# Patent

## Title
Polymer compositions based on PXE

## Abstract

New polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210° C. These materials can be made with either homopolymers or with block copolymers.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application No. 61/346,398, filed May 19, 2010 and to International Patent Application Number PCT/US11/37071, filed May 19, 2011. This application is also related to pending U.S. patent application Ser. No. 13/698,665, filed Nov. 19, 2012. These applications are all incorporated by reference herein.


STATEMENT OF GOVERNMENT SUPPORT
The invention described and claimed herein was made in part utilizing funds supplied by the U.S. Department of Energy under Contract No. DE-OE0000223. The Government has certain rights in this invention.


BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates generally to a newly-synthesized microphase-separated polymer material.
All publications referred to herein are incorporated by reference in their entirety for all purposes as if fully set forth herein.
The increased demand for lithium secondary batteries has resulted in research and development to improve their safety and performance. Many batteries employ liquid electrolytes and 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.
The lithium solid polymer electrolyte rechargeable battery is an especially attractive technology for Li-ion batteries because, among other benefits, the solid polymer electrolyte exhibits high thermal stability, low rates of self-discharge, stable operation over a wide range of environmental conditions, enhanced safety, flexibility in battery configuration, minimal environmental impacts, and low materials and processing costs. Moreover, solid polymer electrolytes may enable the use of lithium metal anodes, which offer higher energy densities than traditional lithium ion anodes.
Despite their many advantages, the adoption of solid polymer electrolytes has been curbed by the inability to develop an electrolyte that exhibits both high ionic conductivity and good mechanical properties. This difficulty arises because high ionic conductivity, according to standard mechanisms, calls for high polymer chain mobility. But high polymer chain mobility, according to standard mechanisms, tends to produce mechanically soft polymers.
As an example, a prototypical polymer electrolyte is one composed of polyethylene oxide (PEO)/salt mixtures. PEO generally offers good mechanical properties at room temperature. However, PEO is also largely crystalline at room temperature. The crystalline structure generally restricts chain mobility, reducing conductivity. Operating PEO electrolytes at high temperature (i.e., above the polymer's melting point) solves the conductivity problem by increasing chain mobility and hence improving ionic conductivity. However, the increased conductivity comes at a cost in terms of deterioration of the material's mechanical properties. At higher temperatures, the polymer is no longer rigid.
Block copolymers have been proposed as materials that may be able to exhibit both good mechanical properties and good conductivity. By using microphase separated block copolymers of two or more blocks, at least one block can impart mechanical integrity while at least one block can impart high conductivity. Polymer electrolytes are plagued by poor conductivity compared to liquid electrolytes. Polymer electrolytes conduct better at higher temperatures, and operating electrochemical cells at very high temperatures >110° C. results in conductivities similar to liquid electrolytes at room temperature. This must be balanced, however, against the melting temperature of the mechanical blocks. Thus far, no block copolymer has been reported that can be operated at high temperatures (>150° C.) while maintaining high mechanical strength.
Therefore, there has been and is still a strong need for a polymeric electrolyte material with sufficient practical ionic conductivity and mechanical stability at high temperature operation.



DESCRIPTION OF THE DRAWINGS
FIG. 1 shows modulus measurements for a PS-PEO block copolymer and an exemplary PXE-PEO block copolymer as a function of temperature.
FIG. 2 is a schematic drawing of a diblock copolymer and a domain structure it can form, according to an embodiment of the invention.
FIG. 3 is a schematic drawing of a triblock copolymer and a domain structure it can form, according to an embodiment of the invention.
FIG. 4 is a schematic drawing of a triblock copolymer and a domain structure it can form, according to another embodiment of the invention.



