WO2011072304A2 - Norbornene-type polymers having quaternary ammonium functionality - Google Patents

Norbornene-type polymers having quaternary ammonium functionality Download PDF

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WO2011072304A2
WO2011072304A2 PCT/US2010/060144 US2010060144W WO2011072304A2 WO 2011072304 A2 WO2011072304 A2 WO 2011072304A2 US 2010060144 W US2010060144 W US 2010060144W WO 2011072304 A2 WO2011072304 A2 WO 2011072304A2
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alkyl
norbornene
polymer
formula
type
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PCT/US2010/060144
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French (fr)
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WO2011072304A3 (en
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Andrew Bell
Edmund Elce
Keitaro Seto
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Promerus Llc
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Priority to EP10822860A priority Critical patent/EP2510036A2/de
Priority to CN201080055973.5A priority patent/CN102695741B/zh
Priority to KR1020127018059A priority patent/KR20120123663A/ko
Priority to JP2012543335A priority patent/JP5964236B2/ja
Publication of WO2011072304A2 publication Critical patent/WO2011072304A2/en
Publication of WO2011072304A3 publication Critical patent/WO2011072304A3/en

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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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    • C08G2261/51—Charge transport
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Definitions

  • Embodiments of the present disclosure relate generally to norbornene-type polymers having quaternary ammonium functionality and more specifically to norbornene-type vinyl addition and ROMP polymers useful for forming hydroxide-ion conducting alkali anion-exchange membranes (AAEMs) and alkali fuel cells (AFCs) encompassing a first electrode, an AAEM and a second electrode, where each electrode's active layer is in contact with the AAEM.
  • AAEMs hydroxide-ion conducting alkali anion-exchange membranes
  • AFCs alkali fuel cells
  • Alkaline fuel cells are one of the most developed technologies and have been used since the mid-1960s by NASA in the Apollo and Space Shuttle programs.
  • the fuel cells on board these spacecraft provided electrical power for onboard systems, as well as drinking water and were selected because they are among the most efficient in generating electricity having an efficiency reaching almost 70%.
  • the NASA AFCs used an aqueous electrolyte, specifically a solution of potassium hydroxide (KOH) retained in a porous stabilized matrix.
  • the charge carrier for an AFC is the hydroxyl ion (OH " ) that migrates from the cathode to the anode where they react with hydrogen to produce water and electrons. The water formed at the anode migrates back to the cathode to regenerate hydroxyl ions. The entire set of reactions is then:
  • NASA AFCs were very sensitive to C0 2 that is likely to be present in the fuel used by the cell or environmentally. This sensitivity comes from even trace amounts of C0 2 , CO, H 2 0 and CH 4 reacting with the KOH electrolyte, poisoning it rapidly, and severely degrading the fuel cell performance by either the Attorney Docket No. PLY209-0003A dilution of the electrolyte or the formation of carbonates that reduce the electrolyte's pH and hence the kinetics of the electrochemical reactions at the level of the electrodes, impairing their performance. Therefore, such AFCs were limited to closed
  • AFCs are the cheapest fuel cells to manufacture as the catalyst that is required on the electrodes can be any of a number of different materials that are relatively inexpensive compared to the noble catalysts required for other types of fuel cells. Therefore, there has been considerable interest in solving their sensitivity to poisoning, in a manner other than providing pure or cleansed hydrogen and oxygen, and take advantage of the AFCs positive attributes such as operation at relatively low temperatures and high efficiency to provide a quick starting power source and high fuel efficiency, respectively.
  • AEMs anion exchange membranes
  • PEM or CEM proton or cation exchange membranes
  • there are no readily available anion exchange membranes that serve as a commercial standard for electrochemical applications such as DuPont's Nafion® PSFA (perfluorosulfonic acid) membranes do in the field of cation exchange membranes.
  • AEMs anionic fuel cells based on solid polymeric anion exchange membranes
  • AFCs alkaline- membrane DMFCs
  • metal-free anion exchange membranes operating at elevated pH potentially lowers or eliminates the need for noble metal based catalysts and improves the kinetics of the electrochemical reactions.
  • AAEMs polymeric alkali anion exchange membranes
  • AFC electrochemical cell without any added electrolyte
  • the localized pH within the ion- conducting channels of the membrane will be quite high.
  • an AFC does not require operating temperatures as high as what is required for fuel cells encompassing proton exchange membranes (PEMs) to achieve adequate reaction kinetics
  • AFCs can also benefit from operation at elevated temperatures as it is expected that such elevated temperatures can enhance hydroxyl transport and thus enhance fuel cell performance.
