Recyclable thermoplastic compositions

Abstract

A recyclable thermoplastic composition made by using at least one polymer and a lignin-based filler is disclosed. Further, the use of the lignin-based filler for making a recyclable thermoplastic composition and a method for making a recyclable thermoplastic composition are disclosed. Further, articles and uses of the thermoplastic composition are disclosed.

Description

Technical Field

[0001] The present disclosure relates to a recyclable thermoplastic composition. The present disclosure further relates to the use of a lignin-based filler. The present disclosure further relates to a method for producing a recyclable thermoplastic composition. The present disclosure further relates to an article and the use of the above thermoplastic composition.

Background Art

[0002] From the viewpoints of sustainability and circular economy, it is desirable to reuse thermoplastic compositions or materials such as packaging materials in a closed loop. Carbon black is usually used as a pigment or filler in black plastics. The sustainability of the components of plastic production is important, and bio-based components and renewable components are required in plastics. Therefore, the inventors recognized the need for a renewable black-colored filler or pigment that enables the selection of polymers in the composition and thus enables the recycling of thermoplastic compositions.

Summary of the Invention

Means for Solving the Problems

[0003] A recyclable thermoplastic composition produced by using at least one polymer and a lignin-based filler is disclosed. The lignin-based filler may be produced from lignin that has been subjected to hydrothermal carbonization treatment. The lignin-based filler may contain, in total, 62 to 70% by weight of carbon and, in total, a maximum of 3% by weight of ash, · The color of the thermoplastic composition may be represented by a maximum L value of 25, a maximum a value of 8, and a maximum b value of 12, determined by DIN EN ISO11664.

[0004] Furthermore, the use of a lignin-based filler, which is prepared from lignin subjected to hydrothermal carbonization, and which contains 62-70% by weight of carbon and up to 3% by weight of ash in total, in order to produce a recyclable thermoplastic composition by using at least one polymer and the lignin-based filler. The color of the above thermoplastic composition is represented by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664. Use will be disclosed.

[0005] Furthermore, a method for producing a recyclable thermoplastic composition comprising at least one polymer and a lignin-based filler, The process of providing at least one polymer and a lignin-based filler, wherein the lignin-based filler is prepared from lignin subjected to hydrothermal carbonization, and the lignin-based filler contains 62-70% by weight of carbon and up to 3% by weight of ash in total, The process involves combining at least one of the above polymers and the above lignin-based filler to form the above recyclable thermoplastic composition, wherein the color of the thermoplastic composition is represented by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664. A method including the following is disclosed.

[0006] Furthermore, articles comprising thermoplastic compositions as defined herein are disclosed.

[0007] Furthermore, the use of thermoplastic compositions as defined herein in packaging, housings, automotive parts, aircraft parts, marine parts, machine parts, sports equipment, sports equipment parts, leisure equipment, leisure equipment parts, tools, tool parts, pipes, membranes, tubes, furnishings, bottles, films, bags, pouches, textiles, ropes, containers, tanks, electrical components, electronic components, energy generating components, toys, appliances, kitchenware, tableware, flooring, fabrics, medical applications, food contact materials, building materials, drinking water applications, and / or furniture is disclosed. [Modes for carrying out the invention]

[0008] A recyclable thermoplastic composition is disclosed, prepared by using at least one polymer and a lignin-based filler. The lignin-based filler may be produced from lignin subjected to hydrothermal carbonization. The lignin-based filler may contain 62-70% by weight of carbon and up to 3% by weight of ash in total. The color of the thermoplastic composition is represented by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664.

[0009] Furthermore, the use of a lignin-based filler, which is prepared from lignin subjected to hydrothermal carbonization, and which contains 62-70% by weight of carbon and up to 3% by weight of ash in total, in order to produce a recyclable thermoplastic composition by using at least one polymer and the lignin-based filler. The color of the above thermoplastic composition is represented by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664. Use will be disclosed.

[0010] Furthermore, a method for producing a recyclable thermoplastic composition comprising at least one polymer and a lignin-based filler, The process of providing at least one polymer and a lignin-based filler, wherein the lignin-based filler is prepared from lignin subjected to hydrothermal carbonization, and the lignin-based filler contains 62-70% by weight of carbon and up to 3% by weight of ash in total, The process involves combining at least one of the above polymers and the above lignin-based filler to form the above recyclable thermoplastic composition, wherein the color of the thermoplastic composition is represented by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664. A method including the following is disclosed.

[0011] Furthermore, articles comprising thermoplastic compositions as defined herein are disclosed. In one embodiment, the thermoplastic composition is formed into an article by extrusion, injection molding, compression molding, blow molding, injection blow molding, injection stretch blow molding, thermoforming, vacuum forming, melt spinning, electrospinning, melt blowing, film blowing, film casting, extrusion coating, rotational molding, co-extrusion, lamination, calendering, fused deposition modeling, or any combination thereof.

[0012] Furthermore, the use of thermoplastic compositions specified herein in packaging, housings, automotive parts, aircraft parts, marine parts, machine parts, sports equipment, sports equipment parts, leisure equipment, leisure equipment parts, tools, tool parts, pipes, membranes, tubes, fittings, bottles, films, bags, pouches, textiles, ropes, containers, tanks, electrical components, electronic components, energy generating components, toys, appliances, kitchenware, tableware, flooring, fabrics, medical applications, food contact materials, building materials, drinking water applications, and / or furniture is disclosed.

[0013] Thermoplastic compositions, also known as thermoplastic plastic compositions, are plastic polymer materials that become flexible or moldable at certain high temperatures and solidify upon cooling.

