Method for forming a biodegradable or recyclable hybrid material composition

Abstract

The present invention relates to a method for forming a biodegradable and recyclable hybrid material composition. Additionally, the invention relates to a biodegradable hybrid material composition obtained by such a method and uses of such a composition. The invention also relates to a coating comprising the composition of the invention and uses thereof. In particular, the present invention relates to a method comprising providing a polymetalloxane-biopolymer composition in a liquid state and curing such a composition to form a hybrid material.

Description

Technical Field

[0001] The present invention relates to a method for forming a biodegradable or recyclable hybrid material composition. In addition, the invention relates to a biodegradable or recyclable hybrid material composition obtained by such a method and the use of such a composition. The invention also relates to a coating comprising the composition according to the invention.

Background Art

[0002] In many applications, such as the packaging of food products, cosmetics, pharmaceuticals, etc., barrier properties are required. Appropriate barrier properties protect the product inside the package from light, oxygen and moisture and prevent contamination. Furthermore, undesirable leaching of the product outside the package is prevented by the barrier properties.

[0003] Currently, the required barrier properties are obtained by using the structure of multilayer or composite films. Materials such as metals such as aluminum or tinplate, glass, polymers such as PP, PE, PET or PVDC, and polymers with evaporated metal thin films or oxide films or combinations thereof are generally adopted as components of these structures.

[0004] Compared with metals and glass, polymers have the advantages of being lightweight and requiring less amount of material. Also, due to particular concerns about the ecosystem, the importance of bio-based recyclable polymers has increased very much. However, due to the structure of polymers and their gas permeability and moisture permeability, polymers cannot meet the very high barrier property requirements needed in some applications, such as high humidity and high temperature conditions. This is particularly true for bio-based recyclable polymers.

[0005] To improve the barrier properties of polymers, polymers are often used in combination with other materials, such as thin films of aluminum, aluminum oxide, or silicon oxide. However, even when using these, especially for polymers based on renewable resources, the permeability remains extremely high in many applications.

[0006] In many patents, inventions are disclosed that require a multilayer structure to achieve appropriate barrier properties. These multilayer structures include, for example, metal and / or metal oxide barrier films, both biodegradable and non - biodegradable polymer films, and organic / inorganic composite films.

[0007] Also, hybrid material compositions in which the properties of biopolymers are modified with polysiloxane are known. Patent US2001 / 0056197A1 describes inventions related to ormocers that can be obtained by hydrolysis and condensation of one or more silicon compounds, their production methods, and their use. The name ORMOCER is an abbreviation for "ORganically MOdified CERamics". The hydrolysis and polycondensation of inorganic oxide components and organofunctional silanes are known methods for producing anti - scratch coating materials and achieving good barrier properties (e.g., DE3828098A1).

[0008] Patent publication JP2011195817(A) presents a polylactic acid / silica - based hybrid material obtained by forming a precursor through silane coupling treatment of polylactic acid and then performing hybridization after reacting the precursor with alkoxysilane. US publication 2019062495(A1) describes a method for producing a silane - modified polyester mixture by dissolving polyester and silane in an organic solvent and reacting silane molecules with polyester and / or condensing them with each other.

[0009] In Patent Gazette US2011313114(A1), a method is presented in which polylactic acid is mixed with amino and / or epoxy-modified polysiloxane. The composition is produced in a dissolved state. Gazette US2011313114(A) presents a method for creating a polysaccharide graft polymer by reacting a polysaccharide with an antibacterial agent containing a silane solution (silane, methanol, HCl, and water).

[0010] Further prior art is presented in JP2007076192 and CN105907098.

Summary of the Invention

[0011] The present invention aims to solve at least some of the problems of the prior art.

[0012] The object of the present invention is to produce an environmentally friendly, biodegradable or recyclable coating structure having good barrier properties suitable for packaging, for example, food, cosmetics, etc. The material produced by the method of the present invention has a homogeneous chemical composition or structure and may even be transparent in some cases.

[0013] Accordingly, the present invention relates to a method for obtaining a new type of biodegradable or recyclable chemical composition, which is formed by mixing a biopolymer and a metaloxane prepolymer to form a liquid state polymetaloxane - biopolymer composition, and then curing the composition to form a hybrid material. The metaloxane prepolymer is prepared in a liquid state by hydrolysis and condensation polymerization of the corresponding monomers in the presence of the biopolymer or is provided as a ready - made prepolymer mixed with the biopolymer.

[0014] A metaloxane - biopolymer composition is formed by mixing at least partially condensed prepolymer and a biopolymer and reacting the prepolymer with the biopolymer. As a result, generally, a homophasic material is obtained.

[0015] Thus, in an embodiment, a modified polymetallooxane prepolymer is formed and reacted with a biopolymer to obtain a new type of hybrid material composition.

[0016] In addition, the present invention relates to a composition obtained by the above-described method and the use of such a composition. The present invention also relates to a coating comprising the composition according to the invention.

[0017] In particular, the present invention is characterized by what is described in the independent claims. Some specific embodiments are defined in the dependent claims.

[0018] By using the present invention, several advantages are obtained. In particular, by the method of the invention, a biodegradable or recyclable hybrid material composition having good barrier properties combined with biodegradability or recyclability is obtained. The invention also solves the problem of polymer structures having gas permeability and moisture permeability. The material composition of the present invention is generally homophasic and may even be transparent in some cases. The material composition can take the form of a self-supporting film and / or object and can also serve as an adhesive for various microcellulose and clay compositions. Since the material is suitable for use as a single layer, a multilayer structure is not necessary. Also, problems related to microplastics can be avoided.

[0019] The material composition of the present invention is suitable for use as a relatively thin barrier coating layer for both hard and soft packaging materials. By applying the composition of the present invention to a bio-based, biodegradable, recyclable and / or compostable substrate, the present invention ensures the recyclability of the entire packaging in line with a circular economy.

[0020] In one embodiment, according to the present invention, a homogeneous material is obtained that can be used as a barrier even in the form of a monolayer. In a further embodiment, the material can be used as a barrier in the form of a free-standing monolayer. According to another further embodiment, the material can be used as a barrier in the form of a monolayer without a metal layer. Thus, the barrier material of the present invention exhibits sufficient barrier properties when used as a monolayer, i.e., as the only layer, i.e., usually even without a multilayer structure including a metal layer.

[0021] The barrier coating produced by the method of the present invention can be applied by conventional coating techniques (spraying, brushing, rolling, etc.). Generally, a simple method is preferred and physical vaporization techniques are not necessary.

Brief Description of the Drawings

[0022]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0023] In this context, the term "metaloxane prepolymer" relates to a partially or fully condensed metaloxane polymer having at least one functional group capable of reacting with a biopolymer, and the polymer may further contain oligomeric or monomeric organic residues or segments.

[0024] In this context, the term "liquid state" also includes solutions. Thus, according to the present invention, a material is in the liquid state when the material is the liquid itself, a melt obtained by heating the material above its melting temperature, or is dissolved or at least dispersed in a medium, preferably a solvent.

[0025] Hereinafter, the terms "prepolymer solution" and "biopolymer solution" are generally used when describing the liquid state of a prepolymer and a biopolymer, respectively. In these contexts, the term solution includes any of the above-described types of liquid states.

[0026] The hybrid materials of the present invention are based on the interaction between inorganic and organic species. In the materials, the metaloxane prepolymer and the biopolymer react by forming chemical bonds, such as covalent bonding with each other.

[0027] In the present invention, the term "homogeneous phase" refers to a material having an overall uniform composition that cannot be mechanically separated into different materials.

[0028] The present invention relates to a method for forming a new type of biodegradable or recyclable chemical composition, which is formed by mixing a biopolymer and a metaloxane prepolymer to form a polymetaloxane-biopolymer composition in a liquid state, and then curing the composition to form a hybrid material.

[0029] According to one embodiment, the weight ratio of the biopolymer to the metalloxane prepolymer in the material composition is from 1:99 to 99:1, for example 10:99 or 99:10 or 20:80 or 80:20 or 30:70 or 70:30 or 50:50.

[0030] The method of the present invention includes mixing a metalloxane prepolymer and a biopolymer, each in a liquid state. By mixing the biopolymer with a prepolymer that is at least partially condensed and reacting the prepolymer with the biopolymer, a liquid-state metalloxane-biopolymer composition is formed. As a result, a material that is generally a homogeneous phase is obtained.

