Process for preparation and manufacture of amine-containing polybutadiene polymers

Abstract

The production of amine-containing polymers from commodity polyolefins has been achieved by functionalization of polybutadiene. The pre-functionalized polybutadiene is composed of butadiene and optionally other monomers such as styrene. The butadiene monomer may be linked with a mixture of a 1, 4-subunit and a 1, 2-subunit. Amine functionalization of polybutadiene substrates has been achieved using a single step catalytic reaction referred to as hydroaminoalkylation (HAA).

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 330,696, filed on April 13, 2022, the entire contents of which are incorporated by reference in their entirety for all purposes. Technical Field

[0003] The present disclosure provides a hydroaminoalkylation reaction of polybutadiene for making an aminated polybutadiene having branched pendant amine groups. Background Art

[0004] Functionalization of polyolefins with polar groups can be used for a variety of applications. Franssen et al., Chem. Soc. Rev. 2013, 42(13): 5809-5832. Incorporation of amine functional groups into polyolefins is attractive but remains relatively difficult to achieve through conventional approaches. For example, amine-containing monomers are generally incompatible with the most commonly used polymerization methods (such as Ziegler-Natta, metallocene or free radical polymerization). Some metallocene catalysts can be used to incorporate rare tertiary amine-containing monomers. Post-polymerization methods generally have poor selectivity and / or atom efficiency. In other cases, organoaluminum protection of pendant amines has enabled incorporation into polyolefin chains through olefin-protected amine enchainment. This route has proven to be very complex because the protected amine olefin is difficult to recover, the protected amine olefin reacts with impurities, and the deprotection step is expensive and complicated.

[0005] Therefore, the synthesis of amine-functionalized polymers remains a challenge due to the nucleophilicity and basicity of amines. Amines hinder most polymerization mechanisms and are difficult to directly catalyze through metal-based reactions. In general, such pathways are not simple; they may involve multiple steps and expensive reagents. Rodriguez et al., Macromolecules 2021, 54(11): 4971-4985. Despite the difficulty in installation, amine functional groups can impart improved polarity, hydrogen bonding ability, and / or amphiphilic properties to the material. Franssen et al., Chem. Soc. Rev. 2013, 42(13):5809-5832; Pelton, Langmuir 2014, 30(51):15373-15382; Gilmour et al., ACS Applied Polymer Materials 2021, 3(5):2330-2335; Kuanr et al., Macromolecules 2020, 53(7):2649-2661. Such amine-containing materials can be used as fuel additives and lubricants, in paints, adhesives and coatings, as drug delivery systems, anion exchange membranes and as components in reactive polymer blends compatible with immiscible polymer blends.

[0006] A common method for placing amines on polyolefins involves functionalizing unsaturated polyolefins via a high-pressure reaction sequence of hydroformylation followed by reductive amination. This process is often referred to as a tandem process of hydroaminomethylation / aminomethylation. Rodriguez et al., Macromolecules 2021, 54(11): 4971-4985; McGrath et al., Chem. Rev. 1995, 95(2): 381-398. The hydroaminomethylation / hydroformylation-reductive amination sequence generally favors the formation of a CC bond on the terminal carbon of the pendant vinyl group of the 1,2-polybutadiene repeating unit, thereby providing a "linear" aminated variant. Although these are industrially well-established methods, these reactions result in stoichiometric waste and poor control of amine incorporation.

[0007] US Patent Application Publication No. US2021 / 0002407 A1 discloses a hydroformylation / reductive amination reaction sequence (also known as hydroaminomethylation) for placing amines onto polyolefin mixtures. The hydroaminomethylation reaction produces primarily "linear" products.

[0008] Scenario 1:

[0009]

[0010] Hydroaminoalkylation has some advantages as a one-step catalytic reaction that can directly amine functionalize unsaturated polyolefins. Edwards et al., Chemical Communications 2018, 54(89): 12543-12560. Hydroaminoalkylation has recently been reported to be an effective post-polymerization amination route for providing terminal aminated polyolefins from vinyl terminated polypropylene. Scott et al., ACS Macro Letters 2021, 10(10): 1266-1272; Daneshmand et al., J. Am. Chem. Soc. 2020, 142(37): 15740-15750.

[0011] The present disclosure describes a one-step catalytic method for installing amine groups onto polymers containing a large number of unsaturation points, such as polybutadiene, which was not known before. Hydroaminoalkylation is a known method for functionalizing small molecules, but has only been reported for functionalizing polymers with polyolefins carrying a single reactive unsaturation at the terminal end. Recent advances in the generation of highly electrophilic and robust early transition metal catalysts have enabled us to predictably and efficiently install amine groups onto challenging polymer substrates without forming stoichiometric waste products. The present disclosure describes highly electrophilic early transition metal catalysts for efficiently installing amine groups onto polybutadiene substrates by hydroaminoalkylation, which were not known before the present disclosure herein. Summary of the invention

[0012] The disclosure described herein is based on the discovery that catalytic hydroaminoalkylation of polybutadiene produces aminated polybutadiene with a predominance of branched pendant amine functional groups. This reaction can be applied with a wide range of amine and polybutadiene polymer reactants to produce products with controlled amine incorporation. The introduction of amines provides polar groups that increase the utility and applicability of these products.

[0013] The present disclosure includes the hydroaminoalkylation reaction of unsaturated polyolefins with catalysts such as tantalum urate complexes. Compared to related processes such as Ta(NMe2)5 and Ta(NEt2)2Cl3 catalysts in U.S. Pat. No. 8,669,326 to Hagadorn et al., the process of the present invention produces products with controlled amine incorporation with shorter reaction times, lower temperatures, and an expanded amine substrate range. A further advantage is the ability to conduct the reactions described herein at ambient pressure. This reaction can enable new connection modes by preferentially and selectively utilizing pendant vinyl groups to form branched products; thereby providing new compositions of matter.

[0014] In a first embodiment, provided herein is a polymer comprising:

[0015] Polybutadiene backbone;

[0016] 1,2-Olefin units,

[0017] 1,4-olefin units; and

[0018] Branched substituted units having functional groups of formula (I):

[0019]

[0020] A linear substituted unit having a functional group of formula (I):

[0021] wherein the molar ratio of branched substituted units to linear substituted units is 6:1 or greater;

[0022] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0023] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0024] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0025] R 3 and R 4 is independently selected from H, -C1-C6 alkyl and -C1-C6 heteroalkyl at each occurrence;

[0026] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0027] wherein the polymer optionally comprises other units; and

[0028] The units can be arranged in series, in blocks, or randomly distributed.

[0029] In a second embodiment, provided herein is a compound of formula (II)

[0030] A polymer, or a fragment thereof, wherein

[0031] When there is R on the c unit 5 When there is no R on the c unit, the dashed line represents a single bond. 5 When , the dotted line represents a double bond;

[0032] R 5 Optionally a compound of formula (I)

[0033] in

[0034] R 1 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0035] R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or

[0036] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 3 and R 4 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0037] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0038] R 6 is hydrogen, -C1-C 20 Alkyl, -C6-C 20 Aryl, -C 1-6 Alkyl-C1-C 20 Alkyl, -C 1-6 Alkyl-C6-C 20 Aryl, -C 1-6 Heteroalkyl-C1-C 20 Alkyl or -C 1-6 Heteroalkyl-C6-C 20 aryl; and

[0039] a, b, c, d, e and f are independently at each occurrence from 0 to 100,000; wherein the ratio of d:e is 6:1 or greater, and wherein the units may be ordered or randomly distributed.

[0040] In a third embodiment, provided herein is a polymer comprising:

[0041] Polybutadiene backbone;

[0042] 1,2-Olefin units,

[0043] 1,4-olefin units; and

[0044] 1,4-addition unit substituted with a functional group of formula (I):

[0045] in

[0046] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0047] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0048] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0049] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0050] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0051] wherein the polymer optionally comprises other units; and

[0052] The cells can be ordered or randomly distributed.

[0053] In a fourth embodiment, provided herein is a polymer comprising:

[0054] Polybutadiene backbone;

[0055] A unit comprising a repeating unit of a 1,2-olefin,

[0056] units comprising repeating units of 1,4-olefins; and

[0057] Branching units substituted with functional groups of formula (I):

[0058]

[0059] A linear substituted unit having a functional group of formula (I): wherein

[0060] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0061] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0062] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0063] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0064] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0065] wherein the polymer optionally comprises other units; and

[0066] The cells can be ordered or randomly distributed.

[0067] In a fifth embodiment, provided herein is a process for making a polymer comprising:

[0068] Hydroaminoalkylation of a polymerized polybutadiene polymer in the presence of at least 5 mol% of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is from 110°C to 165°C,

[0069] Produces a polymer comprising:

[0070] Polybutadiene backbone;

[0071] 1,2-Olefin units,

[0072] 1,4-olefin units; and

[0073] Branching units substituted with functional groups of formula (I):

[0074]

[0075] The linear substitution pattern of the vinyl polymer units having the functional groups of formula (I):

[0076] wherein the molar ratio of branched units to linear units is 6:1 or greater;

[0077] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0078] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0079] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -thio C1-C6 alkyl, or a combination thereof, wherein R 2 The aryl group in is optionally para-substituted;

[0080] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0081] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0082] wherein the polymer optionally comprises other units; and

[0083] The cells can be ordered or randomly distributed.

[0084] In a sixth embodiment, provided herein is a process for making a polymer comprising:

[0085] Hydroaminoalkylation of a polymerized polybutadiene polymer in the presence of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is 110° C. to 165° C.,

[0086] Produces a polymer comprising:

[0087] Polybutadiene backbone;

[0088] 1,2-Olefin units,

[0089] 1,4-olefin units; and

[0090] Branching units substituted with functional groups of formula (I):

[0091]

[0092] The linear substitution pattern of the vinyl polymer units having the functional groups of formula (I):

[0093] wherein the molar ratio of branched units to linear units is 6:1 or greater;

[0094] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0095] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0096] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -thio C1-C6 alkyl, or a combination thereof, wherein R 2 The aryl group in is optionally para-substituted;

[0097] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0098] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0099] wherein the polymer optionally comprises other units; and

[0100] The cells can be ordered or randomly distributed.

[0101] In a seventh embodiment, provided herein is a process for making a polymer comprising:

[0102] Functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol% of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140°C, wherein the functionalized polymer comprises:

[0103] Polybutadiene backbone;

[0104] 1,2-Olefin units;

[0105] 1,4-olefin units; and

[0106] 1,4-addition unit substituted with a functional group of formula (I):

[0107] in

[0108] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0109] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0110] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0111] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0112] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0113] wherein the polymer optionally comprises other units; and

[0114] The cells can be ordered or randomly distributed.

[0115] In an eighth embodiment, provided herein is a process for making a polymer comprising:

[0116] Hydroaminoalkylation of a polybutadiene polymer in the presence of at least 10 mol% of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140°C, wherein the functionalized polymer comprises:

[0117] Polybutadiene backbone;

[0118] 1,2-Olefin units;

[0119] 1,4-olefin units; and

[0120] Branching units substituted with functional groups of formula (I):

[0121]

[0122] A linear substituted unit having a functional group of formula (I): wherein

[0123] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0124] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0125] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0126] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0127] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0128] wherein the polymer optionally comprises other units; and

[0129] The cells can be ordered or randomly distributed.

[0130] In a ninth embodiment, provided herein is a process for making a polymer comprising:

[0131] Hydroaminoalkylation of a polybutadiene polymer in the presence of at least 10 mol% of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140°C, wherein the functionalized polymer comprises:

[0132] Polybutadiene backbone;

[0133] 1,2-Olefin units;

[0134] 1,4-olefin units; and

[0135] Branching units substituted with functional groups of formula (I):

[0136]

[0137] A linear substituted unit having a functional group of formula (I): wherein

[0138] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0139] R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or

[0140] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0141] R 3 and R 4 is independently selected from hydrogen, -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4-10 Aryl and C 4-10 heteroaryl;

[0142] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0143] wherein the polymer optionally comprises other units; and

[0144] The cells can be ordered or randomly distributed. BRIEF DESCRIPTION OF THE DRAWINGS

[0145] Figure 1A The compound 1 1 H NMR spectroscopy.

[0146] Figure 1B The compound 1 13 C{ 1 H} NMR spectrum.

[0147] Figure 2A The compound 2 1 H NMR spectroscopy.

[0148] Figure 2B The compound 2 13 C{ 1 H} NMR spectrum.

[0149] Figure 3A The compound 3 1 H NMR spectroscopy.

[0150] Figure 3B The compound 3 13 C{ 1 H} NMR spectrum.

[0151] Figure 3C The compound 3 1 H- 1 H COSY NMR spectroscopy.

[0152] Figure 3D The compound 3 1 H- 13 C{ 1 H} HSQC NMR spectroscopy.

[0153] Figure 3E The compound 3 1 H- 13 C{ 1 H}HMBC NMR spectrum.

[0154] Figure 4A The compound 4 1 H NMR spectroscopy.

[0155] Figure 4B The compound 4 13 C{ 1 H} NMR spectrum.

[0156] Figure 5A The compound 5 1 H NMR spectroscopy.

[0157] Figure 5B The compound 5 13 C{ 1H} NMR spectrum.

[0158] Fig. 6A The compound 6 1 H NMR spectroscopy.

[0159] Figure 6B The compound 6 13 C{ 1 H} NMR spectrum.

[0160] Figure 7 The compound 7 1 H NMR spectroscopy.

[0161] Figure 8 The stacked compound 8 before and after the reaction is shown. 1 H NMR spectrum.

[0162] Fig. 9A The compound 9 1 H NMR spectroscopy.

[0163] Fig. 9B The compound 9 13 C{ 1 H} NMR spectrum.

[0164] Fig. 9C The compound 9 1 H- 1 H COSY NMR spectroscopy.

[0165] Fig.9D The compound 9 1 H- 13 C{ 1 H} HSQC NMR spectroscopy.

[0166] Fig.9E The compound 9 1 H- 13 C{ 1 H}HMBC NMR spectrum.

[0167] Fig.10 Compound P6 1 H NMR spectroscopy (300 MHz, CDCl3).

[0168] Fig.11 Compound P7 1 H NMR spectroscopy (300 MHz, CDCl3).

[0169] Fig. 12A Compound P9A 1 H NMR spectrum (300 MHz, CDCl3, 298 K).

[0170] Fig. 12B P9A 13 C NMR (75 MHz, CDCl3, 298 K) spectrum.

[0171] Fig. 12C The IR spectrum of P9A is shown.

[0172] Fig.13 Shown are the IR spectra of P10 and P10A superimposed.

[0173] Fig.14 The FT-IR spectrum of compound P12A is shown.

[0174] Fig.15A P13A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0175] Fig. 15B P13A 13 C NMR (75 MHz, CDCl3, 298 K) spectrum.

[0176] Fig. 15C The IR spectrum of P13A is shown.

[0177] Fig.16 Compound P14A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0178] Fig.17A Compound P15A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0179] Fig. 17B Compound P15A 13 C{1H}NMR (75MHz,CDCl3,298K) spectrum.

[0180] Fig.18A Compound P16A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0181] Fig.18B The FT-IR spectrum of compound P16A is shown.

[0182] Fig.19A Compound P17A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0183] Fig.19B Compound P17A 13 C{1H}NMR (75MHz,CDCl3,298K) spectrum.

[0184] Fig. 20 The FT-IR spectrum of compound P18A is shown.

[0185] Fig.21A Compound P19A 1 H NMR (300 MHz, CD3OD, 298 K) spectrum.

[0186] Fig. 21B Compound P19A 13 C{1H} NMR (75 MHz, CD3OD, 298 K) spectrum.

