SUBSTITUTED POLYSTYRENES AND METHODS

Abstract

Substituted polystyrenes and methods for making substituted polystyrenes. The substituted polystyrenes may be formed by a ring opening metathesis polymerization (ROMP). The ROMP may provide analogs having a precise periodicity. The substituted polystyrenes may have improved conductivities. The substituted polystyrenes may be substituted with N-(phenylsulfonyl)-N-(haloalkylsulfony)imide salts.

Claims

1. A polymer comprising repeat units according to Formula (B): ##STR00023## wherein R.sub.1-R.sub.10 are independently selected from (i) hydrogen, (ii) a substituent of formula (a), (iii) a substituent of formula (b), or (iv) a monovalent C.sub.1-C.sub.10 hydrocarbyl; ##STR00024## wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen; wherein at least one of R.sub.1-R.sub.5 is the substituent of formula (a) or the substituent of formula (b), and wherein n and m independently are 1 to 10,000.

2. The polymer of claim 1, wherein R′ is a perhalogenated C.sub.1-C.sub.5 hydrocarbyl.

3. The polymer of claim 2, wherein R′ is a trifluoromethyl, and the substituent of formula (a) has the following structure: ##STR00025##

4. The polymer of claim 1, wherein the cation of the substituent of formula (a) or the substituent of formula (b) is an inorganic cation.

5. The polymer of claim 4, wherein the inorganic cation comprises lithium.

6. The polymer of claim 1, wherein the polymer has a degree of substitution of (i) the substituent of formula (a), (ii) the substituent of formula (b), or (iii) the substituent of formula (a) and the substituent of formula (b), in total, of about 1% to about 125%.

7. The polymer of claim 1, wherein the polymer has a degree of substitution of (i) the substituent of formula (a), (ii) the substituent of formula (b), or (iii) the substituent of formula (a) and the substituent of formula (b), in total, of about 80% to about 120%.

8. The polymer of claim 1, wherein at least one of R.sub.6-R.sub.10 is— the substituent of formula (a), and the polymer has a degree of substitution of the substituent of formula (a) of about 100% to about 120%; or the substituent of formula (b), and the polymer has a degree of substitution of the substituent of formula (b) of about 100% to about 120%.

9. The polymer of claim 1, wherein the polymer has a glass transition temperature (T.sub.g) of about 5° C. to about 145° C.

10. The polymer of claim 1, wherein the polymer has a glass transition temperature (T.sub.g) of about 10° C. to about 30° C.

11. The polymer of claim 1, wherein the polymer is at least partially cross-linked.

12. A polymer comprising a repeat unit according to Formula (A): ##STR00026## wherein R.sub.1-R.sub.5 are independently selected from (i) hydrogen, (ii) a substituent of formula (a), (iii) a substituent of formula (b), or (iv) a monovalent C.sub.1-C.sub.10 hydrocarbyl; ##STR00027## wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen; wherein at least one of R.sub.1-R.sub.5 is the substituent of formula (a) or the substituent of formula (b); and wherein n is 1 to 10,000.

13. The polymer of claim 12, wherein the polymer has a glass transition temperature (T.sub.g) of about 5° C. to about 145° C.

14. The polymer of claim 12, wherein the polymer has a glass transition temperature (T.sub.g) of about 10° C. to about 30° C.

15. The polymer of claim 12, wherein R.sub.1, R.sub.2, R.sub.4, and R.sub.5 are hydrogen, and R.sub.3 is the substituent of formula (a) or the substituent of formula (b).

16. The polymer of claim 12, wherein R′ is a perhalogenated C.sub.1-C.sub.5 hydrocarbyl.

17. The polymer of claim 16, wherein R′ is a trifluoromethyl.

18. The polymer of claim 12, wherein the cation of the substituent of formula (a) or the substituent of formula (b) is an inorganic cation.