  • the combination of high pH and elevated temperature can lead to chemical attack on the quaternary ammonium groups, most commonly by either an E2 (Hofmann degradation) mechanism or by an SN2 substitution reaction.
  • the elimination reaction pathway can be avoided by using quaternary ammonium groups that do not have ⁇ - hydrogens, such as the benzyltrimethylammonium group.
  • the substitution pathway cannot be avoided so easily, and several approaches have been tried to reduce the susceptibility of the ammonium group to the substitution reaction.
  • Einsla et al. also explored the effect of hydration on cation stability by preparing solutions of the benzyltrimethylammonium cation in ammonium hydroxide to eliminate the presence of any sodium cations.
  • sealed solutions heated to 120°C showed more significant degradation in 48 hours than seen in the 29 day study.
  • Einsla et al. suggested that solvation of OH " anions was important for the stability of the head groups (ibid. p. 1 178 and Figure 5, p. 1179). Therefore it is believed likely that membrane conditions that lead to good solvation will provide greater stability of the cations than those that lead to poor solvation.
  • Coates II is directed to the use of Compound 1 :
  • some hydrogenated ROMP polymer embodiments of the present disclosure are hydroxide ion conducting polymers derived from two or more
  • m is from 0 to 3
  • Ri, R 2 , R 3 and R4 is the pendent group represented by Formula III (alternately referred to as QAS for quaternary ammonium salt) and the others are independently a hydrogen, a Cj to Cig alkyl, an aryl or an alkyl-aryl group.
  • m is as defined above and at least one of R5, Re, R 7 and R 8 is a substituted or unsubstituted maleimide-alkyl pendent group where the alkyl is a Ci to Ce alkyl or other cross-linkable groups such as NB-ether-NB (e.g.,
  • NB-Bu-NB, and NB-Hx-NB NB-aryl-NB (e.g., NBC 6 H 4 NB and NBCH 2 C 6 H 4 CH 2 NB), and the others are independently selected from a hydrogen, a Ci to C 12 alkyl, a terminally halogenated alkyl, an alkyl-aryl where the aryl portion is optionally halogenated or a methyl glycol ether such as -CH 2 -(OCH 2 CH 2 ) q -OMe where q is from 1 to 4.
  • NB-aryl-NB e.g., NBC 6 H 4 NB and NBCH 2 C 6 H 4 CH 2 NB
  • the others are independently selected from a hydrogen, a Ci to C 12 alkyl, a terminally halogenated alkyl, an alkyl-aryl where the aryl portion is optionally halogenated or a methyl glycol ether such as -CH 2 -(OCH 2 CH 2
  • R' is selected from -(CH 2 ) P -, where p is from 0 to 12; Ar is an optional aromatic group having one or more aromatic rings; R" is selected from - (CH 2 ) P - where p is from 0 to 12, or -(CH 2 ) s -0-(CH 2 ) t -, where s and t are
  • R a , Rb and Rc are independently from 1 to 6, and R" is coupled to the nitrogen of the quaternary Attorney Docket No. PLY209-0003A ammonium functional group by a covalent bond, each of R a , Rb and Rc are
  • each ROMP polymer derived from the above monomers there is a first type of norbornene-type repeating unit that
  • hydroxide ion conducting polymers derived from two or more norbornene-type monomers where a first such monomer is represented by Formula A and a second such monomer is represented by Formula B, both shown below:
  • m is from 0 to 3
  • at least one of R9, Rio, R11 and R12 is a functional group (FG) capable of quaternization, as discussed below, and the others are independently a hydrogen, a C i to C5 alkyl, an aryl or an alkyl-aryl group.
  • m is as defined above and at least one of R13, R14, R1 5 and Ri 6 is a substituted or unsubstituted maleimide-alkyl pendent group where the alkyl is a Ci to C4 alkyl or another cross-linkable group, as described above, and the others are independently selected from a hydrogen, a Ci to C) 2 alkyl, an alkyl-aryl or a methyl glycol ether such as -CH 2 -(OCH 2 CH 2 ) q -OMe where q is from 1 to 4.
  • Exemplary monomers in accordance with Formula I include, but are not limited to: Attorney Docket No. PLY209-0003 A
  • Both the ROMP and vinyl addition polymer embodiments of the present disclosure are formed having a weight average molecular weight (Mw) that is appropriate to their use.
  • Mw weight average molecular weight
  • a Mw from 5,000 to 500,000 is found appropriate for some embodiments, while for other embodiments other Mw ranges can be advantageous.