[0187] Fig. 21C The FT-IR spectrum of compound P19A is shown.

[0188] Fig.22A Compound P20A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0189] Fig. 22B Compound P20A 13 C{1H}NMR (75MHz,CDCl3,298K) spectrum.

[0190] Fig. 22C The FT-IR spectrum of compound P20A is shown. DETAILED DESCRIPTION

[0191] The present disclosure provides a hydroaminoalkylation reaction of polybutadiene for producing aminated polybutadiene with branched pendant amine functional groups. The reaction can be applied with a wide range of amine and polybutadiene polymer reactants to produce products with controlled amine incorporation. The introduction of amines provides polar groups that increase the practicality and applicability of these products.

[0192] definition

[0193] Unless otherwise defined, all technical terms, notations and other scientific terms used herein are intended to have the meanings commonly understood by those skilled in the art to which the present disclosure belongs. In some cases, for clarity and / or convenient reference, the terms with commonly understood meanings are defined herein. The techniques and procedures described or quoted herein are generally well known and are generally performed by those skilled in the art using conventional methods. Where appropriate, procedures involving the use of commercially available kits and reagents are generally performed according to the protocols and conditions defined by the manufacturer, unless otherwise stated.

[0194] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0195] The term "about" indicates and encompasses a specified value and a range above and below that value. In certain embodiments, the term "about" indicates a specified value ± 10%, ± 5%, or ± 1%. In certain embodiments, the term "about" indicates a specified value ± one standard deviation of that value. In certain embodiments, for example, a logarithmic scale (e.g., pH), the term "about" indicates a specified value ± 0.3, ± 0.2, or ± 0.1.

[0196] As used herein, the symbol Is used to denote the point of attachment of a repeat unit within a polymeric material to another group within the polymeric material, such as another repeat unit or a terminal group.

[0197] An asterisk (*) indicates the point of attachment of the pendant group to a polymer chain, such as to a carbon atom in the polymer chain.

[0198] The term "polymer" refers to a macrostructure having a number average molecular weight (Mn) of at least 2,000 Daltons, at least 5,000 Daltons, at least 10,000 Daltons, at least 25,000 Daltons, at least 50,000 Daltons, at least 100,000 Daltons, at least 300,000 Daltons, at least 500,000 Daltons, at least 750,000 Daltons, at least 1,000,000 Daltons, or even at least 1,500,000 Daltons. The polymer may be a homopolymer, a copolymer, a terpolymer, etc. The polymer may be a random copolymer or a block copolymer.

[0199] The term "polymer backbone" refers to the main continuous chain of only carbon atoms of a polymer.

[0200] When referring to the compounds provided herein, the following terms have the following meanings unless otherwise indicated. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. If a term is defined in multiple ways herein, the definition in this section shall prevail unless otherwise indicated.

[0201] As used herein, the term "alkyl" refers to a saturated straight chain or branched hydrocarbon, unless otherwise specified. In certain embodiments, the alkyl group is a primary hydrocarbon, a secondary hydrocarbon, or a tertiary hydrocarbon. In certain embodiments, the alkyl group contains one to ten carbon atoms (i.e., C1 to C2). 10 In certain embodiments, the alkyl group is a lower alkyl group, such as C 1-6In some embodiments, the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl and 2,3-dimethylbutyl. In some embodiments, "substituted alkyl" refers to an alkyl group substituted by one, two or three groups independently selected from halogen (e.g., fluorine (F), chlorine (Cl), bromine (Br) or iodine (I)), alkyl, haloalkyl, hydroxyl, amino, alkylamino, alkoxy, aryl, heteroaryl, cycloalkyl, cyano, oxo, alkynyl and heterocycloalkylalkylene. In some embodiments, the alkyl group is unsubstituted.

[0202] Unless otherwise indicated, the term "alkylene" as used herein refers to a divalent alkyl group as defined herein. "Substituted alkylene" refers to an alkylene group that is substituted as described herein for an alkyl group. In some embodiments, the alkylene group is unsubstituted.

[0203] "Alkoxy" and "alkoxyl" refer to the group -OR", where R" is alkyl or cycloalkyl. Alkoxy includes, in certain embodiments, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, and the like.

[0204] "Amino" refers to the group -NH2.

[0205] Unless otherwise indicated, the term "alkylamino" as used herein refers to the group -NHR", wherein R" is, for example, C as defined herein. 1-10 In certain embodiments, the alkylamino group is C 1-6 Alkylamino.

[0206] Unless otherwise indicated, the term "dialkylamino" as used herein refers to the group -NR"R", wherein each R" is independently a C 1-10 In certain embodiments, dialkylamino is diC 1-6 Alkylamino.

[0207] Unless otherwise indicated, the term "aryl" as used herein refers to phenyl, biphenyl or naphthyl. The term includes substituted and unsubstituted parts. Aryl can be substituted by any described part, and the part includes but is not limited to one or more parts (for example, one, two or three parts) selected from the group consisting of halogen (for example, fluorine (F), chlorine (Cl), bromine (Br) or iodine (I)), alkyl, haloalkyl, hydroxyl, amino, alkylamino, arylamino, alkoxy, aryloxy, nitro, cyano, sulfonic acid, sulfate / ester group, phosphonic acid, phosphate / ester group and phosphonate / ester group, wherein each part is independently unprotected or protected as needed, as understood by those skilled in the art (for example, Greene et al., Protective Groups in Organic Synthesis, John Wiley and Sons, Second Edition, 1991); and wherein the aryl in arylamino and aryloxy substituents is not further substituted.

[0208]

[0046] The term "arylene" as used herein, unless otherwise stated, refers to a divalent aromatic radical as defined herein.

[0209] The term "haloalkyl" refers to an alkyl group, as defined herein, substituted with one or more independently selected halogen atoms (eg, in some embodiments, one, two, three, four, or five).

[0210] The term "heteroalkyl" refers to an alkyl group as defined herein in which one or more carbon atoms are replaced by heteroatoms. As used herein, "heteroalkenyl" refers to an alkenyl group as defined herein in which one or more carbon atoms are replaced by heteroatoms. As used herein, "heteroalkynyl" refers to an alkynyl group as defined herein in which one or more carbon atoms are replaced by heteroatoms. Suitable heteroatoms include, but are not limited to, nitrogen (N), oxygen (O) and sulfur (S) atoms. Heteroalkyl, heteroalkenyl and heteroalkynyl are optionally substituted. Examples of heteroalkyl moieties include, but are not limited to, aminoalkyl, sulfonylalkyl and sulfinylalkyl. Examples of heteroalkyl moieties also include, but are not limited to, methylamino, methylsulfonyl and methylsulfinyl. "Substituted heteroalkyl" refers to a heteroalkyl group substituted by one, two or three groups independently selected from halogen (e.g., fluorine (F), chlorine (Cl), bromine (Br) or iodine (I)), alkyl, haloalkyl, hydroxyl, amino, alkylamino and alkoxy. In some embodiments, heteroalkyl may contain one, two, three or four heteroatoms. Those skilled in the art will recognize that a 4-membered heteroalkyl group may typically contain one or two heteroatoms, a 5- or 6-membered heteroalkyl group may typically contain one, two or three heteroatoms, and a 7- to 10-membered heteroalkyl group may typically contain one, two, three or four heteroatoms.

[0211]

[0043] The terms "halo" or "halogen" or "halide," by themselves or as part of another substituent, mean, unless otherwise stated, an atom or ion of fluorine, chlorine, bromine, or iodine.

[0212] As used herein, "oxo" refers to =0.

[0213] As used herein, the term "substituted", whether or not preceded by the term "optionally", generally refers to the replacement of hydrogen atoms in a given structure with a group of a specified substituent. Specific substituents are described in the definitions above and in the description of compounds and examples thereof below. Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted by more than one substituent selected from a specified group, the substituent may be the same or different at each position. Unless explicitly stated, a substituent is not further substituted.

[0214] As used herein, the term "catalyst" refers to a compound that accelerates a chemical reaction without being affected itself. "Catalyst" can be used interchangeably with terms such as "precatalyst", "catalyst system" or "catalytic system". As used herein, "catalyst" includes catalytic intermediates or substances formed in situ.

[0215] As used herein, "Group 5 metal" refers to transition metals containing d electrons listed as Group 5 in the periodic table, including the transition metals vanadium (V), niobium (Nb), tantalum (Ta), and thallium (Nb).

[0216] As used herein, "hydroaminoalkylation" refers to the reaction between a secondary amine-containing moiety and an olefin. A catalyst can generally be used to promote this reaction.

[0217] As used herein, "secondary amine" refers to an amine in which the amino group is directly bonded to any two C atoms that are hybridized. The two C atoms alpha to the N atom may be sp 3 Hybridization.

[0218] As used herein, "olefin" or "alkene" refers to an unsaturated hydrocarbon containing one or more pairs of C atoms connected by double bonds.

[0219] The term "1,2-olefin repeating unit" or "1,2 olefin unit" refers to a polymer chain having butadiene monomers added in a 1,2-addition reaction pathway.

[0220] The term "1,4-olefin repeating unit" or "1,4 olefin unit" refers to a polymer chain having butadiene monomers added in a 1,4-addition reaction pathway.

[0221] As used herein, the term "branched substitution pattern of vinyl polymer units" refers to the product of an amination reaction pathway in which the olefin carbon alpha to the polymer backbone of the vinyl group is aminated to produce a vinyl group of formula III Exemplary branched repeating units.

[0222] As used herein, the term "linear substitution pattern of vinyl polymer units" refers to the functionalization of the terminal olefinic carbon of the vinyl group exemplified by Formula IV. The subscript c depicts the number of repeating sequences which may be in tandem or may be randomly distributed throughout the polymer.

[0223] As used herein, the term "branch unit" refers to the alkylation product of a hydroaminoalkylation reaction pathway in which the olefin carbon alpha to the polymer backbone of the vinyl group is aminated to produce a branch unit of formula III Exemplified repeating units. The subscript d depicts the number of repeating sequences which may be in tandem or may be randomly distributed throughout the polymer.

[0224] As used herein, the term "linear unit" refers to the linear unit from Formula IV The exemplified vinyl functionalized alkylation products of the terminal olefinic carbon.

[0225] The term "salt thereof" refers to a quaternary ammonium salt of a polymer described herein, including but not limited to hydrochlorides and oxalates of quaternary ammonium-containing polymers. A salt thereof may include any ionic form of a polymer described herein. Unless otherwise expressly stated, a salt thereof refers to a quaternary ammonium salt of a polymer described herein.

[0226] For example, "-[PEG] 0-10 " or "-[PEG] 0-10 The term PEG as used in "-(C2H4-O)" refers to the polymer chain - poly(ethylene glycol). This polymer is characterized by repeating ethylene glycol units having the structure (-O-CH2-CH2-) n , wherein n can range from 1 to 10, inclusive; or wherein n can range from 1 to 50, inclusive. In some embodiments, the PEG polymer chain is attached to the epoxide.

[0227] The term "reduced polybutadiene backbone" means that the residual olefinic portion of the primary alkyl chains (including branched terminal olefins (also referred to as backbone) in the polybutadiene polymers described herein are hydrogenated such that the olefinic bonds become saturated alkane bonds.

[0228] Polymer Manufacturing

[0229] Typically, the dominant branched unit polymers are composed of

[0230] Polymer preparation, including:

[0231] The polymerized polybutadiene polymer is subjected to hydroaminoalkylation in the presence of at least 5 mol% of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is 110-165°C,

[0232] Produces a polymer comprising:

[0233] Polybutadiene backbone;

[0234] 1,2-Olefin units,

[0235] 1,4-olefin units; and

[0236] Branching units substituted with functional groups of formula (I):

[0237]

[0238] The linear substitution pattern of the vinyl polymer units having the functional groups of formula (I):

[0239] wherein the molar ratio of branched units to linear units is 6:1 or greater;

[0240] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0241] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0242] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0243] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0244] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0245] wherein the polymer optionally comprises other units; and

[0246] wherein the units may be ordered or randomly distributed. In certain embodiments, the process is optionally solvent-free.

[0247] In certain embodiments, the temperature is 110-165°C. In certain embodiments, the temperature is at least 110°C. In certain embodiments, the temperature is at least 115°C. In certain embodiments, the temperature is at least 120°C. In certain embodiments, the temperature is at least 125°C. In certain embodiments, the temperature is at least 130°C. In certain embodiments, the temperature is at least 135°C. In certain embodiments, the temperature is 140°C. In certain embodiments, the temperature is 145°C. In certain embodiments, the temperature is 150°C. In certain embodiments, the temperature is 155°C.

[0248] In certain embodiments, the temperature is 110-165°C. In certain embodiments, the temperature is 110°C. In certain embodiments, the temperature is 115°C. In certain embodiments, the temperature is 120°C. In certain embodiments, the temperature is 125°C. In certain embodiments, the temperature is 130°C. In certain embodiments, the temperature is 135°C. In certain embodiments, the temperature is 140°C. In certain embodiments, the temperature is 145°C. In certain embodiments, the temperature is 150°C. In certain embodiments, the temperature is 155°C.

[0249] In certain embodiments, the catalyst is a Ta-based catalyst. In certain embodiments, the catalyst is Ta(CH2SiMe3)3Cl2. In certain embodiments, the catalyst is

[0250] In certain embodiments, the amount of catalyst is at least 5 mol%. In certain embodiments, the amount of catalyst is 0.5 mol%. In certain embodiments, the amount of catalyst is 1 mol%. In certain embodiments, the amount of catalyst is 2 mol%. In certain embodiments, the amount of catalyst is 3 mol%. In certain embodiments, the amount of catalyst is 4 mol%. In certain embodiments, the amount of catalyst is 5 mol%.

[0251] A typical 1,4-addition polymer unit is composed of

[0252] Polymer preparation, including:

[0253] Functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol% of a metal-based catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140°C, wherein the functionalized polymer comprises:

[0254] Polybutadiene backbone;

[0255] 1,2-Olefin units;

[0256] 1,4-olefin units; and

[0257] 1,4-addition unit substituted with a functional group of formula (I):

[0258] in

[0259] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0260] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0261] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0262] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0263] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0264] wherein the polymer optionally comprises other units; and

[0265] wherein the units may be ordered or randomly distributed. In certain embodiments, the process is optionally solvent-free.

[0266] In certain embodiments, the substituted aminated polybutadiene is prepared by

[0267] A polybutadiene polymer is subjected to hydroaminoalkylation in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140° C., wherein the functionalized polymer comprises:

[0268] Polybutadiene backbone;

[0269] 1,2-Olefin units;

[0270] 1,4-olefin units; and

[0271] Branching units substituted with functional groups of formula (I):

[0272] as well as

[0273] A linear substituted unit having a functional group of formula (I): wherein

[0274] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0275] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0276] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0277] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0278] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0279] wherein the polymer optionally comprises other units; and

[0280] wherein the units may be ordered or randomly distributed. In certain embodiments, the process is optionally solvent-free. In certain embodiments, the amine is N-benzylsilylamine.

[0281] In some other embodiments, the substituted aminated polybutadiene is prepared by hydroaminoalkylating a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140° C., wherein the functionalized polymer comprises:

[0282] Polybutadiene backbone;

[0283] 1,2-Olefin units;

[0284] 1,4-olefin units; and

[0285] Branching units substituted with functional groups of formula (I):

[0286] as well as

[0287] A linear substituted unit having a functional group of formula (I): wherein

[0288] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0289] R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or

[0290] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0291] R 3 and R 4 is independently selected from hydrogen, -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4-10 Aryl and C 4-10 heteroaryl;

[0292] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0293] wherein the polymer optionally comprises other units; and

[0294] wherein the units may be ordered or randomly distributed. In certain embodiments, the process is optionally solvent-free. In certain embodiments, the amine is N-benzylsilylamine.