DETAILED DESCRIPTION
Disclosed herein are new microphase domain polymer materials with high softening temperatures. The polymers have ionically-conductive polymer domains and structural polymer domains that have higher softening temperatures (Ts) than have been possible before in ionically-conductive polymers. In one embodiment of the invention, the microphase domain polymer material has domains made up of ionically-conducive homopolymers and domains made of structural homopolymers with high softening temperatures (Ts). The ionically-conductive polymers and the structural polymers self-order and microphase separate. In another embodiment of the invention, the microphase domain polymer material is a block copolymer that has an ionically-conductive polymer block and a structural polymer block that has a high softening temperature (Ts). The microphase domain polymer materials can be combined with salts (such as lithium salts) to create ionically-conductive materials that are solid at desirable high operating temperatures for use in batteries and the like.
For the purposes of this disclosure, we use the term “softening temperature (Ts)” to mean either glass transition temperature (for glassy polymers) or melting temperature (for crystalline polymers). In many embodiments, we discuss glassy polymers so we use the term “glass transition temperature (Tg).” It should be understood that for embodiments where crystalline polymers are used, the term “melting temperature (Tm)” can be substituted for Tg.
Highly conducting polymer electrolytes based on block copolymers of polystyrene (PS) and polyethylene oxide (PEO) have been disclosed previously, for example, in U.S. patent application Ser. No. 12/225934, filed Oct. 1, 2008, U.S. patent application Ser. No. 12/2711828, filed Nov. 14, 2008, and International Patent Application Number PCT/US09/31356, filed Jan. 16, 2009, all of which are included by reference herein. The approximate chemical structures of these polymers are shown as (1) below, wherein m and n are the numbers of repeat units for the polystyrene and polyethylene oxide blocks, respectively.




Such block copolymers have a unique lamella microphase domain morphology that results in both high modulus and relatively high ionic conductivity at 80° C. However, such polymers cannot operate at temperatures higher than about 90° C. or 100° C., where the PEO would have even higher conductivity.
Example of structural blocks that have been used in such block copolymers polymers include, but are not limited to, polystyrene, hydrogenated polystyrene, polymethacrylate, poly(methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polypropylene, polyolefins, poly(t-butyl vinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), polyethylene, fluorocarbons, such as polyvinylidene fluoride, or copolymers that contain styrene, methacrylate, or vinylpyridine. In general these materials have softening temperatures that are no higher than about 180° C.










Softening Temperatures for Some Exemplary


Low Ts Polymers










Polymer
Ts (° C.)














polystyrene
95



hydrogenated polystyrene
146



Polymethacrylates
75



poly(methyl methacrylate)
114



polyvinylpyridine
110-180



polyvinylcyclohexane
146



polypropylene
173



poly(t-butyl vinyl ether)
74



poly(cyclohexyl methacrylate)
104



poly(cyclohexyl vinyl ether)
61



polyethylene
100



polyvinylidene fluoride
160










In general, it would be useful to have solid polymer electrolytes that can operate at temperatures where they are most conductive without losing their structural integrity. In one embodiment of the invention, a matrix of microphase separated solid polymers has both conductive phases and mechanically hard phases that can operate at high temperatures and still maintain their mechanical properties. For example, poly (2,6-dimethyl-1,4-phenylene oxide) (PXE) is a well-known thermoplastic polymer with a very high Tg (210° C.). Thus ionically-conductive polymer materials in which PXE is a major component can operate at temperatures up to 210° C. without softening. Because the Tg of the polymer material is higher than, for example, the melting point of lithium metal (180° C.), it can maintain its mechanical integrity even when used as an electrolyte in a lithium cell that experiences thermal runaway reaction and melting of the lithium anode. Additionally, PXE has excellent properties such as high toughness, high dimensional stability, good flame retardation and low moisture uptake that make it an ideal mechanical block for a microphase separated polymer electrolyte.
For example, block copolymers of PXE, the diblock PXE-PEO and the triblock PXE-PEO-PXE, can operate as electrolytes at elevated temperatures, resulting in higher ionic conductivity and longer cell cycling lifespan than is possible for the block copolymers shown in (1). The block polymer PXE-b-PEO has not been reported before. This is the first time that block polymer PXE-b-PEO has been synthesized using commercial available PXE and metal free anionic polymerization. In one embodiment of the invention, the structure of a PXE-PEO diblock polymer is given as (2) and the structure of a PXE-PEO-PXE triblock polymer is given as (3) below.




