SK8663Y1 - Biodegradable polymeric mixture - Google Patents

Abstract

A biodegradable polymer blend comprises at least one component (A), at least one component (B) and at least one component (D), wherein component (A) comprises polymers based on lactic acid, component (B) comprises thermoplastic starch TPS and component (D) comprises homopolymers or copolymers of polyhydroxyalkanoates PHA and/or mixtures thereof. The biodegradable polymer blend may optionally comprise component (F), which includes plasticizers for polylactic acid PLA and/or for polyhydroxyalkanoate PHA.

Description

Technical field

The invention relates to biodegradable polymer compositions having improved mechanical properties.

BACKGROUND OF THE INVENTION

The interest in biodegradable polymers, especially from renewable sources, is steadily increasing, mainly for two reasons: environmental concerns with applications mainly in agriculture and packaging, but also the awareness of the depletion of oil resources. An important class of such polymers are also bacterial polymers of PHA polyhydroxyalkanoates, in particular poly-3-hydroxybutyrate and its copolymers. In addition, the use of polylactic acid, in particular polylactic acid, has been increasing in recent years. polylactide in all forms and combinations of optically active isomers of lactic acid, which is produced from agricultural products and is readily biodegradable. The lactide is a cyclic dimer prepared from lactic acid, which is obtained by fermentation of starch or sugar from various sources (L. Yu et al. / Pro. Polym. Sci. 31, 576-602; 2006). PLA has been a polymer for many years, but until the monomer preparation technology from agricultural raw materials has improved its economy, today it is at the forefront of the biodegradable plastics industry (Y. Tokiwa et al., Int. J. Mol. Sci., 10, 3722-3742 ; 2009).

A special class of polyesters, called polyhydroxyalkanoates PHA, is naturally produced by a wide range of microorganisms, which serve as a source of carbon and energy. Poly-β-liydroxybutyrate PHB as a polymer from the PHA group has been studied in the scientific literature (since the beginning of the last century) rather than a curiosity. Only in connection with the environmental aspects of the manufacture and application of plastics did research lead to the commercialization of PHB, in particular P3HB and some other poly hydroxyalkanoates. especially copolymers PHBHx, most commonly PHBHV and P3HB4HB. The brittleness of PHB was improved by copolymerization of β-liydroxybutyrate with β-liydroxyvalcate (EP 0052459). Although polyhydroxyalkanoates can be processed on conventional thermoplastic processing machines, the problems in their processing limit their commercial applications. This is related to the limited processing conditions, mainly due to its low thermal stability and relatively slow crystallization kinetics. Another limiting factor for the wider use of PHAs is their relatively high cost.

Another important polymer from natural sources, which has been the subject of research for many years for its use in technical applications, is starch. A disadvantage of starch for thermoplastic processing is that it degrades below the melting point. Starch is found in parts of plants in the form of starch semicrystalline granules, which consist of two polymers, namely the bed and amylopectin. Natural unmodified starch is not thermoplastic because of its thermal decomposition prior to melting. Natural starch can therefore only be used as a particulate filler in polymer blends. On the other hand, the natural starch may be modified to form a thermoplastic material. The modification of natural starch to thermoplastic starch TPS is based on processes which, by the action of heat, shear and plasticizers, transform starch into its thermoplastic form. Because of its high hydrophilicity and sensitivity to atmospheric humidity, it is often mixed with other, especially hydrophobic, polymers. TPS-containing polymeric materials have a relatively broad application potential. They can be used for the production of food packaging materials, foils, injection molded products and various technical moldings. The main limitations of TPS for its mass application are high moisture sensitivity and low strength. Therefore, research in this field aims to address the shortcomings of TPS itself, in particular by mixing TPS with other polymers, adding nanofillers to the starch matrix, applying various types of plasticizers, modifying the starch itself by introducing various functional groups, reducing the starch molecular weight, and the like. TPS can be prepared in principle by two technological processes, either by casting from aqueous starch solutions or by melt plasticization during extrusion. In the case of casting from the solution, the suspension of the mixture of starch, plasticizers and other additives is heated to gelatinize the starch grains and then poured onto a flat support, cooled, dried and the resulting TPS granulated (Koch K. et al., Int. J). Biol. Macromol., 46, 13-19, 2010). This method is more suitable for laboratory research, for industrial practice almost exclusively extrusion is used. In the case of extrusion technology, the most common mixture of starch and plasticizer is fed to the extruder, whereby during extrusion at elevated temperature and under the action of shear forces, starch grains are destroyed, thereby forming an amorphous continuous starch phase. Residual water in the starch, together with a plasticizer, which is most often a diol or polyol, usually glycerol, interacts with starch via hydroxyl groups. Thus, under the given conditions, starch becomes melt and flows like synthetic plastics (Moscicke L., et al., Food Res. Int., 47, 291-299, 2012). Thanks to suitable plasticizers, it is possible to prepare TPS which can then be processed by conventional plastics processing technologies. Water is the best plasticizer for starch, followed by glycerol, ethylene glycol, sorbitol, fructose, glucose, urea and amino acids (Abdorezza M.N. et al. Food Hydrocolloid, 25, 56-60, 2011). According to (Zhang, Y, Han, J.H.,

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J. Food. Sci., 71, E109-E118, 2006), glycerine can be considered to be the best and at the same time usable plasticizer for starch in the art.

BACKGROUND OF THE INVENTION Various biodegradable and renewable-based materials are known from the state of the art and processes for their processing e.g. by extrusion, the resulting materials often resulting from mixtures of polymeric components with adequate morphology given by the distribution of the components, their dispersion and their interaction. Polymeric mixtures are the physical or mechanical mixtures of two or more polymers and other additives, in particular fillers, antidegradants, nucleating agents, or other additives. The preparation of polymer blends is often the only way to obtain polymer materials with properties that individual polymers cannot provide by themselves. Most often, polymer blends are used as construction plastics in applications, particularly in the automotive, electronics and electronics industries. They are usually polymer blends formed from conventional polymers (polymers based on raw materials from fossil sources, especially oil and natural gas). Natural polymer blends usually improve some of the utility properties of pure ingredients, with the aim of extending the use of natural polymer polymers for higher value-added products (many applications of biomaterials in medicine), with a view to being used in packaging, especially for special food packaging. Polymer blends often address improvements in processing properties in addition to performance settings. All three mentioned groups of biodegradable polymers - PLA, PHA - especially PHB and TPS have many disadvantages as individual polymers, which limit their application in common practice. PHA, especially PHB, are highly sensitive polymers for thermal degradation during melt processing and also for hydrolytic degradation in the presence of compounds containing OH groups. The authors (Janigová, I. et al. Polymer Degradation and Stability, 77, 35-41, 2002) found that the degradation of PHB is significantly accelerated by the presence of glycerin, which is a stronger prodegradant than water, since it leads to much faster alcoholysis of PHB ester bonds chain such as the rate of hydrolysis due to the presence of water. An even more potent prodegradant causing PHB alcoholysis is ethylene glycol (Spitalsky Z., et al. Polymer degradation and stability, 91, 856-861, 2006). TPS, PLA and PHB as biodegradable polymers from renewable natural resources are destined to produce environmentally acceptable, plastic materials with excellent performance properties, but on the other hand these polymers themselves are fragile with minimal ductility, limiting their potential applications. PLA and PHB are highly brittle, although rigid polymers and the manufacture of flexible products, especially packaging thin films, are problematic. TPS itself is fragile and very sensitive to relative humidity. In addition, PLA and PHA, including PHB, are considerably more expensive compared to synthetic polymers, while TPS is inexpensive. Of all the three mechanical properties, their fragility can be considered the greatest deficiency. Numerous processes have been published to improve the toughness of PHBs. The most effective are copolymerization of β-hydroxy bulbitite with β-hydroxyxyvalerate (Holmes et al., EP 0052459; 1982), or other higher homologues of poly hydroxyalkanoates. However, this procedure results in a relatively significant increase in the cost of the material (Organ S.J., Barham P.J. J. Mater. Sci. 26, 1368, 1991). Another possibility is the addition of a plasticizer, but the effect achieved is relatively small and insufficient without further adjustments (Billingham N.C., Henman T. J., Holmes P. A. Development in Polymer Degradation 7, chapter 7, Elesevier Sci pub., 1987). Theoretical study of PHB / PLA mixtures has shown that the mechanical properties are somewhere between the properties of the individual components. In addition, most of these mixtures cannot be simply mixed with other polymers, resulting in reduced mechanical properties (T. Yokohara and M. Yamaguchi, Eur. Polym. J. 44, 677-685; 2008). The blending of brittle PHA polymers, especially PHBs with different types of PLAs, leads to an improvement in the processing stability of these materials compared to the PHAs themselves, especially PHBs. PLA and PHA mixtures are not yet commonly used in practice, mainly due to their limited processability and insufficient mechanical properties. On the other hand, both types of polymers are perspective and based on theoretical studies, it can be concluded that their mixtures have great potential for use in special applications, for example in food packaging. The improvement of the mechanical properties, in particular the improvement of the toughness, is solved by the invention according to the application (WO 2012/141660 A1), where a significant improvement of the toughness, brittle PLA and PHA, especially PHB is achieved by combining them together with at least one ester type plasticizer in suitable concentration ratios. Further improvement in the toughness of such mixtures is achieved by the application of Joncryls. Surprisingly, the combination of brittle polymers produces a tough material.

