WO2022224082A1 - Biopolymer composite material based on polyactic acid. - Google Patents
Biopolymer composite material based on polyactic acid. Download PDFInfo
- Publication number
- WO2022224082A1 WO2022224082A1 PCT/IB2022/053440 IB2022053440W WO2022224082A1 WO 2022224082 A1 WO2022224082 A1 WO 2022224082A1 IB 2022053440 W IB2022053440 W IB 2022053440W WO 2022224082 A1 WO2022224082 A1 WO 2022224082A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite material
- biopolymer
- biopolymer composite
- weight
- material based
- Prior art date
Links
- 229920001222 biopolymer Polymers 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims abstract description 6
- 210000003278 egg shell Anatomy 0.000 claims abstract description 17
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 13
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 13
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N 2-Amino-2-Deoxy-Hexose Chemical compound NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical group [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
Definitions
- the invention relates to a material composition of a biopolymer composite with a wear-resistant particulate filler of animal origin.
- Biopolymer materials and their composites are among the most progressively de veloping materials, not only in terms of application possibilities but also in terms of environmental aspects. These materials represent an essential segment of production, for example, in the packaging industry, food processing, healthcare or the automotive industry, wherein their share is constantly growing.
- the biopolymer PLA material polylactic acid polymer - polylactide
- PLA material polylactic acid polymer - polylactide
- the most common additivation is to add one-dimensional fibrous fillers to the polymer matrix in order to increase the final properties.
- metal fillers based on aluminium alloys, copper alloys, steel or glass fillers in the form of fibres or beads are added to the matrix for this purpose.
- Another possible filler is calcium silicate, which, however, significantly absorbs water or air humidity and thus negatively affects the PLA polymer matrix.
- these types of fillers place a significant burden on production equipment, such as injection moulding machines, extrusion machines, moulds, calibration units, etc., regarding their wear and lifetime.
- Another disadvantage is their problematic recycling and almost zero biodegradation.
- the object of the invention is to provide a biopolymer composite material that would eliminate the prior art’s disadvantages.
- biopolymer polyactic acid-based composite material contains 50 to 80% by weight of polylactic acid polymer and 20 to 50% by weight of crushed dry egg shells.
- the particles of the crushed dry matter of the eggshells preferably have a size from 50 qm to 350 mhi.
- the invention provides a biopolymer composite material with a PLA matrix filled with a high proportion of particulate filler of animal origin - eggshell dry matter.
- the biopolymer composite material comprises a biopolymer matrix and a natural filler in the form of a fine crushed eggshell dry matter, which contains 95 to 98% calcium carbonate and significantly increases hardness and resistance to abrasion and wear.
- the particulate filler increases the modulus of elasticity in tension and bending. Injected and extruded parts and products are characterized by minimal deformation, reduced tendency to form sink marks, reduced shrinkage value and overall quasi-isotropic behaviour. It is possible to use standard machinery for the production of parts, which is also used for other types of fillers. The wear and abrasive load of machinery is lower compared to metal or glass fillers.
- composition of the biopolymer composite i.e. the matrix and the filler, is of completely natural origin and all its components are subject to biodegradation.
- the material is extremely environmentally friendly and suitable for industrial composting, as the calcium carbonate contained acts as a natural fertilizer.
- the biopolymer composite material does not contain any chemical compatibilizers and additives, and the cohesion at the interfacial interface between the filler and the polymer matrix is given mainly by the geometric bond and adhesive forces.
- the eggshell dry matter needs to be soaked in warm soapy water at before grinding, thus removing cuticle residues containing substances such as galactose and mannose peptides and hexosamine, reducing cohesion of particles with a polymer matrix. After soaking, it is necessary to rinse eggshells with clean water and dry.
- An exemplary biopolymer polyactic acid-based composite material contains 80% by weight of polylactic acid polymer and 20% by weight of crushed eggshell dry matter.
- the particles of the crushed eggshell dry matter preferably have a size in the range from 150 pm to 300 pm.
- component A consists of biopolymer matrices based on polylactic acid (PLA) and component B consists of particles of finely crushed or ground eggshells in size from 50 pm to 350 mih.