19. The polymer of claim 12, wherein the polymer is at least partially cross-linked.

20. A method of making a polymer, the method comprising: providing a polymer of formula (I)— ##STR00028## wherein R.sub.11-R.sub.15 are independently selected from (i) hydrogen, (ii) a sulfonyl halide, or (iii) a monovalent C.sub.11-C.sub.10 hydrocarbyl, wherein at least one of R.sub.11-R.sub.15 is the sulfonyl halide, and wherein n is 1 to 10,000; and contacting the polymer of formula (I) with a halo-C.sub.1-C.sub.5 alkylsulfonamide or a halosulfonamide to convert the sulfonyl halide to a substituent of formula (a) or a substituent of formula (b); ##STR00029## wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen.

Description

DETAILED DESCRIPTION

[0014] In some embodiments, the polymers herein include a repeat unit having the following structure:

##STR00007##

wherein R.sub.1-R.sub.5 are independently selected from (i) hydrogen, (ii) a substituent of formula (a), (iii) a substituent of formula (b), or (iv) a monovalent C.sub.1-C.sub.10 hydrocarbyl;

##STR00008##

wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen; wherein at least one of R.sub.1-R.sub.5 is the substituent of formula (a) or the substituent of formula (b); and wherein n is 1 to 10,000.

[0015] In some embodiments, R.sub.1, R.sub.2, R.sub.4, and R.sub.5 are hydrogen, and R.sub.3 is a substituent of formula (a) or a substituent of formula (b). For example, when R.sub.1, R.sub.2, R.sub.4, and R.sub.5 are hydrogen, and R.sub.3 is a substituent of formula (a), the polymers herein may include a repeat unit having the following structure:

##STR00009##

[0016] In some embodiments, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are hydrogen, and R.sub.1 is a substituent of formula (a) or a substituent of formula (b). In some embodiments, R.sub.1, R.sub.3, R.sub.4, and R.sub.5 are hydrogen, and R.sub.2 is a substituent of formula (a) or a substituent of formula (b). In some embodiments, R.sub.1, R.sub.2, R.sub.3, and R.sub.5 are hydrogen, and R.sub.4 is a substituent of formula (a) or a substituent of formula (b). In some embodiments, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen, and R.sub.5 is a substituent of formula (a) or a substituent of formula (b).

[0017] In some embodiments, “n” of Formula (A) is about 200 to about 1,200, about 300 to about 1,075, about 500 to about 1,075, about 500 to about 1,000, about 500 to about 800, or about 600 to about 700.

[0018] In some embodiments, R′ is a perhalogenated C.sub.1-C.sub.5 hydrocarbyl, a perhalogenated C.sub.1-C.sub.4 hydrocarbyl, a perhalogenated C.sub.1-C.sub.3 hydrocarbyl, a perhalogenated C.sub.1-C.sub.2 hydrocarbyl, or a perhalogenated C.sub.1 hydrocarbyl. In some embodiments, the perhalogenated C.sub.1 hydrocarbyl is a perfluorinated methyl, and the substituent of formula (a) has the following structure:

##STR00010##

[0019] The substituent of formula (a) or the substituent of formula (b) may include any cation. The cation may be organic or inorganic. In some embodiment, the cation is an inorganic cation, such as lithium.

[0020] In some embodiments, the polymers herein comprise the repeat units of Formula (B):

##STR00011##

wherein R.sub.1-R.sub.10 are independently selected from (i) hydrogen, (ii) a substituent of formula (a), (iii) a substituent of formula (b), or (iv) a monovalent C.sub.1-C.sub.10 hydrocarbyl;

##STR00012##

wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen; wherein at least one of R.sub.1-R.sub.5 is the substituent of formula (a) or the substituent of formula (b), and wherein n and m independently are 1 to 10,000.

[0021] In some embodiments, at least one of R.sub.1-R.sub.5 may differ from at least one of R.sub.6-R.sub.10 in the polymers of Formula (B). Therefore, the term “polymer” as used herein, refers to and includes both polymers and copolymers. The copolymers, as described herein, may be block copolymers.

