POLY(ESTER AMIDE)S AND PREPARATION METHOD THEREFOR

Abstract

Disclosed in the present invention is poly(ester amide)s and method for preparing thermoplastic poly(ester amide)s therefor. The poly(ester amide)s are prepared using diamine or alkamine as initiator, with diacid and dialcohol-based cyclicester as the monomer, in the catalyst, and by cascade polycondensation-coupling ring-opening polymerization. The obtained poly(ester amide)s have good mechanical properties, solvent resistance and thermal stability. It effectively solves the deficiencies in the current poly(ester amide)s, such as low crystallization temperature and poor heat resistance of polyester parts, and low modulus and rigidity from polyamides part. For aliphatic poly(ester amide)s, they are biodegradable. By means of altering such factors as the ratio of ester bonds and amide bonds and polymer molecular weight and distribution, the performance of the poly(ester amide)s material can be adjusted, causing the invention to have broad application in such fields as engineering plastics, thermoplastic elastomers, tissue engineering, and controlled release.

Claims

1. Poly(ester amide)s of the following chemical formula: ##STR00006## R.sub.1 is -(CH.sub.2).sub.nNH-, -(CH.sub.2).sub.6O-, or -C(CH.sub.3).sub.2CH.sub.2O-; or R.sub.1 is ##STR00007## R.sub.2 is -(CH.sub.2).sub.m Or ##STR00008## n is from 4 to 16; m is from 4 to 11; t is from 2 to 4; x is from 10 to 250; y is from 2 to 200.

2. A method of preparing the poly(ester amide)s of claim 1, comprising: reacting diamines or aminoalcohols with sodium arylsulfinates as initiators, diacid and dialcohol-based cyclicesters as monomers, in the presence of a catalyst, the poly(ester amide)s are prepared by cascade polycondensation-coupling ring-opening polymerization.

3. The method according to claim 2, the diamine is 1,6-hexanediamine, 1, 8-octanediamine, 1,10-decanediamine, 1,12-diaminodode-cane, 1,3-cyclohexanedimethylamine, or 1,4-xylylenediamine; the aminoalcohol is 6-amino-1-hexanol or isobutanolamine; the diacid and dialcohol-based cyclicesters are cyclic oligoesters or aromatic macrolide; the catalyst is titanate compound.

4. The method according to claim 2, wherein the reaction is conducted under the nitrogen atmosphere or vacuum condition; after the reaction, the polymerization product is directly obtained without post-treatment.

5. The method according to claim 2, wherein the reaction is conducted at 200 to 280° C., for 10 to 240 hours.

6. The method according to claim 2, wherein the molar ratio of the monomer to the initiator is 2:100; wherein a molar ratio of the catalyst is 0.03% to 1% of the total mass of monomer and initiator.

7. The method according to claim 2, the initiator and the monomer are mixed and heated before the catalyst is added, and the cascade polycondensation-coupling ring-opening polymerization is performed to prepare the poly(ester amide)s; or the initiator, the monomer and the catalyst are mixed and heated, and cascade polycondensation-coupling ring-opening polymerization is performed to prepare the poly(ester amide)s.

8. An application of poly(ester amide)s in preparation of poly(ester amide)s materials.

9. An application of n-butyl titanate or isobutyl titanate as catalyst in catalyzing diamine or aminoalcohol as initiator to initiate a cascade polycondensation-coupling ring-opening polymerization of dialcohol-based cyclicester is aliphatic macrolide to prepare poly(ester amide)s.

10. The application according to claim 9, the diamine is 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-diaminodode-cane, 1,3-cyclohexanedimethylamine, or 1,4-xylylenediamine; the aminoalco-hol is 6-amino-l-hexanol or isobutanolamine; the diacid and dialcohol-based cyclicesters are cyclic oligoesters or aromatic macrolide.

