Compounds, Compositions and Polymer Films

Abstract

A polymer film obtainable by curing a composition comprising a compound of Formula (I) wherein: R′ is vinyl, epoxy C.sub.1-3_alkylenethiol: n has a value of 1 or 2; m has a value of 1, 2 or 3; M′.sup.+ is a cation; wherein X is as defined in the claims; and wherein the molar fraction of the compound of Formula (I) in relation to all curable compounds in the composition is greater than 0.25. Also claimed are compositions, processes membranes and their uses.

##STR00001##

Claims

1. A polymer film obtainable by curing a composition comprising a compound of Formula (I): ##STR00029## wherein: R′ is vinyl, epoxy or C.sub.1-3_alkylenethiol: n has a value of 1 or 2; m has a value of 1, 2 or 3; M′.sup.+ is a cation; wherein: (i) when m and n both have a value of 1 then X is vinylphenyl or of Formula (II): ##STR00030## wherein in Formula (II): R″ is vinyl, epoxy or C.sub.1-3_alkylenethiol; M″.sup.+ is a cation; and n in Formula (II) has a value of 1 or 2; (ii) when m has a value of 2 or 3 then X is C.sub.1-6-alkylene, C.sub.6-18-arylene, or N(R′″).sub.(3-m) wherein each R′″ independently is H or C.sub.1-4 alkyl; and (iii) when m has a value of 1 and n shown in Formula (I) has a value of 2 then X is of Formula (II) (as defined above) or C.sub.1-6-alkyl, C.sub.6-18-aryl, or N(R′″).sub.2 wherein each R′″ independently is H or C.sub.1-4 alkyl; wherein the molar fraction of the compound of Formula (I) in relation to all curable compounds in the composition is greater than 0.25.

2. The polymer film according to claim 1 wherein n shown in Formula (I) has a value of 1 and m has a value of 2.

3. The polymer film according to claim 1 wherein the composition further comprises a compound comprising one and only one polymerisable group and a bissulfonylimide group.

4. The polymer film according to claim 1 wherein the composition comprises the following ingredients: (a) a compound of Formula (I); optionally (b) a compound comprising one and only one polymerisable group; optionally (c) a solvent; and optionally (d) a radical initiator.

5. The polymer film according to claim 1 which comprises: (a) 20 to 80 wt % of component (a); (b) 0 to 50 wt % of component (b); (c) 10 to 40 wt % of component (c); and (d) 0 to 10 wt % of component (d).

6. (canceled)

7. The polymer film according to claim 1 which is a cation exchange membrane.

8. A bipolar membrane comprising the polymer film according to claim 1.

9. The polymer film according to claim 1 which further comprises a porous support.

10. A method of using the polymer film according to claim 7 for the treatment of polar liquids, for the generation of hydrogen or for the generation of electricity.

11. A method of using the bipolar membrane according to claim 8 for production the acids and bases, for the separation and treatment of organic acids or for the generation of electricity.

12. The polymer film according to claim 1 wherein the composition comprises 20 to 80 wt % of the compound of Formula (I).

13. The polymer film according to claim 1 wherein the molar fraction of the compound of Formula (I) in relation to all curable compounds in the composition is greater than 0.30.

14. The polymer film according to claim 1 being free from perfluoro-groups.

15. The polymer film according to claim 1 wherein M′.sup.+ and M″.sup.+ are independently selected from H.sup.30, Li.sup.+, Na.sup.+, K.sup.+ or NL.sub.4.sup.+ wherein each L independently is H or C.sub.1-3-alkyl.

16. The polymer film according to claim 3 wherein said compound comprises a compound of Formula (III): ##STR00031## wherein R is C.sub.1-4 alkyl, NH.sub.2, C.sub.6-12 aryl; and M.sup.+ is H.sup.30, Li.sup.+, Na.sup.+, K.sup.+, or NL.sub.4.sup.+ wherein L is H or C.sub.1-3 alkyl.

