POLYMER COMPRISING A PLURALITY OF ACTIVE AMINE GROUPS, RELATED POLYMERS AND RELATED METHODS THEREOF

Abstract

There is provided a polymer or derivative thereof comprising a plurality of active amine groups in the backbone, wherein the polymer is a reaction product of a reaction between one or more bis-carbonates and one or more amine compounds having at least two terminal amino groups. Also provided are use of the polymer or derivative thereof and a method of preparing the polymer or derivative thereof.

Claims

1. A polymer or derivative thereof comprising a plurality of active amine groups in the backbone, wherein the polymer is a reaction product of a reaction between one or more bis-carbonates and one or more amine compounds having at least two terminal amino groups.

2. The polymer or derivative thereof of claim 1, wherein the polymer is a bio-based polymer and at least one of the bis-carbonates and/or at least one of the amine compounds having at least two terminal amino groups is derived from a bio-based source.

3. The polymer or derivative thereof of claim 2, wherein the content of the polymer derived from a bio-based source ranges from 30% to 90% by weight of the polymer.

4. The polymer or derivative thereof of claim 1, wherein the plurality of active amine groups comprise a plurality of different amine functionalities.

5. The polymer or derivative thereof of claim 1, wherein the one or more amine compounds having at least two terminal amino groups are represented by general formula (1) and the one or more bis-carbonates are represented by general formula (2): ##STR00037## and wherein A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one active amine group; and B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester and combinations thereof.

6. The polymer or derivative thereof of claim 1, wherein the polymer comprises one or more structural units represented by general formula (3), one or more structural units represented by general formula (4): ##STR00038## wherein A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one active amine group; and B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester or combinations thereof.

7. The polymer or derivative thereof of claim 1, wherein the structural units represented by general formula (3) are linked to structural units represented by general formula (4) via carbamate/urethane linkages.

8. The polymer or derivative thereof of claim 1, wherein A is selected from the following general formula (5), (6), (7) or (8): ##STR00039## wherein R.sup.1, R.sup.2 and R.sup.3 are each independently selected from a single bond, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl or optionally substituted cycloalkenyl; R.sup.a and R.sup.b are each independently selected from the group consisting of H, optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl; ring N.sup.1 and N.sup.2 are each independently an optionally substituted 5-membered or 6-membered nitrogen-containing cyclic ring; p≥1; and q≥0.

9. The polymer or derivative thereof of claim 8, wherein ring N.sup.1 and N.sup.2 are each independently selected from the group consisting of 3-pyrroline, 2-pyrroline, 2H-pyrrole, 1H-pyrrole, 2-pyrazoline, 2-imidazoline, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, isoxazole, isothiazole, thiazole, 1,2,5-oxadiazole, 1,2,3-oxadizole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, diphenylamine, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,4-triazine, 1,3,5-triazine, oxazine, thiazine, pyrazolidine, imidazolidine, piperidine, N-methylpiperidine, N-phenylpiperidine, pyrrolidine, piperazine, morpholine, thiomorpholine, 1,4-diazepane, quinoline, acridine and combinations thereof.

10. The polymer or derivative thereof of claim 1, wherein B is selected from the following general formula (9), (10) or (11): ##STR00040## wherein R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are each independently selected from a single bond, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl or optionally substituted cycloalkenyl; X.sup.1 and X.sup.2 are each independently selected from the group consisting of a single bond, —O—, —NR.sup.c—, —C(═O)—O— and —O—C(═O)—, wherein R.sup.c is selected from the group consisting of H, optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl; and ring Z is an optionally substituted 5-membered or 6-membered hydrocarbon cyclic ring or an optionally substituted 5-membered or 6-membered heterocyclic ring having up to three heteroatoms independently selected from the group consisting of O, N, S and NH.

11. The polymer or derivative thereof of claim 8, wherein R.sup.1 to R.sup.7 are each independently selected from a single bond, optionally substituted C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 optionally substituted alkenyl, C.sub.1-C.sub.20 optionally substituted alkynyl, C.sub.1-C.sub.20 optionally substituted cycloalkyl and C.sub.1-C.sub.20 optionally substituted cycloalkenyl; and R.sup.a and R.sup.b are each independently selected from the group consisting of H, optionally substituted C.sub.1-C.sub.20 alkyl, optionally substituted C.sub.1-C.sub.20 alkenyl and optionally substituted C.sub.1-C.sub.20 alkynyl.

12. The polymer or derivative thereof of claim 1, wherein the one or more amine compounds having at least two terminal amino groups are selected from the group consisting of diethylenetriamine (DETA), diamino-N-methyldiethylamine (DMA), triethylenetetramine (TETA), diamino-N-methyldipropylamine (DMPA), pentaethylenehexamine (PEHA), bis(3-aminopropyl)piperazine (BAP), spermine, spermidine, lysine salt (LyS) and diaminopentane (DAP); and/or the one or more bis-carbonates are selected from the group consisting of succinic bis-carbonate (SuBC), adipic bis-carbonate (ABC), butanediol bis-carbonate (BBC), isomers of pyridine bis-carbonate (PBC1), (PBC2), (PBC3), (PBC4), (PBC5) and/or (PBC6): ##STR00041## ##STR00042## ##STR00043##

13. (canceled)

14. The polymer or derivative of claim 1 selected from the following: ##STR00044## ##STR00045## ##STR00046## optionally wherein the polymer or derivative thereof has one or more of the following properties: water-soluble: hydrolysable; biodegradable; and biocompatible.

