Application for Letters Patent

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NORBORNENE-TYPE POLYMERS HAVING QUATERNARY AMMONIUM FUNCTIONALITY

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INVENTOR(S)

Andrew Bell

Edmund Elce

eitaro Seto

ATTORNEY'S DOCKET NO. PLY209-0003 Attorney Docket No. PLY209-0003A

NORBORNENE-TYPE POLYMERS HAVING QUATERNARY AMMONIUM

FUNCTIONALITY

TECHNICAL FIELD

[0001] 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.

BACKGROUND

[0002] Alkaline fuel cells (AFCs) 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%.

[0003] 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:

Anode Reaction: 2 H. + 4 OH ^' => 4 H ₂ 0 + 4 e ^"

Cathode Reaction: 0 ₂ + 2 H ₂ 0 + 4 e ^' => 4 OH ^"

Overall Net Reaction: 2 H ₂ + 0 ₂ => 2 H ₂ 0

[0004] Despite their high efficiency, reasonable operating temperatures and other positive attributes, the 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

environments, such as space and undersea vehicles, running on pure hydrogen and oxygen can be worthwhile.

[0005] On the positive side, and in addition to their high efficiency and low operating temperature, 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.

[0006] In recent years, interest has grown in the development of anion exchange membranes (AEMs) for use in AFCs and electrolyzers due to the low overpotentials associated with many electrochemical reactions at high pH and the potential to forego noble metal catalysts. AEMs serve as an interesting counterpoint to the more widely developed and understood proton or cation exchange membranes (PEM or CEM). However, 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.

[0007] The use of anionic fuel cells based on solid polymeric anion exchange membranes (AEMs) have been demonstrated and their use in both AFCs and alkaline- membrane DMFCs (direct methanol fuel cells). Further, the use 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. There are additional advantages to AEMs, and in particular to polymeric alkali anion exchange membranes (AAEMs). For example, it is likely that electrode construction and orientation limitations can be overcome for AAEMs as the conducting species would be incorporated into the fixed solid polymer AAEM. Additionally, even though some CC>3 ^"2 /HC0 ₃ ^" formation at the anode is likely to occur, there are no mobile Attorney Docket No. PLY209-0003A cations (Na ⁺ or K ⁺ ) present in the AAEM to precipitate solid crystals of metal carbonate to block or destroy the electrode layers since with AAEMs the cations are immobilized. Further, as there is no liquid caustic electrolyte present, electrode weeping and component corrosion should be minimized.

[0008] Therefore there is a need for AAEMs that have the necessary conductivity, resistance to water swelling, mechanical strength, and chemical stability at operating temperatures to provide the next generation of AFCs.

DETAILED DESCRIPTION

[0009] As previously mentioned, chemical stability, with respect to the cationic groups attached to the membrane, at operating temperatures is a property that is an area of focus in developing new AAEMs for fuel cells. If one were to consider an

electrochemical cell without any added electrolyte, the localized pH within the ion- conducting channels of the membrane will be quite high. Also, while 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. However, 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 β- 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.

[0010] Many anion exchange polymers employ quaternary ammonium groups attached to a hydrocarbon polymer backbone, and most recently, ammonium functionalized norbornene-type monomers were incorporated directly via a ring-opening metathesis polymerization (ROMP) route with dicyclopentadiene to form what is reported as mechanically strong AAEMs with high hydroxide ion conductivities and exceptional methanol tolerance, G. W. Coates et al. J. Am. Chem. Soc. 2009, 131, 12888-12889 (Coates I). However, ROMP copolymers of Coates I (shown below), having Attorney Docket No. PLY209-0003A unsaturated C to C bonds are known to be less oxidatively stable than analogous vinyl addition polymers that are free of such unsaturation.

[0011] Further, while Coates I report that the thickness and properties of films made from non-hydrogenated ROMP polymers can be easily controlled by varying the amount and ratios of their Structure 1 to dicyclopentadiene (ibid. p.12888) they also reported that the range of such variations was limited as a film with ratio greater than 1 :1 (Structure 1 :DCPD) demonstrated swelling and hydrogel formation, while films having the inverse ratio were not sufficiently conductive (ibid. pl2888- 12889).

[0012] It has also been reported by Chempath et al. in J. Phys. Chem. C, 2008, 112, 3179-3182 and Einsla et al. in ECS Transactions, 11(1) 1173-1180 (2007) that tetraalkylammonium-based cations show reasonable stability in alkaline media, i.e., benzyltrimethylammonium hydroxides displayed much better stability than the phenyltrimethylammonium hydroxides under similar conditions. Specifically it was reported that solutions of benzyltrimethylammonium cation in IN, 3N and 5N sodium hydroxide showed little degradation after being held at 80°C for 29 days (Einsla et al., Figure 4, p.l 179). 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. Here 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.

[0013] Recently, G. W. Coates et al. J. Am. Chem. Soc. 2010, 132, 3400-3404 (Coates II), reported the use of tetraalkylammonium-functionalized cross-linkers, rather than the Attorney Docket No. PLY209-0003A

DCPD used in Coates I, as such new cross-linkers were found not to detract from ion concentration and thus conductivity of the material (ibid. p. 3400). In particular, Coates II is directed to the use of Compound 1 :

[0014] as a comonomer of cyclooctene (COE) to directly form the cross-linked polymer: -

[0015] However, as was observed above for Coates I, the resulting polymer of Coates II is also unsaturated and is thus likely to be less oxidatively stable than a

hydrogentated ROMP polymer or a saturated polymer resulting from a vinyl addition polymerization.