17. The polymer film according to claim 1 wherein (i) the composition comprises 20 to 80 wt % of the compound of Formula (I); (ii) the molar fraction of the compound of Formula (I) in relation to all curable compounds in the composition is greater than 0.30; and (iii) polymer film is free from perfluoro-groups.

18. The polymer film according to claim 17 wherein the composition further comprises a compound comprising one and only one polymerisable group and a bissulfonylimide group.

19. The polymer film according to claim 18 wherein n shown in Formula (I) has a value of 1 and m has a value of 2.

Description

EXAMPLES

[0185] In the following non-limiting Examples all parts and percentages are by weight unless specified otherwise.

TABLE-US-00001 TABLE 1 Ingredients Component Abbreviation Type Description XL-B (a) Benzenesulphonamide, 4-ethenyl-N-[(4- ethenylphenyl)sulphonyl]-, lithium salt 4OH- 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, a TEMPO polymerization inhibitor from Sigma-Aldrich LiSS Styrene sulphonate, lithium salt from Tosoh Chemicals (A Comparative Example) MM-Tf Benzenesulphonamide, 4-ethenyl-N- [(trifluoromethyl)sulphonyl]-, lithium salt (A Comparative Example) MM-M (b) Benzenesulphonamide, 4-ethenyl-N- (methylsulphonyl)-, lithium salt MM-A (b) Benzenesulphonamide, 4-ethenyl-N- (aminosulphonyl)-, lithium salt MM-P (b) Benzenesulphonamide, 4-ethenyl-N- (phenylsulphonyl)-, lithium salt XL-D (a) Benzenesulphonamide, 2,4-diethenyl-N- (methylsulphonyl)-, lithium salt XL-2 (a) 1,3-[N-(ethenylphenylsulphonyl)benzene sulphonamide], dilithium salt MeOH (c) Methanol from Sigma-Aldrich IPA (c) Isopropyl alcohol from Sigma-Aldrich MCH (c) Methylcyclohexane from Sigma-Aldrich 1MP (c) 1-methyl pyrrole from Sigma-Aldrich DMSO (c) Dimethylsulfoxide from Sigma-Aldrich TEOA (c) Triethanolamine from Sigma-Aldrich THF Tetrahydrofuran from Sigma-Aldrich LiH Lithium hydride from Sigma-Aldrich Celite ™ Celite ™ S, diatomaceous earth (SiO.sub.2) from Sigma- Aldrich DVBS-Na Divinylbenzenesulphonate, Sodium salt from Tosoh Chemicals LAP (d) phenyl-2,4,6-trimethylbenzoylphosphinate, lithium salt from Sigma-Aldrich (a photoinitiator) Na-AMPS Sodium salt of 2-acrylamideo-2-methylpropane sulfonic acid, 50 wt % in water from Sigma-Aldrich. (A Comparative Example) M-11 Sodium 5-(prop-2-enoylamino)-2-[4-(prop-2- enoylamino)-2-sulfonato-phenyl]benzenesulfonate. Structure is shown below, preparation method was as described in EP2965803. Omnirad ™ (d) Ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate, TPO-L a photoinitiator from IGM Resins Omnirad ™ (d) 2-hydroxy-2-methyl-1-phenylpropanone, a 1173 photoinitiator from IGM Resins PP/PE A polypropylene/polyethylene porous support Support obtained under the name FO2223-10 from Freudenberg PE support A non-woven polyethylene fabric obtained under the name Soluporfrom Lydall performance materials [00016]

[0186] Inductively coupled plasma atomic emission spectroscopy (ICP-OES) was used to quantify the lithium content of the prepared compounds of Formula (I). The ICP-OES analyses were performed using a Thermo iCAP™ PRO XP ICP-OES apparatus from Thermo Fisher Scientific. A concentric nebulizer was used in conjunction with a Cyclonic spray chamber. Approximately 50 mg of each compound under test was dissolved in 50 cm.sup.3 of Milli-Q water. The dissolved compounds were diluted 100 times, and acidified with 0.5% concentrated nitric acid containing Yttrium as internal standard. All samples were prepared and measured in duplicate. Results are expressed as g of Li per kg monomer.