In one embodiment of the invention, each block of the linear block copolymers (2) and (3) is a linear polymer. In another embodiment of the invention, at least one of the blocks in the block copolymers (2) and (3) is not a linear polymer. In one arrangement, at least one of the blocks in the block copolymers (2) and (3) is a comb or branched polymer.
In one arrangement, a is an integer ranging from about 10 to 90, and b is an integer ranging from about 10 to 90, and c is an integer ranging from about 10 to 90. In one arrangement, R1, R2, R3, R4 can be any of hydrogen, alkyl, halogenated alkyl, alkene, aromatic rings, siloxane and alkyl with O and S ether bonds. R5 can be any of hydrogen, alkyl, halogenated alkyl, alkene, an aromatic ring, siloxane and alkyl with O and S ether bonds. In one arrangement, R1 and R2 are hydrogen, R3 and R4 are CH3, and R5 is CH3O(CH2CH2O)3C3H6Si(CH3)2OSi(CH3)2C3H6OCH2.
FIG. 1 shows modulus measurements for a PS-PEO block copolymer and an exemplary PXE-PEO block copolymer as a function of temperature. The modulus of the PS-PEO sample drops dramatically at around 100° C. while the PXE-PEO sample retains much of its rigidity even at temperatures above 150° C.
The embodiments of the invention are not limited to the examples shown in (2) and (3) above. There are a number of structural, high Ts polymers that can be substituted for PXE above. There are also a number of conductive polymers that can be substituted for the PEO above. A generalized diblock structure can be shown as:




and a generalized triblock structure can be shown as:





Ar can be any of:





Y can be any of ketones, sulfones, isopropylidene, hexafluoroisopropylidene, amides and oxygen. R1, R2, R3, R4, and R5 can be any of hydrogen, alkyl, halogenated alkyl, alkene, aromatic rings, siloxane and alkyl with O and S ether bonds, n is an integer ranging from 1 to 10, a is an integer ranging from about 10 to 90, b is an integer ranging from about 10 to 90, and c is an integer ranging from about 10 to 90. Although these generalized structures have been shown here as block copolymers, this is not the only possibility. The conductive molecules and structural molecules can also each be homopolymers as long as they can self-assemble into a microphase domain structure.

In one embodiment of the invention, the structural polymer has a softening temperature that is no less than 190° C. In another embodiment of the invention, the structural polymer has a softening temperature that is no less than 200° C. In another embodiment of the invention, the structural polymer has a softening temperature that is no less than 210° C. In another embodiment of the invention, the structural polymer has a softening temperature that is no less than 220° C.
In one embodiment of the invention, the structural phase can be made of polymers with high softening temperatures. In one embodiment of the invention, the structural phase can be made of poly(phenylene oxide). In one embodiment of the invention, the structural phase can be made of poly(2,6-dimethyl-1,4-phenylene oxide) (PXE). In one embodiment of the invention, the structural phase can be made of poly(phenylene sulfide). In one embodiment of the invention, the structural phase can be made of poly(phenylene sulfide sulfone). In one embodiment of the invention, the structural phase can be made of poly(phenylene sulfide ketone). In one embodiment of the invention, the structural phase can be made of poly(phenylene sulfide amide). In one embodiment of the invention, the structural phase can be made of polysulfone. In general, the softening temperatures of the microphase domain polymers disclosed herein are the same as the softening temperatures of their highest Ts major component. The major components of the microphase domain polymers disclosed herein are the ionically-conductive polymer and structural polymer.










Softening Temperatures for Some Exemplary


High Ts Polymers










Polymer
Ts (° C.)







