Polymers, their method of manufacture and use thereof

Abstract

A method for the manufacture of a polymer is provided, the method comprising: Providing a first monomer, the first monomer comprising a bicyclic diamine moiety, a first nucleophilic group provided on a carbon atom of an aromatic moiety, and a second nucleophilic group provided on a carbon atom of an aromatic moiety; Providing a bridging compound comprising at least two sites vulnerable to nucleophilic attack; and Contacting the first monomer with the bridging compound. Polymers made by said method and uses of such polymers are also disclosed.

Claims

1. A non-network polymer comprising a first repeat unit comprising a bicyclic diamine moiety or a quaternary ammonium cation derivative thereof, the first repeat unit comprising the bicyclic diamine moiety or quaternary ammonium cation derivative thereof being bonded to each of a second repeat unit and a third repeat unit with no more than one linkage, the second and third repeat unit being the same as, or different from, the first repeat unit and wherein the non-network polymer is linear and further wherein the non-network polymer has an average degree of polymerization of 10 or more.

2. The non-network polymer of claim 1, wherein the first repeat unit comprises general structure: ##STR00019## or its enantiomer, or the quaternary ammonium cation derivative of the above structure or its enantiomer, which may be substituted or unsubstituted, and wherein each Y is independently selected from the group consisting of H and CN; each X is independently selected from the group consisting of O, S, NH and NR where R is a C.sub.1 alkyl.

3. The non-network polymer of claim 2, wherein the first repeat unit comprises general structure: ##STR00020## or its enantiomer, or the quaternary ammonium cation derivative of the above structure or its enantiomer, which may be substituted or unsubstituted.

4. The non-network polymer of claim 2 wherein at least one of the second repeat unit and the third repeat unit further comprises general structure: ##STR00021## each Y is independently selected from the group consisting of H and CN; each X is independently selected from the group consisting of O, S, NH and NR where R is a C.sub.1 alkyl.

5. The non-network polymer of claim 4 wherein at least one of the second repeat unit and the third repeat unit further comprises general structure: ##STR00022##

6. A non-network polymer comprising a bicyclic diamine moiety or a quaternary ammonium cation derivative thereof having a repeat unit which comprises: ##STR00023## or its enantiomer, or the quanternary ammonium cation derivative of the above structure or its enantiomer, which may be substituted or unsubstituted, and wherein and wherein the non-network polymer has an average degree of polymerization of 10 or more.

7. The non-network polymer of claim 6 wherein the repeat unit comprises: ##STR00024##

8. The non-network polymer of claim 6 wherein the repeat unit comprises: ##STR00025##

9. A non-network polymer comprising a bicyclic diamine moiety or a quaternary ammonium cation derivative thereof ##STR00026## or its enantiomer, or the quaternary ammonium cation derivative of the above structure or its enantiomer, which may be substituted or unsubstituted, and wherein and wherein the non-network polymer has an average degree of polymerization of 10 or more.

10. The non-network polymer of claim 9 wherein the repeat unit comprises: ##STR00027##

11. The non-network polymer of claim 9 wherein the repeat unit comprises: ##STR00028##

12. The non-network polymer of claim 2 wherein the first repeat unit comprises: ##STR00029## or its enantiomer, or the quaternary ammonium cation derivative of the above structure or its enantiomer, which may be substituted or unsubstituted, and wherein each Y is independently selected from the group consisting of H and CN; each X is independently selected from the group consisting of O, S, NH and NR wherein R is a C.sub.1 alkyl.

13. The non-network polymer of claim 12 wherein the first repeat unit comprises: ##STR00030##

Description

EXAMPLE 1

(1) A monomer comprising a bicyclic diamine structure and four nucleophilic groups may be prepared as indicated in reaction scheme 1. A catechol derivative 1 (Sigma Aldrich, UK) is mixed with paraformaldehyde under acidic conditions (paraformaldehyde, trifluoroacetic acid, room temperature, 24 hours) to form monomer 2. The monomer 2 may be demethylated (BBr.sub.3 in CH.sub.2Cl.sub.2 for four hours) to produce monomer 3 (2,3,8,9-tetrahydroxy-6H,12H-5,11-methanodibenzo[1,5]-diazocine). Those skilled in the art will realise that both stereoisomers of compounds 2 and 3 will be formed in the reaction mixture.

(2) ##STR00007##

(3) Monomer 3 may then be reacted with 2,3,5,6-tetrafluoroterephthalonitrile as shown in Reaction Scheme 2 to form a polymer 4 in accordance with the present invention.

