaltene and wax inhibitors, refinery antifouling agents, industrial or household surfactants, pesticide additives, ceramic capacitor or indicator additives, emulsion explosive additives, antimicrobial coatings, crude oil transportation and refining additives, and carbon capture additives, and can be used in a variety of applications.)

[0073] Methods for making ADAMS and ACAMPS copolymers and homopolymers Novel polymers of functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to a phenyl ring, or of functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety, can be made by an anionic polymerization method.) The anionic polymerization method in which there is no functionalized styrene monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring or no functionalized conjugated (non-aromatic) monomer containing a nitrogen-containing moiety is generally known in the art and is described, for example, in U.S. Patent Nos. 5,736,612, 5,773,521, 8,604,136, and 9,809,671, and these documents are hereby incorporated by reference in their entirety. The anionic polymerization method generally includes at least the following steps: (a) polymerizing one or more monomers in an inert hydrocarbon solvent in the presence of an alkyllithium initiator until the conversion is substantially complete; (b) optionally adding one or more monomers of the same or different composition in one or more sequential additions to allow polymerization of each sequential addition of the monomers until the conversion is substantially complete; (c) optionally adding a polyfunctional coupling agent to couple some or all of the polymer or copolymer; (d) adding a terminator.

[0074] Anionic polymerization is generally initiated using an alkyllithium reagent, most frequently sec-butyllithium, but other monofunctional and difunctional 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, p. 2835 (1997)].

[0075] The monofunctional initiators that can be used are generally C2-C 12It may also be an alkyllithium compound, an alkylsodium compound, or an alkylpotassium compound within the range. Preferred alkyllithium compounds include, for example, methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, iso-butyllithium, sec-butyllithium, tert-butyllithium, n-amyllithium, iso-amyllithium, sec-amyllithium, tert-amyllithium, hexyllithium, or a combination thereof. More preferred are secondary alkyllithium compounds, such as sec-butyllithium, sec-amyllithium, or a combination thereof. sec-Butyllithium is most preferred. Substituted alkyllithium, such as aralkyllithium compounds, for example, benzyllithium, 1-lithioethylbenzene, and 1-lithio-3-methylpentylbenzene can also be used.

[0076] The difunctional initiator that can be used is generally an alkyldilithium compound, an alkyldisodium compound, or an alkyldipotassium compound within the range of C2 to C 12 For example, 1,3-propanediyldilithium, 1,4-butanediyldilithium, 1,5-pentanediyldilithium, 1,6-hexanediyllithium, or a combination thereof. Additional difunctional initiators are disclosed in U.S. Patent No. 6,492,469, which is hereby incorporated by reference in its entirety. A functionalized styrenic monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or a functionalized conjugated (non-aromatic) monomer containing a nitrogen-containing moiety, can copolymerize with isoprene, butadiene, styrene, and combinations thereof. Other non-limiting exemplary comonomers that may be copolymerized with a functionalized styrenic monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or a functionalized conjugated (non-aromatic) monomer containing a nitrogen-containing 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, and 2-methyl-4-propylstyrene, etc.), vinylnaphthalene, vinylpyridine, piperylene, methylpentyldiene. In another form, a functionalized styrenic monomer containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or a functionalized conjugated (non-aromatic) monomer containing a nitrogen-containing moiety, may be homopolymerized either as an isolatable homopolymer or as a homopolymer block in a copolymer.

[0077] Novel polymers of functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or of functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety, can be prepared by an anionic polymerization process in which the monomer or combinations thereof are polymerized in solution in an inert hydrocarbon solvent in the presence of an alkyllithium initiator. The inert hydrocarbon solvent does not react with the alkyllithium initiator or the "living" anionic chain ends of the polymer backbone and provides the product polymer with suitable solubility characteristics and can generally be any hydrocarbon having 5 to 8 carbons or mixtures thereof. Non-limiting examples of suitable solvents are cyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, all of which are relatively nonpolar. Other suitable solvents are known to those skilled in the art and can be selected to function effectively under a given set of process conditions, and one of the main factors considered is the polymerization temperature.

[0078] The polymerization is preferably carried out in the presence of a polar additive that reduces the association between the ions of the reactive "living" anionic chain ends of the polymer backbone and thereby promotes the polymerization. Non-limiting examples of polar additives include various ethers (i.e., dimethyl ether, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, anisole, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxybenzene, and 1-methoxy-2-(2-methoxyethoxy)ethane, etc.), various amines (i.e., trimethylamine, triethylamine, N,N,N’,N’-tetramethylethylenediamine, and N,N,N’,N’’,N’’-pentamethyldiethylenetriamine, etc.), or combinations thereof. Among the above polar additives, ethers are preferred. The polymerization reaction conditions for preparing novel polymers of functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to the phenyl ring, or functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety, are typically the same as those generally 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, alternatively 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 examples, the polymerization of the functionalized monomer and the copolymerization with other monomers and blocks can be carried out at room temperature, or alternatively at 15 to 70 °C, alternatively at 20 to 60 °C, alternatively at 25 to 50 °C, or a combination of such above-mentioned temperatures, or at individual temperatures within such ranges.

[0079] The polymerization reaction is carried out under a dry inert atmosphere, preferably under nitrogen, and may also be carried out under a pressure in the range of about 0 bar to about 10 bar. Once the polymerization reaction is complete, a terminating agent may be added to terminate the reaction and quench the reactive "living" anionic chain ends of the polymer backbone. The polymerization terminating agent may be any of various primary or secondary alcohols or epoxide terminating agents. Non-limiting examples of various primary or secondary alcohols include methanol, ethanol, isopropanol, and 2-ethyl-1-hexanol, etc., or combinations thereof. Non-limiting examples of epoxide terminating agents include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, and phenyl glycidyl ether, etc., or combinations thereof. Among the polymerization terminating agents, when one or more -OH functional groups are desired at one or more ends of the polymer chain, ethylene oxide or propylene oxide is preferred, and otherwise, methanol or isopropanol is preferred.