[0022] The degree of substitution of (i) the substituent of formula (a), (ii) the substituent of formula (b), or (iii) the substituent of formula (a) and the substituent of formula (b), in total, of the polymers provided herein may be about 1% to about 150%, about 1% to about 125%, about 1 to about 100%, about 75% to about 125%, or about 80% to about 120%. The phrase “in total” indicates that when a polymer includes both the substituent of formula (a) and the substituent of formula (b), the sum of the degree of substitution of the substituent of formula (a) and the degree of substituent of the substituent of formula (b) satisfies one of the foregoing ranges, e.g., “about 1% to about 150%.”

[0023] In some embodiments, at least one of R.sub.6-R.sub.10 is the substituent of formula (a) or the substituent of formula (b), and the degree of substitution is at least 100%, about 100% to about 150%, about 100% to about 125%, or about 100% to about 110%.

[0024] In some embodiments, the sum of “m” and “n” of Formula (B) is about 200 to about 1,200, about 300 to about 1,075, about 500 to about 1,075, about 500 to about 1,000, about 500 to about 800, or about 600 to about 700.

[0025] The “degree of substitution of the substituent of formula (a) [or formula (b)]”, which is provided as a percentage herein, generally indicates the average number of substituents of formula (a) [or formula (b)] per phenyl pendant group of the polymers provided herein. For example, a degree of substitution of 100% indicates an average of one substituent of formula (a) [or formula (b)] per phenyl pendant group. Degrees of substitution less than 100% indicate an average of less than one substituent of formula (a) [or formula (b)] per phenyl pendant group, and degrees of substitution greater than 100% indicate an average of more than one substituent of formula (a) [or formula (b)] per phenyl pendant group, thereby indicating that a least a portion of the phenyl pendant groups should be substituted with more than one substituent of formula (a) [or formula (b)]. For example, a degree of substitution of 80% indicates that an average of 80 out of every 100 phenyl pendant groups are substituted with one substituent of formula (a) [or formula (b)].

[0026] Generally, the polymers of Formula (B) herein may include any ratio of “m” to “n” in order to achieve a desired degree of substitution. For example, R.sub.3 may be a substituent of formula (a); R.sub.1, R.sub.2, and R.sub.4-R.sub.10 may be hydrogen; and the ratio of n:m may be 80:20, thereby imparting the polymer with a degree of substitution of 80%.

[0027] The polymers may include any end groups known in the art, including, but not limited to end groups derived from ethyl vinyl ether, or by end groups derived from telechelic chain transfer agents.

[0028] The polymers herein may be cross-linked. The cross-linking may be achieved via olefins in a polymer's “backbone”. Therefore, as used herein, the symbol “” may represent one bond in polymers that are not cross-linked, or two bonds in polymers that are cross-linked. For example, when the polymers are not cross-linked, the symbol “” may represent one bond between the carbon atom of the monomer and [1] an adjacent monomer of the polymer chain, or [2] an end group; and when the polymers are cross-linked, the symbol

“” may represent two bonds, such as a first bond between the carbon atom of the monomer and [1] an adjacent monomer of the polymer chain or [2] an end group, and a second bond between the carbon atom of the monomer and [1] a non-adjacent monomer of the polymer chain or [2] a monomer of a different polymer chain. The terms “monomer” and “repeat unit” are used interchangeably herein.

[0029] The glass transition temperature (T.sub.g) of the polymers provided herein may be about 5° C. to about 145° C., about 5° C. to about 125° C., about 5° C. to about 100° C., about 5° C. to about 75° C., about 5° C. to about 50° C., about 5° C. to about 40° C., about 10° C. to about 30° C., about 15° C. to about 20° C., or about 17° C.

[0030] The polymers provided herein may be employed in block copolymers. For example, the products provided herein may be employed in block copolymers through utilization of chain transfer agents which may install functionalities for sequential growth of alternative polymer segments.

