WO2010083325A1

WO2010083325A1 - Polymer electrolytes having alkylene oxide pendants with polar groups

Info

Publication number: WO2010083325A1
Application number: PCT/US2010/021065
Authority: WO
Inventors: Bing Hsieh
Original assignee: Seeo, Inc
Priority date: 2009-01-16
Filing date: 2010-01-14
Publication date: 2010-07-22

Abstract

Comb polymers with mono-functional pendant chains grafted onto a polymer backbone for use as electrolytes in lithium batteries have been made in the past. First mono-functional pendant chains that facilitate ion transport and second mono-functional pendant chains that facilitate dissociation of lithium salts are often both used. But the density of these chains is limited by the density of graft sites on the backbone molecule. In the embodiments of the invention, as disclosed herein, inventive polymer electrolyte materials are based on comb polymers with dual-functional pendant chains. Compounds that facilitate ion transport and compounds that facilitate dissociation of lithium salts are joined together to make a dual-functional pendant group. Thus the density of functional groups within a comb polymer can be increased by as much as a factor of two or more.

Description

POLYMER ELECTROLYTES HAVING ALKYLENE OXIDE PENDANTS

WITH POLAR GROUPS

Inventors: Bing R. Hsieh

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Patent Provisional Application 61/145518, filed January 16, 2009, which is incorporated by reference herein.

BACKGROUND OF THE INVENTION Field of the Invention

[0001] This invention relates generally to high ionic conductivity polymer electrolytes, and, more specifically, to high ionic conductivity polymer electrolytes with comb structures wherein any individual pendant chain can contain both alkylene oxide and polar groups.

[0002] The increased demand for lithium secondary batteries has resulted in research and development to improve the safety and performance of these batteries. Many batteries employ liquid electrolytes which are associated with high degrees of volatility, flammability, and chemical reactivity. With this in mind, the idea of using a solid electrolyte with a lithium-based battery system has attracted great interest, and a variety of polymer-based electrolytes have been developed. While low molecular weight oligoethylene oxide is a sufficiently conductive material as a liquid, its conductivity in solid form is too low to be practical for many applications. Other electrolytes containing polysiloxane materials have also been developed. Although these materials offer reasonably good ionic conductivity, many are not solid at battery operating temperatures. Work continues to find even better polymer electrolyte materials that are solid at battery operating temperatures and have very good ionic conductivity.

DETAILED DESCRIPTION

[0003] The embodiments of the present invention relate to polymers with comb structures. These comb polymers have a polymer backbone and a plurality of pendant chains grafted to the backbone. At least one pendant chain has both an oligomeric alkylene oxide group(s) and a polar group(s) in a single pendant chain. Various other pendant chains can have either an oligomeric alkylene oxide group or a polar group. There can also be additional pendant chains with yet other groups. These polymers can be used as electrolytes when combined with salts (e.g., lithium salts) to enhance their ionic conductivity. Such ionically-conductive polymers can be used advantageously for batteries and other energy storage devices such as capacitors. The skilled artisan will readily appreciate, however, that the materials and methods disclosed herein will have application in a number of other contexts where polymers with high ionic conductivity are desirable.

[0004] For the purpose of this disclosure, a single pendant chain that has at least two different functional groups is referred to as a dual-functional pendant chain. A single pendant chain that has one functional group is referred to as a mono-functional pendant chain.

[0005] Comb polymers with mono-functional pendant chains grafted onto polymer backbones for use as electrolytes in lithium batteries have been proposed in the past. For example, a first mono-functional side chain that includes a poly(alkylene oxide) moiety, and a second mono-functional side chain that includes a polar group such as a cyclic carbonate moiety have been grafted onto a polymer backbone. It is believed that the alkylene oxide moiety facilitates ion transport, while the polar group facilitates dissociation of lithium salts. But the density of alkylene groups and polar groups is limited by the density of graft sites on the backbone as only one group can attach to each graft site.

[0006] In one embodiment of the invention, inventive polymer electrolyte materials are based on graft polymers that have both an oligomeric alkylene oxide group(s) and a polar group(s) in a single pendant chain - a dual-functional pendant. The general structure for such a polymer is:

By including both functional groups - an alkylene oxide group to facilitate ion transport, and a polar group to facilitate dissociation of lithium salts - at a graft site, the polymer can have a higher density of functional groups than had been possible previously. The <iαα/-functional pendant is subject to the same attachment density limitations as the mowo-functional pendants. But with at least two functional groups in each dual-functional pendant, at least double the number of functional groups can be grafted onto a backbone molecule than has been possible in the past. The higher density of functional groups creates electrolyte materials with higher ionic conductivity.

[0007] In another embodiment of the invention, polymer electrolyte materials are based on graft polymers whose grafts are a combination of dual-functional pendant chains and mono- functional pendant chains. In one arrangement, dual-functional chains each contain one or more alkylene groups and one or more polar groups. There can be additional mono- functional pendant chains that contain either an oligomeric alkylene oxide group or a polar group. Examples of such structures include:

[0008] There is no limitation to the composition of the backbone. The composition can be any type of oligomer or polymer. Examples include, but are not limited to, vinyl polymers, such as vinyl ethers, acrylic or methacrylate polymers, ethylene oxide-type polymers (including poly(epichlorohydrin), poly(epibromohydrin) and poly(epiiodohydrin), polyphosphazene, polynorbornene, polysiloxanes, and condensation polymers, such as polyester, polyurethane, polyimide, and polyurea.