[0080] Novel polymers of functionalized styrenic monomers containing a nitrogen-containing moiety other than as a pendant to a phenyl ring or of functionalized conjugated (non-aromatic) monomers containing a nitrogen-containing moiety can optionally be isolated or purified by various common polymer isolation or purification techniques known in the art, for example, by pouring the polymerization reaction solution into a poor solvent for the polymer, such as methanol, to solidify the polymer, or by pouring the polymerization reaction solution into hot water together with steam to remove the solvent by azeotropy (steam stripping) and drying the resulting product. In view of the difficulty in preparing and polymerizing such monomers, Applicants have explored other potential structures of functional monomers that are simpler both to manufacture and further to polymerize. Functional monomer compositions containing aromatic and / or conjugated (non-aromatic) structures each containing at least one amine nitrogen are described in co-owned related U.S. Patent Application No. 63 / 483,365, filed February 6, 2023, the contents of which are hereby incorporated by reference in their entirety. To the knowledge of Applicants, the inventive monomers disclosed in U.S. Patent Application No. 63 / 483,365 have not been polymerized previously.

[0081] Additional Embodiments / EP Clauses In addition or alternatively, the present disclosure may include one or more of the following embodiments.

[0082] 1. A copolymer, comprising (a) Structure (V)

Chemical formula

[0083] 2. The copolymer according to clause 1, wherein k = 2.

[0084] 3. One or more ADAMS repeat units according to Structure (V) are 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-quinolinyl)-3-phenylbut-3-ene, 1-(1,2,3,1-(4-Tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N’-bis(3-phenylbut-3-enyl)diazepane, N,N’-bis(3-phenylbut-3-enyl)piperazine, N,N’-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N’-bis(3-phenylbut-3-enyl)dihydrobenzoimidazole, N,N’-bis(3-phenylbut-3-enyl)dihydropelmidine, 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, or a reaction form of a combination thereof, the copolymer according to clause 1 or 2.,

[0085] 4. One or more repeat units according to structure (VI) include a reaction form of styrene, and structure (VII a ) and (VII b ) One or more repeat units according to include a reaction form of isoprene, 1,3-butadiene, or a combination thereof, the copolymer according to clauses 1 to 3., 5. An alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone; or an alkyl residue derived from a bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the center of the polymer backbone, the copolymer according to clauses 1 to 4.,

[0086] 6. The alkyl residue derived from a monofunctional initiator includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof, or the alkyl residue derived from a difunctional initiator includes a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof, the copolymer according to item 5. 7. The copolymer according to items 1 to 6, which is partially or substantially hydrogenated. 8. One or more repeat units of structure (V) are scattered within at least one polymer block containing one or more repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof, the copolymer according to items 1 to 7.

[0087] 9. One or more repeat units of structure (V) are partially or substantially alternating with one or more repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof, thereby forming one or more repeat units corresponding to structure (IX), (X a ), (X b )

Chemical formula

[0088] 10. One or more polymer blocks containing one or more repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof and not containing one or more repeat units of structure (V), the copolymer according to item 9. 11. One or more polymer blocks of the copolymer are the copolymer according to clause 10, forming a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or a combination thereof. 12. The copolymer according to clauses 1 to 11, wherein in structure (V), R1, R2, R'1, R'2, or a combination thereof is a cleavable chemical protecting group.

[0089] 13. The copolymer according to clause 12, wherein at least one cleavable chemical protecting group is a benzyl group. 14. The copolymer according to clauses 1 to 13, further comprising one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or a combination thereof at one or more terminals of the copolymer backbone. 15. The copolymer according to clauses 1 to 14, wherein the amino group of one or more repeat units of structure (V) is protonated or alkylated to the corresponding ammonium salt. 16. The copolymer according to clause 15, wherein the protonated or alkylated ammonium salt comprises chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, triflate, nitrate counterion, or a combination thereof.

[0090] 17. A polymer, (a) structure (V) [Chemical formula] (wherein k is an integer from 1 to 3, and R1 and R2 are each independently a hydrocarbyl group or hydrocarbon group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R1 and R2 are connected to form a moiety comprising at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, R is selected from the group consisting of hydrogen, a phenyl ring covalently bonded to the phenyl ring in the notation and two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring in the notation, a C1-C4 hydrocarbyl group, O, N, S, P, Se, and a C1-C6 hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of these and combinations thereof, or structure (III)

Chemical formula

[0091] 18. The polymer according to clause 17, wherein k = 2. 19. Three or more ADAMS repeat units according to structure (V) are 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-(1,2,3,1-(4-Tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N’-bis(3-phenylbut-3-enyl)diazepane, N,N’-bis(3-phenylbut-3-enyl)piperazine, N,N’-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N’-bis(3-phenylbut-3-enyl)dihydrobenzoimidazole, N,N’-bis(3-phenylbut-3-enyl)dihydropyrimidine, 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, or a reaction form of a combination thereof, the polymer according to clause 17 or 18.,

[0092] 20. The polymer according to clauses 17 to 19, further comprising an alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at the end of the polymer chain, or an alkyl residue derived from a bifunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the middle of the polymer chain.,

[0093] 21. The alkyl residue derived from the monofunctional initiator includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof, or the alkyl residue derived from the bifunctional initiator includes a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof, the polymer according to clause 20., 22. The polymer according to clauses 17 to 21, wherein in structure (V), R1, R2, R'1, R'2, or a combination thereof is a cleavable chemical protecting group. 23. The polymer according to clause 22, wherein at least one cleavable chemical protecting group is a benzyl group.

[0094] 24. The polymer according to clauses 17 to 23, further comprising one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or a combination thereof, at one or more ends of the polymer backbone. 25. The polymer according to clauses 17 to 24, wherein the amino group of one or more repeat units of structure (V) is protonated or alkylated to the corresponding ammonium salt. 26. The polymer according to clause 25, wherein the protonated or alkylated ammonium salt comprises chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, triflate, nitrate counterion, or a combination thereof.

[0095] 27. A copolymer, comprising: (a) structure (VIII)

Chemical formula

Chemical formula

[0096] 28. The copolymer according to clause 27, wherein k = 2. 29. One or more repeat units having structure (VI) include a reactive form of styrene, and structure (VII a ) and (VII b ) one or more repeat units by include a reactive form of isoprene, 1,3-butadiene, or a combination thereof, the copolymer according to clause 27 or 28. 30. The copolymer according to clauses 27 to 29, further comprising an alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone, or an alkyl residue derived from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the center of the polymer backbone.

