COPOLYMER BLENDS

Abstract

Copolymer blends comprising a first copolymer and a second copolymer, wherein the first and second copolymers each independently comprise units of A and B as defined herein.

Claims

1. A copolymer blend comprising a first copolymer and a second copolymer, wherein the first and second copolymers each independently comprise units of A and B, wherein: A is: ##STR00070## and B is selected from optionally substituted: ##STR00071## wherein R.sub.1 is an optionally substituted aliphatic, optionally substituted aromatic or optionally substituted heteroaromatic moiety, optionally wherein R.sub.1 is unsubstituted; wherein each X is independently selected from ##STR00072## wherein n is an integer greater than 1, optionally an integer greater than 2, optionally wherein n is 2 or 3, optionally wherein n is 2; and wherein the first copolymer comprises at least one of B(i) to (iii) and the second copolymer comprises at least one other of B(i) to (iii).

2. The copolymer blend according to claim 1, wherein the blend further comprises a third copolymer, comprising units of A and B, wherein: A is: ##STR00073## and B is selected from optionally substituted: ##STR00074## wherein R.sub.1 is an optionally substituted aliphatic, optionally substituted aromatic or optionally substituted heteroaromatic moiety, optionally wherein R.sub.1 is unsubstituted; wherein each X is independently selected from ##STR00075## wherein n is an integer greater than 1, optionally an integer greater than 2, optionally wherein n is 2 or 3, optionally wherein n is 2; and wherein the first copolymer comprises at least one of B(i) to (iii), the second copolymer comprises at least one other of B(i) to (iii), and the third copolymer comprises at least one further other of B(i) to (iii).

3. The copolymer blend according to claim 1, wherein the first and/or second copolymer and/or, when present, the third copolymer, each independently comprise: ##STR00076## wherein n is an integer greater than 0, optionally wherein n is 1 or 2, optionally wherein n is 1.

4. The copolymer blend according to claim 1, wherein the first and/or second copolymer and/or, when present, the third copolymer each independently comprise: ##STR00077## wherein each Y is independently selected from ##STR00078## optionally wherein each Y is independently selected from ##STR00079## wherein p is an integer, optionally wherein p is 0 or 1, optionally wherein p is 0; and wherein k is an integer greater than 0, optionally wherein k is 1.

5. The copolymer blend according to claim 4, wherein the first and/or second copolymer and/or, when present, the third copolymer each independently comprise: ##STR00080## wherein each q is independently an integer greater than 0, optionally 1 or 2, optionally 1.

6. The copolymer blend according to claim 5, wherein the first and/or second copolymer and/or, when present, the third copolymer each independently comprise: ##STR00081## wherein q is an integer, optionally wherein q is 0 or 1, optionally wherein q is 0; and wherein k is an integer, optionally wherein k is 0; wherein l is an integer greater than 10.

7. The copolymer blend according to claim 1, wherein the first and/or second copolymer and/or, when present, the third copolymer each independently comprise: ##STR00082## wherein n is an integer, optionally wherein n is 0 or 1, optionally wherein n is 0; wherein j is an integer greater than 10.

8. The copolymer blend according to claim 1, wherein each R.sub.1 is identical.

9. The copolymer blend according to claim 1, wherein the first and/or second copolymer and/or, when present, the third copolymer each independently comprise: ##STR00083## wherein each Y is independently selected from ##STR00084## optionally wherein each Y is independently selected from ##STR00085## wherein each R.sub.1 is identical; wherein each R.sub.1a is identical and selected from an optionally substituted aliphatic, optionally substituted aromatic or optionally substituted heteroaromatic moiety, optionally wherein R.sub.1a is unsubstituted; wherein R.sub.1a and R.sub.1 are different to one another; wherein p is an integer, optionally wherein p is 0 or 1, optionally wherein p is 0; and wherein k is an integer greater than 0, optionally wherein k is 1.

10. The copolymer blend according to claim 9, wherein the first and/or second copolymer and/or, when present, the third copolymer each independently comprise: ##STR00086## wherein each q is independently an integer greater than 0, optionally 1 or 2, optionally 1; and optionally wherein each Y is independently selected from ##STR00087##

11. The copolymer blend according to claim 10, wherein the first and/or second copolymer and/or, when present, the third copolymer each independently comprise: ##STR00088## wherein q is an integer, optionally wherein q is 0 or 1, optionally wherein q is 0; and wherein k is an integer, optionally wherein k is 0; and wherein l is an integer greater than 10.