(4) ##STR00008##

(5) 2,3,8,9-Tetrahydroxy-6H,12H-5,11-methanodibenzo[1,5]-diazocine (1.000 g, 3.49 mmol) and 2,3,5,6-tetrafluoroterephthalonitrile (698 mg, 3.49 mmol, Sigma Aldrich, UK) were added to a two-necked round bottom flask, under inert atmosphere, in dry dimethylformamide (25 mL). The mixture was heated to 65? C., until the two starting materials were completely dissolved, then dry potassium carbonate (3.85 g, 27.92 mmol, 8 equivalents) was added and the mixture kept stirred for 96 h. The solution was quenched with water (80 mL), filtrated and washed repeatedly with water and acetone then filtered and dried under high vacuum to give a yellow solid (1.13 g, 80% based on the molecular weight of the repeated unit). BET surface area=570 m.sup.2/g; total pore volume=0.35 cm.sup.3/g at (P/P.sub.0) 0.98, adsorption; TGA analysis (nitrogen): 5% loss of weight occurred at ?380? C. Initial weight loss due to thermal degradation commences at ?440? C. Those skilled in the art will realise that polymer 4 will comprise both stereoisomers of the bicyclo diamine group.

EXAMPLE 2

(6) The general principle of Example 1 may be used to make heteropolymers. For example, monomer 3 may be reacted with 2,3,5,6-tetrafluoroterephthalonitrile in the presence of spiro monomer 5 as shown in Reaction Scheme 3 to produce polymer 6 in accordance with the present invention.

(7) 2,3,8,9-Tetrahydroxy-6H,12H-5,11-methanodibenzo[1,5]-diazocine (400 mg, 1.397 mmol), 3,3,3,3-tetramethyl-2,2,3,3-tetrahydro-1,1-spirobi[indene]-5,5,6,6-tetraol (476 mg, 1.397 mmol, Sigma Aldrich, UK), 2,3,5,6-tetrafluoroterephthalonitrile (559 mg, 2.794 mmol) were added to a two-necked round bottom flask, under inert atmosphere, in dry dimethylformamide (25 mL). The mixture was heated to 65? C., until the two starting materials were completely dissolved, then dry potassium carbonate (3.08 g, 22.35 mmol, 8 equivalents) was added and the mixture stirred for 96 h. The reaction mixture was quenched with water (60 mL), and the resulting precipitate filtrated and washed repeatedly with water and acetone. The solid was dissolved in THF (15 mL), filtered through cotton wool, poured into a flask containing a mixture of acetone/methanol (2/1, 40 ml). The product was collected by filtration and was dried under high vacuum overnight to give the final product as yellow solid (85% yield). .sup.1H NMR (400 MHz; CDCl.sub.3) ? 6.82 (br m, 4H), 6.61 (br s, 2H), 6.42 (br s, 2H), 4.56 (br s, 2H), 4.24 (br s, 2H), 4.01 (br s, 2H), 2.35 (br s, 2H), 2.17 (br s, 2H), 1.34 (br m, 12H); BET surface area=633 m.sup.2/g; total pore volume=0.42 cm.sup.3/g at (P/P.sub.0) 0.98, adsorption; TGA analysis (nitrogen): 5% loss of weight occurred at ?380? C. Initial weight loss due to thermal degradation commences at ?450? C. Those skilled in the art will realise that polymer 6 will comprise both stereoisomers of the bicyclo diamine group.

(8) ##STR00009##

EXAMPLE 3

(9) A monomer comprising a bicyclic diamine structure and two nucleophilic groups may be prepared as indicated in reaction scheme 4. A dinitro derivative of 5,11-methanodibenzo[1,5]-diazocine catechol is made by mixing nitro-aniline with paraformaldehyde under acidic conditions (paraformaldehyde, trifluoroacetic acid, room temperature, 24 hours) to form monomer 7. The monomer 7 may be reduced to produce monomer 8. The synthesis of monomer 8 was disclosed by Kiehne et al., (Org. Lett. 2007, 9, 1283)

(10) ##STR00010##

(11) Monomer 8 may then be reacted with bisanhydride 9 as shown in Reaction Scheme 5 to form a polymer in accordance with the present invention.