poly(phenylene oxide)
210



poly(2,6-dimethyl-1,4-phenylene oxide) (PXE)
210



poly(phenylene sulfide)
218



poly(phenylene sulfide sulfone)
217



poly(phenylene sulfide ketone)
218



polysulfone
185










In one embodiment of the invention, the conductive phase can be made of a linear or branched polymer. Conductive linear or branched polymers that can be used in the conductive phase include, but are not limited to, polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, and combinations thereof. The conductive linear or branched polymers can also be used in combination with polysiloxanes, polyphosphazines, polyolefins, and/or polydienes to form the conductive phase.
In another exemplary embodiment, the conductive phase is made of comb (or branched) polymers that have a backbone and pendant groups. Backbones that can be used in these polymers include, but are not limited to, polysiloxanes, polyphosphazines, polyethers, polydienes, polyolefins, polyacrylates, polymethacrylates, and combinations thereof. Pendants that can be used include, but are not limited to, oligoethers, substituted oligoethers, nitrile groups, sulfones, thiols, polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, other polar groups, and combinations thereof.
FIG. 2A is a simplified illustration of an exemplary diblock polymer molecule 200 that has a first polymer block 210 and a second polymer block 220 covalently bonded together. In one arrangement both the first polymer block 210 and the second polymer block 220 are linear polymer blocks. In another arrangement, either one or both polymer blocks 210, 220 has a comb (or branched) structure. In one arrangement, neither polymer block is cross-linked. In another arrangement, one polymer block is cross-linked. In yet another arrangement, both polymer blocks are cross-linked.
Multiple diblock polymer molecules 200 can arrange themselves to form a first domain 215 of a first phase made of the first polymer blocks 210 and a second domain 225 of a second phase made of the second polymer blocks 220, as shown in FIG. 2B. Diblock polymer molecules 200 can arrange themselves to form multiple repeat domains, thereby forming a continuous nanostructured block copolymer material 240, as shown in FIG. 2C. The sizes or widths of the domains can be adjusted by adjusting the molecular weights of each of the polymer blocks.
In another arrangement, the domains 215, 225 can be made by two different homopolymers (not shown) that form microphase-separated structures. The homopolymers may or may not be bonded together as block copolymers.
In one arrangement the first polymer domain 215 is ionically-conductive, and the second polymer domain 225 provides mechanical strength to the material.
FIG. 3A is a simplified illustration of an exemplary triblock polymer molecule 300 that has a first polymer block 310a, a second polymer block 320, and a third polymer block 310b that is the same as the first polymer block 310a, all covalently bonded together. In one arrangement the first polymer block 310a, the second polymer block 320, and the third copolymer block 310b are linear polymer blocks. In another arrangement, either some or all polymer blocks 310a, 320, 310b have a comb (or branched) structure. In one arrangement, no polymer block is cross-linked. In another arrangement, one polymer block is cross-linked. In yet another arrangement, two polymer blocks are cross-linked. In yet another arrangement, all polymer blocks are cross-linked.
Multiple triblock polymer molecules 300 can arrange themselves to form a first domain 315 of a first phase made of the first polymer blocks 310a, a second domain 325 of a second phase made of the second polymer blocks 320, and a third domain 315b of a first phase made of the third polymer blocks 310b as shown in FIG. 3B. Triblock polymer molecules 300 can arrange themselves to form multiple repeat domains 325, 315 (containing both 315a and 315b), thereby forming a continuous nanostructured block copolymer 330, as shown in FIG. 3C. The sizes of the domains can be adjusted by adjusting the molecular weights of each of the polymer blocks.
In another arrangement, the domains 315, 325 can be made by two different homopolymers (not shown) that form microphase-separated structures. The homopolymers may or may not be bonded together as block copolymers.
In one arrangement the first and third polymer domains 315a, 315b are ionically-conductive, and the second polymer domain 325 provides mechanical strength to the nanostructured block copolymer. In another arrangement, the second polymer domain 325 is ionically-conductive, and the first and third polymer domains 315 provide a structural framework.
FIG. 4A is a simplified illustration of another exemplary triblock polymer molecule 400 that has a first polymer block 410, a second polymer block 420, and a third polymer block 430, different from either of the other two polymer blocks, all covalently bonded together. In one arrangement the first polymer block 410, the second polymer block 420, and the third copolymer block 430 are linear polymer blocks. In another arrangement, either some or all polymer blocks 410, 420, 430 have a comb (or branched) structure. In one arrangement, no polymer block is cross-linked. In another arrangement, one polymer block is cross-linked. In yet another arrangement, two polymer blocks are cross-linked. In yet another arrangement, all polymer blocks are cross-linked.
