Composite Material Comprising Polybutylene Succinate And Poly(Butylene Succinate-Co-Adipate), And Compostable Article Containing Said Composite Material

Abstract

What are described are a polymer mixture or polymer blend comprising polybutylene succinate and polybutylene succinate-co-adipate, a composite material or compound comprising polybutylene succinate and polybutylene succinate-co-adipate and/or said polymer mixture or polymer blend and one or more filler constituents, an article and/or single-use article comprising or consisting of said composite material or compound, and processes for producing the aforementioned composite material or compound or the aforementioned article or single-use article. Also described are the use of the polymer mixture or polymer blend for production of said composite material or compound, and the use of the composite material or compound for production of an article or single-use article that is compostable in particular.

Claims

1. A polymer mixture or polymer blend comprising polybutylene succinate and polybutylene succinate-co-adipate.

2. The polymer mixture or polymer blend as claimed in claim 1, wherein the mass ratio of the polybutylene succinate present in the polymer mixture or polymer blend to the polybutylene succinate-co-adipate present in the polymer mixture or polymer blend is in the range from 10:90 to 90:10, preferably from 20:80 to 80:20, more preferably from 30:70 to 70:30, especially preferably from 40:60 to 60:40 and most preferably from 45:55 to 55:45.

3. The polymer mixture or polymer blend of claim 1, wherein the polybutylene succinate comprises structural constituents of the formula I ##STR00003## and/or the polybutylene succinate-co-adipate comprises structural constituents of the formula II ##STR00004##

4. The polymer mixture or polymer blend of claim 1, wherein the polybutylene succinate present in the polymer mixture or polymer blend and/or the polybutylene succinate-co-adipate present in the polymer mixture or polymer blend each independently have a weight-average molar mass M.sub.w in the range from 50 000 to 150 000, preferably in the range from 75 000 to 140 000, and/or a melt flow rate MFR in the range from 0.5 to 50 g/10 min, preferably from 1 to 40 g/10 min, determined to DIN EN ISO 1133-1:2011, Method A.

5. A composite material or compound comprising as polymer constituent polybutylene succinate and polybutylene succinate-co-adipate, and/or the polymer mixture or polymer blend of claim 1, preferably in a total amount in the range from 30% to 75% by mass, more preferably from 35% to 70% by mass, based on the total mass of the composite material or compound, and one or more organic and/or inorganic filler constituents, preferably in a total amount in the range from 5% to 70% by mass, more preferably from 10% to 55% by mass, based on the total mass of the composite material or compound.

6. The composite material or compound as claimed in claim 5, wherein the one filler constituent or at least one of the multiple filler constituents comprises at least one, preferably particulate and/or fibrous, cellulose-containing material and/or comprises at least one particulate inorganic material selected from the group consisting of calcium carbonate, clay minerals and silicates.

7. The composite material or compound of claim 5, comprising C1) as polymer constituent polybutylene succinate and polybutylene succinate-co-adipate, and/or the polymer mixture or polymer blend- of claim 1, preferably in a total amount in the range from 30% to 75% by mass, more preferably from 35% to 70% by mass, based on the total mass of the composite material or compound, and C2) as first filler constituent at least one, preferably particulate and/or fibrous, cellulose-containing material, preferably in a total amount in the range from 3% to 50% by mass, preferably from 3.5% to 47.5% by mass, more preferably from 5% to 45% by mass, based on the total mass of the composite material or compound.

8. The composite material or compound of claim 6, wherein the preferably particulate and/or fibrous cellulose-containing material comprises one or more natural fibers and/or one or more regenerated cellulose fibers and/or is selected from the group consisting of cellulose, wood, flax, hemp, sunflower seed shells, bamboo, jute, kenaf, ramie, coconut fibers, fibers from stems of the gorse plant, fibers from stems of the hop plant, fibers from leaves and infructescences of bulrushes, and mixtures thereof, wherein the preferably particulate and/or fibrous cellulose-containing material is selected from the group consisting of wood, flax, hemp, sunflower seed shells, and mixtures thereof.