[0295] How to use

[0296] In certain embodiments, the aminated materials disclosed herein may have applications in adhesives and coating formulations. In certain embodiments, the aminated materials disclosed herein may have applications as additives for materials such as rubbers, plastics, composites, waxes, etc. In certain embodiments, the aminated materials disclosed herein may have applications as lubricants, polymer membranes, and filters. In certain embodiments, the aminated materials disclosed herein may have applications as polymer compatibilizers. In certain embodiments, the aminated materials disclosed herein may have applications as drug delivery agents. In certain embodiments, the aminated materials disclosed herein may have applications as rheology modifiers, fuel additives, or dispersants.

[0297] Compound

[0298] In one embodiment, provided herein is a polymer comprising:

[0299] Polybutadiene backbone;

[0300] 1,2-Olefin units;

[0301] 1,4-olefin units; and

[0302] Branched substituted units having functional groups of formula (I):

[0303]

[0304] A linear substituent unit having a functional group of formula (I). In certain embodiments

[0305] The molar ratio of branching units to linear units is 6:1 or greater.

[0306] In formula (I), R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4In each case, each is independently selected from hydrogen, C1-C6 alkyl and C1-C6 heteroalkyl; the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone. In certain embodiments, the polymer optionally comprises other units. In certain embodiments, the units may be arranged in series, in blocks, or randomly distributed.

[0307] In certain embodiments, R 1 is hydrogen. In certain embodiments, R 1 Yes-C1-C 20 In certain embodiments, R 1 Yes-C6-C 20 Aryl.

[0308] In certain embodiments, R 2 Yes-C1-C 20 In certain embodiments, R 2 Yes-C6-C 20 In certain embodiments, R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 In certain embodiments, R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; in certain embodiments, R 2 The aryl group in is optionally substituted at the para position.

[0309] In certain embodiments, R 3 and R 4 Each occurrence is independently selected from hydrogen, -C1-C6 alkyl and -C1-C6 heteroalkyl; in certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 4 In certain embodiments, R 4 In certain embodiments, R 4 It is -C1-C6 heteroalkyl.

[0310] In certain embodiments, the molar ratio of branched units to linear unit products is 6: 1 or greater. In certain embodiments, the ratio of branched units to linear unit products is 6: 1. In certain embodiments, the ratio of branched units to linear unit products is 9: 1. In certain embodiments, the molar ratio of branched units to linear unit products can be changed by changing the reaction conditions. In certain embodiments, the amount of 1,2-olefin units and 1,4-olefin units can be equal or can be variable. In certain embodiments, the polymer comprises 92% 1,4-olefin units and 8% 1,2-olefin units.

[0311] In certain embodiments, the polymer comprises at least 60% branched substituted units relative to linear substituted units. In certain embodiments, the polymer comprises at least 90% branched substituted units relative to linear substituted units.

[0312] In certain embodiments, the polymer optionally comprises other units. In certain embodiments, the other units include styrene units optionally substituted by alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene or a mixture. In certain embodiments, the other units include styrene units optionally substituted by alkyl. In certain embodiments, the other units include alkyl. In certain embodiments, the other units include heteroalkyl. In certain embodiments, the other units include substituted heteroalkyl. In certain embodiments, the other units include styrene. In certain embodiments, the other units include substituted styrene. In certain embodiments, the monomer units are connected in a head-to-head manner. In certain embodiments, the monomer units are connected in a head-to-tail manner. In certain embodiments, the monomer units are connected in a tail-to-tail manner.

[0313] In certain embodiments, the units may be arranged in series, in blocks, or randomly distributed.

[0314] In one embodiment, provided herein is a compound of formula (II)

[0315] polymer, or a fragment thereof.

[0316] In one embodiment, provided herein is a composition comprising formula (II)

[0317] In some examples, the fragment forms a polymer with isoprene units. In certain examples, these polymers are formed by copolymerizing butadiene with isoprene and adding an amine functional group (e.g., a functional group of formula (I)) to one or more polymers formed by copolymerizing butadiene with isoprene.

[0318] In formula (II), R 5 Optionally, a compound of formula (I):

[0319] In certain embodiments, when R is present on the c unit 5 In certain embodiments, when R is absent from the C unit, 5 The dashed line represents a double bond.

[0320] In formula (I), R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from H, C1-C6 alkyl, and C1-C6 heteroalkyl; the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone.

[0321] In certain embodiments, R 1 is hydrogen. In certain embodiments, R 1 Yes-C1-C 20 In certain embodiments, R 1 Yes-C6-C 20 Aryl.

[0322] In certain embodiments, R 2 Yes-C1-C 20 In certain embodiments, R 2 Yes-C6-C 20 In certain embodiments, R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 In certain embodiments, R 1 and R 2Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; in certain embodiments, R 2 The aryl group in is optionally substituted at the para position.

[0323] In an embodiment, R 3 and R 4 In certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 4 In certain embodiments, R 4 In certain embodiments, R 4 It is -C1-C6 heteroalkyl.

[0324] In formula (II), R 6 is hydrogen, -C1-C 20 Alkyl, -C6-C 20 Aryl, -C 1-6 Alkyl-C1-C 20 Alkyl, -C 1-6 Alkyl-C6-C 20 Aryl, -C 1-6 Heteroalkyl-C1-C 20 Alkyl, or -C 1-6 Heteroalkyl-C6-C 20 In certain embodiments, R 6 is hydrogen. In certain embodiments, R 6 Yes-C1-C 20 In certain embodiments, R 6 Yes-C6-C 20 In certain embodiments, R 6 Yes-C 1-6 Alkyl-C1-C 20 In certain embodiments, R 6 Yes-C 1-6 Heteroalkyl-C1-C 20 In certain embodiments, R 6 Yes-C 1-6 Heteroalkyl-C6-C 20 Aryl.

[0325] In formula (II), a, b, c, d, e and f are independently 0 to 100,000 at each occurrence. In certain embodiments, the ratio of d:e is 6:1 or greater. In certain embodiments, the ratio of d:e>9:1. In certain embodiments, the blocks may be ordered or randomly distributed. In certain embodiments, the ratio of d:c can be changed by changing the reaction conditions. In certain embodiments, in the starting polymer where "a" is much larger than "b", the c units are more relative to the d units. In certain embodiments, the d block is usually formed first, and if the reaction stops, the ratio of d>>c. In certain embodiments, if the reaction has enough time and amine loading, more and more "a" reacts, resulting in a ratio of d:c that is not always d>>>c. In certain embodiments, the ratio of a:b (blocks derived from 1,4 and 1,2 additions of butadiene in the polymer, respectively) in the starting polymer reactants can also vary.

[0326] In formula (II), the units may be ordered or randomly distributed. In certain embodiments, the units are ordered. In certain embodiments, the units are randomly distributed.

[0327] In certain embodiments of Formula (II), the ratio of a:b is 0.1, 0.5, 1, 1.5, 2, or 10. In certain embodiments, the ratio of d:e is 6:1.

[0328] In certain embodiments, the compound of formula (II) has the structure of formula (IIa):

[0329]

[0330] In certain embodiments, the compound of formula (II) has the structure of formula (IIb):

[0331]

[0332] In certain embodiments, the compound of formula (II) has the structure of formula (IIc):

[0333]

[0334] In certain embodiments, the compound of formula (II) has the structure of formula (IId):

[0335]

[0336] In certain embodiments, the compound of formula (II) has the structure of formula (IIe):

[0337]

[0338] In certain embodiments of Formula (IIa), (IIb), (IIc), (IId) or (IIe), R 5 Optionally, a compound of formula (I):

[0339]

[0340] In formula (I), R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; wherein R 2 The aryl group in is optionally substituted at the para position; R 3 and R 4 is independently selected at each occurrence from H, C1-C6 alkyl, and C1-C6 heteroalkyl; the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone.

[0341] In certain embodiments, R 1 is hydrogen. In certain embodiments, R 1 Yes-C1-C 20 In certain embodiments, R 1 Yes-C6-C 20 Aryl.

[0342] In certain embodiments, R 2 Yes-C1-C 20 In certain embodiments, R 2 Yes-C6-C 20 In certain embodiments, R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 In certain embodiments, R 1 and R 2Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; in certain embodiments, R 2 The aryl group in is optionally substituted at the para position.

[0343] In an embodiment, R 3 and R 4 In certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 4 In certain embodiments, R 4 In certain embodiments, R 4 It is -C1-C6 heteroalkyl.

[0344] In certain embodiments of Formula (IIa), (IIb) or (IIc), R 6 is hydrogen, -C1-C 20 Alkyl, -C6-C 20 Aryl, -C 1-6 Alkyl-C1-C 20 Alkyl, -C 1-6 Alkyl-C6-C 20 Aryl, -C 1-6 Heteroalkyl-C1-C 20 Alkyl, or -C 1-6 Heteroalkyl-C6-C 20 In certain embodiments, R 6 is hydrogen. In certain embodiments, R 6 Yes-C1-C 20 In certain embodiments, R 6 Yes-C6-C 20 In certain embodiments, R 6 Yes-C 1-6 Alkyl-C1-C 20 In certain embodiments, R 6 Yes-C 1-6 Heteroalkyl-C1-C 20 In certain embodiments, R 6 Yes-C 1-6 Heteroalkyl-C6-C 20 Aryl.

[0345] In certain embodiments of formula (IIa), (IIb), (IIc), (IId) or (IIe), a, b, c, d, e and f are independently 0 to 100,000 at each occurrence. In certain embodiments, the ratio of d:e is 6:1 or greater. In certain embodiments, the ratio of d:e is >9:1. In certain embodiments, the blocks may be ordered or randomly distributed. In certain embodiments, the ratio of d:c can be changed by changing the reaction conditions. In certain embodiments, in the starting polymer where "a" is much greater than "b", there are more c units relative to d units. In certain embodiments, the d block is usually formed first, and if the reaction is stopped, the ratio of d>>c. In certain embodiments, if the reaction has sufficient time and amine loading, more and more "a" reacts, resulting in a ratio of d:c that is not always d>>>c. In certain embodiments, the ratio of a:b (blocks derived from 1,4 and 1,2 addition of butadiene in the polymer, respectively) in the starting polymer reactants can also vary.

[0346] In one embodiment, provided herein is a polymer comprising:

[0347] Polybutadiene backbone;

[0348] 1,2-Olefin units,

[0349] 1,4-olefin units; and

[0350] 1,4-addition unit substituted with a functional group of formula (I):

[0351] in

[0352] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0353] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0354] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0355] R3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0356] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0357] wherein the polymer optionally comprises other units; and

[0358] The cells can be ordered or randomly distributed.

[0359] In another embodiment, provided herein is a polymer comprising:

[0360] Polybutadiene backbone;

[0361] A unit comprising a repeating unit of a 1,2-olefin,

[0362] units comprising repeating units of 1,4-olefins; and

[0363] Branching units substituted with functional groups of formula (I):

[0364]

[0365] A linear substituted unit having a functional group of formula (I). In certain embodiments, the polymer optionally comprises other units. In certain embodiments, the units may be ordered or randomly distributed.

[0366] In formula (I), R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, C1-C6 alkyl, and C1-C6 heteroalkyl; the asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone.

[0367] In certain embodiments, R1 is hydrogen. In certain embodiments, R 1 Yes-C1-C 20 In certain embodiments, R 1 Yes-C6-C 20 Aryl.

[0368] In certain embodiments, R 2 Yes-C1-C 20 In certain embodiments, R 2 Yes-C6-C 20 In certain embodiments, R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 In certain embodiments, R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; in certain embodiments, R 2 The aryl group in is optionally substituted at the para position.

[0369] In certain embodiments, R 3 and R 4 Each occurrence is independently selected from hydrogen, -C1-C6 alkyl and -C1-C6 heteroalkyl; in certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 3 In certain embodiments, R 4 In certain embodiments, R 4 In certain embodiments, R 4 It is -C1-C6 heteroalkyl.

[0370] In certain embodiments, the compound is The sum of the subscripts d and e is 9.

[0371] In certain embodiments, provided herein are compounds in the following table:

[0372]

[0373]

[0374]

[0375] Implementation

[0376] Embodiment 1: A polymer comprising: a polybutadiene backbone;

[0377] 1,2-Olefin units;

[0378] 1,4-olefin units; and

[0379] Branched substituted units having functional groups of formula (I):

[0380]

[0381] A linear substituted unit having a functional group of formula (I):

[0382] wherein the molar ratio of branched units to linear units is 6:1 or greater;

[0383] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0384] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0385] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 Heterocyclic ring,

[0386] Where R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0387] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0388] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0389] wherein the polymer optionally comprises other units; and

[0390] The units may be arranged in series, in blocks, or randomly distributed.

[0391] Embodiment 2: A polymer as described in Embodiment 1, wherein the product contains at least 60% branched substituted units relative to linear substituted units.

[0392] Embodiment 3: A polymer as described in any of Embodiments 1-2, wherein the amount of 1,2-olefin units and 1,4-olefin units can be equal or can be variable.

[0393] Embodiment 4: The polymer of any one of Embodiments 1-3, comprising 92% 1,4-olefin units and 8% 1,2-olefin units.

[0394] Embodiment 5: The polymer of any of Embodiments 1-4, wherein the other units include styrene units optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or mixtures thereof.

[0395] Embodiment 6: A polymer as described in Embodiment 5, wherein the other units include styrene units.

[0396] Embodiment 7: A polymer as described in Embodiment 1, wherein the other units are isoprene units.

[0397] Embodiment 8: A polymer as described in any one of embodiments 1-7, wherein R 2 The aryl group in is optionally substituted at the para position.

[0398] Embodiment 9: A formula (II)

[0399] A polymer, or a fragment thereof, wherein

[0400] R 5 to exist or not to exist;

[0401] When there is R on the c unit 5 When there is no R on the c unit, the dashed line represents a single bond. 5 When , the dotted line represents a double bond;

[0402] R 5 Optionally a compound of formula (I)

[0403] in

[0404] R 1 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0405] R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C20 Aryl; or

[0406] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 3 and R 4 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof,

[0407] Where R 2 The aryl group in is optionally substituted at the para position;

[0408] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0409] R 6 is hydrogen, -C1-C 20 Alkyl, -C6-C 20 Aryl, -C 1-6 Alkyl-C1-C 20 Alkyl, -C 1-6 Alkyl-C6-C 20 Aryl, -C 1-6 Heteroalkyl-C1-C 20 Alkyl or -C 1-6 Heteroalkyl-C6-C 20 aryl; and

[0410] a, b, c, d, e and f are independently at each occurrence an integer from 0 to 100,000; wherein the ratio of d:e is 6:1 or greater, wherein the units may be ordered or randomly distributed.

[0411] Embodiment 10: A polymer as described in Embodiment 9, wherein the ratio of a:b is 0.1, 0.5, 1, 1.5, 2 or 10.

[0412] Embodiment 11: The polymer of any of Embodiments 9 and 10, wherein the ratio of d:e is 6:1.

[0413] Embodiment 12: A polymer as described in any one of Embodiments 9-11, wherein R 2 The aryl group in is optionally substituted at the para position.

[0414] Embodiment 13: A polymer of formula (II) having a structure of formula (IIa)

[0415]

[0416] Embodiment 14: A polymer of formula (II) having a structure of formula (IIb)

[0417]

[0418] Embodiment 15: A polymer of formula (II) having a structure of formula (IIc)

[0419]

[0420] Embodiment 16: A polymer of formula (II) having a structure of formula (IId)

[0421]

[0422] Embodiment 17: A polymer of formula (II) having a structure of formula (IIe)

[0423]

[0424] Embodiment 18: A polymer as described in any one of embodiments 1 and 9, which is selected from the following compounds:

[0425]

[0426]

[0427] Embodiment 19: A polymer comprising: a polybutadiene backbone;

[0428] 1,2-Olefin units,

[0429] 1,4-olefin units; and

[0430] 1,4-addition unit substituted with a functional group of formula (I):

[0431] in

[0432] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0433] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0434] R 1 and R 2Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0435] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0436] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0437] wherein the polymer optionally comprises other units; and

[0438] The cells may be ordered or randomly distributed.