Multiple triblock polymer molecules 400 can arrange themselves to form a first domain 415 of a first phase made of the first polymer blocks 410a, a second domain 425 of a second phase made of the second polymer blocks 420, and a third domain 435 of a third phase made of the third polymer blocks 430 as shown in FIG. 4B. Triblock polymer molecules 400 can arrange themselves to form multiple repeat domains, thereby forming a continuous nanostructured block copolymer 440, as shown in FIG. 4C. The sizes of the domains can be adjusted by adjusting the molecular weights of each of the polymer blocks.
In one arrangement the first polymer domains 415 are ionically-conductive, and the second polymer domains 425 provide mechanical strength to the nanostructured block copolymer. The third polymer domains 435 provides additional functionality that may improve mechanical strength, ionic conductivity, chemical or electrochemical stability, may make the material easier to process, or may provide some other desirable property to the block copolymer. In other arrangements, the individual domains can exchange roles. In one arrangement, the third polymer domain 435 is ionically-conductive and different from the first ionically-conductive polymer block 415. In another arrangement, the third polymer domain 435 provides mechanical strength and is different from the second polymer domain 425.
In another arrangement, the domains 415, 425, 435 can be made by three different homopolymers (not shown) that form microphase-separated structures. The homopolymers may or may not be bonded together as block copolymers.
Choosing appropriate polymers for the block copolymers described above is important in order to achieve desired electrolyte properties. In one embodiment, the conductive polymer: (1) exhibits ionic conductivity of at least 10−5 Scm−1 at electrochemical cell operating temperatures when combined with an appropriate salt(s), such as lithium salt(s); (2) is chemically stable against such salt(s); and (3) is thermally stable at electrochemical cell operating temperatures. In one embodiment, the structural material has a modulus in excess of 1×105 Pa at electrochemical cell operating temperatures. In one embodiment, the third polymer: (1) is rubbery and (2) has a glass transition temperature lower than operating and processing temperatures. In another embodiment, the third polymer: (1) exhibits ionic conductivity of at least 10−5 Scm−1 at electrochemical cell operating temperatures when combined with an appropriate salt(s), such as lithium salt(s); (2) is chemically stable against such salt(s); and (3) is thermally stable at electrochemical cell operating temperatures. It is useful if all materials are mutually immiscible.
In one embodiment of the invention, the conductive phase can be made of a linear or branched polymer. Conductive linear or branched polymers that can be used in the conductive phase include, but are not limited to, polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, and combinations thereof. The conductive linear or branched polymers can also be used in combination with polysiloxanes, polyphosphazines, polyolefins, and/or polydienes to form the conductive phase.
In another exemplary embodiment, the conductive phase is made of comb (or branched) polymers that have a backbone and pendant groups. Backbones that can be used in these polymers include, but are not limited to, polysiloxanes, polyphosphazines, polyethers, polydienes, polyolefins, polyacrylates, polymethacrylates, and combinations thereof. Pendants that can be used include, but are not limited to, oligoethers, substituted oligoethers, nitrile groups, sulfones, thiols, polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, other polar groups, and combinations thereof.
There are no particular restrictions on the electrolyte salt that can be used in the block copolymer electrolytes. 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.
Suitable examples include alkali metal salts, such as Li salts. Examples of useful Li salts include, but are not limited to, LiPF6, LiN(CF3SO2)2, Li(CF3SO2)3C, LiN(SO2CF2CF3)2, LiB(C2O4)2, B12FxH12-x, B12F12, and mixtures thereof.
In one embodiment of the invention, single ion conductors can be used with electrolyte salts or instead of electrolyte salts. Examples of single ion conductors include, but are not limited to sulfonamide salts, boron based salts, and sulfates groups.
In one embodiment of the invention, the structural phase can be made of polymers with high softening temperatures such as poly(phenylene oxide), poly(2,6-dimethyl-1,4-phenylene oxide) (PXE), poly(phenylene sulfide), poly(phenylene sulfide sulfone), poly(phenylene sulfide ketone), poly(phenylene sulfide amide), and polysulfone.
Additional species can be added to nanostructured block copolymer electrolytes to enhance the ionic conductivity, to enhance the mechanical properties, or to enhance any other properties that may be desirable.