[0016] Thus believing that norbornene-type polymers formed by vinyl addition polymerization or by ROMP polymerization of two or more types of norbornene-type monomers, followed by hydrogenation, would provide more oxidatively stable polymers than reported by either Coates I or II, as well as providing additional flexibility in tailoring the polymer's conductive, chemical and physical properties, the polymer embodiments in accordance with the present disclosure encompass both norbornene-type vinyl addition polymers and hydrogenated norbornene-type ROMP polymers where the latter exclude copolymers of DCPD or cyclootene. Attorney Docket No. PLY209-0003A

[0017] To this effect, some hydrogenated ROMP polymer embodiments of the present disclosure are hydroxide ion conducting polymers derived from two or more

norbornene-type monomers where a first such monomer is represented by Formula I and a second such monomer is represented by Formula II, both shown below:

[0018] where for Formula I, m is from 0 to 3, at least one of 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. For Formula II, 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.,

NBCH ₂ OCH ₂ NB, NBCH ₂ (OCH ₂ CH ₂ ) ₂ 0CH ₂ NB, and

NBCH ₂ (OCH ₂ CH ₂ ) ₃ 0CH 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), 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. For Formula III, 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

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

independently selected from a methyl, an aryl or alkyl-aryl group where the alkyl is a Ci to C ₄ alkyl, and v is either 1 or 2. Thus, in each ROMP polymer derived from the above monomers, there is a first type of norbornene-type repeating unit that

encompasses a QAS group and a second repeating unit that encompasses a substituted or unsubstituted maleimide-alkyl pendent group or one of the aforementioned other cross-linkable pendent groups.

[0019] With regard to vinyl addition polymer embodiments in accordance with the present disclosure, such are also 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:

[0020] For Formula A, 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. For Formula B, 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.

[0021] Exemplary monomers in accordance with Formula I include, but are not limited to: Attorney Docket No. PLY209-0003 A

[0022] With respect to monomers in accordance Formula A, the above monomers while not directly polymerizable via vinyl addition polymerization, can be made available by post-polymerization functionalization. Additionally, it is believed that monomers that incorporate a quaternary amine such as those represented by general formulae IVa below, as well as the specific examples for each general formula that follow in exemplary formulae IVb, are suitable for embodiments in accordance with the present disclosure. Such pendent groups include: Attorney Docket No. PLY209-0003A

[0023] With regard to the polymerization of the above and below monomers, exemplary ROMP polymerization processes employing Ru and Os transition metal initiators are described in US Patent No. 6,838,489, which is incorporated herein by reference in its entirety; and exemplary vinyl addition polymerization processes employing Group VIII transition metal catalysts are described in US 2006/0020068 Al, which is incorporated herein by reference in its entirety.

[0024] 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. Generally, a Mw from 5,000 to 500,000 is found appropriate for some embodiments, while for other embodiments other Mw ranges can be advantageous. For example, for some embodiments, 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. In some embodiments, 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.

[0025] While some 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. 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)).

Attorney Docket No. PLY209-0003A

IX

[0026] It should be understood, of course, that where an unsaturated ROMP polymer is desired, only Reaction 1 of the above scheme need be performed provided that the starting monomer is in accordance with Formula I. Such reaction sequence is as shown below:

X XI

[0027] For polymer embodiments in accordance with forming a vinyl addition polymer, generally a monomer having a pendent functional group that can be Attorney Docket No. PLY209-0003A quaternerized, for example an aryl-alkyl halide such as in the above Formula IV, the reaction scheme illustrated below is generally employed.

FG = Functional Group CI, Br, or I

Halide to Hydroxide

Metathesis

[0028] Since, it is believed that the base stability of quaternary amine pendent groups improves as the aliphatic chain length of the alkyl substituent increases, and further as it is believed that incorporating repeating units into a polymer with two or more quaternary amine cations allows more freedom in the selection of other repeating units that will allow for the tailoring of polymer properties while maintaining high conductivity. Thus unlike the limited range of monomer ratios reported in Coates I with a DPCD copolymer, or the slightly less limited range of monomer ratios reported in Coates II with a COE copolymer, 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. For example such polymers can incorporate a higher ratio of cross-linking repeating units where repeating units containing quaternary ammonium moieties are polyfunctional. Additionally, improvements in membrane stability under alkaline conditions can be accomplished by the incorporation of trimethylammonium groups in structures which do not possess /^-hydrogen atoms, thereby preventing degradation by a Hofmann elimination. Still further, as a design option, functionalized Attorney Docket No. PLY209-0003A tetracyclododecene (TDFG) monomeric units may be incorporated into the polymer backbone to effect changes in mechanical, thermal, and transport properties

[0029] Exemplary repeating units that are available from the above vinyl

olymerization scheme include, but are not limited to, the following:

[0030] Further to the vinyl addition polymerization plus post-functionalization scheme, 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

initiator/catalyst) or a palladium catalyst, such as [Pd(P-i-

Pr ₃ )2(NCCH3)(OAc)][B(C6F5)4] or [Pd(PCy ₃ )2(NCCH3)(H)][B(C ₆ F ₅ )4] or an in-situ generated palladium catalyst) to generate the saturated polymer shown. 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.

[0031] Still further to the vinyl addition polymerization plus post-functionalization scheme, 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

diastereomeric mixture of such monomers has been employed.

[0032] 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 α,ω-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 to norbornene hydroxyls which are readily converted to chloro, bromo, or iodo alkyls, i.e., NB(endo-CH ₃ )(exo-C0 ₂ H) -> NB(CH ₃ )(CH ₂ OH) -»NB(CH ₃ )(CH ₂ C1) or NBCN -» NBCHO -» NBCH ₂ OH -> NBCH ₂ C1.