[0439] Embodiment 20: A polymer comprising:

[0440] Polybutadiene backbone;

[0441] A unit comprising a repeating unit of a 1,2-olefin,

[0442] units comprising repeating units of 1,4-olefins; and

[0443] Branching units substituted with functional groups of formula (I):

[0444]

[0445] A linear substituted unit having a functional group of formula (I): wherein

[0446] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0447] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0448] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0449] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0450] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0451] wherein the polymer optionally comprises other units; and

[0452] The cells may be ordered or randomly distributed.

[0453] Embodiment 21: A polymer as described in Embodiment 20, which has the following structure:

[0454] The sum of the subscripts d and e is 9.

[0455] Embodiment 22: A process for producing a polymer, comprising:

[0456] Hydroaminoalkylation of a polymerized polybutadiene polymer in the presence of at least 5 mol% of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is from 110°C to 165°C,

[0457] Produces a polymer comprising:

[0458] Polybutadiene backbone;

[0459] 1,2-Olefin units,

[0460] 1,4-olefin units; and

[0461] Branching units substituted with functional groups of formula (I):

[0462]

[0463] Branched units substituted with functional groups of formula (I):

[0464] wherein the molar ratio of branched units to linear units is 6:1 or greater;

[0465] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0466] R 2C1-C 20 Alkyl or -C6-C 20 aryl; or

[0467] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0468] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0469] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0470] wherein the polymer optionally comprises other units; and

[0471] The cells may be ordered or randomly distributed.

[0472] Embodiment 23: A process as described in Embodiment 22, wherein the catalyst is a Ta-based catalyst.

[0473] Embodiment 24: A process for producing a polymer, comprising:

[0474] Functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol% of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140°C, wherein the functionalized polymer comprises:

[0475] Polybutadiene backbone;

[0476] 1,2-Olefin units,

[0477] 1,4-olefin units; and

[0478] 1,4-addition unit substituted with a functional group of formula (I):

[0479] in

[0480] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0481] R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0482] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0483] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0484] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0485] wherein the polymer optionally comprises other units; and

[0486] The cells may be ordered or randomly distributed.

[0487] Embodiment 25: A process for producing a polymer, comprising:

[0488] Hydroaminoalkylation of a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140° C., wherein the functionalized polymer comprises:

[0489] Polybutadiene backbone;

[0490] 1,2-Olefin units;

[0491] 1,4-olefin units; and

[0492] Branching units substituted with functional groups of formula (I):

[0493]

[0494] A linear substituted unit having a functional group of formula (I): wherein

[0495] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0496] R2 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0497] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0498] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0499] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0500] wherein the polymer optionally comprises other units; and

[0501] The cells may be ordered or randomly distributed.

[0502] In some other embodiments, described herein is a process for making a polymer, comprising:

[0503] Hydroaminoalkylation of a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140° C., wherein the functionalized polymer comprises:

[0504] Polybutadiene backbone;

[0505] 1,2-Olefin units;

[0506] 1,4-olefin units; and

[0507] Branching units substituted with functional groups of formula (I):

[0508]

[0509] A linear substituted unit having a functional group of formula (I): wherein

[0510] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0511] R2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or

[0512] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0513] R 3 and R 4 is independently selected from hydrogen, -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4-10 Aryl or C 4-10 heteroaryl;

[0514] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0515] wherein the polymer optionally comprises other units; and

[0516] The cells may be ordered or randomly distributed.

[0517] Embodiment 26. A process as described in Embodiment 25, wherein the amine is N-benzylsilylamine.

[0518] Embodiment 27: A polymer produced by the process of any one of Embodiments 22-26.

[0519] Embodiment 28: A polymer made by the process of any one of Embodiments 22-26, wherein the polymer is optionally free of solvent.

[0520] Embodiment 29: A polymer comprising:

[0521] Polybutadiene backbone;

[0522] 1,2-Olefin units;

[0523] 1,4-olefin units; and

[0524] A branched substituted unit having a functional group of formula (I) or a salt thereof:

[0525]

[0526] A linear substituted unit having a functional group of formula (I) or a salt thereof:

[0527] wherein the molar ratio of branched substituted units to linear substituted units is 6:1 or greater;

[0528] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0529] R 2 For -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl or -L 1 -C6-C 20 aryl; or

[0530] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 Heterocyclic ring,

[0531] Where R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0532] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0533] L 1 is independently a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR 3 )-C1-C3 alkylene;

[0534] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0535] wherein the polymer optionally comprises one or more other units; and

[0536] The units may be arranged in series, in blocks, or randomly distributed.

[0537] Embodiment 30: A polymer as described in Embodiment 29, wherein L 1 is the key.

[0538] Embodiment 31: A polymer as described in Embodiment 29 or 30, wherein R 2 Yes-C1-C 20 Alkyl or -C6-C 20 Aryl.

[0539] Embodiment 32: A polymer as described in any of Embodiments 29-31, wherein the polymer contains at least 60% branched substituted units relative to linear substituted units.

[0540] Embodiment 33: A polymer as described in any of embodiments 29-32, wherein the amount of 1,2-olefin units and 1,4-olefin units can be equal or can be variable. A polymer as described in any of embodiments 1-5, comprising 92% 1,4-olefin units and 8% 1,2-olefin units.

[0541] Embodiment 34: A polymer as described in any of Embodiments 29-33, wherein the one or more other units include styrene units optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or mixtures thereof.

[0542] Embodiment 35: A polymer as described in Embodiment 34, wherein the one or more other units include styrene units.

[0543] Embodiment 36: A polymer as described in any of Embodiments 29-35, wherein the one or more other units are isoprene units.

[0544] Embodiment 37: A polymer as described in any one of Embodiments 29-36, wherein R 2 The aryl group in is para-substituted.

[0545] Embodiment 38: A polymer of formula (II)

[0546]

[0547] or a fragment thereof, wherein

[0548] R 5 to exist or not to exist;

[0549] When there is R on the c unit 5 When R is absent on the c unit, the dashed line represents a single bond. 5 When , the dotted line represents a double bond;

[0550] R 5 A compound of formula (I) or a salt thereof:

[0551] in

[0552] R 1 C1-C 20 Alkyl or -C6-C 20 aryl; or

[0553] R 2 For hydrogen, --L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl or -L 1 -C6-C 20 aryl; or

[0554] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 3 and R 4 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0555] Where R 2 The aryl group in is optionally substituted at the para position;

[0556] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0557] L 1 is independently a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR 3 )-C1-C3 alkylene;

[0558] R 6 is hydrogen, -C1-C 20 Alkyl, -C6-C 20 Aryl, -C 1-6 Alkyl-C1-C 20 Alkyl, -C 1-6 Alkyl-C6-C 20 Aryl, -C 1-6 Heteroalkyl-C1-C 20 Alkyl or -C 1-6 Heteroalkyl-C6-C 20 aryl; and

[0559] a, b, c, d, e and f are independently at each occurrence an integer from 0 to 100,000; wherein the ratio of d:e is 6:1 or greater, wherein the units may be ordered or randomly distributed.

[0560] Embodiment 39: A polymer as described in Embodiment 38, wherein L 1 is the key.

[0561] Embodiment 40: A polymer as described in Embodiment 38 or 39, wherein R 2 Yes-C1-C 20 Alkyl or -C6-C 20 Aryl.

[0562] Embodiment 41: A polymer as described in any of Embodiments 38-40, wherein the ratio of a:b is 0.1, 0.5, 1, 1.5, 2 or 10.

[0563] Embodiment 42: A polymer as described in any of Embodiments 38-41, wherein the ratio of d:e is 6:1.

[0564] Embodiment 43: A polymer as described in any of Embodiments 38-42, wherein R 2 The aryl group in is para-substituted.

[0565] Embodiment 44: A polymer as described in any of Embodiments 38-43, wherein Formula (II) has a structure of Formula (IIa)

[0566]

[0567] Embodiment 45: A polymer as described in any of Embodiments 38-44, wherein Formula (II) has a structure of Formula (IIb)

[0568]

[0569] Embodiment 46: A polymer as described in any of Embodiments 38-45, wherein Formula (II) has a structure of Formula (IIc)

[0570]

[0571] Embodiment 47: A polymer as described in any of Embodiments 38-46, wherein Formula (II) has a structure of Formula (IId)

[0572]

[0573] Embodiment 48: A polymer as described in any of Embodiments 38-48, wherein Formula (II) has a structure of Formula (IIe)

[0574]

[0575] Embodiment 49: A polymer as described in any of embodiments 38 and 48, wherein the polymer is selected from the following compounds:

[0576]

[0577]

[0578]

[0579] Embodiment 50: A polymer comprising:

[0580] Polybutadiene backbone;

[0581] 1,2-Olefin units,

[0582] 1,4-olefin units; and

[0583] 1,4-addition unit substituted with a functional group of formula (I) or a salt thereof:

[0584] in

[0585] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0586] R 2 For -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl or -L 1 -C6-C 20 aryl; or

[0587] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0588] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0589] L 1 is independently a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR 3 )-C1-C3 alkylene;

[0590] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0591] wherein the polymer optionally comprises one or more other units; and

[0592] The cells may be ordered or randomly distributed.

[0593] Embodiment 51: A polymer as described in Embodiment 50, wherein R 2 Yes-C1-C 20 Alkyl or -C6-C 20 Aryl.

[0594] Embodiment 52: A polymer comprising:

[0595] Polybutadiene backbone;

[0596] A unit comprising a repeating unit of a 1,2-olefin,

[0597] units comprising repeating units of 1,4-olefins; and

[0598] A branched substituted unit having a functional group of formula (I) or a salt thereof:

[0599]

[0600] A linear substituted unit having a functional group of formula (I) or a salt thereof:

[0601] in

[0602] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0603] R 2 For -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl or -L 1 -C6-C 20 aryl; or

[0604] R 1 and R 2Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0605] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0606] L 1 is independently a bond, C1-C3 alkylene, -(C=O)-C2-C4 alkylene, or -(C=O)(NR 3 )-C1-C3 alkylene;

[0607] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0608] wherein the polymer optionally comprises one or more other units; and

[0609] The cells may be ordered or randomly distributed.

[0610] Embodiment 53: A polymer as described in Embodiment 52, wherein R 2 Yes-C1-C 20 Alkyl or -C6-C 20 Aryl.

[0611] Embodiment 54: A polymer as described in Embodiment 52, which has the following structure:

[0612] The sum of the subscripts d and e is 9.

[0613] Embodiment 55: A process for making a polymer, comprising:

[0614] Hydroaminoalkylation of a polymerized polybutadiene polymer in the presence of at least 5 mol% of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is from 110°C to 165°C,

[0615] This produces a functionalized polymer comprising:

[0616] Polybutadiene backbone;

[0617] 1,2-Olefin units,

[0618] 1,4-olefin units; and

[0619] A branched substituted unit having a functional group of formula (I) or a salt thereof:

[0620]

[0621] A linear substituted unit having a functional group of formula (I) or a salt thereof:

[0622] wherein the molar ratio of branched substituted units to linear substituted units is 6:1 or greater;

[0623] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0624] R 2 For -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl or -L 1 -C6-C 20 aryl; or

[0625] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0626] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0627] L 1 is independently a bond, C1-C3 alkylene, -(C=O)-C1-C3 alkylene, or -(C=O)(NR 3 )-C1-C3 alkylene;

[0628] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0629] wherein the polymer optionally comprises one or more other units; and

[0630] The cells may be ordered or randomly distributed.

[0631] Embodiment 56: A process as described in Embodiment 55, wherein the catalyst is a Ta-based catalyst.

[0632] Embodiment 57: A process as described in Embodiment 56, wherein R 2 C1-C 20 Alkyl or -C6-C 20 Aryl.

[0633] Embodiment 58: A process for making a polymer, comprising:

[0634] Functionalizing an internal olefin of a polybutadiene polymer in the presence of at least 5 mol% of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140°C, wherein the functionalized polymer comprises:

[0635] Polybutadiene backbone;

[0636] 1,2-Olefin units,

[0637] 1,4-olefin units; and

[0638] 1,4-addition unit substituted with a functional group of formula (I) or a salt thereof:

[0639] in

[0640] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0641] R 2 For -L 1 -C1-C 20 Alkyl, -L 1 -C2-C 20 Alkenyl or -L 1 -C6-C 20 aryl; or

[0642] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof;

[0643] R 3 and R 4is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0644] L 1 is independently a bond, C1-C3 alkylene, -(C=O)-C1-C3 alkylene, or -(C=O)(NR 3 )-C1-C3 alkylene;

[0645] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0646] wherein the polymer optionally comprises one or more other units; and

[0647] The cells may be ordered or randomly distributed.

[0648] Embodiment 59: A process as described in Embodiment 58, wherein R 2 C1-C 20 Alkyl or -C6-C 20 Aryl.

[0649] Embodiment 60: A process for making a polymer, comprising:

[0650] Hydroaminoalkylation of a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140° C., wherein the functionalized polymer comprises:

[0651] Polybutadiene backbone;

[0652] 1,2-Olefin units;

[0653] 1,4-olefin units; and

[0654] A branched substituted unit having a functional group of formula (I) or a salt thereof:

[0655]

[0656] A linear substituted unit having a functional group of formula (I) or a salt thereof:

[0657] in

[0658] R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl;

[0659] R 2 For -L 1 -C1-C 20 Alkyl, -L 1 -C2-C20 Alkenyl or -L 1 -C6-C 20 aryl; or

[0660] R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof;

[0661] R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl;

[0662] L 1 is independently a bond, C1-C3 alkylene, -(C=O)-C1-C3 alkylene, or -(C=O)(NR 3 )-C1-C3 alkylene;

[0663] Asterisks (*) indicate the points of attachment of the functional group to a carbon atom in the polymer backbone;

[0664] wherein the polymer optionally comprises other units; and

[0665] The cells may be ordered or randomly distributed.

[0666] Embodiment 61. A process as described in Embodiment 60, wherein the amine is N-benzylsilylamine.

[0667] Embodiment 62: A process as described in Embodiment 60, wherein R 2 C1-C 20 Alkyl or -C6-C 20 Aryl.

[0668] Embodiment 63: A polymer produced by the process of any one of Embodiments 55-62.

[0669] Embodiment 64: A polymer made by the process of any one of Embodiments 55-62, wherein the process is solvent-free.

[0670] Embodiment 65: A process for hydrogenating the backbone of a polybutadiene polymer to produce an aliphatic backbone polymer, comprising reacting a polybutadiene polymer as described herein under hydrogenation conditions to produce the aliphatic backbone polymer.

[0671] Embodiment 66: A process as described in Embodiment 65, wherein the hydrogenation conditions include using p-toluenesulfonyl hydrazide, tripropylamine, xylene, or a combination thereof.

[0672] Embodiment 67: A process as described in any of Embodiments 65-66, wherein the hydrogenation conditions include a N2 atmosphere.

[0673] Embodiment 68: A process as described in any of Embodiments 65-67, wherein the hydrogenation conditions include heating the polymer of any of Embodiments 1-21 or 27-28 to at least 100°C under hydrogenation conditions.

