EP4271745A1

EP4271745A1 - A polymer composition having inorganic additive and production method thereof

Info

Publication number: EP4271745A1
Application number: EP20968186.5A
Authority: EP
Inventors: Mehmet Aydin
Original assignee: Gema Elektro Plastik Ve Elektronik San Dis Tic A S
Current assignee: Gema Elektro Plastik Ve Elektronik San Dis Tic A S
Priority date: 2020-12-31
Filing date: 2020-12-31
Publication date: 2023-11-08
Also published as: WO2022177514A1

Abstract

The present invention relates to a polymer composition for use in various applications, preferably film application, comprising a component A selected from a petroleum-based biodegradable polymer, preferably between 15% to 75% by weight, a component B of an inorganic additive between 35% to 85% by weight and a component C between 0% to 25%.

Description

A POLYMER COMPOSITION HAVING INORGANIC ADDITIVE AND PRODUCTION

METHOD THEREOF

TECHNICAL FIELD

The present invention relates to polymer compositions containing inorganic additives with a mixture of natural and synthetic polymers and a production method for the polymer compositions for use in various industries.

The invention particularly relates to a polymer composition and production method therefor suitable for use in film applications having mixtures of inorganic additives in different proportions to the flexible polymers such as co-polyesters, aliphatic, aliphatic-aromatic dicarboxylic acids and aliphatic dihydroxy compounds. Adding various synthetic polymers such as hard rigid thermoplastic and aliphatic polymers to the said polymer compositions is possible in the technical field.

PRIOR ART

Polymers are high-weight molecules composed of repeating monomers of the same structural unit linked by covalent bonds. Longer polymer chains are obtained in synthesis processes such as condensation or addition polymers, known as polymerization. Polymers can have different physical and chemical inherent properties compared to their constituent monomers. Even the properties between similar polymers can be variant according to the number of repeating units in the polymer. Polymers can be classified as natural (organic) or synthetic polymers. There are many natural polymers available in nature, and with the development of the industry, synthetic polymers are introduced. Particularly, polysaccharides represent the most characteristic family of the natural polymers.

Currently, environmental pollution of the polymer mixtures used for various purposes, particularly in film applications, obtained from polymers with large molecular mass such as plastics and synthesized from petrochemicals cannot be prevented due to the fact that the degradation in nature takes quite a long time. For this reason, it is necessary to convert the polymers produced in the industry, especially the products with large molecular mass such as plastics, into biodegradable materials and to minimize the current degradation- decomposition times. Regulations prohibiting use of polymers with inappropriate degradation times are enacted. Addition to the environmental pollution sensitivity, it is expected that these polymeric compounds will have properties that do not harm the health of humans and animals, since the majority of the products produced are in direct contact with the consumer. Instead of using large-molecule hard-to-degrade plastic coating and plastic packaging materials, film applications that allow biological degradation from natural or synthetic polymers are preferred and are made obligatory by laws and sanctions. Biodegradable or bio-based polymers are called biopolymers.

Polymer must be completely or partially derived from biomass to be classified as biopolymer. Biopolymers can be obtained from two types of sources, either bio-based or petroleum- based. Bio-based polymers are polymers derived from renewable sources. Sometimes natural and synthetic polymers can be mixed in different ratios to obtain products with certain characteristics. However, obtaining determined and desired characterization values of biopolymers and polymer compositions consisting of mixtures or matrices with other polymers and additives in different combinations is problematic. Particularly, the manufacturing processes of synthetic polymers must always be controlled with due care in parameters to obtain the desired product.

Various additives can be added to a polymer composition to enhance or improve its physical or chemical properties. Said additives can be selected from organic or inorganic additives. For example, these are various materials such as plasticizer, compatibilizer, lubricant, antioxidant and antimicrobial agents, emulsifiers, anti-browning agents, aromatic agents, colorants and other functional agents. According to the use of these materials, the cost of the product increases. In addition, obtaining the desired properties becomes difficult due to the characteristics of different components.

The polymer compositions with different properties and especially their film applications are produced using different raw materials. CN106084700A discloses a film structure comprising PBAT, PLA and inorganic additives in the range of a certain percentage.

CN106084700A relates to a low cost, controllable, biodegradable mulching film and a method of preparation thereof. A low-cost, controllable biodegradable film is prepared from the components by weight of 15% to 35% PBAT, 15% to 35% PHA, 15% to 35% PLA, 20% to 50% calcium carbonate, 0,1% to 0,5% an antioxidant, 0,1% to 0,1% It is based on the preparation of 0,5% ultraviolet absorber, 0,5% to 3% adapter and 0% to 1% fully degradable color mastic components. The low cost, controllable biodegradable mulching film is provided by the subject matter invention. A plastic mulching film application of the invention has the desired mechanical properties and its preparation is provided at low cost. The degradation time based on local environment and degradation cycle can be controlled. There is also a synthetic polymer blend. Instead of the difficulty of using polylactic acid (PLA), one of the synthetic polymers here, another synthetic polymer polyhydroxyalkanoate (PHA) and antioxidant materials are used as reinforcements.