[0009] There is no limitation to the molecular structure for the backbone. The structure can have any of a variety of types including, but not limited to, linear or branched homopolymer structures, linear or branched block copolymer structures, dendrimers, rings (such as cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane, cyclophosphazenes, and the like), cages (such as octasilsesquioxane, C_6O and the like), and cross-linked molecules.

[0010] Possible alkylene oxide groups that can be used in the dual-functional pendants (or additional mono-functional pendants) include, but are not limited to, crown ethers, ethylene oxides, trimethylene oxides, and corresponding fluorinated derivatives. In one arrangement, there is only one ethylene oxide unit in the dual-functional pendant. In another arrangement, the number of ethylene oxide repeat units in the dual-functional pendant ranges from about 2 to 20. In another arrangement, the number of ethylene oxide repeat units in the dual- functional pendant ranges from about 3 to 10. Among the ethylene oxide units, one or more units may be replaced by a trimethylene oxide unit

[0011] Possible polar groups that can be used in the dual-functional pendants (or additional mono-functional pendants) include, but are not limited to nitriles, perfluorocarbons, and alkyl carbonates, cyclic carbonates, nitro, amide, N-pyrrolidinone, N-succinimide, sulfolane, sulfoxide, phthalimide, sulfonyl, and sulfonic acids. In one arrangement, there is only one polar group in the dual-functional pendant. In another arrangement, the number of polar group repeat units in the dual-functional pendant ranges from about 2 to 20. In another arrangement, the number of polar group repeat units in the dual-functional pendant ranges from about 3 to 10.

[0012] In one embodiment of the invention, the synthesis of exemplary dual-functional pendant chains is as follows. Ethylene glycol Ia (n=0), diethylene glycol Ib (n=l), Methylene glycol Ic (n=2), or tetraethylene glycol Id (n=3) is reacted with allyl bromide in the presence of sodium hydroxide to give compound 2. Compound 2 is reacted with acrylonitrile in the presence of a trace amount of sodium hydroxide to give a dual-functional compound 3. The vinyl-ending compound 3 can be grafted onto a polyhydrosiloxane backbone via hydro silylation to give an electrolyte material with dual-functional pendants. In one arrangement, compound 3 is reacted with tetramethyldisiloxane in the presence of a platinum or a rhodium catalyst to give a different dual-functional pendant molecule 4. The hydrosiloxane-ended compound 4 can be grafted onto a polyvinylsiloxane backbone (or other backbones that contain vinyl pendants, such as 1,2-poly(butadienes)) via hydrosilylation to make the corresponding electrolyte material with dual-functional pendants.

[0013] In another embodiment of the invention, the synthetic scheme for a pair of dual- functional pendants containing two cyano groups is shown below. Oxidation of compound 2 gives a corresponding aldehyde 5. The aldehyde 5 reacts with potassium cyanide and ethyl cyanoacetate to give the dicyano pendant 6, which can be grafted onto a polyhydrosiloxane backbone (or other backbones that contain vinyl pendants, such as 1,2-poly(butadienes)) via hydro silylation to give an electrolyte material with dual-functional pendants. The dicyano 6 can be further converted to a hydrosiloxane pendant 7 upon reaction with tetramethyldisiloxane in the presence of a platinum or rhodium catalyst. The hydroxiloxane pendant 7 can be grafted onto a polyvinylsiloxane backbone via hydro silylation to make an electrolyte material with dual-functional pendants.

[0014] In another embodiment of the invention, the synthesis of a pair of dual-functional pendants containing a cyclic ethylene carbonate polar group is shown below. Compound 2 reacts with Tosylate of solketal to give compound 8, which is then hydrolyzed with concentrated hydrochloric acid to give a corresponding diol 9. The diol 9 is treated with ethyl carbonate to give a cyclic ethylene carbonate pendant 10. In another arrangement, the synthetic sequence may be simplified by reacting 2 with mesylateof 4-(hydroxymethyl)-1,3- dioxolan-2-one (or the tosylate or nosylate analogue) to give the cyclic ethylene carbonate pendant 10 in one step. The cyclic ethylene carbonate pendant 10 can be grafted onto a polyhydrosiloxane backbone (or other backbones that contain vinyl pendants, such as 1,2- poly(butadienes)) via hydrosilylation to make an electrolyte material with dual-functional pendants. In another embodiment of the invention, the cyclic ethylene carbonate pendant 10 can be further reacted with tetramethyl disiloxane to give compound 11. Compound 11 can be grafted onto a polyvinylsiloxane backbone via hydrosilylation to make an electrolyte material with dual-functional pendants.

[0015] In another embodiment of the invention, the synthesis of a dual-functional pendant 12 with a hydroxyl end is shown below. A large excess of compound 1 (any of la-Id) is reacted with acrylonitrile in the presence of trace sodium hydroxide to give compound 12. Such dual-functional compounds with a hydroxyl end group can be grafted onto a polyepichlorohydrin or polyphosphazene backbone via esterification to give an electrolyte material with dual-functional pendants. In addition, compound 12 can react with acryloyl chloride or methacryloyl chloride to form a corresponding acrylic or methacrylate monomer, respectively, which can then be polymerized to make an electrolyte material with dual- functional pendants.