  • the polymer it is advantageous for the polymer to have a Mw from at Attorney Docket No. PLY209-0003A least 30,000, while in others from at least 60,000.
  • the upper range of the polymer's Mw is up to 400,000, while in others is up to 250,000. It will be understood that since an appropriate Mw is a function of the desired physical properties in the anionic polymer membrane formed therefrom, it is a design choice and thus any Mw within the ranges provided above is within the scope of the present disclosure.
  • ROMP polymer embodiments of the present disclosure can be formed directly from a monomer having an ammonium cation pendent group in accordance with Formula III, where a saturated polymer is desired, monomers in accordance with Formulae A and B can be contacted with a ring-opening metathesis polymerization (ROMP) initiator and the resultant unsaturated polymer hydrogenated to a saturated polymer.
  • ROMP ring-opening metathesis polymerization
  • This ring-opening metathesis polymerization can be accomplished in either in solution or as 100% reactive solids, that is to say as a mass polymerization with little or no solvents.
  • the following scheme exemplifies the hydrogenation of the ring-opened metathesized polymer (ROMP) followed by conversion of an aryl-alkyl halide pendent group to a quaternary ammonium salt (see the following reaction sequence of reactions 1 (polymerization), 2 (hydrogenation), 3 (quaternization), and 4 (chloride to hydroxide metathesis)).
  • the above vinyl addition plus post functionalization scheme of some embodiments of the current disclosure can provide for the inclusion of monomers present in an amount sufficient to address swelling in hot methanol, ion exchange capacity (IEC), polymer stability, and mechanical strength without decreasing hydroxide ion conductivity.
  • monomers present in an amount sufficient to address swelling in hot methanol, ion exchange capacity (IEC), polymer stability, and mechanical strength without decreasing hydroxide ion conductivity can incorporate a higher ratio of cross-linking repeating units where repeating units containing quaternary ammonium moieties are polyfunctional.
  • TDFG tetracyclododecene
  • olymerization scheme include, but are not limited to, the following:
  • the initial monomer can be, for exampleNBPhCH ⁇ (where X is selected from CI, Br, or I). That is to say that the functional group of that first type of monomer is an aryl-halogenated-alkyl.
  • This polymerization can be performed in solution employing a nickel initiator/catalyst Ni(Toluene)(C6Fs)2 or an in-situ generated nickel
  • Quatemization of these halogenated groups can be effected through appropriate contacting with trimethylamine (N(CH 3 ) 3 ) (e.g., immersing in a solution of 40-75% trimethylamine at room temperature for a time sufficient to result in the desired degree of amination). That is to say that the halogen of the pendent group is replaced by the quaternary ammonium function N + (CH 3 )3 and a halogen counter-ion which is replaced by a hydroxide ion.
  • monomers having a particular exo- or endo- configuration can be polymerized Attorney Docket No. PLY209-0003A to form repeating units that retain the original configuration, see the exemplary repeating units provided below. It should be understood that through the use of such configuration specific monomers, some physical and chemical properties of the resulting polymers can be altered from that which would be provided if the
  • the norbornene monomers useful for the preparation of the quaternary ammonium containing vinyl polymerized polynorbornenes can be generated, as exemplified below, by the (i) Diels-Alder reaction of cyclopentadiene and ⁇ , ⁇ -halogen olefins, those containing a terminal olefin and a terminal halogen, such as 4-chloro-l- butene , chloromethylstyrene, or 1 -(chloromethyl)-4-(2-propenyl)benzene; (ii) hydroarylation of norbornadiene in the presence of a palladium catalyst and haloarene (e.g.,l-(bromomethyl)-4-iodobenzene to yield NBPhCH 2 Br XXIV-a); and (iii) by reduction of norbornene carboxaldehydes, carboxylic acids, carboxylic acid esters, and nitriles
  • embodiments in accordance with the present disclosure are made to take advantage of such differences by using monomers that are either a mixture of isomers that is rich in the advantageous isomer or are essentially the pure advantageous isomer.
  • the XXI-a and XXII-a structures exemplified are embodiments of this disclosure where the monomer employed possesses an exo-substituted functional group and as such is anticipated as being more readily polymerized and converted to the quaternary ammonium salt.
  • IEC ion exchange capacity
  • the polymers will be substituted with a single alkyl trimethylammonium cation per polycyclic structure, but by appropriate selection of a functional norbornene additional quaternary ammonium moieties may be introduced to improve ion conductivity.