Description

DRAWINGS

[0026] FIG. 1 is diagram of Synthesis of poly(ester amide)s;

[0027] FIG. 2 is shown the size exclusion chromatography curve for PEBHA in Example 1 (solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0028] FIG. 3 is shown the size exclusion chromatography curve for PEBOA-1 in Example 2 (solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0029] FIG. 4 is shown the thermogravimetric curve of PEBOA-2 in Example 3(heating rate: 10° C. per minute, atmosphere: nitrogen);

[0030] FIG. 5 is shown the stress-strain curve of PEBOA-2 in Example 3(stretching rate: 10 mm per minute, temperature: 25.7° C., humidity: 79.0%);

[0031] FIG. 6 is shown the differential scanning calorimetry curve of PEBOA-3 in Example 4(heating rate: 10° C. per minute, atmosphere: nitrogen);

[0032] FIG. 7 is shown the size exclusion chromatography curve for PEBDA in Example 7(solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0033] FIG. 8 is shown the size exclusion chromatography curve for PEBDDA in Example 8(solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0034] FIG. 9 is shown the size exclusion chromatography curve for PEAHA in Example 9(solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0035] FIG. 10 is shown the size exclusion chromatography curve for PEBCHA in Example 10(solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0036] FIG. 11 is shown the size exclusion chromatography curve for PEBXA in Example 11(solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0037] FIG. 12 is shown the size exclusion chromatography curve for PEBAHA in Example 12(solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0038] FIG. 13 is shown a comparison chart of the solubility of aliphatic polyesters and poly(ester amide)s;

[0039] FIG. 14 is shown the size exclusion chromatography curve for PEBDA-2 in Example 13(solvent: tetrahydrofuran concentration: 1.00 mg/ml);

[0040] FIG. 15 is shown the degradation curves which the quality at 37° C. of PEBDA-2 in lipase-free and lipase-containing phosphate buffered saline solutions over time;

[0041] FIG. 16 is shown the degradation curves which the molecular weight at 37° C. of PEBDA-2 in lipase-free and lipase-containing phosphate buffered saline solutions over time.

EXAMPLES OF THE INVENTION

[0042] The following further describes the present invention with reference to the examples: reacting diamines or aminoalcohols with sodium arylsulfinates as initiators, diacid and dialcohol-based cyclicesters as monomers, in the presence of the catalyst, poly(ester amide)s are prepared by cascade polycondensation-coupling ring-opening polymerization. It effectively solves the deficiencies in the current poly(ester amide)s, such as low crystallization temperature and poor heat resistance of polyester parts, and low modulus and rigidity from polyamides part.

[0043] As shown in FIG. 1, the present invention obtains a series of aliphatic poly(ester amide)s and semi-aromatic poly(ester amide)s through a cascade polycondensation-coupling ring-opening polymerization method.

EXAMPLE 1

[0044] Aliphatic poly(ester amide) poly(ethylene brassylate-co-1,6-hexa-methylene brassylamide) (PEBHA) by cascade polycondensation-coupling ring-opening polymerization of 1,6-hexanediamine and ethylene brassylate under nitrogen condition.

[0045] Ethylene brassylate (9.00 g), 1,6-hexanediamine (1.00 g) and n-butyl titanate (20.0 μL) were added into a 250 ml single-necked flask at room temperature. The flask was heated to 240° C. with mechanical stirring. The polymerization was carried under vacuum for 60 minutes to finally generate the corresponding polymer PEBHA. The size exclusion chromatography curve for PEBHA is shown in FIG. 2, and the measured number-average molecular weight is 36.1 kg/mol, which proves the successful synthesis of the target product.

EXAMPLE 2

[0046] Aliphatic poly(ester amide) poly(ethylene brassylate-co-1,8-octamethylene brassylamide) (PEBOA-1) by cascade polycondensation-coupling ring-opening polymerization of 1,8-octanediamine and ethylene brassylate under nitrogen condition.

[0047] 1,8-Octanediamine (0.50 g) and ethylene brassylate (9.50 g) were added into a 100 ml three-necked flask with nitrogen inlet. The flask was heated to 220° C. with mechanical stirring, and n-butyl titanate (20.0 μL) was added. The cascade polycondensation-coupling ring-opening polymerization was carried out under nitrogen for 60 minutes to generate the corresponding polymer PEBOA-1. The size exclusion chromatography curve for PEBOA-1 is shown in FIG. 3, and the measured number-average molecular weight is 8.30 kg/mol, which proves the successful synthesis of the target product.