[0187] The structures of the compounds of Formula (I) were confirmed by .sup.1H-NMR using a Magritek Spincolve 60 Carbon (60 MHz, 4 scans) NMR spectrometer. Samples for analysis were prepared by dissolving 5 wt % of each compound of Formula (I) in DMSO-d.sub.6.

[0188] Example structures of compounds of Formula (I):

##STR00017##

[0189] The purity of the compounds of Formula (I) was determined by HPLC-MS. A

[0190] Waters ACQUITY UPLC System with 2D Technology was used. The UPLC was equipped with 2 pumps (BSM and QSM), FTN sample manager, column manager and a PDA detector (192 until 400 nm). The HPLC was equipped with a Waters Xbridge C8 5 μm 2.1*150 mm column, using 45° C. as working temperature. Additionally, the instrument was also equipped with Waters Q-TOF premier mass spectrometer with ESI and ESCi ionisation options. Dual detection mode was used to collect the chromatogram. The PDA detector collected signals at 245 nm. The mass detector was set in negative mode to detect anionic molecules. Samples containing compounds of Formula (I) were prepared as follows: 5 mg of the compounds of Formula (I) was dissolved in 50 ml Milli-Q water. The resultant solution was diluted 10 times with Milli-Q water and 10 μl volume was injected into the abovementioned HPLC-MS apparatus for analysis.

[0191] Table 2 shows the typical method employed to elute the samples of the compounds of Formula (I) indicated in Table 3. In Table 3, an overview of the retention times and molecular weights recorded for material identification is given

TABLE-US-00002 TABLE 2 HPLC method Flow Solvent Solvent Rate 1 (%): 2 (%): Time (min) (ml/min) water MeOH 0.0 0.6 95.0 5.0 1.0 0.6 95.0 5.0 30.0 0.6 0.0 100.0 34.1 0.6 95.0 5.0 40.0 0.6 95.0 5.0

TABLE-US-00003 TABLE 3 Identification of example materials and impurities. Exact Mass Retention mass observed time Compound (Daltons) (Daltons) (min)* LiSS 190 183 12.2 Na-DVBS 232 209 19.5 XL-2 580 573 17.5 XL-B 355 348 25.4 XL-D 293 286 20.2 *Retention times are indicative. Small shifts retention times were observed between samples depending on the sample's purity among other factors. CI-SS and CI-DVBS were converted into their sulphonic acids upon dissolution in water.

[0192] The solubility of the compounds of Formula (I) was determined visually or by UV-spectrometry. For each compound of Formula (I), three solutions were prepared at 40° C.: one solution at 30 wt %, one solution at 60 wt %, and one solution at 70 wt %. 500 ppm 4OH-TEMPO was included in all three solutions to prevent premature polymerisation. The solutions were kept in a water bath of 40° C. overnight and centrifuged prior inspection. UV spectra were recorded in a Cary ™ 100 UV-visible spectrophotometer from Agilent Technologies using a 1 mm path length quartz cuvette.

##STR00018##

TABLE-US-00004 TABLE 4 Solubility in water of several compounds of Formula (I) and of a comparative compound (DVBS-Na) Compounds of Formula (I) Solubility in water Name R n m X M at 40° C. (wt %) XL-D vinyl 2 1 methyl Li >70 XL-B vinyl 1 1 p-vinylphenyl Li 56 XL-2 vinyl 1 2 phenylene Li >70 (C.sub.6H.sub.4) DVBS-Na — — — — — 8

[0193] In separate experiments from those shown in Table 4 and for comparison, the highest solubility achieved by combining lithium styrene sulphonate (LiSS) and DVBS-Na was 55 wt % whereas when such monomers (e.g. LiSS and NaSS) were combined with the compounds of Formula (I), compositions were achieved with solid contents of more 70 wt %.