Efforts to develop environmentally friendly materials that at the same time meet the demanding technical performance and cost-effectiveness requirements have led to the development of partially or totally biodegradable polymer compositions obtained by combining synthetic non-biodegradable or synthetic biodegradable polymers and TPS. These include, in particular, mixtures of TPS in combination with PE, EVOH, PCL, PBS, PBAT, PVA and other synthetic polymers and combinations thereof. These include, for example, the solutions of (US 9156980 B2), (US 8889945 B2), (US 8846825 B2), (US 9327438 B2)

The mixing of TPS with PHA, especially with PHB and its copolymer, is particularly problematic because the polyols, most commonly glycerin contained in TPS, cause intense alcoholytic degradation of the PHA chain, resulting in a sharp decrease in the viscosity of the PHA matrix and thus of the mixture. there is a significant decrease in the processing stability of the mixture and at the same time there is a decrease in the mechanical properties of the resulting product. Nega

The effect of polyols on PHA, especially glycerin and polyethylene glycol, has been described in the aforementioned papers (Janigová, I. et al. Polymer degradation and stability, 77, 35-41, 2002) and (Spitalský Z., et al. Polymer degradation and stability, 91, 856-861, 2006).

The main drawbacks of the blend based on biodegradable polymer materials, in particular from renewable sources, based on the state of the art in the field, can be identified as follows:

1. The required processing stability of such mixtures, as well as the appropriate mechanical properties, are achieved by the addition of synthetic polymers, most recently in particular PBAT, which reduces the overall ecological value and the ecological safety of these materials.

2. Solutions that lead to technically acceptable materials are costly and are not able to compete effectively on the market with synthetic non-biodegradable but also synthetic biodegradable materials.

3. Starch, often in plasticized form of TPS, is often used as a constituent of the costly ecological polymers, but this results in a significant deterioration in the processing and mechanical properties of these materials, particularly those containing PHA.

4. The application of TPS, which contains polyol as a plasticizer in materials in which PHA is present, causes a dramatic decrease in processing stability and mechanical properties, making it impossible to introduce them into normal industrial practice.

The essence of the technical solution

The aforementioned drawbacks of hitherto known organic polymer blends are solved by the blend of the present invention, wherein the biodegradable polymers obtained or made from renewable raw materials are used as polymer components, further using the blend of PLA and PHA, preferably a tough blend of the invention (WO 2012/141660 A1) to which TPS and a modifier are added, the TPS being formed directly in the process of mixing with the PLA and need not be dried before mixing with the PHA. This effectively disperses the TPS in the matrix of biodegradable polymers. A PLA / PHA / TPS mixture with good processing stability and good mechanical properties is obtained. Surprisingly, according to the invention, a homogeneous mixture is formed comprising simultaneously PHA and TPS, which has improved mechanical properties. The desired effect can only be achieved if the PLA / PHA / TPS mixture also contains a suitable modifier and is prepared according to a process in which the modifier is added to the starch / PLA mixture before it is added to the PHA mixture. Despite the well-known fact that plasticizers for TPS based on OH-containing substances (especially glycerol and other OH-containing organic substances) cause severe degradation of PHA and thus deteriorate the mechanical properties of PHA, the present invention surprisingly makes it possible to prepare a homogeneous mixture containing PHA and TPS simultaneously. plasticized with substances containing OH groups, the resulting material prepared according to the invention having improved mechanical properties.

The compositions according to the invention are to have an improved tensile strength at break and / or an improved relative elongation at break. It is an object of the present invention to provide a homogeneous biodegradable polymer blend with improved mechanical properties. For the purposes of the invention, the terms used herein will have the following meanings:

starch

Starch is a substance stored in plants by a photosynthetic assimilation process and is a mixture of amylose and amylopectin, which may contain, in addition to these polymers, a small amount of lipids, proteins and a limited amount of water. For purposes of the invention, starch is starch in the form in which it is obtained from plants by mechanical milling and scrubbing without any further chemical or physical treatment. For the purposes of the invention, starch is further understood to mean starch obtained from any plant, for example, maize, potatoes, cereals, rice, amaranth and other plants.

Component (A)

The term component (A) includes lactic acid polymers, in particular PLLA, PDLA homopolymers, as well as copolymers thereof, or mixtures of homopolymers thereof, mixtures of homopolymers and copolymers thereof, or mixtures of their copolymers, preferably PLA polymers having a relative elongation at break equal to or less than 10%, preferably equal to or less than 5% and further preferably equal to or less than 3%, wherein the determination of the relative elongation at break is carried out according to the methodology described in the description of the invention.

Component (B)

The term component (B) includes thermoplastic starch TPS representing a mixture of starch, at least one plasticizer from the group of substances (C) and at least one modifier from the group of substances (E), wherein

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- the substance group (C) comprises plasticizers for starch which are selected from the group of substances: mono-, di- and polyhydric alcohols and polyols, in particular glycerin, ethylene glycol, propylene glycol, diols, triols and polyols, polyethylene glycol, polypropylene glycol, neopentyl glycol, sorbitol mannitol;

- the group of substances (E) comprises modifiers selected from the group of substances: saturated or unsaturated carboxylic, dicarboxylic, tricarboxylic or polycarboxylic acids, saturated or unsaturated anhydrides, dianhydrides and polyanhydrides, and solid carboxylic acid anhydrides, substances containing isocyanate groups, preferably diisocyanates, preferably diisocyanates substances containing epoxy groups, carboxylic acid halides, acylimidazoles, acyl phosphates, acid thioesters or a combination thereof.

Component (D)

The term component (D) includes homopolymers or copolymers of PHA polyhydroxyalkanoates and / or mixtures thereof, being PHB homopolymers or copolymers and / or mixtures thereof, further preferably P3HB homopolymers or copolymers and / or mixtures thereof preferably when the P3HB-based copolymers are P3HB4HB copolymers, preferably PHA homopolymers or copolymers with a relative elongation value equal to or less than 10%, preferably equal to or less than 5%, further preferably equal to or less than 3%, wherein the determination of the relative the elongation at break is performed according to the methodology outlined in the description of the invention.

Component (F)

The term component (F) includes PLA and / or PHA plasticizers selected from the group of: esters and low viscosity polyesters, especially esters or low viscosity polyesters of citric acid, esters or low viscosity polyesters of glycerin, esters or low viscosity polyesters of diols and polyols, esters or low viscosity phosphoric acid polyesters, esters or low viscosity sebacic acid polyesters, esters or low viscosity adipic acid polyesters, esters or low viscosity halic polyesters and other liquid esters and / or low viscosity polyesters and copolyesters, or mixtures thereof, wherein the viscosity and plasticizer / PLA The PHA (component (F)) measured at 25 ° C according to the process of the disclosure is less than or equal to 20,000 mPas, preferably less than or equal to 5,000 mPas, further preferably less than or equal to 3000 mPas.

Substance group (G)

The term substance group (G) includes additives to modify the processing and / or performance properties of the mixture, wherein the substance group (G) includes inorganic or organic fillers, compatibilizers and interfacial agents, pigments and dyes, nucleating agents, processing aids, anti-blocking and glidants, cross-linking agents, blowing agents, antistatic agents, flame retardants, antidegradants and other additives and modifiers including polymers and oligomers to modify the processing and / or utility properties of the mixture.

Mixing process

The term mixing process includes the process of mixing at least two components of the mixture in one or more mixing devices intended to prepare polymer blends, wherein the mixing devices may be, for example, single screw or twin screw extruders, the mixing process being completed when the final blend is formed. of the last mixer is cooled and granulated. optionally directly may lead to an apparatus for producing finished products, for example extruded films.

Mixing step

The term mixing step is a mixing process to which the individual components enter under prescribed technological conditions at once or sequentially, depending on whether one or more phases of the mixing process take place in a single mixing step, the mixing step beginning with at least one component entering the mixing device and ending with the final a mixture or a mixture of at least two prescribed components from a mixing device.

Stage of the mixing process

The term mixing stage includes a mixing period of a prescribed number of components of a mixture, the mixing stage starting from the moment the prescribed components of the mixture enter the mixing device and end either by terminating or interrupting the mixing process or by entering the at least one component of the mixture into a continuous mixing process. The entry of at least one component into an ongoing mixing process always marks the beginning of the next phase of the mixing process.

Extrusion step

The term extrusion step represents a mixing step that takes place in an extruder, preferably in a single screw extruder, further preferably in a twin screw extruder.

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Dry mixture (Diyblend)

It is a dry mixture of at least two components which have been physically mixed at room temperature, whether or not liquid substances are mixed into the mixture.

The present invention is based on the preparation of a biodegradable polymer blend based on PLA, PHA and TPS, wherein the blend comprises at least 3 components: PLA (component (A)), PHA (component (D)), TPS (component (B)) and optionally a plasticizer for PLA and / or PHA (component (F)), wherein the TPS is based on a mixture of starch, a starch plasticizer (a substance of group (C)) and a modifier (a substance of group (E)). The solution according to the invention is characterized in that the most effective plasticizers for starch can be used as a plasticizer for the preparation of TPS, in particular alcohols and polyols, in particular glycerin, ethylene glycol, propylene glycol, diols, triol apolyols, polyethylene glycol, polypropylene glycol, neopentyl glycol, sorbitol, mannitol. The solution is further characterized in that compounds which have a high reactivity with OH groups are used as modifiers, in particular saturated or unsaturated compounds containing isocyanate, anhydride, carboxylic or cpoxy reactive groups, furthermore carboxylic acid halides, acylimidazoles, acylphosphates, thioesters of carboxylic acids acids, anhydrides of saturated or unsaturated carboxylic acids. The solution according to the invention is further characterized in that component (B) is present in the mixing process together with component (A) before it is added to the mixture of components (D). The use of modifiers which contain an unsaturated bond in the molecule, in particular a double bond, allows further modification of the mixtures thus prepared, e.g. crosslinking and / or vaccination, e.g. using peroxides. The solution according to the invention advantageously utilizes a PLA / PHA / plasticizer mixture as the polymers, wherein the plasticizer for PLA and / or PHA is an ester or a low viscosity polyester (component (F)). The solution according to the invention is then a mixture prepared from biopolymers comprising at least one PLA polymer (component (A)), at least one PHA polymer (component (D)) and TPS (component (B)), characterized by improved mechanical properties, wherein TPS ( Component (B)) is based on a mixture of starch, plasticizer (substance from group (C)) and reactive modifier (substance from group (E)).