12. The copolymer blend according to claim 1, wherein the first copolymer and/or the second copolymer and/or, when present, the third copolymer further comprise one or more units of C, selected from optionally substituted: ##STR00089##

13. The copolymer blend according to claim 1, wherein the first copolymer comprises at least two units selected from B(i), B(ii) and B(iii).

14. The copolymer blend according to claim 13, wherein the second copolymer comprises at least two units selected from B(i), B(ii) and B(iii).

15. The copolymer blend according to claim 13, wherein each of the first copolymer and/or the second copolymer and/or, when present, the third copolymer comprise units of all three of B(i)-(iii).

16. A copolymer comprising units of A and at least two different units of B selected from B(i), B(ii) and B(iii), wherein: A is: ##STR00090## and each B is independently selected from optionally substituted: ##STR00091## wherein R.sub.1 is an optionally substituted aliphatic, optionally substituted aromatic or optionally substituted heteroaromatic moiety, optionally wherein R.sub.1 is unsubstituted, wherein each X is independently selected from and ##STR00092## wherein n is an integer greater than 1, optionally wherein n is 2 or 3, optionally wherein n is 2.

17. The copolymer according to claim 16, comprising B(i) and B(ii).

18. The copolymer according to claim 16, comprising: ##STR00093## wherein each a is independently an integer, optionally 0 or 1, optionally 0.

19. The copolymer according to claim 18, comprising: ##STR00094## wherein each Y is independently selected from ##STR00095## optionally wherein each Y is independently selected from ##STR00096## wherein each b is independently an integer greater than 0, optionally 1 or 2, optionally 1; and wherein c is an integer greater than 0, optionally wherein c is 1 or 2, optionally wherein c is 1.

20. The copolymer according to claim 19, comprising: ##STR00097## wherein a is an integer, optionally wherein a is 0; wherein c is an integer, optionally wherein c is 0 or 1, optionally wherein c is 0; and wherein m is an integer greater than 10.

21. The copolymer according to claim 18, comprising: ##STR00098## wherein w is an integer greater than 10.

22. The copolymer according to claim 16, wherein each R.sub.1 is identical.

23. The copolymer according to claim 16, comprising: ##STR00099## wherein each R.sub.1 is identical; wherein each R.sub.1a identical and selected from an optionally substituted aliphatic, optionally substituted aromatic or optionally substituted heteroaromatic moiety, optionally wherein R.sub.1a is unsubstituted, wherein R.sub.1 and R.sub.1a are different to one another; and wherein each a is independently an integer, optionally 0 or 1, optionally 0.

24. The copolymer according to claim 23, comprising: ##STR00100## wherein each R.sub.1 is identical; wherein each R.sub.1a identical and selected from an optionally substituted aliphatic, optionally substituted aromatic or optionally substituted heteroaromatic moiety, optionally wherein R.sub.1a is unsubstituted, wherein each Y is independently selected from ##STR00101## optionally wherein each Y is independently selected from ##STR00102## wherein each b is independently an integer greater than 0, optionally 1 or 2, optionally 1; and wherein c is an integer greater than 0, optionally wherein c is 1 or 2, optionally wherein c is 1.

25. The copolymer according to claim 24, comprising: ##STR00103## wherein a is an integer, optionally wherein a is 0; wherein c is an integer, optionally wherein c is 0 or 1, optionally wherein c is 0; and wherein m is an integer greater than 10.

26. The copolymer according to claim 23, comprising: ##STR00104## wherein w is an integer greater than 10.

27. The copolymer according to claim 16, comprising units of all three of (a)-(c).

28. The copolymer according to claim 16, further comprising one or more units of C, selected from optionally substituted: ##STR00105##

29. The copolymer blend or copolymer according to claim 1, wherein each B is independently selected from optionally substituted: ##STR00106##

30. The copolymer blend or copolymer according to claim 1, wherein each R.sub.1 and/or each R.sub.1a, when present, is independently an optionally substituted straight-chain, branched or cyclic C.sub.2 to C.sub.10 saturated alkylene, optionally a C.sub.2 to C.sub.8 optionally substituted saturated alkylene, optionally a C.sub.2 to C.sub.6 optionally substituted saturated alkylene, and optionally C.sub.2 to C.sub.4 optionally substituted saturated alkylene, optionally wherein R.sub.1 is unsubstituted.