[0016] In another embodiment of the invention, the synthesis of a dual-functional pendant 17 that has a hydroxyl end group is shown below. A large excess of compound 1 (any of la-Id) is reacted with pyran in the presence of hydrochloric acid to give compound 13, which reacts with allyl bromide in the presence of sodium hydroxide to give compound 14. Oxidation of the ethylene group gives diol 15 which is then reacted with ethyl carbonate to give compound 16. In another arrangement, the compound 13 is deprotonated with sodium hydride and then reacts with mesylate of 4-(hydroxymethyl)-1,3-dioxolan-2-one (or the tosylate or nosylate analogue) to give the compound 16. The compound 16 is hydrolyzed with weak acid to give compound 17. Alternatively, the alkyl group of compound 10 can be removed, such as by treating it with polymethylhydrosiloane, ZnCl₂ and Pd(PPh₃ )₄ to give the dual-functional pendant 17. The compound 17 can be grafted onto a polyepichlorohydrin or a polyphosphazene backbone via esterification of polydichlorophosphazene to make an electrolyte material with dual-functional pendants. In addition, compound 17 can react with acryloyl chloride or methacryloyl chloride to form a corresponding acrylic or methacrylate monomer, respectively, which can then be polymerized to the electrolyte material with dual- functional pendants.

[0017] In another embodiment of the invention, the synthesis of a dual-functional pendant 19 that has a polar chain and two strings of ethylene oxide is shown in the following scheme. Reaction of the compound 12c with methylsulfonyl chloride gives mesylate 18. The mesylate 18 is reacted with a sodium salt of 3-allyloxy-1,2-propanediol to give compound 19. The compound 19 can be grafted onto a polyhydrosiloxane backbone via hydro silylation to make an electrolyte material with dual-functional pendants.

[0018] In another embodiment of the invention, the synthesis of other dual-functional pendants is shown in the following scheme. Reaction of 3-allyloxy-1,2-propanediol with trityl chloride gives compound 20, which is then alkylated with a ethylene-oxide-containing alkylating agent to give compound 21, which is then hydrolyized with acid to give compound 22. The compound 22 undergoes hydro silylation with an ethylene-carbonate-containing hydrosiloxane 23 to give compound 24. In this embodiment, dual-functional groups are designed to form a non-linear branched structure. The compound 24 can be grafted onto a polyepichlorohydrin or a polyphosphazene backbone via esterification of polydichlorophosphazene to give an electrolyte material with dual-functional pendants. In addition , compound 24 can react with acryloyl chloride or methacryloyl chloride to form a corresponding acrylic or methacrylate monomer respectively which can then be polymerized to make an electrolyte material with dual-functional pendants.

[0019] In yet another embodiment of the invention, the synthesis of an aromatic dual- functional pendant (28), which contains an ethylene oxide linkage and two different polar groups, is shown in the following scheme. Reaction of 25 with 26 (which can be prepared from reacting 12c with phosphourous tribromide) gives 27. This is then hydro silylated with 23 to give 28. This example shows that dual-functional groups can be designed to form a non-linear branched structure. Compound 28 can be grafted onto a polyphosphazene backbone via esterification to give an electrolyte material with dual-functional pendants. In addition, compound 28 can react with acryloyl chloride or methacryloyl chloride to form a corresponding acrylic or methacrylate monomer, respectively, which can then be polymerized to make an electrolyte material with dual-functional pendants.

[0020] In another embodiment of the invention, the synthesis of a pendant containing a cyclic sulfone polar group is shown below. Compound 2d reacts with 3-sulfolene in the presence of sodium hydroxide to give compound 29, which then reacts with tetramethyl disiloxane in the presence a catalytic amount of tris(triphenylphosphine)rhodium(I) chloride to give compound 30.

[0021] In another embodiment of the invention, the synthesis of a pendant containing a linear sulfone polar group is shown below. Compound 2d reacts with sulfonyl chloride to give compound 31, which then reacts with ethanethiol to give 32. This is then oxidized to give a sulfone compound 33 which then reacts with tetramethyl disiloxane in the presence a catalytic amount of tris(triphenylphosphine)rhodium(I) chloride to give compound 34.

[0022] In yet another embodiment of the invention, the synthesis of a pendant containing a pyrrolidone polar group is shown in the following scheme. Reaction of 2d with methane sulfonyl chloride gives 35, which reacts with l-(2-hydroxyethyl)-2-pyrrolidone in the presence of a phase transfer catalyst to give 36. Then this reacts with tetramethyl disiloxane in the presence a catalytic amount of tris(triphenylphosphine)rhodium(I) chloride to give compound 37.

[0023] In another embodiment of the invention, the synthesis of graft polymers with dual- functional pendant groups is shown in the following scheme. A polymethylhydrosiloxane is grafted with compound 3, 6, or 10, as shown above to give corresponding polysiloxane electrolyte materials, Pl, P2, or P3, respectively, having both an ethylene glycol group and a polar group.

[0024] In another embodiment of the invention, the synthesis of a class of graft polymers with dual-functional pendant groups is shown in the following scheme. A polystyrene-b- polyvinylmethylsiloxane is grafted with compounds 4, 7 or 11, as shown above, to give corresponding grafted block copolymer electrolyte materials, P4, P5, or P6, respectively, with dual-functional pendant groups.