  • the mechanical strength of the films is adjusted via the incorporation of one or more functional norbornene monomers, such as alkylNB (e.g., decylNB, hexylNB, butylNB); methyl glycol ether NB (e.g., NBCH 2 (OCH 2 CH 2 ) 2 0Me and NBCH 2 (OCH 2 CH 2 ) 3 OMe); NB-ether-NB (e.g., NBCH 2 OCH 2 NB,
  • alkylNB e.g., decylNB, hexylNB, butylNB
  • methyl glycol ether NB e.g., NBCH 2 (OCH 2 CH 2 ) 2 0Me and NBCH 2 (OCH 2 CH 2 ) 3 OMe
  • NB-ether-NB e.g., NBCH 2 OCH 2 NB
  • NB-alkylene-NB e.g., NB-NB, NB-Et-NB NB-Bu-NB, and NB-Hx-NB
  • NB-aryl-NB e.g., NBC 6 H 4 NB and NBCH 2 C 6 H 4 CH 2 NB
  • maleimide-alkyl-NB e.g., NBMeDMMI, NBPrDMMI, NBBuDMMI, and NBHxDMMI
  • a difunctional amine, polycyclic amine or dendrimer polyamine, or a cyclic diamine, such as DABCO (l,4-diazabicyclo(2,2,2)octane) can be employed during film casting as a crosslinker unit to create ammonium functions that are less sensitive to the Hoffman elimination reaction and the substitution by hydroxyl group, and it allows for the thermal crosslinking via its second nitrogen.
  • DABCO l,4-diazabicyclo(2,2,2)octane
  • cross-linker moieties that can be employed during film casting include, among others, bis(dimethylamino) moieties such as: l ,4-diazabicyclo[2.2.2]octane, 2- methyl-l ,4-diazabicyclo[2.2.2]octane, l ,3-propanediamine, ,3-propanediamine, N 1 ,N 1 ,N 3 ,N 3 -2-pentamethyl-l ,3- propanediamine,
  • bis(dimethylamino) moieties such as: l ,4-diazabicyclo[2.2.2]octane, 2- methyl-l ,4-diazabicyclo[2.2.2]octane, l ,3-propanediamine, ,3-propanediamine, N 1 ,N 1 ,N 3 ,N 3 -2-pentamethyl-l ,3- propanediamine,
  • Aromatic cross-linker moieties include, but are not limited to, N 3 , N 3 , N 6 ,N 6 - tetramethyl-3,6-Phenanthrenedimethanamine, Ng, N 9 , ⁇ , ⁇ -tetramethyl- 9,10- Anthracenedimethanamine, Nj, Ni, N5,N5-tetramethyl- l,5-Naphthalenedimethanamine, N 2 , N 2 , N 6 ,N 6 -tetramethyl-2,6-Naphthalenedimethanamine, N 1 , N 1 , N 8 ,N 8 -tetramethyl- 1,8-Naphthalenedimethanamine, N 2 , N 2 , N 6 ,N 6 -tetramethyl-l ,8-
  • Still other cross-linker moieties can be employed during film casting include, among others, dibromo, chloro/bromo, tri-bromo, iodo and chloro moieties such as: 1 ,2- dibromopropane, 1,2-dibromoethane, 1 ,2,3-tribromopropane, 1,3-dibromobutane, 1 ,3- dibromo-2,2-dimethylpropane, 2,4-dibromopentane, 1 ,4-dibromobutane, l-bromo-3- (bromomethyl)octane, 2,5-dichloro-2,5-dimethylhexane, 2-bromo-4-(2- bromoethyl)octane, 1 ,5-dibromooctane, l-bromo-4-(bromomethyl)octane, l-bromo-3-
  • cross-linker moieties include: N',N 2 -bis[2-(dimethylamino)ethyl]- N l ,N 2 -dimethyl-l ,2-Ethanediamine N'.N'-bis ⁇ - dimethylam ⁇ ethy ⁇ -N 2 ⁇ 2 - dimethyl-l ,2-Ethanediamine N 1 -[2-(diethylamino)ethyl]-N 2 ,N 2 -diethyl-N 1 -methyl-l ,2- Ethanediamine N'-[2-(dimethylamino)ethyl]- N',N 2 ,N 2 -trimethyl-l ,2-Ethanediamine N- [(dimethylamino)methylethyl]-N,N',N , -trimethyi-l,2-Propanediamine N'-[2-[[2- (dimethylamino)ethyl]methylamino]ethyl
  • the precipitated white powder (700 g) was recrystallized in hexanes ( ⁇ 50 wt %) to give transparent crystals of NB(endo-Me)(exo-C0 2 H) (621 g, 29 %) upon cooling over 24 hours.
  • the monomer was characterized by ⁇ NMR and 13 C NMR.
