KR102174995B1 - A bio-based polymer additive, a process for preparing the bio-based polymer additive and a biodegradable polymer composition comprising said bio-based polymer additive - Google Patents

Abstract

The present invention discloses a bio-based polymer additive, a method for preparing the same, and a biodegradable polymer composition comprising the bio-based polymer additive for use in the production of biodegradable plastics. The additives are prepared from biomass of pulverized microbial cells such as microalgae, yeast or other microorganisms. In particular, the bio-based polymer additive improves the flow properties and/or biodegradability of the polymer. In particular, the additive is used as a pigment.

Description

A bio-based polymer additive, a process for preparing the bio-based polymer additive and a biodegradable polymer composition comprising the bio-based polymer additive, and the bio-based polymer additive -based polymer additive}

The present invention relates to a bio-based polymer additive, a method for preparing the bio-based polymer additive, and a biodegradable polymer composition comprising the bio-based additive. According to a specific aspect, the bio-based polymer additive is used as a pigment.

The fast-growing biotech industry is creating a new kind of contamination problem with solid residues derived from microbial biomass. Microorganisms are used as single cell factories, for example, brewer's yeast produces ethanol, which is used as an alternative energy in the automobile industry through a fermentation process, and the yeast remains as a by-product or waste after ethanol purification.

Similarly, microalgae, conventionally used in the food production and food additive industries, have attracted the attention of the biofuel industry in recent years because some species can produce oils and lipids. Microalgae are good candidates for fuel production due to the combination of advantages such as high photosynthetic efficiency, biomass production and faster growth compared to other energy crops. Microalgae are grown in large-scale photobioreactors for industrial scale production of biofuels, and accordingly, a large amount of microalgae remains after the oil extraction process. After the end of the production process, the discarded microorganisms remain as a large amount of solid waste, causing a new kind of pollution problem as described above. In order to solve this pollution problem, there is a need to find a better way for the treatment of microbial waste or the addition of economic value.

One of the common methods of treating microbial solid waste by the biotech industry is to treat these tons of waste as landfill. Several other solutions have also been proposed. For example, Shiho et . al ., (2011) suggested that waste from microalgae Botryococcus biomass could be used as a heating element, where the heat of combustion of the solid component was experimentally measured, and 31 to 34 MJ/at 3% moisture content. was found to be kg. However, the drying process prior to obtaining this very low moisture content is expensive and inefficient. In another example, yeast solid waste from the bio-ethanol industry was used as a feed supplement. However, this consumption is very limited due to the difficulty of controlling the quality of the yeast solid waste. Therefore, the proposed application cannot be a sustainable solution for removing large amounts of yeast biomass.

Another suggested solution to this problem is to incorporate biomass into the plastic. U.S. Patent No. 5346929 discloses a method for preparing a resin prepared from a mixture of a synthetic biodegradable polymer and starch from Aspergillus bacteria, but the method/process for producing a resin including the advantage is not clear. . U.S. Patent No.8026301 describes petroleum resins (e.g., polyethylene, polypropylene, polystyrene and polyvinyl chloride) and cellulose, chemically based nitrogen sources, blue-green algae, or A polymer composition comprising a complex of natural nutrients from yeast is taught.

However, the incorporation of biomass into plastics additionally requires supplementation of additives, e.g., compatibilizers to maintain polymer properties and their compatibility, otherwise the amount of biomass added to the plastic is very Will be limited. In addition, any known method not only improves the biodegradability of biodegradable polymers, but also increases the use of biomass to enhance properties such as viscosity or compatibility of biodegradable polymer compositions, which are very important for the production of biodegradable plastics. It does not teach or imply valuable skills.

Biodegradable plastics are considered environmentally friendly. They are produced from plants and their derivatives or from some other renewable resource. Biodegradable plastics can be degraded when attacked by microorganisms in natural or artificial conditions, whereby, as the molar mass of the degraded biodegradable plastics decreases, it can be transferred to microorganisms and can be supplied to appropriate metabolic pathways. It is plastic. As a result, the end products of this metabolic process include water and carbon dioxide (CO ₂ ) along with newly produced biomass. A good example of a biodegradable plastic is polylactide or polylactic acid (PLA). PLA can be produced by polymerization of bacterial fermented lactic acid, which is believed to solve environmental problems without using non-renewable resources. Therefore, PLA is attracting attention as a material alternative to existing plastics or fibers manufactured through petroleum routes. Another example of a biodegradable plastic is poly(butylene succinate) (PBS).

Indeed, currently available biodegradable resins require the addition of polymer additives such as color thickeners or pigments for their application. There have been attempts to perform color concentration on standard equipment and to use techniques known in the plastics industry. For example, US Patent No. 8,133,558 discloses a method of manufacturing a PLA blown film consisting of 1 to 20% titanium oxide (TiO ₂ ) in order to express a special color of the PLA blown film. U.S. Patent No. 7,273,896 discloses a method for visualization of medical biomaterials from polysaccharides by the use of Fluorescein. U.S. Patent No. 7,687,568 discloses a method of preparing a polyester coloring thickener by the use of a carbon black pigment, a monoazo pigment, a disazo pigment, a phthalocyanine pigment, an anthraquinone pigment or a quinacridone pigment. .

None of the aforementioned patents teach or imply a method of making a biodegradable product composed entirely of bio-based materials. All of the coloring additive materials described in these patents are derived from non-renewable resources, causing much more serious environmental problems, because molecules that disperse around when the biodegradation process of the resin occurs, such as fluorescein, Because it is toxic to the human body.

On the other hand, natural colorants in which the main component or material is derived from natural products and/or by-products thereof provide an effective solution for removing or reducing pollution on the planet. For example, U.S. Patent No. 5205863 discloses a method of making bioplastics from starch acetate (starch acetate polymer) using 1% of a red natural pigment from berries fruits as a coloring additive. However, this method raises at least two new problems. First, the above-described production faces the difficulty of controlling the quality of raw materials, especially the color of the fruit, because the color of the fruit is affected by climate and physical parameters such as light intensity, water supply, nutrients in the soil, etc. Because it depends. Second, securing raw materials is a problem, because these fruits are required in large quantities, and this can directly affect human food supply. Therefore, commercial production according to this method is almost impossible.

The inventors have claimed the problems of the prior art, and as a sustainable solution to these problems and better use and treatment of waste of microbial biomass, collected from natural resources, bioreactors or fermenters or wastes from microbial biomass. It provides a bio-based polymer additive prepared from biomass of microbial cells including biomass. In addition, there is provided a biodegradable polymer composition comprising the bio-based polymer additive prepared from the biomass of the microbial cells.

Accordingly, a bio-based polymer additive used in the production of a biodegradable polymer is provided. The bio-based polymer additive is prepared from biomass of pulverized microbial cells. In addition, there is provided a biodegradable polymer composition comprising a biodegradable polymer and a bio-based polymer additive prepared from the biomass of pulverized microbial cells according to the present invention. In particular, the bio-based polymer additive according to any aspect of the present invention is in the form of a powder obtained by pulverizing biomass of pulverized microbial cells or concentrating a biomass solution.

According to a specific aspect of the present invention, the microbial cells of the microbial biomass contain one or more colored molecules. According to this aspect, the bio-based polymer additive according to the invention is used as a pigment. Accordingly, the bio-based polymer additive according to the present invention includes or is a bio-based polymer additive pigment. Accordingly, there is also provided a biodegradable plastic comprising the bio-based additive of the present invention made entirely of natural colorants, wherein the ingredients or materials used are derived from products prior to the agricultural or biotech industry such as biomass, which Due to its ease of production and quality control, it is of considerable economic value. According to this aspect, the bio-based polymer additive according to the present invention can be used as a colorant. In the present invention, microbial biomass containing colored molecules is used as a natural pigment in some biotech industries.