Attorney Docket No. PLY209-0003A

[0033] While each formula XVIII-a, XX-a and XXV-a, provided above, are depicted without indication of any stereochemistry, it should be noted that generally each of these monomers and other monomers produced for the purpose of this disclosure, unless indicated otherwise, are obtained as diastereomeric mixtures that retain their configuration when converted into repeating units. As previously noted and discussed, Attorney Docket No. PLY209-0003A the exo- and endo- isomers of such diastereomeric mixtures can have slightly different chemical and physical properties, it should be further understood that some

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.

[0034] In some embodiments, the base stability of the quaternary amines can be improved, for example in compound XI, by increasing the aliphatic chain length of the alkyl substituent, NB(CH ₂ ) _n [NMe ₃ ]Cl (n = 1 -6). Improvements in base properties are, for example, low swelling in hot methanol, high ion exchange capacity (IEC), good hydroxide ion conductivity, polymer stability, and mechanical strength.

[0035] Compounds XIX through XXIV have improved membrane stability under alkaline conditions compared to compound XVI because the incorporation of trimethylammonium groups in structures which do not possess β-hydrogen atoms thus preventing degradation by Hofmann elimination.

[0036] In other embodiments, 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,

NBCH ₂ (OCH ₂ CH ₂ ) ₂ OCH ₂ NB, and NBCH ₂ (OCH ₂ CH ₂ ) ₃ 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); and maleimide-alkyl-NB (e.g., NBMeDMMI, NBPrDMMI, NBBuDMMI, and NBHxDMMI), which may be crosslinked in either 100% reactive solids polymerization, or via acid or base catalyzed, thermal, and photochemical reactions of polynorbornene films. Attorney Docket No. PLY209-0003A

[0037] In other embodiments in accordance with the present disclosure, the use of 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. Quinuclidine has a structure that is similar to that of DABCO which confers a good resistance with respect to Hoffman degradation and nucleophilic substitution by OH ^" ion. The method to produce crosslinked films is exemplified as follows:

[0038] Other 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,

1,2-propanediam

tetramethyl- 1 ,6-hexanediamine, , 10-decanediamine, N ¹ ,Ν ¹ ,N ^l2 ,N ¹² -tetramethyl- 1 , 12-dodecanediamine, N ¹ ,Ν ¹ ,N ³ ,N ³ -tetramethyl- 1,3- butanediamine, N ³ -[2-(dimethylamino)ethyl]-N ¹ ,N ¹ -dimethyl-l,3-propanediaraine, N ¹ - [2-(dimethy lamino)ethyl] -N ¹ -( 1 -methy lethyl)- 1 ,3-propanediamine, N ¹ - [2- Attorney Docket No. PLY209-0003A

(dimethylamino)ethyl]-N ² ,N ² -dimethyl-l,2-propanediamine _s N^N'.N^N^tetramethyl- 1 ,4-benzenedimethanamine, 4-[2-(dimethylamino)ethyl]-N,N- dimethylbenzenemethanamine, N^N^^^-tetramethyl-ljS-benzenedimethanamine, N ¹ ,N ¹ ,N ,N ⁴ -tetramethyl-l,4-cyclohexanedimethanamine, and Ν',Ν',Ν^Ν ⁴ - tetramethylbicyclo[2.2.2]octane-l,4-dimethanamine.

[0039] 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 , Νιο,Νιο-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-

Naphthalenedimethanamine, N ¹ , N ¹ , N ⁴ ,N ⁴ -tetramethyl-l,4-Benzenedimethanamine, N ¹ , N ¹ , N ³ ,N ³ -tetramethyl- l,3-Benzenedimethanamine, N ¹ , N ¹ , N ² ,N ² -tetramethyl-l,2- Benzenedimethanamine, I^.KT'^'^'-tetramethyl- [1,1 '-Biphenyl]-4,4'- dimethanamine, N ⁵ ,N ⁵ ,N ¹⁴ ,N ¹⁴ -tetramethyl-Tricyclo[9.3.1.14,8]hexadeca- 1(15),4,6,8(16),1 l,13-hexaene-5,14-dimethanamine and 9,10-dihydro-N ² ,N ² ,N ⁷ ,N ⁷ - tetramethyl-2,7-Anthracenediamine, 2,7-bis[(dimethylamino)methyl]-9,10- Anthracenedione, 2,6-bis[(dimethylamino)methyl]-9,10 Anthracenedione, 9,10- dihydro-N ² ,N ² ,N ⁶ ,N ⁶ -tetramethyl-2,6-Anthracene dimethanamine, N ³ ,N ³ ,N ⁶ ,N ⁶ - tetramethyl-9H-Fluorene-3,6-diamine, 2,6-bis[(dimethylamino)methyl]-l,5-dihydroxy- 9, 10-Anthracenedione.

