Compositions and Polymer Films

Abstract

A polymer film obtainable by polymerising a composition comprising: (a) a compound Formula (I); wherein: R is C.sub.1-4-alkyl, NH.sub.2 or C.sub.6-12-aryl; and M.sup.+ is a cation; (b) a monomer comprising at least two polymerisable groups; and (c) a solvent. Also claimed are compositions and processes for making the polymer films.

##STR00001##

Claims

1. A polymer film obtainable by polymerising a composition comprising: (a) a compound Formula (I); ##STR00023## wherein: R is C.sub.1-4-alkyl, NH.sub.2 or C.sub.6-12-aryl; and M.sup.+ is a cation; (b) a monomer comprising at least two polymerisable groups; and (c) a solvent.

2. The polymer film according to claim 1 wherein the composition comprises: (a) 5 to 60 wt % of component (a); (b) 10 to 70 wt % of component (b); (c) 10 to 50 wt % of component (c).

3. The polymer film according to claim 1 wherein R is methyl, phenyl, benzyl or NH.sub.2.

4. The polymer film according to claim 1 wherein the polymerisable groups are each independently selected from (meth)acrylic groups and vinyl groups.

5. The polymer film according to claim 1 wherein component (b) further comprises an anionic group.

6. The polymer film according to claim 5 wherein the anionic groups comprises a sulpho group or a bissulphonylimide group.

7. The polymer film according to claim 1 wherein component (a) is free from fluorine atoms.

8. The polymer film according to claim 1 which further comprises (d) a radical initiator.

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

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

11-14. (canceled)

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

16-17. (canceled)

18. The polymer film according to claim 8 which further comprises: (d) 0 to 10 wt % of component (d).

19. A method of using the polymer film according to claim 9 for treatment of polar liquids, for the generation of hydrogen or for the generation of electricity.

20. A method of using the bipolar membrane according to claim 10 for production of acids and bases, for the separation and treatment of organic acids or for the generation of electricity.

21. The bipolar membrane according to claim 10 further comprising an anion exchange layer (AEL) obtainable by curing a composition comprising a compound of Formula (IV): ##STR00024## wherein: L.sup.1 is an alkylene group or an alkenylene group; R.sup.a, R.sup.b, R.sup.c and R.sup.d are each independently an alkyl group or an aryl group, or R.sup.a and R.sup.b, and/or R and R.sup.d, together with the atoms to which they are attached, form a ring; n1 and n2 each independently represent an integer having a value of 1 to 10; and X.sub.1.sup. and X.sub.2.sup. each independently represent an anion.

22. The polymer film according to claim 1 wherein: (i) component (a) is free from fluorine atoms; (ii) in component (a) R is methyl, phenyl, benzyl or NH.sub.2; (iii) in component (b) the anionic group comprises a sulpho group or a bissulphonylimide group; and (iv) in component (b) the polymerisable groups are each independently selected from (meth)acrylic groups and vinyl groups.

23. The bipolar membrane according to claim 10 wherein: (i) component (a) is free from fluorine atoms; (ii) in component (a) R is methyl, phenyl, benzyl or NH.sub.2; (iii) in component (b) the anionic group comprises a sulpho group or a bissulphonylimide group; and (iv) in component (b) the polymerisable groups are each independently selected from (meth)acrylic groups and vinyl groups.