[0097] 31. The alkyl residue derived from a monofunctional initiator includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof, or the alkyl residue derived from a difunctional initiator includes a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof, the copolymer according to clause 30. 32. The copolymer according to clauses 27 to 31, which is partially or substantially hydrogenated. 33. One or more repeat units of structure (VIII) are structures (VI), (VII a ), (VII b) or one or more repeat units of these combinations, scattered within at least one polymer block, the copolymer described in clauses 27 to 32.

[0098] 34. One or more repeat units of structure (VIII) are partially or substantially alternating with one or more repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof, thereby forming one or more repeat units corresponding to structure (XI), (XII a ), (XII b ),

Chemical Structure

[0099] 35. The copolymer described in clause 34, which contains one or more polymer blocks containing one or more repeat units of structure (VI), (VII a ), (VII b ), or a combination thereof, and does not contain one or more repeat units according to structure (VIII).

[0100] 36. One or more polymer blocks of the copolymer form a dispersed polymer architecture, diblock, triblock, tetrablock, pentablock, hexablock, star polymer architecture, or a combination thereof, the copolymer described in clause 35. 37. In structure (VIII), R1, R2, R’1, R’2, or a combination thereof is a cleavable chemical protecting group, the copolymer described in clauses 27 to 36. 38. At least one cleavable chemical protecting group is a benzyl group, the copolymer described in clause 37. 39. The copolymer described in clauses 27 to 38 further contains one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or a combination thereof, at one or more terminals of the copolymer backbone. 40. The copolymer according to clauses 27 to 39, wherein one or more amino groups of the repeat unit(s) of structure (VIII) are protonated or alkylated to the corresponding ammonium salt.

[0101] 41. The copolymer according to clause 40, wherein the protonated or alkylated ammonium salt comprises a chloride, bromide, iodide, alkyl or aryl sulfonate, sulfate, phosphate, formate, acetate, propionate, butyrate, benzoate, triflate, nitrate counterion, or a combination thereof. 42. A polymer comprising (a) structure (VIII)

Chemical formula

[0102] 43. The polymer according to clause 42, wherein k = 2. 44. The polymer according to clause 42 or 43, further comprising an alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone, or an alkyl residue derived from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the middle of the polymer backbone. 45. The polymer according to clause 44, wherein the alkyl residue derived from a monofunctional initiator comprises a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof, or the alkyl residue derived from a difunctional initiator comprises a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof.

[0103] 46. The polymer according to clauses 42 to 45, which is partially or substantially hydrogenated. 47. The polymer according to clauses 42 to 46, wherein in structure (VIII), R1, R2, R'1, R'2, or a combination thereof is a cleavable chemical protecting group. 48. The polymer according to clause 47, wherein at least one cleavable chemical protecting group is a benzyl group. 49. The polymer according to clauses 42 to 48, further comprising one or more -OH functional groups, -NH- functional groups, or -NH2 functional groups, or a combination thereof, at one or more terminals of the copolymer backbone. 50. The polymer according to clauses 52 to 49, wherein the amino group of one or more repeat units of structure (VIII) is protonated or alkylated to the corresponding ammonium salt. 51. The polymer according to clause 50, wherein the protonated or alkylated ammonium salt comprises a chloride, a bromide, an iodide, an alkyl or aryl sulfonate, a sulfate, a phosphate, a formate, an acetate, a propionate, a butyrate, a benzoate, a triflate, a nitrate counterion, or a combination thereof.

[0104] 52. A copolymer, comprising: (a) structure (I)

Chemical formula

Chemical Formula

[0105] 53. One or more monomers are 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-(1,2,3,1-(4-Tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N’-bis(3-phenylbut-3-enyl)diazepane, N,N’-bis(3-phenylbut-3-enyl)piperazine, N,N’-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N’-bis(3-phenylbut-3-enyl)dihydrobenzoindazole, N,N’-bis(3-phenylbut-3-enyl)dihydropelmidine, 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, or a combination thereof, the copolymer according to clause 52.,

[0106] 54. A method for using a copolymer, comprising the steps of preparing a copolymer according to clauses 1 to 53, or an additive mixture comprising a copolymer according to clauses 1 to 53, and using the copolymer or the additive mixture comprising the copolymer in an application selected from the group consisting of lithium ion battery additives, plastic additives, resistance reducers, magnetic rheology fluids, electrochlorination additives, industrial coating additives, adhesive additives, asphaltene and wax inhibitors, refinery antifoulants, industrial or household surfactants, pesticide additives, ceramic capacitor or inductor additives, emulsion explosive additives, antimicrobial coatings, crude oil transportation and refining additives, and carbon capture additives., Hereinafter, the present invention will be described by way of examples that are merely non-limiting.,

Examples

[0107] Unless otherwise specified, all reactions were carried out in a glass vessel of appropriate size equipped with a magnetic stirrer and were performed inside a VAC OMNI-LAM inert atmosphere (e.g., N2) glove box. The atmosphere inside the glove box was maintained at less than 10 ppm oxygen and 0.2 ppm moisture. All monomers used in the anionic polymerization were purified by either distillation of the monomer, filtration of the monomer through basic aluminum oxide, or a combination of both, using methods that would be well known to one of ordinary skill in the art to remove added stabilizers or adventitious moisture. During the polymerization reactions described below, before reacting the main portion of the initiator solution, a small amount of the initiator solution is slowly added dropwise to the reaction. This “extra initiator” is immediately consumed by residual stabilizers or adventitious moisture in the solvent or reactants, and the exact volume will vary depending on the effectiveness of the monomer purification described above. The ADAMS-derived “living” anions responsible for the polymerization are dark orange in color. Once sufficient initiator has been added to the reaction mixture and a pale yellow color persists (indicating the presence of very little “living” anion), it is determined that the reaction contains no inhibitor / moisture, and the target volume of initiator solution can be added.

