Patent Application: US-201615065291-A

Abstract:
provided herein is a class of copolymers , including triblock brush copolymers having specific block configurations , for example , abc triblock brush copolymers and aba triblock brush copolymers . in an embodiment , for example , copolymers of the invention incorporate various polymer side chain groups which contribute beneficial physical , chemical , or electronic properties such as increased mechanical or elastic strength , improved ionic or electric conductivity . in some embodiments , the provided copolymers exhibit advantageous steric properties allowing for rapid self - assembly into a variety of morphologies that are substantially different than non - brush , block copolymers .

Description:
in general , the terms and phrases used herein have their art - recognized meaning , which can be found by reference to standard texts , journal references and contexts known to those skilled in the art . the invention is further detailed in the following examples , which are offered by way of illustration and are not intended to limit the scope of the invention in any manner . the present example provides description and experimental results supporting the following aspects of the present invention : synthesis of fully grafted aba brush triblock copolymers . brush architectures conferring important advantages and opening opportunities for the design of polymer electrolyte membranes with high conductivity . the provided bbcps have polynorbornene backbones fully grafted with ps and peo side chains ( fig1 ). different architectures have been synthesized , including ab brush diblock copolymers and aba brush triblock copolymers ( gps - gpeo - gps , 6 ). a denotes ps side chains and b denotes peo side chains . a . are grafted in all blocks , not only the peo block ; the precision in the bbcp structure is enabled by the synthetic strategy . the bbcps are synthesized by grafting - through ring - opening metathesis polymerization ( romp ) ( fig2 ). romp affords excellent control over molecular weight ( mw ) and extremely low mw - dispersity . the synthesis , self - assembly , conductivity , and rheological properties of aba triblock brush polymers ( bbcps ) with grafted polystyrene ( a block , n ps = 21 ) and poly ( ethylene oxide ) ( b block , n peo = 45 ) side - chains is described . all bbcps reported herein feature 1 ) 100 % grafting density for all blocks , 2 ) controlled polynorbornene backbone and ps / peo side - chain molecular weights , and 3 ) low molecular weight dispersities ( 0 ) for all components . full bbcp synthetic details are provided in the supporting information . briefly , polystyrene macromonomer ( m n ≈ 2500 g / mol , n ps = 21 ) was synthesized using atom transfer radical polymerization with subsequent end - group functionalization to install a single norbornene moiety ( schemes s1 - s5 ). 17 commercially - available mono - methoxy peo ( m n ≈ 2000 g / mol , n peo = 45 ) was end - functionalized with norbornene via edc coupling ( schemes s6 - s7 ). macromonomer size exclusion chromatograms are provided in fig4 and characterization data are summarized in table s1 . sequential romp ( scheme s8 ) produced two aba bbcps with measured norbornene backbone degrees of polymerization n a : n b : n a = 11 : 78 : 11 ( gps 11 - gpeo 78 - gps 11 ) and n a : n b : n a = 15 : 119 : 15 ( gps 15 - gpeo 119 - gps 15 ). bbcp molecular weight data are summarized in fig5 - 9 and tables s2 - s4 . the volume fractions φ peo of gps 11 - gpeo 78 - gps 11 and gps 15 - gpeo 119 - gps 15 are approximately 0 . 75 and 0 . 77 , respectively , using literature - reported densities for ps and peo . 18 additionally , gpeo brush homopolymers were synthesized ( fig1 , table s5 ) to directly compare with the two bbcps . azimuthally integrated one - dimensional synchrotron small angle x - ray scattering ( saxs ) data of gps 11 - gpeo 78 - gps 11 and gps 15 - gpeo 119 - gps 15 annealed at 120 ° c . are presented in fig1 and summarized in tables s6 - s7 . both neat bbcps exhibit bragg reflections at approximate peak positions q *, 3 1 / 2 q *, and 7 1 / 2 q *, consistent with hexagonal cylinders ( hex ) of the minority gps block . additionally , the two - dimensional pattern for gps 15 - gpeo 119 - gps 15 clearly shows six - fold symmetry fig1 , thus reinforcing the hex assignment . lithium blends between 10 : 1 - 20 : 1 [ eo ]:[ li + ] ( gps 11 - gpeo 78 - gps 11 ) and 5 : 1 - 20 : 1 [ eo ]:[ li + ] ( gps 15 - gpeo 119 - gps 15 ) are also consistent with the hex morphology , where the unlabeled arrows in fig1 mark bragg reflections 3 1 / 2 q * and 2q *. the domain spacing increases in samples doped with litfsi , presumably due to an increase in segregation strength derived from an increase in the block - block interaction parameterx χ . this effect appears to saturate at high ionic contents for gps 11 - gpeo 78 - gps 11 ( c . f . fig1 ( a ) , 15 : 1 and 10 : 1 blends ). the interplay between ionic content , segregation strength , χ , and domain spacing remains poorly understood , even for linear symmetric diblocks . 