[0025] In another embodiment of the invention, the synthesis of another class of graft polymers with dual-functional pendant groups is shown in the following scheme. A poly(phosphazene)-containing ethylene oxide compound is further grafted with an ethylene- carbonate-containing compound such as compound 23 to make a corresponding poly(phosphazene) electrolyte material P7 with dual-functional pendant groups.

[0026] In another embodiment of the invention, the synthesis of another poly(phosphazene) electrolyte is shown below, where poly(dichlorophosphazene) is reacted with compound 24, as shown above, to make a dual-functional electrolyte material, P8.

[0027] In another embodiment of the invention, the synthesis of a random copolymer- containing dual-functional pendant group is shown in the following scheme. A random acrylic-polymer-containing Methylene glycol pendant group prepared by radical polymerization of two triethylene glycol-containing acrylic monomers is grafted to an ethylene-carbonate-containing pendant such as compound 23 to make a corresponding acrylic copolymer electrolyte material P9 with dual-functional pendant groups.

[0028] In another embodiment of the invention, the synthesis of a random copolymer- containing dual-functional pendant group is shown in the following scheme. A random polyvinyl-ether-containing triethylene glycol pendant group prepared by cationic polymerization of two triethylene-glycol-containing vinyl ether monomers is grafted with an ethylene-carbonate-containing pendant group to make a corresponding polyvinyl ether copolymer electrolyte material PlO with dual-functional pendant groups.

[0029] In another embodiment of the invention, the synthesis of a random copolymer- containing dual-functional pendant groups is shown in the following scheme. A random polymer, poly(epichlorohydrin-co-ethylene oxide), is reacted first with potassium iodide in acetone to give the corresponding iodo copolymer which is then react with the sodium salt of 12d to give PIl with dual-functional pendant groups.

[0030] In one embodiment of the invention, an electrolyte salt is added to the inventive polymer so that it can be used as an electrolyte for a battery cell. In one arrangement, the electrolyte salt is an alkali metal salt. In another arrangement, the electrolyte salt is a lithium salt. In order to ensure good mechanical properties, high molecular weight backbone molecules are preferred. In one arrangement, the polymer backbone has a molecular weight between about 1,000 and 500,000 Daltons. In another arrangement, the backbone has a molecular weight between about 50,000 and 400,000 Daltons.

[0031] There are no particular restrictions on the electrolyte salt that can be used in the embodiments of the present invention. Any electrolyte salt that includes the ion identified as the most desirable charge carrier for the application can be used. It is especially useful to use electrolyte salts that have a large dissociation constant within the polymer electrolyte.

[0032] Suitable examples include alkali metal salts, quaternary ammonium salts such as (CH₃)₄NBF₆, quaternary phosphonium salts such as (CH₃)₄PBF₆, transition metal salts such as AgClO₄, or protonic acids such as hydrochloric acid, perchloric acid, and fluoroboric acid.

[0033] Examples of salts include, but are not limited to metal salts selected from the group consisting of chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphates, sulfonamides, triflates, thiocynates, perchlorates, borates, or selenides of lithium, sodium, potassium, copper, silver, zinc, barium, lead, magnesium, calcium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten or vanadium. Examples of specific lithium salts include LiSCN, LiN(CN)₂, LiClO₄, LiBF₄, LiAsF₆, LiPF₆, LiCF₃SO₃, LiN(CF₃SO₂)₂, Li(CF₃SO₂)₃C, LiN(SO₂C₂Fs)₂, LiN[SO₂CF₂CF₃]₂, [LiTFSI] (lithium bis(trifluoromethane sulfone imide)), lithium alkyl fluorophosphates, lithium oxalatoborate, as well as other lithium bis(chelato)borates having five to seven membered rings, LiPF₃(C₂Fs)₃, LiPF₃(CF₃)₃, LiB(C₂O₄)₂, and mixtures thereof. Other exemplary salts include, but are not limited to AgSO₃CF₃, NaSCN, NaSO₃CF₃, KTFSI, NaTFSI, Ba(TFSI)₂, Pb(TFSI)₂, and Ca(TFSI)₂. Electrolyte salts may be used either singularly, or in mixtures of two or more different salts.

[0034] In the following examples, all chemical identifications were done using nuclear magnetic resonance (NMR). Example 1 - Synthesis of 2c

[0035] Triethylene glycol Ic (150 g, 1.0 mol), sodium hydroxide (20 g, 0.5 mol), tetrahydrofuran (200 ml), and allyl bromide (40 g or 28 ml, 0.33 mol) were added to a IL round-bottom flask equipped with a condenser and a magnetic stirrer. The mixture was refluxed for 3 hours and then cooled. Upon cooling, the mixture was concentrated in vacuo. Water (200 ml) was added, and the resulting mixture was transferred into a IL separatory funnel. The mixture was extracted with methylene chloride (150 ml). The aqueous layer was extracted once more with methylene chloride (100 ml). The combined organic layers were washed with water (3 x 100 ml), dried through sodium sulfate, and then concentrated thoroughly in vacuo to give an orange oil (46 g). This was vacuum distilled through a short reflux column (10 cm) to give the first fraction (83-85 ºC) and the second fraction (93- 98°C/0.5-0.3 mmHg), which was identified as 2c,

(26 g, 41%), a colorless oil.