9. The composite material or compound of claim 5, comprising or additionally comprising C3) as second filler constituent at least one particulate inorganic material selected from the group consisting of calcium carbonate, clay minerals and silicates, preferably in a total amount in the range from 3% to 30% by mass, preferably from 5% to 25% by mass, more preferably from 7.5% to 20% by mass, based on the total mass of the composite material, and preferably C4) further additives and/or auxiliaries, preferably selected from the group consisting of adhesion promoters, waxes, lubricants, antioxidants and light stabilizers, preferably in a total amount in the range from 0.1% to 10% by mass, preferably from 0.2% to 5% by mass, based on the total mass of the composite material.

10. The composite material or compound of claim 6, wherein the at least one particulate inorganic material and/or the second filler constituent C3) comprise(s) at least one particulate inorganic material, selected from the group consisting of calcium carbonate, talcum, talc, kaolin, iron mica, wollastonite mica, muscovite mica, phlogopite mica and mixtures thereof, and preferably selected from the group consisting of talc, kaolin, iron mica, wollastonite mica, muscovite mica, phlogopite mica and mixtures thereof, and/or the particles of which have an average aspect ratio of ≥5:1, preferably of ≥7:1 and more preferably of ≥10:1.

11. An article and/or single-use article, preferably compostable, comprising or consisting the a polymer mixture or polymer blend of claim 1 and/or comprising or consisting of the composite material or compound of claim 5.

12. The use of the polymer mixture or polymer blend of claim 1 and/or of the composite material or compound of claim 5 for or in the production of a preferably compostable article and/or single-use article.

13. The use of the polymer mixture or polymer blend of claim 1 for or in the production of a composite material or compound.

14. A process for producing the composite material or compound of claim 5, comprising the steps of V1) producing or providing the polymer mixture or polymer blend of claim 1 comprising polybutylene succinate and polybutylene succinate-co-adipate, and/or polybutylene succinate and/or polybutylene succinate-co-adipate, V2) producing or providing at least one, preferably particulate and/or fibrous, cellulose-containing material as first filler constituent, preferably as defined in claim 6, V3) preferably producing or providing at least one particulate inorganic material as second filler constituent, preferably as defined in claim 6, V4) combining the polymer mixture or polymer blend from step V1) and/or the polybutylene succinate and/or polybutylene succinate-co-adipate from step V1), with the at least one, preferably particulate and/or fibrous, cellulose-containing material from step V2) and preferably additionally with the at least one particulate inorganic material from step V3), preferably comprising a step of compounding, more preferably comprising a step of melt extrusion, so as to result in the or a composite material or the or a compound.

15. A process for producing an article and/or single-use article, comprising the steps of V5) producing or providing a composite material or compound comprising, as polymer constituent, polybutylene succinate and polybutylene succinate-co-adipate and/or the polymer mixture or polymer blend as of claim 1, and one or more organic and/or inorganic filler constituents, where the producing or providing of a composite material or compound is preferably executed by providing the composite material or compound of claim 5 and/or producing a composite material or compound by the process of claim 14; and V6) forming the composite material or compound, preferably comprising at least one step selected from the group consisting of extrusion, preferably comprising film extrusion, blown film extrusion, extrusion blow molding and foam extrusion; injection molding, deep drawing and/or thermoforming.

16. A single-use article, preferably coffee capsule, comprising or consisting of a composite material or compound comprising C1) as polymer constituent polybutylene succinate and polybutylene succinate-co-adipate, and/or a polymer mixture or polymer blend comprising polybutylene succinate and polybutylene succinate-co-adipate, where the mass ratio of the polybutylene succinate present in the polymer constituent to the polybutylene succinate-co-adipate present in the polymer constituent is in the range from 10:90 to 90:10, in a total amount in the range from 30% to 75% by mass, based on the total mass of the composite material or compound, C2) as first filler constituent at least one particulate and/or fibrous cellulose-containing material, in a total amount in the range from 3% to 50% by mass, based on the total mass of the composite material or compound, and C3) as second filler constituent at least one particulate inorganic material selected from the group consisting of calcium carbonate, clay minerals and silicates, in a total amount in the range from 12.5% to 25% by mass, based on the total mass of the composite material or compound.

Description

FIGURE

[0163] FIG. 1: FIG. 1 shows a graph of the experimental results of the comparison of the composting speeds of inventive and noninventive articles and of cellulose (cf. example 9, table 1).