EXAMPLE 3

[0048] Aliphatic poly(ester amide) poly(ethylene brassylate-co-1,8-octamethylene brassylamide) (PEBOA-2) by cascade polycondensation-coupling ring-opening polymerization of 1,8-octanediamine and ethylene brassylate under vacuum conditions.

[0049] 1,8-Octanediamine (7.50 g), ethylene brassylate (22.5 g) and n-butyl titanate (60.0 μl) were added into a 250 ml single-necked flask. The mixture was heated to 240° C. under mechanical stirring, and polymerized under vacuum for 60 minutes to finally generate the corresponding polymer PEBOA-2.

[0050] The thermogravimetric curve of PEBOA-2 is shown in FIG. 4. The 5% weight loss thermal decomposition temperature of the polymer is 382° C., indicating that the aliphatic poly(ester amide) has good thermal stability.

[0051] The stress-strain curve of PEBOA-2 is shown in FIG. 5. The Young's modulus of the polymer is 145 MPa, with the strength of 26.8 MPa, and the elongation at break of 101%, indicating that the polymer has good mechanical properties.

EXAMPLE 4

[0052] Aliphatic poly(ester amide) (PEBOA-3) by cascade polycondensation-coupling ring-opening polymerization of 1,8-octanediamine and ethylene brassylate under vacuum conditions.

[0053] 1,8-Octanediamine (3.00 g), ethylene brassylate (27.0 g) and n-butyl titanate (60.0 μl) were added into a 250 ml single-necked flask. The mixture was heated to 240° C. under mechanical stirring, and polymerized under vacuum for 60 minutes to finally generate the corresponding polymer PEBOA-3.

[0054] The differential scanning calorimetry curve of PEBOA-3 is shown in FIG. 6. It shows that the polymer has two melting points. The one around 36° C. is assigned to the melting point of PEB part of the poly(ester amide), and the other around 137° C. to poly(octamethylene brassylamide) (nylon 6,13) polyamide part, indicating that the polymer of the present invention has a higher melting point and proving the successful synthesis of the target product.

EXAMPLE 5

[0055] Aliphatic poly(ester amide) (PEBOA-4) by cascade polycondensation-coupling ring-opening polymerization of 1,8-octanediamine and ethylene brassylate under vacuum conditions.

[0056] 1,8-Octanediamine (9.00 g), ethylene brassylate (21.0 g) and n-butyl titanate (60.0 μl) were added into a 250 ml single-necked flask. The mixture was heated to 240° C. under mechanical stirring, and polymerized under vacuum for 60 minutes to finally generate the corresponding polymer PEBOA-4.

[0057] The viscosity of the PEBOA-4 measured is 0.77 dL/g in the mixture solvent (phenol and tetrachloroethane with a mass ratio of 3:2) at 25° C.

EXAMPLE 6

[0058] Semi-aromatic poly(ester amide) poly(butylene terephthalate-co-1,8-octamethylene terephthalamide) (PBTOA) by cascade polycondensation-coupling ring-opening polymerization of 1,8-octanediamine and cyclic oligo(butylene terephthalate)s (COBTs) under vacuum conditions.

[0059] 1,8-Octanediamine (4.00 g), COBTs (36.0 g) and n-butyl titanate (80.0 μl) were added into a 250 ml single-necked flask. The flask was heated to 270° C. with mechanical stirring. The polymerization was carried under vacuum for 60 minutes to finally generate the corresponding polymer PBTOA.

[0060] The viscosity of the PBTOA measured is 0.94 dL/g in the mixture solvent (phenol and tetrachloroethane with a mass ratio of 3:2) at 25° C., which proved the successful synthesis of the target product.

EXAMPLE 7

[0061] Aliphatic poly(ester amide) poly(ethylene brassylate-co-1,10-decamethylene brassylamide) (PEBDA) by cascade polycondensation-coupling ring-opening polymerization of 1,10-decanediamine and ethylene brassylate under vacuum conditions.