[0014] The thermoplastic composition may be prepared by using at least one polymer and a lignin-based filler. Further components or materials, such as additives, lubricants, stabilizers, antioxidants, and other fillers, may also be used to prepare the thermoplastic composition. In one embodiment, the step of combining the at least one polymer and the lignin-based filler also includes the step of combining one or more additives, lubricants, stabilizers, and / or antioxidants to form the recyclable thermoplastic composition.

[0015] In one embodiment, combining the at least one polymer and the lignin-based filler includes preparing a masterbatch and then compounding this masterbatch with the at least one polymer. In one embodiment, combining the at least one polymer and the lignin-based filler includes preparing a masterbatch and then compounding this masterbatch with either the same or different polymers and optionally further additives. In one embodiment, combining the at least one polymer and the lignin-based filler includes directly compounding the polymer and the lignin-based filler.

[0016] When preparing the recyclable thermoplastic composition, a so-called masterbatch may be prepared first by using the polymer and the lignin-based filler. This masterbatch may be prepared by mixing the polymer and the lignin-based filler at high temperature. Other additives, lubricants, stabilizers, antioxidants, and other fillers may also be included in the masterbatch as needed. The masterbatch is generally considered a solid product (usually plastic, rubber, or elastomer) in which the pigment or filler is optimally dispersed at high concentrations within a carrier material. The carrier material is compatible with the main plastic blended during molding, thereby allowing the final plastic product, i.e., the thermoplastic composition, to acquire color or properties from the masterbatch.

[0017] Alternatively, the thermoplastic composition is directly compounded from a polymer and a lignin-based filler at a high temperature. Also, if necessary, other additives, lubricants, stabilizers, antioxidants, other fillers, etc. may be directly compounded with the polymer and the lignin-based filler.

[0018] The temperature used when combining at least one polymer and the lignin-based filler may vary depending on the type of polymer used. The appropriate temperature for each polymer is readily available to those skilled in the art. Also, polymer suppliers define the processing temperatures suitable for different polymers. Generally, for example, temperatures of 150 - 440 °C, or 180 - 350 °C, or 200 - 300 °C may be used.

[0019] The thermoplastic composition contains 0.1 - 65% by weight, or 0.3 - 60% by weight, or 0.5 - 50% by weight, or 1 - 40% by weight, or 1.2 - 30% by weight, or 1.5 - 20% by weight, or 2 - 10% by weight, or 2.5 - 5% by weight of the lignin-based filler based on the total weight of the thermoplastic composition. In one embodiment, the thermoplastic composition may contain 0.1 - 10% by weight, or 0.1 - 5% by weight of the lignin-based filler based on the total weight of the thermoplastic composition.

[0020] In this specification, "total weight" should be understood as the weight of all components of the thermoplastic composition (including any possible moisture) unless otherwise specified.

[0021] The thermoplastic composition may contain at least one polymer, for example, at least two different polymers, at least three different polymers, at least four different polymers, and the like. This polymer may be any polymer selected from the group of thermoplastic polymers or combinations of different thermoplastic polymers. This polymer may be selected from one or more of the following: polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate (EVA), polybutylene adipate terephthalate (PBAT), polyamide, polyacrylate, polyester, acrylonitrile-butadiene-styrene (ABS), polycarbonate, polylactic acid (PLA), polyvinyl chloride (PVC), and the like. In one embodiment, the thermoplastic composition contains polyethylene, polypropylene, and / or acrylonitrile-butadiene-styrene. That is, one type of polymer may be used to produce the recyclable thermoplastic composition, or a combination of two or more different polymers may be used.

[0022] The expression "lignin-based filler" should be understood in this specification to refer to a filler prepared from lignin that has been subjected to hydrothermal carbonization treatment (HTC), unless otherwise specified.

[0023] The hydrothermal carbonization treatment of lignin refers to a thermochemical conversion process of lignin-containing materials in an aqueous suspension. The hydrothermal carbonization treatment of lignin produces lignin derivatives having a high carbon content and functional groups.

[0024] Lignin is a biopolymer and an important structural material in the support tissues of most living plants. It is a renewable material that can be used in several applications.

[0025] The lignin used to prepare the lignin-based filler may be selected from the group consisting of kraft lignin, steam-exploded lignin, biorefinery lignin, supercritical separation lignin, hydrolyzed lignin, flash precipitated lignin, biomass-derived lignin, lignin from the alkali pulping process, lignin from the soda process, lignin from organosolve pulping, lignin from the alkali process, lignin from the enzymatic hydrolysis process, and any combination thereof. In one embodiment, the lignin is wood-derived lignin. The lignin may be derived from conifers, deciduous trees, annual plants, or any combination thereof.

[0026] "Kraft lignin" in this specification should be understood, unless otherwise specified, as lignin derived from Kraft black liquor. Black liquor is an alkaline aqueous solution of lignin residue, hemicellulose, and inorganic chemicals used in the Kraft pulping process. Black liquor from the pulping process contains components derived from various proportions of different coniferous and hardwood species. Lignin can be separated from black liquor by different techniques, including precipitation and filtration. Lignin typically begins to precipitate at pH values ​​below 11-12. Different pH values ​​can be used to precipitate lignin fractions with different properties. These lignin fractions differ from each other in terms of molecular weight distribution, e.g., Mw and Mn, polydispersity, hemicellulose content, and extractable content. The molar mass of lignin precipitated at higher pH values ​​is higher than that of lignin precipitated at lower pH values. Furthermore, the molecular weight distribution of lignin fractions precipitated at lower pH values ​​is broader than that of lignin fractions precipitated at higher pH values. The precipitated lignin can be purified from inorganic impurities, hemicellulose, and wood extracts using an acidic washing process. Further purification can be achieved by filtration.