In the bio-based polymer additive according to any aspect of the present invention, the microorganism of the biomass may be selected from microalgae, yeast and bacteria or mixtures thereof. In particular, the microorganisms include Cyanophyta , Prochlorophyta , Rhodophyta , Chlorophyta , Dinophyta , Chrysophyta , Prymnesiophyta , Bacillariophyta , Xanthophyta , Eustigmatophyta , Rhaphidophyta , Phaeophyta , Proteobacteria (Proteobacteria), cyanobacteria door (cyanobacteria), oil bacteria door (Eubacteria), spirochaete door (Spirochetes), Chlamydia door (Chlamydiae), junction gyunmun (Zygomycota), fungal door (Eumycota) or may be combinations thereof have.

In particular, in the biodegradable polymer composition comprising a biodegradable polymer and a bio-based polymer additive (for example, used as a pigment) prepared from the biomass of the pulverized microbial cells according to the present invention, the bio-based polymer additive is 0.05 to 10 It is in the range of weight percent. More particularly, the bio-based polymer additive is in the range of 0.5 to 5% by weight.

The biodegradable polymer may be any biodegradable polymer suitable for the purpose of any aspect of the present invention. In particular, the biodegradable material may be selected from biodegradable polyesters, for example poly(butylene succinate) (PBS) and/or lactic acid (PLA).

The biodegradable polymer composition according to the present invention provides improved flow characteristics compared to the biodegradable polymer composition containing no additives. In addition, the biodegradable polymer composition according to the present invention provides improved biodegradability compared to the biodegradable polymer composition containing no additives.

Accordingly, there is also provided a method for improving the flow properties of a polymer comprising adding to the polymer a bio-based polymer additive according to any aspect of the present invention. In addition, there is provided a method for improving biodegradable properties of a biodegradable polymer comprising the step of adding a bio-based polymer additive according to any aspect of the present invention to the biodegradable polymer. In addition, when the bio-based polymer additive is a bio-based polymer additive pigment, the present invention also provides a method for coloring a polymer comprising the step of adding the bio-based polymer additive pigment according to the present invention to the polymer.

Also provided is a method of making a bio-based polymer additive comprising the following steps:

(a) providing microbial biomass; And

(b) crushing the microbial cells of the biomass obtained from the step (a).

In particular, as step (c), the method for preparing the bio-based polymer additive may further include powdering the biomass of the pulverized microbial cells obtained from step (b). The powdering step may be selected from a thermal powdering method or a cold powdering method. The thermal powdering method may be selected from powder drying, evaporation, rotary drying, flash drying, disk drying, cascade drying, and superheated steam drying. The cold powdering method may be selected from freeze drying, spray coagulation, or spray cooling. Alternatively, step (c) may include the step of concentrating the biomass of the pulverized microbial cells obtained from step (b).

The microbial biomass of step (a) can be obtained by collecting from natural resources, bioreactors or fermenters. In particular, the microbial biomass may be added in the aqueous solution at a solid concentration of 50 to 200 grams per liter. In particular, step (b) of the method may be a mechanical cell pulverization method performed at a temperature of 20 to 80°C. The mechanical cell pulverization method may be selected from a homogenization method, a firing method, a freeze-thaw method, a mortar and pestle method, or an ultrasonic method.

Articles made of the biodegradable polymer composition according to any aspect of the invention are also provided.

1 is a photograph of a biodegradable resin (PBS) in which a bio-based polymer additive pigment from microalgal biomass powder is introduced in several proportions.
2 is a photograph of a biodegradable resin (PLA) in which a bio-based polymer additive pigment from microalgal powder is introduced in several proportions.
3 is a photograph of a biodegradable resin (PBS) in which a bio-based polymer additive pigment from yeast powder is introduced in several proportions.
4 is a photograph of a biodegradable resin (PLA) in which a bio-based additive pigment from yeast powder is introduced in several proportions.
5 is an optical micrograph showing a biodegradable polymer, showing a poly(butylene succinate) (PBS) in which a bio-based polymer additive prepared from microalgal biomass is introduced at a ratio of 1.0% ((A) 500x (Left) and (B) 1000x (Right)).
6 is an optical micrograph showing a biodegradable polymer, showing poly(butylene succinate) (PBS) in which a bio-based polymer additive prepared from microalgal biomass is introduced in a ratio of 5.0% ((A) 500x (Left) and (B) 1000x (Right)).
7 is an optical micrograph showing a biodegradable polymer, showing a polylactic acid (PLA) in which a bio-based polymer additive prepared from microalgal biomass was introduced at a ratio of 1.0% ((A) 500x (left) and ( B) 1000x (right)).
FIG. 8 is an optical micrograph showing a biodegradable polymer, showing polylactic acid (PLA) in which a bio-based polymer additive prepared from microalgal biomass was introduced in a ratio of 5.0% ((A) 500x (left) and ( B) 1000x (right)).
9 is an optical micrograph showing a biodegradable polymer, showing a poly(butylene succinate) (PBS) in which a bio-based polymer additive prepared from yeast biomass is introduced at a ratio of 1.0% ((A) 500x( Left) and (B) 1000x (right)).
FIG. 10 is an optical micrograph showing a biodegradable polymer, and shows poly(butylene succinate) (PBS) in which a bio-based polymer additive prepared from yeast biomass was introduced in a ratio of 5.0% ((A) 500x( Left) and (B) 1000x (right)).
11 is an optical micrograph showing a biodegradable polymer, showing polylactic acid (PLA) in which a bio-based polymer additive prepared from yeast biomass was introduced in a ratio of 1.0% ((A) 500x (left) and (B) ) 1000x (right)).
12 is an optical micrograph showing a biodegradable polymer, showing polylactic acid (PLA) in which a bio-based polymer additive prepared from yeast biomass was introduced in a ratio of 5.0% ((A) 500x (left) and (B) ) 1000x (right)).
13 is a bar chart showing a melt flow rate (MFR) value of a polylactic acid (PLA) polymer into which an additive derived from microalgae is introduced according to exemplary embodiments of the present invention.
14 is a bar chart showing the melt flow rate (MFR) of a polylactic acid (PLA) polymer into which yeast-derived additives are introduced according to exemplary embodiments of the present invention.
15 shows a bar chart showing the percentage of increased biodegradability of a poly(butylene succinate) (PBS) polymer into which an additive derived from microalgae is introduced according to exemplary embodiments of the present invention.
16 shows a bar chart showing the percentage of poly(butylene succinate) (PBS) polymer into which yeast-derived additives are introduced according to exemplary embodiments of the present invention.
17A is a photograph showing a biodegradable polymer, showing poly(butylene succinate) (PBS) in which Spirulina cells were introduced at 0% by weight, 0.001% by weight and 0.005% by weight without cell disruption according to the prior application. do. 17B is a photograph showing a biodegradable polymer, in which spirulina cells pulverized as described in the present invention are introduced at 0% by weight, 0.5% by weight, 1.0% by weight, 3.0% by weight, and 5.0% by weight of poly(butylene succinate). Nate) (PBS) is shown.

All aspects shown in this specification are also intended to cover application to any other aspects of the invention, unless stated otherwise.

Technical terms and scientific terms used herein have the same definitions as understood by one of ordinary skill in the art, unless otherwise stated.

The use of singular nouns or pronouns, when used with the term "comprising" in the claims and/or specification, means "one", "one or more," "at least one," and " Also includes "one or more than one".

