Biological Composite Material

Abstract

A plastics compound includes a biological component, wherein at least (a) at least one biomineral filler and (b) at least one polymer are processed to give a compound. This is done using a renewable biomineral filler having a high proportion of silicon dioxide.

Claims

1. A plastics compound having a biological component, comprising at least (a) at least one biomineral filler and (b) at least one polymer, wherein the proportion of biomineral filler is 15% to 90% by weight and the at least one polymer is a thermoplastic or crosslinkable polymer or thermoset.

2. The composition as claimed in claim 1, wherein the biomineral filler material is obtained from a renewable raw material.

3. The plastics compound as claimed in claim 1, wherein the biomineral filler has a silicon dioxide content of at least 80% by weight.

4. The plastics compound as claimed in claim 1, wherein the biomineral filler comprises ash from rice hulls and/or rice husks.

5. The plastics compound as claimed in claim 1, wherein the at least one polymer is selected from the group consisting of polyolefins, polyolefin copolymers, cycloolefin copolymers, polytetrafluoroethylene (PTFE), ethylene/tetrafluoro-ethylene copolymers (ETFE), polyvinylidene difluoride (PVDF), polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl alcohols, polyvinyl esters, vinyl ester copolymers, polyvinyl alkanals, polyvinyl ketals, polyamides, polyimides, polystyrenes, polycarbonate, polycarbonate copolymers and physical blends of polycarbonates with acrylic-butadiene-styrene copolymers, acrylonitrile-styrene-acrylic ester copolymers, polymethylmethacrylates, polybutyl-acrylates, polybutylmethacrylates, polybutylene terephthalates and polyethylene terephthalates, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), copolymers, transesterification products and physical mixtures (blends) of the aforementioned polyalkylene terephthalates, poly(meth)-acrylates, polyacrylamides, polyacrylonitrile, poly(meth)acrylate/polyvinylidene difluoride blends, polyurethanes, polystyrene, styrene copolymers such as styrene/butadiene copolymers, styrene/acrylonitrile copolymers (SAN), acrylic ester-styrene acrylonitrile (ASA), alpha-methyl-styrene-acrylonitrile copolymer (AMSAN), styrene-butadiene-styrene (SBS), styrene/ethyl methacrylate copolymers, styrene/butadiene/ethyl acrylate copolymers, styrene/acrylonitrile/methacrylate copolymers, acrylonitrile/butadiene/styrene copolymers (ABS) and methacrylate/butadiene/styrene copolymers (MBS), polyethers, polyether ketones, vinyl ester copolymers, polysulfones, polyethylene terephthalate or polybutylene terephthalates, polyether sulfones, polyether imides, polyphenylene oxide, polyphenylene sulfide, polyglycols, polyaryls, silicones, low-density polyethylene (LDPE), high-density polyethylene (HDPE), ionomers, thermoplastic and thermoset polyurethanes and mixtures thereof.

6. The plastics compound as claimed in claim 1, wherein the polymer is polyethylene, polypropylene, or copolymers thereof.

7. The plastics compound as claimed in claim 1, further comprising compatibilizers or couplers.

8. The plastics compound as claimed in claim 7, wherein the couplers are selected from compounds based on maleic anhydride, maleated polyethylenes or maleated polypropylenes, or copolymers of ethylene or propylene and acrylic acid, methacrylic acid or trimellitic acid.

9. The plastics compound as claimed in claim 1, wherein the biomineral filler has a specific density of up to 2.5 g/cm.sup.3.

10. The plastics compound as claimed in claim 1, wherein at least 90% of the particles of the filler have a particle size below 400 m measured by laser diffraction.

11. The plastics compound as claimed in claim 1, further comprising (c) at least one compatibility-promoting additive.

12. The plastics compound as claimed in claim 1, wherein the compound is in the form of pellets.

13. A process for producing a plastics compound having a biological component as claimed in claim 1, wherein at least (a) at least one biomineral filler and (b) at least one polymer are processed to give a compound.