15. The polymer or derivative thereof of claim 1, wherein the polymer or derivative thereof further comprises at least one of a hydroxyl group and an active amine group originally present in the polymer that has been functionalized.

16. The polymer or derivative thereof of claim 1, wherein the polymer or derivative thereof is a grafted polymer obtained by grafting the polymer on a substrate or another polymer.

17. (canceled)

18. Use of the polymer or derivative thereof of claim 1, as an anti-redepositioning agent, an anti-bacterial agent, an adhesive, an adhesion promoter, a fiber modifier, a pigment dispersant, a chelating agent, a flocculating agent, a wet strength improving additive, a pour point depressant, or a carbon dioxide capture agent.

19. A method of preparing the polymer of claim 1, or a derivative thereof, the method comprising: polymerizing one or more diamines represented by general formula (1) with one or more biscarbonates represented by general formula (2) to obtain the polymer: ##STR00047## wherein A comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons comprising at least one active amine group; and B comprises a linear aliphatic, branched aliphatic, cyclic and/or aromatic hydrocarbons that optionally comprises at least one of an ether, amine, ester and combinations thereof.

20. The method of claim 19, wherein the method comprises a) mixing one or more diamines represented by general formula (1) with one or more biscarbonates represented by general formula (2) to obtain a reaction mixture; and b) precipitating the polymer.

21. The method of claim 19, wherein the method further comprises a step of functionalising at least one of a hydroxyl group and an active amine group present in the polymer.

22. The method of claim 19, wherein the method further comprises a step of grafting to at least one of a hydroxyl group and an active amine group present in the polymer to another polymer or substrate.

Description

BRIEF DESCRIPTION OF FIGURES

[0172] FIG. 1 is a schematic diagram 100 showing the application of the polymers designed in accordance with various embodiments (e.g., cationic polymer) as anti-redepositioning agents.

[0173] FIG. 2 shows images captured during chelation experiments of polymers designed in accordance with various embodiments disclosed herein with copper salt. The amount of CuBr used is 10 mg and the amount of polymer used is 24 mg. The left most vial contains CuBr in water. Commercial controls are CuBr+PEI in water; and CuBr+PEI-g-PEG in water. Vial Example 1 contains CuBr+Polymer R-14 in water. Vial Example 2 contains CuBr+Polymer R-12 in water. It was observed that formation of blue coloration (in both commercial controls and Vial Examples 1 and 2) was due to the chelation of polymers containing active amine groups with CuBr.

[0174] FIG. 3 is a schematic diagram 300 for illustrating an experiment designed for evaluating the potential of using the polymers designed in accordance with various embodiments disclosed herein as anti-redepositioning agents. FIG. 3 also show the images captured during the interaction studies with cotton fiber. The amount of cotton fiber used is 250 mg. It was found that cotton (used as control) contains 42.12% C; 6.01% H and 0.00% N. It was found that modified cotton contains 42.88% C; 6.16% H and 0.07% N.

[0175] FIG. 4 shows various types of functionalisation of polymers designed in accordance with various embodiments disclosed herein.

[0176] FIG. 5 is a graph showing the biodegradability rate of a polymer prepared from SuBC and TETA (Polymer R-6). The results were obtained from Singapore Test Services and conducted according to Zahn Wellens OECD-302-B. Ethylene glycol was used as a procedure control.

[0177] FIG. 6 is a schematic diagram 600 for illustrating an experiment designed for evaluating the CO.sub.2 capture of polymers designed in accordance with various embodiments disclosed herein.

[0178] FIG. 7 is a schematic diagram 700 showing the pour point reduction of crude oil or synthetic oil achieved by the usage of a pour point depressant polymer. Pour points were measured on PSL PPT 45150 (ASTM D5985, Rotational method). In various embodiments, the pour point depressant is added up to 1,000 ppm.

[0179] FIG. 8 is a graph showing the pour point reduction of wax solutions (i.e. synthetic oil) by N-functionalised polymers prepared from SuBC and PEHA (Polymer R-153 and R-190). Wax A is paraffin wax with melting point of 53-58° C., and Wax C is paraffin wax with melting point of >65° C., purchased from Aldrich (CAS 8002-74-2).

[0180] FIG. 9 is a graph showing the rheological effect of N-functionalised polymers prepared from SuBC and PEHA on 10 wt % Wax A solutions in dodecane. As shown, the polymers designed in accordance with various embodiments were able to lower the viscosity by 100 times at 15° C. and the transition temperature for Wax A solution. Wax A is paraffin wax with melting point of 53-58° C.

[0181] FIG. 10 is a graph showing the rheological effect of N-functionalised polymers prepared from SuBC and PEHA on 10 wt % Wax A solutions in dodecane. As shown, the polymers designed in accordance with various embodiments were able to lower the storage modulus of Wax A solution by 1000 times at 0.1% shear strain. Wax A is paraffin wax with melting point of 53-58° C.

[0182] FIG. 11 shows images captured from experiments designed for evaluating anti-soil redepositioning (ASR) property of polymers designed in accordance with various embodiments disclosed herein on cotton and polyester cloths. The experiments were performed on a polymer prepared from SuBC and PEHA (Polymer R-14).