Methods of Making Polymers

[0031] Methods of making polymers, such as those of Formula (A) and Formula (B), respectively, are provided herein. In some embodiments, the methods include providing a polymer of formula (I)—

##STR00013##

wherein R.sub.11-R.sub.15 are independently selected from (i) hydrogen, (ii) a sulfonyl halide, or (iii) a monovalent C.sub.1-C.sub.10 hydrocarbyl, wherein at least one of R.sub.11-R.sub.15 is the sulfonyl halide, and wherein n is 1 to 10,000; and contacting the polymer of formula (I) with a halo-C.sub.1-C.sub.5 alkylsulfonamide or a halosulfonamide to convert the sulfonyl halide to a substituent of formula (a) or a substituent of formula (b);

##STR00014##

wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen.

[0032] In some embodiments, the sulfonyl halide is a sulfonyl chloride.

[0033] In some embodiments, the contacting of the polymer of formula (I) with the halo-C.sub.1-C.sub.5 alkylsulfonamide or the halosulfonamide occurs (i) in the presence of dimethylaminopyridine, trimethylamine, acetonitrile, or a combination thereof, (ii) at a temperature of about 20° C. to about 30° C., or (iii) a combination thereof.

[0034] In some embodiments, the halo-C.sub.1-C.sub.5 alkylsulfonamide is a fluoro-C.sub.1-C.sub.5 alkylsulfonamide, such as a perfluoro-C.sub.1-C.sub.5 alkylsulfonamide. In some embodiments, the fluoro-C.sub.1-C.sub.5 alkylsulfonamide is CF.sub.3SO.sub.2NH.sub.2.

[0035] The phrases “C.sub.1-C.sub.10 hydrocarbyl” and the like, as used herein, generally refer to aliphatic, aryl, or arylalkyl groups containing 1 to 10 carbon atoms. The phrase “C.sub.1-C.sub.5 alkyl” and the like, as used herein, generally refer to alkyl groups containing 1 to 5 carbon atoms. Examples of aliphatic groups, in each instance, include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each instance having 1 to 10 carbon atoms, 2 to 8 carbon atoms, 4 to 6 carbon atoms, etc. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl and dodecyl. Cycloalkyl moieties may be monocyclic or multicyclic, and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. Additional examples of alkyl moieties have linear, branched and/or cyclic portions (e.g., 1-ethyl-4-methyl-cyclohexyl). Representative alkenyl moieties include vinyl, allyl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl and 3-decenyl. Representative alkynyl moieties include acetylenyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1-butynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 5-hexynyl, 1-heptynyl, 2-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 7-octynyl, 1-nonynyl, 2-nonynyl, 8-nonynyl, 1-decynyl, 2-decynyl and 9-decynyl. Examples of aryl or arylalkyl moieties include, but are not limited to, anthracenyl, azulenyl, biphenyl, fluorenyl, indan, indenyl, naphthyl, phenanthrenyl, phenyl, 1,2,3,4-tetrahydro-naphthalene, tolyl, xylyl, mesityl, benzyl, and the like, including any heteroatom substituted derivative thereof.

[0036] Unless otherwise indicated, the term “substituted,” when used to describe a chemical structure or moiety, refers to a derivative of that structure or moiety wherein one or more of its hydrogen atoms is substituted with a chemical moiety or functional group such as alcohol, alkoxy, alkanoyloxy, alkoxycarbonyl, alkenyl, alkyl (e.g., methyl, ethyl, propyl, t-butyl), alkynyl, alkylcarbonyloxy (—OC(O)alkyl), amide (—C(O)NH-alkyl- or -alkylNHC(O)alkyl), tertiary amine (such as alkylamino, arylamino, arylalkylamino), aryl, aryloxy, azo, carbamoyl (—NHC(O)O— alkyl- or —OC(O)NH-alkyl), carbamyl (e.g., CONH.sub.2, as well as CONH-alkyl, CONH-aryl, and CONH-arylalkyl), carboxyl, carboxylic acid, cyano, ester, ether (e.g., methoxy, ethoxy), halo, haloalkyl (e.g., —CCl.sub.3, —CF.sub.3, —C(CF.sub.3).sub.3), heteroalkyl, isocyanate, isothiocyanate, nitrile, nitro, phosphodiester, sulfide, sulfonamido (e.g., SO.sub.2NH.sub.2), sulfone, sulfonyl (including alkylsulfonyl, arylsulfonyl and arylalkylsulfonyl), sulfoxide, thiol (e.g., sulfhydryl, thioether) or urea (—NHCONH-alkyl-).