- PVA polylactic acid
- Component A 70% by weight of PLA
- Component B 30% by weight of eggshell particles
- Component A 50% by weight of PLA
- Component B 50% by weight of eggshell particles
- the biopolymer composite material with eggshell particles is suitable for a wide range of injection moulded and extruded parts, where the resistance of the surface to abrasion or increased hardness are essential. Parts made of this biopolymer composite are characterized by high hardness and stiffness, which is now achieved exclusively with the help of metal or glass fillers.
- the advantages of the biopolymer composite are the 100% natural origin of the matrix from renewable sources and particulate filler, biodegradability and environmental friendliness after the end of its life.
- the biopolymer composite material filled with eggshell particles according to the present invention is in the granulated form suitable for the production of injection moulded parts with a thickness of 0.8 to 5 mm or extruded parts.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Biopolymer composite material based on polyactic acid contains 50 to 80% by weight of polylactic acid polymer and 20 to 50% by weight of crushed eggshell dry matter.
Description
Description
Title of Invention: Biopolymer composite material based on polyactic acid.
Field of the Invention
[0001] The invention relates to a material composition of a biopolymer composite with a wear-resistant particulate filler of animal origin.
Background of the Invention
[0002] Biopolymer materials and their composites are among the most progressively de veloping materials, not only in terms of application possibilities but also in terms of environmental aspects. These materials represent an essential segment of production, for example, in the packaging industry, food processing, healthcare or the automotive industry, wherein their share is constantly growing. The biopolymer PLA material (polylactic acid polymer - polylactide) is the most important and widespread biopolymer. It is characterized by workability comparable to standard synthetic ther moplastics and affordable price. Due to the gradual expansion of PLA application pos sibilities, this type of polymer is often added in order to improve mechanical or physical properties. The most common additivation is to add one-dimensional fibrous fillers to the polymer matrix in order to increase the final properties. If it is necessary to obtain a part with increased hardness and abrasion resistance, metal fillers based on aluminium alloys, copper alloys, steel or glass fillers in the form of fibres or beads are added to the matrix for this purpose. Another possible filler is calcium silicate, which, however, significantly absorbs water or air humidity and thus negatively affects the PLA polymer matrix. However, these types of fillers place a significant burden on production equipment, such as injection moulding machines, extrusion machines, moulds, calibration units, etc., regarding their wear and lifetime. Another disadvantage is their problematic recycling and almost zero biodegradation.
[0003] The object of the invention is to provide a biopolymer composite material that would eliminate the prior art’s disadvantages.
Summary of the Invention
[0004] The above-mentioned drawbacks are largely eliminated by the biopolymer polyactic acid-based composite material according to the invention. Its essence is that it contains 50 to 80% by weight of polylactic acid polymer and 20 to 50% by weight of crushed dry egg shells.
[0005] The particles of the crushed dry matter of the eggshells preferably have a size from 50 qm to 350 mhi.
[0006] The invention provides a biopolymer composite material with a PLA matrix filled
with a high proportion of particulate filler of animal origin - eggshell dry matter.
[0007] The biopolymer composite material comprises a biopolymer matrix and a natural filler in the form of a fine crushed eggshell dry matter, which contains 95 to 98% calcium carbonate and significantly increases hardness and resistance to abrasion and wear. At the same time, the particulate filler increases the modulus of elasticity in tension and bending. Injected and extruded parts and products are characterized by minimal deformation, reduced tendency to form sink marks, reduced shrinkage value and overall quasi-isotropic behaviour. It is possible to use standard machinery for the production of parts, which is also used for other types of fillers. The wear and abrasive load of machinery is lower compared to metal or glass fillers.
[0008] The composition of the biopolymer composite, i.e. the matrix and the filler, is of completely natural origin and all its components are subject to biodegradation. The material is extremely environmentally friendly and suitable for industrial composting, as the calcium carbonate contained acts as a natural fertilizer.