[0674] Embodiment 69: A process as described in any of Embodiments 65-32, wherein the hydrogenation conditions include heating the polymer of any of Embodiments 1-21 or 27-28 to at least 100°C to 150°C under hydrogenation conditions.

[0675] Embodiment 70: A process as described in any of Embodiments 65-69, wherein the hydrogenation conditions include heating the polymer of any of Embodiments 1-21 or 27-28 to 130°C under hydrogenation conditions.

[0676] Embodiment 71. The process of any one of Embodiments 65-70, wherein the hydrogenation conditions comprise heating the polymer of any one of Embodiments 1-21 or 27-28 under hydrogenation conditions for 24 hours.

[0677] Embodiment 72: A process as described in any of Embodiments 65-71, wherein the process further comprises reducing at least one or both of R1 or R2 such that at least one or both of R1 or R2 is H.

[0678] Embodiment 73: A process as described in any of Embodiments 65-72, wherein the process further comprises reducing the polymer by reacting the polymer with ammonium cerium (II) nitrate.

[0679] Embodiment 74: A polymer made by the process herein.

[0680] In some embodiments, including any of the foregoing embodiments, the hydrogenation process can be performed using a catalyst. For example, in some embodiments, including any of the foregoing embodiments, the hydrogenation is performed using palladium-carbon catalysis. See the following reaction scheme:

[0681]

[0682] Other metal catalyzed hydrogenation processes are known and are incorporated herein by reference in their entirety for all purposes, such as, but not limited to, Martin P. McGrath, Erik D. Sall, and Samuel J. Tremont. Chemical Reviews 1995 95(2), 381-398.

[0683] In some embodiments, including any of the foregoing embodiments, the hydrogenation process can be accomplished using electrochemical methods.

[0684] Embodiment 75: A process for preparing an epoxide resin comprising reacting a polymer as described herein with at least one epoxide monomer or a precursor thereof to prepare the epoxide resin.

[0685] Embodiment 76: A process for preparing a mixture, comprising providing a polymer as described herein, and at least one epoxide monomer or a precursor thereof, thereby preparing the mixture.

[0686] Embodiment 77: A process as described in any of Embodiments 75 or 76, wherein the epoxide monomer or its precursor has a structure selected from the following:

[0687] Where R 30 Selected from hydrogen, C 1-6 alkyl,

[0688] Embodiment 78: A process as described in any of Embodiments 75-77, wherein the epoxide monomer or its precursor has a structure selected from the following:

[0689] Where R 30 for

[0690] Embodiment 79: A process as described in any of Embodiments 75-78, wherein the epoxide monomer or precursor is poly(ethylene glycol) diglycidyl ether epoxide.

[0691] Embodiment 80: The process of any one of Embodiments 75-78, wherein the epoxide monomer or precursor is trimethylolpropane triglycidyl ether epoxide.

[0692] Embodiment 81: A process as described in any of Embodiments 75-78, wherein the one or more epoxide monomers or precursors thereof include epichlorohydrin or a derivative thereof.

[0693] Embodiment 82: A process as described in any of embodiments 75-78, wherein the one or more epoxide monomers or precursors thereof include bisphenol A, its derivatives, or combinations thereof. In some embodiments, including any of the preceding embodiments, the epoxide monomer or precursor thereof is bisphenol A diglycidyl ether resin, butoxymethylbutyl glycidyl ether resin, bisphenol A-epichlorohydrin resin, bisphenol F resin, polyepoxide resin, bisphenol epoxy resin, novolac resin, polyester resin, aldehyde resin, phenol resin, phenol terpolymer, phenol formaldehyde resin, phenol formaldehyde resin, urea formaldehyde resin, furan resin, furfuryl alcohol resin, urethane resin, or glycidyl ether resin.

[0694] Embodiment 83: The process of any one of Embodiments 75-78, wherein the one or more epoxide monomers or precursors have the following structure:

[0695]

[0696] Embodiment 84: The process of any one of Embodiments 75-78, wherein the one or more epoxide monomers or precursors have the following structure:

[0697]

[0698] Embodiment 85: The process of any one of Embodiments 75-78, wherein the one or more epoxide monomers or precursors have the following structure: Where R 5 , R 6 , R 7 and R 8 In each case, each is independently selected from or comprises -C1-C 20 Alkyl, -C1-C 20 Alkoxy, -[PEG] 0-10 、-[PEG] 0-10 -(C2H4-O), C1-C 10 Heteroalkyl, C6-C 20 Aryl; C3-C having 0 to 2 additional heteroatoms selected from nitrogen and oxygen 20 A heterocyclic ring, wherein the heterocyclic ring may be a fused bicyclic ring, and wherein R 5 , R 6 , R 7 and R 8Each independently in each case is optionally substituted with 1 to 6 members selected from the group consisting of -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, -C1-C6thioalkyl, and combinations thereof.

[0699] Embodiment 86: The process of any one of Embodiments 75-85, wherein the mixture further comprises a combination of epoxide monomers.

[0700] Embodiment 87: The process of any one of Embodiments 75-86, wherein the mixture further comprises one or more additional hardeners.

[0701] Embodiment 88: The process of any one of Embodiments 75-87, further comprising curing the mixture.

[0702] Embodiment 89: The process of any one of Embodiments 75-88, further comprising cross-linking the polymer of any one of Embodiments 1-21, 27-28, or 38-59.

[0703] Embodiment 90: The process of any one of Embodiments 75-89, further comprising hardening the mixture.

[0704] In some embodiments, including any of the foregoing embodiments, the process comprises the following reaction:

[0705]

[0706] In the above reaction, in some preferred embodiments, R 1 For H.

[0707] In the above reaction, in some preferred embodiments, R 1 H and R 2 is an alkyl group, such as C 1-20 Alkyl or C 1-20 In some embodiments, R 2 In some embodiments, R 2 In some embodiments, R 2 In some embodiments, R 2 In some embodiments, R 2 In some embodiments, R 2 In some embodiments, R 2 It is cyclohexyl.

[0708] In the above reaction, in some preferred embodiments, R 1 and R 2Both are H.

[0709] In some embodiments, including any of the foregoing embodiments, the mixture becomes cured or hardened under the action of the amine-functionalized polybutadiene. In this regard, unless otherwise indicated, curing agent is used interchangeably with hardener herein.

[0710] In some embodiments, including any of the foregoing embodiments, the final cured mixture has improved properties, such as mechanical properties, adhesive properties, and improved processing properties.

[0711] In some embodiments, including any of the foregoing embodiments, the product of the aforementioned epoxide ring opening reaction is characterized by a -1 Up to 1115cm -1 Unique infrared (IR) mode at

[0712] In some embodiments, including any of the foregoing embodiments, the product of the aforementioned epoxide ring opening reaction is characterized by a 1110 cm-1 attributable to CO stretching from the reaction product. -1 Unique infrared (IR) mode at

[0713] In some embodiments, including any of the foregoing embodiments, the product of the aforementioned epoxide ring opening reaction is characterized by a 1095 cm-1 attributable to CO stretching from the reaction product. -1 Unique IR pattern at the

[0714] In some embodiments, including any of the foregoing embodiments, the polybutadiene starting material (ie, reagent) is a liquid having an average molecular weight of 2,500 to 4,500 g / mol.

[0715] In some other embodiments, including any of the foregoing embodiments, the polybutadiene starting material (ie, reagent) is a solid having an average molecular weight of 70,000 to 80,000 g / mol.

[0716] In some other embodiments, including any of the foregoing embodiments, the polybutadiene starting material (ie, reagent) is a solid having a molecular weight averaging 72,000 g / mol.

[0717] In some other embodiments, including any of the foregoing embodiments, the polybutadiene starting material (ie, reagent) is a solid having a molecular weight averaging 65,000 g / mol.

[0718] Example

[0719] Additional embodiments are disclosed in further detail in the following examples, which are not intended to limit the scope of the claims in any way.

[0720] Analytical methods and instruments

[0721] Proton nuclear magnetic resonance (NMR) spectroscopy was performed at Bruker Avance TM The NMR spectra were obtained on a 300 or 400 MHz spectrometer. The following are reported: chemical shift δ (ppm), multiplicity, coupling constant J (Hz) and integration. The abbreviations s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet and br = broad are used throughout. COSY, HSQC and HMBC 2D NMR spectroscopy experiments were performed with strict 1 H and 13 C NMR resonances were assigned.

[0722] Mass spectral data were measured using a Jeol AccuTOF-GCv 4G spectrometer equipped with a field desorption / ionization (FD / FI) ion source. The sample was dissolved in DCM and loaded onto a FD probe, then introduced into the ion source of a GC-TOF MS. Mass spectra were obtained in positive mode, and fragments were given with mass / charge number (m / z). FT-IR data were recorded at room temperature on a Perkin Elmer FT-IR equipped with an ATR accessory for direct measurement of oil and polymeric materials.

[0723] Experimental conditions

[0724] Reactions sensitive to air and moisture were prepared in a MBraun LABmaster glove box filled with N2 atmosphere. All glassware was dried overnight in an oven at 160°C before being transferred to a glove box or used on a Schlenk manifold. Toluene was passed through an activated alumina column under N2 gas, collected in a teflon-sealed Strauss flask and purged with N2 for 30 minutes before use. Toluene-d8 was dried over sodium metal, distilled under N2 atmosphere, collected in a teflon-sealed Strauss flask and degassed before use. Screening of hydroaminoalkylation reactions was performed in a J-Young tube (8" x 5mm) sealed with a teflon nut.

[0725] Material

[0726] Liquid polybutadiene material 100(PBD-co-PS4.5-54)R1, 130(PBD2.5-28)R2, and 150 (PBD3.9-70) R3 (as shown in Scheme 2). The number of repeating units is calculated based on the molecular weight and mass percentage (wt%) content report reported by Cray Valley (see example calculation in the equation section). The reported repeating unit value is rounded to the nearest integer. The materials were dissolved in hexane, dried with CaH2, filtered, degassed with three freeze-pump-thaw cycles, and the solvent was removed in vacuo. The materials were stored under an inert N2 atmosphere before use. The tantalum precatalyst was synthesized as described in the previous literature and was generated in situ before use. Daneshmand et al., J.Am.Chem.Soc.2020,142(37):15740-15750. N-methylaniline was purchased from MillaporeSigma, N-methylcyclohexylamine and N-methylbutylamine were purchased from Oakwood Chemical, and all amine reagents were dried and distilled over CaH2 and then stored in an inert N2 glove box atmosphere. 1,3,5-Trimethoxybenzene was purchased from Oakwood Chemical and was sublimed before storage in the glove box.

[0727] Solution 2

[0728]

[0729] Unless otherwise stated, this article uses Material.

[0730] Abbreviations used in the examples include:

[0731] abbreviation name <![CDATA[CaH2]]> Calcium hydride DCM Dichloromethane HAA Hydroaminoalkylation MW Molecular weight MeOH Methanol <![CDATA[N2]]> Nitrogen ％ percentage TON Number of flips <![CDATA[TaCl2(CH2SiMe3)]]> ((Trimethylsilyl)methyl)tantalum(III) chloride Ta Tantalum <![CDATA[Zr(NMe2)4]]> Tetrakis(dimethylamino)zirconium

[0732] General Scheme for the Preparation of Branched HAA Products Scheme A1

[0733]

[0734] Scheme A1. In certain embodiments, the hydroaminoalkylation comprises alkylating polymer P1a with an amine in the presence of a suitable catalyst to produce an alkylated product P1, as shown in Scheme A1. In certain embodiments, a variable degree of functionalization (ratio of b:d in the product) can be achieved by adjusting the reaction conditions. In certain embodiments, the ratio of a:b (blocks derived from 1,4 and 1,2 additions of butadiene in the polymer, respectively) in the starting polymer reactants can also be varied. In certain embodiments, the alkylated product can contain >90% branched HAA product. In certain embodiments, the percentage of vinyl consumed (given by 1 H NMR spectroscopy definition) up to 100%.

[0735] General Scheme for the Preparation of Polymers with Additional Blocks ("e" Blocks) Scheme A2

[0736]

[0737] Scheme A2. In certain embodiments, the functionalized polymer may contain optional additional blocks, such as blocks of polystyrene ("e" units). In certain embodiments, the hydroaminoalkylation comprises alkylating the polymer precursor P2a with an amine in the presence of a suitable catalyst to produce the alkylated product P2.

[0738] General Scheme for the Preparation of Primary Amine Products

[0739] Option A3

[0740]

[0741] Scheme A3. In certain embodiments, the functionalized polymer may contain a primary amine product. In certain embodiments, subjecting polymer precursor P3a to hydroaminoalkylation reaction conditions using a Zr-based catalyst and benzylamine may produce a primary amine product P3.

[0742] General Scheme for the Preparation of 1,4-Addition Products Scheme A4

[0743]

[0744] Scheme A4. In certain embodiments, 1,4 addition products (such as P4) can be prepared by functionalization of internal olefins (such as P4a).

[0745] Catalyst: Hydroaminoalkylation

[0746] Plan A5

[0747]

[0748] Scheme A5. In Scheme A5, p is an integer from 0 to 4, and q is an integer from 0 to 4, or the sum of p and q is 3 or 4; each W is a halogen substituent; R 7 and R 8 are each independently hydrogen, substituted or unsubstituted -C1-C 40 Linear alkyl, substituted or unsubstituted -C1-C 40 Branched alkyl, substituted or unsubstituted -C1-C 40 Cyclic alkyl, substituted or unsubstituted -C1-C 40 Alkenyl, substituted or unsubstituted -C1-C 40 alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic group, or R 7 and R 8 Together with the nitrogen to which they are both attached, they form a heterocyclic ring; R 9is hydrogen, substituted or unsubstituted -C1-C 40 Linear alkyl, substituted or unsubstituted -C1-C 40 Branched alkyl, substituted or unsubstituted -C1-C 40 Cyclic alkyl, substituted or unsubstituted -C1-C 40 Alkenyl, substituted or unsubstituted -C1-C 40 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic group, or R 9 With R 7 and / or R 8 Together they form a heterocyclic ring.

[0749] In some embodiments, including any of the foregoing embodiments, R 7 and R 8 In the above embodiment, R 1 or R 2 For example, in some embodiments, R 7 or R 8 or both are hydrogen. In certain embodiments, R 7 or R 8 or both -C1-C 20 In certain embodiments, R 7 or R 8 or both -C6-C 20 Aryl.

[0750] In certain embodiments, R 7 Yes-C1-C 20 In certain embodiments, R 7 Yes-C6-C 20 In certain embodiments, R 8 Yes-C1-C 20 In certain embodiments, R 8 Yes-C6-C 20 In certain embodiments, R 7 and R 8 Together with the nitrogen to which they are both attached, they form a -C3-C 20 In certain embodiments, R 7 and R 8 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof; in certain embodiments, R 7 In certain embodiments, the aryl group in R is optionally substituted at the para position.8 The aryl group in is optionally substituted at the para position.

[0751] In certain embodiments, p is an integer from 0 to 4, and q is an integer from 0 to 4. In certain embodiments, p is an integer from 0 to 4. In certain embodiments, q is an integer from 0 to 4. In certain embodiments, the sum of p and q is 3 or 4. In certain embodiments, the sum of p and q is 3. In certain embodiments, the sum of p and q is 4.

[0752] In certain embodiments, each W is a halogen substituent.

[0753] In certain embodiments, R 7 and R 8 are each independently hydrogen, substituted or unsubstituted -C1-C 40 Linear alkyl, substituted or unsubstituted -C1-C 40 Branched alkyl, substituted or unsubstituted -C1-C 40 Cyclic alkyl, substituted or unsubstituted -C1-C 40 Alkenyl, substituted or unsubstituted -C1-C 40 In certain embodiments, R 7 and R 8 Together with the nitrogen to which they are both attached, they form a heterocyclic ring.