[0027] The term “flash-precipitated lignin” should be understood herein as lignin precipitated from black liquor in a continuous process by lowering the pH of the black liquor stream to a lignin precipitation level using a carbon dioxide-based acidifying agent, preferably carbon dioxide, under the influence of an overpressure of 200–1000 kPa, and then suddenly releasing the pressure to precipitate the lignin. A method for producing flash-precipitated lignin is disclosed in Finnish Patent Application No. 20106073. The residence time in the above method is less than 300 seconds. Flash-precipitated lignin particles having a particle size of less than 2 μm form aggregates, which can be separated from the black liquor using, for example, filtration. An advantage of flash-precipitated lignin is its higher reactivity compared to ordinary kraft lignin. Flash-precipitated lignin can be purified and / or activated if necessary for further processing.

[0028] Lignin may also be derived from an alkaline process. The alkaline process can begin with liquefying the biomass with a strong alkali, followed by a neutralization process. After the alkaline treatment, the lignin can be precipitated as described above.

[0029] Lignin may also be derived from steam explosion. Steam explosion is a pulping and extraction technique that can be applied to wood and other fibrous organic materials.

[0030] "Biorefinery lignin" should be understood, unless otherwise specified herein, as lignin that can be recovered from a refining facility or refining process in which biomass is converted into fuels, chemicals and other materials.

[0031] "Supercritical separation lignin" should be understood, unless otherwise specified, as lignin that can be recovered from biomass using separation or extraction techniques with supercritical fluids. The supercritical state corresponds to temperatures and pressures exceeding the critical point of a given substance. In the supercritical state, there are no distinct liquid and gas phases. Extraction with supercritical water or supercritical liquid is a method of decomposing biomass using water or liquid under supercritical conditions and converting it into cellulosic sugars. This water or liquid acts as a solvent, extracting sugars from cellulosic plant material, while the lignin remains as solid particles.

[0032] Lignin may be derived from a hydrolysis process. Lignin derived from a hydrolysis process can be recovered from a paper pulp process or a wood chemical process.

[0033] The lignin may be derived from the organosolve process. Organosolve is a pulping technique that uses organic solvents to solubilize lignin and hemicellulose.

[0034] In one embodiment, the lignin-based filler is prepared from lignin derived from an enzymatic hydrolysis process and / or a Kraft process and subjected to hydrothermal carbonization. In one embodiment, the lignin-based filler is prepared from lignin derived from an enzymatic hydrolysis process and subjected to hydrothermal carbonization. In one embodiment, the lignin-based filler is prepared from lignin derived from a Kraft process and subjected to hydrothermal carbonization.

[0035] In one embodiment, the enzymatic hydrolysis process includes the enzymatic hydrolysis of a plant-based feedstock, such as a wood-based feedstock. In one embodiment, the enzymatic hydrolysis process includes the enzymatic hydrolysis of cellulose. In one embodiment, the lignin-based filler is prepared from lignin derived from wood pulping, such as kraft lignin.

[0036] The lignin-based fillers disclosed herein may be prepared as disclosed below. The lignin used may be derived, for example, from a process in which lignin is formed in the enzymatic hydrolysis of lignocellulose raw materials, or the lignin may be derived from a kraft process. Other lignin sources may also be used.

[0037] The derived lignin may be dissolved in an alkaline solution such as NaOH. Dissolution may be achieved by heating the mixture of lignin and the alkaline solution to about 80°C, adjusting the pH to a value greater than 7, such as 9-11, and mixing the mixture of lignin and the alkaline solution for a predetermined time. The mixing time may be continued for about 2-3 hours. The exact pH value is determined based on the product grade target.

[0038] The dissolved lignin may then be subjected to hydrothermal carbonization (HTC).

[0039] The hydrothermal carbonization treatment may be carried out in a batch-operated reactor (HTC reactor), or in several parallel reactors if necessary. The dissolved lignin may be added to the HTC reactor after preheating. The temperature in the HTC reactor may be 150-250°C and the pressure may be 20-30 bar. The residence time in the HTC reactor may be about 3-6 hours. In the HTC reactor, the lignin is carbonized, thereby precipitating a stabilized lignin derivative with a high specific surface area. The formed slurry containing the carbonized lignin may then be removed and cooled.

[0040] This results in the formation of a slurry containing a lignin-based packing agent.

[0041] The slurry containing the lignin-based packing material may be supplied to a separation unit, in which the precipitated lignin may be separated from the slurry. The separated lignin-based packing material may be dried and recovered. Before drying, the lignin-based packing material may be washed as needed. The recovered lignin-based packing material may be further processed before being used as a lignin-based packing material, for example, by crushing, further drying, or grinding. The lignin-based packing material thus formed is a renewable bio-based packing material.

[0042] During the process described above, the lignin polymers are linked together. Therefore, a lignin-based packing material may be considered to contain, or consist of, these linked lignin polymers. The linked or connected lignin polymers may no longer be soluble. However, smaller lignin polymer chains remain soluble and can therefore be subjected to standard analytical techniques such as size exclusion chromatography or nuclear magnetic resonance spectroscopy (NMR spectroscopy), which require the analyte to be dissolved in a solvent. Thus, different properties of the soluble fraction of the lignin-based packing material may be determined.