[0183] FIG. 12 shows the colorimetry results obtained from experiments conducted to evaluate anti-soil redepositioning (ASR) property of polymers designed in accordance with various embodiments disclosed herein on cotton and polyester cloths. The experiments were performed on a polymer prepared from SuBC+TETA (Polymer R-6) and SuBC+PEHA (Polymer R-14).

[0184] FIG. 13 shows the cell viability results obtained from in-vitro skin irritation test of polymers designed in accordance with various embodiments disclosed herein. The results were obtained from Denova Sciences and conducted in accordance with OECD-TG-439. The experiments were performed on a polymer prepared from SuBC+TETA (Polymer R-6) and SuBC+PEHA (Polymer R-14).

[0185] FIG. 14 shows the cell viability results obtained from cytotoxicity test of polymers designed in accordance with various embodiments disclosed herein. The results were obtained from Singapore Polytechnic and conducted using HaCaT Cells. The experiments were performed on a polymer prepared from SuBC+TETA (Polymer R-6) and SuBC+PEHA (Polymer R-14).

[0186] FIG. 15 shows images captured and changes in the water contact angle of polymers designed in accordance with various embodiments disclosed herein before and after functionalization. As shown, the water contact angle of a polymer prepared from SuBC+TETA (Polymer R-6) increased from 20° to 104° after functionalization.

EXAMPLES

[0187] Example embodiments of the disclosure will be better understood and readily apparent to one of ordinary skill in the art from the following examples, tables and if applicable, in conjunction with the figures. It should be appreciated that other modifications related to structural, and chemical changes may be made without deviating from the scope of the invention. Example embodiments are not necessarily mutually exclusive as some may be combined with one or more embodiments to form new example embodiments. The example embodiments should not be construed as limiting the scope of the disclosure.

Example 1: Synthesis of Water Soluble/Dispersible Polymers

[0188] A method for the synthesis/construction of novel water soluble/dispersible polymers with tunable (diverse type of aliphatic and aromatic) active amine groups present in the backbone has been developed. Embodiments of the method disclosed herein allow for green synthesis of polymer. The polymer may be synthesized in the presence of water/moisture or in the absence of a solvent, i.e. under solvent-less conditions. Embodiments of the method disclosed herein allow for easy synthesis of polymer without production of by-product(s) and/or in the absence of a catalyst. The polymer may also be synthesized at room temperature. Embodiments of the method disclosed herein may also be easily scaled up without requiring any specialized external energy input etc. and/or without the production of by-product.

[0189] The present disclosure provides a strategy to create a new type of amine polymers with tunable structure and properties. Bis-carbonates may be easily copolymerized with amine compounds having at least two terminal amino groups to construct amine polymers. Scheme 1 shows the structures of some examples of monomers that can be used to synthesize water soluble/dispersible polymers with tunable active amine groups present in the backbone.

[0190] Scheme 2 shows the synthesis of water soluble succinic acid based active amine polymers from one or more bis-carbonates and one or more amine compounds having at least two terminal amino groups. As shown in Scheme 2, succinic bis-carbonate (SuBC) was used as an example of a bis-carbonate to obtain a water soluble succinic acid based polymer with active amine groups.

[0191] Polymers from succinic acid based bis-carbonate (SuBC) with active amine groups were synthesized using the protocol described in Scheme 2. These polymers can be synthesized in different solvents including water, or even in the absence of a solvent, i.e. under a solvent-less condition. Polymerization can be performed at a temperature ranging from room temperature to about 70° C. In various examples, heating the reaction mixture may speed up reaction and/or increase conversion.

##STR00024##

##STR00025##

Example 2: Characterization and Solubility

[0192] Polymers obtained were characterized with .sup.1H & .sup.13C NMR spectroscopy, gel permeation chromatography (GPC). Conversion, yield and molecular weight data were reported in Table 1. Table 1 also shows the bio-content of polymers synthesized that usually ranges from 50 to 75% by weight. Most of these polymers are soluble in water (in both acidic and basic pH) unlike traditional polyhydroxyurethanes (PHUs) (Table 2). Without being bound by theory, it is believed that the water solubility of the polymers is mainly attributed to the presence of active amine groups. Bio-content of such polymer could also be increased by the use of amines from natural sources. Polymers from butanediol bis-carbonate (BBC) and adipic acid bis-carbonate (ABC) were also reported in Table 1. Pyridine bis-carbonate (PBC) was an optional monomer useful when targeting to introduce aromatic amine into the polymer structure. R-12 is a representative polymer where all type of amine groups (2°, 3° and aromatic) are present in the backbone.