[0040] 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- (2-bromoethyl)heptane, l-bromo-3-(2-bromoethyl)-4,4-dimethylpentane, 2,5- dibromohexane, 1,4-dibromo-heptane, 2,4-dibromo-2-methylpentane, 1,10- dibromoundecane,l-bromo-3-(2-bromoethyl)-4,4-dimethylpentane , 2-bromo-4-(2- bromoethyl)octane, l,5-dibromo-3,3-dimethylpentane, l-bromo-4- (bromomethyl)octane, l-bromo-3-(2-bromoethyl)heptane, l-bromo-3- (bromomethyl)octane, 1,10-dibromodecane, 1,11-dibromoundecane, 1, 10- Attorney Docket No. PLY209-0003A dibromoundecane, 2,4-bis(broraomethyl)pentane, 1,12-dibromododecane, 1,13- dibromotridecane, l,5-dibromo-3-methylpentane, 1,8-dibromooctane, 1,9- dibromononane, 1,5-dibromooctane, 1,2-dibromododecane, 1,4- bis(bromomethyl)cyclohexane, 1 ,2,6-tribromohexane, 1 ,2,5,6-tetrabromohexane, 1,4- bis(bromomethyl)bicyclo[2.2.2]octane, 1 , l-bis(bromomethyl)cyclohexane, 1 , 1 - bis(bromomethyl)cyclooctane, 1 , 1 -bis(bromomethyl)-2-methylcyclohexane, trans- 1 ,4- bis( 1 -bromo- 1 -methylethyl)cyclohexane, 1 ,4-bis( 1 -bromo- 1 -methylethy l)cyclohexane, 1 ,3,5-tris(bromomethyl)- 1 ,3,5-trimethylcyclohexane, cis- 1 ,5- bis(bromomethyl)cyclooctane, trans- l ,2-Bis(bromomethyl)cyclohexane, trans- 1 ,5- bis(bromomethyl)cyclooctane, 1 , 1 -bis(bromomethy l)cycloheptane, 1 ,4- bis(bromomethyl)benzene, 1 -(bromomethyl)-4-(chloromethyl)benzene, 1 -(2- bromoethyl)-4-(bromomethyl)benzene, 1 ,3-diiodo-2,2-dimethylpropane, l,3-diiodo-2,2- bis(iodomethyl)propane, 1,3-diiodopropane, l-bromo-3-chloro-2-methylpropane, 1,3- dibromo-2-methylpropane, l,5-diiodo-3-methylpentane, 1,4-diiodobutane, 1,3- diiodopentane, 1,5-diiodopentane, l-chloro-3-iodopropane, l-bromo-3- iodopropane, 1 ,3-dichloro-2,2-dimethylpropane, 1 ,4-bis(chloromethyl)cyclohexane, 1 ,4- bis(iodomethyl)benzene, ,4-bis(2-iodoethyl)benzene; and l,2-bis(iodomethyl)benzene.

[0041] Yet other 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]-N ^l ,N ³ ,N ³ -trimethyl-l ,3-Propanediamine N ¹ ,N ³ -bis[2-(dimethylamino)ethyl]-N ¹ ,N -dimethyl-l ,3-Propanediamine, and 3-[2- (dimethylamino)ethyl]-N ¹ ,N ¹ ,N ⁵ ,N ⁵ ,3-pentamethyl-l,5-Pentanediamine

[0042] To further illustrate such cross-linking moieties, the following are structural representations of some of the of the above named moieties: Attorney Docket No. PLY209-0003A

[0043] The following prophetic examples are provided to further illustrates aspects of some embodiments of the present disclosure. It should be understood that such examples are in no way limiting to the scope of such embodiments and are presented for illustrative purposes only.

MONOMER SYNTHESIS EXAMPLES

Example Ml - Synthesis of Endo-5-Methyl-Exo-5-Carboxylic Acid-2-Norbornene

[0044] Freshly cracked cyclopentadiene (939 grams, 14.2 moles) and methacrylic acid (1203 grams, 14.2 moles) was added to an appropriately sized container containing a magnetic stirrer. The contents were stirred for 24 hours and then left to stand Attorney Docket No. PLY209-0003A without stirring for 60 hours, over which time a white powder was observed to precipitate from solution. To encourage precipitation, the flask was cooled at 10°C for several hours. The precipitate was collected by vacuum filtration and rinsed with cold pentane (2 L, -10°C) to remove any un-reacted starting material and NB(exo-Me)(endo-C0 ₂ H by product that may have formed. 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.

[0045] The monomer was characterized by Ή NMR and ¹³ C NMR. The numbering system shown in the following figure was used for the assignment of the NMR signals.

7 r

'H NMR (500 MHz, CDC1 ₃ ): δ (ppm) = 6.25 (dd, 1H, J= 5.59 & 2.96, H _2&3 ), 6.12 (dd, 1H, J = 5.59 & 3.17, H _2&3 ), 3.07 (s, 1H, Hi _&4 ), 2.86 (s, 1H, H, _&4 ), 2.45 (dd, 1H, J = 12.02 & 3.96, H ₇ ), 1.48 (m, 2H, H ₆ ), 1.18 (m, 3H, H ₈ ), 0.89 (m, 1H, J = 12.02, H ). ¹³ C NMR (125.6 MHz, CDC1 ₃ ): δ (ppm) = 186.03, 139.03, 133.82, 50.71 , 49.77, 49.32, 43.13, 37.64 and 24.49.

Example M2 Synthesis of Endo-5-Methyl-Exo-5-Methyl Hydroxy-2- Norbornene

[0046] 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). With the container submerged in an ice-water bath, the dilute Vitride® was added dropwise over 3 hours while maintaining pot temperature between 5-20 °C. After the addition was complete, the contents were heated to 100 °C for 6 hours (until thin Attorney Docket No. PLY209-0003A layer chromatography (TLC) indicated a completed reaction). The contents were allowed to cool overnight. The solution was slowly added to a beaker containing vigorously stirring 5N HC1 (1000 mL). The temperature was maintained < 20 °C with the aid of an ice-bath. The mixture was transferred to a separatory funnel once turbidity decreased. The organic phase was then diluted with diethyl ether (1.0 L) and the aqueous phase was discarded. The organics were washed with a solution of IN HC1 (3 x 300 mL), 15 wt % aqueous potassium bicarbonate (3 x 300 mL) and water (500 mL). Following, the organics were dried over MgSC , then filtered, and the solvent removed under reduced pressure to yield NB(endo-Me)(exo-CH ₂ OH) (152 g, 96%, in > 95% purity).