31. The copolymer blend or copolymer according to claim 1, wherein each R.sub.1 and/or each R.sub.1a, when present, is independently a branched or unbranched moiety, optionally wherein one or more instances of R.sub.1 is branched, optionally wherein all instances of R.sub.1 are branched.

32. The copolymer blend or copolymer according to claim 1, wherein (i), (ii) and/or, when present, (iii) is of non-renewable origin.

33. (canceled)

34. An article comprising a copolymer blend or copolymer according to claim 1.

35. The copolymer blend according to claim 1, wherein the first and second copolymers are present at a molar ratio of about 1:14-24 (first to second).

Description

DESCRIPTION OF THE FIGURES

[0229] FIG. 1 shows the .sup.1H NMR spectra for 2,5-polybutyrate adipate furandicarboxylate (2,5-PBAF).

[0230] FIG. 2 shows the .sup.1H NMR spectra for 2,4-polybutyrate adipate pyridinedicarboxylate (2,4-PBAP).

[0231] FIG. 3 shows the .sup.1H NMR spectra for 2,5-polybutyrate adipate pyridinedicarboxylate (2,5-PBAP).

[0232] FIG. 4 shows the 1H NMR spectra for polybutyrate adipate terephthalate (PBAT) produced in accordance with Example 5.

[0233] FIG. 5 shows the .sup.1H NMR spectra for commercial PBAT.

[0234] FIG. 6 shows the Simultaneous Thermal Analysis (STA) trace for 2,5-PBAF.

[0235] FIG. 7 shows the STA trace for 2,4-PBAP.

[0236] FIG. 8 shows the STA trace for 2,5-PBAP.

[0237] FIG. 9 shows the STA trace for PBAT produced in accordance with Example 5.

[0238] FIG. 10 shows the STA trace for commercial PBAT.

[0239] FIG. 11 shows Differential Scanning calorimetry (DSC) traces for 2,5-PBAF, PBAT produced in accordance with Example 5 and commercial PBAT.

[0240] FIG. 12 shows DSC traces for 2,4-PBAP, 2,5-PBAP, PBAT produced in accordance with Example 5 and commercial PBAT.

[0241] FIG. 13 shows the Gel Permeation Chromatography (GPC) spectra for 2,5-PBAF.

[0242] FIG. 14 shows the GPC spectra for 2,4-PBAP.

[0243] FIG. 15 shows the GPC spectra for 2,5-PBAP.

[0244] FIG. 16 shows the GPC spectra for PBAT produced in accordance with Example 5.

[0245] FIG. 17 shows the GPC spectra for commercial PBAT.

[0246] FIG. 18 shows that under the biodegradation test conditions outlined in Example 9, 2,5-PBAF result in a carbon loss of 29.3% after 40 days. The 90% level set for biodegradation in the test accounts for a +/10% statistical variability of the experimental measurement, which one would expect virtually complete biodegradation in the composting environment of the test.

[0247] FIG. 19 shows that under the biodegradation test conditions outlined in Example 9, 2,5-PBAF loses carbon at a steady rate for over 60 days. The 90% level is as defined for FIG. 18 above.

[0248] FIG. 20 shows that under the biodegradation test conditions outlined in Example 9. 2,4-PBAP and 2,5-PBAP result in greater percentage carbon loss (66.4% and 64.2%, respectively) than a compostable sample (47.7%), after 40 days. The 90% level set for biodegradation in the test accounts for a +/10% statistical variability of the experimental measurement, which one would expect virtually complete biodegradation in the composting environment of the test.

[0249] FIG. 21 shows that under the biodegradation test conditions outlined in Example 9, 2,4-PBAP and 2,5-PBAP rapidly lose carbon at a rate faster than that of a compostable sample. 2,5-PBAP reaches 90% carbon loss after about 105 days, which is fast than that of a compostable sample. The 90% level is as defined for FIG. 20 above.

[0250] FIG. 22 shows the attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR) of 2,5-polybutyrate adipate furandicarboxylate (2,5-PBAF) using a Thermo Nicolet Nexus FT-IR spectrometer coupled with a Continuum IR microscope.

[0251] FIG. 23 shows the attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR) of 2,4-PBAP using a Thermo Nicolet Nexus FT-IR spectrometer coupled with a Continuum IR microscope.