25 the absence of well - defined higher - order reflections for the remaining blends with high li + content precludes definitive morphological assignment based on scattering alone . these blends exhibit some order as evidenced by a relatively sharp primary peak . possible form factor scattering at high q is suggestive of a morphological change into disordered spheres , which may account for the relative increase in q * ( c . f . fig1 ( a ) , 10 : 1 vs . 5 : 1 and fig1 ( b ) , 5 : 1 vs . 2 : 1 ). frequency - dependent melt rheology data are reported in fig1 for gps 11 - gpeo 78 - gps 11 and fig1 for gps 15 - gpeo 119 - gps 15 . the storage modulus ( g ) is on the order of 10 4 pa between 0 . 01 and 100 rad / sec at temperatures 45 - 105 ° c . and is always larger than the loss modulus ( g ′) ( tan δ & lt ; 1 ). both bbcps are thus viscoelastic solids , albeit considerably softer than linear ps - peo with 38 vol % peo ( g ′= 10 7 pa at 90 ° c ). 5 a van gurp - palmen plot 36 of the loss tangent versus the magnitude of the complex modulus reveals time - temperature superposition fails with these materials in the temperature range of interest ( fig1 ) and the data reported in fig1 are therefore un - shifted . we anticipate based on linear ps - peo literature s that li + doped samples will be marginally more elastic , perhaps an order of magnitude , but the relative softness is likely an intrinsic limitation of the brush architecture . 21 , 37 combining the bbcp architecture with techniques such as polymerization - induced phase separation 2 - 3 may provide a route towards stiffer materials with similar conductivity profiles . the synthesis , self - assembly , conductivity , and mechanical properties of densely - grafted aba triblock brush polymers containing grafted polystyrene ( a block , n ps = 21 ) and poly ( ethylene oxide ) ( b block , n peo = 45 ) side chains are reported . 1 . hallinan , d . t . ; 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lohse , d . j . ; richter , d . ; witten , t . a . ; zirkel , a ., connection between polymer molecular weight , density , chain dimensions , and melt viscoelastic properties . macromolecules 1994 , 27 ( 17 ), 4639 - 47 . 19 . young , w .- s . ; albert , j . n . l . ; schantz , a . b . ; epps , t . h ., mixed - salt effects on the ionic conductivity of lithium - doped peo - containing block copolymers . macromolecules 2011 , 44 ( 20 ), 8116 - 8123 . 20 . cowie , j . m . g . ; sadaghianizadeh , k ., effect of side chain length and crosslinking on the ac conductivity of oligo ( ethyleneoxide ) comb - branch polymer - salt mixtures . solid state ionics 1990 , 42 ( 3 - 4 ), 243 - 249 . 21 . zhang , y . ; costantini , n . ; mierzwa , m . ; pakula , t . ; neugebauer , d . ; matyjaszewski , k ., super soft elastomers as ionic conductors . polymer 2004 , 45 ( 18 ), 6333 - 6339 . 22 . lascaud , s . ; perrier , m . ; vallee , a . ; besner , s . ; prud &# 39 ; homme , j . ; armand , m ., phase diagrams and conductivity behavior of poly ( ethylene oxide )- molten salt rubbery electrolytes . macromolecules 1994 , 27 ( 25 ), 7469 - 7477 . 23 . heimenz , p . c ., lodge , t . p ., polymer chemistry , 2nd ed . crc press : boca raton , pi , 2007 . 24 . zhao , c . ; wu , d . ; huang , n . ; zhao , h ., crystallization and thermal properties of plla comb polymer . journal of polymer science part b : polymer physics 2008 , 46 ( 6 ), 589 - 598 . 25 . teran , a . a . ; balsara , n . p ., thermodynamics of block copolymers with and without salt . the journal of physical chemistry b 2014 , 118 ( 1 ), 4 - 17 . 26 . meyer , w . h ., polymer electrolytes for lithium - ion batteries . advanced materials 1998 , 10 ( 6 ), 439 - 448 . 27 . panday , a . ; mullin , s . ; gomez , e . d . ; wanakule , n . ; chen , v . l . ; hexemer , a . ; pople , j . ; balsara , n . p ., effect of molecular weight and salt concentration on conductivity of block copolymer electrolytes . macromolecules 2009 , 42 ( 13 ), 4632 - 4637 . 28 . hu , m . ; xia , y . ; mckenna , g . b . ; kornfield , j . a . ; grubbs , r . h ., linear rheological response of a series of densely branched brush polymers . macromolecules 2011 , 44 , 6935 - 6943 . 