[0047] The monomer was characterized by Ή NMR and ¹³ C NMR. The numbering system shown in the following figure was used for the assignment of the NMR signals.

Ή NMR (300 MHz, CDC1 ₃ ): δ (ppm) = 6.12 (m, 2H, H _2&3 ), 3.56 (m, 2H, H ₉ ), 2.76 (bs, 1H, HUM), 2.55 (bs, 1H, H,^), 2.14 (m, 1H, H ₁₀ ), 1.55 (d, 1 H, J = 8.62, H ₆ ), 1.44 (m,

IH, J = 11.72 & 3.71, H ₇ ), 1.35 (d, 1H, J = 8.62, H ₆ ), 0.91 (s, 3H, H ₈ ), 0.77 (m, 1H, J =

I I.72 & 2.68, H ₇ ). ¹³ C NMR (75 MHz, CDC1 ₃ ): δ (ppm) = 136.75, 135.68, 72.26, 47.85, 47.61, 43.70, 37.34, 22.87.

Example M3-Synthesis of Endo-5-Methyl-Exo-5-Methoxy-Mesylate-2- Norbornene

[0048] NB(endo-Me)(exo-CH ₂ OH) (74.8 g, 540 mmol) was dissolved in 250 ml

dichloromethane in appropriately sized container. Methanesulfonyl chloride (MsCl) (65.6 g, 0.54 mol) was added. The mixture was then cooled to -12.5°C with a methanol-ice bath. Triethylamine (65.6 g, 650 mmol) was added slowly dropwise while maintaining the reaction temperature below -1.0 °C. Copious white solids Attorney Docket No. PLY209-0003A precipitated. The addition was complete after 30 minutes. The reaction warmed to 14 °C over 40 minutes. GC analysis showed all starting material had been consumed. The mixture was treated with 200 ml water and the phases separated. The organic phase was washed with 200 ml IN HC1 followed by brine until the washing gave pH~6. The organic portion was dried over anhydrous magnesium sulphate, filtered, and rotary evaporated to give 100 g (90% yield) of NB(endo- Me)(exo-CH ₂ OMs) as a pale orange liquid.

[0049] The monomer was characterized by Ή NMR. The numbering system shown in the following was used for the assignment of the NMR signals.

'H NMR (400 MHz, CDC1 ₃ ): δ (ppm) = 6.11 (m, 1H, H _2&3 ), 6.10 (m, 1H, H _2&3 ), 4.10 (s,

2H, H ₉ ), 2.96 (s, 3H, H ₁₀ ), 2.78 (s, 1H, Hi _&4 ), 2.57 (s, 1H, H _1&4 ), 1.48 (m, 2H), 1.39 (m,

1H), 0.91 (s, 3H, H ₈ ), 0.80 (m, 1H, H _r ).

Example M4- Synthesis of Endo-5-Methyl-Exo-5-Bromomethyl-2-Norbornene

[0050] NB(endo-Me)(exo-CH ₂ OMs) (10.3 g, 46.3 mmol), anhydrous lithium bromide (6.2 g, 69.4 mmol), and 100 ml 2-pentanone were mixed together at room

temperature to give a yellow solution. The mixture was refluxed for two hours and then allowed to stir at room temperature overnight. Water was added to dissolve the salts. Ethyl acetate was added and mixed. The phases were separated and the aqueous phase was extracted with 2 x 100 ml ethyl acetate. The organic portions were dried over anhydrous sodium sulfate, filtered, and rotary evaporated to give a brown oil and solid. The crude product was shown to contain a ratio of NB(endo- Me)(exo-CH ₂ OMs) : NB(endo-Me)(exo-CH ₂ Br) = 1 : 3 respectively by Ή NMR. The crude product was purified via column chromatography on silica gel (35g) and cyclohexane (250 mL) to give clear, colourless oil. R _f (cyclohexane) = 0.80. Yield = 65%. Attorney Docket No. PLY209-0003A

[0051] 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.

Ή NMR (400 MHz, CDCI3): δ (ppm) = 6.15 (dd, 1H, J = 5.60 & 2.80, H ₃ ), 6.11 (dd, 1H, J = 5.60 & 3.20, ¾), 3.56 (s, 1H, H ₈ ), 2.82 (s, 1H, H ), 2.65 (s, 1H, Hi), 1.65 (dd, 1H, J = 11.98 & 3.75, H ₇ ), 1.54 (d, 1H, J = 8.91, H ₆ ), 1.42 (d, 1H, J = 8.91, ¾), 1.01 (s, 1H, H ₉ ), 0.97 (dd, 1H, J = 12.98 & 2.72, H _r ). ¹³ C NMR (101 MHz, CDC1 ₃ ): δ (ppm) = 137.09 (C ₂ ), 135.78 (C ₃ ), 50.24 (C ₄ ), 48.29 (C ₈ ), 47.96 (C ₆ ), 43.68 (d), 40.16 (C ₇ ), 27.15 (C ₅ ), 24.86 (C ₉ ).