[0043] In one embodiment, the starting material for preparing the lignin-based filler is lignin obtained from an enzymatic hydrolysis process. Enzymatic hydrolysis is a process in which enzymes(s) help to break bonds in molecules by adding water. In one embodiment, the enzymatic hydrolysis includes the enzymatic hydrolysis of cellulose.

[0044] In one embodiment, the lignin-based filler is prepared from lignin derived from an enzymatic hydrolysis process subjected to hydrothermal carbonization.

[0045] In one embodiment, the lignin-based filler contains 0.1 to 3% by weight, or 0.1 to 2.5% by weight, or 0.2 to 2.0% by weight, or 0.3 to 1.5% by weight, or 0.4 to 1.0% by weight of ash in total. The ash content can be determined according to standard DIN 51719.

[0046] The inventors have surprisingly found that when lignin obtained, for example, from an enzymatic hydrolysis process is used to produce a lignin-based filler, the ash content of the lignin-based filler can be reduced. A lower ash content has the additional benefit of, for example, higher purity of the lignin-based filler.

[0047] The lignin-based filler may contain 62-70% by weight of carbon in total. In one embodiment, the lignin-based filler contains 63-69% by weight or 64-68% by weight of carbon in total. The amount of carbon in the lignin-based filler may be determined according to standard DIN 51732 (1997).

[0048] In one embodiment, the solubility of the lignin-based packing material in 0.1 M NaOH is 1-40% by weight, or 3-35% by weight, or 5-30% by weight. Solubility may be measured as follows: First, the sample is dried at a temperature of 60°C for 4 hours. 0.5 grams of the sample is weighed and suspended in 50 ml of 0.1 M NaOH at a concentration of 1% at a temperature of 22°C. Mixing is continued for 1 hour, after which the sample is placed on glass microfiber paper (1.6 μm), and the filter paper containing the sample is dried at a temperature of 60°C for 2 hours. The portion of the dissolved sample can be determined by gravimetric measurement.

[0049] In one embodiment, the lignin-based packing material has a weight-average molecular weight (Mw) of 1000-4000 Da, or 1300-3700 Da, or 1700-3200 Da, or 2500-3000 Da, or 2600-2900 Da, or 2650-2850 Da, depending on the soluble fraction of the lignin-based packing material. The weight-average molecular weight may be determined by size exclusion chromatography (SEC) using 0.1 M NaOH as the eluent and a sample volume of approximately 1 mg / ml dissolved in 0.1 M NaOH. The molecular weight is measured against a polystyrene sulfonate standard. A UV detector with a wavelength of 280 nm is used.

[0050] The polydispersity index (PDI) of the lignin-based packing material may be 1.5–5.0, or 1.8–4.5, or 1.9–4.3, or 2.1–4.0, or 2.4–3.5, or 2.6–3.2, depending on the soluble fraction of the lignin-based packing material. The polydispersity index may also be determined by size exclusion chromatography (SEC). PDI is a measure of the distribution of molecular mass in a given polymer sample. PDI is calculated by dividing the weight-average molecular weight (Mw) by the number-average molecular weight (Mn). PDI indicates the distribution of individual molecular masses in a batch of polymer.

[0051] This lignin-based filler is suitable for 3 to 150 m 2 / g, or 5-100m 2 / g, or 7-60m 2 It may have an STSA number of / g. The STSA number may be determined according to the standard ASTM D6556.

[0052] In one embodiment, the lignin-based filler is present in a maximum of 1.5 g / cm³. 3 It has a density of 1.0 to 1.5 g / cm³. In one embodiment, the lignin-based filler is 1.0 to 1.5 g / cm³. 3 , or 1.15~1.35 g / cm³ 3 , or 1.1~1.4 g / cm³ 3 It has a density of . The density may be determined according to the standard ISO 21687.

[0053] The term "recycling process" should be understood herein, unless otherwise specified, as referring to a process in which the recyclability of a thermoplastic composition is tested. The thermoplastic composition may be compounded in an extruder when prepared using at least one polymer and a lignin-based filler, and any additional materials. The term "recycling process" herein means a process that includes subjecting the prepared thermoplastic composition to an additional extrusion cycle or loop. That is, the recyclability of the thermoplastic composition is tested by subjecting the thermoplastic composition to an additional extrusion. An example of an extruder that may be used is the Leistritz ZSE 27 MAXX, which is a high-speed co-rotating twin-screw extruder with a screw diameter of 27 mm and an L / D of 48. When referring to a recycling process, it should be understood that the thermoplastic composition is subjected to one or more additional extrusion cycles or loops.

[0054] The melt flow index (MFI) may be determined according to ISO 1133-1:2012 (Plastics - Determination of the melt mass-flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics - Part 1: Standard method). The melt flow index may be considered an indicator of the fluidity, and therefore the processability, of a thermoplastic composition. A higher melt flow index indicates lower viscosity of the thermoplastic composition.

[0055] In one embodiment, the melt flow index of the thermoplastic composition after being subjected to the recycling process described herein differs from the melt flow index of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0056] In one embodiment, the melt flow index of the thermoplastic composition after being subjected to the recycling process described herein is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the melt flow index of the same thermoplastic composition before being subjected to the recycling process.

[0057] In one embodiment, the melt flow index of the thermoplastic composition after being subjected to the recycling process described herein nine times differs from the melt flow index of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0058] In one embodiment, the melt flow index of the thermoplastic composition after being subjected to the recycling process described herein nine times is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the melt flow index of the same thermoplastic composition before being subjected to the recycling process.