[0108] Samples of each polymer were purified for analysis by polymer isolation techniques well known to those of ordinary skill in the art, essentially 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. Samples of either the crude reaction mixture or the isolated polymer product were dissolved in stabilized tetrahydrofuran (THF) to prepare gel permeation chromatography (GPC) samples on a 3.0 - 5.0 ml scale such that the final sample concentration was 1.0 - 5.0 g polymer / ml THF. The samples were filtered through a PALL ACRODISC 0.45 μm PTFE filter prior to analysis. GPC was performed using an AGILENT 1260 INFINITY II system equipped with three AGILENT PLGEL 10μm Mixed B chromatography columns maintained at 35 °C by an AGILENT 1260 refractive index detector and a GPC column heater. A 50 μL injection volume was used, and stabilized THF (1.0 ml / min, isocratic) was used as the mobile phase, and the sample was flowed through with an experimental run time of 45.0 minutes. For GPC data analysis, AGILENT CIRUS GPC / SEC software, version 3.4.2 was used.

[0109] GPC was calibrated using a WATERS ACQUITY APC polystyrene (PS) test kit standard with Mn = 266 - 1,760,000 Da. All Mn, Mw, and Mz values of the polymer are reported relative to the PS standard unless otherwise specified. To prepare the NMR sample, approximately 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 well until the sample was completely dissolved, then transferred to an NMR tube. Using a Bruker AVANCE™ - 300 instrument, 1 1H NMR spectra (16 scans) were recorded at 300 MHz. The sample was prepared in benzene - d6. Chemical shifts (δ) are reported in parts per million (ppm) relative to TMS contained in the NMR solvent or, preferably, relative to the benzene - d6 solvent peak calibrated to 7.16 ppm for the solvent singlet.

[0110] Example 1 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 about 1 minute and then a 1.4 M solution of sec - butyllithium (0.20 ml, 0.28 mmol) was added all at once to obtain a bright orange solution. Enable stirring of the reactants at room temperature and extract an approximately 0.1 ml aliquot of the reaction mixture to 1 Monitor periodically by 1 H NMR. After about 6 hours, it was determined that the reaction was substantially complete, and isopropanol (0.2 ml, 2.6 mmol) was added to quench the reaction.

[0111] Example 2 Add anhydrous cyclohexane (15.0 ml) and anhydrous unstabilized THF (0.5 ml) to a 50 ml reactor, 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). Stir the solution for about 1 minute and then add 1.4 M sec-butyllithium solution (0.60 ml, 0.84 mmol) all at once to obtain a bright orange solution. Enable stirring of the reactants at room temperature and extract an approximately 0.1 ml aliquot of the reaction mixture to 1 Monitor periodically by 1 H NMR. After about 2 hours, it was determined that the reaction was substantially complete, and propylene oxide (0.065 ml, 0.93 mmol) was added to the reactants. The reactants gradually became colorless. Enable stirring of the reactants at room temperature for 1 hour. Then 1 1 H NMR indicated that the reaction was complete.

[0112] Example 3 Add anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) to a 50 ml reactor, followed by 1-(dibenzylamino)-3-phenylbut-3-ene (1.0 ml, 4.1 mmol) and isoprene (0.5 ml, 5.0 mmol). Stir the solution for about 1 minute and then add 1.4 M sec-butyllithium solution (0.40 ml, 0.56 mmol) all at once to obtain a bright orange solution. Enable stirring of the reactants at room temperature, 1While periodically monitoring by \(^1\)H NMR (as described above), additional amounts of isoprene (0.5 ml each, 5.0 mmol each) were added every 30 minutes until 3.5 hours had elapsed (a total of 4.0 ml of isoprene). Once the addition was complete, the reaction mixture was allowed to stir for an additional 1.5 hours at room temperature, after which the substantial completion of the reaction was 1 determined by \(^1\)H NMR and the reaction was quenched by adding isopropanol (0.4 ml, 5.2 mmol).

[0113] Example 4 Anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added to a 50 ml reactor, followed by styrene (3.0 ml, 26.2 mmol). The solution was stirred for about 1 minute and then a 1.4 M solution of sec-butyllithium (0.40 ml, 0.56 mmol) was added all at once to obtain a bright orange solution. The reaction mixture was allowed to stir at room temperature and an approximately 0.1 ml aliquot of the reaction mixture was withdrawn and 1 periodically monitored by \(^1\)H NMR. After about 1 hour, when the reaction was determined to be substantially complete, 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 mixture was allowed to mix for an additional approximately 3 hours at room temperature. 1 When \(^1\)H NMR indicated substantially complete consumption of the monomer, 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 mixture was mixed for an additional approximately 3 hours. Then, 1 \(^1\)H NMR also indicated substantially complete consumption of the monomer in this case, and the reaction was quenched by adding isopropanol (0.4 ml, 5.2 mmol).

[0114] Example 5 To a 50 ml reactor, anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added, followed by 1-(N-thiomorpholinyl)-3-phenylbut-3-ene (1.0 ml, 4.2 mmol). The solution was stirred for about 1 minute, and then a 1.4 M sec-butyllithium solution was added dropwise until a very slight orange color from the lithium anion persisted (about 0.012 ml). Thereafter, styrene (0.50 ml, 4.4 mmol) was added, followed by a second amount of 1.4 M sec-butyllithium (0.10 ml, 0.14 mmol) added all at once to obtain a bright orange solution. Allowed stirring of the reaction mixture at room temperature, 1 While periodically monitoring by 1H NMR (as above), additional amounts of styrene (each 0.5 ml, each 4.4 mmol) were added according to the timing in Table 1 below (a total of 3.0 ml of isoprene, 26.2 mmol in total over 3 hours). After the addition was complete, further stirring of the reaction mixture at room temperature for 1 hour was allowed. Thereafter, 1 1H NMR showed substantially complete consumption of the remaining monomer. Isoprene (4.0 ml, 39.9 mmol) was added to the reaction mixture and mixed at room temperature for an additional 2 hours. Thereafter, 1 1H NMR showed substantially complete consumption of isoprene. Additional amounts of styrene (each 0.5 ml, each 4.4 mmol) were added starting again at 0 minutes according to the timing in Table 1 below (a further 3.0 ml of isoprene, 26.2 mmol in total over 3 hours). After the addition was complete, stirring of the reaction mixture at room temperature overnight was allowed, and the reaction was quenched with isopropanol (0.10 ml, 1.31 mmol). [Table 1]