EP1699872B1, which is another example of the state of the art, discloses a mixture of biodegradable polymers containing polymer A, polymer B and a compatibilizer C in the following ratios. The total weight of this polymer blend; at least one biodegradable polymer (A) from about 5% to about 95% by weight and having a glass transition temperature of less than about 0°C, at least one solid biodegradable polymer (B) from about 5% to about 95% by weight, glass transition greater than 10°C and at least one compatibilizer (C) of about 0.25- 10% by weight. The polymer blend in the present invention has a higher zero shear melt viscosity than the individual polymers (A) and (B). There is also a synthetic polymer blend. According to the disclosure, the inorganic reinforcing material should be less than 15% by weight, and a compatibilizer at the rate of 0.25-10% by weight.

CN110079063A, describes a film structure with certain PLA, PBAT ratios. The present invention discloses a bio-based alloy material and a packaging film. The bio-based material mix in this document comprises the following components; 10-70% PLA, 10-70% PBAT, 5- 30% bio-based polyurethane, 0,5-30% enhancer, 0,3-5% plasticizer. 0,3-5% by weight of a compatibilizer, 0,1-1% of a thermal oxidation stabilizer and 0,2-2% of a lubricant.

CN110079063A discloses a packaging film which is manufactured from a bio-based alloy material. The bio-based alloy material as disclosed has excellent comprehensive performance advantages such as low carbon, environmentally friendly, biodegradable, tear resistance, high tensile strength and good strength, and it is especially suitable for the packaging industry. There is also a synthetic polymer blend. According to the subject matter invention, the polymer composition is having the mixture of 30% by weight of the inorganic reinforcement material as additive material of the natural and synthetic polymeric mixture, as well as 20% of the total weight of additional additives (5% of a compatibilizer, 5% of a plasticizer, 7% of a lubricant, 3% of an antioxidant) should be used.

Consequently, polymer compositions are obtained by a mixture of natural or synthetic polymers in different proportions described above and using various materials as additives in the mixture. Until now, difficulties have been experienced in use of high amounts of additives at the polymer compositions, particularly for film applications, and therefore only in a very small amount of additives can be added. Additionally, the polymer compositions obtained with the mixtures has to be environmentally friendly and do not cause pollution. For this reason, it is only possible to obtain products similar to the existing characteristics of synthetic or natural polymers. In the technique, there is no example of a polymeric mixture or cure with few components and improved physical properties. There is a need for the use of at least one additive such as a compatibilizer to improve the physical properties in the mixture of natural and synthetic polymers. At least one third polymer component is needed in the absence of additive material for the inorganic reinforcing material to combine effectively. There is a need for economical and environmentally friendly products that can be obtained by mixing polymers consisting of less materials to form polymer compositions with the desired properties in the art, and a new product that will enable them to be produced successfully, and a production process suitable for them.

BRIEF DESCRIPTION OF THE INVENTION

The primary objective of the present invention is to reduce the production cost of the polymer composition by reducing the weight ratio of the polymeric-based material, which is the main component in the polymer composition, and by increasing the ratio of the inorganic additive. Additionally, improving the physical properties, together with the cost advantage in the polymer or compound it is added.

Another object of the present invention is to provide an environmentally friendly polymer composition comprising environmentally friendly, biodegradable polymers and their easy processability replacing the large molecule plastic materials.

The present invention relates to a polymer composition comprising at least one component A selected from petroleum-based biodegradable polymers in a weight ratio between 15% to 75%, at least one component B selected from an inorganic additive material in a weight ratio of between 35% to 85%. The polymer composition further comprising and at least one component C selected from biodegradable polymers preferably from biobased polymers with a weight ratio between 0 to 25%. Surprisingly, it has been observed that the visible texture of the cost-effective polymer composition has a soft touch. This allows the use of the polymer mixture in applications that require a soft texture.

In a preferred embodiment of the present invention, comprises a polymer composition wherein, at least one component A of petroleum-based biodegradable polymers is selected from group of flexible biodegradable polymers or mixtures thereof comprising aliphatic or aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds of polybutylene sebacate terephthalate (PBST), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polycaprolactone (PCL), more particularly polybutylene adipate terephthalate (PBAT). At least one component B of the inorganic additive is selected from group comprising; sand, granite, limestone, sandstone, mica, clay, kaolin, silica, calcium carbonate, calcium hydroxide, calcium sulfate, talc, ceramic materials or mixtures thereof. At least one component C of bio-based polymers, preferably hard biodegradable polymers is selected from group of polymers comprising; polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyhydroxybutyrate-valerate (PHBV), polyhydroxybutyrate-hexanoate (PHBH), polyhydroxyhexanoate (PHH), polyglycolide, cellulose acetate, or mixtures thereof.