[0252] FIG. 24 shows the attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR) of 2,5-PBAP using a Thermo Nicolet Nexus FT-IR spectrometer coupled with a Continuum IR microscope.

[0253] FIG. 25 shows the attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR) of commercial PBAT using a Thermo Nicolet Nexus FT-IR spectrometer coupled with a Continuum IR microscope.

[0254] FIG. 26 shows a DSC trace for a mixture of 2,4 PBAP and 2,5 PBAF.

[0255] FIG. 27 shows the GPC spectra for a mixture of 2,4 PBAP and 2,5 PBAF.

[0256] FIG. 28 shows the .sup.1H NMR spectra for a mixture of 2,4 PBAP and 2,5 PBAF.

[0257] FIG. 29 shows the results of tensile strength analysis for a mixture of 2,4 PBAP and 2,5 PBAF.

[0258] The following examples are merely illustrative examples of the disclosure disclosed herein and are not necessarily intended to be limiting upon the scope of the disclosure.

EXAMPLES

[0259] General Methodology for the Formation of Copolymers

[0260] A flange flask between 50 and 500 mL with 5 quick-fit ports was used in connection with a Dean-Stark apparatus. Stirring was achieved either via a magnetic stirrer using a large precious metal stirrer bar or overhead stirrer equipped with a PTFE/stainless steel stirrer paddle. The rates of stirring were gradually decreased from the initial 120 rpm down to 40 rpm to avoid issues as a result of the increasing viscosity of the reaction mixture. Reagents were added to the reactor over time; once the reactor had reached 110 to 130 C., all reactants were fully miscible. The reactor was evacuated (4 mbar) and backfilled with inert gas (either Ar or N.sub.2) four times to remove oxygen from the system. The temperature was then increased to the desired point as stated below. After a further four hours of very low inert flow the Dean-Stark was drained and a low vacuum applied (200 mbar) and slowly increased as stated below.

Example 1Synthesis of 2,5-polybutyrate Adipate Furandicarboxylate (2,5-PBAF)

[0261] ##STR00067##

[0262] 2,5-Diethyl-2,5-furandicarboxylate (149.46 g; 705 mmol), 1,4-butane diol (158.63 g, 1762.5 mmol) and antimony trioxide (6.18 g, 21.2 mmols) were combined. The reaction vessel was evacuated and purged with Argon four times and then heated to 130 C. for 2 hours at atmospheric pressure with stirring at 120 rpm. After 2 hours diethyl adipate (142.41 g; 705 mmol) was added to the reaction vessel under an inert purge and left to stir for 2 hours. After this the temperature was increased to 150 C. for 17 hours, then the pressure gradually reduced to 200 mbar over 2.5 hours, then the temperature increased to 180 C. for 3.5 hours, then the pressure reduced over one hour to 1 mbar and held for a further 17 hours. The polymer was formed (277.78 g). The .sup.1H NMR spectra for 2,5-PBAF can be found at FIG. 1.

[0263] The molar ratio of 2,5-furandicarboxylate:adipate was determined by .sup.1H NMR spectroscopy to be 1:0.92. The molecular weight of the 2,5-PBAF was estimated using end-group analysis, wherein the ratio of end groups to those of the bulk polymer were calculated using .sup.1H NMR spectroscopy to give the number of constitutional repeating units (CRU), which was estimated to be 22.2. One ideal CRU is 410.43 gmol.sup.1. Therefore, the molecular weight of the 2,5-PBAF was estimated to be 9120.7 gmol.sup.1.

Example 2Synthesis of 2,4-polybutyrate Adipate Pyridinedicarboxylate (2,4-PBAP)

[0264] ##STR00068##

[0265] 2,4-Diethyl-2,4-pyridinedicarboxylate 1.115 g; 5 mmol), 1,4-butane diol (1.1265, 12.5 mmol) and antimony trioxide (42.3 mg, 0.145 mmol) were combined. The reaction vessel was evacuated and purged with Argon four times and then heated to 110 C. for 20 hours at atmospheric pressure with stirring at 300 rpm, followed by the addition of diethyl adipate (1.011 g, 5 mmol) and further stirring at 110 C. for two hours at 500 mbar. The vessel was then heated to 180 C. for 22 hours at 200 mbar and 250 rpm, at 180 C. for 1.5 hours at 25 mbar 200 rpm and at 180 C. for 5 hours at 1 mbar and 100 rpm. The copolymer was formed (2.07 g). The .sup.1H NMR spectra for 2,4-PBAP can be found at FIG. 2.