  • the numbering system shown in the following figure was used for the assignment of the NMR signals.
  • NB(endo-Me)(exo-C0 2 H) (174.8 g, 1.15 mmol) and anhydrous toluene (1000 mL) were added to an appropriately sized container and kept under nitrogen.
  • the container was equipped with a magnetic stirrer bar, thermometer, addition-funnel and condenser.
  • a pre-mix of Vitride ® 500 g, 70 wt % in toluene, 1.73 mol
  • was added to the addition funnel (short exposure to air is acceptable if ⁇ 2 minutes).
  • the dilute Vitride® was added dropwise over 3 hours while maintaining pot temperature between 5-20 °C.
  • the monomer was characterized by ⁇ NMR and 13 C NMR.
  • the numbering system shown in the following figure was used for the assignment of the NMR signals.
  • the monomer was characterized by ⁇ NMR.
  • the numbering system shown in the following was used for the assignment of the NMR signals.
  • the monomer was characterized by 1H NM and 13 C NMR.
  • the numbering system shown in the following figure was used for the assignment of the NMR signals.
  • Endo-/exo-norbornenebutyl mesylate 5-(2-hydroxybutyl)norbornene (1000 g, 6 mol), 2000 ml dichloromethane, and methanesulfonyl chloride (723.4g, 6.32 mol) were added to an appropriately sized container equipped with a thermowell, nitrogen inlet, addition funnel and mechanical stirrer. An additional 500 mL dichloromethane was added to rinse in the methanesulfonyl chloride (MsCl). The stirred mixture was chilled to -14.0 °C with a dry ice-isopropanol cooling bath.
  • Triethylamine (733.6 g, 7.26 mol) was added rapidly dropwise over a 2 hr and 20 minute period with the temperature ranging from -14° to -6 °C. GC analysis showed no remaining NBBuOH. The resulting slurry was allowed to warm during 3 hrs to room temperature. 1000 ml water was then added. The phases were separated and the aqueous phase extracted with 1000 ml dichloromethane. The combined dichloromethane extracts were washed with 2 times 1L 1 N HC1 and then washed with 1000 ml brine, 1000 ml saturated NaHC0 3 , and 2000 ml brine. The
  • Endo-/exo-bromobutylnorbornene Lithium bromide (LiBr) (782 g, 9.0 mol) and 12L of 2-pentanone were added to an appropriately sized container equipped with a thermowell, condenser with nitrogen adapter, and mechanical stirrer. The mixture was stirred yielding a yellow solution.
  • Norbornene-butylmethanesulfonate (1570 g, ⁇ 6.01 mol) was dissolved in 2 L of 2-pentanone and added to the LiBr solution.
  • An additional 4L of 2-pentanone total volume of 2-pentanone totaled 18L was added as rinse.
  • the material was vacuum distilled through a 14" Vigreux column at 74.2-76.2°C (0.22- 0.53 Torr) to give 5 1 1 .2 g with 98.5% purity, 379.4 g (69.3-76.0°C at 0.164-0.33 Torr) with 97.5% purity, and 309 g (68-77°C at 0.245-0.72 Torr) with 95-96% purity.
  • the GC analysis completed on a DB5 Column, 30 meters, 0.32 mm ID, Attorney Docket No. PLY209-0003A
  • Endo-/exo-norborneneethylmesylate 5-(2-hydroxyethyl)norbornene (1000 g, 7.235 mol), 2000 ml dichloromethane, and methanesulfonyl chloride (871.6 g, 7.609 mol) were added to an appropriately sized container equipped with a thermowell, nitrogen inlet, addition funnel and mechanical stirrer. An extra 1500 mL
  • dichloromethane was added to rinse in the methanesulfonyl chloride.
  • the stirred mixture was chilled to -14°C with a dry ice-isopropanol cooling bath.
  • Triethylamine (883 g, 8.74 mol) was added rapidly dropwise over 70 minutes as the temperature ranged from -14°C to -4°C. The reaction mixture became very thick, therefore, to improve mixing an additional 550 ml of dichloromethane was added.
  • the GC analysis showed 0.3% NBEtOH.
  • the resulting slurry was allowed to warm to room temperature while stirring overnight.
  • the GC analysis showed 95.5% mesylate, 1.0% NBEtCl, and ⁇ 0.2% NBEtOH. 1000 ml of water was added to clear the mixture. A second 500 ml portion of water was added, which clouded the mixture.
  • the phases were separated and the aqueous phase extracted with two times 500 ml of dichloromethane.
  • the combined dichloromethane extracts were washed with 1000 ml 1 N HC1 , 1000 ml saturated NaHC0 3 , and 2 times 1000 ml of brine.