[0037] The terms “a,” “an,” and “the” are intended to include plural alternatives, e.g., at least one. For instance, the disclosure of “a C.sub.1-C.sub.10 hydrocarbyl,” “a monomer,” and the like, is meant to encompass one, or mixtures or combinations of more than one C.sub.1-C.sub.10 hydrocarbyl, monomer, and the like, unless otherwise specified.

[0038] In the descriptions provided herein, the terms “includes,” “is,” “containing,” “having,” and “comprises” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to.” When compositions or methods are claimed or described in terms of “comprising” various steps or components, the devices, systems, or methods can also “consist essentially of” or “consist of” the various steps or components, unless stated otherwise.

[0039] Various numerical ranges may be disclosed herein. When Applicant discloses or claims a range of any type, Applicant's intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. Moreover, all numerical end points of ranges disclosed herein are approximate. As a representative example, Applicant discloses, in one embodiment, that “the glass transition temperature (T.sub.g) of the polymer is about 15° C. to about 20° C.”. This range should be interpreted as encompassing values in a range of about 15° C. to about 20° C., and further encompasses “about” each of 16° C., 17° C., 18° C., and 19° C., including any ranges and sub-ranges between any of these values.

[0040] The processes described herein may be carried out or performed in any suitable order as desired in various implementations. Additionally, in certain implementations, at least a portion of the processes may be carried out in parallel. Furthermore, in certain implementations, less than or more than the processes described may be performed.

[0041] Many modifications and other implementations of the disclosure set forth herein will be apparent having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosure is not to be limited to the specific implementations disclosed and that modifications and other implementations are intended to be included within the scope of the appended claims.

EMBODIMENTS

[0042] The following listing of embodiments describes various features and combinations of features that may be present in the compositions and methods described herein:

[0043] Embodiment 1. A polymer comprising a repeat unit according to Formula (A):

##STR00015##

wherein R.sub.1-R.sub.5 are independently selected from (i) hydrogen, (ii) a substituent of formula (a), (iii) a substituent of formula (b), or (iv) a monovalent C.sub.1-C.sub.10 hydrocarbyl;

##STR00016##

wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen; wherein at least one of R.sub.1-R.sub.5 is the substituent of formula (a) or the substituent of formula (b); and wherein n is 1 to 1,000,000, 1 to 500,000, 1 to 100,000, 1 to 50,000, 1 to 10,000, 1 to 7,500, 1 to 5,000, 1 to 2,500, 1 to 1,000, 1,000 to 10,000, 2,500 to 10,000, 5,000 to 10,000, or 7,500 to 10,000.

[0044] Embodiment 2. A polymer comprising repeat units according to Formula (B):

##STR00017##

wherein R.sub.1-R.sub.10 are independently selected from (i) hydrogen, (ii) a substituent of formula (a), (iii) a substituent of formula (b), or (iv) a monovalent C.sub.1-C.sub.10 hydrocarbyl;

##STR00018##

wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen; wherein at least one of R.sub.1-R.sub.5 is the substituent of formula (a) or the substituent of formula (b), and wherein n and m independently are 1 to 1,000,000, 1 to 500,000, 1 to 100,000, 1 to 50,000, 1 to 10,000, 1 to 7,500, 1 to 5,000, 1 to 2,500, 1 to 1,000, 1,000 to 10,000, 2,500 to 10,000, 5,000 to 10,000, or 7,500 to 10,000.