[0266] The ratio of 2,4-pyridinedicarboxylate:adipate was determined by .sup.1H NMR spectroscopy to be 1:0.971. The molecular weight of the 2,4-PBAP was estimated using end-group analysis, wherein the ratio of end groups to those of the bulk polymer were calculated using .sup.1H NMR spectroscopy to give the number of constitutional repeating units (CRU), which was estimated to be 10.94. One ideal CRU is 421.46 gmol.sup.1. Therefore, the molecular weight of the 2,4-PBAP was estimated to be 4,611.2 gmol.sup.1.

Example 3Synthesis of 2,5-polybutyrate Adipate Pyridinedicarboxylate (2,5-PBAP)

[0267] ##STR00069##

[0268] 2,5-Diethyl-2,5-pyridinedicarboxylate 1.115 g; 5 mmol), 1,4-butane diol (1.1265, 12.5 mmol) and antimony trioxide (42.3 mg, 0.145 mmol) were combined. The reaction vessel was evacuated and purged with Argon four times and then heated to 110 C. for 20 hours at atmospheric pressure with stirring at 300 rpm, followed by the addition of diethyl adipate (1.011 g, 5 mmol) and further stirring at 110 C. for two hours at 500 mbar. The vessel was then heated to 180 C. for 22 hours at 200 mbar and 250 rpm, at 180 C. for 1.5 hours at 25 mbar 200 rpm and at 180 C. for 5 hours at 1 mbar and 100 rpm. The copolymer was formed (2.06 g). The .sup.1H NMR spectra for 2,5-PBAP can be found at FIG. 3.

[0269] The molecular weight of the 2,5-PBAP was estimated by .sup.1H NMR spectroscopy using end-group analysis as described for 2,4-PBAP. The ratio of 2,5-pyridinedicarboxylate:adipate was determined to be 1:0.953. The number of CRUs was estimated to be 18.45. One ideal CRU is 421.46 gmol.sup.1. Therefore, the molecular weight of the 2,5-PBAP was estimated to be 7776.0 gmol.sup.1.

Example 4Synthesis of 2,5-polybutyrate Adipate Furanoate 2,4-pyridinedicarboxylate (2,5-PBAF-2,4-P)

[0270] 2,5-Diethyl-2,5-furandicarboxylate (141.99 g; 669.75 mmol), 2,4-Diethyl-2,4-pyridinedicarboxylate (7.87 g; 35.25 mmol), 1,4-butane diol (152.28 g, 1692 mmol) and antimony trioxide (6.87 g, 21.15 mmols) were combined. The reaction vessel was evacuated and purged with Argon four times and then heated to 130 C. at 120 rpm. After 4 hours, diethyl adipate (158.77 g, 705 mmols) was added to the reaction mixture under an inert purge and stirrer for 14 hours. After this, 800 mbar vacuum was applied and the temperature increased to 150 C. at 120 rpm. The vacuum was gradually increased to 200 mbar after 1 hour, followed by an increase in temperature to 180 C. After 5 hours, the vacuum was gradually increased to 2 mbar at 80 rpm and held for a further 17 hours. The copolymer was formed (271.95 g).

[0271] The molecular weight of the co-polymer was estimated by .sup.1H NMR spectroscopy using end-group analysis. The ratio of 2,5-furandicarboxylate:2,4-pyridinedicarboxylate:adipate was determined to be 0.904:0.047:1. The number of constitutional repeating units (CRUs) was estimated to be 12.05. One ideal CRU is 411.27 gmol.sup.1. Therefore, the molecular weight of the 2,5-PBAF-2,4-P was estimated to be 4955 gmol.sup.1.

Example 5Synthesis of Polybutyrate Adipate Terephthalate (PBAT)

[0272] (BP054)

[0273] Diethyl terephthalate (2.222 g, 10 mmols), 1,4-butane diol (2.252 g, 25 mmol) and antimony trioxide (84.6 mg, 0.29 mmol) were combined. The reaction vessel was evacuated and purged with Argon four times and then heated to 110 C. for 2 hours at atmospheric pressure with stirring at 300 rpm, followed by the addition of diethyl adipate (1.011 g, 5 mmol) and further stirring at 110 C. for two hours at 500 mbar. The vessel was then heated to 200 C. for 17 hours at 200 mbar and 250 rpm, at 200 C. for 3 hours at 25 mbar 200 rpm and at 200 C. for 5 hours at 1 mbar and 100 rpm. The copolymer was formed (3.91 g). The .sup.1H NMR spectra for PBAT can be found at FIG. 4.