In a preferred embodiment of the present invention, at least one component A of petroleum- based biodegradable polymers with a weight ratio between 15% to 45%, preferably between 20% to 40%, preferably between 23% to 29%; calcium carbonate (CaC03) selected as at least one component B from inorganic additives, between 35% to 85%, preferably between 40% to 80%, more preferably between 60% to 70% by weight, and PLA polymer as at least one C component as bio-based polymers preferably hard biodegradable polymers with a weight ratio between 0% to 25%, preferably 5% to 20%, more preferably 5% to 10% by weight. In this way, the mechanical properties of the polymer composition are improved, due to the simplification of the production process with less ingredients and additives, which provides a cost advantage. This allows the polymer mixture to be utilized in applications where desired mechanical strength, high elongation ability, and high breaking forces are required.

In a preferred embodiment of the invention, at least one component B of the inorganic additive material has a weight ratio of the polymer composition between 35% to 85%, preferably between 40% to 80%, most preferably between 60% to 70%; selected from group comprising sand, granite, limestone, sandstone, mica, clay, kaolin, silica, calcium carbonate, calcium hydroxide, calcium sulfate, talc (talc), ceramic materials etc. or mixtures thereof. In this way, the air permeability properties of the cost-effective polymer composition are improved. This allows the use of the polymer mixture in applications where the desired product needs to be air permeable.

In a preferred embodiment of the invention, at least one component C is a bio-based polymers, preferably hard biodegradable polymers, wherein the weight ratio of the polymer composition is between 0% to 25%, preferably 0% to 20%, especially preferably between 5% to 15%, selected from the group comprising polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyhydroxybutyrate-valerate (PHBV), polyhydroxybutyrate-hexanoate (PHBH), polyhydroxyhexanoate (PHH), polyglycolide, cellulose acetate, or mixtures thereof. The biodegradable and compostable properties of an advantageous polymer composition is improved. This allows the polymer mixture to be used in applications where the desired fast biodegradability is required.

In a preferred embodiment of the invention, polymer composition comprising at least one component A of petroleum-based biodegradable polymers is selected as PBAT polymer with a weight ratio between 10% to 75%, preferably between 15% to 60%, most preferably between 20% to 40%, at least one component B of the inorganic additive is calcium carbonate (CaC03) with a weight ratio of preferably between 35% to 85%, preferably between 40% to 80%, preferably between 60% to 70%, and at least one component C selected as PLA polymer from the biobased polymers, preferably hard biodegradable polymers in the weight ratio between 0 and 25%, preferably between 0 and 20%, particularly preferably from 5% to 15% bio-based polymers.

In a preferred embodiment of the invention, polymer composition comprises at least one component A, selected as PBAT as petroleum based biodegradable polymer in the weight ratio between 15% to 45%, preferably between 20% to 40%, especially preferably between 23% to 29%; at least one component B of calcium carbonate (CaC03) selected as inorganic additive with a weight ratio of between 35% to 85%, preferably 40% to 80%, most preferably 60% to 70%, and at least one C component from bio-based polymers preferably hard biodegradable polymers selected as the PLA with a weight ratio of 0 to 25%, preferably 5 to 20%, most preferably 5% to 10%.

In a preferred embodiment of the invention, at least one component B of the inorganic additive material in the polymer composition has a particle size of 15-25 microns, preferably 18-22 microns.

In a preferred embodiment of the invention, the glass transition temperature of the component A of the above-mentioned petroleum-based preferably flexible biodegradable polymer is less than -10°C, preferably between -15°C and -35°C, and/or the melt flow index is between 1 g/10 and 10g/10 min, preferably 5 g/10 min and/or the bulk density of the polymer is between 0,5 g/cm3 and 1 ,00 g/cm3, preferably 0,7 g/cm3, and/or the melting point is between 100°C and 190°C, preferably 110°C to 120°C. In a preferred embodiment of the invention, the tensile strength of the above-mentioned petroleum-based preferably flexible biodegradable polymer, component A, is between 7 MPa and 70 MPa, preferably between 18 MPa and 65 MPa, and/or elongation at break preferably more than 500%, preferably between 500% to 550%.

In a preferred embodiment of the invention, the glass transition temperature of the component C, which is the bio-based preferably hard biodegradable polymer, in the polymer composition described above is preferably greater than +10°C, preferably between +45°C to +70°C and/or the melt flow index is between 1 g/10 to 5g/10 minutes preferably 3 g/10 minutes and/or the melting point is between 120°C and 180°C, preferably between 135°C and 155°C.

