Biodegradable polyester composition

Abstract

A biodegradable polyester composition based on a total weight of the biodegradable polyester composition, including a weight content of a cyclic ester compound having a structure shown as formula (I), which is 100 ppm-950 ppm is provided. The cyclic ester compound is added into the composition and controlling the content of the cyclic ester compound in a range of 100 ppm-950 ppm to realize an anti-thermal oxidative aging property of the biodegradable polyester composition. In addition, a film is prepared by blow molding or a part prepared by injection molding after being digested with 95% ethanol at 40 C. for 240 hours. ##STR00001##

Claims

1. A biodegradable polyester composition comprising the following components in parts by weight: i) 60 to 100 parts of biodegradable aliphatic-aromatic polyester; ii) 0 to 40 parts of polylactic acid; iii) 0 to 35 parts of an organic filler and/or an inorganic filler; iv) 0 to 1 part of a copolymer which contains epoxy group and is based on styrene, acrylate and/or methacrylate; and wherein based on a total weight of the biodegradable polyester composition, a weight content of a cyclic ester compound having a structure shown as formula (I) is 100 ppm-950 ppm; ##STR00003##

2. The biodegradable polyester composition according to claim 1, wherein based on the total weight of the biodegradable polyester composition, the weight content of the cyclic ester compound having the structure shown as formula (I) is 160 ppm-750 ppm.

3. The biodegradable polyester composition according to claim 1, comprising the following components in parts by weight: i) 65 to 95 parts of the biodegradable aliphatic-aromatic polyester; ii) 5 to 35 parts of the polylactic acid; iii) 5 to 25 parts of the organic filler and/or the inorganic filler; iv) 0.02 to 0.5 part of the copolymer which contains epoxy group and is based on styrene, acrylate and/or methacrylate.

4. The biodegradable polyester composition according to claim 2, wherein the weight content of the cyclic ester compound is measured by a method as follows: 1.2000 g of the biodegradable polyester composition is weighed accurately, added into a 25 ml volumetric flask, and dissolved by adding chloroform; after the biodegradable polyester composition is dissolved completely, the biodegradable polyester composition is diluted to 25 ml; a peak area of the cyclic ester compound in the prepared solution is measured by a GC-MS test; the content of the cyclic ester compound in the biodegradable polyester composition is calculated according to the peak area of the cyclic ester compound in the prepared solution and a standard curve of the cyclic ester compound; and the standard curve is calibrated by a solution of the cyclic ester compound/chloroform.

5. The biodegradable polyester composition according to claim 1, wherein the biodegradable aliphatic-aromatic polyester is one or more of poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST) and poly(butylenesebacate-co-terephthalate) (PBSeT).

6. The biodegradable polyester composition according to claim 1, wherein the organic filler is selected from a group consisting of natural starch, plasticized starch, modified starch, natural fiber and wood flour, or a mixture thereof; and the inorganic filler is selected from a group consisting of talcum powder, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, ferric oxide; dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber and mineral fiber, or a mixture thereof.

7. The biodegradable polyester composition according to claim 1, further comprising 0 to 4 parts of at least one of following substances: plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer and other plastic additives.

8. The biodegradable polyester composition according to claim 2, wherein the biodegradable polyester composition is sealed in a non-vacuum aluminum foil bag, and a time of thermal oxidative aging for putting the aluminum foil bag in an air dry oven at 70 C. for conducting a thermal oxidative aging test is equal to or more than 10 days.

9. The biodegradable polyester composition according to claim 2, wherein a L value of the biodegradable polyester composition is less than 0.80 after the biodegradable polyester composition is digested with 95% ethanol at 40 C. for 240 hours.

10. The biodegradable polyester composition according to claim 2, comprising the following components in parts by weight: i) 65 to 95 parts of the biodegradable aliphatic-aromatic polyester; ii) 5 to 35 parts of the polylactic acid; iii) 5 to 25 parts of the organic filler and/or the inorganic filler; iv) 0.02 to 0.5 part of the copolymer which contains epoxy group and is based on styrene, acrylate and/or methacrylate.

11. The biodegradable polyester composition according to claim 3, wherein the weight content of the cyclic ester compound is measured by a method as follows: 1.2000 g of the biodegradable polyester composition is weighed accurately, added into a 25 ml volumetric flask, and dissolved by adding chloroform; after the biodegradable polyester composition is dissolved completely, the biodegradable polyester composition is diluted to 25 ml; a peak area of the cyclic ester compound in the prepared solution is measured by a GC-MS test; the content of the cyclic ester compound in the biodegradable polyester composition is calculated according to the peak area of the cyclic ester compound in the prepared solution and a standard curve of the cyclic ester compound; and the standard curve is calibrated by a solution of the cyclic ester compound/chloroform.