The process for preparing a composition according to the invention is characterized by first mixing TPS (component (B)) and PLA and then adding PHA to the mixture, which process can be conducted as a single or multi-step mixing process, preferably single or multi-step extrusion, without the need to remove excess water from the melt before mixing PHA with TPS or PHA with TPS + PLA.

For the purposes of the invention, whenever any concentration expression of the composition of the mixture, the relative proportions of the ingredients of the mixture, or the percentage composition of the mixture is stated, it is always meant to be expressed in weight units.

The invention provides a biodegradable polymer composition with improved mechanical properties. The biodegradable polymer composition of the invention comprises at least one component (A), at least one component (B), at least one component (D), and may or may not comprise component (F). The biodegradable polymer blend of the invention solves blends comprising TPS - component (B) - wherein the ratio of the other two components of blend (A) and (D) is within a wide range, providing improved mechanical properties represented by relative elongation at break Eb and / or limit the tensile strength om, wherein the relative elongation at break Eb is greater than 100%, or the tensile strength om is greater than 15 MPa, preferably greater than 20 MPa, further preferably greater than 25 MPa.

The compositions according to the invention are characterized in that if they comprise only components (A), (B), (D) and optionally component (G), they have a tensile strength om equal to or higher than 15 MPa, preferably equal to or higher than 20 MPa, further preferably equal to or greater than 25 MPa, the relative elongation at break Eb being greater than or equal to 2.0%. If the compositions according to the invention comprise a component (F), they have a relative elongation at break Eb equal to or greater than 100%, the tensile strength being greater than or equal to 3.0 MPa, preferably greater than or equal to 5.0 MPa, preferably it is greater than or equal to 10 MPa.

The compositions of the invention are characterized in that if the relative elongation at break Eb is less than 100%, the tensile strength om is equal to or greater than 15 MPa, preferably equal to or greater than 20 MPa, preferably equal to or greater than 15 MPa. 25 MPa.

The compositions according to the invention are characterized in that when the tensile strength σ is less than 10 MPa, preferably less than 15 MPa, the relative elongation at break Eb is equal to or greater than 100%.

Said effect is achieved by a composition of the mixture wherein the ratio of components (A) / (D) is in the range from 5/95 to 95/5, preferably from 10/95 to 95/5, further preferably from 20/80 to 95/5 further preferably from 30/80 to 95/5, further preferably from 20/80 to 90/10, further preferably from 20/80 to 80/20, further preferably from 30/70 to 70/30.

This effect is achieved in that the amount of starch used in component (B) is such that the [(A) + (D)] / (starch) ratio is in the range from 97/3 to 40/60, preferably from 97/3 to 50/50, further preferably from 97/3 to 70/30.

Said effect is further achieved in that the amount of the substance of group (C) in component (B) is such that the ratio of the substance of group (C) / starch is at least 5/95, preferably at least 10/90, further preferably at least 20 / 80, further preferably at least 30/70, further preferably at most up to 40/60, further preferably up to 50/50.

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Said effect is further achieved in that the amount of the substance of group (E) is such that the ratio (E) / [starch + (C)] is at least 0.05 / 100, preferably at least 0.1 / 100, further preferably at least 0.5 / 100 and further preferably at least 1.1 / 100, further preferably up to 10/100, further preferably up to 5/100 and further preferably up to 3.0 / 100.

This effect is further achieved in that the mixture may or may not contain a substance of group (F). If the mixture comprises a substance of group (F), then in order for the mixture to achieve a relative elongation of at least 100%, the ratio of (F) / [(A) + (D)] is at least 5/95, preferably at least 7/93, further preferably at least 10 / 90, further preferably at least 15/85, further preferably at most 50/50, further preferably at most 40/60 and further preferably at most 30/70.

The biodegradable composition according to the invention may further comprise other substances for achieving the special, in particular processing and utility properties of the mixture, in particular of the group (G), such as e.g. inorganic or organic fillers, compatibilizers and interfacial agents, pigments and dyes, nucleating agents, processing aids, anti-blocking and glidants, crosslinkers, blowing agents, antistatic agents, flame retardants, antidegradants and other additives and modifiers including polymers andohomers.

The process for preparing the composition according to the invention is characterized in that any mixing device for the production of the polymer mixtures is used for the preparation of the composition, the preparation of the mixture can be carried out in one or more mixing steps, preferably in one or two steps, further preferably in one step. preferably extruders, preferably single-screw or double-screw extruders, are used as mixing devices.

Regardless of whether it is a one-step or multi-step mixing process, the process according to the invention is characterized in that component (B) is present in the mixture in at least one phase of the mixing process in which at least one component (B) is mixed simultaneously. and at least one component (A) and optionally component (F) and / or component (G) may be present. Such a mixing phase of the mixing process precedes at least one phase of the mixing process phase in which component (D) is added to the mixing process.

Thus, the preparation process is characterized in that component (D) is mixed into the mixture so as to add at least one phase of the mixing process later than at least one component (B) and at least one component (A) have been mixed together.

The solution according to the invention is further characterized in that the TPS component (B) is prepared by plasticizing starch in the process of preparing the mixtures and does not need to be prepared separately.

The method of preparing a composition according to the invention is further characterized in that if one or more components (F) are added to the composition to provide a toughness composition, the component (F) may be added at any one or more stages of the mixing process in one or more stages. in multiple doses.

The process for preparing the composition according to the invention is further characterized in that it is advantageous to add to the mixture another additive modifying the properties of the resulting mixture from the group of substances (G), which substances can be added in any one or more stages of the mixing process. multiple doses.

The process according to the invention is further characterized in that the excess water is removed from the mixture by atmospheric or vacuum degassing only in the last stages of the mixing process, first after a phase in which at least component (A), component (B) is already present in the mixture. and component (D). The preparation process according to the invention is further characterized in that any mixing device for preparing polymer blends can be used for mixing the mixture, preferably an extruder, preferably a single or twin screw extruder, further preferably a twin screw coring extruder with overlapping worms. In the case of a multi-step mixing process, a different type of mixing device may be used for each mixing step.

The process of preparing the composition according to the invention is further characterized in that preferably a twin-screw extruder is used as a mixing device, equipped in addition to the main shaft feeders with melt-dispensing pumps along the extruder and side screw dispensers allowing the solids of the mixture to be melt-mixed. further preferably provided in the last part of the extruder with atmospheric or vacuum degassing, and further preferably equipped with an air or liquid cooling device for extruding the cold and a device for granulating the cooled side. In addition, the composition process so constructed may advantageously be provided with a head and a device for producing finished products, for example blown or cast films, extruded open or closed profiles, and the like, instead of a granulation device.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 Example of viscosity versus shear rate of acetylbutyl citrate plasticizer, measured according to STN ISO 3219

Fig. 2 Flow diagram of a process for producing a polymer blend according to the PA process in two extrusion steps PA1 and PA2

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Fig. 3 Flow diagram of the process of producing a polymer blend according to the PB process in two extrusion steps PB1 and PB2

Fig. 4 Flow diagram of a polymer blend production process according to the PC process in two extrusion steps PC1 and PC2

Fig. 5 is a flow diagram of a process for producing a polymer blend according to the PD process in one extrusion step

Fig. 6 is a flow diagram of a process for producing a polymer blend according to the PE process in one extrusion step

Fig. 7 Flow diagram of a process for producing a polymer blend according to the PF process in a single extrusion step

Fig. 8 Scheme of the process of production of polymer mixture according to process G in one extrusion step in two possible alternatives PG1 and PG2

EXAMPLES

In order to determine the properties of the mixtures according to the invention, the following procedures are used:

Measurement of mechanical properties of mixtures

The mechanical properties of the mixtures according to the invention were measured according to STN ISO 527 standards on a Zwick Roel shredder equipped with a mechanical extensometer, measuring at 25 ° C, 50% relative humidity (RH) and jaw displacement 50 mm / mm. The clamping length of the test body was 50 mm and the distance of the jaws of the extensometer was 30 mm The parameters of the elongation at break Eb and the tensile strength OM were evaluated according to STN ISO 527,

Test specimens for measuring mechanical properties and preparation

For the preparation of the test specimens for measuring the mechanical properties, the films were produced from films with a thickness of 0.040 mm by chill roll technology, namely by extruding the melt of the mixture onto the water-cooled cylinders of the laboratory chill roll line, which consisted of the following individual devices:

- Towing equipment from Göttfert, which is equipped with two successive water-cooled cooling rollers and subsequently a withdrawal and winding unit. Chilled cylinder temperature: 20 ° C.

- A flat die extruder head of 70 mm width and 0.4 mm slot thickness, which was either attached directly to the last extrusion step extruder instead of the pelletizer, or attached to a 19 mm L-screw Brabender single screw extruder. / D = 25 and screw compression ratio 1: 2. Screw geometry: plain screw without mixing elements with continuously increasing screw core diameter. In case a Brabender single screw extruder was used, the process parameters were as follows:

Melting point: 190 ° C

Screw speed: 30 rpm.