[0194] ER (ohm.cm.sup.2) of the polymer films prepared in the Examples was measured by the method described by Dlugolecki et al., J. of Membrane Science, 319 (2008) on page 217-218 with the following modifications: [0195] the auxiliary membranes were CMX and AMX from Tokuyama Soda, Japan; [0196] the capillaries as well as the Ag/AgCl references electrodes (Metrohm type 6.0750.100) contained 3M KCl; [0197] the calibration liquid and the liquid in compartment 2, 3, 4 and 5 was 0.5 M NaCl solution at 25° C.; [0198] the effective polymer film area was 9.62 cm.sup.2; [0199] the distance between the capillaries was 5.0 mm; [0200] the measuring temperature was 25° C.; [0201] a Cole Parmer Masterflex console drive (77521-47) with easy load II model 77200-62 gear pumps was used for all compartments; [0202] the flowrate of each stream was 475 ml/min controlled by Porter Instrument flowmeters (type 150AV-B250-4RVS) and Cole Parmer flowmeters (type G-30217-90); and [0203] the samples of polymer film were equilibrated for at least 1 hour at room temperature in a 0.5 M solution of NaCl prior to measurement.

[0204] Preferably, the ER (for 0.5 M NaCl) is lower than 5 ohm.cm.sup.2, more preferably lower than 2.5 ohm.cm.sup.2.

Measurement of Permselectivity (PS)

[0205] The permselectivity PS (%) that is the selectivity to the passage of ions of opposite charge to that of the polymer films prepared in the examples, was measured as follows. The polymer film to be analysed was placed in a two-compartment system. One compartment is filled with a 0.05M solution of NaOH and the other with a 0.5M solution of NaOH.

[0206] Settings: [0207] the capillaries as well as the Ag/AgCl reference electrodes (Metrohm type 6.0750.100) contained 3M KCl; [0208] the effective polymer film area was 9.62 cm.sup.2; [0209] the distance between the capillaries was ca 15 mm; [0210] the measuring temperature was 21.0±0.2° C.; [0211] a Cole Parmer Masterflex console drive (77521-47) with easy load II model 77200-62 gear pumps was used for the two compartments; [0212] Porter Instrument flowmeters (type 150AV-B250-4RVS) and Cole Parmer flowmeters (type G-30217-90) were used to control the flow constant at 500 ml/min; [0213] The samples of polymer film were equilibrated for 1 hr in a 0.5M NaOH solution prior to measurement. The voltage was read from a regular VOM (multitester) after 20 minutes.

[0214] Preferably the PS for NaOH is at least 50%.

pH Stability

[0215] Stability in acidic and/or alkaline conditions is preferred as it widens the scope of applications the polymer films can be used in. Stability is typically tested by immersing samples of the polymer film under evaluation in 4M of HCl or NaOH at 80 degrees for 7 days. After this treatment, the selectivity of the polymer film should be at least 80% of the original selectivity to be judged as stable.

Extraction Analysis

[0216] In order to analyse the polymerisation degree of polymer films and show the presence of the claimed materials in polymer films, samples of the polymer films were extracted with purified water (10 cm.sup.2 in 50 mL purified water) after which the extraction liquid was analysed using the HPLC-MS method described above

Preparation of Compounds of Formula (I) and Comparative Compound

Synthesis of Starting Materials

[0217] ##STR00019##

[0218] Thionyl chloride (109 mL, 178.46 g, 1.5 mol, 3 moleq) was added dropwise to a solution of 4-vinylbenzenesulfonic acid lithium salt (95.08 g, 0.500 mol, 1 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in DMF (300 mL) in a double-walled reactor that was actively cooled to 5° C. After the addition was completed, the solution was allowed to slowly heat to room temperature and was stirred for another 16 hours. Then the reaction mixture was poured into 1 liter of cold 1M KCl in a separation funnel. The bottom layer was removed and dissolved in 500 mL diethylether. This solution was washed with a 1M KCl-solution (300 mL). The organic layer was dried over sodium sulfate, filtered and concentrated in vacuum to give a yellow oil. The crude product was used without further purification in the next step. Typical yield was 89.5 g (88%). HPLC-MS purity>98%; .sup.1H-NMR:<2 wt % DMF, 0% diethyl ether.