In a preferred embodiment of the invention, the tensile modulus of the component C, which is the bio-based preferably hard biodegradable polymer, in the polymer composition described above, has a tensile modulus between 2500 MPa and 4000 MPa, preferably between 3500 MPa, 40 to 60 MPa, preferably 45 MPa, and/or the tensile strength at break between 0 to 20 20%, preferably below 6%.

In a preferred embodiment of the invention, at least one component C is selected as PLA as the aforementioned bio-based preferably hard biodegradable polymer in the polymer composition described above contains between 75% to 100% preferably more than 80% L isomer. Lactic acid, the monomer block of PLA, is produced by bacterial fermentation or by processing sugar or starch from plant sources by a petrochemical route. The fermentation approach is more widely used because it is more environmentally friendly. PLA exists as two optical isomers, L- and D-lactic acid. L-lactic acid rotates the polarized light plane clockwise and D-lactic acid rotates counterclockwise. PLA is a mixture of L- and D-lactic acid form. In the preferred embodiment of the invention, the ratio of the L isomer is predominant.

In a preferred embodiment of the invention, the polymer composition described above has a melt flow index of 0g/10 to 20g/10 min, preferably 0g/10 to 10g/10 min, and/or 1,0 g/cm3 to 2,5 g/cm3, preferably 1 ,0 g/cm3 to 2,5 g/cm3. Density of 1,5 g/cm3 to 2 g/cm3 and/or ash value between 30% to 90%, preferably 40% to 80%, and/or elongation at break between 200% to 700%, preferably 300 to 600%, and / or preferably between 5 MPa and 50 MPa, preferably between 10 MPa and 30 MPa. In a preferred application of the invention, the elongation at break and breaking force are provided by using PBAT as a petroleum-based biopolymer and preferably when mixed at a rate of 30 to 70%, preferably 40% to 60%.

In a preferred embodiment of the invention, the moisture content of the petroleum-based biodegradable polymer A or the bio-based biodegradable polymer C in the polymer composition described above is less than 0,03%, preferably 0,01% to most preferably 0,00%.

A preferred embodiment of the invention comprises the application of a film produced with the polymer composition described above.

A preferred embodiment of the invention comprises a thermoform application produced with the polymer composition described above.

In a preferred embodiment of the invention, the components of the polymer composition described above consist of food contact materials.

A preferred embodiment of the invention comprises an injection mold application produced with the polymer composition described above.

In one embodiment of the invention, the following steps are applied for the production of the polymer composition: Mixing using a device capable of obtaining a polymeric mixture of at least one continuous system or at least one semi-continuous system or a batch system - while the addition of the inorganic additive component to the composition, cutting through the head in the twin screw extruder, -adjustment of predetermined parameters according to the characteristics of the inorganic additive. Thus, during mixing of the polymer mixture with the dense inorganic additive, the mixture is provided effectively, and the conformity of the additive is facilitated.

DETAILED DESCRIPTION OF THE INVENTION

In this detailed explanation, the embodiments of the invention and its preferred applications are explained only for a better understanding of the subject matter and without any limiting effect.

The invention is based on at least one biodegradable polymer A, also referred to as relatively high-resilience flexible biodegradable A, at least one relatively high-strength biopolymer (rigid) biodegradable polymer C, inorganic additive B, which can be increased up to eighty percent by mixture achieve the improvements in its cost advantage and environmentally friendly features mentioned above. The new polymer composition has improved the texture of the structure characterized by soft tissue compared to the individual polymer components. Moreover, such polymer composition is superior to conventional plastics and polymers, which suffer from non-degradation when disposed of in the environment.

In a preferred embodiment of the invention, said polymer composition is composed of suitable predetermined aliphatic or aliphatic and aromatic dicarboxylic acids and/or aliphatic dihydroxy compounds, esters, anhydrides or salts, suitable diol or diol mixtures and any polymeric mixture using typical polycondensation reaction conditions, PLA polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyhydroxybutyrate-valerate (PHBV), polyhydroxybutyrate-hexanoate (PHBH), polyhydroxyhexanoate (PHH), polyglycolide, cellulose acetate and sand, granite, limestone, It is easily prepared from inorganic additives such as sandstone, mica, clay, kaolin, silica, calcium carbonate, calcium hydroxide, calcium sulfate, talc, and ceramics. In addition, Aliphatic or aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds: Polybutylene adipate terephthalate (PBAT), polybutylene sebacate terephthalate (PBST), polybutylene succinate (PBS), polycaprolactone (PCL) may also be utilized.

In a preferred application of the invention, suitable input parameters of the mixture are adjusted to form the following polymer composition in the devices used in the production of the polymer composition given in Example 1 and Example 2 below.