EXAMPLES

Example 1: Production of a Polymer Mixture of the Invention or of a Polymer Blend

[0164] 5.41 kg of polybutylene succinate of the BioPS™ FZ 71 PM type (from PTT MCC Biochem Co. Ltd, MFR=22 g/10 min) is mixed with 5.41 kg of polybutylene succinate-co-adipate of the BioPS™ FD 92 PM type (from PTT MCC Biochem Co. Ltd, MFR=4 g/10 min) and compounded together in a twin-screw extruder at a temperature in the region of 140° C. in the intake and melting zone and of 180° C. downstream (although the melt temperature at the pelletizing die may be higher), so as to give a polymer mixture of the invention or a polymer blend of the invention.

Example 2: Production of a Composite Material or Compound of the Invention from a Polymer Mixture or Polymer Blend of the Invention

[0165] A polymer mixture or polymer blend of the invention produced as described above (see example 1) is mixed with 6 kg of ground sunflower seed shells, 3 kg of pulverulent kaolin and 180 g of adhesion promoter based on maleic anhydride, and the commixed constituents are compounded/mixed in a twin-screw extruder at a temperature in the region of 140° C. in the intake and melting zone and 180° C. downstream (although the melt temperature at the pelletizing die may be higher), so as to give a composite material of the invention or a compound of the invention (referred to hereinafter as “VM-E1”).

Example 3: Production of a Composite Material or Compound of the Invention by Separate Addition of Polybutylene Succinate and Polybutylene Succinate-Co-Adipate (1)

[0166] 5.41 kg of polybutylene succinate of the BioPS™ FZ 71 PM type (see example 1 for details) is mixed with 5.41 kg of polybutylene succinate-co-adipate of the BioPS™ FD 92 PM type (see example 1 for details), 6 kg of ground sunflower seed shells, 3 kg of pulverulent kaolin and 180 g of adhesion promoter based on maleic anhydride, and the commixed constituents are compounded/mixed in a twin-screw extruder at a temperature in the region of 140° C. in the intake and melting zone and 180° C. downstream (although the melt temperature at the pelletizing die may be higher), so as to give a composite material of the invention or a compound of the invention (referred to hereinafter as “VM-E2”).

Example 4: Production of a Composite Material or Compound of the Invention by Separate Addition of Polybutylene Succinate and Polybutylene Succinate-Co-Adipate (2)

[0167] 3.25 kg of polybutylene succinate of the BioPS™ FZ 71 PM type (see example 1 for details) is mixed with 7.57 kg of polybutylene succinate-co-adipate of the BioPS™ FD 72 PM type (from PTT MCC Biochem Co. Ltd, MFR=22 g/10 min), 6 kg of ground sunflower seed shells, 3 kg of pulverulent kaolin and 180 g of adhesion promoter based on maleic anhydride, and the commixed constituents are compounded in a twin-screw extruder at a temperature in the region of 140° C. in the intake and melting zone and 180° C. downstream (although the melt temperature at the pelletizing die may be higher), so as to give a composite material of the invention or a compound of the invention (referred to hereinafter as “VM-E3”).

Example 5: Production of a Noninventive Comparative Composite Material or Comparative Compound

[0168] 10.82 kg of polybutylene succinate of the BioPS™ FZ 71 PM type (see example 1 for details) is mixed with 6 kg of ground sunflower seed shells, 3 kg of pulverulent kaolin and 180 g of adhesion promoter based on maleic anhydride, and the commixed constituents are compounded in a twin-screw extruder at a temperature in the region of 140° C. in the intake and melting zone and 180° C. downstream (although the melt temperature at the pelletizing die may be higher), so as to give a noninventive comparative composite material or comparative compound (referred to hereinafter as “VM-V1”).

Example 6: Production of an Inventive Article (1)

[0169] 2 kg of an inventive composite material or compound (VM-E2) produced according to the above example 3 is formed by injection molding at a temperature of 185 to 195° C. to give single-use plant pots (diameter: 12 cm, height: 12 cm, mass: 42 g, each per individual article/plant pot). What are obtained are single-use plant pots as articles or single-use articles of the invention (referred to hereinafter as “A-E1”).

Example 7: Production of an Inventive Article (2)

[0170] 2 kg of an inventive composite material or compound (VM-E3) produced according to the above example 4 is formed by injection molding at a temperature of 185 to 195° C. to give single-use plant pots (diameter: 12 cm, height: 12 cm, mass: 42 g, each per individual article/plant pot). What are obtained are single-use plant pots as articles or single-use articles of the invention.