[0115] Example 6 To a 50 ml reactor, anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added, followed by 1-(N-morpholinyl)-3-phenylbut-3-ene (3.0 ml, 13.5 mmol) and isoprene (3.0 ml, 30.0 mmol). The solution was stirred for about 1 minute, and then a 1.4 M solution of sec-butyllithium (about 0.1 ml) was added dropwise until a very slight orange color from the lithium anion persisted, and then a second amount of 1.4 M sec-butyllithium (0.10 ml, 0.14 mmol) was added all at once to obtain a bright orange solution. Allowed stirring of the reactants at room temperature, and an approximately 0.1 ml aliquot of the reaction mixture was extracted and 1 monitored periodically by 1H NMR. After about 6 hours, it was determined that the reaction was substantially complete, and then divinylbenzene [technical grade, 80%] (0.10 ml, 0.56 mmol) was added to the reactants to obtain a dark red solution. Further mixing of the reactants at room temperature for 2 hours was allowed. Then, 1 the presence of residual divinylbenzene was not detected by 1H NMR. Isopropanol (0.1 ml, 1.31 mmol) was added to quench the reaction.

[0116] Example 7 To a 50 ml reactor, anhydrous cyclohexane (23.5 ml) and anhydrous unstabilized THF (0.5 ml) were added, followed by isoprene (3.0 ml, 30.0 mmol). The solution was stirred for about 1 minute, and then a 1.4 M solution of sec-butyllithium (0.050 ml, 0.070 mmol) was added all at once to obtain a bright orange solution. Allowed stirring of the reactants at room temperature, and an approximately 0.1 ml aliquot of the reaction mixture was extracted and 1 monitored periodically by 1H NMR. After about 1 hour, 1 1H NMR showed substantially complete consumption of isoprene, at which point 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 reactants. Further mixing of the reactants at room temperature for 4 hours was allowed. Then, 11H NMR indicated substantially complete consumption of the remaining monomers. Divinylbenzene [technical grade, 55%] (0.055 ml, 0.21 mmol) was added to the reaction to give a dark red solution. After allowing the reaction to mix for an additional 2 h at room temperature, 1 the presence of residual divinylbenzene was not detected by 1H NMR. Isopropanol (0.050 ml, 0.65 mmol) was added to quench the reaction.

[0117] Example 8 To a 250 ml dry glass bottle equipped with a magnetic stirrer was added 200 ml of anhydrous cyclohexane and 4.0 ml of anhydrous tetrahydrofuran, followed by 1.0 ml of 1-(N-morpholinyl)-3-phenylbut-3-ene (4.5 mmol) and 36.0 ml of isoprene (359.5 mmol). The solution was stirred for about 1 minute and a 0.1 ml aliquot of the solution was withdrawn 1 for 1H NMR. A small amount (typically 0.05 - 0.20 ml) of a 1.12 M sec-butyllithium solution in cyclohexane was slowly added dropwise to the reaction mixture until the solution turned a persistent pale yellow, after which an additional 0.45 ml of the 1.12 M sec-butyllithium solution (0.50 mmol) was added all at once. The reaction was allowed to stir at room temperature and about 0.1 ml aliquots of the reaction mixture were withdrawn and 1 monitored periodically by 1H NMR. When substantial completion of the reaction was 1 determined by 1H NMR, 0.45 ml of isopropanol (5.9 mmol) was added to quench the reaction.

[0118] Example 9 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) and 35.0 ml of isoprene (349.5 mmol) were added instead. Example 10 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) and 32.0 ml of isoprene (319.5 mmol) were added instead. Example 11 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 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.

[0119] Example 13 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 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 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 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.

[0120] Example 17 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 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 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.

[0121] Example 20 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 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 using 2.4 ml of isopropanol (2.0 mmol). Example 22 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 using 2.4 ml of isopropanol (0.7 mmol).

[0122] Example 23 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 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.

[0123] Example 25 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, and 14.0 ml of isoprene (139.8 mmol) and 0.56 ml of 1.12 M sec-butyllithium (0.62 mmol) were added instead. Example 26 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 (159.5 mmol) was added instead. When the substantial completion of the initial reaction was 1 determined by 1H NMR, 2.0 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (9.1 mmol) and 16.0 ml of isoprene (159.8 mmol) were added, and the reaction was continued until the completion of the second stage of the reaction was 1 determined by 1H NMR.

[0124] Example 27 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. When the substantial completion of the initial reaction was 1 determined by 1H NMR, an additional portion of 1.4 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (6.4 mmol) and 11.0 ml of isoprene (109.8 mmol) was added and the reaction was continued. When it was determined by 1H NMR that the second stage of the reaction was substantially complete 1 an additional portion of 1.4 ml of 1-(N-piperidinyl)-3-phenylbut-3-ene (6.4 mmol) and 11.0 ml of isoprene (109.8 mmol) was added, and the completion of the third stage of the reaction was 1The reaction was continued until judged by 1H NMR. Example 28 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. When the substantial completion of the initial reaction was 1 judged by 1H NMR, 0.45 ml of technical grade divinylbenzene (55%, 1.7 mmol) was added, and the reaction was continued for an additional 1 hour before quenching the reaction.

[0125] Example 29 To a 250 ml dry glass bottle equipped with a magnetic stirrer, 100 ml of anhydrous cyclohexane and 4.0 ml of anhydrous tetrahydrofuran were added, followed by 2.1 ml of 1-benzylmethylamino-3-phenylbut-3-ene (8.2 mmol) and a 15% 1,3-butadiene solution in 100 ml of hexane (189.1 mmol). The solution was stirred for about 1 minute, and a 0.1 ml aliquot of the solution was 1 extracted for 1H NMR. A 1.12 M sec-butyllithium solution in a small volume (typically 0.5 - 1.5 ml) of cyclohexane was slowly added dropwise to the reaction mixture until the solution turned a persistent pale yellow, after which an additional 1.0 ml of 1.12 M sec-butyllithium solution (1.1 mmol) was added all at once. Stirring of the reaction mixture was allowed at room temperature, and about 0.1 ml aliquots of the reaction mixture were extracted and 1 monitored periodically by 1H NMR. When the substantial completion of the reaction was 1 judged by 1H NMR, 1.0 ml of isopropanol (13.1 mmol) was added to quench the reaction. Example 30 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.