Example 2 - Synthesis of 2d

[0036] Tetraethylene glycol Id (194 g, 1.0 mol), sodium hydroxide (20 g, 0.5 mol), tetrahydrofuran (200 ml), and allyl bromide (40 g or 28 ml, 0.33 mol) were added to a IL round-bottom flask equipped with a condenser and a magnetic stirrer. The mixture was refluxed for 3 hours and then cooled. Upon cooling, the mixture was concentrated in vacuo. Water (200 ml) was added, and the resulting mixture was transferred into a IL separatory funnel. The mixture was extracted with methylene chloride (150 ml). The aqueous layer was extracted once more with methylene chloride (100 ml). The combined organic layers were washed with water (3 x 100 ml), dried through sodium sulfate, and then concentrated thoroughly in vacuo to give an orange oil (46 g). The orange oil was vacuum distilled through a short reflux column (10 cm) to give the first fraction (2.5 g, 110-120ºC) and the second fraction (120-140°C/0.5-0.3 mmHg). The second fraction was identified as 2d, (42 g, 54%) as a colorless oil.

Example 3 - Synthesis of 3d

[0037] Into a 250 ml round-bottom flask equipped with magnetic stirrer and a 25 ml addition funnel was added 2d (23.4 g, 0.1 mol) and 50 wt% aqueous sodium hydroxide (4 drops). The solution was cooled in an ice water bath. Into the addition funnel acrylonitrile (13 ml, 0.38 mol) was added dropwise. The reaction mixture was stirred overnight and neutralized by adding five drops of concentrated hydrochloric acid, and then methylene chloride (150 ml). The resulting mixture was transferred into a 500 ml separatory funnel and water (150 ml) was added. The mixture was extracted and allowed to stand overnight to achieve complete separation of the organic and aqueous layers. The organic layer was further extracted with water (100 ml), then dried through sodium sulfate, and concentrated in vacuo to give a yellow oil (14.5 g). This was vacuum distilled (150-158ºC, 0.01 mmHg) to give 3d,

a colorless oil.

Example 4 - Synthesis of 4d

[0038] Compound 3d (14.4 g, 0.05 mol), tetramethyldisiloxane (8.0 g, 0.06 mol),

RhCl(PPh₃)₃ (0.01 g), and toluene (30 ml) were added to a 100 ml round-bottom flask which was then enclosed with a rubber septum. The resulting solution was heated at 80ºC for 2 days, cooled, and then concentrated in vacuo to give a lightly colored oil (20.3 g, 96%).

NMR spectra from the lightly colored oil identified it as 4d,

Example 5 - Synthesis of 8d

[0039] Into a 500 ml round-bottom flask equipped with a condenser and magnetic stirrer was added 2d (23.4 g, 0.1 mol), 2,2-dimethyl-1,3-dioxolane-4-ylmethyl-p-toluenesulfonate (30.0 g, 0.1 mol, from Aldrich), tetrabutylammonium bisulfate (5.5 g, 0.0162 mol), toluene (50 ml). The resulting mixture was heated until complete dissolution of the tosylate, followed by addition of 50% NaOH solution (50 ml). Precipitation occurred quickly after some heating. The mixture was heated to reflux (130-135ºC bath temperature) for 2 h and then cooled. Water (200 ml) was added to dissolve the precipitate, followed by the addition of methylene chloride (200 ml). The resulting mixture was transferred into a separatory funnel. The organic phase was extracted with brine (100 ml x 3), dried through sodium sulfate, and concentrated in vacuo, followed by fractional vacuum distillation to give the following fractions:

g, 58%). The last fraction was identified by NMR as the desired 8d.

Example 6 - Synthesis of 9d

Into a 100 ml round-bottom flask

joint) equipped with a condenser and magnetic stirrer was added 8d (20.3 g, 0.058 mol), IM aqueous hydrochloric acid (6.0 g), and methanol (60 ml). The resulting solution was heated to reflux for 2 days and then cooled. Solvent was removed in vacuo to give a colorless oil (18.0 g, 100%) which showed the expected NMR spectrum. This was used as 9d directly for the next step without further purification.

Example 7 - Synthesis of IQd

Diethyl carbonate (23 ml, 0.27 mol) and potassium carbonate (0.75 g) were added into a 100 ml round-bottom flask containing crude 9d (18.0 g, 0.058 mol) and equipped with a jacketed Dean Stark trap, a condenser, and a magnetic stirrer.The flask was heated to reflux (130ºC bath temperature) overnight ( 8 -12 h) and then cooled. Excess diethyl carbonate was removed in vacuo and methylene chloride (100 ml) was added. The resulting solution was washed with water (50 ml x 2) and brine (50 ml x 2), dried through sodium sulfate, and then concentrated to give an oil (14.3 g).The oil was passed through a short silica gel column (3in x lin) using 1:1 hexane:ethyl acetate to give a clear oil (13.0 g) whose NMR spectrum indicated high-purity product 1Od.