Example 8: Production of a Noninventive Comparative Article

[0171] 2 kg of a noninventive composite material or compound produced according to the above example 5 is formed by injection molding at a temperature of 185 to 195° C. to give single-use plant pots (diameter: 12 cm, height: 12 cm, mass: 42 g, each per individual article/plant pot). What are obtained are single-use plant pots as noninventive comparative article or comparative single-use article (referred to hereinafter as “A-V1”).

Example 9: Comparison of Composting Speeds of Inventive and Noninventive Articles and of Cellulose

[0172] An inventive single-use plant pot (A-E1, original mass: 42 g) produced according to the above example 6, a noninventive comparative single-use plant pot (A-V1, original mass: 42 g) produced according to the above example 8, and cellulose (“Z”, comparison, powder as used for thin-layer chromatography) were finely ground and added at 28° C. to a simulated garden compost. The composting speeds were ascertained in accordance with DIN EN ISO 14855-1:2013-04, by means of analysis of the carbon dioxide (CO.sub.2) released in the course of composting.

[0173] For this purpose, over an observation period, the amount of carbon dioxide released in the course of composting was determined in each case relative to the amount of carbon dioxide released in the breakdown of cellulose, and these were used to ascertain the relative degradation speed of the samples (A-E1 and A-V1) versus the degradation speed of cellulose (reference).

[0174] The values ascertained as specified above for the progression of composting of articles A-E1 and A-V1 and of cellulose were each reported as “% of the theoretically possible total amount of carbon dioxide”, and reported as composting speeds in table 1 below against the number of days past in the respective measurements since the start of the experiment. A graph of the results is shown in FIG. 1.

[0175] Sampling for the noninventive comparative article A-V1 was stopped after 110 days since distinct stagnation in the formation of carbon dioxide resulting from biodegradation was observed.

[0176] After 117 days from the start of the experiment, fresh simulated garden compost was added to the experiments of article A-E1 and the cellulose reference in order to compensate for the declining microbial activity.

TABLE-US-00001 TABLE 1 Determination of composting speeds Days since Z A-V1 A-E1 start of [% CO.sub.2 [% CO.sub.2 [% CO.sub.2 experiment formation] formation] formation] 0 ./. ./. ./. 5 23.8 1.5 1.9 10 35.3 2.6 4.4 20 57.9 5.5 13.8 30 75.8 8.1 22.9 40 84.0 10.5 30.5 53 88.1 12.7 36.9 90 91 16.4 50.9 105 92.1 16.7 54.5 120 93.7 No data found 58.1 159 94.9 No data found 69.8 202 96.0 No data found 78.4 245 96.9 No data found 83.0 299 97.7 No data found 86.1 330 97.8 No data found 87.7

[0177] It is apparent from the data in table 1 above that CO.sub.2 formation as a result of biodegradation takes place much more slowly for the noninventive comparative article A-V1 than in the case of the inventive article A-E1 or in the case of cellulose. Even after 80 days from the start of the experiment, distinctly slowed biodegradation is observed for the noninventive comparative article A-V1. At the time of stopping of the experiment after 110 days (see also above), only about 16% by mass of the organic constituents (comprising the polybutylene succinate and the sunflower seed shells) of the noninventive comparative article A-V1 had indeed been biodegraded.

[0178] It is also apparent from the data in table 1 above that the loss of mass as a result of biodegradation does take place more slowly for the inventive article A-E1 than in the case of cellulose, but that, at the end of the experiment (after 365 days), the loss of mass as a result of biodegradation for the inventive article A-E1 was about 90% by mass of the organic constituents (comprising polybutylene succinate, polybutylene succinate-co-adipate and sunflower seed shells) of the inventive article A-E1 and hence reached >90% of the corresponding value for cellulose.

[0179] It can be concluded from this result that the increase in the composting speed and the increase in the proportion of composted mass for the inventive article A-E1 compared to the noninventive comparative article A-V1 is attributable to the additional content of polybutylene succinate-co-adipate in the inventive article A-E1, and that the extent of this increase in the composting speed and the extent of this increase in the proportion of composted mass was higher than would have been expected for a purely additive effect of the additional content of polybutylene succinate-co-adipate in the inventive article A-E1 (in addition to the polybutylene succinate used in the noninventive comparative article A-V1).