29 . gomez , e . d . ; panday , a . ; feng , e . h . ; chen , v . ; stone , g . m . ; minor , a . m . ; kisielowski , c . ; downing , k . h . ; borodin , 0 . ; smith , g . d . ; balsara , n . p ., effect of ion distribution on conductivity of block copolymer electrolytes . nano letters 2009 , 9 ( 3 ), 1212 - 1216 . 30 . ganesan , v . ; pyramitsyn , v . ; bertoni , c . ; shah , m ., mechanisms underlying ion transport in lamellar block copolymer membranes . acs macro letters 2012 , 1 ( 4 ), 513 - 518 . 31 . hou , w .- h . ; chen , c .- y . ; wang , c .- c . ; huang , y .- h ., the effect of different lithium salts on conductivity of comb - like polymer electrolyte with chelating functional group . electrochimica acta 2003 , 48 ( 6 ), 679 - 690 . 32 . chintapalli , m . ; chen , x . c . ; thelen , j . l . ; teran , a . a . ; wang , x . ; garetz , b . a . ; balsara , n . p ., effect of grain size on the ionic conductivity of a block copolymer electrolyte . macromolecules 2014 , 47 ( 15 ), 5424 - 5431 . 33 . hong , s . w . ; gu , w . ; huh , j . ; sveinbjornsson , b . r . ; jeong , g . ; grubbs , r . h . ; russell , t . p ., on the self - assembly of brush block copolymers in thin films . acs nano 2013 , 7 ( 11 ), 9684 - 9692 . 34 . yuan , r . ; teran , a . a . ; gurevitch , i . ; mullin , s . a . ; wanakule , n . s . ; balsara , n . p ., ionic conductivity of low molecular weight block copolymer electrolytes . macromolecules 2013 , 46 ( 3 ), 914 - 921 . 35 . teran , a . a . ; mullin , s . a . ; hallinan , d . t . ; balsara , n . p ., discontinuous changes in ionic conductivity of a block copolymer electrolyte through an order — disorder transition . acs macro letters 2012 , 1 ( 2 ), 305 - 309 . 36 . van gurp , m ., palmen , j ., time - temperature superposition for polymer blends . rheol . bull . 1998 , 67 , 5 - 8 . 37 . pakula , t . ; zhang , y . ; matyjaszewski , k . ; lee , h .- i . ; boerner , h . ; qin , s . ; berry , g . c ., molecular brushes as super - soft elastomers . polymer 2006 , 47 ( 20 ), 7198 - 7206 . supporting information : aba triblock brush polymers : synthesis , self - assembly , conductivity , and rheological properties all reagents were used as received unless otherwise noted . carbic anhydride was purchased from acros organics . propargylamine , copper ( i ) bromide , 1 - ethyl - 3 -( 3 - dimethylaminopropyl ) carbodiimide ( edc ), methyl α - bromoisobutyrate , n , n , n ′, n ′, n ″- pentamethyldiethylenetriamine ( pmdeta ), sodium azide , triethylamine , 6 - aminohexanoic acid , 4 - dimethylaminopyridine , poly ( ethylene glycol ) methyl ether ( mn = 2000 g / mol ), and pyridine were purchased from sigma aldrich . grubbs &# 39 ; second generation catalyst [( h2imes )( pcy3 )( cl ) 2ru ═ chph ] was generously supplied by materia . cdcl3 and c6d6 were purchased from cambridge isotopes labs . toluene , benzene , dichloromethane ( dcm ), dimethylformamide ( dmf ), methanol , tetrahydrofuran ( thf ), pentane , sodium sulfate , and magnesium sulfate were purchased from vwr . a 500 ml round bottom flask was half filled with commercially available norbornene endo - anhydride ( carbic anhydride ), fitted with a reflux condenser , and heated neat at 180 ° c . for 16 hours . the resulting molten yellow solid was slowly cooled to 75 ° c . and benzene was added before the entire volume crystallized to facilitate dissolution . the resulting mixture was heated to reflux and crystallized at room temperature . the recrystallization in benzene was repeated three additional times to yield a white or slightly off - white crystalline solid ( ca . 30 g isolated mass ). 1 h nmr ( cdcl3 ) δ ( ppm ): 6 . 31 ( 2h , t ), 3 . 43 ( 2h , s ), 2 . 99 ( 2h , s ), 1 . 65 ( 1 h , m ), 1 . 42 ( 1 h , m ). norbornene exo - anhydride ( 1 ) ( 1 . 0 eq ., 62 . 59 g , 381 . 2 mmol ), propargylamine ( 1 . 0 eq ., 21 . 00 g , 381 . 2 mmol ), triethylamine ( 0 . 1 eq ., 3 . 86 g , 38 . 1 mmol ) and toluene ( 300 ml ) were mixed in a round bottom flask equipped with a dean - stark trap . the mixture was heated to reflux for 15 hours . the resulting orange solution was cooled to room temperature , and the toluene was removed in vacuo . the crude solid was recrystallized in ethanol to yield light brown , plate - like crystals ( 56 . 25 g ). 1 h nmr ( cdcl 3 ) δ ( ppm ): 6 . 28 ( 2h , m ), 4 . 20 ( 2h , d ), 3 . 30 ( 2h , m ), 2 . 70 ( 2h , d ), 2 . 17 ( 1h , t ), 1 . 50 ( 1 h , d ), 1 . 25 ( 1 h , d ). styrene monomer ( 500 ml ) was stirred with basic alumina for 30 min and filtered to yield a clear liquid . styrene ( 50 . 0 eq ., 350 ml , 3 . 054 mol ) was added to a 500 ml schlenk flask equipped with a stir bar and septum . the flask was charged with ligand n , n , n ′, n ′, n ″- pentamethyldiethylenetriamine ( 0 . 3 eq ., 3 . 83 ml , 0 . 