[0126] Example 31 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 (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. When the substantial completion of the initial reaction was 1 determined by 1H NMR, an additional portion of 10.0 ml of styrene (87.3 mmol) was added and the reaction was continued until the completion of the second stage of the reaction was 1 determined by 1H NMR. Example 32 Under a nitrogen atmosphere in a 250 ml round-bottom flask equipped with a magnetic stirring water-cooled condenser, 6.0 g of the isolated polymer of Example 17 (approximately 3.9 wt% of ADAMS repeat units) was dissolved in 80 ml of stabilized tetrahydrofuran. To this solution, 0.14 ml of benzyl bromide (1.2 mmol, 1.1 molar equivalents relative to the ADAMS repeat units) was added and the solution was subsequently heated at 65 °C for 3 hours. The reaction mixture was allowed to cool and the polymer solution was used directly in the emulsification step without further purification. For GPC analysis, a small aliquot of the solution was evaporated under reduced pressure.

[0127] Example 33 The sample was prepared according to the procedure of Example 38, except that the isolated polymer of Example 18 (approximately 7.8 wt% of ADAMS repeat units) was used instead of the polymer of Example 17 and 0.29 ml of benzyl bromide (2.4 mmol, 1.1 molar equivalents relative to the ADAMS repeat units) was added instead. Example 34 The sample was prepared according to the procedure of Example 38, except that the isolated polymer of Example 19 (approximately 15.3 wt% ADAMS repeat units) was used instead of the polymer of Example 17, and 0.56 ml of benzyl bromide (4.7 mmol, 1.1 molar equivalents relative to the ADAMS repeat units) was added instead.

[0128] Example 35 To a reactor equipped with a water-cooled reflux condenser, anhydrous THF (20 ml), a sample of the poly(isoprene-co-1-(pyrrolidin-1-yl)-3-phenylbut-3-ene) of Example 1 (0.467 g), and benzyl bromide (0.13 g, 0.77 mmol) were added at ambient temperature. The mixture was heated to reflux for 3 hours (about 66 °C). Cooling of the mixture to ambient temperature was enabled, and the solvent was removed under reduced pressure to obtain a dry solid powder. This powder was poorly soluble in THF at ambient temperature (and thus could not be analyzed under standard GPC conditions). In 1 1H NMR analysis in methanol-d4, the presence of a polymer showing a sharp peak at about 3.74 ppm was indicated (this peak is thought to correspond to the benzyl CH2 protons adjacent to the quaternary ammonium salt). Example 36 In a pressure reactor, 1.1 g of the isolated polymer of Example 8 was dissolved in 100 ml of cyclohexane, followed by the addition of 0.2 g of rhodium(I) tris(triphenylphosphine) chloride. The reactor was then sealed and purged first with N2 gas and then with hydrogen gas. The reaction solution was heated to 140 °C for 4 hours under a hydrogen gas pressure of 425 psi and then cooled and the reactor was opened. The product solution was filtered through an activated carbon pad (NORIT AS5) and CELITE 545 to remove residual catalyst, and then the polymer solution filtrate was concentrated under reduced pressure. 1 1H NMR analysis showed that the alkene C-H bonds in the range of 4.0 - 6.0 ppm were reduced by 85% compared to the morpholine group CH2-O peak at about 3.8 ppm.

[0129] Example 37 (predicted example) Under an inert atmosphere, 3.0 g of a sample of the poly(isoprene-co-1-(dibenzylamino)-3-phenylbut-3-ene) of Example 3 is dissolved in 20 ml of cyclohexane, and then 1.0 ml of a solution of cobalt neodecanoate-triethylaluminum (a 0.0962 mol / L cyclohexane solution) is added as a hydrogenation catalyst. The atmosphere in the reactor is purged with hydrogen gas, and the hydrogenation reaction is carried out at a maximum hydrogen pressure of 2 MPa and a maximum temperature of 150 °C until hydrogen consumption (monitored by the pressure difference in the reactor) ceases. After cooling and depressurization, an aqueous phosphoric acid solution is added under an air atmosphere. The solution is washed with an excess amount of aqueous potassium hydroxide solution and then with water. Then, the polymer solution is concentrated under reduced pressure to obtain a hydrogenated block copolymer.

[0130] Example 38 (Predicted Example) Under an inert atmosphere, 3.0 g of a sample of the poly(isoprene-co-1-dibenzylmethylamino-3-phenylbut-3-ene) of Example 7 is dissolved in 20 ml of cyclohexane, and then 1.0 ml of a solution of cobalt neodecanoate-triethylaluminum (a 0.0962 mol / L cyclohexane solution) is added as a hydrogenation catalyst. The atmosphere in the reactor is purged with hydrogen gas, and the hydrogenation reaction is carried out at a maximum hydrogen pressure of 2 MPa and a maximum temperature of 150 °C until hydrogen consumption (monitored by the pressure difference in the reactor) ceases. After cooling and depressurization, an aqueous phosphoric acid solution is added under an air atmosphere. The solution is washed with an excess amount of aqueous potassium hydroxide solution and then with water. Then, the polymer solution is concentrated under reduced pressure to obtain a hydrogenated block copolymer.

[0131] Explanation of the data in Table 2: The amine functional groups present within the functional monomers used in Examples 1 - 31 are known or reasonably believed to interact with the stationary phase of standard GPC chromatography columns, thereby shifting the polymer retention times measured by the chromatography system. As a result, significant sources of error can be introduced into the molecular weight values reported by GPC (based on retention times within the GPC column). The magnitude of this error can potentially depend on the individual ADAMS monomer structure, the weight % content of ADAMS repeat units in the copolymer, the distribution of ADAMS repeat units within the polymer backbone, or combinations thereof. Due to such potential sources of error, Table 2 below includes the calculated target number average molecular weight Mn values for the polymers produced in Examples 1 - 31. Such calculated values are based on the molar ratio of the monomers and the alkyllithium initiator used in the reaction, as shown in Equation 1.