[0062] 1,10-Decanediamine (1.00 g), ethylene brassylate (9.00 g) and n-butyl titanate (20.0 μl) were added into a 250 ml single-necked flask. The mixture was heated to 240° C. under mechanical stirring, and polymerized under vacuum for 60 minutes to finally generate the corresponding polymer PEBDA. The size exclusion chromatography curve for PEBDA is shown in FIG. 7, and the measured number-average molecular weight is 39.2 kg/mol, which proved the successful synthesis of the target product.

EXAMPLE 8

[0063] Aliphatic poly(ester amide) poly(ethylene brassylate-co-1,12-dodecamethylene brassylamide) (PEBDDA) by cascade polycondensation-coupling ring-opening polymerization of 1,12-diaminododecane and ethylene brassylate under vacuum conditions.

[0064] 1,12-Diaminododecane (1.00 g), ethylene brassylate (9.00 g) and n-butyl titanate (20.0 μl) were added into a 250 ml single-necked flask. The flask was heated to 240° C. with mechanical stirring, and polymerized under vacuum for 60 minutes to finally generate the corresponding polymer PEBDDA. The size exclusion chromatography curve for PEBDDA is shown in FIG. 8, and the measured number-average molecular weight is 25.9 kg/mol, which proved the successful synthesis of the target product.

EXAMPLE 9

[0065] Aliphatic poly(ester amide) poly(ethylene adipate-co-1,6-hexamethylene adipamide) (PEAHA) by cascade polycondensation-coupling ring-opening polymerization of 1,6-hexanediamine and cyclic oligo(ethylene adipate).

[0066] 1,6-Hexanediamine (0.10 g) and cyclic oligomer(ethylene adipate)s (1.90 g) were added into a 100 ml three-necked flask with nitrogen inlet. The flask was heated to 220° C. with mechanical stirring, and n-butyl titanate (4.0 μL) was added. The polymerization was carried out under nitrogen for 150 minutes to generate the corresponding polymer PEAHA. The size exclusion chromatography curve for PEAHA is shown in FIG. 9, and the measured number-average molecular weight is 12.1 kg/mol, which proved the successful synthesis of the target product.

EXAMPLE 10

[0067] Aliphatic poly(ester amide) poly(ethylene brassylate-co-1,3-cyclohexanebismethylene brassylamide) (PEBCHA) by cascade polycondensation-coupling ring-opening polymerization of 1,3- cyclohexanebis(methylamine) and ethylene brassylate under nitrogen condition.

[0068] 1,3-Cyclohexanebis(methylamine) (0.50 g) and ethylene brassylate (9.50 g) were added into a 100 ml three-necked flask with nitrogen inlet. The flask was heated to 220° C. with mechanical stirring, and n-butyl titanate (20.0 μL) was added. The polymerization was carried out under nitrogen for 60 minutes to generate the corresponding polymer PEBCHA. The size exclusion chromatography curve for PEBCHA is shown in FIG. 10, and the measured number-average molecular weight is 9.53 kg/mol, which proved the successful synthesis of the target product.

EXAMPLE 11

[0069] Semi-aromatic poly(ester amide) poly(ethylene brassylate-co-1,4-xylylene brassylamide) (PEBXA) by cascade polycondensation-coupling ring-opening polymerization of 1,4-xylylenediamine and ethylene brassylate under nitrogen condition.

[0070] 1,4-xylylenediamine (0.50 g) and ethylene brassylate (9.50 g) were added into a 100 ml three-necked flask with nitrogen inlet. The flask was heated to 220° C. with mechanical stirring, and n-butyl titanate (20.0 μL) was added. The polymerization was carried out under nitrogen for 60 minutes to generate the corresponding polymer PEBXA. The size exclusion chromatography curve for PEBXA is shown in FIG. 11, and the measured number-average molecular weight is 6.03 kg/mol, which proved the successful synthesis of the target product.

EXAMPLE 12

[0071] Aliphatic poly(ester amide) (PEBAHA) by cascade polycondensation-coupling ring-opening polymerization of 6-amino-1-hexanol and ethylene brassylate under nitrogen condition.