(12) ##STR00011##

(13) Bisanhydride 9 was prepared from 3,3,33,5,5,6,6-hexamethyl-1,1-spirobisindane, itself prepared by the modification of the procedure described by Warr et al. in Inorganic Chemistry 2008, 47, 9351, by oxidation using an aqueous solution of potassium permanganate, followed by dehydration of the resulting tetra-carboxylic acid by refluxing in acetic anhydride.

(14) The reaction is carried out in a round bottom flask, equipped with Dean-Stark apparatus under nitrogen atmosphere. The monomer 9 (641.7 mg, 1.54 mmol) is dissolved in ethanol (EtOH) (9.6 ml) and triethylamine (0.78 ml) and refluxed for 1 h to form ester-acid precursor. Then the excess of solvents is distilled to give a high viscous liquid. Monomer 8 (431.9 mg, 1.54 mmol) is dissolved in NMP/o-diclorobenzene (o-DCB) mixture (2 ml, NMP/o-DCB=4:1) and added to ester-acid precursor. A container with monomer 8 is rinsed with NMP/o-DCB (3 ml). The reaction is kept under vigorous stirring for 0.5 h at 20? C. and then temperature is raised gradually to 200? C. After 24 h the reaction is cooled to 20? C. and 5 ml of CHCl.sub.3 is added to dilute the reaction mixture. The resulting solution is poured slowly into EtOH (150 ml) to precipitate desirable polymer 12. The precipitated solid is filtered off to give a pale-yellow powder. Polymer 10 is reprecipitated from chloroform into EtOH and dried under reduced pressure at 120? C. for 10 h (yield 870 mg, 81% after the second precipitation). .sup.1H NMR (400 MHz; CDCl.sub.3) ? ppm: 7.76 (br s, 2H, Ar), 7.30 (br s, 2H, Ar), 7.07 (br s, 2H, Ar), 6.82 (br s, 2H, Ar), 4.67-4.64 (br d, 2H, NCH.sub.2), 4.31 (br s, 2H, NCH.sub.2), 4.09-4.05 (br d, 2H, NCH.sub.2), 2.54-2.34 (br m, 4H CH.sub.2, 6H CH.sub.3), 1.48-1.42 (br m, 12H, CH.sub.3); IR (NaCl, CH.sub.2Cl.sub.3/cm.sup.?1): 1774.7 (asym C?O), 1713.9 (sym C?O), 1388.0 (CN), 748.2 (imide ring deformation); Molecular mass: (GPC, eluentCHCl.sub.3, against polystyrene standards: M.sub.w=46600, PDI=2.08. BET surface area=590.93 m.sup.2/g; total pore volume=0.73 cm.sup.3/g at (P/P.sub.0) 0.98, adsorption; TGA analysis (nitrogen): Initial weight loss due to thermal degradation commences at ?490? C.

EXAMPLE 4

(15) Monomer 8 described in Example 3 might be reacted with commercially available hexafluoroisopropylidene bisphthalic dianhydride (6-FDA) comonomer 13 (Aldrich) as shown in Reaction Scheme 6 to form a polymer 14 in accordance with the present invention.

(16) ##STR00012##

(17) The reaction is carried out in a round bottom flask, equipped with Dean-Stark apparatus under nitrogen atmosphere. The co-monomer 13 (604.8 mg, 1.35 mmol) is dissolved in ethanol (EtOH) (10 ml) and triethylamine (0.8 ml) and refluxed for 1 h to form ester-acid precursor. Then the excess of solvents is distilled to give a high viscous liquid. The comonomer 8 (381.2 mg, 1.35 mmol) is dissolved in NMP/o-diclorobenzene (o-DCB) mixture (2 ml, NMP/o-DCB=4:1) and added to ester-acid precursor. A container with co-monomer 8 is rinsed with NMP/o-DCB (3 ml). The reaction is kept under vigorous stirring for 0.5 h at 20? C. and then temperature is raised gradually to 200? C. After 24 h the reaction is cooled to 20? C. and 5 ml of CHCl.sub.3 is added to dilute the reaction mixture. The resulting solution is poured slowly into EtOH (150 ml) to precipitate desirable polymer 14. The precipitated solid is filtered off to give a pale-yellow powder. Polymer 14 is reprecipitated from CHCl.sub.3 into EtOH and dried under reduced pressure at 120? C. for 10 h (720 mg, 74% yield after the second precipitation). .sup.1H NMR (400 MHz; CDCl.sub.3) ? ppm: 8.02-8.00 (br m, 2H, Ar), 7.90-7.84 (br m, 4H, Ar), 7.09 (br s, 2H, Ar), 6.84 (br s, 2H, Ar), 4.69-4.65 (br d, 2H, NCH.sub.2), 4.33 (br s, 2H, NCH.sub.2), 4.11-4.06 (br d, 2H, NCH.sub.2), 2.45 (br s, 6H, CH.sub.3); IR (NaCl, CH.sub.2Cl.sub.3/cm.sup.?1): 1774.7 (asym C?O), 1713.9 (sym C?O), 1388.0 (CN), 748.2 (imide ring deformation); BET surface area=44 m.sup.2/g; total pore volume=0.19 cm.sup.3/g at (P/P.sub.0) 0.98, adsorption; TGA analysis (nitrogen): initial weight loss due to thermal degradation commences at ?500? C.