[0045] Embodiment 3. A method of making a polymer, the method comprising providing a polymer of formula (I)—

##STR00019##

wherein R.sub.11-R.sub.15 are independently selected from (i) hydrogen, (ii) a sulfonyl halide, or (iii) a monovalent C.sub.1-C.sub.10 hydrocarbyl, wherein at least one of R.sub.11-R.sub.15 is the sulfonyl halide, and wherein n is 1 to 1,000,000, 1 to 500,000, 1 to 100,000, 1 to 50,000, 1 to 10,000, 1 to 7,500, 1 to 5,000, 1 to 2,500, 1 to 1,000, 1,000 to 10,000, 2,500 to 10,000, 5,000 to 10,000, or 7,500 to 10,000; and contacting the polymer of formula (I) with a halo-C.sub.1-C.sub.5 alkylsulfonamide or a halosulfonamide to convert the sulfonyl halide to a substituent of formula (a) or a substituent of formula (b);

##STR00020##

wherein R′ is a halogenated C.sub.1-C.sub.5 hydrocarbyl, and X is a halogen.

[0046] Embodiment 4. The polymers or methods of any of Embodiments 1 to 3, wherein R′ is a perhalogenated C.sub.1-C.sub.5 hydrocarbyl, a perhalogenated C.sub.1-C.sub.4 hydrocarbyl, a perhalogenated C.sub.1-C.sub.3 hydrocarbyl, a perhalogenated C.sub.1-C.sub.2 hydrocarbyl, or a perhalogenated C.sub.1 hydrocarbyl.

[0047] Embodiment 5. The polymers or methods of any one of Embodiments 1 to 4, wherein R′ is a trifluoromethyl, and the substituent of formula (a) has the following structure:

##STR00021##

[0048] Embodiment 6. The polymers or methods of any one of Embodiments 1 to 5, wherein the cation of the substituent of formula (a) or the substituent of formula (b) is an inorganic cation or an organic cation, such as an ammonium cation (e.g., a C.sub.1-C.sub.10 hydrocarbyl ammonium).

[0049] Embodiment 7. The polymers or methods of any one of Embodiments 1 to 6, wherein the inorganic cation comprises lithium.

[0050] Embodiment 8. The polymers or methods of any one of Embodiments 1 to 7, wherein the degree of substitution of (i) the substituent of formula (a), (ii) the substituent of formula (b), or (iii) the substituent of formula (a) and the substituent of formula (b), in total, of the polymers is about 1% to about 200%, about 1% to about 175%, about 1% to about 150%, about 1% to about 125%, about 1 to about 100%, about 75% to about 125%, or about 80% to about 120%.

[0051] Embodiment 9. The polymers or methods of any one of Embodiments 1 to 8, wherein the polymer has a degree of substitution of (i) the substituent of formula (a), (ii) the substituent of formula (b), or (iii) the substituent of formula (a) and the substituent of formula (b), in total, of about 80% to about 120%.

[0052] Embodiment 10. The polymers or methods of any one of Embodiments 1 to 9, wherein at least one of R.sub.6-R.sub.10 is (i) the substituent of formula (a), and the polymer has a degree of substitution of the substituent of formula (a) of about 100% to about 120%; or (ii) the substituent of formula (b), and the polymer has a degree of substitution of the substituent of formula (b) of about 100% to about 120%.

[0053] Embodiment 11. The polymers or methods of any one of Embodiments 1 to 10, wherein the glass transition temperature (T.sub.g) of the polymers is about 5° C. to about 145° C., about 5° C. to about 125° C., about 5° C. to about 100° C., about 5° C. to about 75° C., about 5° C. to about 50° C., about 5° C. to about 40° C., about 10° C. to about 30° C., about 15° C. to about 20° C., or about 17° C.