##STR00020##

[0219] Thionyl chloride (75 mL, 123.1 g, 1.034 mol, 3 moleq) was added dropwise to an solution of divinylbenzene sulfonate sodium salt (80 g, 0.345 mol, 1 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in DMF (300 mL) in a double-walled reactor that was actively cooled to 5° C. After the addition was completed, the solution was allowed to slowly heat to room temperature and was stirred for another 16 hours. Then the reaction mixture was poured into 1 liter of cold 1M KCl in a separation funnel. The bottom layer was removed and dissolved in 500 mL diethylether. This solution was washed with a 1M KCl-solution (300 mL). The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo to give a yellow oil. The crude product was used without further purification in the next step. Typical yield was 62 g (79%). HPLC-MS purity>98%; .sup.1H-NMR:<2 wt % DMF, 0% diethyl ether.

##STR00021##

[0220] Thionyl chloride (109 mL, 178.46 g, 1.5 mol, 3 moleq) was added dropwise to a solution of 4-vinylbenzene-sulfonic acid lithium salt (95.08 g, 0.500 mol, 1 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in DMF (300 mL) in a double-walled reactor that was actively cooled to 5° C. After the addition was completed, the solution was allowed to slowly heat to room temperature and was stirred for another 16 hours. Then the reaction mixture was poured into 1 liter of cold 1M KCl in a separation funnel. The bottom layer was removed and was added dropwise to a solution of ammonium hydroxide 25% in water (250 mL, 3.67 mol, 15 moleq) and 4OH-TEMPO (50 mg, 500 ppm) in a double-walled reactor that was actively cooled to 5° C. After the addition was completed, the solution was stirred for 1 hour. The solution was then allowed to heat to room temperature and was stirred for one hour.

[0221] Then the reaction mixture was cooled back to 5° C. and the product was filtered off and washed with 50 mL of cold water. The product was dried overnight in vacuum at 30° C. and used without further purification. Typical yield was 66.8 g (73%). HPLC-MS purity>95%.

Synthesis of Compounds of Formula (I)

Example 1—-XL-D

[0222] ##STR00022##

[0223] Before the synthesis, methane sulfonamide was dried in a vacuum oven overnight (30° C., vac). To a solution of the dried methane sulfonamide (8.32 g, 0.087 mol, 1 moleq) and 4OH-TEMPO (30 mg, 500 ppm) in THF (100 mL) was added LiH (1.53 g, 0.192 mol, 2.2 moleq) as a solid at once. The reaction mixture was stirred for 30 minutes at room temperature. Then, a solution of Cl-DVBS (20 g, 0.087 mol, 1 moleq) in THF (50 mL) was added to the reaction mixture. After addition, the reaction mixture was heated to 60° C. (water bath temperature). After two days, the reaction mixture was filtrated over celite to remove the excess of LiH. The filtrate was concentrated in vacuo to give a light yellow foam. The resulting foam was dissolved in 500 mL ethyl acetate. Celite was added and the resulting slurry was stirred for 5 minutes. Then, the celite was filtered off and washed with 100 mL ethyl acetate. This Celite procedure was then repeated. The solvent was then evaporated in vacuo and the resulting white foam was washed with 500 mL diethyl ether overnight. The resulting white powder was filtered off and dried in a vacuum oven at 30° C. for 16 h yielding a hygroscopic white solid. Typical achieved yield wa 15.5 g (60%). HPLC-MS purity>95%; .sup.1H-NMR:<3 wt % residual solvents; 2 wt % divinylbenzene sulfonate; ICP-OES: 24-30 g Li/kg product.