Strips 15 mm wide and 100 mm long were cut from the films so produced immediately afterwards, which were immediately placed in an air conditioning chamber where they were allowed to condition at 25 ° C and 50% RH for 24 hours. After 24 hours conditioning, mechanical properties were measured immediately.

Measurement of viscosity of plasticizers

The viscosity of the plasticizers was measured using a rotary viscometer with the geometrical arrangement of two coaxial cylinders on a Haake rheoviscosimeter. The measurement was carried out at 25 ° C according to STN ISO 3219, where the average value of all measurements in the range of shear rates from 152 s ¹ to 1170 s ^-1 was determined as the viscosity value, since all the liquids measured had a Newton flow pattern. An example of the viscosity versus shear rate of the acetyl tributyl citrate plasticizer is shown in FIG. First

Examples of the process for preparing a biodegradable polymer blend include the following alternatives to the two-step or one-step arrangement for preparing blends using twin screw extractors, and the following examples do not exclude other alternatives to the mixing process. The extdders in the figures are shown schematically, wherein the division of the extruder into zones is merely illustrative and does not represent a particular order of zones or a particular order of phases of the mixing process.

1. Two-extrusion preparation

Procedure P A

According to the PA process, a dryblend (DB_A) consisting of at least one starch, at least one plasticizer from the group of substances (C) and at least one modifier from the group of substances (E) is prepared, which may or may not contain other additives from the group of substances (G) . Dryblend is metered into the hopper of a twin screw co-extruder together with at least one component in the first PA1 extrusion step

N E 8663 Υ1 (A). Subsequently, by means of a pump, the components (F) are metered into the molten mixture, if necessary for the resulting properties of the mixture. Upon exiting the extruder, the mixture is cooled and granulated without aspirating excess water. The granulate is then metered again into the hopper of the twin screw extruder in the second extrusion step of PA2 together with at least one component (D). If necessary, another component (F) can be fed into the melt again by means of a pump. At the end of the extruder, excess water is removed through the vacuum degassing zone, the mixture is cooled with air or liquid and granulated. Moisture of the resulting granulate can be adjusted by drying prior to further processing if desired. Instead of granulating, in the PA2 step, the final product unit (chill roll film, blown film, etc.) can be advantageously attached to the extruder in step PA2. Other substances of group (G), if necessary, can be added to the mixture either in the first extrusion step PA1 into the hopper of the extruder or by means of a side melt dispenser along the extruder. In the same way, other additives of group (G) can be dosed also in the extrusion step of PA2. Schematically, this process is illustrated in FIG. Second

Procedure PB

According to the PB process, a dryblend (DB_B) consisting of at least one starch, at least one substance in group (C) and at least one modifier in substance group (E) is prepared, which may or may not contain other additives in group substance (G) . The dry mixture (Dryblend) is fed into the hopper of a twin screw coring extruder in the first extrusion step of PB1. Subsequently, at least one component (A) is metered into the melt and subsequently can be metered into the molten mixture of components (F) by means of a pump, if necessary for the resulting properties of the mixture.

Upon exiting the extruder, the mixture is cooled and granulated without removing excess water. The granulate is then metered again into the hopper of the twin screw extruder in the second extrusion step PB2 together with at least one component (D). If necessary, another component (F) can be dosed again by means of a melt pump in the extender. At the end of the extruder, excess water is removed through the vacuum or atmospheric degassing zone, the mixture is cooled with air or liquid and granulated. Instead of granulation, a unit for producing the final product (chill roll film, blown film, etc.) can advantageously be attached to the extruder in step PB2 instead of the granulation unit. The moisture content of the resulting granulate may be adjusted by drying prior to further processing if necessary. Other compounds of group (G), if necessary, may be added to the mixture either in the first extrusion step PB1 into the extruder hopper or by means of a side melt dispenser along the extruder. . In the same way, other additives from the group of substances (G) can be dosed also in the PB2 extrusion step. Schematically, this process is shown in FIG. Third

PC procedure

According to the PC procedure, a dryblend (DB_C) consisting of at least starch and at least one modifier from the group of substances (E) is prepared, which may or may not contain other additives from the group of substances (G) in addition to these components. The dryblend is fed into the hopper of a twin screw coring extruder in the first extrusion step of PC1. Subsequently, at least one plasticizer from the group of substances (C) is metered into the melt in the extruder, followed by at least one component (A) and subsequently metered into the molten mixture of components (F) by pump, if necessary for the resulting properties of the mixture.

Upon exiting the extruder, the mixture is cooled and granulated without removing excess water. The granulate is then metered again into the hopper of the twin-screw extruder in the PC2 low extrusion step together with at least one component (D). If necessary, another component (F) can be dosed again by means of a melt pump in the extender. At the end of the extruder, excess water is removed through a vacuum or atmospheric degassing zone, the mixture is cooled with air or liquid and granulated. If necessary, the moisture content of the resulting granulate can be adjusted by drying prior to further processing. Advantageously, instead of the granulation unit, a unit for producing the final product (chill roll film, blown film, etc.) can be attached to the extruder in step PC2. Other substances of group (G), if necessary, may be added to the mixture either in the first extrusion step PC1 into the hopper of the extruder or by means of a side melt dispenser along the extruder. In the same way, other additives from the group of substances (G) can also be dosed in the PC2 extrusion step. Schematically, this process is shown in FIG. 4th

Alternatively, for all PA to PC processes, PHA (component (D)) may be metered in the extrusion step PA2 to PC2 in the hot extrusion step not only into the hopper, but also / or by the side melt dispenser before or after component (F) dosing. 2-4.

2. Single-extrusion preparation

Procedure PD

According to the PD process a dry blend (DBJD) is prepared consisting of at least one starch, at least one plasticizer from the group of substances (C) and at least one modifier from the group of substances (E), which may or may not contain other additives from the group. (G). The dryblend is metered into the hopper of a twin screw coring extruder together with at least one component (A). It is then melted

In the extruder, the pump feeds component (F), if necessary for the resulting properties of the mixture, and at least one component (D) is dosed by the side dispenser in the other half of the extruder and, if necessary, additives from the substance group (G). At the end of the extruder, excess water is removed through the vacuum or atmospheric degassing zone, the mixture is cooled with air or liquid and granulated. Moisture of the resulting granulate can be adjusted by drying prior to further processing if desired. Advantageously, instead of the granulation unit, a final product unit (chill roll film, blown film, etc.) can be attached to the extruder. Schematically, this process is shown in FIG. 5th

Procedure PE

According to the PE process a dry blend (DB_E) is prepared consisting of starch, at least one plasticizer from the group of substances (C) and at least one modifier from the group of substances (E), which may or may not contain other additives from the group of substances (G). The dryblend is metered into the hopper of a twin screw coring extruder and subsequently at least one component (A) is metered into the extruder. In the next part of the extruder it is dosed by means of the pump component (F), if necessary for the resulting properties of the mixture. In the second half of the extruder, at least one component (D) is dosed by the side dispenser and, if necessary, additives from the group of substances (G) are subsequently dosed. At the end of the extruder, excess water is removed through the vacuum degassing zone, the mixture is cooled with air or liquid and granulated. Moisture of the resulting granulate can be adjusted by drying prior to further processing if desired. Advantageously, instead of the granulation unit, a final product unit (chill roll film, blown film, etc.) can be attached to the extruder. Schematically, this process is illustrated in FIG. 6th

Procedure PF

According to the PF process, a dry blend (DB_F) is prepared consisting of at least one starch and at least one modifier from the group of substances (E), which may or may not contain other additives from the group of substances (Gr) in addition to these components. The dryblend is metered together with at least one component (A) into the hopper of a twin screw coring extruder and subsequently at least one plasticizer of the substance group (C) is metered into the extruder by means of a pump. In the next part of the extruder it is dosed by means of the pump component (F), if necessary for the resulting properties of the mixture. In the second half of the extruder, at least one component (D) is dosed by the side dispenser and, if necessary, additives from the group of substances (Gr) are subsequently dosed. At the end of the extruder, the excess degassing zone is removed with excess water, the mixture is cooled with air or liquid and granulated. Moisture of the resulting granulate can be adjusted by drying prior to further processing if desired. Instead of granulating, a final product unit (chill roll film, blown film, etc.) can be advantageously attached to the extruder instead of the granulation unit. Schematically, this process is shown in FIG. 7th

PG procedure

According to the PG procedure a dry blend (DB G) consisting of starch and at least one modifier from the group of substances (E) is prepared, which may or may not contain other additives from the group of substances (G 1). Dryblend is metered into the hopper of a twin screw coring extruder and then at least one plasticizer of the substance group (C) is metered into the melt in the extruder using at least one component (A) - PG1 procedure or at least one component ( A) and then at least one plasticizer from the group of substances (C) - process PG2. In another part of the extruder, a plasticizer from the group of substances (F) is metered by means of a pump, if necessary for the resulting properties of the mixture. In the second half of the extruder, at least one component (D) is dosed by the side dispenser and, if necessary, additives from the group of substances (Gr) are subsequently dosed. At the end of the extruder, the excess degassing zone is removed with excess water, the mixture is cooled with air or liquid and granulated. Moisture of the resulting granulate can be adjusted by drying prior to further processing if desired. Instead of granulation, an end product manufacturing unit (chill roll film, blown film, etc.) may advantageously be attached to the extruder instead of the granulation unit. Schematically, this process is shown in FIG. 8th

Reference mixtures have been prepared which are not the subject of the invention and serve only to compare the mechanical properties with the mixtures prepared according to the invention. Reference mixtures with the composition given in Tab. 1 and 2 were prepared under the following conditions:

A twin screw mixer with coring worms was used as the device with the following parameters:

screw diameter 26 mm, L / D = 40, screw speed 200 rpm, melt temperature 180 ° C, vacuum degassing at the last zone of the screw.