Description

EXAMPLES

[0185]

TABLE-US-00001 TABLE 1 Ingredients Component Abbreviation Type Description Li-BVBSI (a) Benzenesulphonamide, 4-ethenyl-N-[(4- ethenylphenyl)sulphonyl]-, lithium salt 4OH- 4-hydroxy-2,2,6,6-tetramethylpiperidin- TEMPO 1-oxyl, a 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 (a) Benzenesulphonamide, 4-ethenyl-N- (methylsulphonyl)-, lithium salt MM-A (a) Benzenesulphonamide, 4-ethenyl-N- (aminosulphonyl)-, lithium salt MM-P (a) Benzenesulphonamide, 4-ethenyl-N- (phenylsulphonyl)-, lithium salt XL-D (b) Benzenesulphonamide, 2,4-diethenyl-N- (methylsulphonyl)-, lithium salt XL-2 (b) 1,3-[N-(ethenylphenylsulphonyl)benzene sulphonamide], dilithium salt IPA (c) Isopropyl alcohol from Sigma-Aldrich MCH (c) Methylcyclohexane from Sigma-Aldrich 1MP (c) 1-methyl pyrrole 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 (b) Divinylbenzenesulphonate, Sodium salt from Tosoh Chemicals PETA (b) pentaerythritol tetraacrylate from Sigma-Aldrich EGDMA (b) ethylene glycol dimethacrylate from Sigma-Aldrich 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 A cross-linker with two acrylamide groups obtained from Fujifilm. Structure is shown below, preparation method is described in EP2965803. Omnirad (d) Ethyl(2,4,6-trimethylbenzoyl)-phenyl TPO-L phosphinate, a photoinitiator from IGM Resins Omnirad (d) 2-hydroxy-2-methyl-1-phenylpropanone, a 1173 photoinitiator from IGM Resins [00019]

[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] The purity of the compounds of Formula (I) was determined by HPLC-MS. A 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 C.sub.8 5 m 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 l volume was injected into the abovementioned HPLC-MS apparatus for analysis.

[0189] 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 Rate Solvent 1 (%): Solvent 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 Compound mass (Da) observed (Da) time (min)* LiSS 190 183 12.2 MM-M 267 260 12.5 MM-A 268 261 11.5 MM-P 329 322 17.9 MM-Tf 321 314 17.5 *Retention times are indicative.

[0190] 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: one solution at 30 wt %, one solution at 60 wt %, and one solution at 70 wt % containing a 1:1 molar ratio of the compound of Formula (I) with cross-linker Li-BVBSI. 500 ppm 40H-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.

##STR00020##

TABLE-US-00004 TABLE 4 Solubility in water of several compounds of Formula (I) and of comparative compounds Solubility in water R M at 40 C. (wt %) methyl Li >60 phenyl Li >60 Trifluroromethyl Li >60 (Comparative) amino Li >60 LiSS (Comparative) 40

[0191] In separate experiments from those shown in Table 4 and for comparison, the highest solubility achieved by mixing lithium styrene sulphonate (LiSS) and DVBS-Na was found to be 55 wt %. Furthermore, when the compounds of Formula (I) shown in Table 2 where M is Li were combined with DVBS-Na the solubility achieved was at least 60 wt % in all cases. When the compounds of Formula (I) shown in Table 4 where M is Li were combined with crosslinkers from the bis-sulphonimide family (e.g. of Formula (11)), the highest solubility achieved reached solid contents over 70 wt %.

[0192] ER (ohm.Math.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: [0193] the auxiliary membranes were CMX and AMX from Tokuyama Soda, Japan; [0194] the capillaries as well as the Ag/AgCl references electrodes (Metrohm type 6.0750.100) contained 3M KCl; [0195] the calibration liquid and the liquid in compartment 2, 3, 4 and 5 was 0.5 M NaCl solution at 25 C.; [0196] the effective membrane area was 9.62 cm.sup.2; [0197] the distance between the capillaries was 5.0 mm; [0198] the measuring temperature was 25 C.; [0199] a Cole Parmer Masterflex console drive (77521-47) with easy load II model 77200-62 gear pumps was used for all compartments; [0200] 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 [0201] the samples were equilibrated for at least 1 hour at room temperature in a 0.5 M solution of NaCl prior to measurement.

[0202] Preferably, the ER (for 0.5 M NaCl) is lower than 5 ohm.Math.cm.sup.2, more preferably lower than 2.5 ohm.Math.cm.sup.2.