14. The process as claimed in claim 13, wherein the compounding is effected in a mixing apparatus with high shear forces.

15. A shaped body produced using a compound as claimed in claim 1.

16. A masterbatch comprising a compound as claimed in claim 1, having a content of at least 50% by weight of biological filler.

17. The masterbatch as claimed in claim 16, wherein the biomineral filler has a silicon dioxide content of at least 80% by weight.

Description

[0121] Test results for the filler and the shaped bodies produced are shown in the figures.

[0122] FIG. 1 particle size distribution of filler I (ACS 851);

[0123] FIG. 2 particle size distribution of filler II (ACS 901);

[0124] FIG. 3 particle size distribution of filler III (ACS 931);

[0125] FIG. 4 particle size distribution of filler IVa (ACS 952);

[0126] FIG. 5 tensile tests according to DIN EN ISO 527-2 at 1.8 N/mm.sup.2;

[0127] FIG. 6 tensile tests according to DIN EN ISO 527-2 at 8 N/mm.sup.2;

[0128] FIG. 7 tensile tests according to DIN EN ISO 527-2 at 8 N/mm.sup.2;

[0129] FIG. 8 tensile tests according to DIN EN ISO 527-2 at 20 N/mm.sup.2.

EXAMPLES

[0130] Experiments were conducted with pure and mixed samples of rice hull ash with different silicon dioxide contents. The particle size distributions of the individual samples I to V are listed in tables 5 and 6. Particle size distributions of the samples are shown in FIGS. 1 (I), 2 (II), 3 (III) and 4 (IVa). The figures show the size in m (size (microns)) against the proportion that has passed through in % (% passing as a bar) and the percentage of the measurements (% channel; line). The values were determined by means of laser diffraction. The filler IV was additionally analyzed as IVb and IVc with another instrument (ANALYSETTE 22 NanoTec plus, laser diffraction). The filler V was also analyzed twice with the aforementioned instrument. The values in the table indicate the sizes below which there are X % of the particles analyzed; for example 90% 45.56 m means that a size of less than 45.56 m was determined for 90% of the particles analyzed.

[0131] The exact size distributions are listed in tables 7, 8 and 9.

[0132] Fillers of the invention were incorporated into polypropylene in different proportions by weight. The properties of the samples are shown in tables 1 and 2. A refers here to samples in which constituents >60 m were removed by a sieving process, whereas B shows the properties of samples with unsieved filler. Comparative samples with 20% by weight of talc as filler show a higher density of 1.11 g/cm.sup.3. Comparative samples with 30% by weight of talc as filler show a higher density of 1.15 g/cm.sup.3. Comparative samples with 40% by weight of talc as filler show a higher density of 1.26 g/cm.sup.3.

[0133] The experiments with fillers I to V gave similar results in mixtures as well.

[0134] The properties of samples comprising nylon-6,6 (N 66) are shown in tables 3 and 4. A refers here to samples in which constituents >60 m were removed by a sieving process, whereas B shows the properties of samples with unsieved filler. Comparative samples with 30% by weight of wollastonite as filler show a density of 1.36 g/cm.sup.3, and those with 40% by weight of wollastonite a density of 1.48 g/cm.sup.3. The sieving-out leads to a distinct improvement in the properties.

[0135] The bending test was conducted according to DIN EN ISO 178 (ISO standard specimens (80104 in mm); Sample preparation: storage at 23 C. in a closed vessel for equilibration for 16 to 24 hours; test instrument: Instron 4466; test speed: 2 ram/min; span: 64 mm; test temperature: 23 C.; number of samples: 2-3).

[0136] The Charpy impact resistance was measured according to DIN EN ISO 179/1 (test instrument: pendulum impact tester with exchangeable pendulums (from Zwick); specimens: ISO standard specimens (80105 mm.sup.3); sample preparation: storage at 23 C. in a closed vessel for equilibration for 16 to 24 hours; test instrument: 5J pendulum impact tester; test conditions: 1 eU; specimen type 1; e for impact on the narrow side; test temperature: 30 C.; number of samples: 5).