[0059] The inventors have surprisingly found that the melt flow index of the thermoplastic composition does not change essentially, for example, increase or decrease, during the recycling process (multiple times are possible). Therefore, since the melt flow index of the thermoplastic composition does not change essentially, for example, increase, as a result of subjecting the thermoplastic composition to one or more recycling processes, it can be concluded that the polymers in the thermoplastic composition do not decompose or break down during recycling. Accordingly, the thermoplastic compositions specified herein exhibit good stability.

[0060] Oxidation induction time (OIT) is a measure of a material's resistance to oxidative degradation. To achieve this, the sample may be heated at a constant rate in an inert atmosphere, and once the set temperature (ideally the processing temperature) is reached, the gas flow is switched to an air atmosphere. From this point until the oxidation reaction is detected by an exothermic shift in the differential scanning calorimetry (DSC) curve, the temperature is kept constant. The time interval between the start of the oxygen-air flow and the oxidation reaction is the OIT. The temperature used depends on the polymer being analyzed.

[0061] In one embodiment, the oxidation induction time of the thermoplastic composition after being subjected to the recycling process described herein differs from the oxidation induction time of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, or up to 10 percent.

[0062] In one embodiment, the oxidation induction time of the thermoplastic composition after being subjected to the recycling process described herein is up to 15 percent, or up to 10 percent, longer than the oxidation induction time of the same thermoplastic composition before being subjected to the recycling process.

[0063] In one embodiment, the oxidation induction time of the thermoplastic composition after being subjected to the recycling process described herein is up to 15 percent, up to 10 percent, or up to 5 percent shorter than the oxidation induction time of the same thermoplastic composition before being subjected to the recycling process.

[0064] In one embodiment, the oxidation induction time of the thermoplastic composition after being subjected to the recycling process described herein nine times is at least 4 percent, or at least 6 percent, or at least 8 percent longer than the oxidation induction time of the same thermoplastic composition before being subjected to the recycling process. The increase in oxidation unit time is an indicator of good thermal stability of the thermoplastic composition.

[0065] In one embodiment, the color of the thermoplastic composition is represented by an L value of up to 25, or up to 23, or up to 20, or up to 15, or up to 10. In one embodiment, the color of the thermoplastic composition is represented by an a value of up to 8, or up to 7, or up to 6, or up to 5, or up to 4.8, or up to 4.5, or up to 4.3. In one embodiment, the color of the thermoplastic composition is represented by a b value of up to 12, or up to 10, or up to 8, or up to 7, or up to 6.5, or up to 6.3, or up to 6.1.

[0066] In one embodiment, the color of the thermoplastic composition is represented by an L value of at least 2 or at least 4. In one embodiment, the color of the thermoplastic composition is represented by an a value of at least 1 or at least 2. In one embodiment, the color of the thermoplastic composition is represented by a b value of at least 4, at least 6, at least 8, or at least 10.

[0067] In one embodiment, the color of the thermoplastic composition is represented by an L value of up to 25, or up to 23, or up to 20, or up to 15, or up to 10; an a value of up to 8, or up to 7, or up to 6, or up to 5, or up to 4.8, or up to 4.5, or up to 4.3; and a b value of up to 12, or up to 10, or up to 8, or up to 7, or up to 6.5, or up to 6.3, or up to 6.1.

[0068] In one embodiment, the color of the thermoplastic composition is represented by an L value of at least 2 or at least 4, the color of the thermoplastic composition is represented by an a value of at least 1 or at least 2, and the color of the thermoplastic composition is represented by a b value of at least 4, at least 6, at least 8, or at least 10.

[0069] Surprisingly, the inventors found that the color of the thermoplastic composition is not substantially affected by the fact that the thermoplastic composition is subjected to a recycling process.

[0070] In one embodiment, the L, a, and / or b values ​​of the thermoplastic composition after being subjected to the recycling process described herein differ from the L, a, and / or b values ​​of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0071] In one embodiment, the L-value of the thermoplastic composition after being subjected to the recycling process described herein differs from the L-value of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0072] In one embodiment, the L-value of the thermoplastic composition after being subjected to the recycling process described herein is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the L-value of the same thermoplastic composition before being subjected to the recycling process.

[0073] In one embodiment, the L-value of the thermoplastic composition after being subjected to the recycling process described herein nine times differs from the L-value of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0074] In one embodiment, the L-value of the thermoplastic composition after being subjected to the recycling process described herein nine times is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the L-value of the same thermoplastic composition before being subjected to the recycling process.

[0075] In one embodiment, the a-value of the thermoplastic composition after being subjected to the recycling process described herein differs from the a-value of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0076] In one embodiment, the a-value of the thermoplastic composition after being subjected to the recycling process described herein is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the a-value of the same thermoplastic composition before being subjected to the recycling process.

[0077] In one embodiment, the a-value of the thermoplastic composition after being subjected to the recycling process described herein nine times differs from the a-value of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0078] In one embodiment, the a-value of the thermoplastic composition after being subjected to the recycling process described herein nine times is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the a-value of the same thermoplastic composition before being subjected to the recycling process.

[0079] In one embodiment, the b-value of the thermoplastic composition after being subjected to the recycling process described herein differs from the b-value of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0080] In one embodiment, the b-value of the thermoplastic composition after being subjected to the recycling process described herein is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the b-value of the same thermoplastic composition before being subjected to the recycling process.

[0081] In one embodiment, the b-value of the thermoplastic composition after being subjected to the recycling process described herein nine times differs from the b-value of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent.