[0274] The molecular weight of the PBAT was estimated by .sup.1H NMR spectroscopy using end-group analysis as described for 2,4-PBAP. The molar ratio of terephthalate:adipate was determined to be 1:0.91. The number of CRUs was estimated to be 9.79. One ideal CRU is 420.45 gmol.sup.1. Therefore, the molecular weight of the PBAT was estimated to be about 34,000 gmol.sup.1.

[0275] PBAT is available commercially under a range of trade names. The molecular weight of one particular commercial PBAT was estimated by .sup.1H NMR spectroscopy using end-group analysis as described for 2,4-PBAP. The molar ratio of terephthalate:adipate was determined to be 0.93:1. The number of CRUs was estimated to be 25.7. One ideal CRU is 420.45 gmol.sup.1. Therefore, the molecular weight of the commercial PBAT was estimated to be 10,809 gmol.sup.1. The .sup.1H NMR spectra for commercial PBAT can be found at FIG. 5.

Example 6Thermal Analysis of Polymers Using (STA and DSC)

[0276] The thermal stability of 2,5-PBAF, PBAT (Example 5) and Commercial PBAT copolymers were analysed using Simultaneous Thermal Analysis (STA) using a Stanton Redcroft STA 625. Approximately 10-20 mg of copolymer was heated from ambient temperature to 625 C. at a heating rate of 10 C. min.sup.1 under nitrogen. Typically, two distinct decompositions were observed; when present, the first may be the decomposition of end-groups and is thus often small, the second may be the major decomposition of the copolymer backbone. The results can be found in Table 1.

TABLE-US-00001 TABLE 1 STA analysis of polymers Temperature Temperature of 5 wt % loss of decomp. Copolymer C. C. STA trace 2,5-PBAF 315.0 391.7 FIG. 6 PBAT (Example 5) 289.5 406.0 FIG. 9 Commercial PBAT 341.5 409.5 FIG. 10

[0277] The thermal stability of cured 2,4-PPAP, 2,5-PBAP, PBAT (Example 5) and Commercial PBAT copolymers were analysed using Simultaneous Thermal Analysis (STA) using a Stanton Redcroft STA 625. Approximately 10-20 mg of copolymer was heated from ambient temperature to 625 C. at a heating rate of 10 C. min-1 under nitrogen. Typically, two distinct decompositions were observed; when present, the first may be the decomposition of end-groups and is thus often small, the second may be the major decomposition of the copolymer backbone. The results can be found in Table 2.

TABLE-US-00002 Temperature Temperature Temperature of 5 wt % loss of 50 wt % loss of 2.sup.nd decomp. Copolymer C. C. C. 2,4-PBAP 319.04 375.59 2,5-PBAP 332.77 381.26 PBAT (Example 5) 361.83 401.88 Commercial PBAT 341.5 409.5

[0278] The glass transition temperature (T.sub.g) and melting point (T.sub.m) of the copolymers were obtained by Differential Scanning calorimetry (DSC) analysis using a TA Instruments Q2000 DSC. Indium was used as the standard to calibrate the temperature and heat capacity. Copolymer samples (7-10 mg) were sealed in Tzero aluminum hermetic DSC pans. The method was carried out under a constant flow of dry nitrogen of 50 mL/min, at 10 C./min over a temperature range of 80 C. to 200 C. The results can be found in Table 3. The DSC traces can be found at FIG. 11 (a: 2,5-PBAF, PBAT produced in accordance with Example 5 and commercial PBAT; and b: 2,5-PBAF) and 12 (a: 2,4-PBAP, b: commercial PBAT; c: 2,5-PBAP, d: PBAT produced in accordance with Example 5).