[0009] The research has shown that the best properties both in terms of wear resistance and final properties and in terms of preparation and processing of biopolymer composite are achieved by crushed eggshell dry matter in size from 50 pm to 350 pm. In the given particle size range, the filler has the highest effect on increasing the tensile modulus in tension and the flexural modulus up to 30 per cent, increasing hardness up to 40 per cent, wherein the biopolymer composite has excellent abrasion resistance.
[0010] In terms of material composition, the biopolymer composite material does not contain any chemical compatibilizers and additives, and the cohesion at the interfacial interface between the filler and the polymer matrix is given mainly by the geometric bond and adhesive forces. To ensure sufficient compatibility and interconnection at the interfacial interface, the eggshell dry matter needs to be soaked in warm soapy water at before grinding, thus removing cuticle residues containing substances such as galactose and mannose peptides and hexosamine, reducing cohesion of particles with a polymer matrix. After soaking, it is necessary to rinse eggshells with clean water and dry.
Examples of the Invention Embodiments
[0011] An exemplary biopolymer polyactic acid-based composite material contains 80% by weight of polylactic acid polymer and 20% by weight of crushed eggshell dry matter. The particles of the crushed eggshell dry matter preferably have a size in the range from 150 pm to 300 pm.
[0012] The biopolymer composite with increased abrasion resistance is further described by the following examples, including a suitable application, wherein component A consists of biopolymer matrices based on polylactic acid (PLA) and component B consists of particles of finely crushed or ground eggshells in size from 50 pm to 350
mih.
Examples of variants [0013] Variant no. 1
[0014] Component A: 70% by weight of PLA
[0015] Component B: 30% by weight of eggshell particles
[0016] Variant no. 2
[0017] Component A: 50% by weight of PLA
[0018] Component B: 50% by weight of eggshell particles
[0019] The biopolymer composite material with eggshell particles is suitable for a wide range of injection moulded and extruded parts, where the resistance of the surface to abrasion or increased hardness are essential. Parts made of this biopolymer composite are characterized by high hardness and stiffness, which is now achieved exclusively with the help of metal or glass fillers. The advantages of the biopolymer composite are the 100% natural origin of the matrix from renewable sources and particulate filler, biodegradability and environmental friendliness after the end of its life.
Industrial Applicability
[0020] The biopolymer composite material filled with eggshell particles according to the present invention is in the granulated form suitable for the production of injection moulded parts with a thickness of 0.8 to 5 mm or extruded parts.
Claims
[Claim 1] Biopolymer composite material based on polyactic acid, characterized in that it contains 50 to 80% by weight of polylactic acid polymer and 20 to 50% by weight of crushed eggshell dry matter.
[Claim 2] The biopolymer composite material according to claim 1, char acterized in that the particles of the crushed eggshell dry matter have a size in the range from 50 inn to 350 pm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CZ202138746U CZ35169U1 (en) | 2021-04-20 | 2021-04-20 | Biopolymer composite material based on polylactic acid |
| CZPUV2021-38746 | 2021-04-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022224082A1 true WO2022224082A1 (en) | 2022-10-27 |
Family
ID=76474438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2022/053440 WO2022224082A1 (en) | 2021-04-20 | 2022-04-12 | Biopolymer composite material based on polyactic acid. |
Country Status (2)
| Country | Link |
|---|---|
| CZ (1) | CZ35169U1 (en) |
| WO (1) | WO2022224082A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665619A (en) * | 2009-09-27 | 2010-03-10 | 上海大学 | Egg-shell powder filled poly-lactic acid composite material and preparation method thereof |
| CN111662725A (en) * | 2020-06-24 | 2020-09-15 | 代彦霞 | Repair material for reducing migration state lead ions in soil and preparation method thereof |
-
2021
- 2021-04-20 CZ CZ202138746U patent/CZ35169U1/en active IP Right Grant
-
2022
- 2022-04-12 WO PCT/IB2022/053440 patent/WO2022224082A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665619A (en) * | 2009-09-27 | 2010-03-10 | 上海大学 | Egg-shell powder filled poly-lactic acid composite material and preparation method thereof |
| CN111662725A (en) * | 2020-06-24 | 2020-09-15 | 代彦霞 | Repair material for reducing migration state lead ions in soil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ35169U1 (en) | 2021-06-15 |
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