[0031] According to one embodiment, the obtained liquid-state metalloxane-biopolymer composition is a liquid, a solution, or a gel. Preferably, the composition of the present invention is transparent, that is, a transparent liquid, a transparent solution, or a transparent gel.

[0032] In the first step of the method, the biopolymer is brought into a liquid state. According to one embodiment, this is carried out by dissolving the biopolymer in a solvent, at least basically.

[0033] Preferably, the biopolymer is a water-soluble polymer, and according to a preferred embodiment, the liquid phase of the biopolymer is provided as an aqueous solution. Thus, no organic solvent is required.

[0034] According to another embodiment, a solvent other than water, such as an aqueous solvent, an organic solvent, or a solvent mixture, can be used.

[0035] According to one embodiment, the aqueous biopolymer solution is preferably prepared by mixing the biopolymer and DI water by stirring at room temperature in a round-bottom flask. The stirring time may vary; typically less than 1 hour, preferably less than 30 minutes, for example about 15 minutes. Next, the mixture is preferably gradually heated to a temperature of about 50 - 100 °C, for example about 90 °C, and typically held there for less than 1 hour, typically less than 30 minutes. Once a clear solution is obtained, the hot mixture is filtered, for example by using a 25-micron filter.

[0036] According to another embodiment, the liquid phase containing the biopolymer is provided as a melt. The melt is typically obtained by heating the biopolymer in a round-bottom flask in an oil bath at about 80 - 100 °C above its melting temperature. The melting temperature of the biopolymers used in the present invention is typically in the range of 80 - 300 °C, preferably in the range of 80 - 170 °C, and most preferably in the range of 80 - 100 °C.

[0037] Biopolymers are materials produced from renewable resources such as agricultural raw materials, fatty acids, and organic waste. Biodegradable polymers are defined as materials that degrade and completely decompose when exposed to microorganisms, carbon dioxide processes, methane treatment, and / or water treatment. Many bio-based polymers are biodegradable, but there are also non-degradable bio-based polymers. Furthermore, not all biodegradable polymers are bio-based, and there are also oily biodegradable polymers.

[0038] Natural bio-based polymers are bio-based polymers of the types found in nature, such as proteins, nucleic acids, and polysaccharides. The biological materials of polymers can be classified into polymers that are degradable by hydrolysis and polymers that are enzymatically degradable, depending on their degradation forms. Considering the present invention, biodegradable polymers are preferred, and bio-based biodegradable polymers are most preferred.

[0039] Biobased polymers can be produced in three main ways: (1) partially modifying natural biobased polymers (e.g., starch), (2) producing biobased monomers by fermentation / conventional chemistry followed by polymerization (e.g., polylactic acid), and (3) directly producing biobased polymers by bacteria (e.g., polyhydroxyalkanoates).

[0040] The biodegradable polymers of the present invention are derived from, for example, agricultural residues, waste, and crops, although in some cases oil-based biodegradable polymers can also be used. The biobased materials can be polymers derived from monomers consisting of different components such as, for example, alcohols, organic acids, alkenes, and the like.

[0041] According to a preferred embodiment, the biopolymers used in the method exhibit terminal OH groups and / or double bonds.

[0042] In this context, the term "biodegradable" has its conventional meaning of a material that can be decomposed (broken down) by the action of microorganisms such as bacteria or fungi or both, when used in relation to materials such as biopolymers or hybrid material compositions, particularly when utilized in their organic portion. The decomposition can occur via aerobic and anaerobic processes and ultimately typically results in the generation of carbon dioxide from the organic material. Biodegradation generally occurs in the presence of water. The biodegradation of organic matter can be affected by the temperature and pH of the surrounding environment and may take from days to months or even years to complete.

[0043] In embodiments, the material is biodegradable or recyclable or both. In embodiments, the organic portion of the hybrid material is typically biodegradable and enables the recovery of the typically recyclable non-organic portion. Depending on the degree of biodegradability of the organic portion, the non-organic portion can also be at least partially recycled.

[0044] "Recyclability" refers to the ability of a material to be collected, typically sorted, aggregated into the recycling process stream, and ultimately become a raw material that can be used in the production of new products.

[0045] According to one embodiment of the present invention, the biopolymer is a cellulose ester such as cellulose acetate (CA), cellulose acetate butyrate (CAB), cellulose acetate phthalate (CAP), nitrocellulose (CN), a cellulose mixed ester such as carboxymethyl cellulose (CMC), other ionic water-soluble celluloses such as sodium carboxymethyl cellulose, other non-ionic celluloses, crystalline cellulose (MCC), microfibrillated cellulose (MFC), nanofibrillated cellulose (NFC), methyl cellulose (MC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC); or polyvinyl pyrrolidone (PVP); biopolybutylene succinate (BioPBS); polyhydroxyalkanoate (PHA); polyhydroxybutyrate (PHB); poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV); polylactic acid or polylactide (PLA); polyglycolic acid or polyglycolide (PGA); starch; chitosan; xylan; lignin, etc., a biodegradable polymer material, or a combination of two or more of the foregoing polymer materials.

[0046] According to another embodiment of the present invention, the biopolymer is poly(butylene adipate) (PBA), polybutylene adipate terephthalate (PBAT), poly(butylene succinate) (PBS), poly(butylene succinate adipate) (PBSA), poly(butylene sebacate) (PBSE), poly(ethylene adipate) (PEA), poly(ethylene succinate) (PES), poly(ethylene succinate coadipate) (PESA), poly(ethylene sebacate) (PESE), poly(orthoester) (POE), polyphosphazene (PPHOS), poly(propylene succinate) (PPS), poly(tetramethylene adipate) (PTA), poly(tetramethylene succinate) (PTMS), poly(tetramethylene sebacate) (PTSE), poly(trimethylene terephthalate (PTT), polyanhydride, poly(butylene succinate colactide) (PBSL), poly(butylene succinate coterephthalate) (PBST), polybutylene adipate coterephthalate (PBAT), polycaprolactone (PCL), polymethylene adipate / terephthalate (PTMAT), poly(vinyl alcohol) (PVOH, PVA, or PVAl), polydioxanone (PDS), polyglycolide or poly(glycolic acid) (PGA) and / or polyethylene glycol (PEG), and the like, which are fossil-based polymer materials.

[0047] According to a preferred embodiment, the biopolymer is selected from the group consisting of polyvinyl alcohol, polylactic acid, polylactide, polyglycolic acid, polyglycolide, polybutylene succinate, polyhydroxyalkanoic acid, polyhydroxybutyric acid, and combinations thereof.

[0048] According to one embodiment, the biopolymer is a polyester. Preferably, the polyester is selected from the group consisting of polylactic acid, polylactide, polyglycolic acid, polyglycolide, polybutylene succinate, polyhydroxyalkanoic acid, polyhydroxybutyric acid, and combinations thereof. The polyester is poorly soluble in water. Therefore, according to a preferred embodiment, the polyester is used as a melt.

[0049] According to another embodiment, the polyester can be used in a liquid state, preferably by using a solvent other than water, such as an organic solvent.

[0050] According to one embodiment, the concept of the biopolymer in the present invention also includes bio-monomers, dimers and oligomers that can be derived from the biopolymer or act as components of the biopolymer. As an example, L-lactide can be mentioned.

[0051] In the present invention, one or more different biopolymers may be used. For example, two different biopolymer solutions can be mixed. When more than one biopolymer solution is used, the solutions are usually mixed by stirring at room temperature before being mixed with the metaloxane prepolymer.

[0052] According to one embodiment, the biopolymer solution formed by the polyester is mixed with other biopolymer solutions, such as biopolymer solutions based on cellulose or lignin biopolymers. By adding cellulose or lignin biopolymers to the polyester biopolymer, the mechanical properties and thermal stability of the polyester can be improved.

[0053] The metaloxane prepolymer used in this method is prepared in a liquid state by hydrolysis and condensation polymerization of the corresponding monomer. The metaloxane prepolymer can be supplied as a ready-made prepolymer to the mixture of the prepolymer and the biopolymer. Also, the prepolymer can be prepared in a liquid state in the presence of the biopolymer, that is, in situ.

[0054] Accordingly, the next step of the method is to provide a liquid state metaloxane prepolymer or metaloxane. The metaloxane monomer may be added directly to the liquid phase of the biopolymer. When adding a metaloxane solution or metaloxane monomer to the biopolymer in the liquid state, the metaloxane prepolymer is formed in situ in the liquid state biopolymer, such as a biopolymer solution.

[0055] As described above, the biopolymer in the liquid state may be the liquid itself, a melt obtained by heating the material above its melting temperature, or a solution, i.e., dissolved or at least dispersed in a medium, preferably a solvent.