Example 2—-XL-B

[0224] Before the synthesis, benzene sulfonamide was dried in a vacuum oven overnight (30° C., vac). To a solution of the dried benzene sulfonamide (11.12 g, 0.061 mol, 1 moleq) and 4OH-TEMPO (30 mg, 500 ppm) in THF (100 mL) was added LiH (1.06 g, 0.134 mol, 2.2 moleq) as a solid at once. The reaction mixture was stirred for 30 minutes at room temperature. Then, a solution of Cl-SS (12.3 g, 0.061 mol, 1 moleq) in THF (50 mL) was added to the reaction mixture. After

##STR00023##

addition, the reaction mixture was heated to 60° C. (water bath temperature). After two days, the reaction mixture was filtrated over celite to remove the excess of LiH. Celite was added and the resulting slurry was stirred for 5 minutes. Then, the celite was filtered off and washed with 100 mL ethyl acetate. The solvent was then evaporated in vacuo and the resulting white foam was washed with 500 mL diethyl ether overnight. The resulting white powder was filtered off and dried in a vacuum oven at 30° C. for 16 h yielding a white solid. Typical yield was 11 g (51%). HPLC-MS purity>94%; .sup.1H-NMR:<1 wt % residual solvents, <5 wt % styrene sulfonate or styrene sulfonamide; ICP-OES: 21-26 g Li/kg product.

Example 3—-XL-2

[0225] ##STR00024##

[0226] Before the synthesis, styrene sulfonamide was dried in a vacuum oven overnight (30° C., vac). To a solution of the dried styrene sulfonamide (16.90 g, 0.092 mol, 2.05 moleq) and 4OH-TEMPO (30 mg, 500 ppm) in THF (100 mL) was added LiH (1.50 g, 0.189 mol, 4.2 moleq) as a solid at once. The reaction mixture was stirred for 30 minutes at room temperature. Then, a solution of 1,3 benzene disulfonyl chloride (12.38 g, 0.045 mol, 1 moleq) in THF (50 mL) was added to the reaction mixture. After addition, the reaction mixture was heated to 60° C. (water bath temperature). After 2 days, the reaction mixture was filtrated over celite to remove the excess of LiH. The filtrate was concentrated in vacuo to give a light yellow foam. The resulting foam was dissolved in 500 mL ethyl acetate. Celite was added and the resulting slurry was stirred for 5 minutes. Then, the celite was filtered off and washed with 100 mL ethyl acetate. This Celite procedure was then repeated. The solvent was then evaporated in vacuo and the resulting white foam was washed with 500 mL diethyl ether overnight. The resulting white powder was filtered off and dried in a vacuum oven at 30° C. for 16 h yielding a hygroscopic white solid. Typical achieved yield was 14.5 g (54%). HPLC-MS purity>96%; .sup.1H-NMR:<2 wt % residual solvents; <2 wt % styrene sulfonamide; ICP-OES: 35-40 g Li/kg product.

Example 4—-XL-SAS

Step 1

[0227] ##STR00025##

[0228] To a solution of bisbenzylsulfonamide in THF LiH was added. The reaction mixture was stirred for 15 minutes. Then vinylbenzenesulfonylchloride was added at once and the reaction mixture was heated to 50° C. After 20 h at 50° C. the reaction mixture was cooled down to room temperature, filtered and the residue was washed with THF. The filtrate was concentrated in vacuo. The resulting solid was stirred in ether, and filtered again. The filtrate was concentrated in vacuo and purified by column chromatography.

Step 2

[0229] ##STR00026##

[0230] The benzylprotected LiBVBSAS was dissolved in DCM and TFA, and stirred overnight at room temperature. The product was filtered off, dried in vacuum and isolated as a white solid. Typical yield of the two steps was 45%, HPLC-MS purity>96%; .sup.1H-NMR:<2 wt % residual solvents; <2 wt % styrene sulfonamide; ICP-OES: 35-40 g Li/kg product.

Preparation of Component (b)

[0231] MM-Tf, MM-A, MM-P and MM-M (referred to above) had the structures shown below.