12. The biodegradable polyester composition according to claim 10, wherein the weight content of the cyclic ester compound is measured by a method as follows: 1.2000 g of the biodegradable polyester composition is weighed accurately, added into a 25 ml volumetric flask, and dissolved by adding chloroform; after the biodegradable polyester composition is dissolved completely, the biodegradable polyester composition is diluted to 25 ml; a peak area of the cyclic ester compound in the prepared solution is measured by a GC-MS test; the content of the cyclic ester compound in the biodegradable polyester composition is calculated according to the peak area of the cyclic ester compound in the prepared solution and a standard curve of the cyclic ester compound; and the standard curve is calibrated by a solution of the cyclic ester compound/chloroform.

13. The biodegradable polyester composition according to claim 2, wherein the biodegradable aliphatic-aromatic polyester is one or more of poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST) and poly(butylenesebacate-co-terephthalate) (PBSeT).

14. The biodegradable polyester composition according to claim 3, wherein the biodegradable aliphatic-aromatic polyester is one or more of poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST) and poly(butylenesebacate-co-terephthalate) (PBSeT).

15. The biodegradable polyester composition according to claim 10, wherein the biodegradable aliphatic-aromatic polyester is one or more of poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST) and poly(butylenesebacate-co-terephthalate) (PBSeT).

16. The biodegradable polyester composition according to claim 2, wherein the organic filler is selected from a group consisting of natural starch, plasticized starch, modified starch, natural fiber and wood flour, or a mixture thereof; and the inorganic filler is selected from a group consisting of talcum powder, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, ferric oxide, dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber and mineral fiber, or a mixture thereof.

17. The biodegradable polyester composition according to claim 3, wherein the organic filler is selected from a group consisting of natural starch, plasticized starch, modified starch, natural fiber and wood flour, or a mixture thereof; and the inorganic filler is selected from a group consisting of talcum powder, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, ferric oxide, dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber and mineral fiber, or a mixture thereof.

18. The biodegradable polyester composition according to claim 10, wherein the organic filler is selected from a group consisting of natural starch, plasticized starch, modified starch, natural fiber and wood flour, or a mixture thereof; and the inorganic filler is selected from a group consisting of talcum powder, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, ferric oxide, dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber and mineral fiber, or a mixture thereof.

19. The biodegradable polyester composition according to claim 2, further comprising 0 to 4 parts of at least one of following substances: plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer and other plastic additives.

20. The biodegradable polyester composition according to claim 3, further comprising 0 to 4 parts of at least one of following substances: plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer and other plastic additives.

21. The biodegradable polyester composition according to claim 10, further comprising 0 to 4 parts of at least one of following substances: plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer and other plastic additives.

22. The biodegradable polyester composition according to claim 4, wherein the biodegradable polyester composition is sealed in a non-vacuum aluminum foil bag, and a time of thermal oxidative aging for putting the aluminum foil bag in an air dry oven at 70 C. for conducting a thermal oxidative aging test is equal to or more than 10 days.

23. The biodegradable polyester composition according to claim 4, wherein a L value of the biodegradable polyester composition is less than 0.80 after the biodegradable polyester composition is digested with 95% ethanol at 40 C. for 240 hours.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

(1) The present invention will be further described below by way of specific implementations, and the following embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited by the following embodiments.

(2) In the embodiments of the present invention, PBAT is chosen as a component i), ADR4370 is chosen as a component iv), starch is chosen as an organic filler, talcum powder and calcium carbonate are chosen as inorganic fillers, tributyl citrate is chosen as a plasticizer, palmitate is chosen as a surfactant, and stearamide is chosen as a wax. The above-mentioned promoters, PBAT, ADR4370, PLA and cyclic ester compound are commercially available.

Embodiments 1-16 and Comparative Embodiments 1-2

(3) according to formulas shown in Table 1, PBAT, PLA, ADR4370, organic fillers, inorganic fillers, promoters such as plasticizer, surfactant, wax and the like, and a cyclic ester compound were mixed evenly and put into a single screw extruder. After being extruded at 140 C.-240 C. and prilled, the compositions were obtained. Data of performance tests is shown in Table 1.