In the present specification, the term "microbial biomass" refers to biomass derived from microorganisms, which is derived from the biotechnology industry including biomass of microorganisms. Microorganisms according to the invention may be microalgae, yeast and/or bacteria. Other microorganisms suitable for the present invention may be used. Microbial biomass is a natural resource, bioreactor or fermenter, or part of solid waste from the biotech industry (e.g., brewer's yeast after the production of ethanol in a fermentation process, Saccharomyces cerevisiae cerevisiae )). Throughout this application, all types of microorganisms may be referred to as unicellular forms, multicellular forms, or both.

As used herein, the term "microbial cell comprising an additive pigment" or "microbial cell comprising a colored pigment" refers to a microbial cell comprising a natural colored pigment molecule, for example, microalgae, yeast and/or bacteria . For example, the colored molecule can be selected from anthocyanins, chlorophyll, carotenoids and picobilins or mixtures thereof.

In this specification, the term "bio-based polymer additive" refers to an additive(s) obtained by crushing cells of microbial biomass.

As used herein, the term "bio-based polymer additive pigment" refers to an additive pigment(s) obtained by pulverizing cells of a microbial biomass, wherein the microbial cells contain colored molecules.

In this specification, the term “pigment” refers to insoluble or soluble colored particles.

As used herein, the term “biodegradable polymer composition” refers to a composition comprising at least one biodegradable polymer and at least one bio-based polymer additive, eg, a bio-based polymer additive pigment according to the present invention.

Throughout this application, the term “about” used to specify any value shown or indicated herein may vary or have variations. Such changes or deviations can be caused by errors in the apparatus and methods used to measure various values.

The terms "comprise", "hvae" and "include" are open-ended linking verbs. Such as "comprise", "which comprise", "have", "which have", "include" and "which include" One or more forms of these verbs are also open-ended. For example, any method of "comprise", "have" or "include" one or more steps, is not limited to only owning one or more steps, but all Covers steps not specified.

Any instrument, device, method or reagent referred to herein is intended to mean an instrument, device, method or reagent generally used or performed by one of ordinary skill in the art, unless otherwise indicated. do.

Microorganisms are an important tool in the field of biotechnology. Several developments for microbial culture in bioreactors have occurred for a long time. For example, the brewer's yeast Saccharomyces cerevisiae plays an important role in the production of ethanol through the fermentation process, with the by-products being important not only in beer production, but also as an alternative energy supply in the automotive industry. After purification of ethanol in the fermentor, the yeast biomass is considered as a by-product or waste. It is known that Saccharomyces cerevisiae biomass contains a red molecule, anthocyanin, and can be used as a colorant. Thus, large amounts of Saccharomyces cerevisiae yeast biomass are considered a by-product or waste in such ethanol production plants and can be used as natural colorants.

Algae production is well known in food and food additive applications. Recently, some types of microalgae are known to produce oils and lipids, and are attracting attention in the biofuel industry. After biomass fractionation, it undergoes transesterification with methanol, which will provide the formation of biodiesel. Therefore, microalgae has been proposed as an excellent candidate for fuel production due to its combination of advantages such as high photosynthetic efficiency, biomass production and faster growth compared to other energy crops. In addition, since these organisms can grow photoautotrophically, their simple growth requirements are suitable for growing in large-scale photobioreactors for the production of biofuels on an industrial scale in the 21st century.

Microalgae contain organic pigments for light energy harvesting. There are three main species of pigments: chlorophyll, carotenoids and picobilins. Chlorophyll (green pigment) and carotenoid (yellow or orange pigment) are lipophilic, and are associated with chlorophyll-protein complexes, while picobilin is hydrophilic. The chlorophyll molecule consists of a tetrapyrrole ring containing a magnesium atom in the center and a long-chain terpenoid alcohol. Structurally, the various types of chlorophyll molecules designated as a, b, c and d differ in the lateral substituents on the tetrapyrrole ring. All chlorophyll molecules have two main absorption bands: blue or blue-green (450-475 nm) and red (630-675 nm).

Chlorophyll a appears in all photoautotrophs as part of the core and reactive central pigment protein complex, and is accompanied by chlorophyll b or chlorophyll c in the light-harvesting antennae.

Carotenoids represent a large group of biological chromophores with an absorption range of 400 to 550 nm. The basic structural elements of carotenoids are two hexacarbonyl rings linked by 18 carbons conjugated with a double bond chain. These are generally hydrocarbons (carotene, e.g. alpha-carotene, beta-carotene) or oxygenated hydrocarbons (xanthophyll, e.g. lutein, violaxanthin, zeaxanthin). , Fucoxanthin, peridinin).

Carotenoids play several roles in the photosynthetic machinery, namely (1) auxiliary light harvesting pigments that deliver excitation to chlorophyll a, (2) structural entities in light harvesting and reaction-centered pigment-protein complexes; And (3) a molecule required for protection against excessive irradiation, a chlorophyll triplet and a reactive oxygen species.

In cyanobacteria and red algae such as spirulina species, the main antennae contain phycobilins, such as phycoerythrobilin, phycocyanobilin and phycourobilin. These auxiliary pigments absorb blue-green, blue, green, or orange light (500-650 nm). Phycobiliprotein is water-soluble, and the pigments are covalently bound to apoprotein.

In the present invention, the microalgae is the prokaryotic algae of the blue- green algae ( Cyanophyta ) and the prokaryotic green algae ( Prochlorophyta ); Or red algae ( Rhodophyta ), green algae ( Chlorophyta ), and flagellum ( Dinophyta ), Chrysophyta , Prymnesiophyta , Bacillariophyta , Xanthophyta , Eustigmatophyta , Rhaphidophyta , and brown algae ( Phaeophyta ) can be selected from eukaryotic algae. Examples of prokaryotic algae are Spirulina species, which are chlorophyll, phycocyanin , phycoerythrin, beta - carotene , and Beta creep torque Santin (beta - cryptoxanthin) and the Southern Dynasties plants containing zeaxanthin (Zeaxanthin) is a no-contact cyano bacteria. An example of a eukaryotic algae is nannochloropsis sp.

In the present invention, the microorganism may be selected from prokaryotic microorganisms containing colored molecules from the proteobacteria, cyanobacteria, eubacteria, spiroheta and chlamydia.

In the present invention, the microorganism may be selected from conjugated mycelia, eukaryotic microorganisms containing colored molecules in the fungal colony, for example, Saccharomyces cerevisiae containing red molecules of anthocyanins.

In one aspect, the present invention provides a bio-based polymer additive for use in preparing a biodegradable polymer composition. The bio-based polymer additive is prepared from biomass of pulverized microbial cells.

In the bio-based polymer additive according to an aspect of the present invention, the biomass of microorganisms may be selected from microalgae, yeast, and bacteria or mixtures thereof. In particular, the biomass is blue-green algae plant, prokaryotic green algae plant, red algae plant, green algae plant, and flagellum Yellow brown algae plant, olfactory flagellum plant, diatom plant, yellow algae plant, Jinan point plant, acupuncture flagellum, brown algae plant, proteobacteria, cyanobacteria, eubacteria, spiroheta, It may be selected from Chlamydia, conjugated mycelia, or mycelia, or combinations thereof. More specifically, the biomass is selected from microalgal biomass or yeast biomass or a combination thereof.

In another aspect of the present invention, the present invention provides a biodegradable polymer composition comprising a biodegradable polymer and a bio-based polymer additive prepared from biomass of pulverized microbial cells. More preferably, the bio-based polymer additive is in the range of 0.05 to 10% by weight. Most preferably, the bio-based polymer additive is in the range of 0.5 to 5% by weight. Any biodegradable polymer suitable for the purposes of any aspect of the invention can be used. The biodegradable polymer may be selected from biodegradable polyesters. Thus, for example, the biodegradable polyester may be, but is not limited to, poly(butylene succinate) (PBS) or polylactic acid (PLA), or a mixture thereof.