##STR00027##

[0232] The compounds MM-Tf, MM-A, MM-P and MM-M were synthesized according to the following general scheme and procedure:

##STR00028##

General Procedure

[0233] Before the synthesis, the corresponding sulfamide was dried in a vacuum oven overnight at 30° C. To a solution of the dried sulfamide (0.100 mol, 1 moleq) and 4OH-TEMPO (30 mg, 500 ppm) in THF (100 mL) was added LiH (0.300 mol, 3 moleq) as a solid at once. The reaction mixture was stirred for 30 minutes at room temperature. Then, a solution of vinyl benzyl sulphonyl chloride (0.100 mol, 1 moleq) in THF (50 mL) was added and the reaction mixture was heated to 60° C. (water bath temperature) for 16 h. The resulting solution was filtrated over celite and the resulting foam was dissolved in 500 mL ethyl acetate. Celite was added and the resulting slurry was stirred for 5 minutes. Then, the celite was filtered off and washed with 100 mL ethyl acetate. The solvent was then evaporated in vacuum and the resulting white foam was crushed with 500 mL diethyl ether overnight. The resultant compound of Formula (b) was collected by filtration and isolated as a white hygroscopic powder. Data on yield and purity are given in Table 5 below.

TABLE-US-00005 TABLE 5 Compounds of Formula (b) and comparative compound Residual Residual Li R Yield Purity solvent LiSS content methyl 80% >94% <1% <4% 26-30 g/kg phenyl 79% >96% <1% <2% 23-28 g/kg trifluoromethyl 70%  81% 17% amino 63% >92% <1% <6% 26-40 g/kg

Composition Examples 1 to 11, Comparative Examples CEx1 to CEx5 and Polymer Films

[0234] Table 6 below describes compositions of Examples 1 to 11 according to the second aspect of the present invention and Comparative Examples CEx1 to CEx5. Each of the compositions was polymerised to form a polymer film of thickness 100 μm by coating the compositions described in Table 6 below onto PP/PE Support for reinforcement with the aid of a 100 μm Meyer bar. The electrical resistance (ER) of the resultant polymer films was measured using 0.5N NaCl, the permselectivity (PS) was measured as described above and the result is shown in Table 7 below. The pH of the resultant polymer films were measured by the method described above and the results are also shown in Table 7 below.

TABLE-US-00006 TABLE 6 Compositions Components and their amount in the composition (d) Molar Exam- (b) (b) (a) (a) (c) (LAP) fraction ple (b) (wt %) (M) (a) (wt %) (M) (c) (wt %) (wt %) (a) Ex.1 MM-M 25 0.94 XL-2 35 0.60 water/1 MP 29/10 1 0.39 Ex.2 none 0 0 XL-2 60 1.03 Water/1 MP 29/10 1 1.0 Ex.3 none 0 0 XL-D 60 2.05 MeOH 38 2 1.0 Ex.4 none 0 0 XL-D 66 2.25 MeOH 32 2 1.0 Ex.5 none 0 0 XL-2 66 1.14 water/IPA/ 20.5/3.5/ 1 1.0 1 MP  9 Ex.6 none 0 0 XL-2 67 1.15 water/IPA/ 20.5/3.5/ 1 1.0 1 MP  8 Ex.7 MM-M 12 0.45 XL-D 54 1.84 water/MCH/ 20.5/3.5/ 1 0.80 1 MP  9 Ex.8 MM-M 25 0.94 XL-B 35 0.99 Water/DMSO/ 19.3/6.4/ 1 0.51 IPA/1 MP 3.3/10 Ex.9 MM-M 19 0.71 XL-2 41 0.71 Water/IPA/ 24.9/4.1/ 1 0.50 1 MP 10 Ex.10 MM-P 34 1.03 XL-B 36 1.01 Water/TEOA 26/3 1 0.50 Ex. 11 MM-A 30 1.12 XL-B 40 1.13 Water/TEOA 26/3 1 0.50 CEx LiSS 36 1.89 Na- 20 0.86 Water/TEOA 39.5/3.5 1 0.31 1 DVBS CEx LiSS 26 1.37 XL-2 31 0.53 Water/TEOA 38/4 1 0.28 2 CEx MM-tF 39 1.21 XL-B 31 0.87 Water/TEOA 26/3 1 0.42 3 CEx Na- 30 1.31 M-11 30 0.60 Water 39 1 0.31 4 AMPS CEx. Mm-M 41 1.53 XL-2 19 0.33 Water/IPA/ 24.9/4.1/ 1 0.18 5 1 MP 10 Na-AMPS amount in the Table is based on Na-AMPS being 100% solids. The water content of Na-AMPS (as provided by the supplier) was included in the amount of component (c). M means mol per kg.