[0082] In one embodiment, the b-value of the thermoplastic composition after being subjected to the recycling process described herein nine times is up to 15 percent, up to 10 percent, or up to 5 percent higher or lower than the b-value of the same thermoplastic composition before being subjected to the recycling process.

[0083] The values ​​L, a, and b indicate the color values ​​of the recyclable thermoplastic composition. These values ​​may be determined by DIN EN ISO 11664 or by any device that enables measurement in the CIELab color space. Surprisingly, the inventors of this application have found that the use of lignin-based fillers results in a "darker" thermoplastic composition than the use of lignin that does not have the properties specified herein for the lignin-based filler. The recyclable thermoplastic composition has the additional utility of having a color that does not change intrinsically when subjected to the recycling process. The recyclable thermoplastic composition also has the advantage of achieving the desired color of the composition and not requiring other colorants or pigments to maintain the color during recycling.

[0084] The thermoplastic compositions disclosed herein have the additional benefit of exhibiting a black color that is quite similar to that provided by carbon black. The thermoplastic compositions disclosed herein have the additional benefit of exhibiting better stability compared to compositions prepared, for example, by using carbon black as a filler. Furthermore, the thermoplastic compositions have the additional benefit of being thermally stable. In addition, the use of the lignin-based fillers described herein has the additional benefit of making the thermoplastic compositions recyclable, as their use allows for the sorting of the thermoplastic compositions. [Examples]

[0085] Various embodiments will be described in detail below.

[0086] The following description discloses several embodiments in such detail that a person skilled in the art can utilize the embodiments based on this disclosure. Not all steps or features of the embodiments are discussed in detail, as many steps or features will be obvious to a person skilled in the art based on this specification.

[0087] Example 1 - Testing of thermoplastic compositions In this example, the objective was to evaluate the performance of lignin-based fillers (LBFs) in different thermoplastic compositions. In addition, comparative examples were prepared by using carbon black (CB) or pure (unmodified) lignin (PL) in the thermoplastic composition instead of lignin-based fillers.

[0088] Lignin-based fillers were prepared according to the description provided above by using lignin material derived from the enzymatic hydrolysis process of wood and subjected to hydrothermal carbonization. Pure lignin was obtained from the same enzymatic hydrolysis process of wood but not subjected to hydrothermal carbonization. The carbon black used was MONARCH® 800, provided by Cabot. The properties of the lignin-based fillers and pure lignin were measured. These are shown in Table 1 below.

[0089] [Table 1]

[0090] Carbon black has a carbon content of >95% and a density of 1.8 g / cm³. 3 That was the case.

[0091] First, the following masterbatch was prepared.

[0092] [Table 2]

[0093] The masterbatch was prepared by combining the following components at a processing temperature suitable for each type of polymer: 40% by weight of filler, 52% by weight of polymer, and a total of 8% by weight of additive packages (consisting of 2% calcium stearate (lubricant), 2% Irganox 1010 antioxidant, and 4% polyethylene wax (lubricant)).

[0094] Three kilograms of various masterbatches were prepared and filled with 40% by weight filler. The prepared masterbatches were then physically dry-blended with 3% by weight and injection-molded to replicate standard injection molding practices. The following combinations were injection-molded: • Polypropylene (PP) as a masterbatch in polypropylene (PP) (hereinafter referred to as PP thermoplastic composition) • Polystyrene (PS) as a masterbatch in acrylonitrile butadiene styrene (ABS) (hereinafter referred to as ABS thermoplastic composition)

[0095] Each of the prepared thermoplastic compositions contained 1.2% by weight of a different filler.

[0096] The samples were subjected to the recycling process described herein. In the table below, "Run 1" refers to a thermoplastic composition that was extruded into a thermoplastic composition but not recycled. Run 5 represents a composition that was extruded into a thermoplastic composition and then subjected to the recycling process four times, and Run 10 represents a composition that was extruded into a thermoplastic composition and then subjected to the recycling process nine times.

[0097] The samples were analyzed. The results are shown in the table below.

[0098] [Table 3]

[0099] [Table 4]

[0100] As can be seen from Tables 3 and 4, the thermoplastic compositions prepared using lignin-based fillers are more stable when recycled than those prepared using pure lignin. The values ​​when using lignin-based fillers are the same as, or even better than, those when using carbon black.

[0101] [Table 5]

[0102] [Table 6]

[0103] As can be seen from Tables 5 and 6, the values ​​of thermoplastic compositions prepared using lignin-based fillers are better than those of compositions using pure lignin when subjected to recycling. For PP thermoplastic compositions, the oxidation induction time increased with increasing recycling rounds. For ABS thermoplastic compositions, the oxidation induction time did not substantially decrease as a result of recycling. All of these results indicate that the thermoplastic compositions have excellent thermal stability.

[0104] [Table 7]

[0105] [Table 8]

[0106] [Table 9]

[0107] [Table 10]

[0108] [Table 11]

[0109] [Table 12]

[0110] As can be concluded from Tables 7 to 12, the use of lignin-based fillers for manufacturing thermoplastic compositions provides a more "black-like" color to the thermoplastic compositions than the use of pure lignin, especially when they are to be recycled.

[0111] Example 2 - Testing of thermoplastic compositions Similar to Example 1, the objective of this example was to evaluate the performance of lignin-based fillers (LBFs) in thermoplastic compositions. In this example, the following masterbatches were prepared.

[0112] [Table 13]

[0113] Therefore, the masterbatch contained: 40% by weight of filler, 52% by weight of polymer, and a total of 8% by weight of additive packages (consisting of 2% calcium stearate (lubricant), 2% Irganox 1010 antioxidant, and 4% polyethylene wax (lubricant)).