[0056] According to one embodiment, the metaloxane solution is formed at room temperature, typically in less than 1 hour, such as about 15 minutes, by mixing one or several different metaloxane monomers. The mixture can be diluted, for example, with 1-propanol.

[0057] According to another embodiment, the metaloxane prepolymer is formed at room temperature, typically in less than 1 hour, such as 15 minutes, by mixing one or several different metaloxane monomers. Typically, a catalyst is added and stirring is continued for several hours. The mixture can be diluted.

[0058] Also, different prepolymers can be used and the prepolymer solutions are preferably mixed together prior to mixing with the biopolymer. According to another embodiment, a further prepolymer solution can be added to the already mixed prepolymer - biopolymer composition.

[0059] The method of the present invention includes mixing a biopolymer with a polymethoxane prepolymer. According to one embodiment, the polymethoxane prepolymer, the methoxane solution or the methoxane monomer in the liquid state is gradually added to the biopolymer in the liquid state, i.e., the biopolymer liquid, the dissolved matter or the solution. Preferably, the liquid phase is stirred, especially vigorously stirred, during the addition or formation of the polymethoxane prepolymer.

[0060] According to one embodiment, the mixture of the methoxane prepolymer and the biopolymer can be stirred at room temperature. According to another embodiment, the stirring is carried out at a temperature rise of about 60 to 100 °C, for example about 80 to 90 °C.

[0061] According to one embodiment, a colloidal solution is formed by gradually adding a polymethoxane prepolymer, a methoxane solution or a methoxane monomer to the liquid phase of the biopolymer.

[0062] The polymethoxane prepolymer is a polymer formed in a liquid state by hydrolysis and condensation polymerization of the corresponding monomer, and a polymer having a methoxane skeleton formed by repeating -metal-O- units can be obtained. Properties such as the molecular weight of the prepolymer are controlled by hydrolysis and condensation conditions. Typically, the molecular weight of the produced prepolymer, i.e., the weight average molar mass, is measured by GPC (gel permeation chromatography) with respect to standard polystyrene and is 1000 to 100000 g / mol, especially 2000 to 20000 g / mol. By changing the conditions, different structures such as linear structures, more branched structures, and branched structures are formed. The degree of condensation of the prepolymer can also be adjusted to an appropriate level.

[0063] According to one embodiment, pH and temperature conditions can be used to affect the properties of prepolymers. Generally, alkaline conditions favor condensation over hydrolysis. By changing the pH conditions and temperature, it is possible to "manipulate" the structure and reactivity of the metaloxane compound. For example, more OH groups can be introduced into the structure to increase the reactivity of the compound. Adjustment of pH and temperature can be carried out prior to, during, or after the bonding of the metaloxane component and the biopolymer.

[0064] According to one embodiment, the polymetaloxane prepolymer is selected from the group consisting of siloxane, germanooxane, aluminoxane, titanoxane, zirconoxane, ferroxane, and stannoxane prepolymers and is formed by hydrolyzing and at least partially condensing the corresponding monomers.

[0065] According to one embodiment, at least 20 mol%, particularly at least 40 mol%, for example 50 - 99 mol% of the corresponding monomers are hydrolyzed and condensed to form the polymetaloxane prepolymer.

[0066] Hydrolysis and condensation of the corresponding monomers are carried out under acidic, alkaline, or neutral conditions.

[0067] According to a preferred embodiment, hydrolysis and condensation are carried out in the presence of an acid, preferably an organic acid.

[0068] According to an even more preferred embodiment, the organic acid includes monomeric organic acids and the biopolymer is at least partially bound to the metaloxane prepolymer using these monomeric organic acids. Thus, the organic acid may be bound to the polymer backbone and no harmful acid remains free.

[0069] According to a further preferred embodiment, the organic acid used is polyfunctional, particularly bifunctional. Such an acid can react with the prepolymer and / or biopolymer from both of its ends. Preferably, the organic acid has a group capable of reacting with at least the end groups of the biopolymer.

[0070] According to one embodiment, the organic acid monomer reacts with the monomer corresponding to the metaloxane polymer, thereby becoming part of the formed metaloxane prepolymer.

[0071] Thus, according to one embodiment, the prepolymer is formed in the presence of an acid selected from the group consisting of inorganic acids including nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, or organic acids including lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, itaconic acid, fumaric acid, succinic acid, gluconic acid, glutamic acid, malic acid, maleic acid, 2,5-furandicarboxylic acid, 3-hydroxypropionic acid, glucaric acid, aspartic acid, levulinic acid and combinations thereof.

[0072] According to a preferred embodiment, the prepolymer is formed in the presence of an acid selected from the group consisting of bifunctional acids, particularly nitric acid, phosphoric acid, sulfuric acid, lactic acid, citric acid, oxalic acid, fumaric acid, succinic acid, gluconic acid, glutamic acid, malic acid, maleic acid, 2,5-furandicarboxylic acid, 3-hydroxypropionic acid, glucaric acid, aspartic acid, levulinic acid and combinations thereof.

[0073] Preferably, the bifunctional acid is selected from the group consisting of levulinic acid, succinic acid, malic acid and combinations thereof. Levulinic acid, succinic acid and malic acid are bifunctional acids having both a hydroxyl group and a carboxyl group. Therefore, these acids can efficiently react through two different types of suitable functional groups and change the properties of the produced molecule / (pre)polymer.

[0074] According to one embodiment, the diluted acid has a pH in the range of 0 to 7, preferably 1 to 6, and most preferably 2 to 3.

[0075] One or more organic acids can be used simultaneously. According to one embodiment, at least one organic acid is bifunctional. According to another embodiment, at least two, for example, two to four organic acids are bifunctional. According to a further embodiment, the bifunctional acid or acids are used in combination with one or more monofunctional acids.

[0076] According to one embodiment, at least 50 mol% of the organic acid is bifunctional.

[0077] According to a preferred embodiment, the prepolymer formed in the presence of the above acids contains polysiloxane.

[0078] The metaloxane prepolymer is typically formed at a temperature of 20 to 90 °C. The hydrolysis that occurs prior to condensation can be further limited by adjusting the temperature and pH of the solution. Therefore, the degree of polymerization of the metaloxane monomer can be adjusted by the temperature and pH of the reaction conditions. Typically, the temperature is in the range of 20 to 80 °C and the pH is in the range of 1 to 5, for example, 1.5 to 4. According to another embodiment, the pH is in the range of 8 to 12.

[0079] According to one embodiment, the method of the present invention includes the in situ formation of a polymetaloxane prepolymer in the presence of a biopolymer. Therefore, the method may include the step of combining the biopolymer with one or more metaloxane monomers to form a colloidal solution.

[0080] According to an embodiment, prior to mixing with the biopolymer or in the presence of the biopolymer, either way, the metaloxane monomer that forms the prepolymer is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane (GPTMS), bis(triethoxysilyl)ethane (BTESE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS), and (3-aminopropyl)triethoxysilane (APTES), and combinations thereof.

[0081] According to another embodiment, prior to mixing with the biopolymer or in the presence of the biopolymer, the metaloxane monomer used either way to form the prepolymer is triethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, methyldiethoxyvinylsilane, 1,2-bis(triethoxysilyl)ethane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, phenyltrimethoxysilane, n-butyltriethoxysilane, n-octadecyltriethoxysilane, acryloxypropyltrimethoxysilane, allyltrimethoxysilane, aminopropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, phenanthrene-9-triethoxysilane, 3-glycidoxypropyltrimethoxysilane, diphenylsilanediol, 1,2-bis(trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, epoxycyclohexylethyltrimethoxysilane, 1-(2-(trimethoxysilyl)ethyl)cyclohexane-3,4-epoxide, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane, trimethoxy(3,3,3-trifluoropropyl)silane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, glycidyl methacrylate and mixtures thereof. These can be used alone, in combination with each other, or with the above-described metaloxane monomers.

[0082] According to one embodiment, at least a portion of the metaloxane monomers are monomers having a functional group. Preferably at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol% of the monomers have a functional group.

[0083] According to one embodiment, at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol% of the metaloxane monomers are selected from the group consisting of 3-glycidoxypropyltrimethoxysilane (GPTMS), bis(triethoxysilyl)ethane (BTESE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS) and (3-aminopropyl)triethoxysilane (APTES) and combinations thereof.