The extruded mixture was air-cooled and subsequently granulated. Films having a thickness of 0.040 mm were prepared from the blends prepared according to the procedure described in the invention.

N E 8663 Υ1

If the TPS was prepared separately, the preparation was carried out under the following conditions: A dry premix was mixed in a Labtech high-speed laboratory mixer, the mixture consisting of starch and a plasticizer of the substance group (C). Such premix was fed into the hopper of a twin screw extender under the following conditions: screw diameter 26 mm, L / D = 40, screw speed 200 rpm, melt temperature 150 ° C, vacuum degassing at the last screw zone.

The resulting TPS was extruded in the form of a string, cooled with air and subsequently granulated.

Table 1 Composition of reference mixtures without plasticizer from group (F) and without modifier from group (E)

no. mixtures (A) :( D) Starch: [(A) + (D)] (C): starch F: [(A) + (D)] Technological process 1 80:20 30:70 30:70 0 TP1 2 40:60 30:70 30:70 0 TP1 3 5:95 30:70 30:70 0 TP1 4 95: 5 30:70 30:70 0 TP2 5 80:20 30:70 30:70 0 TP2 6 40:60 30:70 30:70 0 TP2 7 5:95 30:70 30:70 0 TP2 8 95: 5 30:70 30:70 0 TP3 9 80:20 30:70 30:70 0 TP3 10 40:60 30:70 30:70 0 TP3 11 5:95 30:70 30:70 0 TP3

Table 2 Composition of reference mixtures with plasticizer from group (F) and without modifier from group (E)

No. mixtures (A) :( D) Starch: [(A) + (D)] (C): starch F: [(A) + (D)] Technological process 12 80:20 30:70 30:70 15:85 TP1 13 40:60 30:70 30:70 15:85 TP1 14 5:95 30:70 30:70 15:85 TP1 15 95: 5 30:70 30:70 15:85 TP2 16 40:60 30:70 30:70 15:85 TP2 17 5:95 30:70 30:70 15:85 TP2 18 95: 5 30:70 30:70 15:85 TP3 19 40:60 30:70 30:70 15:85 TP3 20 5:95 30:70 30:70 15:85 TP3

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerin

TP1 - technological process of preparation in one extrusion step, in which all the components of the mixture were fed into the main hopper of the twin screw extruder and the excess moisture was removed under vacuum before the melt exiting the extruder, the melt cooled air and granulated after leaving the extruder.

TP2 - a process in which a dry premix of starch, anhydrous glycerin and PLA was first mixed on a twin screw extruder in a first extrusion step, so that all ingredients were fed into the main hopper of the extruder and excess moisture was removed from the melt by vacuum before leaving the extruder and mixture was granulated after air cooling. The granulate was fed into the main hopper together with the PHB in the second extrusion step. The melt was evacuated from excess moisture by vacuum degassing before leaving the extruder.

TP3 - a technological process in which the thermoplastic starch itself was first prepared on a twin screw in the first extrusion step. Excess moisture was removed in vacuo before the melt was discharged from the extender, and after granules, the thus prepared TPS was dosed in a dark extrusion step together with PLA and PHB into the main hopper of the extender. The sapo melt granulated with air.

Subsequently, according to the process described in the description of the invention, chill roll casting foils with a thickness of 0.040 mm were prepared and the mechanical properties given in Table 2 were measured. Third

N E 8663 Υ1

Table 3 Mechanical properties of reference mixtures prepared according to Tables 1 and 2.

No. mixtures (A) :( D) F: [(A) + (D)] OM [MPa] Sb [%] 1 80:20 0 7.3 1.4 2 40:60 0 on the on the 3 5:95 0 on the on the 4 95: 5 0 13.4 1.1 5 80:20 0 12.7 1.2 6 40:60 0 on the on the 7 5:95 0 on the on the 8 95: 5 0 11.2 1.1 9 80:20 0 1.4 1.1 10 40:60 0 on the on the 11 5:95 0 on the on the 12 80:20 15:85 4.5 71 13 40:60 15:85 1.7 9 14 5:95 15:85 on the on the 15 95: 5 15:85 9.2 89 16 40:60 15:85 1.6 8 17 5:95 15:85 on the on the 18 95: 5 15:85 6.5 63 19 40:60 15:85 4 7 20 5:95 15:85 3 4

om - tensile strength limit

Eb - relative elongation at rupture n / a - could not be measured because foil could not be made from the mixture

Example 1

According to the invention, a process without the component (F), the composition of which is shown in Table 4 and the mechanical properties of Table 5, has been prepared by the process procedure PA PROCEDURE PA.

An extruder with the following design parameters was used as a mixing device in the first and second mixing steps:

twin screw coring, with screw overlap, screw diameter 26 mm, L / D ratio = 40;

mixing was carried out under the following technological conditions:

melt temperature: 190 ° C, screw rotation speed: 250 rpm, first extrusion step of degassing second extrusion step with vacuum degassing at penultimate zone of the die with circular cross section of the melt air flow cooling and subsequent granulation of the cooled strand with a rotary granulator.

The preparation of the test specimens and the conditions for measuring the mechanical properties are given in the description of the invention.

Table 4 Composition of blends without plasticizer with modifier

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (Cýškrob (E): [Starch + (C)] 21 95: 5 0 30:70 30:70 1.1: 100 22 80:20 0 30:70 30:70 1.1: 100 23 40:60 0 30:70 30:70 1.1: 100 24 5:95 0 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerine

S K 8663 Υ1 (E) - phthalic anhydride

Table 5 Mechanical properties of the mixtures prepared according to Table 4

No. mixtures (A) :( D) Gm [MPa] Eb [%] 21 95: 5 48.9 3.3 22 80:20 41.7 3.4 23 40:60 41.1 2.2 24 5:95 27.5 2.1

Example 2

According to the invention, the mixtures listed in Table 8 were prepared according to the process described under PROCEDURE PB under the process conditions as in Example 1.

Table 8 Composition of blends with plasticizer and modifier

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (Cýškrob (E): [Starch + (C)] 25 95: 5 15:85 30:70 30:70 1.1: 100 26 80:20 15:85 30:70 30:70 1.1: 100 27 5:95 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerin (E) - phthalic anhydride

Table 11 lists the properties of the compositions prepared according to Table 8.

Table 11 Characteristics of mixtures prepared according to Tab. 8

No. mixtures (A) :( D) OM [MPa] £ b [%] 25 95: 5 22.3 304 26 80:20 22.1 316 27 5:95 26.1 105

Example 3

According to the invention, the mixtures according to Table 13 were prepared according to the process described under PROCESS PC under the process conditions as in Example 1.

Table 13 Composition of mixtures with different modifier contents

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (Cýškrob (E): [Starch + (C)] 28 80:20 0 30:70 30:70 0.1: 100 29 80:20 0 30:70 30:70 0.5: 100 30 80:20 0 30:70 30:70 1.0: 100 31 80:20 0 30:70 30:70 2.0: 100 32 80:20 0 30:70 30:70 5.0: 100 33 80:20 0 30:70 30:70 10.0 100 34 80:20 15:85 30:70 30:70 0.05: 100 35 80:20 15:85 30:70 30:70 0.23: 100 36 80:20 15:85 30:70 30:70 0.46: 100 37 80:20 15:85 30:70 30:70 2.75: 100 38 80:20 15:85 30:70 30:70 5.00: 100 39 80:20 15:85 30:70 30:70 6.88: 100 40 80:20 15:85 30:70 30:70 9.18: 100

SK 8663 Υ1 (A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 ( F) acetyltributyl citrate starch - corn starch (C) - glycerin (E) - phthalic anhydride

Table 14 shows the mechanical properties of the prepared compositions of Table 13.

Table 14 Mechanical properties of ready-to-mix mixtures. 13

No. mixtures (A) :( D) [F]: [(A) + (D)] (E): [Starch + (C)] OM [MPa] sb [%] 28 80:20 0 0.1: 100 44.0 2.2 29 80:20 0 0.5: 100 45.0 2.3 30 80:20 0 1.0: 100 38.4 2.5 31 80:20 0 2.0: 100 41.1 2.5 32 80:20 0 5.0: 100 41.8 3.1 33 80:20 0 10.0 100 36.9 3.5 34 80:20 15:85 0.05: 100 10.3 110 35 80:20 15:85 0.23: 100 11.6 112 36 80:20 15:85 0.46: 100 13.8 159 37 80:20 15:85 2.75: 100 14.7 270 38 80:20 15:85 5.00: 100 12.1 255 39 80:20 15:85 6.88: 100 12.1 265 40 80:20 15:85 9.18: 100 12.0 253

Example 4

According to the invention, according to the process described under the PROCEDURE PA under technological conditions as in Example 1, mixtures of Table 15 were prepared, the mechanical properties of which are given in Table 16.