The ionic conductivity of nanostructured block copolymer electrolyte materials can be improved by including one or more additives in the ionically-conductive phase. An additive can improve ionic conductivity by lowering the degree of crystallinity, lowering the melting temperature, lowering the glass transition temperature, increasing chain mobility, or any combination of these. A high dielectric additive can aid dissociation of the salt, increasing the number of Li+ ions available for ion transport, and reducing the bulky Li+[salt] complexes. Additives that weaken the interaction between Li+ and PEO chains/anions, thereby making it easier for Li+ ions to diffuse, may be included in the conductive phase. The additives that enhance ionic conductivity can be broadly classified in the following categories: low molecular weight conductive polymers, ceramic particles, room temp ionic liquids (RTILs), high dielectric organic plasticizers, and Lewis acids.
Other additives can be used in the polymer electrolytes described herein. For example, additives that help with overcharge protection, provide stable SEI (solid electrolyte interface) layers, and/or improve electrochemical stability can be used. Such additives are well known to people with ordinary skill in the art. Additives that make the polymers easier to process, such as plasticizers, can also be used.
In one embodiment of the invention, high Ts block copolymers are synthesized using a metal-free initiation reaction. The reaction uses a strong metal-free base such as the phospazene base (t-BuP4) instead of an alkali metal or metal base to activate the OH ends of the high Ts structural polymer. Activation of the OH ends of the high Ts structural polymer is necessary so that the conductive molecules can be attached or grown to form the block copolymer. This method has not been used heretofore for block copolymer syntheses. The metal-free method offers significant advantages for synthesis of block copolymers as no homopolymer of the second block will be present. The metal-free strong base is neutral and and any excess metal-free base will not initiate anionic polymerization as would occur with a metal base. Thus, it offers more pure products with fewer purification steps. This is especially significant for large-scale manufacturing of block copolymers. Another important advantage offered by the metal-free method is for the synthesis of block copolymers that are intended for use as electrolytes in electrochemical cells. Even with the best purification protocols, there are still trace amounts of metals left behind in block copolymers synthesized using metal catalysts or initiators. Metals in the electrolyte can interfere with the electrochemical functioning of the cell, leading to shorting and/or premature failure. Metal-free synthesis methods eliminate this risk.
EXAMPLES
The following examples provide details relating to composition, fabrication and performance characteristics of block copolymer electrolytes in accordance with the present invention. It should be understood the following is representative only, and that the invention is not limited by the detail set forth in these examples.
Example 1
A metal-free initiation reaction was used to synthesize PXE-PEO. PXE (Sigma-Aldrich, Mw ̃50K) (2 g) was dissolved in 60 ml dried THF. Then, in a glove-box, 0.15 ml of 0.5M t-BuP4 benzene solution (t-BuP4 from Sigma-Aldrich) was added to the solution. The mixture was stirred at 50° C. for 24 hrs under an inert atmosphere. Ethyleneoxide (EO) (6 ml) was transferred into the mixture via a high vacuum line. The mixture was stirred at 45° C. for 48 hrs. After cooling down to 25° C., the mixture was precipitated in hexane, filtered under vacuum, and washed with isopropanol. After further vacuum drying, the yield was 5.2 g of white solid. Proton NMR (in D-benzene) showed 68 wt % PEO and 32 wt % PXE.
Example 2
PXE (Sigma-Aldrich, Mw ̃50K) (2 g) was dissolved in 60 ml dried THF. In a glove-box, 0.5M DPMK (diphenylmethylene potassium) THF solution (0.15 ml) was added to the solution. The mixture was stirred at 50° C. for 24 hrs under an inert atmosphere. Ethyleneoxide (EO) (6 ml) was transferred into the mixture via a high vacuum line. The mixture was stirred at 45° C. for 48 hrs. After cooling down to 25° C., the mixture was precipitated in hexane, filtered under vacuum, and washed with isopropanol. After further vacuum drying, the yield was 5.5 g of white solid. Proton NMR (in D-benzene) showed 70 wt % PEO and 30 wt % PXE.
Example 3
PXE (Sigma-Aldrich, Mw ̃50K) (2 g) was dissolved in 60 ml dried THF. In a glove-box, 0.15 ml of 0.5M t-BuP4 benzene solution (t-BuP4 from Sigma-Aldrich) was added to the solution. The mixture was stirred at 50° C. for 24 hrs under an inert atmosphere. Then 5.0 ml allyl glycidyl ether (AGE) was added to the mixture. The mixture was stirred at 45° C. for 48 hrs. After cooling down to 25° C., the mixture was precipitated in hexane, filtered under vacuum, and washed with isopropanol. After further vacuum drying, the yield was 2.4 g of white solid PXE-b-PAGE. Proton NMR (in D-benzene) showed 23 wt % PAGE (polyallyl glycidyl ether) and 77 wt % PXE
PXE-b-PAGE (1.0 g) was dissolved in 12 ml toluene, and 100 ul Pt catalyst (Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution in xylene, Pt ̃2 wt % from Aldrich) and 1.16 g HSi(CH3)2OSi(CH3)2C3H6O(C2H4O)3CH3 were added to the solution. The mixture was stirred at 65° C. for 18 hrs. The solution was then diluted with an additional 24 ml of toluene. Silica gel (0.5 g) was added to the mixture, and it was stirred at 25° C. for 4 hrs. The solution was filtered to remove the silica gel, precipitated in hexane, and vacuum dried. Polymer in the amount of 1.0 g was obtained, and proton NMR showed 63.8 wt % PXE and 36.2 wt % grafted PAGE. The reaction sequence is shown in (4) below.