[0084] According to one embodiment, all of the metaloxane monomers are selected from the group consisting of 3-glycidoxypropyltrimethoxysilane (GPTMS), bis(triethoxysilyl)ethane (BTESE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS) and (3-aminopropyl)triethoxysilane (APTES) and combinations thereof.

[0085] According to one embodiment, the metaloxane monomers always include at least one dipodal monomer, preferably a BTESE silane monomer. As a bissilyl-functional silane, BTESE has six hydrolyzable groups and can therefore form more cross-links than trifunctional and tetrafunctional analogs. The resulting cross-linked sites can, for example, result in better barrier properties. In addition, the unique structure of BTESE can improve adhesion and weather resistance. According to one embodiment, at least 20 mol%, preferably at least 50 mol% of the metaloxane monomers are of the BTESE monomer species.

[0086] According to one embodiment, GPTMS can be used as a metaloxane monomer. GPTMA is an epoxy-functional silane that is particularly employed as an adhesion-promoting additive, eliminating the need for a separate primer. GPTMS can potentially react in various ways via its epoxy group. According to a further embodiment, GPTMS can be combined with APTES to form a resin-based material.

[0087] According to another embodiment, MTMS can be used alone or in combination with other metaloxane monomers. MTMS is one of the most common alkoxy crosslinking agents due to its high reactivity. The reaction usually proceeds by nucleophilic substitution in the presence of an acid catalyst or a base catalyst. The alkoxide either reacts directly with the silanol or reacts with water to produce silanol. The newly formed silanol can react with other alkoxides or self - condense to produce siloxane bonds and water. When an acid catalyst is used, the reactivity of the leaving group is increased by protonation of the alkoxysilane. When a base catalyst is used, a reactive silonate anion is formed by deprotonation of the silanol. Acid catalysts and base catalysts are each used in the present invention and can prepare prepolymers with various molecular weights. MTMS has high miscibility with standard organic solvents.

[0088] According to one embodiment, PTMS can be used alone or in combination with other metaloxane monomers. PTMS contains phenyl groups that exhibit excellent thermal stability and impart flexibility to the system. All three alkoxy groups can be hydrolyzed to obtain a strong and highly hydrophobic material. PTMS is particularly suitable for polymers treated at elevated temperatures as it reduces the viscosity of the polymer melt.

[0089] According to one embodiment, APTES can be used alone or in combination with other metaloxane monomers. APTES is a versatile amino - functional binder used in a wide range of applications and provides excellent bonding between inorganic substrates and organic polymers. The silicon - containing part of the molecule provides a strong bond to the substrate. The primary amine functional group reacts with some thermosetting resins, thermoplastics, and elastomeric materials. In the present invention, APTES reacts with sites suitable for biopolymers. The amine group of APTES can react, for example, with the carbonyl group of a biopolymer or with the ortho - position of the free phenolic hydroxyl group of lignin.

[0090] Only one type of metaloxane monomer or a mixture of two or more different metaloxane monomers can be used. Preferably, the metaloxane prepolymer is formed from a mixture of metaloxane monomers containing at least two different metaloxane monomers.

[0091] The combination of metaloxane monomers defines the structure (linear or branched) of the resulting hybrid material.

[0092] According to one embodiment of the present invention, in addition to the metaloxane prepolymer, the corresponding dimer or monomer can be used in the composition. The dimer has a molecular weight, i.e., a weight-average molar mass, typically of 500 to 2000 g / mol as measured by gel permeation chromatography (GPC) relative to standard polystyrene.

[0093] According to a preferred embodiment, the biopolymer is chemically bonded, particularly cross-linked, to the metaloxane prepolymer during the method of the present invention. This is achieved by modifying the prepolymer to contain reactive groups.

[0094] According to a preferred embodiment, the metaloxane prepolymer of the present invention is a siloxane prepolymer formed by hydrolyzing the hydrolyzable groups of the silane monomer and subsequently at least partially further polymerizing it by a condensation process.

[0095] The hybrid material composition of the present invention is obtained from the polymetaloxane - biopolymer composition through a curing stage.

[0096] The curing stage is a chemical reaction that strengthens or cures the polymer hybrid material composition by scientifically bonding the metaloxane prepolymer and the biopolymer. The curing stage can be initiated, for example, by heat, radiation, an electron beam, or a chemical additive.

[0097] According to one embodiment, the curing stage is carried out by raising the temperature of the composition, adding a catalyst to the composition, or adjusting the pH of the composition, or by combining two or all of the above options.

[0098] According to one embodiment, the catalyst is used in the curing stage of the composition. Preferably, the catalyst composition used includes metal alkoxides such as magnesium isopropoxide, calcium isopropoxide, aluminum isopropoxide, titanium isopropoxide, zirconium isopropoxide, titanium acetylacetonate, titanium butoxide, aluminum lactate, iron lactate, and zinc lactate, or non-metal alkoxides, or oxides such as zinc oxide, titanium oxide, and tin oxide, or non-metal octoate complexes such as zinc octoate, germanium octoate, iron octoate, and tin octoate.

[0099] According to one embodiment, the method of the present invention includes forming one or more mixed biopolymer solutions, forming a metaloxane prepolymer solution, and mixing the biopolymer solution and the metaloxane solution, followed by curing the obtained composition.

[0100] The present invention also relates to a biodegradable or recyclable hybrid material composition obtained by the above-described method. According to one embodiment, the material composition is homogeneous. In one embodiment, the material composition, preferably the homogeneous composition, is transparent, translucent, or opaque.

[0101] The composition of the present invention can be used as a single layer or as one or several layers of a multilayer coating, preferably on a bio-based substrate, to obtain a recyclable packaging or article.

[0102] "Bio-based substrate" refers to materials generally obtained from biomass, such as in the form of carbohydrates (e.g., carbohydrate materials, lignocellulosic materials, especially fibrous materials), proteinaceous materials, and lipid-containing materials and combinations thereof. Typically, such materials are biodegradable, recyclable, and / or compostable. Specific examples of bio-based substrates include fibrous sheets, fabrics, or objects, especially sheets or fabrics of cellulose or lignocellulosic materials such as paper and cardboard. Other materials that can be made into sheets or fabrics can also be used as coatings, and such materials include, for example, thermoplastic polymers (e.g., polyesters) such as biopolymers, especially polyhydroxyalkanoates such as polylactic acid, polylactide, polyglycolide, polycaprolactone, polyhydroxybutyric acid, and copolymers of monomers that form one or several of the foregoing polymers.

[0103] In addition, the present invention relates to a coating comprising the material composition according to the invention, and the coating can be homogeneous. The coating can also be used as a free-standing coating and can have a thickness of 0.01 to 1000 μm, for example 0.1 to 250 μm, such as 0.05 to 500 μm. In one embodiment, the thickness is about 1 to 200 μm, for example about 2 to 150 μm or 5 to 100 μm.

[0104] The coating of the present invention may be applied by any conventional method, such as by spraying, brushing, rolling, or curtain coating. According to an embodiment, the coating can be applied by a non-contact method, i.e., without contacting the surface to be coated.

[0105] It should be understood that the embodiments of the disclosed invention are not limited to the specific structures, process steps, or materials disclosed herein and extend to equivalents thereof that would be recognized by those skilled in the art. It should also be understood that the technical terms used herein are used only for the purpose of describing specific embodiments and are not intended to be limiting.

[0106] References to one embodiment or an embodiment throughout this specification mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. For example, when referring to a numerical value using terms such as about or substantially, the exact numerical value is also disclosed.

[0107] As used herein, a plurality of items, structural elements, components, and / or materials may be presented together in a common list for convenience. However, such lists should be construed so that each member of the list is individually recognized as a separate and unique member. Thus, just because the individual members of such a list are presented in a common group without an indication to the contrary, they should not be construed as de facto equivalents of any other member of the same list. Additionally, various embodiments and examples of the invention may be referred to herein with alternative arrangements of their various components. It should be understood that such embodiments, examples, and alternatives are not to be construed as de facto equivalents of one another, but rather as separate and autonomous presentations of the invention.

[0108] Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In this description, numerous specific details are provided, such as examples of length, width, shape, etc., for the purpose of providing a thorough understanding of the embodiments of the invention. However, one of ordinary skill in the art will recognize that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, etc.

[0109] The previous examples have illustrated the principles of the present invention in one or more specific applications, but it will be apparent to those skilled in the art that numerous modifications are possible in the form of implementation, use, and details without exercising inventive talent and without departing from the principles and concepts of the invention. Accordingly, the invention is not intended to be limited except as defined by the claims described below.