[0114] A 3 kg masterbatch was prepared and filled to 40% by weight. The prepared masterbatch was then physically dry-blended with polypropylene at 3%, 5%, or 10% by weight, and injection-molded to replicate standard injection molding practices. The following combinations were injection-molded: • Polypropylene (PP) as a masterbatch in polypropylene (PP) (hereinafter referred to as PP thermoplastic composition)

[0115] Each of the prepared thermoplastic compositions contained 1.2% by weight, 2% by weight, or 4% by weight of a lignin-based filler.

[0116] [Table 14]

[0117] These results indicate that the color of the thermoplastic composition becomes darker as the amount of lignin-based filler in the composition increases.

[0118] Those skilled in the art will see that, with advances in the technology, the basic idea may be implemented in a variety of ways. Therefore, the embodiments are not limited to the examples given above, and instead, the embodiments may vary within the scope of the claims.

[0119] The embodiments described herein may be used in any combination with each other. Some of the embodiments may be combined together to form further embodiments. Thermoplastic compositions, uses, or methods disclosed herein may include at least one of the embodiments described herein. It will be understood that the above benefits and advantages may relate to one embodiment or to several embodiments. Embodiments are not limited to solving any or all of the described problems or having any or all of the described benefits and advantages. It will be further understood that references to items “a” refer to one or more of these items. The term “comprising” is used herein to mean including the features or actions that follow the phrase without prejudice to the presence of one or more additional features or actions.

Claims

1. A recyclable thermoplastic composition prepared by using at least one polymer and a lignin-based filler, wherein the lignin-based filler is prepared from lignin subjected to hydrothermal carbonization, and the lignin-based filler contains 62 to 70% by weight of carbon and up to 3% by weight of ash in total. The solubility of the lignin-based packing material in 0.1 M NaOH is 5 to 40% by weight. The color of the thermoplastic composition is represented by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664. A recyclable thermoplastic composition.

2. The recyclable thermoplastic composition according to claim 1, wherein the thermoplastic composition contains 0.1 to 65% by weight, or 0.3 to 60% by weight, or 0.5 to 50% by weight, or 1 to 40% by weight, or 1.2 to 30% by weight, or 1.5 to 20% by weight, or 2 to 10% by weight, or 2.5 to 5% by weight of the lignin-based filler, based on the total weight of the thermoplastic composition.

3. The melt flow index of the thermoplastic composition after being subjected to the recycling process differs from the melt flow index of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent. The recyclable thermoplastic composition according to claim 1 or 2, wherein the recycling process refers to a process for testing the recyclability of the thermoplastic composition, and comprises subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop.

4. The oxidation induction time of the thermoplastic composition after being subjected to the recycling process differs by up to 15 percent, or up to 10 percent, from the oxidation induction time of the same thermoplastic composition before being subjected to the recycling process. The recyclable thermoplastic composition according to any one of claims 1 to 3, wherein the recycling process refers to a process for testing the recyclability of the thermoplastic composition, and comprises subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop.

5. The melt flow index of the thermoplastic composition after being subjected to the recycling process nine times differs from the melt flow index of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent. The recyclable thermoplastic composition according to any one of claims 1 to 4, wherein the recycling process refers to a process for testing the recyclability of the thermoplastic composition, and comprises subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop.

6. The L, a, and b values ​​of the thermoplastic composition after being subjected to the recycling process differ from the L, a, and b values ​​of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent, respectively. The recyclable thermoplastic composition according to any one of claims 1 to 5, wherein the recycling process refers to a process for testing the recyclability of the thermoplastic composition, and comprises subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop.

7. The recyclable thermoplastic composition according to any one of claims 1 to 6, wherein the starting material of the lignin-based filler is lignin derived from an enzymatic hydrolysis process and / or a kraft process.

8. The recyclable thermoplastic composition according to any one of claims 1 to 7, wherein the lignin-based filler comprises 0.1 to 2.5% by weight, or 0.2 to 2.0% by weight, or 0.3 to 1.5% by weight, or 0.4 to 1.0% by weight of ash in total.

9. The recyclable thermoplastic composition according to any one of claims 1 to 8, wherein the solubility of the lignin-based filler in 0.1 M NaOH is 5 to 30% by weight.

10. The recyclable thermoplastic composition according to any one of claims 1 to 9, wherein the lignin-based filler has a weight-average molecular weight of 1000 to 4000 Da, or 1300 to 3700 Da, or 1700 to 3200 Da, or 2500 to 3000 Da, or 2600 to 2900 Da, or 2650 to 2850 Da, when determined based on the soluble fraction of the lignin-based filler.

11. A recyclable thermoplastic composition according to any one of claims 1 to 10, wherein the polydispersity index of the lignin-based filler is determined based on the soluble fraction of the lignin-based filler to be 1.5 to 5.0, or 1.8 to 4.5, or 1.9 to 4.3, or 2.1 to 4.0, or 2.4 to 3.5, or 2.6 to 3.

2.

12. The use of a lignin-based filler, wherein the lignin-based filler is prepared from lignin subjected to hydrothermal carbonization, and the lignin-based filler contains 62 to 70% by weight of carbon and up to 3% by weight of ash in total, in order to produce a recyclable thermoplastic composition by using at least one polymer and the lignin-based filler. The solubility of the lignin-based packing material in 0.1 M NaOH is 5 to 40% by weight. The color of the thermoplastic composition is expressed by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664.