TABLE-US-00003 TABLE 3 DSC analysis of copolymers Tg1 Tg2 Tm Copolymer C. C. C. 2,5-PBAF 30.6 66.0 99.3 2,4-PBAP 22.95 2,5-PBAP 29.66 71.01 105.01 2,5-PBAF-2,4-PBAP 30.92 48.19 87.07 (1:19:20 PDEE:FDEE:DEA) PBAT (Example 5) 37.81 117.81 131.92 Commercial PBAT 30.1 45.4 122.2 Ecoflex 30.41 50.59 119.04

Example 7

[0279] The molecular weight (M.sub.n and M.sub.w) and polydispersity (Pd.sub.i) data as generated by GPC can be found in Table 4. GPC was conducted on an Agilent SECurity GPC System 1260 Infinity using diphenyl ether as the solvent, a polystyrene standard, and a light scattering detector.

TABLE-US-00004 TABLE 4a GPC analysis of copolymers Copolymer Diol Mn Mw PD Diethyl terephthalate 1,4-butanediol 1331 1550 1.165 Diethyl terephthalate 1,6-hexanediol 3033 4484 1.478 Diethyl terephthalate 1,8-octanediol 6257 9893 1.581 Diethyl-2,5- 1,4-butanediol 1342 1889 1.408 furandicarboxylate Diethyl-2,5- 1,6-hexanediol 2703 4725 1.748 furandicarboxylate Diethyl-2,5- 1,8-octanediol 3709 5908 1.593 furandicarboxylate Diethyl isophthalate 1,4-butanediol 2447 4084 1.669 Diethyl isophthalate 1,6-hexanediol 2726 8855 3.248 Diethyl isophthalate 1,8-octanediol 3180 15783 4.963 Diethyl-2,4-pyridine 1,4-butanediol 1884 4190 2.224 dicarboxylate Diethyl-2,4-pyridine 1,4-butanediol 2131 4427 2.077 dicarboxylate Diethyl-2,4-pyridine 1,6-hexanediol 5902 17621 2.986 dicarboxylate Diethyl-2,4-pyridine 1,8-octanediol 14315 32119 2.244 dicarboxylate Diethyl-2,5-pyridine 1,4-butanediol 914 1578 1.726 dicarboxylate Diethyl-2,5-pyridine 1,4-butanediol 1154 1883 1.632 dicarboxylate Diethyl-2,5-pyridine 1,6-hexanediol 4844 10824 2.235 dicarboxylate Diethyl-2,5-pyridine 1,8-octanediol 8124 12088 1.488 dicarboxylate Diethyl-2,6-pyridine 1,4-butanediol 574 727 1.267 dicarboxylate Diethyl-2,6-pyridine 1,6-hexanediol 1775 4040 2.276 dicarboxylate Diethyl-2,6-pyridine 1,6-hexanediol 2196 4279 1.949 dicarboxylate Diethyl-2,6-pyridine 1,8-octanediol 3225 7040 2.183 dicarboxylate

TABLE-US-00005 TABLE 4b GPC analysis of copolymers Copolymer M.sub.n M.sub.w Pd.sub.i GPC chromatogram 2,5-PBAF 4963 7094 1.43 FIG. 13 2,4-PBAP 18,036 28,025 1.55 FIG. 14 2,5-PBAP 16972 38622 2.28 FIG. 15 2,5-PBAF-2,4-PBAP 17,345 27,904 1.61 FIG. 27 (1:19:20 PDEE:FDEE:DEA) PBAT (Example 5) 15,524 21,739 1.40 FIG. 16 Commercial PBAT 42,190 113,100 2.680 Ecoflex 52,700 121,800 2.31 FIG. 17

Example 8Tensile Strength Measurement

[0280] Mechanical properties including tensile strength, elongation at break and Young's modulus of samples are summarised in Table 5. Film samples were prepared by heating about 8 g of copolymer in a fan-assisted oven at 160 C. for 15 min (180 C. for PBAT). The resulting films were cut into standard dumb-bell shapes (60 mm10 mm). Film thickness was in the region of 1.5-2.0 mm. Tensile studies were conducted in triplicate using an Instron 3367 universal testing machine fitted with 1000 N capacity load cell. The initial grip separation was set at 35 mm and the crosshead speed was 20 mm/min. The results reported were the average of the three measurements (the elongation at break was obtained automatically from the software). Commercial PBAT is a typical elastomer with elongation over 293%. It has the highest tensile strength over 19.5 MPa and good Young's modulus of 100.8 MPa.