[0754] In certain embodiments, R 7 is hydrogen. In certain embodiments, R 7 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 7 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 7 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 7 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 7 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 7 is a substituted or unsubstituted aryl group. In certain embodiments, R 7 is a substituted or unsubstituted heterocyclic group.

[0755] In certain embodiments, R 8 is hydrogen. In certain embodiments, R 8is substituted or unsubstituted -C1-C 40 In certain embodiments, R 8 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 8 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 8 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 8 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 8 is a substituted or unsubstituted aryl group. In certain embodiments, R 8 is a substituted or unsubstituted heterocyclic group.

[0756] In certain embodiments, R 9 is hydrogen. In certain embodiments, R 9 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 9 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 9 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 9 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 9 is substituted or unsubstituted -C1-C 40 In certain embodiments, R 9 is a substituted or unsubstituted aryl group. In certain embodiments, R 9 is a substituted or unsubstituted heterocyclic group.

[0757] In Scheme A5, the Ta-based catalyst used for the hydroaminoalkylation reaction is selected from catalysts C1, C2 and C3. In certain embodiments, polymer functionalization is achieved by using a reactive group 4 or 5 hydroaminoalkylation catalyst. In certain embodiments, in order to obtain reactivity, it is necessary to use a N, O chelating ligand to form a highly reactive electrophilic catalyst, such as a cyclic urate C1 or C2. In certain embodiments, the N, O-chelate catalyst can be separated or generated in situ by providing Ta(CH2SiMe3)3Cl2 with an equivalent of a N, O-chelate basic salt (e.g., sodium urate). In certain embodiments, the catalyst is C2.

[0758] Overall scheme: Hydroaminoalkylation

[0759] Plan A6

[0760]

[0761] Scheme A6. In certain embodiments, Scheme A5 illustrates the reaction conditions for hydroaminoalkylation of 5000 g / mol of liquid polybutadiene having 92% 1,4-repeat units and 8% 1,2-repeat units. In certain embodiments, polymer P5a is treated with N-methylaniline (P5c) in the presence of a Ta-based catalyst and ligand P5b to obtain the alkylated product P5. The detailed reaction procedure and additional examples of polymers that can be prepared according to Scheme A6 are described below.

[0762] General Procedure 1: For in situ catalyst generation

[0763] The tantalum precursor (TaCl2(CH2SiMe3)) was added to a vial containing the ligand and toluene-d8 (0.10 mL). The mixture was stirred to generate a green precatalyst. Liquid polybutadiene ( 100. 130. 150) (0.10 g), amine (various amounts) and 1,3,5-trimethoxybenzene (0.016 mg). The chemical structures of these polybutadiene polymers are shown in Scheme 2 above. The amine was transferred to the precatalyst mixture, which was then quantitatively transferred to a J-Young NMR spectrometer tube along with toluene-d8 and liquid polybutadiene and 1,3,5-trimethoxybenzene internal standards. The total mass of each reaction solution was 0.60 mg. The mass at t = 0 hours before heating was recorded. 1 H NMR spectroscopy. Reactions were heated to 140°C using a silicone oil bath with the solvent line aligned with the bath level (unless otherwise stated). After heating for 1 hour, the t = 1 hour time point was recorded. 1 H NMR spectroscopy. For selected reactants, the reaction vessel was heated for an additional 2 hours, 4 hours, and 23 hours to obtain 1 H NMR spectroscopy. The reaction was stopped by removing from the heat source and exposing the reactants to air to oxidize the catalyst. The material was isolated by filtration through a pad of Celite® and three precipitations from the concentrated DCM solution into cold MeOH or acetone. The final product was collected and dried overnight in vacuo before characterization. In certain embodiments, the molar ratio of tantalum precursor to ligand is 1:1.

[0764] Example 1: Synthesis of Compound 1

[0765] Use the same procedure as general procedure 1 130R2 and N-methylaniline (50 mg) were used to synthesize compound 1 using catalyst C2 (12 mg Ta(CH2SiMe3)3Cl2 and 3.8 mg urate ligand salt) in situ. The chemical structures of these polybutadiene polymers are shown in Scheme 2 above. Compound 1 (91 mg, 81%) was obtained. 1 H NMR (300 MHz, CDCl3, 298 K) δ = 7.16 (t, br, H1); 6.67-6.61 (overlapping t and d, br, 2H); 5.56 (m, br, 1H); 5.38 (m, br, 2H); 4.96 (m, br, 1H); 3.08-2.94 (d, m, br, 1H); 2.03 (m, br, 2H); 1.63-0.85 (m, br, 7); 0.88 (overlapping s, 3H); 13 C{ 1 H} NMR (300 MHz, CDCl3, 298 K) δ = 148.6, 142.8, 131.4, 128.5, 117.1, 114.4, 112.8, 48.3, 38.3, 34.2, 32.9, 32.8, 30.3, 27.5, 25.0, 22.7 and 14.3; LCMS: C 17 H 25 N3O4 required value: 335, measured value: m / z = 336 [M + H] + In certain embodiments, 13 C{ 1 Some of the H}NMR chemical shifts are difficult to see, so the combination Figure 1A These values ​​are determined from the spectra of Figure 1B The compound 1 13 C{ 1 H} NMR spectrum.

[0766] Example 2: Synthesis of Compound 2

[0767] Use the same general procedure 1 130R2 synthesized compound 2. 1 HNMR (300MHz, CDCl3, 298K) δ=6.77,6.75(H3);6.59,6.56,6.53(H4);5.83(H14);5.36(H17&H18);4.96(H15);3.73(H1);3.03,2.88(H7);2.06,2.02(H16&H19);1.63,1.60,1.44,1.37,1.26,0.88(H8-H13 overlap)ppm; 13C{ 1 H} NMR (75MHz, CDCl3, 298K) δ = 152.0, 142.9, 130.2, 115.1, 114.2, 56.0, 49.3, 34.3, 32.9, 30.4, 27.6, 14.3ppm. Figure 2A The compound 2 1 H NMR spectroscopy. Figure 2B The compound 2 13 C{ 1 H} NMR spectrum.

[0768] Example 3: Synthesis of Compound 3

[0769] Use the same procedure as general procedure 1 130R2 and 150 wt% N-methylcyclohexylamine (150 mg) were reacted in the presence of a tantalum catalyst (34 mg Ta(CH2SiMe3)3Cl2 and 10.9 mg urate ligand salt) and the reaction mixture was heated at 140°C for 1 hour to synthesize compound 3. Compound 3 (82 g, 65%) was obtained. 1 H NMR (300 MHz, CDCl3, 298 K) δ = 5.64, 5.62, 5.61, 5.58, 5.56, 5.54, 5.54, 5.50, (m, br, H13); 5.42, 5.41, 5.39, 5.37 (m, br, H16 and H17); 5.01, 5.00, 4.99, 4.97, 4.96, 4.95, 4.94, 4.93, 4.91 (m, br, H14); 2.62, 2.61, 2.59, 2.57, 2.47, 2.44, 2.41 (d, m, br, H6 overlaps with H4); 2.12, 2.08, 2.04 (m, br, H15 and H17); 8 overlaps with H3); 1.78, 1.76, 1.75, 1.74, 1.72, 1.70 (H2); 1.65, 1.64, 1.62, 1.61, 1.60, 1.59 (H1); 1.57 (H7); 1.54, 1.52, 1.51, 1.50, 1.49, 1.47, 1.45, 1.43, 1.42, 1.39, 1.37, 1.36, 1.34, 1.33, 1.31, 1.30, 1.28, 1.27, 1.25, 1.23 (H9-H12); 0.98, 0.96 (d, H8); 0.91, 0.89, 0.86, 0.84 (m, br, end group) ppm. 13C{ 1H} NMR (75MHz, CDCl3, 298K) δ=143.2, 142.8, 142.7 (C13); 131.4, 131.1, 130.7, 130.6, 130.5, 130.2, 120.1, 129.9, 129.7, 129.5, 129.4, 128.6, 128.5, 128.3, 128.2, 128.0 (C16, C17 overlap); 115.0, 114.4, 114.3, 114.0 ( C14); 57.1 (C4); 51.0 (C6); 43.9, 43.7, 43.6 (C11); 41.7, 41.2, 40.9 (C9); 34.8, 34.2, 34.1 (C7, C12 overlap) 32.8 (C15 and C18-trans); 31.7 (C10); 30.3, 30.2 (C3); 27.5 (C15 and C18-cis); 26.3 (C1); 25.4, 25.2, 25.1, 25.0 (C2) ppm. C8 was not detected. Figure 3A The compound 3 1 H NMR spectroscopy. Figure 3B The compound 3 13 C{ 1 H} NMR spectrum. Figure 3C The compound 3 1 H- 1 H COSY NMR spectroscopy. Figure 3D The compound 3 1 H- 13 C{ 1 H} HSQC NMR spectroscopy. Figure 3E The compound 3 1 H- 13 C{ 1 H}HMBC NMR spectrum.

[0770] Example 4: Synthesis of Compound 4

[0771] Use the same procedure as general procedure 1 Compound 4 was synthesized by in situ generation of 130R2 and N-methylbutylamine using catalyst C2. 1H NMR (300 MHz, CDCl3, 298 K) δ = 5.42, 5.41, 5.40, 5.37, 5.36, 5.34 (overlapping of H16 and H17); 4.99, 4.98, 4.95, 4.91 (H14); 2.60, 2.57, 2.55, 2.53, 2.51, 2.48, 2.40, 2.37 (overlapping of H4 and H6); 2.08, 2.07, 2.02, 1.89 (overlapping of H15 and H17); 8 overlaps with H9 and H11 shoulders); 1.64, 1.63, 1.60, 1.58; 1.45, 1.43 (H3); 1.39, 1.37, 1.35, 1.33, 1.32, 1.30, 1.27, 1.25 (overlaps with H2, H10, H12); 0.98, 0.96, 0.93, 0.91, 0.88, 0.85, 0.83, 0.82, 0.81, 0.67 (overlaps with H1, H8 and end groups) ppm. 13 C{ 1 H} NMR (75 MHz, CDCl3, 298K) δ = 130.3, 129.7, 129.6 (C14); 114.4 (C13 observed by HSQC); 68.8 (C4 when activated in HAA to form methine); 50.0 (C4); 48.4 (C6); 32.9 (C15 and C18-trans); 32.4 (C3); 27.5 (C15 and C18-cis); 20.8, 20.7 (C2); 18.1; 14.2 (C1) ppm. Not observed: C9-C12. Figure 4A The compound 4 1 H NMR spectroscopy. Figure 4B The compound 4 13 C{ 1 H} NMR spectrum.

[0772] Example 5: Synthesis of Compound 5

[0773] Use the same procedure as general procedure 1 Compound 5 was synthesized by in situ generation of 100R1 and N-methylaniline using catalyst C2. 1 H NMR (300 MHz, CDCl3, 298 K) δ = 7.18 (H2 and H13 overlap); 6.71 (H1); 6.61 (H3); 5.83 (H16); 5.37 (H19 & H20); 4.98 (H17); 3.80, 3.79; 3.08, 2.92, 2.57 (H6); 2.04 (H18 & H121); 1.39, 1.38, 1.29, 1.28, (H7, H9-H12, overlap); 0.92 (H8, end group overlap) ppm. 13 C{1 H}NMR (75MHz, CDCl3, 298K) δ=148.4(C4); 142.8(C16); 129.4, 129.4, 128.3, 127.9, 126.0(C2, C16, C17 overlap); 117.3(C1); 112.9(C3); 48.4(C6); 38.0(C7); 32.9(C18&C21-trans); 34.4, 30.6, 29.8, 22.7, (C9-C12 overlap); 27.7(C18&C21-trans); 16.7, 14.3(C8) ppm. Not observed: C17. Figure 5A The compound 5 1 H NMR spectroscopy. Figure 5B The compound 5 13 C{ 1 H} NMR spectrum.

[0774] Example 4: Synthesis of Compound 6

[0775] Use the same procedure as general procedure 1 100R1 and N-methylaniline (101 mg) were used to synthesize compound 6 using catalyst C2 (24.2 mg Ta(CH2SiMe3)3Cl2 and 7.7 mg urate ligand salt) to obtain compound 6 (124 mg, 71%). 1 HNMR (300MHz, CDCl3, 298K) δ = 7.18 (H2 and H13 overlap); 6.71 (H1); 6.61 (H3); 5.83 (H16); 5.37 (H19&H20); 4.98 (H17); 3.80, 3.79; 3.08, 2.92, 2.57 (H6); 2.04 (H18&H121); 1.39, 1.38, 1.29, 1.28, (H7, H9-H12, overlap); 0.92 (H8, end group overlap) ppm. 13 C{ 1 H}NMR (75MHz, CDCl3, 298K) δ=148.4(C4); 142.8(C16); 129.4, 129.4, 128.3, 127.9, 126.0(C2, C16, C17 overlap); 117.3(C1); 112.9(C3); 48.4(C6); 38.0(C7); 32.9(C18&C21-trans); 34.4, 30.6, 29.8, 22.7, (C9-C12 overlap); 27.7(C18&C21-trans); 16.7, 14.3(C8) ppm. Not observed: C17. Fig. 6A The compound 6 1 H NMR spectroscopy. Figure 6B The compound 6 13 C{ 1 H} NMR spectrum.

[0776] Example 7: Synthesis of Compound 7

[0777] Use the same procedure as general procedure 1 Compound 7 was synthesized by in situ generation of 100R1 and N-methylcyclohexylamine using catalyst C2. 1 H NMR (300 MHz, CDCl3, 298 K) δ = 7.13 (H13), 5.79, 5.52 (H16); 5.34 (H19 & H20); 4.95 (H17); 2.56, 2.36, 2.26 (overlapping of H4 and H6); 2.02 (H18 & H21); 1.70, 1.63, 1.59, 1.35, 1.28, 1.26, 1.23, 1.20, 0.88, 0.85, 0.83 (overlapping of H1-H3, H9-H15) ppm. Figure 7 The compound 7 1 H NMR spectroscopy.

[0778] Example 8: Synthesis of Compound 8

[0779] Compound 8 was synthesized using 9.4 wt% Zr(NMe2)4, 42 wt% N-benzyltrimethylsilylamine and 0.1 g Ricon 130R1. The reactants were heated at 145°C for up to 400 hours to achieve maximum reaction of the vinyl groups. A mixture of branched and linear products was obtained. 1 HNMR (300MHz, C6D6, 298K) δ7.08, δ5.45, δ4.99, δ3.99, δ3.75, δ2.37, δ2.09-1.00. Figure 8 The stacked compound 8 reaction before and after heating is shown. 1 H NMR spectroscopy.

[0780] Example 5: Synthesis of Compound 9

[0781] Use the same procedure as general procedure 1 130R1 and 200 wt% N-methylaniline (200 mg) were reacted in the presence of 5 mol% tantalum catalyst (47.9 mg Ta(CH2SiMe3)3Cl2 and 15.3 mg urate ligand salt) and the reaction mixture was heated at 140°C for 1 hour to synthesize compound 9. Compound 9 (42.3 mg, 23%) was obtained. 1H NMR (300 MHz, CDCl3, 298 K) δ = 7.18 (H2 and H13 overlap); 6.71 (H1); 6.61 (H3); 5.83 (H16); 5.37 (H19 & H20); 4.98 (H17); 3.80, 3.79; 3.08, 2.92, 2.57 (H6); 2.04 (H18 & H121); 1.39, 1.38, 1.29, 1.28, (H7, H9-H12, overlap); 0.92 (H8, end group overlap) ppm. 13 C{ 1 H}NMR (75MHz, CDCl3, 298K) δ=148.4(C4); 142.8(C16); 129.4, 129.4, 128.3, 127.9, 126.0(C2, C16, C17 overlap); 117.3(C1); 112.9(C3); 48.4(C6); 38.0(C7); 32.9(C18&C21-trans); 34.4, 30.6, 29.8, 22.7, (C9-C12 overlap); 27.7(C18&C21-trans); 16.7, 14.3(C8) ppm. Not observed: C17. Fig. 9A The compound 9 1 H NMR spectroscopy. Fig. 9B The compound 9 13 C{ 1 H} NMR spectrum. Fig. 9C The compound 9 1 H- 1 H COSY NMR spectroscopy. Fig.9D The compound 9 1 H- 13 C{ 1 H} HSQC NMR spectroscopy. Fig.9E The compound 9 1 H- 13 C{ 1 H}HMBC NMR spectrum.