[0054] Embodiment 12. The polymers or methods of any one of Embodiments 1 to 11, wherein the polymer is at least partially cross-linked.

[0055] Embodiment 13. The polymers or methods of any one of Embodiments 1 to 12, wherein R.sub.1, R.sub.2, R.sub.4, and R.sub.5 are hydrogen, and R.sub.3 is the substituent of formula (a) or the substituent of formula (b); wherein R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are hydrogen, and R.sub.1 is a substituent of formula (a) or a substituent of formula (b); wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.5 are hydrogen, and R.sub.2 is a substituent of formula (a) or a substituent of formula (b); or wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.5 are hydrogen, and R.sub.4 is a substituent of formula (a) or a substituent of formula (b).

[0056] Embodiment 14. The polymers or methods of any one of Embodiments 1 to 13, wherein n, such as n of Formula (A), is about 200 to about 1,200, about 300 to about 1,075, about 500 to about 1,075, about 500 to about 1,000, about 500 to about 800, or about 600 to about 700.

[0057] Embodiment 15. The polymers or methods of any one of Embodiments 1 to 14, wherein the sum of “m” and “n” of Formula (B) is about 200 to about 1,200, about 300 to about 1,075, about 500 to about 1,075, about 500 to about 1,000, about 500 to about 800, or about 600 to about 700.

[0058] Embodiment 16. The polymers or methods of any one of Embodiments 1 to 15, wherein X is fluorine, chlorine, bromine, iodine, or a combination thereof.

[0059] Embodiment 17. The polymers or methods of any one of Embodiments 1 to 16, wherein the polymers include any end groups known in the art, including, but not limited to end groups derived from ethyl vinyl ether, or by end groups derived from telechelic chain transfer agents.

[0060] Embodiment 18. The polymers or methods of any one of Embodiments 1 to 17, wherein the polymers are block copolymers.

[0061] Embodiment 19. The polymers or methods of any one of Embodiments 1 to 18, wherein the sulfonyl halide is a sulfonyl chloride.

[0062] Embodiment 20. The polymers or methods of any one of Embodiments 1 to 19, wherein the contacting of the polymer of formula (I) with the halo-C.sub.1-C.sub.5 alkylsulfonamide or the halosulfonamide occurs (i) in the presence of dimethylaminopyridine, trimethylamine, acetonitrile, or a combination thereof, (ii) at a temperature of about 20° C. to about 30° C., or (iii) a combination thereof.

[0063] Embodiment 21. The polymers or methods of any one of Embodiments 1 to 20, wherein the halo-C.sub.1-C.sub.5 alkylsulfonamide is a perfluoro-C.sub.1-C.sub.5 alkylsulfonamide, such as CF.sub.3SO.sub.2NH.sub.2.

Examples

[0064] The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims. Thus, other aspects of this invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.

Synthesis of Polymer Substituted with Bis-Sulfonyl Lithium Salt

[0065] In this example, a precision phenylsulfonic acid sodium salt was converted to N-(phenylsulfonyl)-N-(trifluoromethylsulfony)imide lithium salt. It was believed that the synthesis of this example proceeded according to the following scheme:

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[0066] In this example, a precision polymer including sulfonate substituents was prepared as a starting material using the methods described at U.S. Pat. No. 10,640,587, which is incorporated by reference herein.

[0067] The sulfonate substituents were converted to sulfonyl chloride substituents by contacting the polymer starting material with the reagents depicted in the foregoing scheme, which included oxalyl chloride.

[0068] The sulfonyl chloride groups were then converted to bis-(trifluorosulfonyl)imide lithium salt groups by contacting the sulfonyl chloride substituents with the reagents depicted at the foregoing scheme, which included CF.sub.3SO.sub.2NH.sub.2.

[0069] Yields of at least 75% were achieved, and it is expected that yields range from 75% to 99%.