[0110] The following non-limiting examples are for merely explaining the advantages obtained by embodiments of the present invention.

Example

[0111] Example 1 Preparation of Solution 1 - Aqueous Solution of Biodegradable Polymer 376 g of DI water was added to 24 g of Poval 25 - 98R powder (PVA) and charged into a round-bottom flask. The mixture was stirred at room temperature for 15 minutes. After obtaining a homogeneous and cloudy solution, the round-bottom flask was equipped with a condenser and placed in an oil bath. The mixture was gradually heated to 90°C over 45 minutes and held at 90°C for 15 minutes. After obtaining a transparent solution, the hot mixture was filtered using a 25-micron filter. Preparation of Solution 2 - Aqueous Solution of Biodegradable Polymer 376 g of DI water was added to 24 g of Exeval HR3010 powder (PVOH) and charged into a round-bottom flask. The mixture was stirred at room temperature for 15 minutes. After obtaining a homogeneous and cloudy solution, the round-bottom flask was equipped with a condenser and placed in an oil bath. The mixture was gradually heated to 90°C over 45 minutes and held at 90°C for 15 minutes. After obtaining a transparent solution, the hot mixture was filtered using a 25-micron filter. Preparation of Solution 3 - Mixture of Biodegradable Polymers Solution 1 (75 g) and Solution 2 (225 g) were mixed in a round-bottom flask and stirred at room temperature for 15 minutes. To the transparent mixture, 1.68 g of acetic acid was slowly added using a dropping funnel. The reaction mixture was stirred at room temperature for 1 hour. Preparation of Solution 4 - Siloxane Solution BTESE (2.65 g, 0.0075 mol), MTMS (0.25 g, 0.0018 mol) and GPTMS (3.78 g, 0.0160 mol) were charged into a round-bottom flask. The monomer mixture was stirred at room temperature for 15 minutes and diluted with 1-propanol (6.63 g). Preparation of Solution 5 - Final Product Solution 4 was added dropwise to Solution 3 and placed in an oil bath. The reaction mixture was warmed to 88 °C and stirred continuously for 1 hour. The obtained clear solution was stirred overnight at room temperature. After cooling, the mixture was diluted by using EtOH (40 g, 60%).

[0112] Example 2 Preparation of Solution 1 - Aqueous Solution of Biodegradable Polymer It was prepared as the corresponding solution of Example 1. Preparation of Solution 2 - Aqueous Solution of Biodegradable Polymer It was prepared as the corresponding solution of Example 1. Preparation of Solution 3 - Polysiloxane Prepolymer BTESE (20.0 g, 0.05640 mol), GPTMS (105.0 g, 0.44428 mol) and 2-propanol (51 g) were charged into a round-bottom flask. The monomer mixture was stirred at room temperature for 15 minutes, and then 0.01 M nitric acid (26.9 g) was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 3 hours and diluted with 2-propanol (100.0 g). The molecular weight of the polymer was in the range of 1000 - 20000 g / mol based on gel permeation chromatography (GPC) measurement. Preparation of Solution 4 - Final Product Solution 1 (5 g) and Solution 2 (10 g) were mixed in a round-bottom flask and stirred at room temperature for 15 minutes. To the clear mixture, 1.14 g of Sivo140; 0.85 g of Solution 3; 0.19 g of Coatosil200, and 0.76 g of 1-propanol were added at room temperature. The reaction mixture was stirred at room temperature for 15 minutes in a flask equipped with a reflux condenser and then transferred to an oil bath. The mixture was gradually heated to 88 °C over 45 minutes and held at 88 °C for 60 minutes. After obtaining a clear solution, the hot mixture was cooled by stirring at room temperature for 12 hours and filtered using a 0.45 PTFE filter.

[0113] Example 3 Preparation of Solution 1 - Aqueous solution of biodegradable polymer It was prepared as the corresponding solution of Example 1. Preparation of Solution 2 - Aqueous solution of biodegradable polymer It was prepared as the corresponding solution of Example 1. Preparation of Solution 3 - Final product Solution 1 (5 g) and Solution 2 (10 g) were mixed in a round-bottom flask and stirred at room temperature for 15 minutes. To the clear mixture, 0.6 g of 1-propanol; 0.03 g (0.00016 mol) of MTEOS; and 0.15 g of propylene carbonate were added at room temperature. The reaction mixture was stirred at room temperature for 15 minutes in a flask equipped with a reflux condenser and then transferred to an oil bath. The mixture was gradually heated to 88 °C over 45 minutes and held at 88 °C for 60 minutes. After obtaining a clear solution, the hot mixture was cooled by stirring at room temperature for 12 hours and filtered using a 0.45 PTFE filter.

[0114] Example 4 Preparation of Part A Preparation of Solution 1A - Aqueous solution of biodegradable polymer It was prepared as the corresponding solution of Example 1. Preparation of Solution 2A - Aqueous solution of biodegradable polymer It was prepared as the corresponding solution of Example 1. Preparation of Solution 3A - Polysiloxane prepolymer BTESE (20.0 g, 0.05640 mol), GPTMS (105.0 g, 0.44428 mmol) and 2-propanol (51.0 g) were charged into a round-bottom flask. The monomer mixture was stirred at room temperature for 15 minutes, and then 0.01 M nitric acid (26.9 g) was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 3 hours and diluted with 2-propanol (100.0 g). Preparation of Solution 4A - Part A Final Product Solution 1 (5 g) and Solution 2 (10 g) were mixed in a round-bottom flask and stirred at room temperature for 15 minutes. To the clear mixture, 0.15 g of Coatosil 200; 0.67 g of Solution 3; 0.15 g of propylene carbonate, and 0.60 g of 1-propanol were added at room temperature. The reaction mixture was stirred at room temperature for 15 minutes. Preparation of Part B Preparation of Solution 1B - Polysiloxane Prepolymer APTES (30.3 g, 0.1369 mol), and 2-propanol (9.16 g) were charged into a round-bottom flask and stirred at room temperature for 15 minutes. Subsequently, 0.01 M nitric acid (5.52 g) was added dropwise at room temperature for 30 minutes. The reaction mixture was stirred at room temperature for 12 hours and diluted with PGME (30.0 g) to 33% of the solids. Preparation of Solution 2B - Part B Final Product To 0.6 g of Solution 1B, 0.1 g of Carbosil 530 was added. The mixture thus obtained was stirred at room temperature for 1 hour. Preparation of Final AB Material Solution 4A was mixed with Solution 2B at room temperature and stirred for 2 hours.

[0115] Example 5 Preparation of Solution 1 - L-Lactide L-Lactic acid (50 g, 0.56 mol) was charged into a round-bottom flask and stirred at 175 °C for 3 hours. Subsequently, a 0.1 wt% solid tin oxide catalyst was added and the temperature was raised to 230 °C. The formed L-lactide was separated from the mixture by a vacuum of 5 mbar. The pure solid L-lactide was dissolved by heating at 100 °C in an oil bath in the round-bottom flask. L-Lactide can be obtained from L-lactic acid as described, but commercially available L-lactide is also suitable. Preparation of Solution 2 - Polysiloxane prepolymer 1 GPTMS (14.0 g, 0.0592 mol) and 2-propanol (1.0 g) were charged into a round-bottom flask. The mixture was stirred at room temperature for 15 minutes, and subsequently, 0.01 M nitric acid (3.19 g) was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 3 hours. Preparation of Solution 3 - Polysiloxane prepolymer 2 APTES (30.3 g, 0.1369 mol), and 2-propanol (9.16 g) were charged into a round-bottom flask, stirred at room temperature for 15 minutes, and subsequently, 0.01 M nitric acid (5.52 g) was added dropwise at room temperature for 30 minutes. The reaction mixture was stirred at room temperature for 12 hours and diluted with PGME (30.0 g) to 33% of the solids. Preparation of Solution 4 - Final product Solution 2 (2 g) and Solution 3 (0.5 g) were mixed in a round-bottom flask and added dropwise to Solution 1 (2 g) placed in an oil bath. After the addition, the mixture was heated to 110 °C, held at 110 °C for 5 minutes, and cooled to room temperature by stirring in an oil bath. A transparent yellow liquid was obtained.