018 mol ) and subsequently freeze - pump - thawed three times to remove oxygen . the flask was frozen in liquid nitrogen , placed under an active flow of argon ( while still frozen ), and cu l br ( 0 . 3 eq ., 2 . 63 g , 0 . 018 mol ) was quickly added upon removal of the septum . the septum was re - attached , the argon flow stopped , and the flask was evacuated . ( caution : argon condenses at liquid nitrogen temperatures and can cause an explosion upon expansion when thawed .) three additional pump / purge ( argon / vacuum ) cycles were performed and the flask was left under dynamic vacuum for at least 5 min . the flask was thawed in warm water and placed under argon . most , but not all , of the copper dissolved to yield a green solution . ( a blue color indicates oxygen contamination ; a yellow color indicates insufficient copper dissolution — both result in a failed polymerization .) in a separate flask , methyl α - bromoisobutyrate was freeze - pump - thawed three times . methyl α - bromoisobutyrate ( 1 . 0 eq ., 7 . 90 ml , 0 . 061 mol ) was injected into the schlenk flask containing styrene and the mixture was heated in an oil bath pre - set to 100 ° c . aliquots were collected every ca . 30 min under a dynamic flow of argon . conversion was monitored by 1 h nmr . the polymerization was quenched in liquid nitrogen after 2 hr 35 min at approximately 38 % conversion . the viscous solution was warmed to room temperature , diluted with tetrahydrofuran ( 100 ml ), filtered through basic alumina to remove copper , and precipitated into methanol at − 78 ° c . the polymer was redissolved in thf and reprecipitated five more times into methanol at − 78 ° c . and dried in vacuo to yield a white powder . polystyrene ( 3 ) ( 1 . 0 eq ., 73 g , 37 . 0 mmol ), sodium azide ( 3 . 0 eq ., 7 . 12 g , 109 . 5 mmol ), and dimethylformamide ( 350 ml ) were mixed in a round bottom flask equipped with a stir bar and reflux condenser . the mixture was heated at 65 ° c . for 16 hr and then cooled to room temperature . the product was precipitated into methanol at − 78 ° c ., redissolved in thf , and the precipitation procedure was repeated 4 additional times . quantitative conversion of the end group was observed by 1h nmr ( cdcl3 ) δ ( ppm ): ps - br 4 . 6 - 5 . 0 ppm , ps - n3 3 . 75 - 4 . 25 . polystyrene - azide ( 4 ) ( 1 . 0 eq ., 64 . 30 g , 30 . 6 mmol ), norbornene propargyl imide ( 2 ) ( 1 . 5 eq ., 9 . 24 g , 45 . 9 mmol ), and cu l br ( 0 . 4 eq ., 1 . 76 g , 12 . 3 mmol ) were added to a 500 ml three - neck round bottom flask equipped with a stir bar , reflux condenser , and two septa . the flask was pump / purged with argon three times and placed under argon . dry tetrahydrofuran ( 180 ml ) was added via syringe , followed by n , n , n ′, n ′, n ″- pentamethyldiethylenetriamine ( 0 . 4 eq ., 2 . 56 ml , 12 . 3 mmol ), upon which the solution turned light green and clear . the flask was heated at 50 ° c . for 16 hr and cooled to room temperature . the solution was diluted with tetrahydrofuran ( 100 ml ), filtered through basic alumina to remove the copper , and precipitated into methanol at − 78 ° c . the precipitation was repeated 5 additional times to yield a white powder . quantitative conversion of the end group was observed by 1 h nmr ( cdcl3 ) δ ( ppm ): ps - n3 3 . 75 - 4 . 25 , ps - norbornene 4 . 89 - 5 . 05 . norbornene exo - anhydride ( 1 ) ( 1 . 0 eq ., 8 g , 48 . 7 mmol ), 6 - aminohexanoic acid ( 1 . 0 eq ., 6 . 39 g , 48 . 7 mmol ), triethylamine ( 0 . 1 eq ., 0 . 679 ml , 4 . 87 mmol ), and toluene ( 51 ml ) were added to a round bottom flask equipped with a stir bar and reflux condenser . the mixture was heated at 110 ° c . for 19 hr , cooled to room temperature , and the solvent was removed in vacuo . the remaining solid was redissolved in dichloromethane , washed with water ( x3 ), washed with brine ( x3 ), and dried with magnesium sulfate . the solvent was removed in vacuo to yield a white or slightly off white solid . 1h nmr ( cdcl3 ) δ ( ppm ): 6 . 28 ( 2h , m ), 3 . 46 ( 2h , t ), 3 . 27 ( 2h , m ), 2 . 35 ( 2h , t ), 1 . 72 - 1 . 18 ( 10h , m ). norbornene carboxylic acid imide ( 6 ) ( 1 . 2 eq ., 19 . 742 g , 71 . 2 mmol ), polyethylene glycol ) methyl ether ( mn = 2000 g / mol , 1 . 0 eq ., 118 . 641 g , 59 . 3 mmol ), 1 - ethyl - 3 -( 3 - dimethylaminopropyl ) carbodiimide ( 1 . 6 eq ., 18 . 244 g , 117 . 5 mmol ), 4 - dimethylaminopyridine ( 0 . 1 eq ., 0 . 725 g , 5 . 9 mmol ), and dichloromethane ( 790 ml ) were mixed in a 1 l round bottom flask equipped with a stir bar . the reaction was stirred for 24 hr and about half of the dichloromethane was removed in vacuo . the mixture was washed with 1 m hcl (× 3 ), brine (× 1 ), and dried with sodium sulfate . most of the solvent was removed in vacuo and the remaining solution was precipitated into diethyl ether at − 78 ° c . the off - white solid was filtered and dried in vacuo to yield 123 . 