  • the dichloromethane solution was dried over sodium sulfate, filtered, and rotary evaporated to give approximately 1600 g (quantitative yield) of brown liquid.
  • the NMR was consistent with structure and showed 1.4 wt% dichloromethane remaining.
  • the GC analysis was completed on a DB5 Column, 30 meters, 0.32 mm ID, 0.25 ⁇ film, heat from 75°C to 300 °C @15°C/min, hold for 2 min @300°C, Injector temperature: 275°C, Detector temperature: 350°C, Retention time: 7.856 minutes.
  • Endo-/exo-bromoethy Inorbornene Lithium bromide (943 g, 10.83 mol) and 1 1.5 L of 2-pentanone were added to an appropriately sized container equipped with a thermowell, a condenser with nitrogen adapter, and a mechanical stirrer. The mixture was stirred to give a yellow solution.
  • Norbornene-ethylmethanesulfonate (1604 g, ⁇ 7.235 mol) was dissolved in 3.5 L of 2-pentanone and added to the LiBr Attorney Docket No. PLY209-0003A solution.
  • the mixture was heated to reflux over a period of 1.75 hours to give a slurry. Upon reaching reflux (99 °C), the GC analysis showed no starting material. The mixture was heated an additional 30 minutes at 99-102 °C. The mixture was then cooled to 25 °C. Two liters of distilled water was added to clear the mixture and followed with an additional 1 liter water which clouded the mixture. The phases were separated. The reactor was rinsed with two times 1000 ml portions • of ethyl acetate. The aqueous phase was then extracted with two times 1000 ml ethyl acetate washes. The organic portions were combined and rotary evaporated at ⁇ 30 °C.
  • the monomer was characterized by 1H NMR.
  • the numbering system shown in the following figure was used for the assignment of the NMR signals.
  • a catalyst solution of [l,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene] - [2- [[(2-methylphenyl)imino]methyl] -phenolyl]chloro-(3 - phenyl-indenylidene)mthenium(II) in toluene was prepared in a separate vial.
  • the catalyst solution was added to the monomer mixture.
  • the polymerization mixture was poured into a petri dish. The mixture was heated at 80 °C for minutes and 130 °C for 30 minutes to complete.
  • Example 3P3 Synthesis of 53%NB-EtBr/47% Hexyl NB Polymer.
  • the reaction mixture was transferred to a 1L separatory funnel.
  • the reaction solution was washed with deionized water (5x250ml) utilizing tetrahydrofuran (90.2g 100ml) to break the emulsion formed during the washing process.
  • the organic layer was decanted into a 2L round bottomed flask and the solvents were Attorney Docket No. PLY209-0003A removed under reduced pressure.
  • the resultant mixture was a thick honey-like consistency.
  • This thick solution was diluted with tetrahydrofuran (180.4g 200ml) and the resultant solution was added drop wise into methanol (1582g 2000ml) to precipitate the solid polymer.
  • the solid polymer was collected by filtration of the resulting slurry.
  • the filter-cake was washed with a portion of methanol (79. l g 100ml) and allowed to dry on the filter for approximately one hour.
  • the crudely dried polymer was transferred to a crystallization dish, covered with a dust free paper, and dried for 18 hours in a vacuum oven set to 50°C at a pressure of 25 torr.
  • Overall yield was 99g (99%) of dried solid.
  • the polymer composition as measured by 1H NMR was 53 mole % norbornene ethyl bromide and 47 mole % hexyl norbornene.
  • the filtered polymer solution was cast on a glass plate with 20 mil gap using a Gardco adjustable film applicator.
  • the cast film was air dried at room temperature. The edges of film were lifted by a razor and the film was immersed to deionized water to lift off completely from the glass plate. The resulting film was wiped and air dried.
  • a sample film was placed between PTFE flanges.
  • the sample film was
  • a film was placed between PTEE flanges.
  • the sample film was submerged in IN NaOH aqueous solution for 24 hours.
  • the film was rinsed with deionized water and air dried.
  • a 25g sample of a copolymer of 5-(2-bromoethyl)-bicyclo[2.2.1]hept-2-ene (norbornenyl ethyl bromide, 48 mol %) and 5-hexylbicyclo[2.2.1 ]hept-2-ene (hexyl norbornene, 48 mol%) was weighed into a 500 mL amber glass bottle and 75g of chloroform (Fisher, HPLC Grade) was added. The bottle was sealed and placed on a Wheaton laboratory roller at ambient temperature. The bottle was rolled at 50 rpm for 18 hours to produce a homogeneous, viscous solution.