The moisture content of the polymers is preferably adjusted to be less than 0,03%. The particle size of the inorganic additive component B is preferably adjusted to a maximum of 20 microns. In a preferred application of the invention, all input components are selected from food contact materials.

The glass transition temperature of the flexible biodegradable polymer A of the subject matter is preferably chosen below -10 C. The elongation at break of the flexible biodegradable polymer A is preferably set to be equal to or greater than 500%. The tensile strength of the flexible biodegradable polymer A is preferably adjusted to be equal to or greater than 18 MPa. The bulk density of the flexible biodegradable polymer A is preferably adjusted to be approximately 0,7 g/cm3. The melting point of the flexible biodegradable polymer A is preferably set to be 110-120°C. The melt flow index of the flexible biodegradable polymer A is set to a maximum of 5 g/10 minutes. It is preferred that the flexible biodegradable polymer A has high elongation. Biodegradable structure allows the polymer composition to be recycled in nature.

The glass transition temperature of the hard biodegradable polymer C is set to be greater than 10 °C. The melt flow index of the hard biodegradable polymer C is set to be approximately 3 g/10 min.

The hard biodegradable polymer C is set to be more than 90% L-isomer. The melting point of the hard biodegradable polymer C is set to be a minimum of 150 °C. The tensile modulus of hard biodegradable polymer C is set to be 3500 MPa. The tensile strength of the hard biodegradable polymer C is set to be a minimum of 45 MPa. The shrinkage at break of the hard biodegradable polymer C is set to a maximum of 5%. Biodegradable polymer C is compostable allows the polymer composition to be recycled in nature due to the compostable structure. At the same time, the rigid polymer C provides hardness to the polymer composition obtained in the invention.

Example 1

Polymer (A), which can be characterized as "flexible" in general, has a glass transition temperature below 0°C, and said flexible biodegradable polymer A can preferably have a glass transition temperature of less than -10°C in other applications of the invention.

In an exemplary polymer composition of the invention, "flexible" defined as these polymers with a glass transition of 0°C and lower, preferably in the range of 15% to 45% by weight, more preferably in the range of 20% to 30% by weight, more preferably in the range of 23% to 29 is mixed at a higher concentration than the other polymer component B, based on the total weight of the polymer mixture.

For example, polylactic acid (PLA), thermoplastic starch, and cellulose acetate are examples of biobased polymers. Polylactic acid (PLA) thermoplastic starch TPS and cellulose acetate are examples of biobased plastics. Biodegradation is a chemical process in which living organisms such as microorganisms transform these polymers into natural substances such as water, carbon dioxide (CO2) and compost. No additives are required for these processes.

Additionally, environmental effects such as the component of the polymer, the temperature and humidity of the environment determine the duration of the biodegradation process. Apart from bio-based polymers, it is found in biodegradable polymers that are widely used, such as PBAT and PCL, which are petroleum-based and synthesized by biomass production method. Poly(butylenadipate-co-terephthalate) (PBAT) is an aliphatic-aromatic copolyester whose monomers are 1 ,4-butanediol, adipic acid and terephthalic acid. Being a flexible, hydrophobic and completely biodegradable material allows it to be used in the production of films and packaging. In a preferred embodiment of the invention, PBAT has an average length of n< 3, and the average length of aromatic units is added to the polymer composition of the invention when and/or the amount is less than 60% by mole.

Example 2

In an exemplary polymer composition of the invention, "flexible" defined as these polymers with a glass transition of 0°C and lower, preferably in the range of 20-40% by weight, more preferably in the range of 32% by weight, preferably more in the range of 33% to 35% by total weight of the polymer mixture, mixed in a pure concentration as flexible biodegradable polymers without any addition of other polymer component C.

In particular, the breathability and soft tissue properties of the product subject to the invention will be beneficial in film applications in areas such as diapers and adult diapers. Bioplastics are a large family of different materials. Bioplastics are not just a single substance, but constitute a family of materials with various properties and applications. For a plastic material to be defined as a bioplastic, it is expected to have at least one of the properties of biodegradability and bioavailability.

The production of the invention can be done with a device with a batch operation options as a continuous, semi-continuous and batch process and can use various types of reactors. Examples of suitable reactor types are stirred tank, continuous stirred tank, slurry, tubular, wiped film, failed film or extrusion reactors, but are not limited to these as they may also be produced by advanced manufacturing methods.

As used herein, the term "continuous" means a process in which reactants are introduced and products are withdrawn simultaneously in a continuous manner. By "continuous" means that the process is substantially or completely continuous. Normal interruptions in the continuity of the process due to topping up the desired quantity in the production of the polymeric compound product, reactor maintenance or timed shutdown times are not inherently an impediment to replace "Continuous". The "batch tank" process as used herein is where all the reactants are added to the reactor and then each material is introduced at a predetermined rate into the feed or directly into the reactor. The term "semi-continuous" means a process in which some reactants are added all at once at the start of the reaction, and the remaining reactants are fed continuously as the reaction progresses.