Example 8 - Synthesis of Hd

Tetramethyl disiloxane (6.8 g, 0.051 mol), tris(triphenylphosphine)rhodium(I) chloride (0.0075 g), and toluene (18 ml) were added into a 250 ml round-bottom flask containing crude 1Od (13.0 g, 0.039 mol) and equipped with a magnetic stirrer. , The flask was capped with a rubber septum, heated to 80ºC for 2 days, cooled, and then concentrated. The resulting oil was purified by passing it quickly through a short silica column (32 ml of silica was used) using 1:1 hexane/ethyl acetate as the eluent to give Hd as a lightly color oil (17.5 g, 96%) whose NMR spectrum indicated high-purity product Hd.

Example 9 - Synthesis of 12c

[0040] Methylene glycol (300 g, 2.0 mol) and 50% aqueous sodium hydroxide (6 g, 0.075 mol) were added to a IL round-bottom flask equipped with a magnetic stirrer and a 100 mL addition funnel. Acrylonitrile (33 ml, 0.5 mol) was then added dropwise into the addition funnel. The resulting solution was stirred overnight and then quenched by adding concentrated hydrochloric acid (7.0 ml, 0.087 mol). The resulting solution was transferred into a IL separatory funnel, brine (400 ml) was added, and then the solution was extracted with methylene chloride (150 ml x 2, 100 ml). The combined organic layers were extracted with brine (150 ml x 3), dried through sodium sulfate and then concentrated in vacuo to give an orange oil (36g, 35%), which was confirmed by NMR to be high-purity compound 12c. The orange oil was vacuum fractional distilled (133-150°C/0.025 mmHg ) to give 12c,

as a colorless liquid (18.3 g, 25%).

Example 10 - Synthesis of 12d

[0041] Triethylene glycol (388 g, 2.0 mol) and 50% aqueous sodium hydroxide (6 g, 0.075 mol) were added to a IL round-bottom flask equipped with a magnetic stirrer and a 100 mL addition funnel. Acrylonitrile (33 ml, 0.5 mol) was then added dropwise into the addition funnel. The resulting solution was stirred overnight and then quenched by adding concentrated hydrochloric acid (7.0 ml, 0.087 mol). The resulting solution was transferred into a IL separatory funnel, brine (400 ml) was added, and then the solution was extracted with methylene chloride (150 ml x 2, 100 ml). The combined organic layers were extracted with brine (150 ml x 4), dried through sodium sulfate and then concentrated in vacuo to give H, as an orange oil (65g, 53%), which showed

good purity according to NMR. To prevent decomposition, which would occur during vacuum distillation, crude 12d was used without purification.

Example 11 - Synthesis of 29

Into a round-bottom flask equipped with a magnetic stirrer were added 2d (46.4 g, 0.2 mol), 3-sulfolene (11.8 g, 0.1 mol) and KOH (0.52 g). The flask was capped with a septum and the resulting mixture was stirred for 4 d. Concentrated hydrochloric acid (1.10 g, 30 drops) was added to neutralize the reaction solution. The resulting solution was transferred into a 500 mL separatory funnel and methylene chloride (150 ml) was added, followed by extraction with brine (100 ml x3), drying through a cone of sodium sulfate, and concentration in vacuo to give a crude orange oil (46 g). This was distilled under vaccum using a short path distillation head to remove the unreacted 2d (17 g). The residue was fractionally distilled using a high boiling distillation head from Ace Glass to give the following fractions: (1) below 165°C, 1 g; (2) 165°C, 0.4 g; (3) 175°C, 1.9 g; (4) 192°C, 20 g. Fractions (2), (3) and (4), which showed identical NMR spectra as expected for 29, were combined to give a total yield of 22.3 g (63%). This procedure was based on that reported in U.S. Patent Number 2,419, 082.

Example 12 - Synthesis of 30

Tetramethyl disiloxane (9.0 g, 0.067 mol), tris(triphenylphosphine)rhodium(I) chloride (0.01 g), and toluene (25 ml) were added into a 250 ml round-bottom flask containing crude 29 (17.6 g, 0.05 mol) and equipped with a magnetic stirrer. The flask was capped with a rubber septum, heated to 80ºC for 2 days, cooled, and then concentrated. The resulting oil was purified by passing it quickly through a short silica column (32 ml of silica was used) using 1:1 hexane/ethyl acetate as the eluent to give 30 as a lightly colored oil (23.5 g, 97%) whose NMR spectrum indicated high-purity product 30.

Example 13 - Synthesis of 35

A round-bottom flask containing 2d (23.4 g, 0.1 mol), tetrahydrofuran (70 ml) and triethylamine (125.4 g, 0.15 mol) was cooled with an ice water bath. Methanesulfonyl chloride (11.4 g, 0.1 mol) in tetrahydrofuran (10 ml) was added dropwise. The resulting mixture was stirred overnight and then filtered to remove the precipitate. The filtrate was concentrate in vacuo to give 35 as an orange oil (29.6 g, 95%)

Example 14 - Synthesis of 36

Into a round-bottom flask were added 35 (28 g, 0.09 mol), l-(2-hydroxyethyl)-2-pyrrolidone (17.4 g, 0.134 mol), tetrabutylammonium hydrogen sulfate (7.26 g, 0.021 mol), toluene (50 ml), and 50% NaOH (50 ml). The mixture was heated to reflux for 1 d and then cooled. The mixture was transferred into a separatory funnel. The bottom solid was dissolved with water (100 ml) and then transferred into the separatory funnel. Methylene chloride (200 ml) was added. The aqueous phase at the bottom was separated and extracted with methylene chloride (100 ml). Separation was difficult; the methylene chloride layer seemed heavier than the aqueous layer. The combined organic phases were extracted with brine (100 ml x 3), dried through sodium sulfate and concentrated in vacuo to give crude 36 (26.2 g) which showed an expected NMR spectrum.