3 g ( 93 %) of isolated material . in a glove box , three separate vials were prepared containing solutions of macromonomers in dry dichloromethane . vial a1 : ps macromonomer ( 10 . 0 eq ., 0 . 635 g ), dcm ( 4 . 27 ml ); vial b : peo macromonomer ( 80 . 0 eq ., 4 . 554 g ), dcm ( 40 ml ); vial a2 : ps macromonomer ( 10 . 0 eq ., 0 . 635 g ), dcm ( 5 ml ). a fourth vial was prepared . with the ruthenium catalyst ( 31 . 1 mg , 0 . 025 mmol ) in 1 . 244 ml dcm . the polymerization was initiated by injecting 0 . 726 ml of the catalyst solution into vial al . after 40 minutes , a small aliquot was extracted , quenched with ethyl vinyl ether , and vial b was quickly added in full to vial a1 . after 100 min , a small aliquot was extracted , quenched with ethyl vinyl ether , and vial a2 was added in full to vial al . after 120 min , vial al was removed from the glove box , rapidly stirred , and quenched with 5 ml of ethyl vinyl ether . the aba triblock brush polymer was precipitated into diethyl ether ( 600 ml ) at − 78 ° c ., filtered , and dried in vacuo to yield an off white powder . sec data were collected using two mz - gel sdplus 300 × 8 . 0 mm columns with 10 μm beads , an agilent 1100 series autosampler and pump , and a wyatt viscostar viscometer , optilab rex differential refractive index detector , and three - angle minidawn treos light scattering detector . on - line determination of do / dc assumed 100 % mass elution under the peak of interest . the mobile phase was thf with 1 vol % triethylamine , which eliminated artificial dragging effects in pure thf ( presumably arising from peo / column interactions ). the high molecular weight shoulder in the light scattering sec signal ( fig7 - 8 ) is exacerbated at high peo nb values ( data not shown ). we have evidence that this shoulder is related to an impurity in the commercially available ( sigma aldrich ) mono - functional 2000 g / mol peo . since the ls signal - m * c ( where m is molecular weight and c is polymer concentration ) while the drl signal ˜ c , the concentration of species giving rise to the shoulder for gps11 - gpe078 - gps11 and gps15 - gpeo119 - gps15 is relatively small at this n . the orders of magnitude price difference between small quantities of extensively purified peo ( e . g . from jenkem ) and large quantities of readily available peo may warrant using the latter if a process is capable of tolerating the behavior observed in fig7 - 8 . saxs data were collected at argonne national laboratory aps beamline 12 - id - b on the same blend samples that were subjected to dsc analysis ( i . e ., all samples were prepared in a dry room and hermetically sealed to avoid moisture contamination ). the neat bbcp samples were fabricated as follows : 1 ) bbcp powder ( ca . 20 mg ) was placed between two sheets of kapton film , 2 ) the kapton film was sandwiched between thick glass slides , 3 ) the glass slides were compressed with medium - sized binder clips , 4 ) the films were annealed under vacuum at 120 ° c . for 2 hrs and subsequently slowly cooled to room temperature under vacuum . the neat bbcp samples clearly flowed during annealing and produced a transparent and slightly light brown film . the kapton film was cut with scissors to yield approximate dimensions 2 × 15 × 0 . 07 mm ( height × width × thickness ). saxs data were collected parallel to the kapton film plane through the sample dimension approximately 2 mm thick . all sample preparation was performed in a dry room ( dew point & lt ;− 45 ° c .) to prevent water contamination . the linear peo homopolymer ( 300 kda ) utilized in normalized conductivity experiments was purchased from sigma aldrich and dried in vacuo at 100 ° c . before use . gpeo homopolymer was dried in vacuo at room temperature before use . the following coin cell parts were purchased from pred materials ( part # cr2032 ): coin cell kit ( al - clad case , cap , and gasket ), coin cell wave spring ( 15 . 0 mm diameter , 1 . 4 mm height ), and coin cell spacer disk ( 16 . 0 mm diameter , 1 . 0 mm thickness ). a princeton applied research / ametek versastat mc was used for ac impedance measurements . potentiostatic ac impedance spectra were obtained between 1 mhz and 100 mhz using a 10 mv rms ac signal . bulk ionic conductivity ( a ) was calculated according to the equation σ = l /( ar ), where r is the impedance value corresponding to the high frequency plateau of the bode re ( z ) plot , l is the thickness of the sample and a is the surface area of the polymer electrolyte ( taken as the surface area of the disk upon which it was cast , or as 71 . 