  • the polymer solution was filtered through a 0.5 micron Teflon filter using a 35 psig nitrogen back pressure and filtrate was collected in a low particle, 250 mL amber bottle.
  • a lOg aliquot of the polymer solution was poured into a 60mm Pyrex Petri dish and covered with a glass lid to prevent rapid solvent evaporation.
  • the Petri dish was placed in a fumehood and allowed to stand at ambient temperature for 18 hours. The surface of the resulting film was not tacky when touched.
  • the Petri dish was transferred to a vacuum oven and dried under vacuum (23 inches Hg) at 40°C for a further 18 hours.
  • the resulting film was removed from the Petri dish by cutting the edge bead with a scalpel and immersing the film in 25 mL of deionized water.
  • the film was then Attorney Docket No. PLY209-0003A allowed to dry under ambient conditions.
  • the resulting film weighed 1.30g and was measured to be 97 microns thick.
  • N,N,N ⁇ N etramethyl-l ,6-hexanediamine (0.775g, 9.0 mmol) was added to the bottle containing the polymer solution and the bottle was sealed.
  • the polymer solution was mixed by rolling at ambient temperature for 18 hours on a Wheaton laboratory roller at 50 rpm.
  • a 5.71 g aliquot of the resulting viscous solution was poured into a 60mm Petri dish and covered with a glass lid to prevent rapid solvent evaporation. The Petri dish was placed in a fumehood and allowed to stand at ambient temperature for 18 hours. The surface of the resulting film was not tacky when touched.
  • the Petri dish was transferred to a vacuum oven and dried under vacuum (23 inches Hg) at 40°C for a further 18 hours.
  • the resulting film was removed from the Petri dish by cutting the edge bead with a scalpel and immersing the film in 25 mL of deionized water. The film was then allowed to dry under ambient conditions. The resulting film weighed 1.38 g and was measured to be 102 ⁇ thick.
  • the film embodiments in accordance with the present disclosure were prepared by dissolving 20 grams of a polymer in 24 grams of tetrahydrofuran (45 wt%). The solution was then cast on a glass plate using a Gardco adjustable film applicator with 12 mil setting. The cast film was then air dried at room temperature. Once dried, the edges of film were lifted by a razor and the film was immersed to deionized water to lift off completely from the glass plate. The resulting film was wiped and dried in air. Typical film thickness was found to be 70 microns.
  • Conductivity measure are done in a four-point probe configuration.
  • the outer platinum electrodes are 2.5 cm apart and 1 cm wide. Thus the samples area used is 2.5 cm x 1 cm.
  • the frequency of the sinusoidal voltage is varied and (typically 10 Hz to 100 kHz).
  • the value of resistance is extrapolated to high frequency which captures the sheet resistance of the film.
  • the area here is the cross sectional area: thickness of film times 1 cm (width).
  • a 0.05 to 0.1 gram sample of an AAEM membrane in hydroxide form was immerse in a 10 mL of 0.01 M HC1 standard for 24 hours. The solutions were then titrated with a standardized NaOH solution. Control samples having no membrane added were also titrated with NaOH. The difference between the volume required to titrate the sample and the control was used to calculate the amount of hydroxide ions in the membranes. After titration, the membrane was washed with water and soak in 1 M HC1 solution for 24 hours to converting the hydroxide ions to chloride ions. Following, the membrane was soaked in water for 24 hours to remove residual HC1.
  • each membrane was determined by wiping the excess water from the surface and weighing.
  • the membrane was then dried under vacuum in the presence of P 2 Os at room temperature for 24 hours and then reweighed to determine the dry mass.
  • the membranes were converted to the chloride ion form prior to drying to avoid degradation of the norbornyl alkyl trimethylammonium groups by hydroxide ions.
  • the IEC is expressed as milliequivalents of hydroxide ions per gram of dry membrane (in the chloride ion form).
  • IEC Theoretical Ion Exchange Capacity
  • COND Conductivity
  • the resulting aqueous layers should be combined and washed at least twice with 50 mL heptane and the several organic phases combined, dried with Na 2 S0 4 and then filtered through a pad (2 cm x 4.5 cm) of silica which should then be washed with heptane. After evaporation of the organic solvents and purification of the resulting residue, it is expected that 5-exo-(4-bromomethylphenyl)norbornene will be obtained as a colorless solid.
  • the resulting 5-exo-(4-bromomethylphenyl)norbornene can be polymerized using a toluene solution of (toluene)Ni(C 6 Fs) 2 in toluene and product precipitated into methanol.