[0116] Example 6 Preparation of Solution 1 - PLA The solid material was dissolved by heating at 80 °C in an oil bath in a round-bottom flask. Preparation of Solution 2 - Polysiloxane prepolymer 1 GPTMS (14.0 g, 0.0592 mol) and 2-propanol (1.0 g) were charged into a round-bottom flask. The obtained mixture was stirred at room temperature for 15 minutes, and subsequently, 1% CH3COOH (3.19 g) was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 3 hours. Preparation of Solution 3 - Polysiloxane prepolymer 2 APTES (30.3 g, 0.1369 mol) and 2-propanol (9.16 g) were charged into a round-bottom flask, stirred at room temperature for 15 minutes, and subsequently, 1% CH3COOH (5.52 g) was added dropwise at room temperature for 30 minutes. The reaction mixture was stirred at room temperature for 12 hours and diluted with PGME (30.0 g) to 33% of the solids. Preparation of Solution 4 - Final product Solution 2 (5 g) and Solution 3 (1.6 g) were mixed in a round-bottom flask and added dropwise to Solution 1 (7 g) placed in an oil bath. After the addition, the mixture was heated to 110°C, held at 110°C for 5 minutes, and cooled to room temperature by stirring in the oil bath. A transparent yellow liquid was obtained.

[0117] Example 7 Preparation of Solution 1 - PLA The solid material was dissolved by heating in an oil bath at 80°C in a round-bottom flask. Preparation of Solution 2 - Polysiloxane prepolymer 1 GPTMS (14.0 g, 0.0592 mol) and 2-propanol (1.0 g) were charged into a round-bottom flask. The mixture was stirred at room temperature for 15 minutes. Subsequently, 1% CH3COOH (5.52 g) was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 3 hours. Preparation of Solution 3 - Polysiloxane prepolymer 2 APTES (30.3 g, 0.1369 mol) and 2-propanol (9.16 g) were charged into a round-bottom flask, stirred at room temperature for 15 minutes. Subsequently, 1% CH3COOH was added dropwise at room temperature for 30 minutes. The reaction mixture was stirred at room temperature for 12 hours and diluted with PGME (30.0 g) to 33% of the solids. Preparation of Solution 4 - Polysiloxane prepolymer 3 BTESE (bis(triethoxysilyl)ethane, 5.6 g, 0.01579 mol), acetone (5.6 g), and 2 - propanol (1.40 g) were charged into a round - bottom flask. An amount of 1.32 g of 1% CH3COOH was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 5 hours. Preparation of Solution 5 - Final product Solution 2 (5 g), Solution 3 (1.6 g), and Solution 4 (0.8 g) were mixed in a round - bottom flask and added dropwise to Solution 1 (7 g) placed in an oil bath. After the addition, the mixture was heated to 110 °C, held at 110 °C for 5 minutes, and cooled to room temperature by stirring in the oil bath. A transparent yellow liquid was obtained.

[0118] Example 8 Preparation of Solution 1 - PLA The solid material was dissolved by heating at 80 °C in an oil bath in a round - bottom flask. Preparation of Solution 2 - Polysiloxane prepolymer 1 BTESE (bis(triethoxysilyl)ethane, 5.6 g, 0.01579 mol), acetone (5.6 g), and 2 - propanol (1.40 g) were charged into a round - bottom flask. An amount of 1.32 g of 1% CH3COOH was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 5 hours. Preparation of Solution 3 - Final product Solution 2 (6 g) was added dropwise to Solution 1 (5 g) placed in an oil bath. After the addition, the mixture was heated to 110 °C and held at 110 °C for 5 minutes. A transparent gel material was obtained.

[0119] Example 9 Preparation of Solution 1 - PLA The solid material was dissolved by heating at 80 °C in an oil bath in a round - bottom flask. Preparation of Solution 2 - Polysiloxane prepolymer 1 BTESE (bis(triethoxysilyl)ethane, 5.6 g, 0.01579 mol), acetone (5.6 g), and 2-propanol (1.40 g) were charged into a round-bottom flask. An amount of 1.32 g of 1% aqueous biosuccinum solution was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 5 hours. Preparation of Solution 3 - Polysiloxane prepolymer 2 PTMS (phenyltrimethoxysilane, 14.00 g, 0.07060 mol) was charged into a round-bottom flask. An amount of 3.81 g of 1% CH3COOH was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 5 hours. Preparation of Solution 4 - Final product Solution 2 (0.48 g) and Solution 3 (4.47 g) were added dropwise to Solution 1 (4.75 g) placed in an oil bath. After the addition, the mixture was heated to 110°C, held at 110°C for 5 minutes, and cooled to room temperature. A transparent liquid material was obtained.

[0120] Example 10 Preparation of Solution 1 - PLA The solid material was dissolved by heating in an oil bath at 80°C in a round-bottom flask. Preparation of Solution 2 - Polysiloxane prepolymer 1 BTESE (bis(triethoxysilyl)ethane, 5.6 g, 0.01579 mol), acetone (5.6 g), and 2-propanol (1.40 g) were charged into a round-bottom flask. An amount of 1.32 g of malic acid was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 5 hours. Preparation of Solution 3 - Final product Solution 2 (3.2 g) was added dropwise to Solution 1 (10.02 g) placed in an oil bath. After the addition, the mixture was heated to 110°C and held at 110°C for 5 minutes. A transparent gel material was obtained.

[0121] Example 11 Preparation of Solution 1 - PLA The solid material was dissolved by heating in an oil bath at 80°C in a round-bottom flask. Preparation of Solution 2 - Polysiloxane Prepolymer 1 BTESE (bis(triethoxysilyl)ethane, 5.6 g, 0.01579 mol), acetone (5.6 g), and 2 - propanol (1.40 g) were charged into a round - bottom flask. An amount of 1.32 g of maleic acid was added dropwise at room temperature for 15 minutes. The reaction mixture was stirred at room temperature for 5 hours. Preparation of Solution 3 - Final Product Solution 2 (3.2 g) was added dropwise to Solution 1 (10.02 g) placed in an oil bath. After the addition, the mixture was heated to 110 °C and held at 110 °C for 5 minutes. A transparent gel material was obtained.

[0122] Example 12 Gel permeation chromatography (GPC) measurements were performed on a siloxane prepolymer (Sample 1), a reaction mixture of a siloxane prepolymer and a biopolymer (Sample 2), and a reaction mixture of a siloxane and a biopolymer (Sample 3) according to some embodiments of the invention. The obtained average molecular weight (M W ) results are shown in Table 1, and the GPC graphs are shown in Figures 1 - 3. Sample 1 is a GPTMS prepolymer hydrolyzed and condensed with biosuccinum acid. Sample 2 is a reaction mixture of dissolved lactide and a BTESE / PTMS prepolymer. BTESE was prepared by condensing with biosuccinum acid, and PTMS was prepared by condensing with CH3COOH. Sample 3 is a reaction mixture of lactide and a PTMS siloxane that forms a prepolymer by hydrolysis and condensation with CH3COOH in the presence of lactide.

[0123] [Table 1]

Industrial Applicability

[0124] Generally, instead of the conventional methods for producing hybrid material compositions, the use of this method enables the production of biodegradable or recyclable hybrid material compositions.

[0125] In particular, the present hybrid material composition is useful for coating applications. In particular, the composition can be used as a single-layer coating on a bio-based substrate. The composition can be used, for example, as a coating for soft and hard substrates and for coatings in the packaging of food products, cosmetics, and pharmaceuticals.

[0126] In addition, the hybrid material composition obtained by the method of the present invention can be used as an adhesive.

Prior Art Documents

Patent Documents

[0127] US2001 / 0056197A1 DE3828098A1 JP2011195817(A) US2019062495(A1) US2011313114(A1)