48 mm2 for gpeo homopolymers ). variable temperature experiments were performed using a tenney tujr thermal test chamber , allowing at least 30 minutes for sample equilibration at each temperature before measurement . polymer and litfsi were dissolved in cyclopentanone ( 4 : 1 wt ratio solvent : polymer ), stirred for ca . 1 . 5 hr , and drop cast onto 1 mm thick circular stainless steel discs ( area = 1 . 86 cm2 ). most of the cyclopentanone was slowly evaporated in a fume hood over the course of 18 hr , which yielded relatively smooth and mostly homogenous films . the samples were placed in a vacuum oven , heated at 120 ° c . for 21 hr , and slowly cooled to room temperature under vacuum . separate 1h nmr experiments ( data not shown ) confirmed this sample preparation is sufficient to remove all traces of cyclopentanone within the resolution limits of the analytical technique . the gpeo samples were surrounded by a teflon shell ( inner punched diameter : ⅜ ″, outer diameter : ⅝ ″, thickness 0 . 15 mm ) to prevent cell shorting during annealing . a second stainless steel spacer was placed on top of the polymer film and the sandwich was pressed into a coin cell using a coin cell wave spring to ensure good electrical contact . the coin cells were annealed under vacuum at 120 ° c . for 2 hours , cooled to room temperature under vacuum , and then studied by ac impedance spectroscopy . film thicknesses used in the conductivity calculations were determined after conductivity experiments by removing the spacer + polymer + spacer sandwich from the coin cell , measuring the stack thickness using calipers , and calculating the polymer thickness by difference ( typical polymer thickness values were 50 - 150 μm ). most bbcp polymer films were within 10 - 20 % of their initial ( pre - conductivity experiment ) thickness . the thickness of the peo homopolymer films shrank significantly due to their rubbery physical state ( t & gt ;& gt ; tg ). the final thickness of the gpeo samples was 0 . 15 mm as expected from the teflon shell thickness . rheology data were collected on a rheometric scientific ares - m using 25 mm diameter parallel plates under constant flow of nitrogen gas . bulk bbcp was heated under compression in a 1 mm thick circular mold ( 25 mm diameter ) under vacuum for ca . 16 hr . the sample was loaded into the rheometer , heated to 125 ° c ., and the gap was reduced to ca . 0 . 75 mm . the sample was equilibrated for 1 hr and subsequently cooled to 50 ° c . under a dynamic n2 purge to visually ensure uniform coverage between the plates . any polymer overflowing from the edges was removed and the sample was again heated to 125 ° c . each temperature was equilibrated for at least 1 . 5 hr before data collection began . strain sweeps were performed at each temperature after equilibration to ensure linear viscoelastic response ( g ′ and g ″ independent of applied strain ). frequency sweep data for temperatures 45 - 125 ° c . were collected on cooling ; temperatures 145 - 185 ° c . were collected on heating . frequency was scanned in the range 0 . 01 - 100 rad / sec at each temperature . compared to ab diblock copolymers , abc triblock terpolymers vastly expand the parameter space for block copolymer self - assembly . whereas eight equilibrium morphologies are known for linear ab diblock copolymers , over thirty morphologies have been identified for linear abc triblock terpolymers ( fig1 ). 1 - 2 although the self - assembly of linear abc triblock terpolymers has been studied by both experiment and theory , the self - assembly of brush abc triblocks is relatively unexplored . our work has closed this gap . it represents the first systematic study of abc brush triblock terpolymer synthesis and self - assembly . we synthesized a series of abc triblock terpolymers having grafted polylactide ( pla ), polystyrene ( ps ), and poly ( ethylene oxide ) ( peo ) side chains of similar molecular weights ( m n = 2 . 62 , 2 . 65 , 2 . 