EXAMPLE 5

(18) A monomer comprising a bicyclic diamine structure and two nucleophilic groups 3,9-diamino-4,10-dimethyl-6H,12H-5,11-methanodibenzo[1,5]-diazocine may be prepared as indicated in reaction scheme 7. A dinitro derivative of 5,11-methanodibenzo[1,5]-diazocine catechol is made by mixing nitro-aniline with paraformaldehyde under acidic conditions (paraformaldehyde, trifluoroacetic acid, 20? C., 24 h) to form precursor 15, which may be reduced to produce monomer 16. The synthesis of monomer 16 is disclosed by Kiehne et al., (Org. Lett. 2007, 9, 1283)

(19) ##STR00013##

(20) Monomer 16 may then be reacted with co-monomer 9 described in Example 2 as shown in Reaction Scheme 8 to form a desirable polymer 17 in accordance with the present invention.

(21) ##STR00014##

(22) The reaction is carried out in a round bottom flask, equipped with Dean-Stark apparatus under nitrogen atmosphere. The monomer 9 (742.0 mg, 1.78 mmol) is dissolved in ethanol (EtOH) (12 ml) and triethylamine (1 ml) and refluxed for 1 h to form ester-acid precursor. Then the excess of solvent is distilled to give a highly viscous liquid. The comonomer 16 (500.0 mg, 1.78 mmol) is dissolved in NMP/o-diclorobenzene (o-DCB) mixture (3 ml, NMP/o-DCB=4:1) and added to ester-acid precursor. A container with comonomer 16 is rinsed with NMP/o-DCB (4 ml). The reaction is kept under vigorous stirring for 0.5 h at 20? C. and then the temperature is raised gradually to 200? C. After 24 h the reaction is cooled to 20? C. and 5 ml of CHCl.sub.3 is added to dilute the reaction mixture. The resulting solution is poured slowly into EtOH (150 ml) to precipitate polymer 17. The precipitated solid is filtered off to give a pale-yellow powder. Polymer 17 is reprecipitated from chloroform into EtOH and dried under reduced pressure at 120? C. for 10 h (yield 873 mg, 74% after the second precipitation). .sup.1H NMR (400 MHz; CDCl.sub.3) ? (ppm) 7.80 (br s, 2H, Ar), 7.30 (br s, 2H, Ar), 6.91 (br s, 4H, Ar), 4.65 (br m, 2H, NCH.sub.2), 4.32 (br s, 2H, NCH.sub.2), 4.06 (br m, 2H, NCH.sub.2), 2.45 (br m, 4H, CH.sub.2), 2.23 (br s, 6H, CH.sub.3) 1.48 (br m, 12H, CH.sub.3); IR (NaCl, CH.sub.2Cl.sub.2/cm.sup.?1): 1774.0 (asym C?O), 1715.0 (sym C?O), 1383.6 (CN), 732.8 (imide ring deformation); Molecular mass: (GPC, eluentCHCl.sub.3, against polystyrene standards: M.sub.w=2600; BET surface area=395 m.sup.2/g; total pore volume=0.59 cm.sup.3/g at (P/P.sub.0) 0.98, adsorption; TGA analysis (nitrogen): initial weight loss due to thermal degradation commences at ?435? C.

EXAMPLE 6

(23) Monomer 16 described in Example 5 may be reacted with co-monomer 13 (Example 4) as shown in Reaction Scheme 9 to form a desirable polymer 18 in accordance with the present invention.