Example M5- Synthesis of Endo-/exo-bromobutylnorbornene

[0052] 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

dichloromethane solution was dried over sodium sulfate, filtered, and rotary evaporated to give 1570 g (quantitative yield) of red-brown liquid. The NMR was Attorney Docket No. PLY209-0003A consistent with structure and showed 5.4 wt% dichloromethane remaining. The GC analysis indicated 96.6% mesylate purity. Furthermore, the GC analysis was completed on a DB5 Column, 30 meters, 0.32 mm ID, 0.25μπι film, heat from 75°C to 300 °C @15°C/min, and held for 2 min @300°C. (Injector temperature: 250°C, Detector temperature: 350°C, Retention time: 1 1 .216 minutes)

53] 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 mixture was heated to reflux over a period of 1.5 hrs to yield a white slurry. Upon reaching reflux (101° C), the GC analysis showed no starting material. The mixture was heated an additional hour at 101 °C and then cooled to 17 °C. Two liters distilled water was added to clear the mixture. The mixture clouded again after a few minutes stirring, therefore, an additional 1 liter of water was added. The phases were separated. The reactor was rinsed with 2 x 1000 ml ethyl acetate. The aqueous phase was then extracted with two times 1L ethyl acetate washes. The organic portions were combined and rotary evaporated at < 30 °C to give 1579 g liquid and solids. The GC analysis showed 96.9% NBBuBr. The residue was mixed with 1 L dichloromethane and 1 L water to dissolve all solids. The phases were separated. The organic portion was washed with 500 ml saturated sodium bicarbonate and 500 ml brine to pH 7. The organic portion was rotary evaporated to yield a 1419 g of a brown, clear oil. The NMR analysis indicated 2.3 wt% of 2-pentanone still remaining. Ten ml of water was added and the material rotary evaporated again. However, the NMR indicated no reduction in 2-pentanone. The product was then dried over sodium sulfate, rinsed with dichloromethane and rotary evaporated to give 1375 g (99.6% yield). GC indicated 97.3% purity. 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

0.25μιη film, heat from 75°C to 300°C at 15°C/min, hold for 2min @ 300°C, Injector temperature: 250°C, Detector temperature: 350°C, Retention time: 8.584 and 8.616 minutes.

Example M6 Synthesis of Endo-/exo-bromoethylnorbornene

[0054] 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 indicated 94.6% mesylate purity. The GC analysis was completed on a DB5 Column, 30 meters, 0.32 mm ID, 0.25μηι 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.

[0055] 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. An additional 1.5 L of 2-pentanone (total volume of 2-pentanone = 16.5 L) was added as rinse. 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. When a substantial amount of 2-pentanone was removed, 200 ml water was added and the mixture rotary evaporated at 45-50 °C. This was done until no additional condensate was recovered. This yielded 1630 g brown liquid. The residue was mixed with 1 L of dichloromethane and 1 L of water. The phases were separated. The organic portion was washed with 500 ml saturated sodium bicarbonate and 1000 ml brine to pH 7. The organic portion was dried over sodium sulfate, filtered, and rotary evaporated to give 1416 g red-brown oil (96.8% yield). The NMR analysis indicated traces of 2-pentanone and some dichloromethane still remaining. GC indicated 96.7% purity.

[0056] The material was initially vacuum-distilled through a 14" Vigreux column, however, the product retained a yellow coloration. Distillation through a 10" glass helix-packed produced slightly yellow-colored material. The distillates with 96- 97.6% purity, totaling 605 g, were dissolved in 1000 ml of dichloromethane, boiled with Darco G-60 activated carbon, filtered, washed with two times 100 ml of 10% aqueous sodium bisulfite, 200 ml brine, a mixture of 100 ml saturated sodium bicarbonate and 100 ml brine, and two times 200 ml of brine. After drying over sodium sulfate, this was rotary evaporated to a nearly colorless material. Vacuum distillation through a 10" glass helix-packed column at 48-53 °C (0.69-0.95 Torr) gave 236 g colorless liquid with 98.3% purity and containing 0.3% NBEtCl, 0.3% NBEtOH, and 0.9% dihydroNBEtBr. Also obtained was 117 g colorless liquid with 97.4-97.8% purity and 168 g colorless liquid with 96.6-96.8% purity.

[0057] The distillates with >98% purity, totaling 576 g, were dissolved in 1000 ml dichloromethane, washed with 2 x 100 ml 10% aqueous sodium bisulfite, 200 ml Attorney Docket No. PLY209-0003A brine, a mixture of 100 ml saturated sodium bicarbonate and 100 ml brine, and 2 x 200 ml brine. After drying over sodium sulfate, this was rotary evaporated to still give a yellow liquid. Vacuum distillation through a 10" glass helix-packed column at 48-54 °C (0.76-1.30 Torr) yielded 245 g colorless liquid with 98.2-98.5% purity and containing 0.3-0.6% NBEtCl, 0.4-0.6% NBEtOH, and 0.6-0.8%

dihydroNBEtBr. Also collected were 35.7 g colorless liquid with 97.8% purity. The last two distillation cuts, totaling 266 g with >98% purity, were still slightly yellow and were redistilled through the 10" glass helix-packed column at 43-50°C (0.46-1.00 Torr) to give 251 g of colorless liquid with 98.2-98.8% purity and containing <0.2% NBEtCl, <0.3% NBEtOH, and 0.8-1.5% dihydroNBEtBr. The overall yield was 733 g of >98% purity (46.8% yield), 153 g with 97.4-97.8% purity (9.8% yield), and 168 g with 96.6-96.8% purity (10.7% yield). GC analysis completed on a DB5 Column, 30 meters, 0.32 mm ID, 0.25μιη film, Heat from 75°C to 300"C at 15°C /min, hold for 2min @ 300°C, Injector temperature: 250°C, Detector temperature: 350°C, Retention time: 4.305 and 4.332 minutes.