Example 4
PXE (Sigma-Aldrich, Mw ̃50K) (2 g) was dissolved in 60 ml dried THF. Then 0.3 ml of 0.5M t-BuP4 benzene solution (t-BuP4 from Sigma-Aldrich) was added to the solution in a glove-box. The mixture was stirred at 50° C. for 24 hrs under an inert atmosphere. Then 4 ml ethyleneoxide (EO) was transferred into the mixture via a high vacuum line. The mixture was stirred at 45° C. for 48 hrs. After cooling down to 25° C., 0.72 ml (0.063M of 1,4-dibromoxylene in benzene solution) was added into the mixture in a glove-box. The mixture was stirred at 50° C. overnight. After cooling down to 25° C., the mixture was precipitated in hexane, filtered under vacuum, and washed with isopropanol. After further vacuum drying, the yield was 5.4 g of white solid triblock copolymer. Proton NMR (in D-benzene) showed 64 wt % PEO and 35 wt % PXE. The reaction sequence is shown in (5) below.




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

1. A polymer composition, comprising:
an ordered nanostructure comprising a matrix of:
first domains defined by association of first polymers; and
second domains defined by association of second polymers;

wherein the first polymers and the second polymers form block copolymers, each block copolymer comprising a first polymer as a first block and a second polymer as a second block; and
wherein the second blocks are selected from the group consisting of poly(phenylene oxide), poly(2,6-dimethyl-1,4-phenylene oxide) (PXE), poly(phenylene sulfide sulfone), poly(phenylene sulfide ketone), and poly(phenylene sulfide amide).

2. The polymer of claim 1 wherein the softening temperature is no less than 200° C.

3. The polymer of claim 1 wherein the softening temperature is no less than 210° C.

4. The polymer of claim 1 wherein the softening temperature is no less than 220° C.

5. The polymer of claim 1 wherein the first blocks are selected from the group consisting of polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, polysiloxanes, polyphosphazines, polyolefins, polydienes, and combinations thereof.

6. The polymer of claim 1 wherein the first blocks comprise comb polymers that have a backbone and pendant groups.

7. The polymer of claim 6 wherein the backbones are selected from the group consisting of polysiloxanes, polyphosphazines, polyethers, polydienes, polyolefins, polyacrylates, polymethacrylates, and combinations thereof.

8. The polymer of claim 7 wherein the pendants are selected from the group consisting of oligoethers, substituted oligoethers, nitrile groups, sulfones, thiols, polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, other polar groups, and combinations thereof.

9. The polymer of claim 1 wherein the softening temperature is no less than 190° C.