[0128] As can be understood from the foregoing description and the exemplary experimental examples of the present invention, the present invention can also be described with reference to the following embodiments: 1. A method for forming a biodegradable or recyclable hybrid material composition, comprising: providing a liquid-state polyoxymethylene-biopolymer composition comprising a biopolymer and a polyoxymethylene prepolymer; curing the composition to form the hybrid material; and a method comprising. 2. providing a liquid-state biopolymer; providing a liquid-state polyoxymethylene prepolymer; Mixing the bio-polymer in the liquid state with the polymethoxane prepolymer in the liquid state to provide a bio-polymer-polymethoxane composition, Curing the composition thus obtained to form the hybrid material, The method according to Embodiment 1, obtained by a method comprising: 3. The method according to Embodiment 1 or 2, wherein the polymethoxane prepolymer in the liquid state is gradually added to the liquid phase of the bio-polymer to form a polymethoxane-bio-polymer composition. 4. The method according to any one of Embodiments 1 to 3, wherein the liquid phase is stirred, particularly vigorously stirred, during the addition or formation of the polymethoxane prepolymer. 5. The method according to any one of Embodiments 1 to 4, comprising forming a polymethoxane prepolymer in the liquid state by hydrolysis and condensation polymerization of the corresponding monomer. 6. The method according to any one of Embodiments 1 to 4, comprising providing a ready-made polymethoxane prepolymer in the liquid state. 7. The method according to any one of Embodiments 1 to 6, wherein the bio-polymer is chemically bonded, particularly cross-linked, to the polymethoxane prepolymer. 8. The method according to any one of Embodiments 1 to 7, wherein the bio-polymer is water-soluble. 9. The method according to any one of Embodiments 1 to 8, wherein the bio-polymer exhibits terminal OH groups or double bonds. 10. The biopolymer is a cellulose ester such as cellulose acetate (CA), cellulose acetate butyrate (CAB), cellulose acetate phthalate (CAP), nitrocellulose (CN), a cellulose mixed ester such as carboxymethyl cellulose (CMC), another ionic water-soluble cellulose such as sodium carboxymethyl cellulose, another non-ionic cellulose, crystalline cellulose (MCC), microfibrillated cellulose (MFC), nanofibrillated cellulose (NFC), methyl cellulose (MC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC); or polyvinyl pyrrolidone (PVP); biopolybutylene succinate (BioPBS); polyhydroxyalkanoate (PHA); polyhydroxybutyrate (PHB); poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV); polylactic acid or polylactide (PLA); polyglycolic acid or polyglycolide (PGA); starch; chitosan; xylan; a biodegradable polymer material such as lignin, or a combination of two or more of the foregoing polymer materials, the method according to any one of Embodiments 1 to 9. 11. The method according to any one of Embodiments 1 to 10, wherein the biopolymer is a fossil-based polymer material such as poly(butylene adipate) (PBA), polybutylene adipate terephthalate (PBAT), poly(butylene succinate) (PBS), poly(butylene succinate adipate) (PBSA), poly(butylene sebacate) (PBSE), poly(ethylene adipate) (PEA), poly(ethylene succinate) (PES), poly(ethylene succinate coadipate) (PESA), poly(ethylene sebacate) (PESE), poly(orthoester) (POE), polyphosphazene (PPHOS), poly(propylene succinate) (PPS), poly(tetramethylene adipate) (PTA), poly(tetramethylene succinate) (PTMS), poly(tetramethylene sebacate) (PTSE), poly(trimethylene terephthalate (PTT), polyanhydride, poly(butylene succinate collactide) (PBSL), poly(butylene succinate coterephthalate) (PBST), polybutylene adipate coterephthalate (PBAT), polycaprolactone (PCL), polymethylene adipate / terephthalate (PTMAT), poly(vinyl alcohol) (PVOH, PVA, or PVAl), polydioxanone (PDS), polyglycolide or poly(glycolic acid) (PGA) and / or polyethylene glycol (PEG). 12. The method according to any one of Embodiments 1 to 11, wherein the biopolymer is selected from the group consisting of polyvinyl alcohol, polylactic acid, polylactide, polyglycolic acid, polyglycolide, polybutylene succinate, polyhydroxyalkanoic acid, polyhydroxybutyric acid, and combinations thereof. 13. The method according to any one of Embodiments 1 to 12, wherein the biopolymer is selected from bio-monomers, dimers and oligomers such as L-lactide and combinations thereof. 14. The method according to any one of Embodiments 1 to 13, wherein the liquid phase comprises the biopolymer being provided as an aqueous solution. 15. The method according to any one of embodiments 1 to 13, wherein the liquid phase comprises the biopolymer being provided as a solute. 16. The polymethoxane - biopolymer composition is cured by a step of raising the temperature of the composition, a step of adding a catalyst to the composition, a step of adjusting the pH of the composition, or a combination of two or three of the above steps, according to the method of any one of embodiments 1 to 15. 17. The catalyst composition includes metal alkoxides such as magnesium isopropoxide, calcium isopropoxide, aluminum isopropoxide, titanium isopropoxide, zirconium isopropoxide, titanium acetylacetonate, titanium butoxide, aluminum lactate, iron lactate, and zinc lactate, or non - metal alkoxides, or oxides such as zinc oxide, titanium oxide, and tin oxide, or non - metal octoate complexes such as zinc octoate, germanium octoate, iron octoate, and tin octoate, according to the method of embodiment 16. 18. The polymethoxane prepolymer is selected from the group consisting of siloxane, germanoxane, aluminoxane, titanoxane, zirconoxane, ferroxane, and stannoxane prepolymers, and is formed by hydrolyzing and at least partially condensing the corresponding monomers in the presence of an acid, according to the method of any one of embodiments 1 to 17. 19. The polymethoxane prepolymer is selected from the group consisting of siloxane, germanoxane, and stannoxane prepolymers, and is formed by hydrolyzing and at least partially condensing the corresponding monomers under alkaline or neutral conditions, according to the method of any one of embodiments 1 to 17. 20. The method according to any one of embodiments 1 to 19, including a step of forming a colloidal solution by gradually adding the polymethoxane prepolymer to the liquid phase of the biopolymer. 21. The method according to any one of embodiments 1 to 20, comprising in situ formation of the polymethoxane prepolymer in the presence of the biopolymer. 22. The method according to embodiment 21, comprising the step of forming a colloidal solution by binding one or more metalloxane monomers, such as 3-glycidoxypropyltrimethoxysilane (GPTMS), bis(triethoxysilyl)ethane (BTESE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS) and (3-aminopropyl)triethoxysilane (APTES), to the biopolymer. 23. The method according to any one of embodiments 1 to 22, wherein the average molecular weight of the prepolymer is about 1000 to 100,000 g / mol, preferably 2000 to 20,000 g / mol. 24. The method according to any one of embodiments 1 to 23, wherein the polymethoxane prepolymer is used in combination with the corresponding dimer having a molecular weight of 500 to 2000 g / mol or the corresponding raw monomer. 25. The method according to any one of embodiments 1 to 24, wherein the prepolymer is formed in the presence of an acid, particularly an organic acid. 26. The method according to embodiment 25, wherein the biopolymer is at least partially bound to the polymethoxane prepolymer using a monomeric organic acid. 27. The method according to embodiment 25 or 26, wherein the organic acid is polyfunctional, particularly bifunctional. 28. The method according to any one of embodiments 25 to 27, wherein the organic acid has a group capable of reacting with at least the end groups of the biopolymer. 29. The method according to any one of embodiments 25 to 28, wherein the monomer of the organic acid reacts with the monomer corresponding to the polymethoxane prepolymer, thereby becoming a part of the formed polymethoxane prepolymer. 30. The prepolymer, preferably comprising a polysiloxane, is formed in the presence of an acid selected from the group consisting of inorganic acids including nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, or organic acids including lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, itaconic acid, fumaric acid, succinic acid, gluconic acid, glutamic acid, malic acid, maleic acid, 2,5-furandicarboxylic acid, 3-hydroxypropionic acid, glucaric acid, aspartic acid, levulinic acid and combinations thereof, according to any one of embodiments 1 to 29. 31. The method according to any one of embodiments 1 to 30, comprising the step of providing a polysiloxane, wherein the silane monomer is hydrolyzed and condensed to form a polysiloxane prepolymer, and at least 20 mol%, particularly at least 40 mol%, for example 50 to 99 mol% of the silane monomer is hydrolyzed and condensed. 32. The method according to any one of embodiments 1 to 31, wherein the polysiloxane prepolymer is formed at a temperature of 20 to 90 °C, the hydrolysis occurs prior to the condensation, and can be further limited by adjusting the temperature and pH of the solution. 33. The method according to embodiment 31 or 32, wherein the degree of polymerization of the silane monomer is adjusted by temperature and pH. 34. The method according to any one of embodiments 31 to 33, wherein the polysiloxane prepolymer is formed from a mixture of silane monomers comprising at least two different silane monomers. 35. The method according to any one of embodiments 31 to 34, wherein the polysiloxane prepolymer is formed by hydrolyzing the hydrolyzable groups of the silane monomer and then further polymerizing it partially by a condensation process. 36. A biodegradable or recyclable hybrid material composition obtained by the method according to any one of embodiments 1 to 35. 37. Use of the composition according to embodiment 36 as a single-layer coating on a bio-based substrate. 38. A single-layer coating comprising the composition according to embodiment 36. 39. The coating according to embodiment 38, characterized in that it is self - standing. 40. The coating according to embodiment 38 or 39, having a thickness of 0.01 to 1000 μm. 41. The coating according to any one of embodiments 38 to 40, applied by spraying, brushing or rolling. 42. The composition according to embodiment 36 or the coating according to any one of embodiments 38 to 41, wherein the composition or the coating is homogeneous. 43. The composition according to embodiment 36 or the coating according to any one of embodiments 38 to 41, wherein the composition or the coating is transparent, translucent or opaque. 44. Use of the composition according to embodiment 36 or the coating according to any one of embodiments 38 to 41 as a coating for a soft substrate or a hard substrate. 45. Use of the composition according to embodiment 36 or the coating according to any one of embodiments 38 to 41 in the packaging of foodstuffs, cosmetics or pharmaceuticals. 46. Use of the composition according to embodiment 36 as an adhesive.