(4) Performance Evaluation Method:

(5) (1) Evaluation Method for Anti-Thermal Oxidative Aging Property of a Biodegradable Polyester Composition:

(6) the biodegradable polyester composition was sealed in a non-vacuum aluminum foil bag. The aluminum foil bag was put in an air dry oven at 70 C. to perform a thermal oxidative aging test. Samples were taken every 3 days for testing a melting index (190 C./2.16 kg, according to ISO 1133). When the melting index of the sample was beyond a normal melting index range of the biodegradable polyester composition, it indicated that an obvious thermal oxidative aging degradation had occurred in the biodegradable polyester composition. A test time that the obvious thermal oxidative aging degradation occurred in the biodegradable polyester composition was recorded. The shorter the test time was, the poorer the anti-thermal oxidative aging property of the biodegradable polyester composition was indicated.

(7) (2) Evaluation Method for a Surface Appearance Property of a Molding Product:

(8) a 2 mm palette was injection molded and put into a solution of 95% ethanol at 40 C. for being digested for 240 hours, followed by being placed in a standard laboratory with an atmosphere temperature of (232) C. and a relative humidity of 45%-55%. After the palette was adjusted for 48 hours, L, a variation of L-value of the palette before treatment and after treatment, was measured via a colorimeter. The greater the L was, the more the precipitate separated out of the surface and the poorer the surface appearance property was.

(9) (3) Determination Method for the Cyclic Ester Compound:

(10) 1.2000 g of the biodegradable polyester composition was weighed accurately, added into a 25 ml volumetric flask, and dissolved by adding chloroform. After the biodegradable polyester composition was dissolved completely, it was diluted to volume. A peak area of the cyclic ester compound in the prepared solution was measured by a GC-MS test. The content of the cyclic ester compound in the biodegradable polyester composition was calculated according to the peak area of the cyclic ester compound in the prepared solution and a standard curve of the cyclic ester compound. The standard curve was calibrated by a solution of the cyclic ester compound/chloroform.

(11) Models and parameters for GC-MS are as follows:

(12) Agilent Technologies 7693 AutoSampler;

(13) Agilent Technologies 5975C inert MSD with Triple-Axis Detector;

(14) Chromatographic column: J&W 122-5532 UI: 350 C.: 30 m250 m0.25 m

(15) Sample injection: front SS injection port He (helium)

(16) Sample production: vacuum.

(17) TABLE-US-00001 TABLE 1 Test data of Comparative Embodiments 1-2 and Embodiments 1-16 (parts by weight) Comparative Comparative Embodiment 1 Embodiment 2 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 PBAT 84.1 84.1 100 84.1 84.1 84.1 PLA 10 10 10 10 10 starch talcum power 1.6 1.6 1.6 1.6 1.6 calcium 3.5 3.5 3.5 3.5 3.5 carbonate ADR4370 0.3 0.3 0.3 0.3 0.3 tributyl citrate palmitate stearamide 0.5 0.5 0.5 0.5 0.5 content of the 54 1152 100 215 282 316 cyclic ester compound (based on the whole composition)/ ppm time for thermal 6 9 12 23 27 28 oxidative aging/ day L 0.08 1.06 0.09 0.19 0.22 0.27 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 PBAT 84.1 84.1 67 66.5 PLA 10 10 15 32 starch 17 talcum power 1.6 1.6 calcium 3.5 3.5 carbonate ADR4370 0.3 0.3 0.3 0.5 tributyl citrate 0.2 palmitate 0.5 stearamide 0.5 0.5 0.5 0.5 content of the 408 437 495 540 cyclic ester compound (based on the whole composition)/ ppm time for thermal 28 29 29 30 oxidative aging/ day L 0.29 0.34 0.35 0.36 Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 9 10 11 12 13 14 15 16 PBAT 84.1 84.1 84.1 84.1 84.1 84.1 84.1 84.1 PLA 10 10 10 10 10 10 10 10 starch talcum 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 power calcium 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 carbonate ADR4370 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 tributyl citrate palmitate stearamide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 content of 160 174 671 750 100 135 839 950 the cyclic ester compound/ ppm time for 18 20 21 22 13 15 16 16 thermal oxidative aging/day L 0.40 0.38 0.61 0.65 0.69 0.71 0.75 0.79

(18) It can be seen from Table 1 that, when the content of the cyclic ester compound in the biodegradable polyester composition is 100-950 ppm, the biodegradable polyester composition has better anti-thermal oxidative aging property. Besides, after the biodegradable polyester composition is digested with 95% ethanol at 40 C. for 240 hours, L is less than 0.80, which indicates that the composition has excellent surface appearance property. When the content of the cyclic ester compound in Comparative Embodiment 1 is less than 100 ppm, though L of the composition is relatively low, the time for thermal oxidative aging of the composition is relatively short. When the content of the cyclic ester compound in Comparative Embodiment 2 is beyond 950 ppm, L reaches above 1.0, which indicates that there is more precipitate separating out of the surface and the surface appearance property of the composition is poor.