The microbial cells of the pulverized biomass provide a biodegradable polymer that is more compatible with the bio-based additives when compared to the microbial cells of the pulverized biomass. It is important to note that it improves). In particular, when using the composition containing a biodegradable polymer and a bio-based polymer additive prepared from the microbial biomass of the pulverized microbial cells according to the present invention, the biodegradable polymer is a compatibilizer (e.g. For example, it can be efficiently mixed with the additives without the addition of oil). Therefore, it is suggested that the pulverization step of the microbial cells is important to produce microorganisms derived from the bio-based polymer additive, even without the addition of an additional additive (different from the bio-based polymer additive according to the present invention).

In methods known in the prior art, microorganisms are generally first dried and then pulverized. In contrast, in the process of the invention, the microbial cells are first crushed and then treated for the production of additives, for example by a drying step or a solution concentration step. In particular, the inventors have found that it is advantageous to pulverize the cells before the drying or concentration step, because after the cell wall and/or cell membrane is destroyed, additive molecules, for example additive pigment molecules, are exposed outside the cell wall. Because it can be. On the other hand, the drying step prior to crushing the cells causes dehydration of water in the cells without disruption of the cell wall/cell membrane. As a result, the additive molecules (including the pigment) are trapped into the dried cells, making it difficult to release the additive molecules (including the pigment) from the dried cells.

In another aspect of the present invention, the present invention relates to a method for preparing a bio-based polymer additive comprising the following steps:

(a) providing microbial biomass; And

(b) crushing the microbial cells of the biomass obtained from the step (a).

The step (a) may include harvesting microalgae or other colored molecule-containing microorganisms from natural lakes or lagoons, open ponds, and closed photobioreactors. The microbial biomass of step (a) can be obtained by collecting it from natural resources, bioreactors or fermenters. In particular, the microbial biomass may be added in an aqueous solution at a solid concentration of 50 to 200 grams per liter. In particular, the step (b) of the method may be a mechanical cell pulverization method performed at a temperature of 20 to 80 °C. The mechanical cell pulverization method can be selected from a homogenization method, a firing method, a freeze-thaw method, a mortar and pestle method, or an ultrasonic method.

In particular, as step (c), the method for preparing the bio-based polymer additive may further include powdering the biomass of the pulverized microbial cells obtained from step (b). The powdering step may be selected from a thermal powdering method or a cold powdering method. The thermal powdering method may be selected from spray drying, evaporation, rotary drying, airflow drying, disk drying, cascade drying, superheated steam drying. The cold powdering method may be selected from freeze drying, spray coagulation or spray cooling.

Alternatively, in step (c), the preparation of the additive may be obtained by a method different from powdering. For example, the additive may be prepared by concentrating the biomass of pulverized microbial cells. More particularly, the step includes concentrating the biomass of the pulverized microorganism and then dispersing it in a suitable liquid carrier compatible with the resin (polymer) to be processed. More particularly, according to this alternative step (c), the additive can be obtained by mixing a concentrated pigment dispersion containing water and an aromatic hydrocarbon in an amount necessary to completely remove the water in the dispersion by azeotropic distillation. Thereafter, the resulting homogeneous slurry is heated at a temperature of 90° C. or less under reduced pressure to remove residual water and aromatic hydrocarbons and lower alcohols added as an azeotropic mixture.

According to one aspect of the present invention, the present invention provides a bio-based polymer additive for use in a method for preparing a biodegradable polymer composition. The bio-based polymer additive is prepared from biomass of degraded microbial cells. The biomass is blue-green algae, prokaryotic green algae, red algae, green algae, and flagellum Yellow brown algae plant, olfactory flagellum plant, diatom plant, yellow algae plant, Jinan point plant, acupuncture flagellum, brown algae plant, proteobacteria, cyanobacteria, eubacteria, spiroheta, It is obtained or derived from a solid biomass of microorganisms selected from Chlamydia, conjugated or fungal species, or combinations thereof. In particular, the biomass is selected from microalgae or yeast or combinations thereof. More particularly, the microalgal biomass is selected from Spirulina, while the yeast biomass is selected from Saccharomyces. The additive according to the invention can be prepared as previously described, i.e. it comprises the following steps:

(a) providing microbial biomass; And

(b) crushing the microbial cells of the biomass obtained from the step (a).

Additionally, the method may include (c) powdering the biomass of the pulverized microbial cells obtained from the step (b). Alternatively, step (c) may include concentrating the biomass of the pulverized microbial cells.

According to one specific embodiment of the present invention, the bio-based polymer additive from microbial biomass according to the present invention can be prepared by a method comprising the following steps:

(a) obtaining microbial biomass, which microbial biomass can be obtained by collecting biomass of microbial discarded as a by-product waste from the biotechnology industry, which is generally in the form of solid waste. It is also possible for the biomass to be harvested from natural resources, for example natural lakes, lagoons, open ponds or cultured plants/reactors, bioreactors or fermenters.

(b) pulverizing the microbial cells of the biomass obtained from step (a), in an exemplary embodiment, the biomass obtained from the step (a) is diluted in an aqueous solution and dried biomass and a predetermined A mixture of positive biomass can be obtained. In one exemplary embodiment, the amount of biomass is 50 to 200 grams per liter in solids concentration. Thereafter, the mixture of biomass is mechanically pulverized at a temperature of 20 to 80°C. The mechanical cell crushing method may be selected from a homogenization method, a firing method, a freeze-thaw method, a mortar and pestle method, or an ultrasonic method.

(c) pulverizing the biomass of the pulverized microbial cells obtained from the step (b), wherein the mixture of the pulverized microbial cells obtained from the step (b) is diluted in an aqueous solution and then dried to powder Polymer additives are obtained. At this stage, the powdering process may be thermal powdering (e.g. spray drying, evaporation, rotary drying, airflow drying, disk drying, cascade drying or superheated steam drying) or cold powdering (e.g. freeze drying, spraying). Coagulation or spray cooling).

The biodegradable polymer composition according to the present invention provides improved flow characteristics compared to the biodegradable polymer composition containing no additives. The biodegradable polymer composition according to the present invention also provides improved biodegradable properties compared to the biodegradable polymer composition containing no additives.

Accordingly, there is also provided a method for improving the flow properties of a polymer comprising adding to the polymer a bio-based polymer additive according to any aspect of the present invention. Also provided is a method of improving the biodegradable properties of a biodegradable polymer comprising the step of adding a bio-based polymer additive according to any aspect of the present invention to the biodegradable polymer.

According to a specific aspect of the present invention, the microbial cells of the microbial biomass contain at least one colored molecule. According to this aspect, the bio-based polymer additive according to the invention is used in particular as a pigment for coloring biodegradable polymers. Thus, the bio-based polymer additive according to this aspect of the present invention may comprise a bio-based polymer additive pigment or is a bio-based polymer additive pigment. Thus, biodegradable plastics comprising bio-based additives (pigments) made entirely of natural colorants are provided, in which the ingredients or materials used are derived from products prior to the agricultural or biotech industries such as microbial biomass, which Due to its ease of production and quality control, it is of considerable economic value. According to this aspect, the bio-based polymer additive according to the present invention can be used as a colorant.

In particular, there is provided a bio-based polymer additive pigment used as a colorant in the production of a biodegradable polymer, wherein the additive pigment is derived from biomass of pulverized microbial cells.