Alternatively, a semi-continuous process may include a process similar to a batch process in which all reactants are added at the start of the process, except that one or more of the products are continuously removed as the reaction progresses. The process is advantageously run as a continuous process for economic reasons.

For example, polybutylene adipate terephthalate (PBAT), a typical biopolyester, is a synthetic degradable plastic. Poly (butylenadipate-co-terephthalate) (PBAT) is an aliphatic-aromatic copolyester whose monomers are 1,4-butanediol, adipic acid and terephthalic acid. Being a flexible, hydrophobic and completely biodegradable material, it is used in the production of films and packaging. The mechanical properties of PBAT are similar to low density polyethylene (LDPE). Lyphatic esters have the property of degrading in the presence of enzymes. The degradation of aliphatic esters generally begins with the enzyme-catalyzed hydrolysis of ester bonds. This process, which is the first step of depolymerization, takes place as surface wear because enzymes cannot penetrate into the polymer pile. Finally, water-soluble intermediates resulting from degradation are metabolized by microorganisms. Aromatic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN) have very low degradation rates as they are not susceptible to microbial or enzymatic attack. In the state of the art, it is known that the degradation of PET fibers in human and animal bodies lasts for 30 years. Polybutylene succinate (PBS) is similar to thermoplastic aliphatic polyesters in properties such as biodegradability, melt processing, and thermal and chemical resistance.

In a preferred application of the Example 2 mixture of the invention, less than 40% mole of PBAT and/or its amount is added to the polymer composition of the invention. In one embodiment of the invention, Polycaprolactone (PCL) is a synthetic polymer that can be degraded by microorganisms. PCL, obtained by ring-opening polymerization from caprolactone formed by the oxidation of cyclohexanone, is a polycaprolactone synthetic aliphatic polyester, obtained by ring-opening polymerization of caprolactone monomer. PCL is compatible with many polymers, making it the most hydrophobic biodegradable polymer available. It is obtained as a result of polymerization of e-caprolactone by ring opening method. It has a hydrophobic, semi-crystalline structure; It is chosen because of the properties of a polymer with adjustable pore size, degradation rate, good mechanical properties and easy to process.

Polybutylene succinate (PBS) is an aliphatic thermoplastic polyester formed by the condensation reaction of 1 ,4-butanediol and succinic acid. PBS is a biodegradable, easily processable, thermal and chemical resistant polymer.

In the invention, PBS, which is preferably white in color and in crystalline form, is between PE and PP in terms of tensile strength; In terms of hardness, it is chosen because it has values between DYPE and HDPE. In the exemplary application of the invention, in order to increase the degradation rate of PBS; It is copolymerized with adipate to increase its biodegradability. Poly(butylene succinate-co-adipate) (PBSA) obtained by the reaction of glycols with aliphatic dicarboxylic acids is selected. In the invention, aliphatic-aromatic copolymers are selected for the desirable biodegradability of the aliphatic unit and good mechanical properties in the structures of the aromatic unit. 1-3 Poly(butylenes succinate- co-terephthalate) (PBST) is one such copolymer. In the practice of the invention, pure and mixed PBST is chosen because it exhibits the desired tensile strength and elongation at break.

The difficulty of mixing a high proportion of inorganic additives into the polymer composition and completely absorbing this mixture is easily solved in one embodiment of the invention by head cutting in a twin screw extruder machine. Machines and devices with similar functions can be used in alternative applications of the invention. With the superior appearance properties of the polymer composition formed, a structure that distinguishes it from its counterparts is obtained. For this, it is provided by a controlled extruder at high temperature. By keeping the components controlled at a high temperature in the mentioned reactors, they have excellent appearance properties, and the occurrence of deterioration is prevented.

Bioplastics are a large family of different materials. Bioplastics are not just a single substance but constitute a family of materials with various properties and applications. For a plastic material to be defined as a bioplastic, it is expected to have at least one of the properties of biodegradability and bioavailability. For a plastic to be biobased, it must be completely or partially derived from biomass. Bioplastics are polymers that are biobased, biodegradable, or both.

The polymer of the invention is bio-based as it can turn into carbon dioxide and water when exposed to microbial decomposition in industrial or public compost facilities. The said decomposition ensures degradation by microorganisms and enzymes. When the biological process is complete, the polymer composition of the invention transforms into C02, water, inorganic compounds and biomass that leaves no visible pollutants or toxic residue/matter. An alternative statement could be the effect of 'technical plastics and living organisms' that will completely decompose into carbon dioxide, methane, water, biomass and inorganic compounds under aerobic or anaerobic conditions.