Number

[0132] The molecular weight calculated values in Table 2 are not corrected against polystyrene standards for comparison purposes. 1 When reaction monitoring by 1H NMR indicated that the ADAMS monomer formed a major alternating copolymer structure with the comonomer (even in the presence of a large molar excess of comonomer, as 1 evidenced by the approximately 1:1 molar consumption rate of both monomers by 1H NMR monitoring), the alternating ADAMS / comonomer polymer blocks are described as separate blocks from the polymer blocks containing the remaining comonomer. (See above). In such cases, the repeat units within the ADAMS / comonomer blocks have the structure (IX), (Xa ) and (X b ) are considered to be combinatorial alternating structures, and there are no additional comonomer repeat units in the ADAMS / comonomer block. The GPC molecular weights reported in Table 2 are based on samples taken from either the polymerization reaction between sequential additions of monomers or the final product polymer after isolation. Therefore, both the calculated and measured molecular weights reported in Table 2 are cumulative molecular weights, indicating the total polymer molecular weight at the completion of each polymer block sampled. When the monomer reactivity ratios first lead to the polymerization of the ADAMS-containing block ( 1 revealed by 1H NMR monitoring), followed immediately by the polymerization of the second block of the remaining comonomer, the ADAMS-containing block cannot be isolated independently, and only the total Mn of both blocks is reported.

[0133] In Table 2, IP refers to isoprene, BD refers to 1,3-butadiene, STY refers to styrene, PDI refers to the polydispersity index, and CR refers to the star polymer coupling ratio. In the case of the alkylated ADAMS copolymers of Polymer Examples 32 - 35, no polymer peaks were visible by GPC because of the strong interaction with the stationary phase of the GPC column.

Table 2-1

Table 2-2

Table 2-3

Table 2-4

Table 2-5

Table 2-6

Table 2-7

[0134] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent not inconsistent with the text. As should be apparent from the foregoing general description and specific embodiments, while 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, the invention is not intended to be limited thereby. The term "comprising" specifies the presence of the described feature, step, integer, or component, but does not preclude the presence or addition of one or more other features, steps, integers, components, or groups thereof. Therefore, the term "comprising" is considered to be essentially synonymous with the term "including". Similarly, whenever a transitional phrase "comprising" precedes a composition, element, or group of elements, it is always contemplated that the same composition or group of elements preceded by transitional phrases "consisting essentially of", "consisting of", "selected from the group of consisting of", or "can be", "may be", "is", which describe the composition, element, or group of elements, and vice versa should be understood. The well-known term "comprising" means "[open]" including the subsequent and any other things, and "consisting of" means "[closed]" including only the subsequent things, while the term "consisting essentially of" is understood to be semi-inclusive according to US judicial interpretation and means including the subsequent and other things that do not substantially affect the basic and novel characteristics.

[0135] The applicant has attempted to disclose all reasonably foreseeable embodiments and applications of the subject matter of this disclosure. However, there may be modifications that are unforeseeable and not substantial, yet still equivalents. While the invention has been described in connection with its particular exemplary embodiments, it will be apparent to those skilled in the art that, in light of the foregoing description, numerous changes, modifications, and variations can be made without departing from the spirit or scope of this disclosure. Accordingly, this disclosure is intended to embrace all such changes, modifications, and variations of the foregoing detailed description.

[0136] All patents, test procedures, and other documents cited herein, including priority documents, are hereby incorporated by reference in their entirety to the extent such disclosure is not inconsistent with the invention and within the scope of all jurisdictions in which such incorporation is permitted.

[0137] Where numerical lower and upper limits are recited herein, ranges from any lower limit to any upper limit are contemplated.

Claims

1. A copolymer, (a) Structure (V) 【Chemical Formula 1】 (wherein, k is an integer from 1 to 3, R 1 and R 2 each independently is a hydrocarbyl group or hydrocarbon group having from 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R 1 and R 2 are connected to form a moiety comprising at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, R is hydrogen, a phenyl ring covalently bonded to the phenyl ring in the notation at two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring in the notation, C 1 to C 4 a C hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof 1 to C 6 a hydrocarbyl group, or Structure (III) 【Chemical 2】 (wherein R' 1 and R' 2 are independently the same as or different from R 1 and R 2 and are identically defined), is a second amino functional group bonded via an asterisk), one or more amine-derivatized alpha-methylstyrene (ADAMS) repeat units, and (b) Structures (VI), (VII a ), (VII b ) [Chemical Formula 3] (wherein, R 5 is a hydrogen or methyl group, R’ is hydrogen, a phenyl ring covalently bonded at the phenyl ring of the notation and two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring of the notation, C 1 ~C 4 hydrocarbyl group, and / or a combination thereof), or one or more repeat units by a combination thereof A copolymer containing.

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

3. One or more ADAMS repeat units according to the structure (V) are 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-quinolinyl)-3-phenylbut-3-ene, 1-(1,2,3,4-Tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)diazepane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzoindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropelmidine, 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)hexahydropyrroloindole, 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 reaction form of a combination thereof, the copolymer according to claim 2.

4. One or more repeat units according to said structure (VI) comprise a reactive form of styrene, said structure (VII a ), and one or more repeat units according to (VII b ) comprise a reactive form of isoprene, 1,3-butadiene, or a combination thereof, the copolymer according to any one of claims 1 to 3.

5. An alkyl residue derived from a monofunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator present at one or more terminals of the polymer backbone or An alkyl residue derived from a difunctional alkyllithium, alkylsodium, and / or alkylpotassium initiator substantially in the center of the polymer backbone The copolymer according to any one of claims 1 to 4, further comprising.

6. The alkyl residue derived from the monofunctional initiator includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an iso-amyl group, a sec-amyl group, a tert-amyl group, a hexyl group, or a combination thereof, or The alkyl residue derived from the difunctional initiator includes a propyl group, a butyl group, a pentyl group, a hexyl group, a 1,4-diphenylbutyl group, or a combination thereof, The copolymer according to claim 5.