In the bio-based polymer additive used as a pigment according to an aspect of the present invention, the microorganism of the biomass can be selected from microalgae, yeast and bacteria or mixtures thereof.

In particular, the microorganisms include blue-green algae, prokaryotic green algae, red algae, green algae, and flagellum Yellow brown algae plant, olfactory flagellum plant, diatom plant, yellow algae plant, Jinan point plant, acupuncture flagellum, brown algae plant, proteobacteria, cyanobacteria, eubacteria, spiroheta, It may be selected from Chlamydia, conjugated or fungal, or combinations thereof.

The colored molecules are anthocyanin, chlorophyll, carotene (e.g., alpha-carotene, beta-carotene or oxidized hydrocarbon xanthophyll (e.g., lutein, violaxanthine, zeaxanthin, fucoxanthine, peridinin, beta-lane). , Porphyrin, picobilin)) or carotenoids or mixtures thereof.

A biodegradable polymer composition is also provided comprising a biodegradable polymer and a bio-based polymer additive prepared from the biomass of pulverized microbial cells according to the invention for use as a pigment. The bio-based polymer additive is in the range of 0.05 to 10% by weight. More particularly, the bio-based polymer additive is in the range of 0.5 to 5% by weight.

The biodegradable polymer may be any biodegradable polymer suitable for the purpose of any aspect of the present invention. In particular, the biodegradable material may be selected from biodegradable polyesters, for example poly(butylene succinate) (PBS) and/or polylactic acid (PLA).

When the bio-based polymer additive is a bio-based polymer additive pigment, in addition to the characteristics already described for the bio-based polymer additive and the biodegradable polymer composition comprising the bio-based polymer additive according to the present invention, the present invention relates to the present invention. It also provides a method for coloring a polymer comprising the step of adding to the polymer a bio-based polymer additive pigment according to the present invention.

Articles made of the biodegradable polymer composition according to any aspect of the invention are also provided.

A method of preparing a bio-based polymer additive according to the principles of the present invention described above will now be discussed in detail with examples. In this specification, the detailed description of the invention is shown by way of example. This is meant to illustrate various embodiments of the invention, and is not meant to limit the principles or concepts of the invention.

Example 1: microalgae From biomass Bio system Polymer Preparation of additive pigment

The following examples aim to prepare a green bio-based additive pigment from microalgal spirulina biomass.

Spirulina cells, which are microalgae harvested from the closed bioreactor, were obtained. Thereafter, the cells were added to deionized water to prepare a mixture having a concentration of 200 g of dried cells per liter. Then, using a homogenizer, the spirulina cells in the mixture were mechanically crushed at 10,000 rpm for 30 minutes, and the temperature was maintained below about 80°C. The mixture obtained by pulverizing Spirulina cells was diluted with deionized water to prepare a mixture having a concentration of 50 g of dried cells per liter. Thereafter, the mixture was dried at about 160° C. at a feed rate of about 0.3 L/h to obtain a polymer additive pigment powder derived from microalgae. The particle size of the resulting microalgae-derived polymer additive pigment powder was measured with a particle size analyzer-Malvern Instrument (Mastersizer 2000). The average distribution of the particles was about 6 to 9 microns.

Example 2: yeast From biomass Bio system Polymer Preparation of additive pigment

The yeast Saccharomyces biomass is known to contain red-orange colored particles, anthocyanins, in cells. The following examples aim to prepare a red-orange biomass additive pigment from yeast Saccharomyces biomass.

Yeast Saccharomyces biomass was obtained from the fermentor. Thereafter, the cells were added to deionized water to prepare a mixture having a concentration of 200gdml of dried cells per liter. Thereafter, the Saccharomyces cells in the mixture were mechanically pulverized at 10,000 rpm for 30 minutes using a homogenizer, and the temperature was maintained below about 80°C. The mixture produced by crushing Saccharomyces cells was diluted with deionized water to prepare a mixture having a concentration of 50 g of dried cells per liter. Thereafter, the mixture was dried at a temperature of about 160° C. at a feed rate of about 0.3 L/h to obtain a yeast-derived polymer additive pigment powder. The particle size of the yeast-derived polymer additive pigment powder was measured with a particle size analyzer-Malvern Instrument (Mastersizer 2000). The average distribution of the particles was about 6 to 9 microns.

Turning now to another aspect of the present invention, the present invention discloses a biodegradable polymer composition comprising a biodegradable polymer and a bio-based polymer additive for use in preparing the biodegradable polymer. The bio-based polymer additive is prepared according to the method described above.

The biodegradable polymer composition according to an exemplary embodiment of the present invention is a biodegradable polymer selected from biodegradable polyester, preferably polylactic acid (PLA) or poly(butylene succinate) (PBS), and in the present invention And a bio-based polymer additive prepared by the method as described.

In one embodiment, the biodegradable polymer composition according to the present invention is a biodegradable polymer selected from a biodegradable polyester, for example polylactic acid (PLA) or poly(butylene succinate) (PBS), and about 0.05 to Bio-based polymer additives in the range of 10% by weight.

In one embodiment, the biodegradable polymer composition according to the present invention is a biodegradable polymer selected from a biodegradable polyester, for example, polylactic acid (PLA) or poly(butylene succinate) (PBS), and about 0.5 to Bio-based polymer additives in the range of 5% by weight.

In one embodiment, the biodegradable polymer composition comprises a bio-based polymer additive prepared from microalgal biomass selected from PBS and spirulina, and the additive is in the range of about 0.5 to 5% by weight.

In one embodiment, the biodegradable polymer composition comprises a bio-based polymer additive prepared from microalgal biomass selected from PLA and spirulina, and the additive is in the range of about 0.5 to 5% by weight.

In one embodiment, the biodegradable polymer composition comprises a bio-based polymer additive prepared from yeast biomass selected from PBS and Saccharomyces, and the additive is in the range of about 0.5 to 5% by weight.

In one embodiment, the biodegradable polymer composition comprises a bio-based polymer additive prepared from yeast biomass selected from PLA and Saccharomyces, and the additive is in the range of about 0.5 to 5% by weight.

The biodegradable polymer composition according to the present invention can be prepared by a method commonly known to those skilled in the art. The method includes the following steps:

-Mixing the biodegradable polymer and the bio-based polymer additive prepared according to the present invention in a predetermined ratio;

-Extruding the mixture by feeding the mixture to an extruder at a predetermined feed rate (the shaft of the extruder is heated at a predetermined temperature, and the screw speed is set at a predetermined speed);

-Cutting the extruded material into small pieces;

-Injecting into a mold to obtain a molded specimen

The biodegradable polymer composition according to the present invention can be produced using the method/process according to the following examples.

Example 3: PBS And microalgae From biomass Manufactured Bio system Polymer Containing additives Polymer Composition

In this example, poly(butylene succinate) (PBS) FZ71PD from Mitsubishi Chemical Corporation was mixed with the bio-based polymer additive powder derived from Example 1 in a ratio of 0.5, 1.0, 3.0 and 5.0% by weight Mixed with. The mixture was fed to an extruder, specifically an extruder line and mixer (Haake Rheometer Os) at a feed rate of about 1.5 g per minute, wherein the shaft of the extruder was heated to about 170° C., and the shaft speed was set to 120 RPM. Then, the extruded polymer composition was cut with Haake Rheometer OS to reduce the size. Then, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg/h. Under the injection pressure of 200 MPa, injection was performed at a barrel temperature of 165°C and a molding temperature of 40°C. Then, the performance of the finished specimen (Fig. 1) was tested.

