# US 2014/0197032 A1 · Anion Exchange Block Copolymers, Their Manufacture And Their Use > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0197032 A1 - Document ID: US20140197032A1 - Status: Published application - Kind: A1 - Application number: 14/154,146 - Filed: 2014-01-13 - Published: 2014-07-17 - Earliest claimed: 2013-01-14 - Assignees: Kraton Polymers U.S. LLC - Applicants: Kraton Polymers U.S. LLC - Inventors: Carl Lesley Willis; Irwan Hidajat; Mike Heniff - Web page: https://patentgrep.com/patent/US20140197032A1 ## CPC - B01D 71/82: characterised by the presence of specified groups, e.g. introduced by chemical after-treatment - B01D 61/44: Ion-selective electrodialysis - B01D 65/10: Testing of membranes or membrane apparatus; Detecting or repairing leaks - B01J 41/14: obtained by reactions only involving unsaturated carbon-to-carbon bonds - B01J 47/12: characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes (electrodialysis or electro-osmosis B01D61/42) - C08F 8/02: Alkylation - C08F 8/04: Reduction, e.g. hydrogenation - C08F 8/20: Halogenation - C08F 8/24: Haloalkylation - C08F 8/30: Introducing nitrogen atoms or nitrogen-containing groups - C08F 8/32: by reaction with amines - C08F 8/40: Introducing phosphorus atoms or phosphorus-containing groups - C08F 8/44: Preparation of metal salts or ammonium salts - C08J 5/2243: {obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231} - C08J 5/2287: {After-treatment} - H01M 8/1023: having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes - B01D 53/228: {characterised by specific membranes} - C08F 2810/20: leading to a crosslinking, either explicitly or inherently - C08J 2353/02: of vinyl aromatic monomers and conjugated dienes - Y02E 60/50: Fuel cells - Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract Selectively amino- or phosphino-functionalized block copolymers, and their preparation, for use as anion exchange membrane materials. The selectively functionalized block copolymers have at least two end blocks A each of which are substantially free of amino- or phosphino-functional groups, and have at least one interior block D which comprises on average at least one amino- or phosphino-functionalized polymer unit of formula (I) wherein Z is nitrogen or phosphorous; R1 is hydrogen or alkyl; R2 is hydrogen or is tertiary alkyl; R each independently, is hydrogen or is alkyl optionally substituted by a moiety -(A1-NRa)xRb; or two R groups, together with the Z to which they are bonded, form an optionally substituted ring; x is 1, 2 or 3; A1 is straight chain alkylene optionally substituted by one or more methyl and/or ethyl groups; and Ra and Rb, each independently, is hydrogen or alkyl; or a corresponding onium salt. ## Claims ### Claim 1 An amino- or phosphino-functionalized block copolymer comprising: (a) at least two end blocks A, wherein each end block A is substantially free of amino- or phosphino-functional groups, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D having a number average molecular weight of from about 1,000 to about 100,000 and comprising on average at least one amino- or phosphino-functionalized polymer unit of formula (I) wherein Z is nitrogen or phosphorous; R1 is hydrogen or alkyl; R2 is hydrogen or is tertiary alkyl; R each independently, is hydrogen or is alkyl optionally substituted by a moiety -(A1-NRa)xRb; or two R groups, together with the Z to which they are bonded, form an optionally substituted ring; x is 1, 2 or 3; A1 is straight chain alkylene optionally substituted by one or more methyl and/or ethyl groups; and Ra and Rb, each independently, is hydrogen or alkyl; or a corresponding onium salt. ### Claim 2 (depends on 1) The functionalized block copolymer according to claim 1, wherein from about 10 to 100% of the functional groups of the block(s) D are in form of the onium salt. ### Claim 3 (depends on 1) The functionalized block copolymer according to claim 1, wherein each block A is independently selected from the group consisting of polymerized (i) ethylene monomers; (ii) propylene monomers, (iii) styrene and alpha-alkyl styrene monomers having a phenyl ring which is optionally substituted by one or more alkyl groups, (iv) (meth)acrylate ester monomers, and (v) mixtures of monomers selected from (i) to (iv). ### Claim 4 (depends on 1) The functionalized block copolymer according to claim 1, wherein each block D is independently selected from the group consisting of (i) segments derived from homo- and copolymers of styrene, (ii) segments derived from homo- and copolymers of styrene having a phenyl ring which is substituted by a primary alkyl group, (iii) segments derived from homo- and copolymer of alpha-alkyl styrene, and (iv) segments derived from homo- and copolymers of alpha-alkyl styrene having a phenyl ring which is