Measurement of Permselectivity (PS)

[0203] The permselectivity PS (%) that is the selectivity to the passage of ions of opposite charge to that of the cationically charged membranes prepared in the examples, was measured as follows. The membrane 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.

[0204] Settings: [0205] the capillaries as well as the Ag/AgCl reference electrodes (Metrohm type 6.0750.100) contained 3M KCl; [0206] the effective membrane area was 9.62 cm.sup.2; [0207] the distance between the capillaries was ca 15 mm; [0208] the measuring temperature was 21.00.2 C.; [0209] a Cole Parmer Masterflex console drive (77521-47) with easy load II model 77200-62 gear pumps was used for the two compartments; [0210] 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; [0211] The samples 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.

[0212] Preferably the PS for NaOH is at least 50%.

pH Stability

[0213] Stability in acidic and/or alkaline conditions is preferred as it widens the scope of applications the CEM's can be used in. Stability is typically tested by immersing the samples in 4M of HCl or NaOH at 80 degrees for 7 days. After this treatment, the selectivity should be at least 80% of the original selectivity to be judged as stable.

Preparation of Compounds of Formula (I) and Comparative Compound

[0214] MM-Tf, MM-A, MM-P and MM-M (referred to above) had the structures shown below.

##STR00021##

[0215] The compounds MM-Tf, MM-A, MM-P and MM-M were synthesized according to the following general scheme and procedure:

##STR00022##

General Procedure

[0216] 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 40H-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 (i) 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 (I) and comparative compound Residual Residual R Yield Purity solvent LiSS Li 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 10. Comparative Examples CEx1 to CEx4 and Polymer Films

[0217] Table 6 below describes compositions of Examples 1 to 10 according to the first aspect of the present invention and Comparative Examples CEx1 to CEx4. Each of the compositions was polymerised to form a polymer film of thickness 100 m by coating the compositions onto a polypropylene/polyethylene porous support for reinforcement with the aid of a 100 m Meyer bar. The electrical resistance ER of the resultant polymer films was measured using 0.5N NaCl, the permselectivity PS as described above and the result is shown in the final column of Table 6.

TABLE-US-00006 TABLE 6 Experimental results Components and their amount in the composition ER PS (a) (b) (c) (0.5N 0.05/0.5N Example (a) (wt %) (b) (wt %) (c) (wt %) NaCl) NaOH) Ex 1 MM-M 25 XL-2 35 water/1MP 29/10 1.2 52% Ex 2 MM-M 17.9 XL-2/ 38.7/ water/IPA/ 20.5/3.5/ 1.9 62% PETA 9.4 1MP 9 Ex 3 MM-M 8.9 XL-2/ 38.7/ water/IPA/ 20.5/3.5/ 2.0 81% PETA 18.4 1MP 9 Ex 4 MM-M 17.9 XL-2/ 25.8/ water/IPA/ 20.5/3.5/ 2.0 67% PETA 22.3 1MP 9 Ex 5 MM-M 17.9 XL-2/ 38.7/ water/IPA/ 20.5/3.5/ 1.8 72% EGDMA 9.4 1MP 9 Ex 6 MM-M 12 XL-D 54 water/MCH/ 20.5/3.5/ 1.5 52% 1MP 9 Ex 7 MM-M 25 Li-BVBSI 35 Water/DMSO/ 19.3/6.4/ 1.5 50% IPA/1MP 3.3/10 Ex 8 MM-M 19 XL-2 41 Water/IPA/ 24.9/4.1/ 1.16 61% 1MP 10 Ex 9 MM-P 34 Li-BVBSI 36 Water/TEOA 26/3 1.3 60% Ex 10 MM-A 30 Li-BVBSI 40 Water/TEOA 26/3 1.4 55% CEx 1 LiSS 36 Na-DVBS 20 Water/TEOA 39.5/3.5 1.1 35% CEx 2 LiSS 26 XL-2 31 Water/TEOA 38/4 0.94 16% CEx 3 MM-tF 39 Li-BVBSI 31 Water/TEOA 26/2 0.87 0% CEx 4 Na-AMPS 30 M-11 30 Water 39 2.5 60% *All formulations shown in Table 6 included 1 wt % of LAP as photoinitator. Na-AMPS amount in the table is based on 100% solids, the water present in the solution as obtained from the supplier is addes to the solvent amount.