TABLE-US-00006 TABLE 5 Tensile strength measurement of copolymers Tensile Elongation at Young's strength break Modulus Copolymer MPa % MPa 2,5-PBAF 6.97 0.62 3.32 mm 75.3 2.0 2,5-PBAP 2.8 0.4 5.2 0.3 90.6 14.0 2,5-PBAF-2,4- 4.91 0.38 44.6 mm PBAP (1:19:20 PDEE:FDEE:DEA) PBAT (Example 5) 4.8 0.5 2.3 0.2 269.80.2 Commercial PBAT >19.5 >293.1 100.8

[0281] The 2,5-PBAF, 2,4-PBAP and 2,5-PBAP copolymers produced are soft like that of the commercial PBAT. The expected ratio of PDCA/FDCA/TPA to adipate of about 1:1 has been incorporated into the copolymer. The observed molecular weight of 2,5-PBAF, 2,4-PBAP, 2,5-PBAP and PBAT (Example 5) are significantly lower than that of commercial PBAT. This is expected given the relatively small scale on which the copolymerisations were conducted and will be higher in a full scale production process. The NMR data provides an indication of the relative number of constitutional repeating units (CRU) and hence an indication of molecule weight, though the GPC provides more accurate values.

[0282] The differences in the data obtained for the copolymers of the disclosure and the commercial PBAP may be attributed to a lack of branching in 2,5-PBAF, 2,4-PBAP and 2,5-P BAP.

Example 9

[0283] Stabilised green waste compost is matured in a composting bin under controlled aeration conditions. Before use, the mature compost is sieved on a screen of 5 mm. The fine fraction forms the inoculum with a total solids content of approximately 50-55% and the volatile content of the total solids is more than 30%.

[0284] The standard and control materials are mixed with the inoculum in a ratio of approximately 1 to 1.5 parts of total solids to 6 parts of total solids and introduced into a reactor. These reactors are closed and put into an incubator. The temperature of the reactors is maintained at 58 C.+/2 C. Pressurised air is pumped through a gas flow controller and blown into the composting vessel at the bottom through a porous plate. During biodegradation, solid carbon of the test sample is converted into CO.sub.2.

[0285] The gas leaving each individual reactor is analysed at regular intervals for CO.sub.2 and 02 concentrations. As the flow rate is continually measured, the cumulative CO.sub.2 production can be determined. The percentage of biodegradation is determined as the percentage of solid carbon of the test compound that is converted into CO.sub.2.

[0286] The results are shown in FIGS. 18 to 21.

Example 10

[0287] FIGS. 22 to 25 show the attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR) of 2,5-polybutyrate adipate furandicarboxylate (2,5-PBAF), 2,4-PBAP, 2,5-PBAP and commercial PBAT, each using a Thermo Nicolet Nexus FT-IR spectrometer coupled with a Continuum IR microscope.

Example 11

[0288] Mixtures of 2,4 PBAP and 2,5 PBAF were prepared. DSC, GPC and NMR analysis were performed and the results are shown in FIGS. 26, 27 and 28 respectively.

[0289] Tensile strength analyses were performed and the results are shown in FIG. 29 and the table below.

TABLE-US-00007 Tensile Tensile Tensile stress at Tensile strain Extension at strain at stress at Modulus Tensile Maximum at Break Break Yield (Offset Yield (Offset Modulus (E-modulus) Strength Load (Standard) (Standard) 0 mm) 0.2%) Rate 1 (Automatic) (MPa) (MPa) (N) (mm/mm) (mm) (%) (MPa) (mm/min) (MPa) 1 6.402 4.611 11.396 227.9254 5.000 1.85991 2 6.343 4.567 11.190 223.8081 5.000 8.08546 3 4.256 3.066 3.307 66.1497 5.000 8.75320 Mean 5.667 4.081 8.631 172.6277 5.000 6.23286 Standard 1.22212 0.87959 4.61178 92.23568 0.00000 3.80177 Deviation

[0290] Any listing or discussion of an apparently prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or common general knowledge. All references disclosed herein are to be considered to be incorporated herein by reference.

[0291] Those skilled in the art will recognise or be able to ascertain using no more than routine experimentation many equivalents to the specific embodiments described herein. The scope of the present embodiments described herein is not intended to be limited to the above description, but rather is as set forth in the appended claims. Those of ordinary skill in the art will appreciate that various changes and modifications to this description may be made without departing from the spirit or scope of the present disclosure, as defined in the following claims.