TABLE-US-00001 TABLE 1 Synthesis and characterization of polymers with active amine groups including approximate bio-content within the polymer. M represents monomers; Calc represents calculated. Ref: ** N content of commercial control PEI = 22.42% and N content of PEI-g-PEG = 10.53% Bio- Examples M.sub.n M.sub.p content (Polymer M Conversion at Polymer Tg, DSC (GPC (GPC calc (by N-content No.) used 1 hr 24 hr Yield (° C.) DMF) DMF) w/w) (E.A.) R-5 SuBC + 86% 95% 77% 13.1 4720 7820 63% 8.45 DETA R-6 SuBC + 92% 97% 66% 3.2 62450 43330 57% 12.45 TETA 1430 1460 R-8 SuBC + 86% 96% 73% −1.8 3520 2555 59% 9.38 TETA + DMA R-9 SuBC + 79% 96% 61% 2.2 5760 7360 61% 10.12 DMA R-12 0.8 77% 94% 87% 2.7 2130 1990 49% 11.39 SuBC + 0.2 PBC2 + 0.8 TETA + 0.2 DMA R-13 SuBC + 83% 96% 71% 13.3 6040 12450 67% 11.03 BAP R-14 SuBC + 94% — 80% −3.1 2200 1730 48% 14.42 PEHA R-15 SuBC + 84% 97% 88% −3.7 5560 9050 57% 9.74 DMPA R-17 BBC + 75% 97% 86% −3.6 1442 976 54% 12.46 TETA R-18 BBC + 72% 80% 97% 17.9 NA NA 45% 15.26 PEHA (1.5 hr) R-20 BBC + 68% 98% 75% −6.1 5900 7280 54% 11.16 TETA + DMPA R-22 SuBC + 81% 98% 89% −8 7660 11730 61% NA BAP R-23 ABC + 86% 96% 87% 3.8 4760 3670 59% 12.04 TETA (6 hr) R-24 ABC + 84% 97% 73% 20.1 3550 3805 59% 9.72 TETA + DMPA R-25 ABC + 90% — 89% 5.0 1488 988 51% 12.87 PEHA (rkn stopped)

TABLE-US-00002 TABLE 2 Solubility of polymers with active amine groups. M represents monomers. Examples Water Organic solvent (Polymer No.) M used pH 4 pH 7 pH 9 DMF MeOH THF Acetone R-5 SuBC + ✓ ✓ ✓ X X DETA R-6 SuBC + Partial X TETA R-8 SuBC + Partial X TETA + DMA R-9 SuBC + ✓ ✓ ✓ X X DMA R-12 0.8 X X SuBC + 0.2 PBC2 + 0.8 TETA + 0.2 DMA R-13 SuBC + ✓ ✓ ✓ X X BAP R-14 SuBC + Partial X X PEHA R-15 SuBC + ✓ ✓ ✓ Partial X DMPA R-18 BBC + Swell Swell Swell Swell Swell X X PEHA .fwdarw. .fwdarw. .fwdarw. soluble soluble soluble (>3 (>3 (>3 days) days) days) R-20 BBC + X X TETA + DMPA R-22 SuBC + Dispersible Dispersible Dispersible Dispersible BAP R-23 ABC + Swell X X TETA R-24 ABC + X X TETA + DMPA R-25 ABC + Swell X X PEHA Concentration of polymer solutions were prepared as ~28 mg/mL ✓ = Form clear solution  = Form cloudy solution, turns into clear solution after some time

Example 3: Properties of Water Soluble/Dispersible Polymers

[0193] ##STR00026##

[0194] Scheme 3 shows that a polymer designed in accordance with various embodiments disclosed herein can contain ester, urethane, hydroxyl, amine (2°, 3° and aromatic) groups. Amount of bio-content and amine can also be controlled. Such polymers can be crosslinked (using bis-acrylate or bis-epoxy), used to make hydrogel or can also be functionalized with fluorinated acrylates to make hydrophobic antibacterial materials etc.

Example 4: Functional Properties of Amine Containing Polymers and their Applications

[0195] ##STR00027##

[0196] Examples of applications of polymers with active amine functionality include: [0197] (i) Additive to shampoo, detergent and cosmetics (e.g., as antibacterial/anti-redepositioning agent); [0198] (ii) Fibre modification, pigment dispersion, paper industry (e.g., to improve wet strength); [0199] (iii) As an adhesive and/or adhesion promoter; [0200] (iv) Water treatment (e.g., as chelating & flocculating agent) due to metal binding ability; [0201] (v) Carbon dioxide capture; and [0202] (vi) Specialty and high performance applications: in biology for tissue/cell culture (e.g., for improved attachment), drug delivery and transfection agent and in electronics (e.g., to improve photovoltaics performance by reducing work function of indium tin oxide (ITO)/solar cells) etc. [0203] (vii) Oil field applications, pour point depressant

[0204] Particularly, the polymer in accordance with various embodiments disclosed herein are useful as additive to laundry products as anti-redepositioning agent, as an adhesive/adhesion promoter, as additive/binder for waterborne coating (e.g., for pigment dispersion and for anti-bacterial formulations).

[0205] FIG. 1 is a schematic diagram 100 showing the application of cationic polymer as an anti-redepositioning agent. [0206] 1) The clay soil 104 redeposit on fabric 106 will lead to whiteness loss of a cloth after washing. [0207] 2) Cationic polymer (such as ethoxylated PEI) 108 has been used in detergent to reduce the redeposition of soil particle on textiles. [0208] 3) At step 102, the positively charged polymer 108 is adsorbed on negatively charged layers of clay particle 104 and fabric surface 106. [0209] 4) This results in repulsive force 110 between the polymer molecules 108 and prevents the redeposition of soil particle on fabrics during a washing cycle, thereby giving a clean fabric.

[0210] As shown in FIG. 1, dirt 104 comprising negatively charged particles are deposited on fabric surface 106. By adjusting the pH value at step 102, secondary amine groups (—NH—) present in the polymer gain protons (H.sup.+) to form positively charged cations (—NH.sub.2.sup.+—) 108. The positive charge(s) 108 on the polymer allow for embodiments of the polymer to be adsorbed onto the negatively charged particles (e.g., clay or soil particles/deposits) 104 and the fabric surface 106, which results in a repulsive force 110 between the polymer molecules 108 and thereby preventing redeposition of such negatively charged particles during washing.