[0782] Example 9: Hydrogenation

[0783] Plan A7

[0784]

[0785] Scheme A7. In certain embodiments, the functionalized polymer can be subjected to hydrogenation reaction conditions to produce a saturated polymer backbone. In certain embodiments, the saturated polymer backbone product is generally expected to exhibit higher thermooxidative stability. In certain embodiments, subjecting polymer P1 to appropriate hydrogenation conditions will yield saturated polymer P6.

[0786] Example 10: Synthesis of Compound P6

[0787] A Schlenk flask containing P1 (500 mg, 0.088 mmol) was heated to 100 ° C overnight under vacuum to dry and degas the compound. A thick-walled container was charged with p-toluenesulfonyl hydrazide (2.9 g, 15.6 mmol) and dried overnight in vacuum. Before using tripropylamine (TPA), it was dried, distilled, and degassed over three freeze-pump-thaw cycles with CaH2. Before using xylene, it was dried, distilled, and degassed over three freeze-pump-thaw cycles with CaH2. 3 mL of xylene was transferred to a Schlenk flask to dissolve P1, and the solution was transferred to a thick-walled container containing dried methanesulfonyl hydrazide. 6 mL of xylene was added to the reaction vessel by a syringe. TPA (1.9 mL, 10.0 mmol) was transferred to a thick-walled reaction vessel by syringe technology. The container was sealed with an airtight PTFE valve under N2 and heated to 130 ° C for 24 hours. The reaction was removed from the heat source and cooled to room temperature. The solution was collected in a separatory funnel with 20 mL of dichloromethane (DCM). The organic layer was washed three times with 15 mL of 1M NaOH. The aqueous layer was washed once with 20 mL of DCM, and the organic layers were collected and combined. The organic layer was dried over MgSO4, filtered by gravity filtration, and concentrated under reduced pressure. The product was precipitated from the concentrated DCM solution into cold MeOH to remove the p-toluenesulfonic acid by-product. The product P6 was collected and dried in vacuo to give a dark red viscous oil (0.443 mg, 86%). 1 H NMR spectrum (300 MHz, CDCl3) ( Fig.10 ). δ=7.26,6.78,6.76,6.58,6.55,3.74,3.03,3.02,2.86,2.32,1.85,1.62,1.26,1.23,1.10,1.08,0.83,0.08ppm.

[0788] Example 11: Reduction of branched p-methoxyarylamine to branched primary amine product Scheme A8

[0789]

[0790] Scheme A8. In certain embodiments, the functionalized polymer can be subjected to reduction reaction conditions to produce a primary amine product.

[0791] Synthesis of P7A

[0792] P7 (0.500 g, 0.190 mmol) was weighed into a round bottom flask and dissolved in 2 mL of toluene. Pure cerium (II) ammonium nitrate was added, followed by 2 mL of deionized water. The reactants were stirred overnight at room temperature. The dark purple solution was concentrated under reduced pressure, and the product was isolated by filtering the dichloromethane solution through a short diatomaceous earth and activated carbon plug. The solution was dried under vacuum, and P7A was isolated as a dark brown oily product in 43% yield. 1 H NMR spectrum, no aromatic signal was observed ( Fig.11 ). 1 H NMR spectrum (300 MHz, CDCl3) δ = 7.26, 5.65, 5.56, 5.50, 5.42, 5.38, 4.96, 4.92, 2.24, 2.07, 2.03, 1.65, 1.64, 1.59, 1.43, 1.30, 1.28, 1.28, 1.26, 1.01, 0.91, 0.88, 0.87, 0.83, 0.07 ppm.

[0793] Example 12: General Scheme: Epoxide Ring Opening Scheme A9

[0794]

[0795] Scheme A9. In certain embodiments, the functionalized polymer can be reacted with epoxides. In certain embodiments, the functionalized polymer can be used to perform epoxide ring opening. Epoxide ring opening is a key step in the curing process of epoxy resins used in adhesives and coatings.

[0796] Example 13: Epoxide Ring Opening of Poly(ethylene glycol) diglycidyl ether Scheme A10

[0797]

[0798] Scheme A10. P9 (0.254 g, 0.053 mmol) was weighed into a round bottom flask and dissolved in 3 mL THF. Polyethylene glycol diglycidyl ether (0.052 g, 0.104 mmol) was weighed separately and quantitatively transferred to the flask containing the amine functionalized polybutadiene as a solution in 2 mL THF. The solution was stirred at room temperature overnight, resulting in minimal conversion, as indicated by aliquoting of the solution. 1 The reaction solution was then heated to 80 °C overnight, resulting in almost quantitative conversion. Fig. 12A P9A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. Fig. 12B P9A 13C NMR (75 MHz, CDCl3, 298 K) spectrum. Fig. 12C The IR spectrum of P9A is shown.

[0799] Example 14: Epoxide Ring Opening of Trimethylolpropane Triglycidyl Ether Scheme A11

[0800]

[0801] Scheme A11. Amine functionalized polybutadiene (0.650 g, 0.135 mmol) was weighed into a Schlenk flask and dissolved in 5 mL of THF. Trimethylolpropane triglycidyl ether (1 mL, 3.83 mmol) was added via syringe. The solution was heated to 40° C. overnight to form an orange solid gel-like insoluble material. Fig.13 Shown are the IR spectra of P10 and P10A superimposed.

[0802] Example 15: Isocyanate Reaction Scheme A12 for Producing Polyurea

[0803]

[0804] Scheme A12. In certain embodiments, the functionalized polymer can react with an isocyanate. The reaction between the amine and isocyanate functional groups can produce a urea functional group. In some embodiments, R 5 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 In some other embodiments, R 5 is -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4-10 Aryl and C 4-10 Heteroaryl.

[0805] Example 16: Reaction Scheme A13 with 4,4'-methylenebis(cyclohexyl isocyanate)

[0806]

[0807] Scheme A13. P12 (0.25 g, 0.055 mmol) was weighed into a round bottom flask and dissolved in 3 mL of DCM. 4,4'-Methylenebis(cyclohexyl isocyanate) (1.3 mL, 5.28 mmol) was transferred to the reaction flask via syringe. The solution was stirred overnight at room temperature. The next morning, the material was concentrated under reduced pressure to give a hard, brittle, insoluble material P12A. The product was characterized by FTIR spectroscopy ( Fig.14 ).

[0808] Example 17: Reaction with Tosylated Polyethylene Glycol Scheme A14

[0809]

[0810] Scheme A14. P13 (290 mg, 0.060 mmol) was weighed into a round bottom flask and dissolved in 3 mL THF. Tosylated polyethylene glycol (180 mg, 0.43 mmol) was weighed separately and quantitatively transferred to the round bottom flask containing P13 along with 2 mL THF. KI (0.138 g, 0.83 mmol) and Cs2SO3 (0.407 mg, 0.13 mmol) were weighed separately and added directly to the round bottom flask. The solution was stirred and refluxed overnight. An off-white precipitate formed overnight. The solution was cooled to room temperature and then passed through a 1 in. The resulting solution was concentrated under reduced pressure and then dissolved in DCM to perform liquid-liquid extraction with DI-H2O. The organic layer was collected and concentrated under reduced pressure. The resulting product was redissolved in a concentrated DCM solution and precipitated into MeOH. After decanting the MeOH, the insoluble material was collected by collecting as a solution in DCM. The product was concentrated under reduced pressure and then dried overnight in a vacuum. Fig.15A P13A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. Fig. 15B P13A 13 C NMR (75 MHz, CDCl3, 298 K) spectrum. Fig. 15C The IR spectrum of P13A is shown.

[0811] Example 18: Preparation of quaternary amine groups using iodomethane Scheme A15

[0812]

[0813] Scheme A15. P14 (0.252 g, 0.053 mmol) was weighed into a round bottom flask and dissolved in 3 mL of DCM. Methyl iodide (0.1 mL, 1.55 mmol) and 2,6-lutidine (0.15 mL, 1.30 mmol) were added to the reaction vessel via a syringe. The solution was stirred overnight at room temperature. A precipitate formed and was removed by filtration through diatomaceous earth. The solution was concentrated under reduced pressure to obtain further precipitates. These precipitates were removed by filtration through diatomaceous earth with hexanes. The solution was concentrated under reduced pressure and dried under vacuum overnight to obtain P14A (247 mg, 92%). Fig.16 .P14A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum.

[0814] Example 19: Scheme: Reaction with benzyl chloride Scheme A16

[0815]

[0816] Scheme A16. P15 (251 mg, 0.044 mmol) was weighed into a round bottom flask and dissolved in 3 mL of THF. Sodium iodide (0.097 mg, 0.647 mmol) was weighed separately and added neat to the reaction flask. Benzyl chloride (0.077 mL, 0.669 mmol) was supplied to the reaction flask via a syringe. The solution was mixed vigorously and refluxed overnight. A precipitate formed and was removed by filtration through diatomaceous earth. The solution was concentrated under reduced pressure and the product was precipitated from the concentrated DCM solution into cold MeOH. The MeOH was poured off and the product was collected in a vial containing DCM, concentrated under reduced pressure, and dried in vacuo overnight. The resulting material P15A was hard and amber (0.077 g, 25%). Fig.17A .P15A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. Fig. 17B Compound P15A 13 C{1H}NMR (75MHz, CDCl 3, 298K) spectrum.

[0817] Example 20: Reaction with triphosgene

[0818] Scheme A17

[0819]

[0820] Scheme A17. P16 (0.25 g, 0.055 mmol) was weighed into a round-bottom flask and dissolved in 3 mL of DCM. Triphosgene (0.77 g, 0.26 mmol) was weighed separately into a sealed vial and then added to the reaction vessel in pure form. The solution was stirred overnight at room temperature. The next morning, the solution was washed with deionized water (3×5 mL), the organic layer was collected and dried over MgSO4. The solution was gravity filtered and concentrated under reduced pressure, then dried overnight in a vacuum. The resulting material P16A was oily, viscous and brown (0.22 g, 84%). Fig.18A .P16A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. Fig.18B .FT-IR spectrum of P16A.

[0821] Example 21: Reaction with linoleic acid

[0822] Scheme A18

[0823]

[0824] Scheme A18. P17 (0.102 g, 0.0210 mmol) was weighed into a round-bottom flask. Linoleic acid (0.121 g, 0.431 mmol) was weighed separately and quantitatively transferred to a round-bottom flask containing DCM. The two were mixed for 1 hour, and then pure N, N'-dicyclohexylcarbodiimide (DCC) (0.095 g, 0.46 mmol) was added. The reactants were stirred overnight at room temperature. The next morning, the solution became turbid and white, and the precipitate (N, N'-dicyclohexylurea-DCU) was removed by filtration. The product P17A was concentrated under reduced pressure and precipitated into acetone from the concentrated DCM solution. This formed a persistent dispersion, the product was separated by centrifugation, and acetone was decanted from the product. 0.156 g (0.0145 mmol, 69%) of the product P17A as a yellow oil was isolated. Fig.19A .P17A 1 H NMR (300 MHz, CDCl3, 298 K) spectrum. Fig.19B .P17A 13 C{1H}NMR (75MHz,CDCl3,298K) spectrum.

[0825] Example 22: Reaction with oxalic acid to obtain pH-responsive material Scheme A19

[0826]

[0827] Scheme A19. P18 (0.50 g, 0.10 mmol) was weighed into a round bottom flask and dissolved in hexane. Oxalic acid (0.10 g, 1.1 mmol) was weighed separately and transferred to the round bottom flask along with 0.1 mL MeOH. One minute after the addition, a white solid waxy precipitate formed at the bottom of the round bottom flask. This precipitate persisted. Then 1 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was added and the precipitate dissolved immediately. The solution remained homogeneous. Then an excess of oxalic acid was added to the solution and the precipitate reformed and the supernatant became clear after 10 minutes. The product P18A is insoluble in most organic solvents (hexane, MeOH, EtOAc, CDCl3). Fig. 20 .FT-IR spectrum of P18A.

[0828] Example 23: Reaction with hydrochloric acid

[0829] Scheme A20

[0830]

[0831] Scheme A20. P19 (0.29 g, 0.064 mmol) was weighed into a round bottom flask and dissolved in 3 mL of DCM. 0.61 mL of 2.0 M HCl in ether was transferred to the reaction flask via a syringe. An insoluble precipitate was formed immediately and the reaction was stirred overnight at room temperature. The next morning, the solvent was removed under reduced pressure and the material was dried overnight under vacuum to give a solid, flaky, amber material, P19A (0.306 g, 0.059 mmol). Fig.21A .P19A 1 H NMR (300 MHz, CD3OD, 298 K) spectrum. Fig. 21B .P19A 13 C{1H} NMR (75 MHz, CD3OD, 298 K) spectrum. Fig. 21C .FT-IR spectrum of P19A.

[0832] Example 24: Reaction with polybutadiene having varying molecular weight

[0833] The following reactions were performed on polybutadiene starting materials with varying molecular weights:

[0834]

[0835] Example 25: Reaction with anhydride

[0836] Carry out the following reaction.

[0837]

[0838] P20 (0.247 g, 0.055 mmol) was weighed into a round bottom flask and then dissolved in 3 mL of THF. Succinic anhydride (0.054 g, 0.540 mmol) was then weighed separately and added to the solution. Two drops of 1 M HCl were added to the solution. (aq) The mixture was stirred at room temperature overnight. The solution was concentrated under reduced pressure, and the viscous product was then dissolved in a concentrated DCM solution and precipitated into DI-H2O. The DI-H2O was decanted, the product was collected as a DCM solution and concentrated under reduced pressure, and then dried in vacuum overnight to give P20A (0.262 g). Fig.22A .P20A 1 H NMR (300 MHz, CD3OD, 298 K) spectrum. Fig. 22B .P20A 13 C{1H} NMR (75 MHz, CD3OD, 298 K) spectrum. Fig. 22C .FT-IR spectrum of P20A.

[0839] The above embodiments and examples are merely illustrative and non-restrictive. One of ordinary skill will recognize or be able to determine many equivalents of specific compounds, materials, and procedures using only routine experimentation. All such equivalents are considered to be within the scope of and are covered by the appended claims.

Claims

1. A polymer comprising: Polybutadiene backbone; 1,2-Olefin units; 1,4-olefin units; and A branched substituted unit having a functional group of formula (I) or a salt thereof: A linear substituted unit having a functional group of formula (I) or a salt thereof: wherein the molar ratio of the branched substitution unit to the linear substitution unit is 6:1 or greater; R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 Heterocyclic ring, Where R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The units may be arranged in series, in blocks, or randomly distributed.

2. The polymer of claim 1, wherein the polymer contains at least 60% branched substituted units relative to linear substituted units.

3. The polymer according to any one of claims 1 to 2, wherein the amount of 1,2-olefin units and 1,4-olefin units may be equal or may vary.