Biodegradable polymers cover a wide range of high molecular weight compounds. It is important to distinguish between biodegradable polymers, often of natural and synthetic origin.

Natural biodegradable polymers are the result of a synthesis developed during millions of years of evolution, which has led to materials tailored for different applications in nature. These biopolymers include proteins, polysaccharides, nucleic acids or lipids that exhibit completely different properties depending on the situation in which they are used. Biodegradation, or the breakdown of chemical substances by living organisms, is one of the most important processes that determine the fate of organic chemicals in the environment. Microorganisms, especially bacteria and fungi, play an important role in biodegradation due to their abundance, species diversity, catabolic versatility and ability to adapt to a wide variety of environmental conditions. Biodegradation can occur under both aerobic and anaerobic conditions. In the natural environment, the former occurs in soil or water where oxygen is present, while anaerobic degradation occurs in sediments or groundwater where oxygen is generally absent. Both aerobic and anaerobic processes may be involved during the biodegradation that takes place in treatments. Unlike other environmental fate processes such as hydrolysis or photochemical reactions, biodegradation is unique in that ultimately organic matter is completely converted into inorganic products (for example, carbon dioxide and water).

Complete destruction is often referred to as ultimate degradation or mineralization. Alternatively, a single change of parent compound is sufficient for primary degradation. Complete degradation is often the end result, as biodegradation in natural environments results from the concerted actions of multiple microbial populations with different metabolic abilities. Biodegradation is an important natural process that converts chemicals released into the environment into other chemicals and eventually carbon dioxide. Most hydrocarbons and aerobic solvents have been shown to be biodegradable and do not persist in the environment.

In one embodiment of the polymer composition of the invention, the polymer composition may have a variable bio-based content. Different ratios of polymeric blend combinations can be used to adjust the content of the bio-based portion.

In one embodiment of the polymer composition of the invention that is biodegradable, blown film will be used for extrusion.

In one application of the polymer composition of the invention that is biodegradable, packaging films will be used for hygienic films.

In an application of the polymer composition of the invention that is biodegradable, it will be used for fertilizer and chemical storage bags. Some characteristic physical properties of the polymer composition of the invention are given below. The United States, European Union A and OECD countries have developed a series of laboratory screening tests that can be used to determine the "ready" and "natural" biodegradability of organic compounds. In such tests, deterioration is usually monitored by measuring the loss of dissolved organic carbon, oxygen consumption (biological oxygen demand), or carbon dioxide formation. In another embodiment of the invention, the polymeric compound can be dissolved in hot water. In another embodiment of the invention, it contains 100% edible raw material. In another embodiment of the invention, there is high carbon content and high thermostability. In another embodiment of the invention, it has excellent heat sealing properties. Such tests are usually performed using higher concentrations of microbial innoculum, higher concentrations of test chemicals, and are performed under conditions that allow the climate of microorganisms. Chemicals that pass a natural biodegradability test are considered non- persistent, even though the chemical's degradation in the environment is slow. The European Standard EN 13432 defines the minimum requirements that packaging must meet in order to be processed with industrial composting. Here, biodegradability: that is, the ability of compostable material to be converted into CO2 under the influence of microorganisms. The standard includes a mandatory threshold of at least 90% biodegradation, which must be reached in less than 6 months. Disintegrability is also defined as the final compost, that is, fragmentation and invisibility. It is measured in a pilot scale composting test in which samples of the test material are composted with biowaste for 3 months. After this time, the mass of test material residues > 2mm will be less than 10% of the original mass. No adverse effects are expected during composting in the test process.

The polymer composition of the invention can reduce carbon dioxide emissions by 30-70% compared to conventional plastics. Green chemistry or sustainable chemistry can be understood as the design of chemical products and processes that reduce or eliminate the use or production of substances that are hazardous to humans, animals, plants and the environment, where energy efficiency must be high and the waste target must be zero; as a result, costs should also be low.

In a variety of applications, bio-based materials show performance benefits over their petroleum-derived counterparts. The granule should be stored in closed PE-inliner bags or aluminum foil bags in a cool, shaded and dry place. Humidity control is expected during storage.

Therefore, after opening the bag, the material must be dried before use. Subsequent to these recommendations, the polymer composition can be used within 6 months after production. The granule should be kept in closed aluminum bags in a cool, shaded and dried form. In an opened bag, the material should be dried for 3-5 hours, preferably 4 hours, preferably at 80°C before use. Storage time in a sealed bag provides a 6-month lifespan at room temperature (23°C).

Claims

1. A polymer composition comprising at least one component A selected from petroleum-based biodegradable polymers in a weight ratio between 15% to 75%, at least one component B selected from an inorganic additive material in a weight ratio of between 35% to 85% to at least one component C selected from biodegradable polymers preferably from biobased polymers with a weight ratio between 0 to 25%.