7. The copolymer according to any one of claims 1 to 6, which is partially or substantially hydrogenated.

8. One or more repeat units of said structure (V) are interspersed within at least one polymer block comprising one or more repeat units of said structure (VI), (VII a ), (VII b ), or combinations thereof, the copolymer according to any one of claims 1 to 7.

9. One or more repeat units of said structure (V) are partially or substantially alternating with one or more repeat units of said structure (VI), (VII a ), (VII b ), or combinations thereof, thereby forming structures (IX), (X a ), (X b ) 【Chemical 4】 The copolymer according to claim 8, which forms one or more repeat units corresponding to these or a combination thereof.

10. Said structure (VI), (VII a ), (VII b ), or one or more repeat units of a combination thereof, and comprising one or more polymer blocks that do not include one or more repeat units according to said structure (V), the copolymer according to claim 9.

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

12. In the structure (V), R 1 , R 2 , R' 1 , R' 2 , or a combination thereof, is a cleavable chemical protecting group, the copolymer according to any one of claims 1 to 11.

13. One or more -OH functional groups, -NH- functional groups, or -NH 2 functional groups, or a combination thereof, are further included at one or more ends of the copolymer backbone, and the copolymer according to any one of claims 1 to 12.

14. The amino group of one or more repeat units of the structure (V) is protonated or alkylated to the corresponding ammonium salt, the copolymer according to any one of claims 1 to 13.

15. A polymer, (a) Structure (V) 【Chemical Formula 5】 (wherein, k is an integer from 1 to 3, R 1 and R 2 is each independently a hydrocarbyl group or hydrocarbon group having from 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R 1 and R 2 are connected to form a moiety comprising at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, R is hydrogen, a phenyl ring covalently bonded to the phenyl ring in the notation at two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring in the notation, C 1 ~C 4 A C hydrocarbyl group containing 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof 1 ~C 6 Hydrocarbyl group, or structure (III) [Chemical Formula 6] (R' 1 and R' 2 are independently the same as or different from R 1 and R 2 and are identically defined), and are second amino functional groups joined via an asterisk), and contains three or more amine-derivatized alpha-methylstyrene (ADAMS) repeat units by (b) There are substantially no other repeat units, A polymer.

16. A copolymer, (a) Structure (VIII) [Chemical Formula 7] (wherein, k is an integer from 1 to 3, R 1 and R 2 is, independently of one another, a hydrocarbyl group or hydrocarbon group having from 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R 1 and R 2 are connected to form one or more repeat units (by forming a moiety comprising at least one 5- to 12-membered ring, from 3 to 28 carbons, and optionally, from 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof), and (b) Structures (VI), (VII a ), (VII b ) 【Chemical 8】 (wherein, R 5 is a hydrogen or methyl group, R' is hydrogen, a phenyl ring covalently bonded at the phenyl ring of the notation and two adjacent ring carbon positions so as to form a naphthalene assembly, a phenyl group bonded to a single carbon of the phenyl ring of the notation, C 1 ~C 4 hydrocarbyl group, and / or a combination thereof), or one or more repeat units by a combination thereof A copolymer containing.

17. A polymer, (a) Structure (VIII) 【Chemical Formula 9】 (wherein k is an integer from 1 to 3, R 1 and R 2 is each independently a hydrocarbyl group or hydrocarbon group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R 1 and R 2 are connected to form a moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof), and contains three or more repeat units by (b) a polymer in which substantially no other repeat units are present. Polymer.

18. A copolymer comprising (a) Structure (I) 【Chemical Formula 10】 (wherein k is an integer from 1 to 3, R 1 and R 2 is each independently a hydrocarbyl group or hydrocarbon group having 1 to 4 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, or R 1 and R 2 are connected to form a moiety containing at least one 5- to 12-membered ring, 3 to 28 carbons, and optionally 1 to 6 additional heteroatoms selected from the group consisting of O, N, S, P, Se, and combinations thereof, R is hydrogen, a phenyl ring covalently bonded to the phenyl ring shown to form a naphthalene assembly at two adjacent ring carbon positions, a phenyl group bonded to a single carbon of the phenyl ring shown, C 1 - C 4 hydrocarbyl group, O, N, S, P, Se, and a C containing 1 to 4 additional heteroatoms selected from the group consisting of combinations thereof 1 - C 6 hydrocarbyl group, or structure (III) 【Chemical 11】 (wherein R' 1 and R' 2 are independently R 1 and R 2 which are the same as or different from, but are identically defined), is a second amino functional group bonded via an asterisk), one or more monomers by (b) isoprene, 1,3-butadiene, styrene, or a combination thereof, and (c) a reaction product of an alkyllithium initiator, an alkylsodium initiator, an alkylpotassium initiator, or a combination thereof A copolymer comprising.

19. The one or more monomers are 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-piperidinyl)-3-phenylbut-3-ene, 1-(N-piperazinyl)-3-phenylbut-3-ene, 1-(N-diazepanyl)-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-quinolinyl)-3-phenylbut-3-ene, 1-(1,2,3,4-Tetrahydro-2-isoquinolinyl)-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-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-diazepanyl)-3-phenylbut-3-ene, N,N'-bis(3-phenylbut-3-enyl)diazepane, N,N'-bis(3-phenylbut-3-enyl)piperazine, N,N'-bis(3-phenylbut-3-enyl)dihydrophenazine, N,N'-bis(3-phenylbut-3-enyl)dihydrobenzoindazole, N,N'-bis(3-phenylbut-3-enyl)dihydropelmidine, 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)hexahydropyrroloindole, 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, the copolymer according to claim 18.,

20. A method for using a copolymer, comprising preparing the copolymer according to claim 18, or an additive mixture comprising the copolymer according to claim 18, and in an application selected from the group consisting of lithium-ion battery additives, plastic additives, resistance reducers, magnetorheological fluids, electrochlorination additives, industrial coating additives, adhesive additives, asphaltene and wax inhibitors, oil refinery antifouling agents, industrial or household surfactants, pesticide additives, ceramic capacitor or inductor additives, emulsion explosive additives, antimicrobial coatings, crude oil transportation and refining additives, and carbon capture additives, using the copolymer or the additive mixture comprising the copolymer A method comprising.

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