(24) ##STR00015##

(25) The reaction is carried out in a round bottom flask, equipped with Dean-Stark apparatus under nitrogen atmosphere. The co-monomer 13 (323.5 mg, 1.16 mmol) is dissolved in ethanol (EtOH) (8 ml) and triethylamine (0.6 ml) and refluxed for 1 h to form ester-acid precursor. Then the excess of solvents is distilled to give a high viscous liquid. The comonomer 16 (323.5 mg, 1.16 mmol) is dissolved in NMP/o-diclorobenzene (o-DCB) mixture (2 ml, NMP/o-DCB=4:1) and added to ester-acid precursor. A container with comonomer 16 is rinsed with NMP/o-DCB (3 ml). The reaction is kept under vigorous stirring for 0.5 h at 20? C. and then temperature is raised gradually to 200? C. After 24 h the reaction is cooled to 20? C. and 5 ml of CHCl.sub.3 is added to dilute the reaction mixture. The resulting solution is poured slowly into EtOH (150 ml) to precipitate desirable polymer 18. The precipitated solid is filtered off to give a pale-yellow powder. Polymer 18 is reprecipitated from chloroform into EtOH and dried under reduced pressure at 120? C. for 10 h (yield 668 mg, 80% after the second precipitation). .sup.1H NMR (400 MHz; CDCl.sub.3) ? (ppm) 8.05-7.93 (br m, 6H, Ar), 7.26-6.94 (br m, 4H, Ar), 4.70-4.66 (br m, 2H, NCH.sub.2), 4.35 (br s, 2H, NCH.sub.2), 4.11-4.06 (br m, 2H, NCH.sub.2), 2.28 (br s, 6H, CH.sub.3); IR (NaCl, (CH.sub.2Cl.sub.2/cm.sup.?1): 1785.2 (asym C?O), 1723.7 (sym C?O), 1382.3 (CN), 731.0 (imide ring deformation); Molecular mass: (GPC, eluentCHCl.sub.3, against polystyrene standards: M.sub.w=16000, PDI=2.5; BET surface area=259 m.sup.2/g; total pore volume=0.36 cm.sup.3/g at (P/P.sub.0) 0.98 adsorption; TGA analysis (nitrogen): initial weight loss due to thermal degradation commences at ?455? C.

EXAMPLE 7

(26) A polymer comprising bicyclic diamine moieties can be modified by quaternisation of an amine group to form the ammonium cation. For example, the addition of dimethyl sulphate solution to the bicyclic diamine polymer 4 causes the formation of a ammonium cation with a halide counter-anion to give bicyclic diamine polymer 19. It is then possible to exchange the counter-anion as desired.

(27) ##STR00016##

(28) The polymer derived from 2,3,8,9-tetrahydroxy-6H,12H-5,11-methanodibenzo[1,5]-diazocine (500 mg, 1.22 mmol) was placed acetonitrile (10 mL) and dimethyl sulfate (1.54 g, 12.2 mmol) was added to the reaction mixture, which was left to stir at 20? C. for 24 h. The reaction was quenched with water, the resulting precipitate was collected under suction and washed with water to afford the desired polymer as a grey powder (475 mg, 92% based on the repeated unit). .sup.1H NMR (400 MHz; DMSO-d6) ? 6.97 (br s, 2H), 6.85 (br s, 2H), 4.50 (br m, 6H), 2.89 (br s, 3H); TGA analysis (nitrogen): 13.80% loss of weight occurred at ?235? C., further loss due to thermal degradation commences at ?370? C.

(29) Further examples of bridging groups which may be used instead of 2,3,5,6-tetrafluoroterephthalonitrile are shown below:

(30) As can be seen, such bridging compounds comprise at least two pairs of leaving groups (a first pair and a second pair), each leaving group of a first pair being located on adjacent carbon atoms and each leaving group of a second pair being located on adjacent carbon atoms.

(31) Referring to Example 2 above, further examples of co-monomers which may be used in lieu of the spiro compound to make a polymer in accordance with the polymer of the present invention are shown below:

(32) ##STR00017##

(33) Referring to Example 3 above, further examples of co-monomers which may be used in lieu of the spiro compound to make a polymer in accordance with the polymer of the present invention are shown below:

(34) ##STR00018##
Where, in the foregoing description, integers or elements are mentioned which have known, obvious or foreseeable equivalents, then such equivalents are herein incorporated as if individually set forth. Reference should be made to the claims for determining the true scope of the present invention, which should be construed so as to encompass any such equivalents. It will also be appreciated by the reader that integers or features of the invention that are described as preferable, advantageous, convenient or the like are optional and do not limit the scope of the independent claims