substituted by a primary alkyl group. ### Claim 5 (depends on 4) The functionalized block copolymer according to claim 4, wherein on average at least about 5% of the styrene or alpha-alkyl styrene derived polymer units of each block D, are polymer units of formula (I) or the corresponding onium salt. ### Claim 6 (depends on 4) The functionalized block copolymer according to claim 4, wherein on average from 25 to 100% of the styrene or alpha-alkyl styrene derived polymer units of each block D, are polymer units of formula (I) or the corresponding onium salt. ### Claim 7 (depends on 4) The functionalized block copolymer according to claim 4, wherein each block D consists of polymer units of formula (I), or the corresponding onium salt, and optionally polymer units derived from one or more monomers selected from the group consisting of styrene and alpha-alkyl styrene in each case having a phenyl ring which is optionally substituted by a primary alkyl group. ### Claim 8 (depends on 1) The functionalized block copolymer according to claim 1, further comprising at least one interior block B, wherein each block B is essentially non-functionalized, has a number average molecular weight of from about 1,000 to about 100,000, and has a glass transition temperature of at most about 20° C. ### Claim 9 (depends on 8) The functionalized block copolymer according to claim 8, wherein each block B is independently selected from the group consisting of polymerized (i) ethylene monomers, (ii) C3-C8 alpha-olefin monomers, (iii) isobutylene monomers, (iv) conjugated diene monomers, (v) (meth)acrylate ester monomers, (vi) a silicon polymer, and (vii) mixtures of monomers selected from (i) to (v), wherein segments containing polymerized conjugated diene monomers are optionally hydrogenated. ### Claim 10 (depends on 8) The functionalized block copolymer according to claim 8, having a general configuration A-D-A, A-D-A-D-A, (A-D-A)nX, (A-D)nX, A-B-D-B-A, A-D-B-D-A, (A-B-D)nX, (A-D-B)n X, or mixtures thereof, wherein n is an integer from 2 to about 30, and X is a coupling agent residue, and wherein the plurality of A blocks, B blocks, or D blocks are the same or different. ### Claim 11 (depends on 1) A membrane or film comprising the functionalized block copolymer of claim 1. ### Claim 12 (depends on 11) An apparatus selected from the group consisting of fuel cells, filtration devices, devices for controlling humidity, devices for forward electro-dialysis, devices for reverse electro-dialysis, devices for pressure retarded osmosis, devices for forward osmosis, devices for reverse osmosis, devices for selectively adding water, devices for selectively removing water, devices for capacitive deionization, devices for molecular filtration, devices for removing salt from water, devices for treating produced water from hydraulic fracturing applications, devices for ion transport applications, devices for softening water, and batteries, and comprising the membrane or film of claim 11. ### Claim 13 (depends on 11) An electro-deionization assembly comprising at least one anode, at least one cathode, and one or more membrane(s) wherein at least one membrane is the membrane of claim 11. ### Claim 14 (depends on 13) The electro-deionization assembly of claim 13 which comprises at least two membranes wherein at least one membrane is a cation-exchange membrane. ### Claim 15 (depends on 14) The electro-deionization assembly of claim 14 wherein the cation-exchange membrane comprises a sulfonated block copolymer comprising at least two polymer end blocks E and at least one polymer interior block F, wherein each E block contains essentially no sulfonic acid or sulfonated ester functional groups and each F block comprises sulfonation susceptible polymer units and, based on the number of the sulfonation susceptible polymer units, from about 10 to about 100 mol % of sulfonic acid or sulfonate ester functional groups. ### Claim 16 A selectively halogenated block copolymer comprising: (a) at least two end blocks A, wherein each end block A is essentially non-halogenated, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D* having a number average weight of from about 1,000 to about 100,000 and comprising on average at least one polymer unit of formula (II) wherein Y is halogen; R1 is hydrogen or alkyl; and R2 is hydrogen or is tertiary alkyl. ### Claim 17 (depends on 16) The selectively halogenated block copolymer according to claim 16, wherein each block A is independently selected from the group consisting of polymerized (i) ethylene monomers; (ii) propylene monomers, (iii) styrene and alpha-alkyl styrene monomers having a phenyl ring which is optionally substituted by one or more alkyl groups, (iv) (meth)acrylate ester monomers, and (v) mixtures of monomers selected from (i) to (iv). ### Claim 18 (depends on 16) The selectively halogenated block copolymer according to claim 16, wherein each block D* is independently selected from the group consisting of (i) segments derived from homo- and copolymers of styrene, (ii) segments derived from homo- and copolymers of styrene having a phenyl ring which is substituted by a primary alkyl group, (iii) segments derived from homo- and copolymer of alpha-alkyl styrene, and (iv) segments derived from homo- and copolymers of alpha-alkyl styrene having a phenyl ring which is substituted by a primary alkyl group. ### Claim 19 (depends on 18) The selectively halogenated block copolymer according to claim 18, wherein each block D* consists of polymer units of formula (II) and optionally polymer units derived from one or more monomers selected from the group consisting of styrene and alpha-alkyl styrene in each case having a phenyl ring which is optionally substituted by a primary alkyl group. ### Claim 20 (depends on 18) The selectively halogenated block copolymer according to claim 18, wherein on average at least about 5% of the styrene or alpha-alkyl styrene derived polymer units of each block D* are polymer units of formula (II). ### Claim 21 (depends on 18) The selectively halogenated block copolymer according to claim 18, wherein on average from about 25 to 100% of the styrene or alpha-alkyl styrene derived polymer units of each block D* are polymer units of formula (II). ### Claim 22 (depends on 16) The selectively halogenated block copolymer according to claim 16, further comprising at least one interior block B, wherein each block B is essentially non-halogenated, has a number average molecular weight of from about 1,000 to about 100,000, and has a glass transition temperature of at most about 20° C. ### Claim 23 (depends on 22) The selectively halogenated block copolymer according to claim 22, wherein each block B is independently selected from the group consisting of polymerized (i) ethylene monomers, (ii) C3-C8 alpha-olefin monomers, (iii) isobutylene monomers, (iv) conjugated diene monomers, (v) (meth)acrylate ester monomers, (vi) a silicon polymer, and (vii) mixtures of monomers selected from (i) to (v), wherein segments containing polymerized conjugated diene monomers are hydrogenated. ### Claim 24 (depends on 22) The selectively halogenated block copolymer according to claim 22, having a general configuration A-D*-A, A-D*-A-D*-A, (A-D*-A)nX, (A-D*)nX, A-B-D*-B-A, A-D*-B-D*-A, (A-B-D*)nX, (A-D*-B)nX, or mixtures thereof, wherein n is an integer from 2 to about 30, and X is a coupling agent residue and wherein the plurality of A blocks, B blocks, or D* blocks are the same or different. ### Claim 25 A precursor block copolymer comprising: (a) at least two end blocks A, wherein each end block A is substantially resistant to halogenation, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D∘ having a number average weight of from about 1,000 to about 100,000 and comprising on average at least one polymer unit of formula (III) wherein R1 is hydrogen or alkyl; and R2 is hydrogen or is tertiary alkyl. ### Claim 26 (depends on 25) The precursor block copolymer according to claim 25, wherein each block A is independently selected from the group consisting of polymerized (i) ethylene monomers; (ii) propylene monomers, (iii) styrene and alpha-alkyl styrene monomers having a phenyl ring which is substituted by one or more tertiary alkyl groups, (iv) (meth)acrylate ester monomers, and (v) mixtures of monomers selected from (i) to (iv). ### Claim 27 (depends on 25) The precursor block copolymer according to claim 25, wherein each block D∘ is independently selected from the group consisting of (i) homo- and copolymers of styrene, (ii) homo- and copolymers of styrene having a phenyl ring which is substituted by a primary alkyl group, (iii) homo- and copolymer of alpha-alkyl styrene, and (iv) homo- and copolymers of alpha-alkyl styrene having a phenyl ring which is substituted by a primary alkyl group. ### Claim 28 (depends on 27) The precursor block copolymer according to claim 27, wherein each block D∘ consists of polymer units of formula (III) and optionally polymer units derived from one or more monomers selected from the group consisting of styrene and alpha-alkyl styrene. ### Claim 29 (depends on 25) The precursor block copolymer according to claim 25, further comprising at least one interior block B, wherein each block B is essentially non-functionalized, is substantially resistant to halogenation, has a number average molecular weight of from about 1,000 to about 100,000, and has a glass transition temperature of at most about 20° C. ### Claim 30 (depends on 29) The precursor block copolymer according to claim 29, wherein each block B is independently selected from the group