[0211] Amine containing polymers (Scheme 4) are useful for a range of applications such as additive to shampoo, detergent & cosmetics (as antibacterial or redepositioning agent), fibre modification (FIG. 1), pigment dispersion, as adhesive and adhesion promoter, in water treatment (as chelating & flocculating agent), in paper industry (to improve wet strength), carbon dioxide capture etc. High performance applications of such polymers include application in biology for tissue/cell culture (for improved attachment), drug delivery and transfection agent and in electronics (to improve photovoltaics performance by reducing work function of ITO/solar cells) etc. This diverse application of amine polymers are due to the three key chemical properties, namely i) metal-chelation or metal-binding ability, ii) hydrogen-bonding ability and iii) well known anti-bacterial properties of amine functionalities (Scheme 4).

[0212] In the following examples, it is shown that the polymer designed/synthesized in accordance with various embodiments disclosed herein can be used for diverse range of specialty applications. The polymers designed in accordance with various embodiments disclosed herein can be synthesized from bio-based monomers (e.g., succinic acid-based monomers) and are easily synthesizable (even in water or bulk) in large quantities. Embodiments of the polymers disclosed herein have also shown/proven to be hydrolysable and are therefore, potentially bio-degradable. Apart from the presence of amine groups, embodiments of the polymers disclosed herein also contain urethane and hydroxyl groups for improved properties and can be further functionalized via catalyst-free room temperature Aza-Michael and amine-epoxy addition reactions for diverse applications. Examples of applications of these polymers include applications as additive (e.g., anti-redepositioning agent) for detergents, cosmetics, as adhesive or adhesion promoter, coatings and as anti-bacterial materials.

Example 5: Metal (Copper) Coordination/Chelation of Amine Polymers

[0213] The presence of amine groups of polymers were confirmed by performing chelation experiments with copper salt. Polymers R-12 and R-14 produced characteristic blue coloration when mixed with copper (I) bromide (CuBr) in water (FIG. 2). Industry gold standards PEI-g-PEG and PEI were used as control. Results from the chelation experiments prove the water solubility of the polymers. Results from the chelation experiments also confirm the presence of nitrogen and chelation property of the polymers. It was observed that the polymers helped to dissolve originally insoluble copper salts in water.

Example 6: Hydrolytic Degradation (Related to Bio-Degradation) of Polymer

[0214] Hydrolytic degradability of succinic acid based PHUs designed in accordance with various embodiments disclosed herein were studied initially at pH 10-11 and at elevated temperature (Scheme 5). Degradability of such polymers at lower pH and at room temperature (RT) was also proven to be successful although degradation was slower (at lower pH and at RT). The degraded products were characterized with NMR and GPC. The results are shown in Table 3 below.

##STR00028##

TABLE-US-00003 TABLE 3 NMR and GPC results obtained from hydrolytic degradation experiments performed on Polymers R-13 and R-14 under different reaction conditions. Results (GPC, Polymer Condition Results (NMR) Mp, DMF) R-13 pH 11 86% conversion of Before: 11960 (SuBC-BAP) 100° C. succinate (polymer) to After: 1560 18 hrs succinic acid after 18 hrs R-13 pH 8.4 65% conversion of Before: 10000 (SuBC-BAP) r.t succinate (polymer) to After: 2840 and 30 days succinic acid after 30 1540 days R-14 pH 8.4 ~73% conversion of — (SuBC-PEHA) r.t succinate (polymer) to 18 days succinic acid after 18 days

Example 7: Interaction with Cotton Fiber

[0215] A preliminary study aiming to apply the amine containing polymers designed in accordance with various embodiments disclosed herein as anti-redepositioning agent was performed via an interaction study with cotton fiber.

[0216] FIG. 3 shows a schematic diagram 300 for illustrating an experiment designed for evaluating the potential of using the polymers designed in accordance with various embodiments disclosed herein as anti-redepositioning agents.

[0217] As shown in FIG. 3, at first, at step 308a, cotton fiber 302 (250 mg) was immersed in a polymer solution (100 mg polymer in 10 ml water) and stirred for 30 minutes, and then washed thoroughly several times (e.g., 3 times) at step 308b to remove free polymer. Finally the washed cotton fiber 304 was dried and analyzed with elemental microanalysis to obtain nitrogen (N) content. Presence of elemental N confirmed the cotton fiber-amine polymer interaction. Cotton with no polymer 306 was used as the control. For the control, cotton fiber 302 was immersed in water and stirred at step 310a, and then washed thoroughly several times (e.g., 3 times) at step 310b. No presence of elemental N was detected for the control. Elemental microanalysis results are provided in Table 4.

TABLE-US-00004 TABLE 4 Elemental Microanalysis Results Elemental Microanalysis C H N Sample (% w/w) (% w/w) (% w/w) Cotton with no polymer (Control) 42.35 6.07 Nil Cotton-R6P 42.49 5.99 0.10 (Immediately after stirring) Cotton-R6P 41.99 5.94 0.00 (After five washes) Cotton-R14P 42.56 6.06 0.12 (Immediately after stirring) Cotton-R14P 43.02 6.27 0.02 (After five washes)

Example 8: Functionalization Reactions

[0218] There are numerous possibilities for further functionalization of amine polymers especially from polymer containing secondary —NH— group. As shown in FIG. 4, the water soluble polymers designed in accordance with various embodiments disclosed herein may be further functionalized to produce i) crosslinked coating, ii) hydrogel, iii) permanently cationic antibacterial polymer, iv) introducing antifouling properties, v) hydrophobic properties, vi) increasing bio-content, vii) synthesis of graft polymer etc. by exploiting room temperature atom-efficient Aza-Michael reaction secondary amine group or amine-epoxide nucleophilic addition reaction in the absence of any other reagents or catalysts and/or formation of by-products as depicted in FIG. 4. Examples of functionalization reaction of amine polymers to produce functional materials are also provided in FIG. 4. A few of such functionalized products have been synthesized as shown in the following examples below.