Example 15 - Synthesis of 37

Tetramethyl disiloxane (4.5 g, 0.034 mol), tris(triphenylphosphine)rhodium(I) chloride (0.005 g), and toluene (12 ml) were added into a 100 ml round-bottom flask containing crude 36 (9.0 g, 0.026 mol) and equipped with a magnetic stirrer. , The flask was capped with a rubber septum, heated to 80ºC for 2 days, cooled, and then concentrated. The resulting oil was purified by passing it quickly through a short silica column (32 ml of silica was used) using 1:1 hexane/ethyl acetate as the eluent to give Hd as a lightly colored oil (12.3 g, 95%), which showed an expected NMR spectrum. Example 16 - Synthesis of Pl

[0042] This synthesis was carried out in a glove box under an argon atmosphere. 1,3,5- trivinyl-1,3,5-trimethyltricyclosiloxane (20.7 g, 0.08 mol) and sodium dried tetrahydrofuran (400 ml) were added to a IL round-bottom reaction flask with a high-vacuum Teflon® stopcock and an magnetic stirrer. Lithium trimethyl silanolate (1.0 M in methylene chloride, 0.6 ml, 0.6 mmol) was added to initiate the polymerization. The stopcock was closed and the polymerization was allowed to proceed for 1 hour. Chlolotrimethyl silane (1.2 ml) was added to terminate the polymerization. The reaction flask was then transferred out of the glove box. The reaction solution was poured into a methanol (2.0 L)/distilled water (1.0 L) solution as it was magnetically stirred in a beaker. The methanol/water layer was decanted to isolate the small amount of separated oil at the bottom of the beaker. The oil was dried by blowing argon overnight and then in vacuo to give a viscous, colorless oil (14.5 g, 70%), a poly(vinylmethylsiloxane) prepolymer. The prepolymer (0.78 g), 4d (5.0 g, 0.0122 mol), and anhydrous toluene (5 ml), were added to a 100 ml round-bottom flask equipped with a magnetic stirrer and then capped under argon with a tightly fitted rubber septum. The mixture was immersed in a 65°C oil bath, and platinum divinyltetramethyldisilane catalyst (2.0% Pt, 40 μL) was added via a syringe. The resulting solution was heated for 40 hours and then diluted with toluene (20 ml). Activated charcoal (0.25 g) was added. The resulting mixture was stirred at 65°C for 2 hours and then cooled. The activated charcoal was removed by filtration and the filtrate with concentrated in vacuo to yield a viscous liquid which was then added into hexane (75 ml) while stirring magnetically to give a bottom layer. The solvent was decanted, and hexane (40 ml) was added. The mixture was stirred about 1 minute and then decanted. This procedure was repeated. The bottom layer was transferred into a sample vial and dried under vacuum overnight to yield Pl (3.5 g).

Example 17 - Synthesis of P4

[0043] High purity benzene was further purified by treatment with sec-butyllithium using 1,1-diphenylethylene as the indicator. High purity tetrahydrofuran was further purified by treatment with sodium using benzophenone as the indicator. Styrene was purified by dibutylmagnesium treatment and then transferred into a solvent transfer/storage flask with a high- vacuum Teflon® valve and degassed using freeze-pump-thaw methods. Tetrahydrofuran was similarly transferred in a solvent transfer/storage flask and moved into a glove box. A more detailed description of the high vacuum line and purification procedures can be found in U.S. Patent Publication Number2009/0075176Al, which is included by reference herein. Dried benzene (about 400 ml) was vacuum transferred into a 2 L reaction flask with a high vacuum valve and a magnetic stirring bar using a freeze-and-thaw technique. The reaction flask was moved into the glove box, and sec-butyl lithium (0.4 ml) was added, followed by addition of styrene (50 ml). The polymerization was allowed to proceed overnight in the glove box (> 12 hr). Hexamethylcyclotrisiloxane (2.0 g) was added through a powder funnel, followed by addition of tetrahydrofuran (200 ml). The yellow color of the polymerization solution disappeared after about 40 minutes. After an hour, 1,3,5- trivinyl-1,3,5-trimethylcyclotrisiloxane (50 ml) was added, and the polymerization was allowed to proceed for about 22 hours. Excess trimethylchlorosilane (2.0 g) was added, and the resulting solution was stirred for 24 hours to ensure thorough termination. The resulting solution was precipitated into methanol (2 L) as it was magnetically stirred. White precipitate was allowed to settle, and most of the solvent was decanted. Methanol (1000 ml) was added to the precipitate, and the resulting mixture was stirred for several minutes. The solvent was decanted, and the precipitate was dried by blowing under nitrogen overnight. Then the precipitate was vacuum dried for 24 hours to yield poly(styrene-b- vinylmethylsiloxane), a white powder (86 g). The styrene/siloxane molar ratio was about 49/51 as determined by NMR analysis. This prepolymer can be grafted with 4d to give P4 using the method described above for Pl.

