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; and based on the total weight of the biodegradable polyester composition, a weight content of tetrahydrofuran is 3 ppm-200 ppm is provided. The cyclic ester compound and tetrahydrofuran is added into the composition and controlling the content of the cyclic ester compound and the content of tetrahydrofuran in a certain range in the composition 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 is prepared by injection molding after being digested with 95% ethanol at 40 C. for 240 hours. ##STR00001##

Claims

1. A biodegradable polyester composition, comprising 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; 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## and based on the total weight of the biodegradable polyester composition, a weight content of tetrahydrofuran is 3 ppm-200 ppm.

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 is 160 ppm-750 ppm, and the weight content of tetrahydrofuran is 8 ppm-100 ppm.

3. The biodegradable polyester composition according to claim 1, wherein 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 claim 1, wherein the biodegradable aliphatic-aromatic polyester is poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST), poly(butylenesebacate-co-terephthalate) (PBSeT), or any combinations thereof.

5. 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.

6. The biodegradable polyester composition according to claim 1, further comprising 0 to 4 parts of plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer, other plastic additives, or any combinations thereof.

7. The biodegradable polyester composition according to claim 1, wherein a L value of the biodegradable polyester composition is less than 0.80 after being digested with 95% ethanol at 40 C. for 240 hours.

8. The biodegradable polyester composition according to claim 1, wherein a level of printing performance of the biodegradable polyester composition reaches to level 3 or above.

9. The biodegradable polyester composition according to claim 2, wherein 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.

10. The biodegradable polyester composition according to claim 2, wherein the biodegradable aliphatic-aromatic polyester is poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST), poly(butylenesebacate-co-terephthalate) (PBSeT), or any combinations thereof.

11. The biodegradable polyester composition according to claim 3, wherein the biodegradable aliphatic-aromatic polyester is poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST), poly(butylenesebacate-co-terephthalate) (PBSeT), or any combinations thereof.

12. The biodegradable polyester composition according to claim 9, wherein the biodegradable aliphatic-aromatic polyester is poly(butyleneadipate-co-terephthalate) (PBAT), poly(butylenesuccinate-co-terephthalate) (PBST), poly(butylenesebacate-co-terephthalate) (PBSeT), or any combinations thereof.

13. 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.

14. 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.

15. The biodegradable polyester composition according to claim 9, 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.

16. The biodegradable polyester composition according to claim 2, further comprising 0 to 4 parts of plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer, other plastic additives, or any combinations thereof.

17. The biodegradable polyester composition according to claim 3, further comprising 0 to 4 parts of plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer, other plastic additives, or any combinations thereof.

18. The biodegradable polyester composition according to claim 9, further comprising 0 to 4 parts of plasticizer, release agent, surfactant, wax, antistatic agent, pigment, UV absorbent, UV stabilizer, other plastic additives, or any combinations thereof.

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

20. The biodegradable polyester composition according to claim 2, wherein a level of printing performance of the biodegradable polyester composition reaches to level 3 or above.

21. The biodegradable polyester composition according to claim 2, wherein based on the total weight of the biodegradable polyester composition, the weight content of the cyclic ester compound is 210-540 ppm, and the weight content of tetrahydrofuran is 15-75 ppm.

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 filler; citric esters 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, cyclic ester compound and tetrahydrofuran are commercially available.

(3) Embodiments 1-16 and Comparative Embodiments 1-2:

(4) According to formulae shown in Table 1, PBAT, PLA, ADR4370, organic fillers, inorganic fillers, promoters such as plasticizer, surfactant, wax and the like, a cyclic ester compound and tetrahydrofuran 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.

(5) Performance evaluation method:

(6) (1) Evaluation method for an anti-thermal oxidative aging property of a biodegradable polyester composition:

(7) 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.

(8) (2) Evaluation method for a surface appearance property of a molding product:

(9) 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 treated and after treated, 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.

(10) (3) Evaluation method for printing performance of the biodegradable polyester composition:

(11) Biodegradable polyester compositions with different printing effects were taken. Based on clarity of a printed label and adherence of ink to a surface of a film, different printing effects were ranked according to following method:

(12) level 1: the label is clear and there is no excessive ink adhering to the film;

(13) level 2: the label is clear but there is a little excessive ink adhering to the film;

(14) level 3: the label is basically clear but there is much ink adhering to the film;

(15) level 4: the label is obscure and there is abundant ink adhering to the film;

(16) level 5: the label can't be shown and there is no ink adhering to the film.

(17) (4) Determination method for the cyclic ester compound: 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 25 ml. 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 of the cyclic ester compound was calibrated by a solution of the cyclic ester compound/chloroform.