Example 9: Biodegradability Results of (SuBC+TETA) NIPU

[0219] ##STR00029##

[0220] FIG. 5 shows the biodegradability results (Zahn Wellens OECD-302-B) obtained from Singapore Test Services. In this example, Public Utilities Board (PUB)'s activated sludge was extracted from Jurong Water Reclamation Plant and used for investigating the biodegradability of a polymer prepared from SuBC and TETA (Polymer R-6). Total organic carbon was used to determine the remaining carbon materials. Ethylene glycol was used as procedure control which achieved 80% biodegradability rate. SuBC-TETA showed 66% biodegradability after 28 days.

Example 10: CO.SUB.2 .Capture Evaluation Results of SuBC+PEHA NIPU

[0221] ##STR00030##

[0222] FIG. 6 shows an experimental setup 600 designed to evaluate the CO.sub.2 capture of a polymer prepared from SuBC and PEHA. A polymer solution of 30% by weight in water was prepared, in which CO.sub.2 was bubbled through at step 602 to facilitate CO.sub.2 capture. The polymer solution was then heated at a temperature of 80° C. to 100° C. over 3 hours at step 604, and monitored for CO.sub.2 release.

[0223] Results obtained from CO.sub.2 capture experiments are provided in Table 5.

TABLE-US-00005 TABLE 5 CO.sub.2 capture evaluation results of SUBC + PEHA NIPU Weight gain (g) g of g of after CO.sub.2 CO.sub.2/g CO.sub.2/Mole bubbling of solution of amines DI water 0.011 g 0.003 g NA Monoethanolamine, MEA 0.307 g 0.130 g 18.7 (commercial benchmark)- 30 wt. % SuBC-PEHA -30 wt. % 0.062 g 0.030 g 8.58 [0224] The CO.sub.2 capture evaluation results suggest that SuBC-PEHA could be a non-toxic, non-volatile CO.sub.2 capture material and can be used as a replacement of well known CO.sub.2 capture small molecular weight/volatile/toxic chemical monoethanolamine (MEA). [0225] SuBC-PEHA showed promising carbon dioxide capture property [0226] SuBC-PEHA required lower temperature for CO.sub.2 release, while MEA required >120° C. [0227] The CO.sub.2 capture evaluation results show that SuBC-PEHA has potential to be grafted on other solid porous substrates like silica, zeolite, metal-organic frameworks (MOF) etc. to be useful for solid state CO.sub.2 capture material.

Example 11: Pour Point Reduction of Crude Oil/Synthetic Oil

[0228] FIG. 7 is a schematic diagram 700 showing pour point reduction of crude oil or synthetic oil achieved by the usage of a pour point depressant polymer. Pour points were measured on PSL PPT 45150 (ASTM D5985, Rotational method). The wax crystals 702 and oil components 704 within the crude oil or synthetic oil is arranged in an orderly manner at the pour point of the oil, which has a temperature that is about 3° C. above the temperature at which the oil lost its fluidity. Upon addition of the pour point depressant 706 up to the concentration of 1000 ppm, it was observed that the pour point of the oil is lowered and the oil is able to flow at a lower temperature as the wax crystals 702 are now hindered in their interconnection, resulting in a disorderly arrangement.

##STR00031##

[0229] N-functionalized polymers R-153 and R-190 which are oil/dodecane soluble, were synthesized according to Scheme 8. In R-153, 50% N-functionalization was achieved, whereby it contains 50% C.sub.18H.sub.37 by formula. In R-190, 100% N-functionalization was achieved, whereby it contains 100% C.sub.18H.sub.37 by formula.

[0230] The evaluation of pour point reduction on wax solutions by N-functionalised SuBC+PEHA NIPUs R-153 and R-190 are shown in FIG. 8. The N-Functionalized SuBC-PEHA NIPUs are able to reduce pour point of wax solution (synthetic oil) up to 18° C., which showed promising pour point depressant (PPD) property as compared to commercial benchmark, i.e. poly(octadecyl acrylate).

[0231] The rheological effects of NIPU on 10 wt % Wax A solution in dodecane are shown in FIG. 9 and FIG. 10. From FIG. 9, the N-functionalised SuBC+PEHA NIPUs R-153 and R-190 having a concentration of 500 ppm were able to lower the viscosity by 100 times at 15° C. and the transition temperature for Wax A solution. From FIG. 10, the N-functionalised SuBC+PEHA NIPUs R-153 and R-190 having a concentration of 500 ppm were able to lower the storage modulus of Wax A solution by approximately 1000 times at 0.1% shear strain. Without being bound by theory, it is believed that lower storage modules are due to lower viscosity, less stiff and less energy stored.