4. The polymer according to any one of claims 1 to 3, comprising 92% of 1,4-olefin units and 8% of 1,2-olefin units.

5. The polymer of any one of claims 1-4, wherein the one or more other units comprise styrene units optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or mixtures thereof.

6. The polymer of claim 5, wherein the one or more other units comprise styrene units.

7. The polymer of any one of claims 1 to 6, wherein the one or more other units are isoprene units.

8. The polymer according to any one of claims 1 to 7, wherein R 2 The aryl group in is para-substituted.

9. A polymer of formula (II) or a fragment thereof, wherein R 5 to exist or not to exist; When there is R on the c unit 5 When R is absent on the c unit, the dashed line represents a single bond. 5 When , the dotted line represents a double bond; R 5 A compound of formula (I) or a salt thereof: in R 1 C1-C 20 Alkyl or -C6-C 20 aryl; or R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 3 and R 4 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof, Where R 2 The aryl group in is optionally substituted at the para position; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; R 6 is hydrogen, -C1-C 20 Alkyl, -C6-C 20 Aryl, -C 1-6 Alkyl-C1-C 20 Alkyl, -C 1-6 Alkyl-C6-C 20 Aryl, -C 1-6 Heteroalkyl-C1-C 20 Alkyl or -C 1-6 Heteroalkyl-C6-C 20 aryl; and a, b, c, d, e and f are independently at each occurrence an integer from 0 to 100,000; wherein the ratio of d:e is 6:1 or greater, wherein the units may be ordered or randomly distributed.

10. The polymer of claim 9, wherein the ratio of a:b is 0.1, 0.5, 1, 1.5, 2 or 10.

11. The polymer of any one of claims 9 and 10, wherein the ratio of d:e is 6:

1.

12. The polymer according to any one of claims 9 to 11, wherein R 2 The aryl group in is substituted at the para position.

13. A polymer of formula (II) having a structure of formula (IIa) 14. A polymer of formula (II) having a structure of formula (IIb) 15. A polymer of formula (II) having a structure of formula (IIc) 16. A polymer of formula (II) having a structure of formula (IId) 17. A polymer of formula (II) having a structure of formula (IIe) 18. The polymer according to any one of claims 1 and 17, selected from the following compounds:

19. A polymer comprising: Polybutadiene backbone; 1,2-Olefin units, 1,4-olefin units; and 1,4-addition unit substituted with a functional group of formula (I) or a salt thereof: Where R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The cells may be ordered or randomly distributed.

20. A polymer comprising: Polybutadiene backbone; A unit comprising a repeating unit of a 1,2-olefin, units comprising repeating units of 1,4-olefins; and A branched substituted unit having a functional group of formula (I) or a salt thereof: A linear substituted unit having a functional group of formula (I) or a salt thereof: in R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The cells may be ordered or randomly distributed.

21. The polymer of claim 20 having the following structure: The sum of the subscripts d and e is 9.

22. The polymer of any one of claims 1-21, wherein the polymer has a molecular weight of 2,500 to 4,500 g / mol.

23. The polymer of any one of claims 1-21, wherein the polymer has a molecular weight of 70,000 to 80,000 g / mol.

24. A process for producing a polymer, comprising: Hydroaminoalkylation of a polymerized polybutadiene polymer in the presence of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is 110° C. to 165° C., This produces a functionalized polymer comprising: Polybutadiene backbone; 1,2-Olefin units, 1,4-olefin units; and A branched substituted unit having a functional group of formula (I) or a salt thereof: A linear substituted unit having a functional group of formula (I) or a salt thereof: wherein the molar ratio of the branched substitution unit to the linear substitution unit is 6:1 or greater; R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The cells may be ordered or randomly distributed.

25. The process of claim 24, wherein the catalyst is a Ta-based catalyst.

26. A process for producing a polymer, comprising: Functionalizing an internal olefin of a polybutadiene polymer in the presence of a Group 4 or Group 5 transition metal catalyst and a secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140° C., wherein the functionalized polymer comprises: Polybutadiene backbone; 1,2-Olefin units, 1,4-olefin units; and 1,4-addition unit substituted with a functional group of formula (I) or a salt thereof: in R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The cells may be ordered or randomly distributed.

27. A process for producing a polymer, comprising: Hydroaminoalkylation of a polybutadiene polymer in the presence of a Zr-based catalyst and a silyl-protected secondary amine to form a functionalized polymer, wherein the reaction temperature is at least 140° C., wherein the functionalized polymer comprises: Polybutadiene backbone; 1,2-Olefin units; 1,4-olefin units; and A branched substituted unit having a functional group of formula (I) or a salt thereof: A linear substituted unit having a functional group of formula (I) or a salt thereof: in R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof; R 3 and R 4 is independently selected from hydrogen, -C1-C6 alkyl, -C1-C6 heteroalkyl, C 4-10 Aryl and C 4-10 heteroaryl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises other units; and The cells may be ordered or randomly distributed.

28. The process of claim 27, wherein the amine is N-benzylsilylamine.

29. A polymer produced by the process of any one of claims 24-28.

30. A polymer made by the process of any one of claims 24-28, wherein the process is solvent-free.

31. A process for hydrogenating a polybutadiene polymer backbone to prepare an aliphatic backbone polymer, comprising: reacting the polymer according to any one of claims 1 to 22 or 29 to 30 under hydrogenation conditions, Thus, the aliphatic main chain polymer is prepared.

32. The process of claim 31, wherein the hydrogenation conditions comprise the use of p-toluenesulfonyl hydrazide, tripropylamine, xylene, or a combination thereof.

33. The process of any one of claims 31 to 32, wherein the hydrogenation conditions comprise a N2 atmosphere.

34. The process of any one of claims 31-33, wherein the hydrogenation conditions comprise heating the polymer of any one of claims 1-21 or 27-28 to at least 100°C under hydrogenation conditions.

35. The process of any one of claims 31-34, wherein the hydrogenation conditions comprise heating the polymer of any one of claims 1-21 or 27-28 to 100°C to 150°C under hydrogenation conditions.

36. The process of any one of claims 31-35, wherein the hydrogenation conditions comprise heating the polymer of any one of claims 1-21 or 27-28 to 130°C under hydrogenation conditions.

37. The process of any one of claims 31-36, wherein the hydrogenation conditions comprise heating the polymer of any one of claims 1-21 or 27-28 under hydrogenation conditions for 24 hours.

38. The process of any one of claims 31 to 37, wherein the process further comprises reducing R 1 or R 2 At least one or both of 1 or R 2 At least one or both of them are H.

39. The process of any one of claims 31-38, wherein the process further comprises reducing the polymer by reacting the polymer with cerium (II) ammonium nitrate.

40. A polymer produced by the process of any one of claims 31-39.

41. A polymer comprising: a reduced polybutadiene backbone; and A branched substituted unit having a functional group of formula (I) or a salt thereof: A linear substituted unit having a functional group of formula (I) or a salt thereof: wherein the molar ratio of the branched substitution unit to the linear substitution unit is 6:1 or greater; R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 Heterocyclic ring, Where R 1 and R 2 Each independently optionally substituted by one to six groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The units may be arranged in series, in blocks, or randomly distributed.

42. The polymer of claim 41, wherein the polymer contains at least 60% branched substituted units relative to linear substituted units.

43. The polymer of any one of claims 40-42, wherein the one or more other units comprise styrene units optionally substituted with alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, styrene, substituted styrene, or mixtures thereof.

44. The polymer of claim 43, wherein the one or more other units comprise styrene units.

45. The polymer of any one of claims 40-44, wherein the one or more other units are isoprene units.

46. ​​A polymer as described in any one of claims 40 to 45, wherein R 2 The aryl group in is substituted at the para position.

47. A polymer of formula (IIIa) or (IIIb): or a fragment thereof, wherein R 5 to exist or not to exist; R 5 A compound of formula (I) or a salt thereof: in R 1 C1-C 20 Alkyl or -C6-C 20 aryl; or R 2 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 3 and R 4 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -C1-C6 thioalkyl, or a combination thereof, Where R 2 The aryl group in is optionally substituted at the para position; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; R 6 is hydrogen, -C1-C 20 Alkyl, -C6-C 20 Aryl, -C 1-6 Alkyl-C1-C 20 Alkyl, -C 1-6 Alkyl-C6-C 20 Aryl, -C 1-6 Heteroalkyl-C1-C 20 Alkyl or -C 1-6 Heteroalkyl-C6-C 20 aryl; and a, b, c, d, e and f are independently at each occurrence an integer from 0 to 100,000; wherein the ratio of d:e is 6:1 or greater, wherein the units may be ordered or randomly distributed.

48. The polymer of claim 47, wherein the ratio of a:b is 0.1, 0.5, 1, 1.5, 2 or 10.

49. The polymer of any one of claims 47 and 48, wherein the ratio of d:e is 6:

1.

50. A polymer as described in any one of claims 46 to 49, wherein R 2 The aryl group in is para-substituted.

51. A polymer of formula (IIIa) having a structure of formula (IIIa) 52. A polymer of formula (III) having a structure of formula (IIIb) 53. A polymer of formula (III) having a structure of formula (IIIc) 54. A polymer of formula (III) having a structure of formula (IIId) 55. A polymer of formula (III) having a structure of formula (IIIe) 56. The polymer of any one of claims 40-55, selected from the following compounds:

57. A polymer comprising: a reduced polybutadiene backbone; and Substituted with a functional group of formula (I) or a salt thereof: in R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OCH3, -OCF3 and -SCH3, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The cells may be ordered or randomly distributed.

58. A polymer comprising: a reduced polybutadiene backbone; and A branched substituted unit having a functional group of formula (I) or a salt thereof: A linear substituted unit having a functional group of formula (I) or a salt thereof: in R 1 is hydrogen, -C1-C 20 Alkyl or -C6-C 20 Aryl; R 2 C1-C 20 Alkyl or -C6-C 20 aryl; or R 1 and R 2 Together with the nitrogen to which they are both attached, they form a -C3-C 20 A heterocyclic ring, wherein R 1 and R 2 Each independently optionally substituted by 1 to 6 groups selected from -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3 and -C1-C6thioalkyl, or a combination thereof; R 3 and R 4 is independently selected at each occurrence from hydrogen, -C1-C6 alkyl, and -C1-C6 heteroalkyl; The asterisk (*) indicates the point of attachment of the functional group to a carbon atom in the polymer backbone; wherein the polymer optionally comprises one or more other units; and The cells may be ordered or randomly distributed.

59. The polymer of claim 58 having the structure: The sum of the subscripts d and e is 9.

60. A process for preparing a mixture, comprising: Providing a polymer as described in any one of claims 1-22, 29-30 or 40-59, and at least one epoxide monomer or a precursor thereof, Thereby, the mixture is prepared.

61. The process of claim 60, wherein the epoxide monomer or its precursor has a structure selected from the group consisting of: Where R 30 Selected from hydrogen, C 1-6 alkyl, 62. The process of claim 60 or 61, wherein the epoxide monomer or precursor thereof has a structure selected from the group consisting of: Where R 30 for 63. The process of claim 60 or 61, wherein the epoxide monomer or precursor is poly(ethylene glycol) diglycidyl ether epoxide.

64. The process of claim 60 or 61, wherein the epoxide monomer or precursor is trimethylolpropane triglycidyl ether epoxide.

65. The process of claim 60 or 61, wherein said one or more epoxide monomers or precursors thereof comprise epichlorohydrin or a derivative thereof.

66. The process of claim 60 or 61, wherein the one or more epoxide monomers or precursors thereof comprise bisphenol A, a derivative thereof, or a combination thereof.

67. The process of claim 60 or 61, wherein the one or more epoxide monomers or precursors have the structure:

68. The process of claim 60 or 61, wherein the one or more epoxide monomers or precursors have the structure:

69. The process of claim 60 or 61, wherein the one or more epoxide monomers or precursors have the structure: Where R 5 , R 6 , R 7 and R8 In each case, each is independently selected from or comprises -C1-C 20 Alkyl, -C1-C 20 Alkoxy, -[PEG] 0-10 、-[PEG] 0-10 -(C2H4-O), C1-C 10 Heteroalkyl, C6-C 20 Aryl; C3-C having 0 to 2 additional heteroatoms selected from nitrogen and oxygen 20 A heterocyclic ring, wherein the heterocyclic ring may be a fused bicyclic ring, and wherein R 5 , R 6 , R 7 and R 8 Each independently in each case is optionally substituted with 1 to 6 members selected from the group consisting of -F, -Cl, -I, -Br, -OH, -OCH3, -OCF3, -C1-C6thioalkyl, and combinations thereof.

70. The process of any one of claims 60 to 69, wherein said mixture further comprises a combination of epoxide monomers.

71. The process of any one of claims 60 to 70, wherein the mixture further comprises one or more additional hardeners.

72. The process of any one of claims 60-71, further comprising curing the mixture.

73. The process of any one of claims 60-72, further comprising cross-linking the polymer of any one of claims 1-21, 27-28, or 38-59.

74. The process of any one of claims 60-73, further comprising hardening the mixture.

75. A polymer produced by the process of any one of claims 60-73.

76. The polymer of claim 75, wherein the polymer is characterized by a -1 Up to 1115cm -1 Infrared (IR) vibration modes at .

77. The polymer of claim 75, wherein the polymer is characterized by a -1 Infrared (IR) vibration modes at .

78. The polymer of claim 75, wherein the polymer is characterized by a -1 Infrared (IR) vibration modes at .

79. The polymer of any one of claims 75-78, wherein the polymer has a molecular weight of 2,500 to 4,500 g / mol.

80. The polymer of any one of claims 75-79, wherein the polymer has a molecular weight of 4,500 g / mol.

81. The polymer of any one of claims 75-79, wherein the polymer has a molecular weight of 70,000 to 80,000 g / mol.

82. The polymer of any one of claims 40-59, wherein the polymer has a molecular weight of 2,500 to 4,500 g / mol.

83. The polymer of any one of claims 40-59, wherein the polymer has a molecular weight of 70,000 to 80,000 g / mol.

84. A process for preparing a functionalized polymer comprising: preparing a reaction mixture comprising a polymer as described in any one of claims 1-22, 29-30, and 40-59 and an electrophilic reagent; as well as The polymer is reacted with the electrophile to produce the functionalized polymer.

85. The process of claim 84, wherein the electrophile is selected from the group consisting of alkyl halides, epoxides, isocyanates and activated esters.

86. The process of claim 84 or 85, wherein the electrophile is an isocyanate.

87. The process of claim 84 or 85, wherein the isocyanate is 4,4'-methylenebis(cyclohexyl isocyanate).

88. The process of claim 84 or 85, wherein the electrophile is mesylated polyethylene glycol.

89. The process of claim 84 or 85, wherein the electrophiles are iodomethane and 2,6-lutidine.

90. The process of claim 84 or 85, wherein the electrophile is benzyl chloride.

91. The process of claim 84 or 85, wherein the electrophile is triphosgene (bis(trichloromethyl) carbonate 72.

92. The process of claim 84 or 85, wherein the electrophile is linoleic acid.

93. The process of claim 84 or 85, wherein the electrophile is oxalic acid.

94. The process of claims 84-93, wherein the polymer is pH responsive.

95. The process of claim 84 or 85, wherein the electrophile is hydrochloric acid.

96. The process of any one of claims 84 to 95, wherein said reaction mixture further comprises one or more catalysts.

97. The process of any one of claims 84 to 96, wherein said one or more catalysts comprises dimethylaminopyridine.

98. The process of claim 84 or 85, wherein the electrophile is an epoxide.

99. The process of claim 84 or 85, wherein the electrophile is an acyl anhydride.

100. The process of claim 99, wherein said acyl anhydride is dihydrofuran-2,5-dione.

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