13. The use according to claim 12, wherein the thermoplastic composition contains 0.1 to 65% by weight, or 0.3 to 60% by weight, or 0.5 to 50% by weight, or 1 to 40% by weight, or 1.2 to 30% by weight, or 1.5 to 20% by weight, or 2 to 10% by weight, or 2.5 to 5% by weight of the lignin-based filler, based on the total weight of the thermoplastic composition.

14. The melt flow index of the thermoplastic composition after being subjected to the recycling process differs from the melt flow index of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent. The recycling process refers to a process for testing the recyclability of a thermoplastic composition, and includes subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop. The use according to either claim 12 or claim 13.

15. The melt flow index of the thermoplastic composition after being subjected to the recycling process nine times differs from the melt flow index of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent. The recycling process refers to a process for testing the recyclability of a thermoplastic composition, and includes subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop. The use according to any one of claims 12 to 14.

16. The oxidation induction time of the thermoplastic composition after being subjected to the recycling process differs from the oxidation induction time of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, or up to 10 percent. The use according to any one of claims 12 to 15, wherein the recycling process refers to a process for testing the recyclability of the thermoplastic composition, and includes subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop.

17. The L, a, and b values ​​of the thermoplastic composition after being subjected to the recycling process differ from the L, a, and b values ​​of the same thermoplastic composition before being subjected to the recycling process by up to 15 percent, up to 10 percent, or up to 5 percent, respectively. The use according to any one of claims 12 to 16, wherein the recycling process refers to a process for testing the recyclability of the thermoplastic composition, and includes subjecting the prepared thermoplastic composition to an additional extrusion cycle or extrusion loop.

18. The use according to any one of claims 12 to 17, wherein the lignin-based filler is formed from lignin derived from an enzymatic hydrolysis process and / or a kraft process.

19. The use according to any one of claims 12 to 18, wherein the lignin-based filler contains 0.1 to 2.5% by weight, or 0.2 to 2.0% by weight, or 0.3 to 1.5% by weight, or 0.4 to 1.0% by weight of ash in total.

20. The use according to any one of claims 12 to 19, wherein the solubility of the lignin-based packing agent in 0.1 M NaOH is 5 to 30% by weight.

21. The use according to any one of claims 12 to 20, wherein the lignin-based filler has a weight-average molecular weight of 1000 to 4000 Da, or 1300 to 3700 Da, or 1700 to 3200 Da, or 2500 to 3000 Da, or 2600 to 2900 Da, or 2650 to 2850 Da, when determined based on the soluble fraction of the lignin-based filler.

22. The use according to any one of claims 12 to 21, wherein the polydispersity index of the lignin-based filler is determined based on the soluble fraction of the lignin-based filler to be 1.5 to 5.0, or 1.8 to 4.5, or 1.9 to 4.3, or 2.1 to 4.0, or 2.4 to 3.5, or 2.6 to 3.

2.

23. A method for producing a recyclable thermoplastic composition comprising at least one polymer and a lignin-based filler, A step of providing at least one polymer and a lignin-based filler, wherein the lignin-based filler is prepared from lignin subjected to hydrothermal carbonization, the lignin-based filler contains 62 to 70% by weight of carbon and up to 3% by weight of ash in total, and the solubility of the lignin-based filler in 0.1 M NaOH is 5 to 40% by weight. A step of forming the recyclable thermoplastic composition by combining at least one polymer and the lignin-based filler, wherein the color of the thermoplastic composition is represented by an L value of up to 25, an a value of up to 8, and a b value of up to 12, as determined by DIN EN ISO 11664. Methods that include...

24. The method according to claim 23, wherein the thermoplastic composition contains 0.1 to 65% by weight, or 0.3 to 60% by weight, or 0.5 to 50% by weight, or 1 to 40% by weight, or 1.2 to 30% by weight, or 1.5 to 20% by weight, or 2 to 10% by weight, or 2.5 to 5% by weight of the lignin-based filler, based on the total weight of the thermoplastic composition.

25. The method according to claim 23 or 24, comprising combining the at least one polymer and the lignin-based filler to prepare a masterbatch, and then compounding the masterbatch with the at least one polymer.

26. The method according to claim 23 or 24, wherein the combination of the at least one polymer and the lignin-based filler includes directly compounding the polymer and the lignin-based filler.

27. The method according to any one of claims 23 to 26, wherein the step of combining the at least one polymer and the lignin-based filler also includes the step of combining one or more additives, lubricants, stabilizers, and / or antioxidants for forming the recyclable thermoplastic composition.

28. An article comprising a recyclable thermoplastic composition according to any one of claims 1 to 11.

29. A method for manufacturing an article according to claim 28, comprising molding the thermoplastic composition into the article by extrusion, injection molding, compression molding, blow molding, injection blow molding, injection stretch blow molding, thermoforming, vacuum forming, melt spinning, electrospinning, melt blowing, film blowing, film casting, extrusion coating, rotational molding, co-extrusion, lamination, calendering, fused deposition modeling, or any combination thereof.

30. Use of the thermoplastic composition according to any one of claims 1 to 11 in packaging, housing, automotive parts, aircraft parts, marine parts, machine parts, sports equipment, sports equipment parts, leisure equipment, leisure equipment parts, tools, tool parts, pipes, membranes, tubes, furnishings, bottles, films, bags, pouches, textiles, ropes, containers, tanks, electrical components, electronic components, energy generating components, toys, appliances, kitchenware, tableware, flooring, fabrics, medical applications, food contact materials, building materials, drinking water applications, and / or furniture.

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