Table 15 Composition of mixtures with a different content of a group (C) plasticizer

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (Cýškrob (E): [Starch + (C)] 41 80:20 15:85 30:70 5:95 1.1: 100 42 80:20 15:85 30:70 10:90 1.1: 100 43 80:30 15:85 30:70 15:85 1.1: 100 44 80:20 15:85 30:70 20:80 1.1: 100 45 80:20 15:85 30:70 30:70 1.1: 100 46 80:20 15:85 30:70 50:50 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerine (E) - phthalic anhydride

Table 16 Mechanical properties of ready prepared mixtures. 15

No. mixtures (C) starch: om [MPa] sb [%] 41 5:95 10.8 196 42 10:90 13.3 215 43 15:85 17.2 250 44 20:80 15.6 257 45 30:70 23.4 299 46 50:50 14.9 337

N E 8663 Υ1

Example 5

According to the invention, mixtures with different types of modifiers from the group of substances (E) according to Table 17 were prepared according to the process PROCEDURE PA under technological conditions as in Example 1, the mechanical properties are shown in Table 18.

Table 17 Composition of mixtures with different types of modifiers from the group of substances (E)

No. mixtures Modifier type (E) (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (Cýškrob (E): [Starch + (C)] 47 M2 80:20 15:85 30:70 30:70 1.1: 100 48 M3 80:20 15:85 30:70 30:70 1.1: 100 49 M4 80:20 15:85 30:70 30:70 1.1: 100 50 M5 80:20 15:85 30:70 30:70 1.1: 100 51 M6 80:20 15:85 30:70 30:70 1.1: 100 52 M7 80:20 15:85 30:70 30:70 1.1: 100 53 M8 80:20 15:85 30:70 30:70 1.1: 100 54 M9 80:20 15:85 30:70 30:70 1.1: 100 55 M10 80:20 15:85 30:70 30:70 1.1: 100 56 MLL 80:20 15:85 30:70 30:70 1.1: 100 57 M12 80:20 15:85 30:70 30:70 1.1: 100 58 M13 80:20 15:85 30:70 30:70 1.1: 100 59 M14 80:20 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerin

M2 - Tetrahydroftalanic anhydride

M3 - trimellitic anhydride

M4 - maleic anhydride

M5 - Hexahydro-phthalic anhydride

M6-dimer of 2,4'-toluene diisocyanate

M7 - 4,4'-diphenylmethane diisocyanate

M8 - cpoxylated styrene / methyl copolymer. Mw 6800g / mol EEW * = 285 g / mol

M9 - Citric acid anhydride

M10 - succinic anhydride (succin anhydride)

Mll - citric acid

M12 - adipic acid

M13 - hexamethylene diisocyanate

M14 - pyromellite dianhydride * EEW = epoxy equivalent weigth

Table 18 Mechanical properties of the mixtures prepared according to Tab. 17

No. mixtures Modifier type (E) om [MPa] sb [%] 47 M2 10.9 251 48 M3 18.6 255 49 M4 21.0 306 50 M5 11.5 200 51 M6 11.7 189 52 M7 12.1 188 53 M8 11.4 181 54 M9 23.5 334 55 M10 17.9 303 56 MLL 21.2 324 57 M12 10.1 153 58 M13 12.0 238 59 M14 20.2 322

N E 8663 Υ1

Example 6

According to the invention, mixtures with different types of PLA from group (A) according to Table 19 were prepared according to the process PROCEDURE PA under process conditions as in Example 1, the mechanical properties are shown in Table 20.

Table 19 Composition of mixtures with different types of PLA from group (A)

No. mixtures Type PLA (A) (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C) starch: (E): [Starch + (C)] 60 PLA 1 80:20 15:85 30:70 30:70 1.1: 100 45 PLA 2 80:20 15:85 30:70 30:70 1.1: 100 61 PLA 3 80:20 15:85 30:70 30:70 1.1: 100 62 PLA 4 80:20 15:85 30:70 30:70 1.1: 100 63 PLA 5 80:20 15:85 30:70 30:70 1.1: 100 64 PLA 6 80:20 15:85 30:70 30:70 1.1: 100 65 PLA 7 80:20 15:85 30:70 30:70 1.1: 100 66 PLA 8 80:20 15:85 30:70 30:70 1.1: 100 67 PLA 6: PLA 4 1: 1 80:20 15:85 30:70 30:70 1.1: 100 68 PLA 7: PLA 1 1: 1 80:20 15:85 30:70 30:70 1.1: 100 69 PLA 3: PLA 4 1: 1 80:20 15:85 30:70 30:70 1.1: 100

(D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4,23 (F) acetyltributyl citrate starch - maize starch (C) - glycerin (E) - phthalic anhydride (A) - type PLA:

(A) -type PLA Mw kDa Polydispersity index D ObsahDizoméru OM [MPa] sb [%] PLA 1 202 2.18 4.20% 44.3 8.9 PLA 2 193 2.18 8% 43.4 3.7 PLA 3 140 1.9 2% 56.8 2.5 PLA 4 188 1.8 12% 37.9 4.7 PLA 5 200 1.8 2% 58.3 2.3 PLA 6 162 1.81 <1% 54.8 2.2 PLA 7 187 1.95 <1% 48.4 4.1 PLA 8 195 1.98 4% 46.9 2.4

Note: The mechanical properties of films prepared according to the procedure described in the description of the invention under "Test specimens for measuring mechanical properties and their preparation" from PLA alone without addition of any additives are given.

Table 20 Mechanical properties of the mixtures prepared according to Tab. 19

No. mixtures Type PLA (A) OM [MPa] sb [%] 60 PLA 1 16.0 276 45 PLA 2 23.4 299 61 PLA 3 16.9 291 62 PLA 4 18.8 390 63 PLA 5 19.8 338 64 PLA 6 17.3 308 65 PLA 7 18.7 328 66 PLA 8 16.1 307 67 PLA 6: PLA 4 1: 1 16.4 333 68 PLA 7: PLA 1 1: 1 14.2 289 69 PLA 3: PLA 4 1: 1 16.2 326

N E 8663 Υ1

Example 7

According to the invention, a mixture with different types of plasticizer of group (F) according to Table 21 was prepared according to the process PROCEDURE PA under the process conditions as in Example 1, the mechanical properties are given in Table 22.

Table 21 Composition of mixtures with different types of PLA plasticizer from group (F)

No. mixtures Type of plasticizer (F) (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C) starch: (E): [Starch + (C)] 45 F 1 80:20 15:85 30:70 30:70 1.1: 100 70 F2 80:20 15:85 30:70 30:70 1.1: 100 71 F 3 80:20 15:85 30:70 30:70 1.1: 100 72 F4 80:20 15:85 30:70 30:70 1.1: 100 73 F5 80:20 15:85 30:70 30:70 1.1: 100 74 F6 80:20 15:85 30:70 30:70 1.1: 100 75 F 7 80:20 15:85 30:70 30:70 1.1: 100 76 F 8 80:20 15:85 30:70 30:70 1.1: 100 77 F9 80:20 15:85 30:70 30:70 1.1: 100 78 F 10 80:20 15:85 30:70 30:70 1.1: 100 79 F 11 80:20 15:85 30:70 30:70 1.1: 100 80 F 12 80:20 15:85 30:70 30:70 1.1: 100 81 F 13 80:20 15:85 30:70 30:70 1.1: 100 82 F 14 80:20 15:85 30:70 30:70 1.1: 100 83 F 15 80:20 15:85 30:70 30:70 1.1: 100 84 F 16 80:20 15:85 30:70 30:70 1.1: 100 85 F 17 80:20 15:85 30:70 30:70 1.1: 100 86 F 18 80:20 15:85 30:70 30:70 1.1: 100 87 F 19 80:20 15:85 30:70 30:70 1.1: 100 88 F 20 80:20 15:85 30:70 30:70 1.1: 100 89 F 21 80:20 15:85 30:70 30:70 1.1: 100 90 F 22 80:20 15:85 30:70 30:70 1.1: 100 91 F 23 80:20 15:85 30:70 30:70 1.1: 100 92 F 24 80:20 15:85 30:70 30:70 1.1: 100 93 F 25 80:20 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 10 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 starch - maize starch (C) - glycerin (E) - lithium anhydride (F) - type of plasticizer for PLA and / or PHA:

(F) Type of plasticizer chemical name viscosity at 25 ° C mPas F1 Acets Itributes Icitrate 33 F2 tributyl 25 F3 tris- (2-ethylhexyl) -o-acetyl Icitrate 85 F4 triacetin 16 F5 adipic acid oligoester 3015 F6 adipic acid oligoester 4082 F7 adipic acid oligoester 589 F8 adipic acid oligoester 1041 F9 dioktyltereftalát 64 F10 dioctyl 12 fll dizononylftalát 55 F12 adipic acid oligoester 19890 F13 F1 / F3 60:40 45

N E 8663 Υ1

F14 50:50 F1 / F3 48 F15 F1 / F3 87:13 37 F16 F1 / F3 83:17 36 F17 F1 / F2 67:33 29 F18 F1 / F4 67:33 24 F19 F2 / F3 50:50 40 F20 F2 / F1 / F3 50:30:20 31 F21 50:50 F2 / F1 28 F22 F1 / F7 67:33 140 F23 F1 / F8 67:33 178 F24 F1 / F5 67:33 350 F25 F1 / F8 67:33 427

Table 22 Mechanical properties of the mixtures prepared according to Tab. 21

No. mixtures Type of plasticizer (F) om [MPa] sb [%] 45 F 1 23.4 299 70 F2 16.0 304 71 F3 16.4 302 72 F4 10.6 215 73 F5 16.0 335 74 F6 17.9 365 75 F7 19.5 198 76 F8 15.9 249 77 F9 16.8 198 78 F 10 10.2 168 79 F 11 24.6 183 80 F 12 18.1 178 81 F 13 27.0 356 82 F 14 16.5 352 83 F 15 23.5 346 84 F 16 17.1 308 85 F 17 15.2 312 86 F 18 17.1 317 87 F 19 26.5 250 88 F 20 24.4 284 89 F 21 20.17 302 90 F 22 22.0 306 91 F 23 17.0 322 92 F 24 18.1 337 93 F 25 17.1 334

Example 8

According to the invention, mixtures with different types of starch according to Table 23 were prepared according to the process PROCEDURE PA under process conditions as in Example 1, the mechanical properties are shown in Table 24.