Example 4: PLA And microalgae From biomass Manufactured Bio system Polymer Containing additives Polymer Composition

In this example, polylactic acid (PLA) 2002D from Naturework was mixed with the bio-based polymer additive powder prepared according to Example 1 in a ratio of about 0.5, 1.0, 3.0 and 5.0% by weight. The mixture was fed to an extruder, specifically an extruder line and mixer (Haake Rheometer Os) at a feed rate of about 1.5 g per minute, where the shaft was heated to about 170° C. and the shaft speed was set to 120 RPM. Then, the extruded polymer composition was cut with Haake Rheometer OS to reduce the size. Then, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg/h. Under the injection pressure of 200 MPa, injection was performed at a barrel temperature of 165°C and a molding temperature of 40°C. Then, the performance of the finished specimen (Fig. 2) was tested.

Example 5: PBS And yeast From biomass Manufactured Bio system Polymer Containing additives Polymer Composition

In this example, poly(butylene succinate) (PBS) from Mitsubishi Chemical Corporation was added to the bio-based polymer additive prepared from the yeast biomass of Example 2 and 0.5, 1.0, 3.0 and 5.0% by weight. It was mixed in a ratio of. Thereafter, the mixture was supplied to an extruder, specifically, an extruder line and mixer (Haake Rheometer Os) at a feed rate of about 1.5 g per minute, at which time the shaft of the extruder was heated to about 170° C., and the shaft speed was set to 120 RPM. . Then, the extruded polymer composition was cut with Haake Rheometer OS to reduce the size. Then, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg/h. Under the injection pressure of 200 MPa, injection was performed at a barrel temperature of 165°C and a molding temperature of 40°C. Then, the performance of the finished specimen (Fig. 3) was tested.

Example 6: PLA And yeast From biomass Manufactured Bio system Polymer Containing additives Polymer Composition

In this example, polylactic acid (PLA) 2002D from Naturework was mixed with a bio-based polymer additive prepared from the yeast biomass of Example 2 at a ratio of about 0.5, 1.0, 3.0 and 5.0% by weight. The mixed material was fed to an extruder, specifically an extruder line and mixer (Haake Rheometer Os) at a feed rate of about 1.5 g per minute, wherein the shaft was heated to a temperature of about 170° C., and the shaft speed was set to 120 RPM. Then, the extruded polymer composition was cut with Haake Rheometer OS to reduce the size. Then, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg/h. Under the injection pressure of 200 MPa, injection was performed at a barrel temperature of 165°C and a molding temperature of 40°C. Then, the performance of the finished specimen (Fig. 4) was tested.

In all Examples 3-6, when using a composition comprising PBS or PLA and a bio-based polymer additive prepared from microalgal biomass or yeast biomass of pulverized microbial cells according to the present invention, both PBS and PLA are like oil. It is noted that even without the addition of a compatibilizer to improve mixing efficiency, it can be efficiently mixed with the additive.

Additionally, it should be noted that it is possible to vary the ratio between the bio-based polymer additive and the biodegradable polymer, depending on the required properties of the final product. According to the present invention and examples, various ratios of the bio-based polymer additive and the biodegradable polymer were determined based on maintaining the mechanical properties of the biodegradable polymer composition. The range of the bio-based polymer additive is 0.05 to 10% by weight, preferably 0.5 to 5% by weight. 1-17 show various features and properties of articles molded from biodegradable polymer compositions produced using bio-based polymer additives according to the present invention. In addition, when the weight% of the bio-based polymer additive is less than 0.05, the properties of the bio-based polymer additive are significantly reduced, and accordingly, a biodegradable polymer composition produced from a biodegradable polymer containing the additive is required. It is noted that it does not have. In contrast, undesirable mechanical properties were observed in biodegradable polymer compositions comprising more than 10% of the bio-based polymer additive.

Therefore, the biodegradable polymer composition produced from the biodegradable polymer containing the bio-based polymer additive prepared from the biomass of the pulverized microbial cells according to the present invention, as in the Examples, has higher polymer properties as well as production efficiency. Demonstrate improvement. These advantages will become more apparent with reference to the following comparative examples.

Comparative example One

A PBS composition was prepared in the same manner as in Examples 3 and 5, except that a bio-based polymer additive prepared from microalgal biomass or yeast biomass according to the present invention was not used. Then, the composition was extruded and molded into a molded article. Then, the performance of the finished specimen was tested.

Comparative example 2

A PLA composition was prepared in the same manner as in Examples 4 and 6, except that a bio-based polymer additive prepared from microalgal biomass or yeast biomass according to the present invention was not used. Then, the composition was extruded and molded into a molded article. Then, the performance of the finished specimen was tested.

Microalgae according to the invention Biomass Or yeast From biomass Derived Bio system Polymer Biodegradable with additives Polymer Measurement of the mechanical properties of the composition

The mechanical properties of the biodegradable polymers from Examples 3 to 6 and Comparative Examples 1 and 2 were measured using the method described below. The results are shown in Table 1. Tensile strength and elongation at break were tested according to the method specified in ASTM D638 using a universal testing machine (brand: Zwick/Roell, model: Z050 TE). The test was performed at a temperature of 23°C and a humidity of 50°C. The tensile stress at break was measured by the following equation (1), and the elongation at break was measured by the following equation (2).

Tensile strength (MPa) = breaking load (N)/ cross-sectional area (mm ² ) (1)

Elongation at break (%) = [(Elongation at break-weekly distance)/ weekly distance] x 100 (2)

Table 1 shows the mechanical properties of the biodegradable polymer composition containing the bio-based polymer additive.

Sample name E (MPa) Tensile stress Elongation at break (%) Upon surrender maximum At break PLA without additives 3740±86 77.5±0.5 77.5±0.5 65.7±1.2 5.1±0.9 PLA + 0.5% microalgae 3800±74 71.9±0.7 71.9±0.7 59.3±1.8 5.4±1.4 PLA + Microalgae 1% 3750±127 69.1±0.4 68.5±1.0 61.8±5.4 3.5±1.4 PLA + microalgae 3% 3650±101 64.1±0.9 64.1±0.9 53.6±0.9 4.6±0.8 PLA+ microalgae 5% 3760±56 62.0±0.2 57.4±6.9 53.6±4.9 2.4±1.0 PLA + Yeast 0.5% 3830±145 69.3±0.3 69.3±0.3 59.6±3.2 5.7±2.3 PLA + Yeast 1% 3920±168 66.7±0.3 66.7±0.3 55.3±1.3 5.9±1.0 PLA + Yeast 3% 3720±127 59.2±0.6 59.2±0.6 51.4±4.4 5.9±3.1 PLA + Yeast 5% 3790±90 56.4±0.3 56.4±0.3 50.2±3.2 3.2±0.8 PBS without additives 786±26 41.4±0.3 41.4±0.3 40.4±0.9 17±1.7 PBS + 0.5% microalgae 815±31 41.1±0.4 40.9±0.5 40.3±1.0 16±2.3 PBS + 1% microalgae 814±8.5 40.0±0.2 40.1±0.2 38.6±1.6 16±1.1 PBS + 3% microalgae 829±15 36.7±0.2 36.8±0.2 35.9±0.9 13±1.2 PBS + 5% microalgae 862±28 34.7±0.4 34.6±0.3 34.0±0.4 12±0.8 PBS + Yeast 0.5% 799±23 40.5±0.5 40.5±0.3 39.8±0.8 16±1.5 PBS + yeast 1% 814±34 39.3±0.1 39.2±0.2 38.5±0.9 14±0.8 PBS + yeast 3% 828±47 37.0±0.2 37.0±0.3 36.3±0.6 14±0.7 PBS + 5% yeast 869±38 34.8±0.2 35.1±0.4 34.4±0.9 14±1.0

The results showed that the mechanical properties of both the PLA and PBS resins containing the bio-based polymer additive decreased with the increase of the additive content. This suggests that the undesirable mechanical properties limit the percentage of additives incorporated into the PLA and PBS resins.