consisting of polymerized (i) ethylene monomers, (ii) C3-C8 alpha-olefin monomers, (iii) isobutylene monomers, (iv) conjugated diene monomers, (v) (meth)acrylate ester monomers, (vi) a silicon polymer, and (vii) mixtures of monomers selected from (i) to (v), wherein segments containing polymerized conjugated diene monomers are hydrogenated. ### Claim 31 (depends on 29) The precursor block copolymer according to claim 29, having a general configuration A-D∘-A, A-D∘-A-D∘-A, (A-D∘-A)nX, (A-D∘)nX, A-B-D∘-B-A, A-D∘-B-D∘-A, (A-B-D∘)nX, (A-D∘-B)nX, or mixtures thereof, wherein n is an integer from 2 to about 30, and X is a coupling agent residue and wherein the plurality of A blocks, B blocks, or D∘ blocks are the same or different. ### Claim 32 A method for preparing the amino- or phosphino-functionalized block copolymer comprising: (1) reacting, in the presence of an inert solvent, a halogenating agent with a precursor block copolymer with the formula: (a) at least two end blocks A, wherein each end block A is substantially resistant to halogenation, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D∘ having a number average weight of from about 1,000 to about 100,000 and comprising on average at least one polymer unit of formula (III) wherein R1 is hydrogen or alkyl; and R2 is hydrogen or is tertiary alkyl; to produce a selectively halogenated block copolymer, (2) reacting the halogenated block copolymer with an amine or phosphine to produce an amino- or phosphino-functionalized block copolymer. ### Claim 33 (depends on 32) The method of claim 32, wherein each block A is independently selected from the group consisting of polymerized (i) ethylene monomers; (ii) propylene monomers, (iii) styrene and alpha-alkyl styrene monomers having a phenyl ring which is substituted by one or more tertiary alkyl groups, (iv) (meth)acrylate ester monomers, and (v) mixtures of monomers selected from (i) to (iv). ### Claim 34 (depends on 33) The method of claim 33, wherein each block A is styrene or tert-butylstyrene. ### Claim 35 (depends on 32) The method of claim 32, wherein each block D∘ is independently selected from the group consisting of (i) homo- and copolymers of styrene, (ii) homo- and copolymers of styrene having a phenyl ring which is substituted by a primary alkyl group, (iii) homo- and copolymer of alpha-alkyl styrene, and (iv) homo- and copolymers of alpha-alkyl styrene having a phenyl ring which is substituted by a primary alkyl group. ### Claim 36 (depends on 35) The method of claim 35, wherein each block D∘ is para-methylstyrene. ### Claim 37 (depends on 32) The method of claim 32, wherein the precursor block copolymer further comprising at least one interior block B, wherein each block B is essentially non-functionalized, is substantially resistant to halogenation, has a number average molecular weight of from about 1,000 to about 100,000, and has a glass transition temperature of at most about 20° C. ### Claim 38 (depends on 32) The method of claim 32, wherein the inert solvent comprises an aprotic hydrocarbon solvent, or a halogenated hydrocarbon solvent, and mixtures thereof. ### Claim 39 (depends on 38) The method of claim 38, wherein the inert solvent comprises an aprotic hydrocarbon solvent. ### Claim 40 (depends on 38) The method of claim 38, wherein the inert solvent consists of cyclohexane and optionally heptane. ### Claim 41 (depends on 32) The method of claim 32 wherein the halogenating agent contains bromine or chlorine. ### Claim 42 (depends on 41) The method of claim 41, wherein the halogenating agent is selected from the group consisting of N-bromo-succinimide (NBS), N-chloro-succinimide, N-bromo-tert-butylamine, N-bromo-hydantoins, and N,N-dibromohydantoin, and mixtures thereof. ### Claim 43 (depends on 42) The method of claim 42, wherein the reaction to prepare the halogenated block copolymer comprises a radical initiator selected from the group consisting of tert-butyl hypochlorite, peroxides, benzoyl peroxide, azo compounds, and azo-bis-isobutyronitrile (AIBN), and mixtures thereof. ### Claim 44 (depends on 32) The method of claim 32, wherein the precursor block copolymer has a general configuration A-D∘-A, A-D∘-A-D∘-A, (A-D∘-A)nX, (A-D∘)nX, A-B-D∘-B-A, A-D∘-B-D∘-A, (A-B-D∘)nX, (A-D∘-B)nX, or mixtures thereof, wherein n is an integer from 2 to about 30, and X is a coupling agent residue and wherein the plurality of A blocks, B blocks, or D∘ blocks are the same or different. ### Claim 45 (depends on 32) The method of claim 32 wherein the halogenated block copolymer comprises: (a) at least two end blocks A, wherein each end block A is essentially non-halogenated, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D* having a number average weight of from about 1,000 to about 100,000 and comprising on average at least one