Table 23 Composition of mixtures with different types of starch

No. mixtures Starch type (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C) starch: (E): [Starch + (C)] 45 corn 80:20 15:85 30:70 30:70 1.1: 100 94 Amaranth 80:20 15:85 30:70 30:70 1.1: 100 95 potato 80:20 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate

S K 8663 Υ1 (C) - Glycerin (E) - Phthalic anhydride

Table 24 Mechanical properties of the mixtures prepared according to Tab. 23

No. mixtures Starch type om [MPa] Eb [%] 45 corn 23.4 299 94 Amaranth 11.9 113 95 potato 19.4 328

Example 9

According to the invention, a mixture with different types of plasticizers of group (C) according to Table 25 was prepared according to the process PROCEDURE PA under technological conditions as in Example 1, the mechanical properties are given in Table 26.

Table 25 Composition of mixtures with different types of plasticizers from group (C)

No. mixtures Type of plasticizer (C) (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C): starch (E): [Starch + (C)] 45 glycerin 80:20 15:85 30:70 30:70 1.1: 100 96 PEG 300 80:20 15:85 30:70 30:70 1.1: 100 97 PEG 600 80:20 15:85 30:70 30:70 1.1: 100 98 PEG 1000 80:20 15:85 30:70 30:70 1.1: 100 99 MPG 80:20 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerin (E) - phthalic anhydride

Table 26 Mechanical properties of the mixtures prepared according to Tab. 25

No. mixtures Type of plasticizer (C) OM [MPa] £ b [%] 45 glycerin 23.4 299 96 PEG 300 12.1 257 97 PEG 600 11.9 234 98 PEG 1000 13.8 211 99 MPG 10.6 244

Example 10

According to the invention, a mixture with different types of component (D) - PHA - according to Table 27 was prepared according to the process PROCEDURE PA under the technological conditions as in Example 1, according to Table 27, the mechanical properties are given in Table 28.

Table 27 Composition of mixtures with different types of component (D) - different types of FHA

No. mixtures Type PHA (D) (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C): starch (E): [Starch + (C)] 45 PHA 1 80:20 15:85 30:70 30:70 1.1: 100 100 PHA 2 80:20 15:85 30:70 30:70 1.1: 100 101 PHA 3 80:20 15:85 30:70 30:70 1.1: 100 102 PHA 4 80:20 15:85 30:70 30:70 1.1: 100 103 PHA 5 80:20 15:85 30:70 30:70 1.1: 100 104 PHA 6 80:20 15:85 30:70 30:70 1.1: 100 105 PHA 7 80:20 15:85 30:70 30:70 1.1: 100

SK 8663 Υ1 (A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2,18 (F) acetyltributyl citrate starch - maize starch (C) - glycerin (E) - phthalic anhydride (D) - PHA type:

PHA mw D index Content comonomy% OM [MPa] Eb [%] PHA 1 P3HB 608 4.23 14.8 1.4 PHA 2 P3HB4HV 460 4:53 3.1% 4HV 27.0 3.5 PHA 3 P3HB4HV 539 4.65 5.1% 4HV 12.3 4.8 PHA 4 P3HB 428 3:54 34.5 2.6 PHA 5 P3HB 652 5.4 34.8 2.6 PHA 6 P3HB 780 3.2 33.9 2.1 PHA 7 P3HB4HB 223 3:35 17.6% 4HB 28.7 2.3

Note: The mechanical properties of films prepared according to the procedure described in the description of the invention under "Test specimens for measuring mechanical properties and their preparation" from PLA alone without addition of any additives are given.

Table 28 Mechanical properties of the mixtures prepared according to Tab. 27

No. mixtures Type PHA (D) OM [MPa] cb [%] 45 PHA 1 23.4 299 100 PHA 2 19.9 287 101 PHA 3 19.0 264 102 PHA 4 18.7 302 103 PHA 5 19.2 286 104 PHA 6 20.2 298 105 PHA 7 12.3 114

Example 11

According to the invention, a mixture with addition of nucleating agents from the group of substances (G) according to Table 29 was prepared according to the process described under the PROCEDURE PA under technological conditions as in example 1, the mechanical properties are given in table 30. Nucleating agents from group (G) were added. according to the procedure PA in the second extrusion step PA2 into the hopper.

Table 29 Composition of mixtures with the addition of nucleating agents

No. mixtures Type and content of nucleating agent (G) (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C) starch: (E): [Starch + (C)] 106 B, 1% 80:20 0 100 30:70 30:70 1.1: 100 107 M, 1% 80:20 0 100 30:70 30:70 1.1: 100 108 B, 1% 40:60 0 100 30:70 30:70 1.1: 100 109 M, 1% 40:60 0 100 30:70 30:70 1.1: 100 110 B, 1% 80:20 15:85 30:70 30:70 1.1: 100 111 M, 1% 80:20 15:85 30:70 30:70 1.1: 100 112 B, 1% 40:60 15:85 30:70 30:70 1.1: 100 113 M, 1% 40:60 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerine (E) - phthalic anhydride

N E 8663 Υ1

M - talc, substance from group (G) as nucleating agent B - boron nitride, substance from group (Gr) as nucleating agent

Table 30 Mechanical properties of the mixtures prepared according to Tab. 29

No. mixtures Type and content a nucleating agent [F]: [(A) + (D)] OM [MPa] Eb [%] 106 B, 1% 0 100 29.7 2.1 107 M, 1% 0 100 30.2 2.8 108 B, 1% 0 100 33.8 3.7 109 M, 1% 0 100 35.0 2.9 110 B, 1% 15:85 18.1 275 111 M, 1% 15:85 18.2 180 112 B, 1% 15:85 15.1 180 113 M, 1% 15:85 15.3 260

Example 12

According to the invention, the process with the procedure PAINT PROCEDURE under the process conditions as in Example 1 prepared blends with the addition of fillers according to Table 31, the mechanical properties are shown in Table 32. Fillers from group (Gr) were added according to the PA procedure in PA2 second extrusion step.

Table 31 Composition of mixtures containing fillers

No. mixtures Type and content of filler (G) (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C): starch (E): [Starch + (C)] 114 PI, 10% 80:20 0 100 30:70 30:70 1.1: 100 115 P2, 10% 80:20 0 100 30:70 30:70 1.1: 100 116 PI, 10% 40:60 0 100 30:70 30:70 1.1: 100 117 P2, 10% 40:60 0 100 30:70 30:70 1.1: 100 118 PI, 10% 80:20 15:85 30:70 30:70 1.1: 100 119 P2, 10% 80:20 15:85 30:70 30:70 1.1: 100 120 PI, 10% 40:60 15:85 30:70 30:70 1.1: 100 121 P2, 10% 40:60 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - Corn starch (C) - glycerin (E) - L-anhydride

% PI - kaolin, a filler of the group (Gr), calculated on 10% by weight to the whole mixture

P2 - limestone, a filler of the group (Gr), calculated with 10 wt. to the whole mixture

Table 32 Mechanical properties of the mixtures prepared according to Tab. 29

No. mixtures Type and content of filler (G) (A) :( D) [F]: [(A) + (D)] OM [MPa] Eb [%] 114 PI, 10% 80:20 0 100 30.6 2.9 115 P2, 10% 80:20 0 100 29.5 2.8 116 PI, 10% 40:60 0 100 29.3 3.2 117 P2, 10% 40:60 0 100 48.7 3.2 118 PI, 10% 80:20 15:85 15.1 255 119 P2, 10% 80:20 15:85 21.3 272 120 PI, 10% 40:60 15:85 12.5 201 121 P2, 10% 40:60 15:85 14.6 282

N E 8663 Υ1

Example 13

According to the invention, according to the process described under PROCEDURE PA under the process conditions as in Example 1 and TP1 as described in Example 2, blends having different starch contents were prepared according to Table 33, the mechanical properties shown in Table 34.

Table 33 Composition of mixtures with different starch contents

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C) starch: (E): [Starch + (C)] 122 80:20 15:85 3:97 30:70 1.1: 100 123 80:20 15:85 10:90 30:70 1.1: 100 124 80:20 15:85 20:80 30:70 1.1: 100 45 80:20 15:85 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - maize starch (C) - glycerin (E) - lithium anhydride

Table 34 Mechanical properties of mixtures prepared according to Tab. 33

No. mixtures Starch: [(A) + (D)] (E): [Starch + (C)] om [MPa] sb [%] 122 3:97 1.1: 100 32.6 328 123 10:90 1.1: 100 28.7 326 124 20:80 1.1: 100 25.9 329 45 30:70 1.1: 100 23.4 299

Example 14

According to the invention, a mixture with a different plasticizer of group (F) according to Table 35, the mechanical properties shown in Table 36, was prepared according to the process described under PROCEDURE PA under process conditions as in Example 1.