[0137] Tensile tests according to DIN EN ISO 527-2 were conducted with tensile specimens according to DIN EN ISO 527-2 as specimens. The specimens were stored at 23 C. in a closed vessel for equilibration for 16 to 24 hours (test instrument: Instron 5900R universal tester; test speed: 1 mm/min and 5 mm/min; test temperature: 80 C.; number of samples: 4).

[0138] FIGS. 5 to 8 show tensile tests according to DIN EN ISO 527-2 for various samples. TD20 here represents PP with 20% by weight of talc. In the case of the other samples, for example, PP 60-40-1 represents a PP content of 60% and a filler content of 40% (each % by weight). Therefore, test specimens with 20% to 60% by weight of filler were tested. None of these showed any disadvantages with respect to talc.

[0139] FIGS. 7 and 8 show experiments with test specimens, with one test specimen having 20% by weight of filler and 20% by weight of long glass fibers in PP compared to test specimens comprising N 6 with 30% by weight of long glass fibers and PP with 40% by weight of long glass fibers.

TABLE-US-00003 TABLE 1 Tensile Tensile Tensile Tensile Proportion modulus modulus strength strength of filler of A of B of A of B Matrix [% by wt.] [GPa] [GPa] [MPa] [MPa] F PP-20 20 20.7 19.3 26 25 F PP-30 30 23.7 22.3 25 25 F PP-40 40 29.6 28.5 24 23 F PP-50 50 36.2 35.4 24 23 F PP-60 60 48.4 47.7 24 22

TABLE-US-00004 TABLE 2 Unnotched Unnotched Charpy Charpy Elongation Elongation impact impact at break at break resistance resistance of A of B of A of B Density Matrix [%] [%] [kJ/m.sup.2] [kJ/m.sup.2] [g/cm.sup.3] F PP-20 6.1 5.2 15 16 1.01 F PP-30 3.6 3.2 8 9 1.06 F PP-40 1.8 1.5 6 7 1.14 F PP-50 1.2 1.0 4 5 1.24 F PP-60 0.8 0.6 3 4 1.36

TABLE-US-00005 TABLE 3 Tensile Tensile Tensile Tensile Proportion modulus modulus strength strength of filler of A of B of A of B Matrix [% by wt.] [GPa] [GPa] [MPa] [MPa] F N 66 - 20 20 4.4 4.2 36 34 F N 66 - 30 30 5.1 4.5 35 34 F N 66 - 40 40 5.8 5.2 37 36 F N 66 - 50 50 7.1 6.5 40 38 F N 66 - 65 65 10.1 9.2 43 41 N 66 1.4 35 N GF 30 GF 5.6 130

TABLE-US-00006 TABLE 4 Unnotched Unnotched Charpy Charpy Elongation Elongation impact impact at break at break resistance resistance of A of B of A of B Density Matrix [%] [%] [kJ/m.sup.2] [kJ/m.sup.2] [g/cm.sup.3] F N 66 - 20 0.9 0.8 38 40 1.22 F N 66 - 30 0.8 0.7 47 50 1.28 F N 66 - 40 0.7 0.65 48 51 1.35 F N 66 - 50 0.6 0.57 55 59 1.45 F N 66 - 65 0.5 0.43 42 45 1.62 N 66 3 1.12 N GF 5 1.38

TABLE-US-00007 TABLE 5 Sample I: ACS 851 (85% by weight of SiO.sub.2) 90% 387.7 m 95% 502.1 m 50% 217.8 m MV 244.3; MN 75.51; MA 177.5; SD 102.1 II: ACS 901 (90% by weight of SiO.sub.2) 90% 226.8 m 95% 269.6 m 50% 125.0 m MV 133.0; MN 19.8; MA 84.05; SD 69.69 III: ACS 931 (93% by weight of SiO.sub.2) 90% 372.3 m 95% 480.5 m 50% 196.9 m MV 220.2; MN 34.92; MA 130.2; SD 114.6 IVa: ACS 952 (95% by weight of SiO.sub.2) 90% 45.29 m 95% 56.37 m 50% 19.89 m MV 23.39; MN 2.097; MA 10.52; SD 15.94