Example 12: Anti-Soil Redepositioning (ASR) Property

[0232] The anti-soil redepositioning (ASR) property of the polymers designed in accordance with various embodiments disclosed herein on cotton and polyester cloths were evaluated. Both cotton and polyester cloths were washed in SuBC-PEHA ASR agent, PEI ASR agent and without additives as a control. Cotton cloth was additionally washed using PEI-g-PEG as ASR agent as a commercial control. Images were captured before and after the washing experiment and shown in FIG. 11. From the washing experiment, the synthesized NIPU SuBC-PEHA showed good anti-soil redeposition property on both cotton and polyester cloths.

[0233] FIG. 12 shows the colorimetry results obtained for the washing experiments for a quantitative analysis of the ASR property of SuBC-PEHA and SuBC-TETA on the cotton and polyester cloths. The synthesized NIPUs SuBC-PEHA and SuBC-TETA showed very good anti-soil redeposition property on both cotton and polyester cloths. Similar performance was observed for the commercially used but expensive ASR agent, PEI-g-PEG.

Example 13: Skin Irritation and Cytotoxicity Results of SuBC+TETA and SuBC+PEHA

[0234] Cell viability experiments were conducted on polymers designed in accordance with various embodiments.

[0235] FIG. 13 shows the cell viability results obtained from in-vitro skin irritation test of polymers designed in accordance with various embodiments disclosed herein. The results were obtained from Denova Sciences and conducted in accordance with OECD-TG-439. The experiments were performed on a polymer prepared from SuBC+TETA (Polymer R-6) and SuBC+PEHA (Polymer R-14).

[0236] FIG. 14 shows the cell viability results obtained from cytotoxicity test of polymers designed in accordance with various embodiments disclosed herein. The results were obtained from Singapore Polytechnic and conducted using HaCaT Cells. The experiments were performed on a polymer prepared from SuBC+TETA (Polymer R-6) and SuBC+PEHA (Polymer R-14).

[0237] Both SuBC-TETA and SuBC-PEHA were proved to be non-skin irritant and non-cytotoxic.

Example 14: Easy Post-Functionalization of Sec-Amine Containing NIPUs to Improve Functional Properties

[0238] As shown in Scheme 9, secondary-amine containing NIPUs designed in accordance with various embodiments disclosed herein can be easily post-functionalized for improvement in functional properties. SuBC-TETA or SuBC-PEHA can be post-functionalized into SuBC-TETA-EH, SuBC-PEHA-EH, SuBC-PEHA-Sy or SuBC-TETA-HF, when reacted with 2-ethylhexyl acrylate, stearyl acrylate or hexafluorobutyl acrylate respectively.

[0239] Scheme 9 shows a specific post-functionalization procedure, whereby SuBC-TETA is reacted with hexafluorobutyl acrylate with DMF or DMSO to obtained SuBC-TETA-HF. The change in water contact angle which represents change in coating surface property was measured to determine the success in post-functionalization. From FIG. 15, it was shown that the water contact angle of SuBC-TETA was 20° before functionalization, and after functionalization of SuBC-TETA into SuBC-TETA-HF, the water contact angle was increased to 104°.

##STR00032##

Example 15: Materials and Methods

i) Synthesis of Succinic Bis-Carbonate (SuBC)

[0240] ##STR00033##

[0241] Succinyl chloride (20 g, 129 mmol) was added slowly to dichloromethane (DCM) (100 mL) in a round bottom flask under nitrogen atmosphere. Glycerol carbonate (32 g, 271 mmol) was added dropwise to the succinyl chloride solution at 0° C. After addition, the reaction mixture was stirred at 35° C. under nitrogen atmosphere for 19 hrs. The precipitated solid was washed with 1 M NaOH solution (85 mL) followed by water (100 mL×2). The solid was dried partially and washed with cold acetone. The white solid was dried under vacuum at 50° C. for overnight and used for polymerization without further purification (27.5 g, yield 67%). .sup.1H NMR (400 MHz, DMSO) δ 5.03 (m, 2H), 4.56 (t, 2H), 4.27 (m, 6H), 2.62 (s, 4H). .sup.13C NMR (101 MHz, DMSO) δ 171.69, 154.81, 74.33, 66.04, 63.66, 28.48.

ii) Synthesis of Adipic Bis-Carbonate (ABC)

[0242] ##STR00034##

[0243] Adipoyl chloride (8 g, 43.7 mmol) was added slowly to dichloromethane (32 mL) in a round bottom flask under nitrogen atmosphere. Glycerol carbonate (10.8 g, 91.4 mmol) was added dropwise to the adipoyl chloride solution at 0° C. After addition, the reaction mixture was stirred at 35° C. under nitrogen atmosphere for 19 hrs. The reaction mixture was diluted with dichloromethane (40 mL), and washed with 1 M NaOH solution (15 mL) followed by water (15 mL) and brine (6 mL). The organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a viscous liquid, which slowly crystallized into white solid. The white solid was dried under vacuum at 50° C. for overnight and used for polymerization without further purification (12.3 g, yield 81%). .sup.1H NMR (400 MHz, DMSO) δ 5.02 (m, 2H), 4.56 (t, 2H), 4.25 (m, 6H), 2.36 (m, 4H), 1.54 (m, 4H). .sup.13C NMR (101 MHz, DMSO) δ 172.31, 154.63, 74.22, 65.97, 63.25, 32.80, 23.58.

iii) Synthesis of Butanediol Bis-Carbonate (BBC)