2. A polymer composition according to claim 1 wherein,

- at least one component A of petroleum-based biodegradable polymers is selected from group of

• flexible biodegradable polymers or mixtures thereof comprising aliphatic or aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds of polybutylene sebacate terephthalate (PBST), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polycaprolactone (PCL), more particularly polybutylene adipate terephthalate (PBAT),

- at least one component B of the inorganic additive selected from group comprising;

• sand, granite, limestone, sandstone, mica, clay, kaolin, silica, calcium carbonate, calcium hydroxide, calcium sulfate, talc, ceramic materials or mixtures thereof,

- at least one component C of bio-based polymers, preferably hard biodegradable polymers selected from group of polymers coprising;

• polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyhydroxybutyrate-valerate (PHBV), polyhydroxybutyrate-hexanoate (PHBH), polyhydroxyhexanoate (PHH), polyglycolide, cellulose acetate, or mixtures thereof.

3. A polymer composition according to claims 2, wherein PBAT is selected as at least one component A of petroleum-based biodegradable polymers with a weight ratio between 15% to 45%, preferably between 20% to 40%, preferably between 23% to 29%; calcium carbonate (CaC03) selected as at least one component B from inorganic additives, between 35% to 85%, preferably between 40% to 80%, more preferably between 60% to 70%, and PLA polymer as at least one C component as bio-based polymers preferably hard biodegradable polymers with a weight ratio between 0% to 25%, preferably 5% to 20%, more preferably 5% to 10%.

4. A polymer composition according to claims 1-3, wherein the particle size of at least one of the component B of the inorganic additive is 15-25 micron, preferably 18-22 micron.

5. A polymer composition according to claims 1 to 4 wherein; the glass transition temperature of a petroleum-based preferably flexible biodegradable polymer as the component A is less than -10°C, preferably between -15°C to -35°C and/or melt flow index between 1 g/10 and 10g/10 min, preferably 5 g/10 minutes and/or polymer bulk density is between 0.5 g/cm³ and 1 g/cm³ preferably 0.7 g/cm³ and/or its melting point is between 100°C to 190°C, preferably 110°C to 120°C.

6. A polymer composition according to claim 5, wherein the tensile strength of component A, preferably a petroleum-based, flexible biodegradable polymer, is between 7 MPa and 70 MPa, preferably between 18 MPa and 65 MPa, and/or breaking strain is more than 500%, between 500 to 550%.

7. A polymer composition according to claims 1 to 6, wherein the glass transition temperature of component C as a bio-based preferably hard biodegradable polymer is preferably greater than +10°C, preferably between +45°C to +70°C and/or melt flow index between 1 g/10 and 5g/10 min, preferably 3 g/10 minutes and/or melting point is between 120°C and 180°C, preferably between 135°C and 155°C.

8. A polymer composition according to claim 8, wherein the tensile modulus of component C of bio-based preferably hard biodegradable polymer is between 2500 MPa and 4000 MPa, preferably 3500 MPa, tensile strength is 40 to 60 MPa, preferably 45 MPa, and/or the tensile amount at break is between 0 and 20%, preferably below 6%.

9. A polymer composition according to claim 8, wherein at least one component C selected as PLA as a bio-based preferably hard biodegradable polymer is comprising L isomer between 75% to 100%, preferably more than 80%.

10. A polymer composition according to any one of the preceding claims, characterized in that; the polymer composition is having

- a melt flow index between 0g/10 and 20g/10 min, preferably between 0g/10 and 10g/10 min, and/or - a density of 1.0 g/cm3 to 2.5 g/cm3 preferably 1.5 g/cm3 to 2 g/cm3 and/or

- 30% to 90%, preferably 40% to 80% ash value, and/or

- elongation at break between 30% to 70%, preferably 40% to 60% to when mixed 200% to 700%, preferably between 300 and 600%, and/or

- a breaking strength of 5 MPa to 50 MPa, preferably 10 MPa to 30 MPa.

11. A polymer composition according to any one of the preceding claims, wherein moisture content of component A of petroleum-based biodegradable polymer or of component C of a bio-based biodegradable is less than 0.03%, preferably 0.01% to especially preferably 0.00%.

12. A polymer composition according to any one of the preceding claims, wherein the components of this polymer composition are made of food-contact suitable materials.

13. A polymer film obtained by the polymer composition according to one of the preceding claims.

14. A thermoforming application obtained by the polymer composition according to one of the preceding claims.

15. An injection mold product obtained by the polymer composition according to one of the preceding claims.

16. A production method for the polymer composition according to any one of the preceding claims, comprising the steps of

- mixing using a device capable of obtaining a polymeric mixture of at least one continuous system or at least one semi-continuous system or a batch system

- while the addition of the inorganic additive component to the composition, cutting through the head in the twin screw extruder.