Example M7 - Synthesis of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-N,N,N- trimethylethanaminium bromide

[0058] An appropriately sized container was charged under nitrogen with

tetrahydrofuran (180g, 202 mL), 2-bromoethyl norbornene (20.1 lg, 100 mmol) and a stock solution of trimethylamine (45% aqueous 65.7g 79.1ml). The contents were stirred for 48 hours, at which time the solvents were removed under reduced pressure. A portion of drum grade toluene (200ml, 173g) was added. The solvents were then removed once again under reduced pressure with the toluene being useful to promote the azeotropic removal of water. The azeotropic removal of water was repeated with toluene (200ml 173g) and subsequently with heptane (200ml, 136g). The resulting powder was dried under vacuum for 18 hours.

[0059] The monomer was characterized by 1H NMR. The numbering system shown in the following figure was used for the assignment of the NMR signals. Attorney Docket No. PLY209-0003A

Ή NMR (500 MHz, CDC1 ₃ ): δ (ppm) = 6.20 (dd, 1H, H _2&3 ), 6.03 (dd, 1H, H _2&3 ), 3.55- 3.75 (2H, H ₉ ) 3.4-3.55 (m, 9H, H _I0 ) 2.84 (s, 1H, 2.63 (s, 1H, Hi _&4 ), 2.05 (1H,

H _r ), 1.48 (2H, H ₅ ), 1.38 (m, 1 H, H ), 1.21 (m, 2H, H ₈ ), 0.59 (dd, 1H, J = 12.02, H ₇ ).

A.Svnthesis of Polymers

Example PI: ROMP Mass Polymerization

[0060] 5-Hexylbicyclo[2.2. l]hept-2-ene (HexNB), 5-(4- bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr) and l,4-di(bicyclo[2.2.1]hept-5-en- 2-yl)butane (NBBuNB) were weighed and transferred into an appropriately sized container. 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 P2: 2, 3 Vinyl Addition Mass Polymerization

[0061] 5-Hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(4- bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr) and l ,4-di(bicyclo[2.2.1]hept-5-en- 2-yl)butane (NBBuNB) were weighed and transferred into an appropriately sized container. A catalyst solution of (acetato-0)(acetonitrile)bis[tris(l- methylethyl)phosphine] palladium tetrakis(2,3,4,5,6-pentafluorophenyl)borate 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. Attorney Docket No. PLY209-0003A

Table 1 : Polymerization*

* All values are in grams

Example(s) P3: Synthesis of NB-alkyl/NB-alkylbromide Polymers

[0062] Example 3P3: Synthesis of 53%NB-EtBr/47% Hexyl NB Polymer.

While the following is the specific procedure used for the synthesis of the named polymer, one of ordinary skill in the art will appreciate that such procedure can also be viewed as a general procedure for solution polymerization to produce the polymers listed in Table 2, or any other NB-alkyl NB-alkylbromide type polymer, where the substitution of appropriate ratios of selected monomers, and appropriate amounts of catalyst and solvents are made.

[0063] An appropriately sized container was charged under nitrogen with drum grade toluene (510g, 589.6 mL), 5-hexylbicyclo[2.2.1]hept-2-ene (Hexyl norbornene, 70.01g, 392.6 mmol), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (Bromobutyl norbornene, 29.99g 130.9mmol) and ethyl acetate (24.95 g, 27.66 ml). The mixture was held at 40°C in a constant temperature oil bath, while being sparged with nitrogen for 15 minutes. A solution of Ni(toluene)(QH ₅ )2 (3.17g 6.54mmol) in ethyl acetate (31.7g 35.2ml) was added in one portion to the vigorously stirred reaction mixture. The reaction was stirred vigorously and held at 40°C for four hours, at which time the reaction was quenched by the addition of deionized water (10ml). Residual nickel metal was removed by treatment of the reaction mixture with hydrogen peroxide (35% aqueous solution l Og) and glacial acetic acid (97+%, lOg) and stirring was continued for two hours while maintaining the temperature at 40°C.

[0064] 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 molecular weight by GPC was Mn = 27,501 a.m.u.; Mw = 107,013 a.m.u.; PDI = 3.89. The polymer composition as measured by 1H NMR was 53 mole % norbornene ethyl bromide and 47 mole % hexyl norbornene.

Table 2:

FORMATION OF FILMS

Film Example Fl: Procedure for Casting Film and Amine/Hydroxide

Treatment of the Film

Step 1 : Preparation of Polymer Solution

65] A copolymer of HexNB/NBBuBr) was dissolved in THF (30 wt%). The polymer solution was filtered through a 2.7 micron glass fiber filter. Attorney Docket No. PLY209-0003A

Step 2: Preparation of Film

[0066] 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.

Step 3:Quarternarization of Film

[0067] A sample film was placed between PTFE flanges. The sample film was

submerged in trimethylamine 50 wt% aqueous solution for 48 hours. The amine treated film was air dried for 12 hours. The film was then vacuum dried for 8 hours.

Step 4: Anion Exchange of Quarternarized Film

[0068] 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.

Film Example F2 Control - no added amine

[0069] 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.

Film Example F3: With added N,N,N',N'-tetramethyl-l,6-hexanediamine

[0070] A 13.08g aliquot of the polymer solution prepared in Example 1 was

transferred into a 50 mL amber bottle. 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 102μηι thick.

B. Ionic Conductivity of the Film

[0071] 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.