[0244] The bis-epoxy product 1,4-bis(oxiran-2-ylmethoxy)butane (10 mmol, 2.02 g), tetrabutyl ammonium iodide (TBAI) (5 mol %, 185 mg, 0.5 mmol) and pyridinedimethanol (5 mol %, 70 mg, 0.5 mmol) were dissolved in 20 mL of dry tetrahydrofuran (THF), transferred into a Parr reactor and pressurized with CO.sub.2 up to 180 psig after purging with N.sub.2. The reaction was carried out under stirring at 105° C. for 24 h. After the reaction, the reactor was cooled to room temperature and depressurized. The solvent THF was removed and redissolved in 50 ml diethyl ether, and the product was precipitated from 30 mL petroleum ether. 1.8 g (63%) of the product was obtained as off white solid. .sup.1H NMR (400 MHz, Chloroform-d) δ 4.84-4.76 (m, 2H), 4.49 (t, J=8.3 Hz, 2H), 4.42-4.35 (m, 2H), 3.74-3.56 (m, 4H), 3.53 (t, J=4.8 Hz, 4H), 1.69-1.61 (m, 4H).

iv) An Example of Polymerization Procedure of SuBC with TETA at High Temperature

##STR00035##

[0245] SuBC (0.5 g, 1.57 mmol) and triethylenetetramine (TETA, 0.23 g, 1.57 mmol) were added into a reaction vial charged with magnetic stirring bar. A few drops of mesitylene were added as internal reference. Dimethylformamide (DMF) (1 mL) was added and the reaction mixture was degassed with nitrogen under stirring. After 15 minutes, the reaction mixture was stirred at 70° C. for 24 hours. The reaction mixture was added into diethyl ether to precipitate the polymer. The precipitated polymer (R-6, SuBC-TETA polymer) was washed with diethyl ether for three times followed by drying under vacuum at 60° C. for overnight (0.48 g, yield 66%). .sup.1H NMR (400 MHz, DMSO) δ 7.05 (br, 2H), 5.07-4.70 (br, 1H), 4.12 (br, 2H), 4.05-3.84 (br, 6H), 3.77 (br, 1H), 3.42 (br, 4H), 2.98 (br, 4H), 2.49 (br, 12H).

v) An Example of Polymerization Procedure of SuBC and PEHA at Room Temperature

[0246] ##STR00036##

[0247] SuBC (0.25 g, 0.79 mmol) and DMF (1 mL) were added into a reaction vial charged with magnetic stirring bar. A few drops of mesitylene were added as internal reference. Pentaethylenehexamine (PEHA, 0.183 g, 0.79 mmol) was added and the reaction mixture was degassed with nitrogen under stirring. After 15 minutes, the reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was added into diethyl ether to precipitate the polymer. The precipitated polymer was washed with diethyl ether for three times followed by drying under vacuum at 60° C. for overnight (0.3 g, yield 69%). .sup.1H NMR (400 MHz, DMSO) δ 7.06 (br, 2H), 4.97 (br, 1H), 4.83 (br, 1H), 4.72 (br, 1H), 4.16-4.02 (br, 2H), 3.97-3.85 (br, 4H), 3.77 (br, 1H), 3.00 (br, 5H), 2.55-2.50 (br, 14H), 2.27 (br, 5H).

vi) NIPU Hydrogel Formation

[0248] The NIPU solution was prepared by dissolving SUBC-TETA polymer (R-6,150 mg) in deionized water (0.75 mL). This NIPU solution was separated into three separate vials (0.25 mL each, 0.2 mmol based on mole of TETA), namely, Control, Sample 1 and Sample 2. Poly(ethylene glycol) diglycidyl ether (54 mg, 0.1 mmol) was added into Sample 1 and Sample 2 vials, respectively. After mixing, the Sample 1 and Sample 2 vials were capped and placed at room temperature and at 50° C., respectively, for 48 hrs. Control vial was used as control example without addition of poly(ethylene glycol) diglycidyl ether.

vii) Procedure for NIPU Functionalization with Hexafluorobutyl Acrylate

[0249] SUBC-TETA polymer (R-6, 200 mg, 0.43 mmol based on mole of TETA) was dissolved in DMF (0.5 mL) followed by addition of 2,2,3,4,4,4-hexafluorobutyl acrylate (200 mg, 0.86 mmol) in a reaction vial. A drop of mesitylene was added as internal reference for NMR analysis. The reaction mixture was stirred at 60° C. for 24 hrs. After cooling to room temperature, the reaction mixture was added into diethyl ether to precipitate the polymer. The precipitated polymer SUBC-TETA—HF (R-6-F) was washed with diethyl ether for 3 times and dried under vacuum at 60° C.

viii) Procedure for Contact Angle Measurement

[0250] R-6 and R-6-F solutions were prepared by dissolving polymer (40 mg) in DMF (0.25 mL). The polymer solution was dropped onto a pre-cleaned glass slide. After drop-casting, the glass slides were placed at room temperature for 2 hours and subsequently dried at 60° C. for 24 hours. The contact angles of water droplet on the R-6 and R-6-F coated glass slides were measured.

[0251] It will be appreciated by a person skilled in the art that other variations and/or modifications may be made to the embodiments disclosed herein without departing from the spirit or scope of the disclosure as broadly described. For example, in the description herein, features of different exemplary embodiments may be mixed, combined, interchanged, incorporated, adopted, modified, included etc. or the like across different exemplary embodiments. The present embodiments are, therefore, to be considered in all respects to be illustrative and not restrictive.