According to the invention Bio system Polymer Biodegradable with additives Polymer Measurement of the thermal properties of the composition

Differential Scanning Calorimeter (DSC) (Brand: NETZSCH, Model: DSC 204 F1) was used to analyze the thermal properties of the biodegradable polymer composition comprising the bio-based polymer additive pigment according to the method specified in ASTM D3418. In addition, the blended resin was analyzed using a thermogravimetric analyzer (TGA) (brand: NETZSCH, model: TG 209 F1). The results are shown in Table 2.

Table 2 shows the thermal properties of PBS and PLA containing bio-based polymer additives according to the present invention as biodegradable plastics.

Sample name Tm (℃) Tg/Tc (℃) Td (℃) PLA 2002D 152.9 57.1 358 PLA 0.5% algae 156.1 56.2 348 PLA 1% algae 155.4 54.9 328 PLA 3% algae 152.9 52.1 320 PLA 5% algae 148.5 48.4 302 PLA 0.5% yeast 155.0 56.4 349 PLA 1% yeast 155.3 55.8 356 PLA 3% yeast 155.1 53.7 341 PLA 5% yeast 154.8 53 337 PBS FZ71PD 113.6 68.5 378 PBS 0.5% algae 113.8 70.8 382 PBS 1% algae 113.7 71.0 377 PBS 3% algae 113.5 69.7 376 PBS 5% algae 113.3 69.3 373 PBS 0.5% yeast 113.7 69.5 384 PBS 1% yeast 113.6 70.9 384 PBS 3% yeast 113.3 70.8 383 PBS 5% yeast 113.1 70.3 381

Tm = melting temperature; Tg = glass transition temperature; Tc = crystallization temperature, Td = decomposition temperature

According to the invention Bio system Polymer Biodegradable with additives Polymer Flowability test of the composition

The flow properties at low shear were measured by the melt flow rate (MFR). MFR was measured using a melt flow index tester (brand: Gottfert, model: MI-4, test condition = PLA: 2.16 kg, 190° C.). As shown in FIG. 13, the MFR value of the PLA polymer composition having microalgal biomass increased rapidly with an additional amount of particles. In addition, as shown in Fig. 14, the MFR value of the PLA polymer composition with yeast biomass also increased with an additional amount of particles. The addition of microalgal and yeast biomass results in an increase in flow properties, for example a decrease in the viscosity of the PLA polymer. The reduced viscosity is advantageous during formation into the product.

According to the invention Bio system Polymer Biodegradable with additives From polymer Produced biodegradability Polymer Biodegradability test of composition

The term biodegradable polymer composition generally refers to the attack of a water-insoluble polymeric material (plastic) by microorganisms. This means that the biodegradation of polymers is usually a heterogeneous process. Due to the lack of water solubility and size of the polymer molecule, microorganisms cannot directly deliver the polymer material to the cells where the most biochemical processes take place. Rather, they must first secrete extracellular enzymes out of the cell that depolymerize the polymer. In conclusion, if the molar mass of the polymer is sufficiently reduced to form water-soluble intermediates, they can be transferred to microorganisms and supplied to the appropriate metabolic pathway(s). As a result, the end products of these metabolic processes include new biomass along with water, carbon dioxide and methane (in the case of anaerobic decomposition).

Static culture titration measurement (Zibilske et al., 1994. Carbon mineralization. Chapter 38. P. 835-863. In Methods of Soil Analysis , Part 2. Microbiological and Biochemical Properties. SSSA Book Series No. 5 Soil Science Society of America, Madison WI.) was used to measure the evolution of CO ₂ of the polymer. A PBS polymer containing the bio-based polymer additives of Examples 3 and 5 and Comparative Example 1 was prepared as a powder using a grinder ultra-thinning machine (Retsch). Each sample was mixed with fertilizer (1 part by weight of sample and 99 parts by weight of fertilizer). The test was performed at normal temperature (37±2° C.). The humidity was maintained at 60±5°C during the test. The test period was 3 months. A blank test was performed using domestic soil. The increase in biodegradability was measured by equation (3).

Increase in biodegradability (%) = [(CO ₂ of polymer composition containing bio-based additives Generation-CO ₂ generation amount of polymer composition without bio-based additives)/ CO ₂ generation amount of polymer composition without bio-based additives] x 100 (3)

The results are shown in FIGS. 15 and 16. The biodegradable polymer composition having a bio-based additive prepared from microalgal biomass and yeast biomass according to the present invention shows an increased biodegradability when compared to a polymer without additives.

According to the invention Bio system Polymer Biodegradable with additives Polymer Measuring the color properties of the composition

The color reproduction of the biodegradable polymer containing the bio-based polymer additive pigment was observed according to the method specified in ASTM E313 using a color spectrophotometer (brand: Data Color, model: D 650). The results are shown in Table 3.

Table 3 shows the colors of PBS and PLA containing bio-based polymer additives according to the present invention as biodegradable plastics.

Sample name DE DL Da Db PLA 2002D 0.11 -0.11 0.01 0.02 PLA + 1% algae pigment powder 45.77 -45.65 3.28 0.35 PLA + 5% algae pigment powder 50.97 -50.34 2.87 -7.41 PLA + 1% yeast pigment powder 35.40 -27.27 8.77 20.80 PLA + 5% yeast pigment powder 42.87 -41.57 10.08 2.88 PBS FZ71PD 0.13 -0.13 0.00 0.01 PBS + 1% algal pigment powder 39.19 -35.05 -7.64 15.81 PBS + 5% algal pigment powder 50.00 -49.28 -1.62 8.30 PBS + 1% yeast pigment powder 22.53 -13.03 4.49 17.83 PBS + 5% yeast pigment powder 38.22 -27.75 10.58 24.06

DL = difference in brightness of each sample for standard samples PLA 2002D or PBS FZ71PD (from 100 completely white to 0 black)

Da = reddish green difference of each sample to the standard sample PLA 2002D or PBS FZ71PD (red for positive, gray for 0, green for negative)

Db = yellowish blue difference of each sample to the standard sample PLA 2002D or PBS FZ71PD (yellow for positive, gray for zero, blue for negative)

DE = (DL ² + Da ² + Db ² ) ^1/2

Particle distribution

The particle distribution of the algal additive pigment powder and the yeast additive pigment powder in PBS was observed with a Canon microscope. The results are shown in Figs. 5, 6, 9 and 10. The particle distribution of the algae additive pigment powder and the yeast additive pigment powder in PLA was observed with a Canon microscope. The results are shown in Figs. 7, 8, 11 and 12.

The biodegradable polymer composition according to the present invention exhibits excellent compatibility with conventional biodegradable polymers such as PLA and PBS without additional addition of a compatibilizer such as oil. They do not cause a significant effect on the mechanical properties of each polymer, and thus satisfy their use as polymer additives in several respects.

Since the microbial cells of the pulverized biomass provide better compatibility of the biodegradable polymer and the bio-based additives compared to the microbial cells of the pulverized biomass, the properties and characteristics of the resulting biodegradable polymer composition, such as color It is important to note that it improves the properties. This can be seen in FIG. 17 showing large aggregates of unground Spirulina cells added to the PBS polymer at a very low content (0.005% unground cells). On the other hand, Figure 18 shows that the additive prepared from the pulverized cells of spirulina microalgal biomass according to the present invention in a high content (5% or 1,000 times higher than the addition of pulverized cells) is very compatible in PBS polymer. Is clearly shown. Therefore, the present invention suggests that the microbial pulverization step is important to prepare a microbial-derived bio-based polymer additive without additional additives.