Example 18 - Synthesis of P7

[0044] Hexachlorophosphazene (5.12 g) was added to a glass ampoule. The ampoule was sealed and heated to 140 ºC for 12 hours and then cooled. The ampoule was opened in a glove box, and the product was dissolved in tetrahydrofuran (40 ml) to give a poly(phosphazene) solution. A mixture of sodium hydride (0.30 g, 0.0125 mol) in tetrahydrofuran (5 ml) was prepared in a vial and then cooled in a freezer within the glove box. Compound 2d (3.37 g, 0.014 mol) was added to the cooled mixture dropwise. The resulting mixture was cooled, before adding a portion of the poly(phosphazene) solution (3.33 ml). The resulting solution was stirred for 5 hours. The reaction was quenched by adding methanol. The solvent was removed in vacuo and benzene was added. The resulting solution was filtered through Celite®, and concentrated again in vacuo to give a poly(phosphazene) prepolymer as a viscous light yellow liquid (3.13 g). The prepolymer underwent hydrosilylation with 23 to give P7. [0045] This invention has been described herein in considerable detail to provide those skilled in the art with information relevant to apply the novel principles and to construct and use such specialized components as are required. However, it is to be understood that the invention can be carried out by different equipment, materials and devices, and that various modifications, both as to the equipment and operating procedures, can be accomplished without departing from the scope of the invention itself.

Claims

WE CLAIM:

1. A polymer, comprising: a backbone molecule; and a first pendant chain comprising an oligomeric alkylene oxide group and a polar group, the first pendant chain attached to the backbone molecule.

2. The polymer of Claim 1 wherein the backbone has a composition selected from the group consisting of vinyl polymers, acrylic or methacrylate polymers, ethylene oxide polymers, polyphosphazene, polynorbornene, polysiloxanes, and condensation polymers, such as polyester, polyurethane, polyimide, and polyurea.

3. The polymer of Claim 1 wherein the backbone has a structure selected from the group consisting of linear or branched homopolymer structures, linear or branched block copolymer structures, dendrimers, rings, cages, and cross-linked molecules.

4. The polymer of Claim 1 further comprising a second oligomeric alkylene oxide group in the first pendant chain.

5. The polymer of Claim 1 further comprising a plurality of oligomeric alkylene oxide group in the first pendant chain.

6. The polymer of Claim 5, wherein there are between about 2 and 20 oligomeric alkylene oxide group in the first pendant chain.

7. The polymer of Claim 1 wherein the oligomeric alkylene oxide group is selected from the group consisting of crown ethers, ethylene oxides, trimethylene oxides, and their corresponding fluorinated derivatives.

8. The polymer of Claim 1 wherein the polar group is selected from the group consisting of nitriles, perfluorocarbons, alkyl carbonates, cyclic carbonates, nitro, n- succinimide, sulfolane, phthalimide, and sulfonyl, and sulfonic acids.

9. The polymer of Claim 1 further comprising a second pendant chain attached to the backbone polymer wherein the second pendant chain comprises either an alkylene oxide group or a polar group.

10. The polymer of Claim 9 further comprising a third pendant chain attached to the backbone polymer wherein the third pendant chain comprises either an alkylene oxide group or a polar group and is different from the second pendant chain.

11. A polymer, comprising: a backbone; and a plurality of pendant chains attached to the backbone; wherein the plurality of pendant chains comprises: first pendant chains comprising both a first oligomeric alkylene oxide group and a first polar group; second pendant chains comprising a second oligomeric alkylene oxide group; and third pendant chains comprising a second polar group.

12. The polymer of Claim 11 wherein the first oligomeric alkylene group and the second oligomeric alkylene group is each selected independently from the group consisting of crown ethers, ethylene oxides, trimethylene oxides, and their corresponding fluorinated derivatives.

13. The polymer of Claim 11 wherein the first polar group and the second polar group is each selected independently from the group consisting of nitriles, perfluorocarbons, alkyl carbonates, cyclic carbonates, nitro, n-succinimide, sulfolane, phthalimide, and sulfonyl, and sulfonic acids.

14. A polymer electrolyte comprising: a polymer comprising: a backbone; and a first pendant chain comprising an oligomeric alkylene oxide group and a polar group, the first pendant chain attached to the backbone; and a salt.

15. The polymer electrolyte of Claim 14 wherein the backbone polymer has a molecular weight between about 1000 and 500,000 Daltons.

16. The polymer electrolyte of Claim 14 wherein the backbone polymer has a molecular weight between about 50,000 and 400,000 Daltons.

17. The polymer electrolyte of Claim 14 wherein the salt is a lithium salt.

18. The polymer electrolyte of Claim 14 wherein the salt is selected from the group consisting of chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphates, sulfonamides, triflates, thiocynates, perchlorates, borates, or selenides of lithium, sodium, potassium, copper, silver, zinc, barium, lead, magnesium, calcium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten or vanadium.

19. The polymer electrolyte of Claim 14 wherein the salt is selected from the group consisting of

lithium alkyl fluorophosphates, lithium oxalatoborate, as well as other lithium bis(chelato)borates having five to seven membered rings, lithium bis(trifluoromethane sulfone imide) (LiTFSI), LiPF₃(C₂F₅)₃, LiPF₃(CF₃)₃, LiB(C₂O₄)₂, and mixtures thereof.