TABLE-US-00008 TABLE 6 Sample IVb: ACS 952 (95% by weight of SiO.sub.2) 90% 45.56 m 50% 18.11 m 10% 2.86 m IVc: ACS 952 (95% by weight of SiO.sub.2) 90% 45.24 m 50% 18.25 m 10% 2.82 m Va: ACS 951 (95% by weight of SiO.sub.2) 90% 36.87 m 50% 17.42 m 10% 2.38 m Vb: ACS 951 (95% by weight of SiO.sub.2) 90% 36.71 m 50% 16.99 m 10% 2.22 m

TABLE-US-00009 TABLE 7 I II III IVa % Tile [m] [m] [m] [m] 10 104.7 45.04 62.73 4.65 20 142.6 68.18 107.1 7.95 30 170.6 89.35 143.1 11.56 40 194.6 108.0 171.3 15.59 50 217.8 125.0 196.9 19.89 60 242.3 142.1 223.5 24.34 70 271.0 161.3 254.2 29.25 80 310.4 185.9 295.1 35.32 90 387.7 226.8 372.3 45.29 95 502.1 269.6 480.5 56.37

TABLE-US-00010 TABLE 8 Size I II III IVa [m] % pass % pass % pass % pass 1408 100.0 100.0 100.0 100.0 1184 99.75 100.0 99.77 100.0 995.6 99.48 100.0 99.53 100.0 837.2 98.79 100.0 98.90 100.0 704.0 97.84 100.0 98.05 100.0 592.0 96.64 100.0 96.98 100.0 497.8 94.9 100.0 95.42 100.0 418.6 92.01 99.51 92.86 100.0 352.0 86.59 98.56 88.21 100.0 296.0 76.88 96.68 80.19 100.0 248.9 62.51 93.06 68.49 100.0 209.3 46.34 86.60 54.79 100.0 176.0 32.12 76.44 41.78 100.0 148.0 21.74 63.24 31.58 100.0 124.5 14.74 49.70 24.41 99.90 104.7 10.01 38.12 19.43 99.48 88.00 6.73 29.32 15.71 98.88 74.00 4.44 22.65 12.62 97.95 62.23 2.88 17.34 9.88 96.38 52.33 1.83 13.01 7.44 93.66 44.00 1.12 9.59 5.37 89.11 37.00 0.61 7.04 3.73 82.24 31.11 0.22 5.20 2.49 73.38 26.16 0.00 3.86 1.57 63.90 22.00 0.00 2.85 0.89 54.79 18.50 0.00 2.06 0.38 46.80 15.56 0.00 1.42 0.00 39.92

TABLE-US-00011 TABLE 9 Size I II III IVa [m] % pass % pass % pass % pass 13.08 0.00 0.90 0.00 33.90 11.00 0.00 0.47 0.00 28.54 9.25 0.00 0.11 0.00 23.74 7.78 0.00 0.00 0.00 19.48 6.54 0.00 0.00 0.00 15.77 5.50 0.00 0.00 0.00 12.59 4.62 0.00 0.00 0.00 9.91 3.89 0.00 0.00 0.00 7.67 3.27 0.00 0.00 0.00 5.81 2.750 0.00 0.00 0.00 4.28 2.312 0.00 0.00 0.00 3.04 1.945 0.00 0.00 0.00 2.07 1.635 0.00 0.00 0.00 1.32 1.375 0.00 0.00 0.00 0.75 1.156 0.00 0.00 0.00 0.32 0.972 0.00 0.00 0.00 0.00