In addition, since the bio-based polymer additive according to the present invention is a bio-based material, it is completely degradable. Therefore, the degradation of the biodegradable polymer composition does not leave toxic substances in the soil. It is safe to use as a food packaging product or in other applications related to animal and human use.

Since the addition of the bio-based polymer additive lowers the viscosity of the biodegradable polymer composition, failed injections of the biodegradable polymer composition injection grade are reduced. At the same time, extrusion of such biodegradable polymer compositions is better than ordinary biodegradable polymer compositions due to the reduced viscosity. In addition, the bio-based polymer additive accelerates the biodegradation of PLS and PBS.

From the above, it was found that bio-based additive pigments, such as those derived from the biomass of microorganisms including microalgae, yeast and bacteria, work well with PBS and PLA plastics. Additionally, it has also been shown that both PBS and PLA are well colored by using a bio-based additive pigment powder from microbial biomass, even without the addition of oil to improve mixing efficiency. Biodegradable plastics derived from additive pigment powders in varying percentages demonstrate a variety of properties suitable for applications of a variety of plastics in a variety of industries.

Finally, in particular, it is possible to provide biodegradable plastics of bio-based additives, for example bio-based additive pigments, from microbial biomass such as microalgae, yeast, bacteria, from the description and data according to the invention. It is clear. The biodegradable plastic according to the invention presents a better solution to reduce environmental problems, and such production is viable, sustainable and economical.

Claims (34)

As a bio-based polymer additive for use in the production of biodegradable polymers, the additive is derived from biomass of whole pulverized microbial cells, and the microorganisms are Cyanophyta, Prochlorophyta, and flagellum plants. Dinophyta, Chrysophyta, Prymnesiophyta, Bacillariophyta, Xanthophyta, Eustigmatophyta, Rhaphidophyta ), Phaeophyta, Proteobacteria, Cyanobacteria, Eubacteria, Spirochetes, Chlamydiae, Zygomycota, Bio-based polymer additives selected from Eumycota or combinations thereof. The method of claim 1,
The microorganism is a bio-based polymer additive containing at least one colored molecule. The method of claim 2,
The colored molecules are bio-based polymer additives selected from anthocyanins, chlorophyll, carotenoids and picobilins, or mixtures thereof. The method according to any one of claims 1 to 3,
The microorganism derived from the blue-green algae plant is Spirulina (Spirulina) bio-based polymer additive. The method according to any one of claims 1 to 3,
The microorganisms derived from the fungal phylum are Saccharomyces, a bio-based polymer additive. The method according to any one of claims 1 to 3,
The additive is a bio-based polymer additive in a powder form obtained by pulverizing biomass of pulverized microbial cells. The method according to claim 2 or 3,
The additive is a bio-based polymer additive used as a pigment. The method of claim 7,
The additive is a bio-based polymer additive for coloring the biodegradable polymer(s). As a biodegradable polymer composition,
At least one bio-based polymer additive in the range of 0.05 to 10% by weight; And
Including a biodegradable polymer;
The bio-based polymer additive is derived from the biomass of the entire pulverized microbial cell, and the microorganisms include blue-green algae, prokaryotic green algae, scutellum algae, yellow brown algae, olfactory flagellum, diatom plants, Select from yellow algae plant, Jinan point plant, acupuncture flagella, brown algae plant, proteobacteria, cyanobacteria, eubacteria, spiroheta, chlamydia, conjugate or fungal, or a combination thereof A biodegradable polymer composition. The method of claim 9,
The bio-based polymer additive is a biodegradable polymer composition in the range of 0.5 to 5% by weight. The method of claim 9 or 10,
The microorganism is a biodegradable polymer composition comprising at least one colored molecule. The method of claim 11,
The colored molecules are biodegradable polymer compositions selected from anthocyanins, chlorophyll, carotenoids and picobilins, or mixtures thereof. The method of claim 9 or 10,
The microorganism derived from the blue-green algae plant is spirulina biodegradable polymer composition. The method of claim 9 or 10,
The microorganism derived from the fungal phylum is Saccharomyces, a biodegradable polymer composition. The method of claim 9 or 10,
The biodegradable polymer is a biodegradable polymer composition selected from biodegradable polyester. The method of claim 9 or 10,
The biodegradable polymer is a biodegradable polymer composition selected from poly(butylene succinate) (PBS) or polylactic acid (PLA), or mixtures thereof. The method of claim 9 or 10,
The bio-based polymer additive is a biodegradable polymer composition that improves rheological properties compared to an additive-free biodegradable polymer composition. The method of claim 9 or 10,
The bio-based polymer additive is a biodegradable polymer composition that improves biodegradability compared to an additive-free biodegradable polymer composition. The method of claim 9 or 10,
The additive is a biodegradable polymer composition used as a pigment for coloring the biodegradable polymer composition. As a method for producing a bio-based polymer additive derived from biomass of whole pulverized microbial cells,
(a) providing microbial biomass;
(b) crushing the microbial cells of the biomass of step (a); And
(c) powdering or concentrating the biomass of the whole pulverized microbial cells obtained in step (b). The method of claim 20,
The microbial biomass is blue-green algae, prokaryotic green algae, and flagellum, yellow brown algae, olfactory flagellum, diatoms, yellow algae, Jinan-joint plant, acupuncture-flag plant, brown algae A method for producing a bio-based polymer additive selected from phylum, proteobacteria phylum, cyanobacteria phylum, eubacteria phylum, spiroheta phylum, chlamydia phylum, conjugated mycelia or fungal phylum, or combinations thereof The method of claim 20 or 21,
The microorganism is a method for producing a bio-based polymer additive containing at least one colored molecule. The method of claim 22,
The colored molecule is anthocyanin, chlorophyll, carotenoid and picobilin, or a method for producing a bio-based polymer additive selected from a mixture thereof. The method of claim 20 or 21,
In the step (a), the microbial biomass is collected from natural resources, a bioreactor or a fermenter, and is added in an aqueous solution at a solid concentration of 50 to 200 grams per liter. The method of claim 20 or 21,
The step (b) is a method for producing a bio-based polymer additive, which is a mechanical cell pulverization method performed at a temperature of 20 to 80°C. The method of claim 25,
The mechanical cell pulverization method is a method for producing a bio-based polymer additive selected from a homogenization method, a firing method, a freeze-thaw method, a mortar and pestle method, or an ultrasonic method. The method of claim 20 or 21,
The step (c) is a method of producing a bio-based polymer additive selected from a thermal powdering method or a cold powdering method. The method of claim 27,
The thermal powdering method is a method for producing a bio-based polymer additive selected from spray drying, evaporation, rotary drying, flash drying, disk drying, cascade drying, and superheated steam drying. The method of claim 27,
The cold powdering method is a method of producing a bio-based polymer additive selected from freeze drying, spray coagulation, or spray cooling. The method of claim 20,
The additive is a method for producing a bio-based polymer additive used as a pigment. A method for coloring a biodegradable polymer comprising the step of adding the bio-based polymer additive according to claim 2 or 3 to the biodegradable polymer. A method of improving the flow properties of a biodegradable polymer, comprising the step of adding the bio-based polymer additive according to any one of claims 1 to 3 to the biodegradable polymer. A method for improving biodegradable properties of a biodegradable polymer comprising the step of adding the bio-based polymer additive according to any one of claims 1 to 3 to the biodegradable polymer. An article made of the biodegradable polymer composition according to claim 9 or 10.

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