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

(19) Agilent Technologies 7693 AutoSampler;

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

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

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

(23) Sample production: vacuum.

(24) (5) Determination method for tetrahydrofuran:

(25) Drawing of a standard curve of tetrahydrofuran:

(26) Tetrahydrofuran/methanol solutions in concentrations of 0.010 g/L, 0.1 g/L, 1.0 g/L, 5.0 g/L, 10.0 g/L, 20.0 g/L, 50.0 g/L and 100.0 g/L were prepared, respectively. Peak areas of tetrahydrofuran in the tetrahydrofuran/methanol solutions in different concentrations were measured respectively by a static headspace method. The standard curve of tetrahydrofuran was drawn, with the peak area of tetrahydrofuran as an ordinate and the concentration of tetrahydrofuran as an abscissa.

(27) Measurement of a content of tetrahydrofuran in the biodegradable polyester composition:

(28) Approximate 1.2000 g of biodegradable polyester composition was weighed accurately and put into a static headspace test flask; the peak area of tetrahydrofuran in the biodegradable polyester composition was measured by the static headspace method; and the content of tetrahydrofuran in the biodegradable polyester composition was calculated according to the peak area of tetrahydrofuran in the biodegradable polyester composition and the standard curve of tetrahydrofuran. The standard curve was calibrated by the tetrahydrofuran/methanol solution.

(29) Conditions for static headspace test are as follows:

(30) Temperature:

(31) Heater: 105 C.

(32) Quantitative loop: 135 C.

(33) Transmission line: 165 C.

(34) Time:

(35) Balance for sample bottle: 120 minutes

(36) Duration for sample injection: 0.09 minute

(37) GC circulation: 30 minutes.

(38) Instrument models and parameters for static headspace are as follows:

(39) Agilent Technologies 7697 Headspace Sampler;

(40) Agilent Technologies 7890AGC System;

(41) Chromatographic column: J&W 122-7032: 250 C.: 30 m250 m0.25 m

(42) Sample injection: front SS injection port N.sub.2

(43) Sample production: front detector FID.

(44) TABLE-US-00001 TABLE 1 Test data of Comparative Embodiments 1-2 and Embodiments 1-16 (parts by weight) Comparative Embod- Embod- Embod- Embod- Embod- Embod- Comparative Embodiment iment iment iment iment iment iment Embodiment Embodiment Embodiment 1 2 1 2 3 4 5 6 7 8 PBAT 84.1 84.1 100 84.1 84.1 84.1 84.1 84.1 67 66.5 PLA 10 10 10 10 10 10 10 15 32 starch 17 talcum powder 1.6 1.6 1.6 1.6 1.6 1.6 1.6 calcium 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 0.5 citric esters 0.2 palmitate 0.5 stearamide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 content of the 54 1152 100 215 282 316 408 437 495 540 cyclic ester compound (based on the whole composition)/ ppm content of 1 227 200 15 19 21 38 44 60 75 tetrahydrofuran (based on the whole composition)/ppm time for 6 9 12 23 27 28 28 29 29 30 thermal oxidative aging/ day L 0.08 1.06 0.09 0.19 0.22 0.27 0.29 0.34 0.35 0.36 level of printing 4 5 3 1 1 1 1 1 1 1 performance 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 powder 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 calcium carbonate 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 ADR4370 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 citric esters palmitate stearamide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 content of the 160 174 671 750 100 135 839 950 cyclic ester compound (based on the whole composition)/ ppm content of 8 12 81 100 3 5 167 200 tetrahydrofuran (based on the whole composition)/ppm time for thermal 18 20 21 22 13 15 16 16 oxidative aging/ day L 0.40 0.38 0.61 0.65 0.69 0.71 0.75 0.79 level of printing 2 2 2 2 3 3 3 3 performance

(45) It can be seen from Table 1 that, in the biodegradable polyester composition, when the content of the cyclic ester compound is 100-950 ppm and the content of tetrahydrofuran is 3-200 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. Also, the level of printing performance can reach above level 3, which indicates that the composition has excellent printing performance. However, in Comparative Embodiment 1, in which the content of the cyclic ester compound is less than 100 ppm and the content of tetrahydrofuran is less than 3 ppm, L of the composition is relatively low, but the time for thermal oxidative aging of the composition is relatively short and the level of printing performance is level 4. In Comparative Embodiment 2, in which the content of the cyclic ester compound is over 950 ppm and the content of tetrahydrofuran is over 200 ppm, L was more than 1.0, and the level of printing performance is level 5. It indicates that there is more precipitate separating out of the surface, and the surface appearance property and the printing performance of the composition are poor.