Table 35 Composition of mixtures with different content of the plasticizer of group (F)

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (Cýškrob (E): [Starch + (C)] 22 80:20 0 100 30:70 30:70 1.1: 100 125 80:20 10:90 30:70 30:70 1.1: 100 126 80:20 13:87 30:70 30:70 1.1: 100 127 80:20 15:85 30:70 30:70 1.1: 100 128 80:20 20:80 30:70 30:70 1.1: 100 129 80:20 25:75 30:70 30:70 1.1: 100 130 80:20 33:67 30:70 30:70 1.1: 100 131 80:20 30:70 30:70 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate , for mixture 181 D100 starch - maize starch (C) - glycerin (E) - lithium anhydride

Table 36 Mechanical properties of the mixtures prepared according to Tab. 35

No. mixtures [F]: [(A) + (D)] Om [MPa] Gb [%] 22 0 100 41.7 2.3 125 10:90 18.8 372

N E 8663 Υ1

126 13:87 31.4 130 127 15:85 26.7 309 128 20:80 18.4 252 129 25:75 18.1 253 130 40:60 12.5 150 131 30:70 14.8 151

Example 15

According to the invention, according to the process described under PROCEDURE PA under the technological conditions as in Example 1, the compositions of Table 37 were prepared, wherein in the extrusion step PA2 a film head and chill roll unit were attached directly to the twin screw extruder. technology. Mechanical properties are given in Table 38.

Table 37 Composition of mixtures with different starch contents

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (Cýškrob (E): [Starch + (C)] 132 80:20 15:85 40:60 30:70 1.1: 100 133 80:20 15:85 50:50 30:70 1.1: 100 134 80:20 15:85 50:50 25:75 1.1: 100 135 80:20 15:85 50:50 20:80 1.1: 100 136 80:20 15:85 60:40 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 8%, Mw = 193 kDa, polydispersity coefficient D = 2.18 (D) P3HB, Mw = 608 kDa, polydispersity coefficient D = 4.23 (F) acetyltributyl citrate starch - corn starch (C) - glycerin (E) - phthalic anhydride

Table 38 Mechanical properties of the mixtures prepared according to Tab. 37

No. mixtures Starch: [(A) + (D)] (Cýškrob OM [MPa] £ b [%] 132 40:60 30:70 21.1 346 133 50:50 30:70 12.5 302 134 50:50 25:75 13.1 301 135 50:50 20:80 11.5 184 136 60:40 30:70 3.6 235

Example 16

According to the invention, according to the process described under PROCEDURE PA under the technological conditions as in Example 1, the compositions of Table 38 were prepared, wherein in the extrusion step PA2 a film head and chill roll unit were attached directly to the twin screw extruder. technology. The mechanical properties are given in Table 39.

Table 38 Composition of mixtures with different content of a plasticizer from group (F)

No. mixtures (A) :( D) [F]: [(A) + (D)] Starch: [(A) + (D)] (C): starch (E): [Starch + (C)] 137 80:20 7:93 40:60 30:70 1.1: 100 138 60:40 7:93 40:60 30:70 1.1: 100 139 80:20 5:95 40:60 30:70 1.1: 100 140 60:40 5:95 40:60 30:70 1.1: 100

(A) D, L-PLA, D-isomer content = 12%, Mw = 188 kDa, polydispersity coefficient D = 1.8 (D) P3HB, Mw = 708 kDa, polydispersity coefficient D = 3.2 (F) - F6 from Example 7; adipic acid oligoester, viscosity at 25 ° C = 4082 mPas starch - maize starch (C) - glycerine (E) - phthalic anhydride

N E 8663 Υ1

Table 39 Mechanical properties of the mixtures prepared according to Tab. 38

No. mixtures (A) :( D) [F]: [(A) + (D)] Om [MPa] Eb [%] 137 80:20 7:93 18.1 268 138 60:40 7:93 12.0 149 139 80:20 5:95 20.2 181 140 60:40 5:95 13.3 115

Industrial usability

The present invention provides for the production of a biodegradable polymer blend comprising a thermoplastic starch and a poly hydroxyalkanoate. which has improved mechanical properties. The biodegradable polymer blend is ecological and economically advantageous, and has the potential to be particularly useful in agricultural applications and in the packaging industry.

Claims (12)

PROTECTION REQUIREMENTS Biodegradable polymer composition, characterized in that it comprises at least one component (A), at least one component (B) and at least one component (D), wherein component (A) comprises lactic acid polymers, in particular L-acid homopolymers poly (PLLA) polymers, D-polylactic acid (PDLA), as well as copolymers thereof, or mixtures of homopolymers thereof, mixtures of homopolymers and copolymers thereof, or mixtures thereof; component (B) comprises a thermoplastic starch TPS, representing a mixture of starch, at least one plasticizer from the group of substances (C) and at least one modifier from the group of substances (E); the group of substances (C) includes plasticizers for starch which are selected from the group of substances: mono-, di- and polyhydric alcohols and polyols, in particular glycerin, ethylene glycol, propylene glycol, diols, triols and polyols, polyethylene glycol, polypropylene glycol, neopentyl glycol, sorbitol, mannitol ; the group of substances (E) comprises modifiers which are selected from the group of substances: saturated or unsaturated carboxylic, dicarboxylic, tricarboxylic or polycarboxylic acids, saturated or unsaturated anhydrides and azmesic anhydrides of carboxylic acids, substances containing isocyanate groups, preferably diisocyanates, substances containing epoxide groups, halides carboxylic acids, acylimidazoles, acyl phosphates, acid thioesters, or a combination thereof; component (D) comprises homopolymers or copolymers of PHA polyhydroxyalkanoates and / or mixtures thereof, being homopolymers or copolymers based on PHB polyhydroxybutyrates and / or mixtures thereof; and that it may optionally comprise component (F), wherein component (F) comprises plasticizers for PLA and / or PHA polyhydroxyalkanoate, selected from the group of: esters and low molecular weight polyesters, especially esters or low molecular weight polyesters of citric acid, esters or low molecular weight polyesters of glycerol, esters or low molecular weight polyesters of diols and polyols, esters or low molecular weight polyesters of phosphoric acid, esters or low molecular weight polyesters of sebacic acid, esters or low molecular weight polyesters of adipic acid, esters or low molecular weight polyesters of phthalic acid and other liquid esters and / or mixtures thereof, wherein the viscosity of the plasticizer for polylactic acid PLA and / or polyhydroxyalkanoate PHA measured at 25 ° C is less than or equal to 20,000 mPas. Biodegradable polymer composition according to claim 1, characterized in that the composition is composed of at least one component (A), at least one component (B) and at least one component (D). Biodegradable polymer blend according to claim 2, characterized in that the blend has a tensile strength om equal to or greater than 15 MPa, wherein the relative elongation at break α is greater than or equal to 2.0%. The biodegradable polymer blend of claim 1, wherein the blend comprises component (F) and has a relative elongation at break of Eb greater than or equal to 100%, wherein the tensile strength limit is greater than or equal to 3.0 MPa. A biodegradable polymer blend according to claims 1-4 wherein the ratio (A): (D) is from 95: 5 to 5: 95. Biodegradable polymer blend according to claims 1-5, characterized in that the amount of starch used in component (B) is such that the ratio [(A) + (D)]: (starch) is in the range 97: 3 to 40: 60 . A biodegradable polymer composition according to claims 1 to 6, characterized in that the amount of the substance of group (C) in component (B) is such that the ratio of the substance of group (C): (starch) is at least 5: 95. A biodegradable polymer composition according to claims 1 to 7, characterized in that in component (B) the ratio of the substance ´ of group (E): [(starch + substance of group (C)] is at least 0.05: 100. The biodegradable polymer blend of claim 1 and claims 4-8, wherein the ratio (F): [(A) + (D)] is at least 5: 95. Biodegradable polymer composition according to claims 1 to 9, characterized in that it comprises component (G) for adjusting the processing and / or utility properties of the composition, wherein component (G) comprises inorganic or organic fillers, compatibilizers and interfacial agents, pigments and dyes, nucleating agents agents, processing aids, anti-blocking and glidants, cross-linking agents, blowing agents, antistatic agents, flame retardants, antidegradants and other additives and modifiers including polymers and oligomers. Biodegradable polymer composition according to claims 1 to 10, characterized in that a composition comprising components (A), (B) and (D) is prepared by mixing components (A) and (B) such that component (B) is present. in the mixture in at least one phase of the mixing process in which at least one component (B) and the at least one component (A) are mixed simultaneously, and this phase of the mixing process precedes at least one phase of the phase of the mixing process in which it is added to the mixture Component (D), and optional components (F) and (G) may be added in any one or more phases of the mixing process, in one or more portions. N E 8663 Υ1 A biodegradable polymer blend according to claim 11, characterized in that a dry blend comprising starch and at least one modifier (E) is prepared by stirring at room temperature, and the dry blend optionally may comprise one or more components (C), and together with the dry mixture, the polymer of group (A) may also be added to the mixture, and if the dry mixture does not contain at least one substance of group (C), it shall be added to the mixture at least at the stage of the mixing process a process in which component (D) is added to the mixture; and if the dry mixture does not contain at least one component of group (A), it is added to a phase of the mixing process that at least one phase precedes the phase of the mixing process in which component (D) is added to the mixture, (A) and (C) are optional, one or more of the components (D) being added to the mixture in a mixing process phase that follows at least one phase of the mixing process later than the mixing phase in which the starch is mixed together, at least one component (A), at least one substance from group (C) and at least one substance from group (E); wherein components (F) and (G) can be added to the mixture at any stage of the mixing process, and before the melt is discharged from the last mixing step, preferably the last extrusion step, excess moisture from the mixture is removed by atmospheric or vacuum degassing, and the resulting mixture in the form of a melt, it is: (i) cooled with a liquid or gas, preferably water or air, and is granulated; (u) or fed into a die for the manufacture of finished products or blanks, preferably by extrusion-based technologies, preferably for the production of cast or blown or biaxially oriented films, extruded profiles and other extruded-based products or blanks.