polymer unit of formula (II) wherein Y is halogen; R1 is hydrogen or alkyl; and R2 is hydrogen or is tertiary alkyl. ### Claim 46 (depends on 32) The method of claim 32, wherein the amine or phosphine has the formula wherein Z is nitrogen or phosphorous; Rd is hydrogen or alkyl, or together with —ZR2 form an optionally substituted ring; R each independently, is hydrogen or is alkyl optionally substituted by a moiety -(A1-NRa)xRb; or two R groups, together with the Z to which they are bonded, form an optionally substituted ring; or x is 1, 2 or 3; A1 is straight chain alkylene optionally substituted by one or more methyl and/or ethyl groups; and Ra and Rb, each independently, is hydrogen or alkyl. ### Claim 47 (depends on 46) The method of claim 46 wherein Z and two R moieties form a ring selected from the group consisting of pyrrolidine, piperidine, piperazine, 1-azabicyclo[2,2,2]nonane, 1,4-diazabicyclo[2,2,2]octane (DABCO), morpholine, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, indole, isoindole, indazole, purine, carbazole, phenoxazine, and azepine. ### Claim 48 (depends on 32) The method of claim 32, wherein the halogenated block copolymer is reacted with an amine. ### Claim 49 (depends on 48) The method of claim 48, wherein the amine is a heterocyclic amine. ### Claim 50 (depends on 48) The method of claim 48, wherein the amine is a tertiary amine. ### Claim 51 (depends on 48) The method of claim 48, wherein the amine is 1,4-diazabicyclo[2,2,2]octane (DABCO) or trimethylamine (TMA). ### Claim 52 (depends on 32) The method of claim 32, wherein the amino- or phosphino-functionalized block copolymer comprises: (a) at least two end blocks A, wherein each end block A is substantially free of amino- or phosphino-functional groups, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D having a number average molecular weight of from about 1,000 to about 100,000 and comprising on average at least one amino- or phosphino-functionalized polymer unit of formula (I) wherein Z is nitrogen or phosphorous; R1 is hydrogen or alkyl; R2 is hydrogen or is tertiary alkyl; R each independently, is hydrogen or is alkyl optionally substituted by a moiety -(A1-NRa)xRb; or two R groups, together with the Z to which they are bonded, form an optionally substituted ring; x is 1, 2 or 3; A1 is straight chain alkylene optionally substituted by one or more methyl and/or ethyl groups; and Ra and Rb, each independently, is hydrogen or alkyl; or a corresponding onium salt. ### Claim 53 (depends on 52) The method of claim 52 wherein Z and two R moieties form a ring selected from the group consisting of pyrrolidine, piperidine, piperazine, 1-azabicyclo[2,2,2]nonane, 1,4-diazabicyclo[2,2,2]octane (DABCO), morpholine, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, indole, isoindole, indazole, purine, carbazole, phenoxazine, and azepine. ### Claim 54 A method for preparing the amino- or phosphino-functionalized block copolymer comprising: reacting a halogenated block copolymer comprising: (a) at least two end blocks A, wherein each end block A is essentially non-halogenated, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D* having a number average weight of from about 1,000 to about 100,000 and comprising on average at least one polymer unit of formula (II) wherein Y is halogen; R1 is hydrogen or alkyl; and R2 is hydrogen or is tertiary alkyl. with an amine or phosphine to produce an amino- or phosphino-functionalized block copolymer. ### Claim 55 (depends on 54) The method of claim 54 wherein the halogenated block copolymer is formed by reacting, in the presence of an inert solvent, a halogenating agent with a precursor block copolymer with the formula: (a) at least two end blocks A, wherein each end block A is substantially resistant to halogenation, has a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature; and (b) at least one interior block D∘ having a number average weight of from about 1,000 to about 100,000 and comprising on average at least one polymer unit of formula (III) wherein R1 is hydrogen or alkyl; and R2 is hydrogen or is tertiary alkyl; to produce a selectively halogenated block copolymer. ### Claim 56 A method for preparing the amino- or phosphino-functionalized block copolymer comprising: polymerizing a monomer substantially resistant to halogenation to form a block A with a monomer substantially resistant to form a block B, and an amine functionalized styrene monomer to form block D, to yield a functionalized block copolymer having the general configuration A-D-A, A-D-A-D-A, (A-D-A)nX, (A-D)nX, A-B-D-B-A, A-D-B-D-A, (A-B-D)n X, (A-D-B)nX, or mixtures thereof, wherein n is an integer from 2 to about 30, and X is a coupling agent residue, and wherein the plurality of A blocks, B blocks, or D blocks are the same or different.