[0072] 6-Amino-1-hexanol (0.50 g) and ethylene brassylate (9.50 g) were added into a 100 mL three-necked flask with nitrogen inlet. The flask was heated to 220° C. with mechanical stirring, and n-butyl titanate (20.0 μL) was added. The polymerization was carried out under nitrogen for 60 minutes to generate the corresponding polymer PEBAHA. The size exclusion chromatography curve for PEBAHA is shown in FIG. 12, and the measured number-average molecular weight is 13.7 kg/mol, which proved the successful synthesis of the target product.

[0073] As shown in FIG. 13, the poly(ester amide) obtained by the present invention (Example 4, PEBOA-4) is insoluble in common organic solvents such as tetrahydrofuran, toluene, chloroform, etc., while the corresponding aliphatic polyester PEB is soluble in these solvents (1 mg/mL), indicating that poly(ester amide)s have good solvent resistance.

EXAMPLE 13

[0074] Aliphatic poly(ester amide) (PEBDA-2) by cascade polycondensation-coupling ring-opening polymerization of 1,10-decanediamine and ethylene brassylate under vacuum conditions.

[0075] 1,10-decanediamine (1.50 g), ethylene brassylate (28.5 g) and n-butyl titanate (60.0 μl) were added into a 250 ml single-necked flask. The mixture was heated to 240° C. under mechanical stirring, and polymerized under vacuum for 60 minutes to finally generate the corresponding polymer PEBDA-2. The size exclusion chromatography curve for PEBDA-2 is shown in FIG. 14, and the measured number-average molecular weight is 30.0 kg/mol, which proved the successful synthesis of the target product.

EXAMPLE 14

[0076] Degradation test of PEBDA-2 at 37° C. in phosphate buffered saline solution.

[0077] The pH of the phosphate buffered saline solution is from7.2 to 7.4, the ingredients include 80.0 g/L of sodium chloride, 2.00 g/L of potassium chloride, 36.3 g/L of disodium hydrogen phosphate dodecahydrate, 2.40 g/L g/L of potassium dihydrogen phosphate; Phosphate buffered salt solution is divided into lipase-free group and lipase-containing group (lipase name: Pseudomonas cepacia lipase, enzyme activity: 30.0×10.sup.3 units per gram, optimal pH value: 7.0).

[0078] Immersed the sample of PEBDA-2(prepared in Example 13, the initial molecular weight of the sample is 30.0 kg/mol) with 10.0 mg of the mass and the disc shape (the diameter is about 5.00 mm) into the 1.00 mg of phosphate buffered salt solution containing lipase (concentration: 1.00 mg/ml), The sample was placed at 37° C. for degradation test. Another set of control experiments were set up in lipase-free group phosphate buffered saline solution and other conditions were unchanged. When it reached the predetermined number of days, took out the sample, rinsed with distilled water, filtered, and dried, measured with an electronic balance and tested molecular weight with gel permeation chromatography. The degradation curves which the mass at 37° C. of PEBDA-2 in lipase-free and lipase-containing phosphate buffered saline solutions over time is shown in FIG. 15. It can be seen from the figure that the (PEBDA-2) at 37° C. in lipase-free phosphate buffered saline solution, the mass was no reduction. However, the mass become lower and lower in lipase-containing phosphate buffered saline solution, and the surplus mass after degradation for 5 days is about 91.4% (degraded mass/initial mass×100%). The degradation curves which the molecular weight at 37° C. of PEBDA-2 in lipase-free and lipase-containing phosphate buffered saline solutions over time is shown in FIG. 16. The degradation rate was very slow in lipase-free and lipase-containing phosphate buffered saline solution, and the molecular weight decreases slightly. The speed of degradation was faster in lipase-containing phosphate buffered saline solution, the molecular weight was from 30.0 kg/mol to 24.3 kg/mol within 5 days. It shows that the aliphatic copolyester (PEB-b-PEO-b-PPO-b-PEO-b-PEB).sub.n has good degradability.

[0079] The foregoing descriptions are only preferred embodiments of the invention and are not intended to limit the invention. For those skilled in the art, the invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.