27 kg / mol , respectively ) ( fig1 ). these abc triblocks were synthesized by the grafting - through ring - opening metathesis polymerization ( romp ) of norbornene - functionalized macromonomers ( fig1 ). as described in earlier documents related to our patent strategy , these brush block copolymers ( bbcps ) are unique compared to previously reported graft polymers . the bbcps have the following advantages our system incorporates blocks with advantageous physical and chemical properties : ( i ) chemically etchable , biorenewable pla ; ( ii ) thermoplastic ps ; and ( iii ) water - soluble , biocompatible peo . other polymers with desired physical or chemical properties can be incorporated in the abc architecture , creating new platforms for polymer materials . the structure can be varied in many ways . there are two approaches to introducing asymmetry : ( 1 ) varying the backbone degrees of polymerization ( a , b , c ) and ( 2 ) varying side chain degrees of polymerization ( x , y , z ). both approaches to introducing asymmetry vary the effective volume fractions of blocks , and therefore potentially affect the self - assembly and properties of the triblocks . romp enables independent variation of all structural parameters as synthesis of abc bottlebrush polymers by other strategies is challenging . there are three general approaches to synthesizing bottlebrush polymers : grafting to , grafting from , and grafting through ( fig1 ). grafting - to and grafting - from approaches to synthesizing brush block copolymers typically result in incomplete grafting of the backbone and / or broad distributions in the lengths of side chains . in addition , they often involve complicated protection / deprotection steps . for these reasons , the grafting - to and grafting - from approaches are not synthetically tractable for generating a library of polymers for systematic study of abc brush triblock self - assembly . the rzayev group recently reported a system of interest . rzayev and coworkers synthesized an abc brush triblock terpolymer by grafting from a poly ( methyl methacrylate ) backbone . 3 the side chains were polystyrene ( ps ), poly ( methyl methacrylate ) ( pmma ), and polylactide ( pla ). because the synthesis required multiple grafting from steps from a pre - formed backbone , only one composition was synthesized and characterized . size - exclusion chromatography ( sec ) indicated a broad distribution of molecular weights , and small - angle x - ray scattering ( saxs ) of a thermally annealed sample suggested minimal long - range order . the ps - pmma - pla triblock self - assembles to two - phase lamellae with domain spacing 79 nm . using romp , we were able to synthesize many abc brush triblock terpolymers rapidly and with excellent control over the polymer architecture . fig2 shows & gt ; 100 abc triblocks we were able to synthesize in under 1 week . the samples spanned various variations in backbone degree of polymerization and side chain molecular weight . this blank ternary diagram shows that the samples cover the entire composition space . the polymers were thermally annealed at 140 ° c . and characterized by synchrotron - source saxs . fig2 provides an example of an abc brush triblock that self - assembles to well - ordered lamellae . sharp diffraction peaks present at relative positions q / q 0 = 1 , 2 , 3 , 4 , 5 , 6 are consistent with lamellar symmetry . the lowest - order reflection at q 0 = 0 . 020 å indicates that the lamellar period is 31 . 4 nm . saxs analysis for all synthesized samples enables assignments for the self - assembled morphologies . in this way , we developed a comprehensive understanding of abc brush triblock copolymer self - assembly . compare fig2 and 22 . the structures that can be unambiguously assigned by saxs appear in color in fig2 . there is a large region of lamellar ( lam , green ) morphologies , a narrow band of stable hexagonally packed cylinder structures ( hex , blue ), and at low midblock content , a disordered region . the different shapes represent different variations in side chain asymmetry . real - space observation by transmission electron microscopy ( tem ) complements structural assignments by saxs . for the abc brush triblock that afforded the scattering pattern in fig2 . tem ( fig2 ) shows three - phase contrast ( dark - medium - dark - light ). remarkably , the observed domain connectivity for these materials is not consistent with widely accepted knowledge in the field of block copolymer self - assembly . 1 . zheng , w . ; wang , z .- g . morphology of abc triblock copolymers . macromolecules 1995 , 28 , 7215 - 7223 . 2 . bates , f . s . ; fredrickson , g . h . block copolymers — designer soft materials . phys . today 1999 , 52 , 32 - 38 . 