Claims

1. A method for forming a biodegradable or recyclable hybrid material composition, comprising: providing a biopolymer in a liquid state, wherein the biopolymer is provided as a melt obtained by heating a polyester above its melting temperature; providing a liquid polymethoxane-biopolymer composition comprising the biopolymer together with a polymethoxane prepolymer; curing the composition to form the hybrid material. A method comprising the steps above.

2. providing a biopolymer in a liquid state; providing a liquid polymethoxane prepolymer in a liquid state; mixing the biopolymer in the liquid state with the polymethoxane prepolymer in the liquid state to provide a biopolymer-polymethoxane composition; curing the composition thus obtained to form the hybrid material. A method according to claim 1, obtained by a method comprising the steps above.

3. The method according to claim 1 or 2, comprising providing a ready-made liquid polymethoxane prepolymer.

4. The method according to any one of claims 1 to 3, comprising providing a ready-made liquid polymethoxane prepolymer formed in a liquid state by hydrolysis and condensation polymerization of the corresponding monomers prior to mixing with the biopolymer.

5. The method according to any one of claims 1 to 4, wherein the biopolymer is chemically bonded to the polymethoxane prepolymer.

6. The method according to any one of claims 1 to 5, wherein the biopolymer is chemically crosslinked to the polymethoxane prepolymer.

7. The method according to any one of claims 1 to 6, wherein the biopolymer is a polyester selected from the group consisting of polylactic acid, polylactide, polyglycolic acid, polyglycolide, polybutylene succinate, polyhydroxyalkanoic acid, polyhydroxybutyric acid, and combinations thereof.

8. The polymethoxane-biopolymer composition is The step of raising the temperature of the composition, The step of adding a catalyst to the composition, The step of adjusting the pH of the composition, or The method according to any one of claims 1 to 7, which is cured by a combination of two or three of the above steps.

9. The polymethoxane prepolymer is selected from the group consisting of siloxane, germanooxane, aluminoxane, titanoxane, zirconoxane, ferroxane and stannoxane prepolymers, and is formed by hydrolyzing and at least partially condensing the corresponding monomers. The method according to any one of claims 1 to 8.

10. The prepolymer is formed in the presence of an acid selected from the group consisting of inorganic acids including nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, or organic acids including lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, itaconic acid, fumaric acid, succinic acid, gluconic acid, glutamic acid, malic acid, maleic acid, 2,5-furandicarboxylic acid, 3-hydroxypropionic acid, glucaric acid, aspartic acid, levulinic acid and combinations thereof. The method according to any one of claims 1 to 9. **Claim 11**: The method according to any one of claims 1 to 10, wherein the prepolymer containing polysiloxane is formed in the presence of an acid selected from the group consisting of inorganic acids including nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, or organic acids including lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, itaconic acid, fumaric acid, succinic acid, gluconic acid, glutamic acid, malic acid, maleic acid, 2,5-furandicarboxylic acid, 3-hydroxypropionic acid, glucaric acid, aspartic acid, levulinic acid and combinations thereof. **Claim 12** The method according to any one of claims 1 to 11, wherein the prepolymer is formed in the presence of an organic acid. **Claim 13**: The method according to any one of claims 1 to 12, wherein the prepolymer is formed in the presence of a monomeric organic acid, and the monomeric organic acid reacts with the monomer corresponding to the polymetalloxane prepolymer and thereby becomes part of the formed polymetalloxane prepolymer. **Claim 14** The method according to claim 12 or 13, wherein the organic acid is polyfunctional. **Claim 15**: The method according to claim 14, wherein the organic acid is bifunctional. **Claim 16**: The method according to claim 15, wherein the organic acid is levulinic acid, succinic acid, malic acid or a combination thereof. **Claim 17** The method according to any one of claims 1 to 16, comprising the step of providing a polysiloxane, wherein the silane monomer is hydrolyzed and condensed to form a polysiloxane prepolymer, and at least 20 mol% of the silane monomer is hydrolyzed and condensed. **Claim 18**: The method according to any one of claims 1 to 17, comprising the step of providing a polysiloxane, wherein the silane monomer is hydrolyzed and condensed to form a polysiloxane prepolymer, and at least 40 mol% of the silane monomer is hydrolyzed and condensed. **Claim 19**: The method according to any one of claims 1 to 18, comprising the step of providing a polysiloxane, wherein the silane monomer is hydrolyzed and condensed to form a polysiloxane prepolymer, and 50 to 99 mol% of the silane monomer is hydrolyzed and condensed. **Claim 20**: The method according to any one of claims 1 to 19, comprising the step of providing a polysiloxane, wherein the silane monomer is hydrolyzed and condensed to form a polysiloxane prepolymer, 50 to 99 mol% of the silane monomer is hydrolyzed and condensed, the polysiloxane prepolymer is formed at a temperature of 20 to 90 °C, and the hydrolysis of the hydrolyzable groups of the silane monomer occurs prior to condensation and may be further limited by adjusting the temperature and pH of the solution. **Claim 21**: The method according to any one of claims 1 to 20, wherein the polymethoxysilane prepolymer is formed from a mixture of silane monomers comprising at least two different silane monomers, and the silane monomer has at least one functional group. **Claim 22**: The method according to any one of claims 17 to 21, wherein the silane monomer is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane (GPTMS), bis(triethoxysilyl)ethane (BTSE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS), and (3-aminopropyl)triethoxysilane (APTES). **Claim 23**: The method according to any one of claims 1 to 22, wherein the polymethoxysilane prepolymer is formed from a mixture of corresponding monomers comprising a methoxysilane monomer, and at least 20 mol% of the corresponding monomer is a BTSE monomer species. **Claim 24** comprising the step of forming a colloidal solution by gradually adding the polymethoxysilane prepolymer to the liquid phase of the biopolymer, wherein the liquid phase is stirred during the addition or formation of the polymethoxysilane prepolymer; the method according to any one of claims 1 to 23. **Claim 25** The method according to any one of claims 1 to 24, comprising the in situ formation of the polymetalloxane prepolymer in the presence of the biopolymer. **Claim 26** The method according to claim 25, comprising the step of forming a colloidal solution by combining one or more metalloxane monomers with the biopolymer. **Claim 27** The method according to claim 26, wherein the one or more metalloxane monomers are selected from 3-glycidoxypropyltrimethoxysilane (GPTMS), bis(triethoxysilyl)ethane (BTSE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS), and (3-aminopropyl)triethoxysilane (APTES). **Claim 28** The method according to any one of claims 1 to 27, wherein the average molecular weight of the prepolymer, i.e., the weight average molar mass, is from about 1000 to 100000 g / mol. **Claim 29** The method according to any one of claims 1 to 28, wherein the average molecular weight of the prepolymer, i.e., the weight average molar mass, is from 2000 to 20000 g / mol. **Claim 30** The polymetalloxane prepolymer is used in combination with a corresponding dimer having a molecular weight of 500 to 2000 g / mol or a corresponding monomer, and the molecular weight is measured by gel permeation chromatography (GPC) with respect to standard polystyrene. The method according to any one of claims 1 to 29. **Claim 31** A biodegradable or recyclable hybrid material composition obtained by the method according to any one of claims 1 to 30. **Claim 32** A single-layer coating comprising the composition according to claim 31, having a thickness of 0.01 to 1000 μm. **Claim 33** A self-supporting single-layer coating according to claim 32. **Claim 34** The coating according to claim 32, applied by spraying, brushing or rolling. **Claim 35** The composition according to claim 31 or the coating according to any one of claims 32 to 34, wherein the composition or coating is homogeneous. **Claim 36** Use of the composition according to claim 31 or the coating according to any one of claims 32 to 34 as a single-layer coating on a bio-based substrate; as a coating for a soft or hard substrate; in the packaging of foodstuffs, cosmetics or pharmaceuticals; or as an adhesive.

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