TABLE-US-00007 TABLE 7 ER, PS and pH stability of the polymer films ER PS after 7 PS after 7 (ohm .Math. PS days 4M HCl @ days 4M NaOH @ cm.sup.2) (%) 80° C. (%) 80° C. (%) (0.5N (0.05/0.5N (0.05/0.5N (0.05/0.5N Example NaCl) NaOH) NaOH) NaOH) Ex 1 1.2 52 51 50 Ex 2 1.5 64 63 64 Ex 3 1.4 51 52 53 Ex 4 1.4 58 57 56 Ex 5 1.9 57 57 58 Ex 6 1.8 70 69 72 Ex 7 1.5 52 53 51 Ex 8 1.5 50 51 50 Ex 9 1.16 61 59 61 Ex 10 1.3 60 58 59 Ex 11 1.4 55 55 56 CEx 1 1.1 25 n.m. n.m CEx 2 0.94 26 n.m. n.m CEx 3 0.87 0 n.m. n.m CEx 4 2.5 60  0  0 CEx. 5 0.7 12 n.m. n.m. n.m. means not measured

Extraction Analysis

[0235] The results of the extraction analysis described above are shown in Table 8 below.

TABLE-US-00008 TABLE 8 Extraction results Extracted Extracted Material material Material material Example (a) (a) (mg/ml) (b) (b) (mg/ml) Ex 8 MM-M 13 XL-B 8 Ex 10 MM-P 12 XL-B 9 Ex 1 MM-M 14 XL-2 11 Ex 11 MM-A 18 XL-B 15

Preparation of the AEL

[0236] An AEL composition was prepared containing N,N,N′,N′-tetramethyldiaminopropane, 1,4-bis[(4-ethenylphenyl)methyl]-, chloride (46.1 wt %), 4-Vinylbenzyl trimethylammonium chloride (23 wt %), water (28 wt %), 4-hydroxy TEMPO (2 wt %), and Omnirad™ 1173 (0.9 wt %). The AEL composition was coated onto PE Support and cured by UV to give an AEL.

Preparation of the CEL and Application to the AEL to Produce a BPM

[0237] The CEL compositions described in Table 7 were prepared (Example 9 & Comparative Example CEx4) and were coated on the AEL prepared as described above, then a second piece of PE Support was placed onto the layer of CEL composition, Excess CEL composition was wiped-off and the CEL composition was cured using UV light to give BPMs.

[0238] The electrochemical properties and bipolar characteristics of the BPMs so prepared were compared to a reference bipolar membrane (Fumasep from Fumatech) using a so-called Current-Voltage characteristic (I-U curve), where the current density was measured as a function of the applied voltage. Typically, a low voltage (U) required to generate a given current density, i.e. 600 mA/cm.sup.2 indicates that one or both of the AEL and CEL and also the BPM have a low ionic resistance. Low ionic resistance, in this case of the CEL, results in membranes that are more energy efficient. The results for Example 9 and comparative Example CEx4 are shown in Table 9 below.

TABLE-US-00009 TABLE 9 ER of CEL and voltage U of BPM at 600 mA/cm.sup.2 ER of CEL U @ 600 mA/cm.sup.2 Example (ohm/cm.sup.2) of BPM (Volt) Ex 9 1.3 3.8 CEx 4 2.5 5.5