TABLE-US-00007 TABLE 7 _pH stability results Fresh PS PS after 7 days PS after 7 days (0.05/0.5N 4M HCl @ 80 C. 4M NaOH @ 80 C. Example NaOH) (0.05/0.5N NaOH) (0.05/0.5N NaOH) Ex 1 52% 51% 50% Ex 9 60% 58% 59% CEx 4 60% 0% 0%

Infrared Analysis

[0218] ATR-FTIR spectra were recorded on polymer films using a PerkinElmer Frontier FT-IR Spectrometer, using the Universal ATR Sampling Accessory equipped with a diamond top plate. The spectra were recorded in the range 4000-580 cm.sup.1, with a spectral resolution of 4 cm.sup.1 and the spectra were averaged over 10 recorded spectra. For optimal peak resolution, the samples of polymer film were pushed against the ATR diamond with a conical shaped tip (force gauge 75). The results for Example 7 and Comparative Example CEx2 are shown in Table 8 below:

TABLE-US-00008 TABLE 8 Infrared Analysis Results Peaks found (cm.sup.1) below Example 60% T % between 900-4000 cm.sup.1 Ex 7 1262, 1151, 1132, 1076, 1048, 1011 CEx 2 1183, 1126, 1035, 1010

[0219] From Table 8, the strong IR peaks at 1262, 1151, 1076 and 1048 can be used to distinguish the bisulfonimide functional group from the sulfonate functional group in polymer film samples.

Extraction Analysis

[0220] In order to analyse the polymerisation degree of polymer films and show the presence of the claimed materials in polymer films, samples of polymer films were extracted with purified water (10 cm.sup.2 in 50 mL purified water) after which the extraction liquid was analysed in the HPLC-MS method described above:

TABLE-US-00009 TABLE 9 Extraction results Extracted Extracted material a material b Example Material a (mg/ml) Material b (mg/ml) Ex 7 MM-M 13 Li-BVBSI 8 Ex 9 MM-P 12 Li-BVBSI 9 Ex 1 MM-M 14 XL-2 11 Ex 10 MM-A 18 Li-BVBSI 15

Preparation of the AEL

[0221] An AEL composition was prepared containing 58 wt % of 1,4-diazoniabicyclo[2.2.2]octane, 1,4-bis[(4-ethenylphenyl)methyl]-, chloride, 19 wt % of water, 6 wt % of IPA, 1 wt % of Omnirad TPO-L and 1 wt % of Omnirad 1173. The AEL composition was coated on a non-woven polyethylene fabric and cured by UV.

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

[0222] CEL compositions were prepared according to Table 7 (Example 9 & Comparative Example CEx4). The CEL compositions were coated on the AEL prepared as described above, then a second non-woven polyethylene fabric was placed onto the layer of CEL composition, excess CEL composition was wiped off and the CEL composition was cured using UV light.

[0223] The electrochemical properties and the bipolar characteristics of this bipolar membrane were compared to a reference membrane using a so-called current-voltage characteristic (I-U curve), where the current density is measured as a function of the applied voltage. Typically, the lower the voltage (U) required to generate a given current density, i.e. 600 mA/cm.sup.2, the lower is the ionic resistance of one or both ion exchange layers in particular, and the bipolar membrane in general. Low ionic resistance, in this case of the cation exchange layer, results in membranes that are more energy efficient.

TABLE-US-00010 TABLE 10 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