  • the poly(exo-(4-bromomethylphenyl)norbornene) should be soluble in an appropriate solvent such as DMF, and convertible to the quaternary amino salt by room Attorney Docket No. PLY209-0003A temperature treatment with 40% trimethylamine solution at room temperature for an appropriate period of time.
  • a DMF solution of the final polymer should be able to be cast onto Teflon® plates and then heated to cause the solvent to evaporate and form a flexible membrane.
  • a membrane thickness of about 100 to 200 ⁇ should be attainable.
  • Any mobile chloride in the aforementioned membrane should be replaceable submerging in aqueous potassium hydroxide (1M) for about one day to form an ammonium hydroxide salt. It is believed that the above method will be effective to form an anionic alkali exchange membrane (AAEM) which can be used in to form an assembly such as shown in Figure 1 of US Patent Application No. 2007/0128500, which is incorporated herein by reference in its entirety.
  • AAEM anionic alkali exchange membrane
  • a thin crosslinked addition polymerized film should be able to be synthesized by first combining a palladium catalyst composition (Pd 1206
  • DANFABA tetrakis(pentafluorophenyl)borate
  • the properties of the films that can be formed by the above method should be able to be controlled by varying the molar ratios of each monomer reduce undesirable swelling in hydroxide ion and hydrogel formation. It is believed that the above method will be effective to form an anionic alkali exchange membrane (AAEM) which can be ' used in to form an assembly such as shown in Figure 1 of US Patent Application No. 2007/0128500 and that such an assembly will be an effective polyelectrolyte for an anionic fuel cell such as is shown in Figure 1 (b) of Varcoe et al.
  • AAEM anionic alkali exchange membrane
  • a thin crosslinked addition polymerized film should be able to be synthesized by first combining a ruthenium initiator (such as tricyclohexylphosphine[l,3-bis(2,4,6- trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidine]ruthenium (TV) dichloride (Second Generation Grubbs catalyst) in a dichloromethane solution to form a pre-catalyst concentrate and adding this mixture to a monomer mixture of 5- (bromomethyl)-5-methylnorbornene (50 mol%) and 1 ,4-di(norbornenyl)butane (50 mol%) monomers to obtain a homogeneous solution at room temperature.
  • ruthenium initiator such as tricyclohexylphosphine[l,3-bis(2,4,6- trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benz
  • the catalyst molar reaction ratio for such a mixture should be about 10,000: 1 (NB monomers:Ru).
  • NB monomers:Ru NB monomers:Ru
  • the properties of the films that can be formed by the above method should be able to be controlled by varying the molar ratios of each monomer reduce undesirable Attorney Docket No. PLY209-0003A swelling in hydroxide ion and hydrogel formation. It is believed that the above method will be effective to form an. anionic alkali exchange membrane (AAEM) which can be used in to form an assembly such as shown in Figure 1 of US Patent Application No. 2007/0128500 and that such an assembly will be an effective polyelectrolyte for an anionic fuel cell such as is shown in Figure 1 (b) of Varcoe et al.
  • AAEM anionic alkali exchange membrane
  • a thin crosslinked addition polymerized film should be able to be synthesized by first combining a ruthenium initiator (such as (l,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium (Second Generation Hoveyda Grubbs catalyst) in a chloroform solution to form a pre-catalyst concentrate and adding this mixture to a monomer mixture of l ,l'-(norbornene-2,2- diyl)bis(trimethylmethanammonium iodide) (35 mol%) and l,4-di(norbornenyl)butane (65 mol%) monomers in chloroform to obtain a homogeneous solution at room temperature.
  • the catalyst molar reaction ratio should be about 5,000: 1 (NB
  • the properties of the films that can be formed by the above method should be able to be controlled by varying the molar ratios of each monomer reduce undesirable swelling in hydroxide ion and hydrogel formation. It is believed that the above method will be effective to form an anionic alkali exchange membrane (AAEM) which can be used in to form an assembly such as shown in Figure 1 of US Patent Application No. 2007/0128500 and that such an assembly will be an effective polyelectrolyte for an anionic fuel cell such as is shown in Figure 1 (b) of Varcoe et al.
  • AAEM anionic alkali exchange membrane
  • the polymer embodiments in accordance with the present disclosure are also useful for forming elements of an AFC other then the AAEM.
  • electrodes 2 and 4 of Fig. 2 encompasses active layers, respectively, and that each of such active layers 2a and 4a encompass an element conducting hydroxide ions. It is believed that some of the polymer embodiments in accordance with the present disclosure would be useful in forming this element of active portions 2a and 4a.

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