[0072] 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. A sinusoidal voltage is applied to the outer two electrodes and the current measured. The voltage across the inner two electrodes is measured. Thus, R=V/I at the inner electrodes. In the configuration, the contact resistance at the inner electrodes is negligible since the current flowing through them is nearly zero. Attorney Docket No. PLY209-0003A

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. R-(rho) (thickness)/(area). The area here is the cross sectional area: thickness of film times 1 cm (width).

[0073] 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. Then the wet mass of 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. Thus the IEC is expressed as milliequivalents of hydroxide ions per gram of dry membrane (in the chloride ion form).

[0074] In the table below, where presented, the values for Theoretical Ion Exchange Capacity (IEC) have the dimension milliequivalents per gram (meq/g) and the values for Conductivity (COND) are in milliSiemens per cemtimeter (mS/cm).

Table 3

Attorney Docket No. PLY209-0003A

PROPHETIC EXAMPLE 1

[0075] Preparation of poly(exo-norbornenylphenmethylammonium hydroxide),

Ni-catalyzed polymerization

[0076] To 4-iodobenzylbromide (32 mmol) and Pd(PPh ₃ ) ₂ Cl ₂ (1.4 mmol) in 1 1 ml DMF) norbornadiene (120 mmol), potassium carbonate (100 mmol), and formic acid (88%, 66 mmol) should be added. The solution should then be heated to 80°C for about 6 hours with periodic TLC monitoring to judge completion. Then the reaction mixture should be transferred to a separatory funnel with 50 mL 10% HC1 and 50 mL heptane and the resulting organic phase extracted at least two times with 50 mL of 10% HC1. 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.

[0077] 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.

[0078] After purification, 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. Where a solution of an appropriate concentration is employed a membrane thickness of about 100 to 200 μιη 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. It is further believed 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., Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells, Fuel Cells 2005, 5 No. 2, 187-200 (2005) (see, Attachment 'C'), which is incorporated herein in its entirety.

PROPHETIC EXAMPLE 2

[0079] Preparation of an addition polymerized crosslinked polynorbornene film.

crosslinks Attorney Docket No. PLY209-0003A

[0080] A thin crosslinked addition polymerized film should be able to be synthesized by first combining a palladium catalyst composition (Pd 1206

((acetonitrile)bis(triisopropylphosphine)palladium(acetat e)

tetrakis(pentafluorophenyl)borate) and dimethylanilinium

tetrakis(pentafluorophenyl)borate) (DANFABA)) in a dichloromethane solution to form a pre-catalyst concentrate and adding this mixture to a monomer mixture of

5-(bromomethyl)-5-methylnorbornene (80 mol%) and 1 ,4-di(norbornenyl)butane (20 mol%) monomers to obtain a homogeneous solution at room temperature. The catalyst molar reaction ratio of such a mixture would be about 10,000:1 :4 (NB

monomers:Pd:DANFABA). A portion of this solution should then be poured into a glass dish to give a thin coating of reaction mixture and then heated to 80°C for about 30 minutes to evaporate excess solvents and then for about an additional 30 minutes at 130°C allow for polymerization and crosslinking. A clear thin film of crosslinked polymer should result which should then be treated with a 40% solution of

trimethylamine to generate a quaternary ammonium bromide functionalized membrane which should then be converted to the hydroxide form as described in Prophetic Example 1.

[0081] 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.

PROPHETIC EXAMPLE 3

[0082] Preparation of a ring-opened metathesis crosslinked polynorbornene film. Attorney Docket No. PLY209-0003A

[0083] 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. The catalyst molar reaction ratio for such a mixture should be about 10,000: 1 (NB monomers:Ru). To form a film, a portion of this solution should be poured into a glass dish to give a thin coating of reaction mixture and allowed to sit at room temperature to gel, after- which it should be slowly heated to 80°C for about 30 minutes for curing. Since the polymer that would be formed by the above method will be unsaturated, optionally, the crosslinked film can be hydrogenated at this point. The crosslinked film should then be treated with potassium hydroxide solution (1M) to convert it to its hydroxide form.

[0084] 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.

PROPHETIC EXAMPLE 4

[0085] Preparation of a ring-opened metathesis crosslinked polynorbornene film.

[0086] 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)rut henium (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

monomers:Ru). To form a film, a portion of this solution should be poured into a glass dish to give a thin coating of reaction mixture and allowed to sit at room temperature to Attorney Docket No. PLY209-0003A gel, after-which it should be slowly heated to 80°C for about 30 minutes for curing. Since the polymer that would be formed by the above method will be unsaturated, optionally, the crosslinked film can be hydrogenated at this point. The crosslinked film should then be treated with potassium hydroxide solution (1M) to convert it to its hydroxide form.

[0087] 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.

[0088] By now it should be realized that a variety of methods for making polymeric materials have been disclosed, where such polymeric materials are useful for forming membranes that are additionally useful for forming membranes that can be employed in forming an Alkali Fuel Cell that addresses the issues with previously known AFCs. For example, it is believed that an AFC that encompasses an AAEM made using a polymer embodiment in accordance with the present disclosure will be long-lived and resistant to being blocked or destroyed by carbonate formation as discussed above. Further it is believe that AAEMs made from the fully saturated polymer embodiments of the present disclosure will be more oxidatively stable than any AAEM made from an unsaturated polymer.

[0089] Additionally, it should be realized that the polymer embodiments in accordance with the present disclosure are also useful for forming elements of an AFC other then the AAEM. For example, referring to paragraphs [0028] through [0039] in US Patent Application No. 2007/0128500, which is incorporated herein by reference in its entirety, it is disclosed that 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.