3 . rzayev , j . synthesis of polystyrene — polylactide bottlebrush block copolymers and their melt self - assembly into large domain nanostructures . macromolecules 2009 , 42 , 2135 - 2141 . all references cited throughout this application , for example patent documents including issued or granted patents or equivalents ; patent application publications ; and non - patent literature documents or other source material ; are hereby incorporated by reference herein in their entireties , as though individually incorporated by reference , to the extent each reference is at least partially not inconsistent with the disclosure in this application ( for example , a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference ). the terms and expressions which have been employed herein are used as terms of description and not of limitation , and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof , but it is recognized that various modifications are possible within the scope of the invention claimed . thus , it should be understood that although the present invention has been specifically disclosed by preferred embodiments , exemplary embodiments and optional features , modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art , and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims . the specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices , device components , methods steps set forth in the present description . as will be obvious to one of skill in the art , methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps . when a group of substituents is disclosed herein , it is understood that all individual members of that group and all subgroups are disclosed separately . when a markush group or other grouping is used herein , all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure . additionally , unless otherwise specified , all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure . for example , it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium . isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use . methods for making such isotopic variants are known in the art . specific names of compounds are intended to be exemplary , as it is known that one of ordinary skill in the art can name the same compounds differently . it must be noted that as used herein and in the appended claims , the singular forms “ a ”, “ an ”, and “ the ” include plural reference unless the context clearly dictates otherwise . thus , for example , reference to “ a cell ” includes a plurality of such cells and equivalents thereof known to those skilled in the art , and so forth . as well , the terms “ a ” ( or “ an ”), “ one or more ” and “ at least one ” can be used interchangeably herein . it is also to be noted that the terms “ comprising ”, “ including ”, and “ having ” can be used interchangeably . the expression “ of any of claims xx - yy ” ( wherein xx and yy refer to claim numbers ) is intended to provide a multiple dependent claim in the alternative form , and in some embodiments is interchangeable with the expression “ as in any one of claims xx - yy .” unless defined otherwise , all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs . although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention , the preferred methods and materials are now described . nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention . whenever a range is given in the specification , for example , a temperature range , a time range , or a composition or concentration range , all intermediate ranges and subranges , as well as all individual values included in the ranges given are intended to be included in the disclosure . as used herein , ranges specifically include the values provided as endpoint values of the range . for example , a range of 1 to 100 specifically includes the end point values of 1 and 100 . it will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein . as used herein , “ comprising ” is synonymous with “ including ,” “ containing ,” or “ characterized by ,” and is inclusive or open - ended and does not exclude additional , unrecited elements or method steps . as used herein , “ consisting of ” excludes any element , step , or ingredient not specified in the claim element . as used herein , “ consisting essentially of ” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim . in each instance herein any of the terms “ comprising ”, “ consisting essentially of ” and “ consisting of ” may be replaced with either of the other two terms . one of ordinary skill in the art will appreciate that starting materials , biological materials , reagents , synthetic methods , purification methods , analytical methods , assay methods , and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation . all art - known functional equivalents , of any such materials and methods are intended to be included in this invention . the terms and expressions which have been employed are used as terms of description and not of limitation , and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof , but it is recognized that various modifications are possible within the scope of the invention claimed . thus , it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features , modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art , and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims .