Composites and uses thereof

Abstract

To provide compositions that yield final composites with preselected and unique mechanical properties.SOLUTION: A composition comprises A) poly(vinyl alcohol) (PVOH) in an amount ranging between 30 and 99 wt.%; B) at least one crosslinking compound being present in an amount ranging between 0.1 and 20 wt.%; C) at least one additional bioplastic in an amount ranging between 0.1 and 50 wt.%; and D) optionally at least one additive in an amount ranging between 0.1 and 20 wt.%.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates generally to methods for producing polymer composite materials and uses thereof. [Background technology]

[0002] Polymers and products made from them represent a significant portion of municipal solid waste. These materials are not biodegradable in nature and some are difficult to recycle. Although it is the general desire of manufacturers to produce biodegradable materials, which would contribute to sustainability and reduce the environmental impacts associated with the disposal of such polymers, significant amounts of contaminating polymers are still produced and disposed of.

[0003] For many years, researchers have been trying to produce polymer compositions that are not only functional, i.e., have certain desired properties, but are also safe, with limited or reduced environmental impact. These attempts are described, for example, in any of the following documents [1]-

[24] : [Prior art documents] [Patent documents]

[0004] [1] International Patent Publication No. 07 / 010553 [2] International Patent Publication No. 13 / 029018 [3] Japanese Patent Publication No. 2009091011 [4] International Patent Publication No. 17 / 214187 [5] International Patent Publication No. 13 / 044266 [6] Japanese Patent No. 4265200 [7] International Patent Publication No. 04 / 037919 [8] International Patent Publication No. 16 / 083667 [9] International Patent Publication No. 14 / 003369

[10] International Patent Publication No. 11 / 098122

[11] International Patent Publication No. 06 / 117801

[12] International Patent Publication No. 06 / 082471

[13] International Patent Publication No. 02 / 053640

[14] International Patent Publication No. 02 / 053610

[15] International Patent Publication No. 07 / 049952

[16] International Patent Publication No. 15 / 142564

[17] International Patent Publication No. 03 / 082970

[18] International Patent Publication No. 91 / 02023

[19] International Patent Publication No. 15 / 145457

[20] International Patent Publication No. 17 / 112878

[21] International Patent Publication No. 95 / 20013

[22] International Patent Publication No. 04 / 074367

[23] International Patent Publication No. 07 / 015261

[24] U.S. Patent No. 7,993,738 Summary of the Invention

[0005] The inventors of the technology disclosed herein have developed a novel method of modifying the properties of raw materials in order to replace long-term degrading polymers, such as plastics, with new materials with pre-tuned degradation. The composite material of the present invention provides a variety of end products constructed based on a selection of materials that, when combined according to the present invention, result in a final composite material with unique pre-selected mechanical properties. It is an essential feature of the technology disclosed herein that a composite material or product with a predetermined life span can be tailored, i.e., how fast the composite material or product will degrade can be determined at the time of manufacture. A product with a predetermined life span can be tailored by selecting an appropriate set of manufacturing parameters, including material composition, amount of material, processing conditions, etc. Such products will, for example, degrade when in contact with water, or will degrade naturally after a pre-designed period of time, leaving less toxic decomposition products, which can sometimes be easily taken up by naturally occurring microorganisms.

[0006] Generally, the present invention provides composites (i.e., raw materials or products) that include an assembly of polymeric and non-polymeric materials in combinations or amounts that impart various properties to the composite. By adjusting the amount of either PVOH, crosslinked moieties, and bioplastics, the properties can be further tailored. Such properties include OTR and / or gas permeability, water solubility (or water degradation), thermal stability, heat seal, and mechanical properties such as tensile strength, Young's modulus, maximum elongation, flexibility, stiffness, shrinkability, or stretchability.

[0007] As disclosed herein, the composition according to the invention is a collection of the disclosed components in a form (composition and amount) suitable for undergoing chemical processing to provide a solid composite material. The composite material is based on and contains the components of the composition from which it is derived, while in the composite material some of the components may be in reacted or crosslinked form. The composite material of the invention may be provided as a raw material, as a masterbatch, in a partially processed form, or in the form of a final product. Non-limiting examples of composite forms include masterbatches, granular raw materials, powdered raw materials, fibers, sheets of any thickness, polymer blocks, and any final product form.

[0008] Accordingly, in a first of its objects, the present invention provides a composition comprising: A - Poly(vinyl alcohol) (PVOH), B - at least one cross-linking compound (e.g., as used herein, selected from polymers, copolymers, and non-polymeric materials); C - at least one additional bioplastic, and D - Optionally, at least one additive A composition comprising:

[0009] In some embodiments, the composition of the present invention comprises: A - poly(vinyl alcohol) (PVOH) in an amount ranging from 30 to 99% by weight; B - at least one cross-linking compound present in an amount ranging from 0.1 to 20% by weight, C - at least one additional bioplastic in an amount ranging from 0.1 to 50% by weight, and D-Optionally, at least one additive in an amount ranging from 0.1 to 20% by weight. Includes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Poly(vinyl alcohol) (PVOH) is a highly hydrophilic, water-soluble polymer. The degree of hydroxylation determines its physical, chemical and mechanical properties; the lower the number of residual acetate groups, the lower its water solubility and the higher its glass transition temperature. Furthermore, the degree of hydroxylation affects the maximum moisture uptake, which acts as a plasticizer, and thus affects the mechanical and physical properties of the polymer. With increasing water uptake, the tensile strength, modulus and hardness decrease, while the impact resistance and elongation at break increase significantly. Both forms of PVOH are encompassed by the invention disclosed herein.

[0011] Films made from PVOH have good heat sealability, excellent barrier properties against gases such as oxygen and carbon dioxide, and are biocompatible, biodegradable and non-toxic. However, the films are highly hydrophilic and highly susceptible to water-induced degradation, making them practically unusable. In order to impart desired mechanical properties to PVOH while controlling the rate of degradation upon exposure to water, the compositions of the present invention further contain one or more additives or materials in specific amounts or in specific material ratios that modify the properties of PVOH and impart one or more desired properties to the composition or composites made therefrom.

[0012] In some embodiments, at least one cross-linking compound is a compound capable of binding or cross-linking to PVOH. As indicated, the cross-linking compound is selected from polymers, copolymers, and non-polymeric materials, each of which has a functional group capable of binding to the PVOH backbone or any functionality present thereon.

[0013] In some embodiments, at least one crosslinking compound is a polymer or oligomer that can crosslink or bond to PVOH. Typically, the crosslinking or bonding to PVOH is chemical in nature, i.e., through the formation of covalent bonds. In other instances, the bonding can be physical, i.e., the polymer chains are intertwined. Regardless of the type of bonding, the crosslinking molecule is selected to allow the bonding to produce the desired physical and mechanical properties.

[0014] The crosslinking compound is one that has a functional group capable of bonding with PVOH. Such functional groups may be native functional groups of the polymer or functional groups that are grafted or bonded or appended to the polymer to provide crosslinking capability. In some embodiments, the functional groups are selected from alcohols, epoxides, anhydrides, carboxylic acids, amines, amides, glycidyl functional groups, aldehyde functional groups, esters, and the like.

[0015] The polymer can be selected from among ionomers, i.e., polymers having functional groups capable of forming ionic groups, in some embodiments, the ionomer is a polyacid, optionally selected from poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), and the like.

[0016] In some embodiments, the crosslinking compound is a polymer grafted with an anhydride, such as maleic anhydride. In some embodiments, the maleic anhydride grafted polymer is selected from polyethylene (PE), poly(lactic acid) (PLA), polycaprolactone (PCL), polyhydroxybutyric acid (PHB), poly(butylene adipate-co-terephthalate) (PBAT), etc. In some embodiments, the crosslinking compound is polyethylene-graft-maleic anhydride.

[0017] In some embodiments, the cross-linking compound is a polymer with carboxylic acid functionality, hi some embodiments, the polymer is selected from poly(ethylene-co-acrylic acid) (PE-co-AA), poly(ethylene-co-methacrylic acid) (PE-co-MAA), poly(lactide-block-acrylic acid) (PLA-block-AA), PVOH with carboxyl groups, carboxymethylcellulose (CMC), and the like.

[0018] In some embodiments, the polymer is poly(ethylene-co-acrylic acid).

[0019] In some embodiments, the polymer is a glycidyl-functional polymer.

[0020] In some embodiments, at least one cross-linking compound is a copolymer.

[0021] In some embodiments, the cross-linking compound is a small molecule cross-linking compound that is not a polymer, oligomer, or copolymer. The compound is typically selected from aldehyde compounds, e.g., compounds having one or more aldehyde functional groups, carboxylic acid compounds, e.g., compounds having one or more carboxylic acid functional groups, and the like.

[0022] In some embodiments, the aldehyde compound can be selected from among monoaldehydes and dialdehydes, hi some embodiments, the aldehyde is selected from formaldehyde, glutaraldehyde, glyoxal, malondialdehyde, succindialdehyde, phthalaldehyde, and the like.

[0023] In some embodiments, the carboxylic acid compounds are selected from monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and higher homologs. Alternatively, these carboxylic acids can be selected based on the number of carboxylate or basic groups that can be formed. Thus, in an equivalent manner, these compounds can be selected from monobasic acids, dibasic acids, tribasic acids, and higher homologs thereof. In some embodiments, the carboxylic acid compounds are selected from citric acid, boric acid, humic acid, phthalic acid, terephthalic acid, malic acid, sulfo-succinic acid, isophthalic acid, aconitic acid, etc.

[0024] The additional bioplastics (or simply "bioplastics") used according to the invention are polymers that are different from the other polymeric components used in the composition, all of which are substantially bioplastics. The additional bioplastics may represent natural polymers produced or derived from natural sources, such as living cells, plants, or other natural sources. Such polymers may be completely natural or partially synthetic, i.e. naturally derived and chemically modified to structurally modify natural polymers. The bioplastics used according to the invention may also represent biodegradable or compostable polymers that are partially or completely derived from petrochemical sources.

[0025] In some embodiments, the additional bioplastics are selected from polypeptides and polysaccharides.

[0026] In some embodiments, the additional bioplastic is selected from an aliphatic or aromatic polyester, copolyester, or polyesteramide.

[0027] In some embodiments, the additional bioplastic is selected from poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polycaprolactone (PCL), poly(lactic acid) (PLA), cellulose and cellulose derivatives, starch, thermoplastic starch (TPS), chitosan, polyhydroxyalkanoates (PHAs) such as polyhydroxybutyrate (PHB).

[0028] Cellulose derivatives are crystalline derivatives or other amorphous forms of such materials. Non-limiting examples include nanocrystalline cellulose (NCC), microfibril cellulose, bacterial cellulose, hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and carboxymethyl cellulose (CMC).

[0029] In some embodiments, the additional bioplastic is PEO.

[0030] In some embodiments, the additional bioplastic is PCL.

[0031] In some embodiments, the additional bioplastic is PEG.

[0032] In some embodiments, the composition comprises both PEO and PCL.

[0033] In some embodiments, the composition comprises PVOH, PAA, PEO, and optionally PCL.

[0034] The at least one additive used in the composition of the present invention can be selected from inorganic additives, fillers or reinforcing agents, and can be selected from low molecular weight additives (molecular weight less than 1000 Da) that improve various properties, such as processing aids, slip agents, light stabilizers, UV absorbers, flame retardants, antibacterial agents, antiviral agents, foaming agents, nucleating agents, antioxidants, antiblocking agents, antistatic agents, etc.

[0035] In some embodiments, the additive is a moisture absorbing agent. Such agents can be selected from CaO, CaCl2, LiCl, NaCl, CaI2, MgCl2, TiO2, CaCO3, alumina silicate filler, SiO2, etc. In some embodiments, the additive is CaO.

[0036] In some embodiments, the additive is an inorganic salt containing a metal element or a non-metal element. In some embodiments, the inorganic salt is an inorganic salt of a metal selected from alkali metals and alkaline metals. In some embodiments, the inorganic salt is a salt of a transition metal. Non-limiting examples of inorganic salts include halide salts of metals selected from Li, K, Ca, Na, Mg, Mn, Zn, etc. Typically, the inorganic salt is a halide salt (the halide atom is the anion of the metal cation). In some embodiments, the inorganic salt is selected from LiCl, NaCl, CaCl2, CaI2, and MgCl2. In some embodiments, the inorganic salt is CaCl2.

[0037] In some embodiments, the compositions used in accordance with the present invention comprise poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA). The compositions may be processed to include one or more additional components selected primarily from inorganic salts, cellulose-derived materials and chitosan.

[0038] The inorganic salts utilized to modify the properties of the solid composite materials of the present invention can be any salt form of a metallic or non-metallic element. In some embodiments, the inorganic salt is an inorganic salt of a metal selected from alkali metals and alkaline metals. In some embodiments, the inorganic salt is a salt of a transition metal. Non-limiting examples of inorganic salts include halide salts of metals selected from Li, K, Ca, Na, Mg, Mn, Zn, etc. Typically, the inorganic salt is a halide salt (the halide atom is the anion of the metal cation). In some embodiments, the inorganic salt is selected from LiCl, NaCl, CaCl2, CaI2, and MgCl2. In some embodiments, the inorganic salt is CaCl2.

[0039] The cellulose-derived material is any such material that includes or is based on cellulose or a cellulose derivative. In some embodiments, the cellulose-derived material is cellulose or its crystalline forms, such as nanocrystalline cellulose (NCC), microfibrillar cellulose, bacterial cellulose, etc. In some embodiments, the cellulose-derived material is selected from hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and carboxymethyl cellulose (CMC).

[0040] By selecting a material composition from the material families disclosed herein, at least one property of the solid polymeric material can be adjusted during the manufacturing process. The property that can be adjusted is a mechanical, chemical or physical property selected from water degradation, gas permeability, stiffness, flexibility and elasticity. More specifically, the property that can be adjusted can be water dissolution or water degradation, oxygen transmission rate (OTR) and / or gas permeability, thermal stability, heat seal, and mechanical properties such as tensile strength, Young's modulus, maximum elongation, flexibility, stiffness, shrinkage or stretch properties.

[0041] Oxygen transmission rate (OTR) measures the amount of oxygen gas that passes through the solid composite material of the present invention at a measured temperature over a given period of time. In addition, increasing the amount of PVOH can prevent the permeation of gases other than oxygen. Such other gases can be, for example, carbon dioxide.

[0042] In some embodiments, the amount of PVOH, the amount of the at least one crosslinking compound, and the amount of the at least one additional bio-plastic are selected to control water degradation of a composite material formed with the composition.

[0043] As mentioned above, it is an essential feature of the technology disclosed herein to be able to tune composites to a given lifespan, i.e., to determine how quickly they will degrade, or in other words, how long they can remain in contact with moisture or water before degrading. The composites of the present invention can be made more or less susceptible to hydrodegradation by controlling the amount of crosslinking materials and / or additional bioplastics utilized, such as PAA and / or PEO or cellulose-derived materials. As used herein, "water degradation" suggests that when a solid composite made from the composition of the present invention comes into contact with water, the composite will partially or completely dissociate. In some cases, the composites of the present invention can be stable against water degradation for a period of time, but will begin to degrade after that period of time. This is referred to herein as the product lifespan. Other products will easily degrade in water only if they are in contact with water for a certain period of time. Such products can be considered to have a chemical self-destruct switch, which can be activated by exposing the composite to water.

[0044] Water degradation can result in the dissociation of the composite material into parts that can be easily decomposed and further hydrolyzed or chemically digested by natural microorganisms. In the present invention, water stability can be tested, verified, or determined based on any such assay known in the art. In some embodiments, one or more of the following can be used: 1- Measuring the time of dissolution or the rate of complete dissolution while stirring in water at room temperature; 2- Determining the time of dissolution or the rate of complete dissolution while stirring in water at a temperature higher than room temperature, or 3-Biodegradability test.

[0045] For example, the rate of water degradation of the composites of the present invention was determined as the time required for the composite to dissolve or decompose under accelerated conditions and stirring at ambient temperature under constant sink conditions, i.e., conditions where the concentration of the composite dissolved in water is negligible compared to the amount of water (three orders of magnitude). Composites containing 0.4-0.55 wt. % PAA exhibited a degradation rate of ∼1 mg / (min × cm). 2 ) decomposition rate. Composites containing 0.6–1.4 wt.% PAA exhibited a decomposition rate of ∼0.2 mg / (min × cm 2 The rate of water decomposition of ) was shown.

[0046] In some embodiments, water degradation increases with increasing amounts of at least one additional bio-plastic relative to the amount of said at least one cross-linked material.

[0047] In some embodiments, water degradation is stopped or slowed or retarded with a decrease in the amount of said at least one additional bio-plastic relative to the amount of said at least one cross-linked material.

[0048] In some embodiments, the at least one cross-linking material and the at least one additional bioplastic are present in a ratio of about 1:5, respectively. In some embodiments, the ratio is PAA:PEO, 1:5.

[0049] In some embodiments, the ratio is 2:8. The ratio is PAA:PEO, 2:8.

[0050] In some embodiments, the ratio of the combined amount of PEO and PAA to PVOH is 2:98, respectively. In other embodiments, the ratio of the combined amount of PEO and PAA to PCL and PVOH is PEO / PAA:PCL:PVOH, 2:5:93.

[0051] Alternatively or additionally, in the composition of the present invention, the amount of the at least one cross-linking material may be from 0.4 to 0.5 wt.%, or from 0.9 to 1.1 wt.%.

[0052] The mechanical properties of flexibility, stiffness and elongation can be similarly adjusted by selecting the appropriate relative amounts of PEO, PAA, cellulose and / or at least one inorganic salt. As is known in the art, flexibility or pliability of a composite measures the stiffness of a product. The more flexible a product is, the less stiff it is. Flexibility is measured as the resistance of a composite to deformation in response to a force applied to the composite. As the amount of PAA increases relative to the other components in the core formulation, the product becomes stiffer and less stretchable.

[0053] Table 1 shows an exemplary list of compositions according to the present invention. It should be noted (as shown in Table 2) that each composition can contain predefined amounts of materials that impart desired properties to a composite material made therefrom.

[0054] The exemplary composites containing 1% PAA and 5% cellulose material exhibited lower sealing temperatures compared to composites containing 1.5% PAA and 1% cellulose material. Similarly, the composites containing 1% PAA and 5% cellulose material exhibited faster water degradation times (10-15 minutes decomposition, measured under agitation at room temperature) compared to composites containing 1.5% PAA and 1% cellulose material, which exhibited moderate range degradation times (20-25 minutes decomposition, measured under agitation at room temperature).

[0055] Composites containing amounts of PAA ranging from 0.1-2 wt% can be tailored to be more or less susceptible to hydrolysis. The higher the amount of PAA present (i.e., amounts closer to the 2 wt% limit), the slower the hydrolysis observed. Lower amounts of PAA (i.e., amounts closer to the 0.1 wt% limit) allow for faster hydrolysis.

[0056] Similarly, composites containing amounts of PEO ranging from 1-10 wt% can be tailored to be more or less susceptible to hydrolysis: the more PEO present (i.e., amounts closer to the 10 wt% limit), the faster the hydrolysis observed.

[0057] TIFF2025072458000001.tif127170

[0058] As Tables 1 and 2 show, increasing the three relative amounts of PAA (see Table 1) increases the sealing temperature (i.e., the temperature required to bond two polymeric materials) (see Table 2) and slows the water degradation. Increasing the amount of PEO accelerates the water degradation (faster under agitation at room temperature).

[0059] TIFF2025072458000002.tif119170

[0060] Compositions 6 and 9 contain the same amount of PEO, but composition 9 contains five times more PAA. As shown in Table 2, the composites made from composition 9 degraded more slowly when in contact with water compared to the composites formed from composition 6, which degraded faster. The sealing temperature of the composites made from composition 6 was lower, while the temperature of the composites made from composition 9 increased with increasing amounts of PAA, as expected.

[0061] When composition 6 is modified by increasing the amount of PAA to produce composites with compositions such as composition 7, the water dissolution rate decreases and the seal temperature increases, consistent with the decrease in dissolution rate due to the relative reduction in the amount of PEO.

[0062] TIFF2025072458000003.tif144170

[0063] The exemplary composite containing 1% PAA and 5% PCL exhibited a lower sealing temperature compared to the composite containing 2% PAA and 1% PCL, and the composite containing 1% PAA and 5% PEO exhibited a faster water degradation time (degraded in 10-15 minutes, measured under stirring at room temperature) compared to the composite containing 2% PAA and 1% PEO, which exhibited a slow range of degradation time (degraded in 40-50 minutes, measured under stirring at room temperature).

[0064] As shown in Table 3, the seal temperature (i.e., the temperature required to bond two polymeric materials) decreased with increasing relative amount of PCL. Compositions 17, 20, and 21 had moderate heat seal temperatures, and compositions 18, 19, and 22 had much lower heat seal temperatures. Increasing the amount of PAA shortened the water decomposition time (under stirring at room temperature). Thus, compositions 14 and 21 have much longer water decomposition times. The amount of PEO can fine-tune the decomposition time, and when a higher amount of PAA is used, the solubility of composition 13 is faster than that of composition 11, and composition 16 has a higher dissolution rate compared to that of composition 15.

[0065] Thus, the compositions of the present invention can include an amount of PVOH that is 80-85% by weight, 80-90% by weight, 80-99% by weight, 85-99% by weight, 90-99% by weight, 78-85% by weight, or 78-90% by weight.

[0066] In some embodiments, the amount of at least one cross-linking component is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

[0067] In some embodiments, the amount of at least one bioplastic is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-19 wt%, 0.1-20 wt%, 0.1-22 wt%, 0.1-25 wt%, 0.1-27 wt%, 0.1-30 wt%, 0.1-32 wt%, 0.1-35 wt%, 0.1-37 wt%, 0.1-40 wt%, 0.1-43 wt%, 0.1-45 wt%, 0.1-47 wt%, 1-5 wt%, 1-7 wt%, 1-8 wt%, 1-10 wt%, 1-12 wt%, 1-15 wt%, 1-17 wt%, 1-19 wt%, 0.1-20 wt%, 0.1-22 wt%, 0.1-25 wt%, 0.1-27 wt%, 0.1-30 wt%, 0.1-32 wt%, 0.1-35 wt%, 0.1-37 wt%, 0.1-40 wt%, 0.1-43 wt%, 0.1-45 wt%, 0.1-47 wt%, 1-5 wt%, 1-10 ... %, 1-10% by weight, 1-12% by weight, 1-15% by weight, 1-17% by weight, 1-20% by weight, 1-22% by weight, 1-25% by weight, 1-27% by weight, 1-30% by weight, 1-32% by weight, 1-35% by weight, 1-37% by weight, 1-40% by weight, 1-42% by weight, 1-45% by weight, 1-47% by weight, 3-20% by weight, 5-20% by weight, 7-20% by weight, 9-20% by weight, 10-20% by weight, 12-20% by weight, 15-20% by weight, 17-20% by weight, 5-20% by weight, 5-25% by weight, 5-30% by weight, 5-35% by weight, 5-40% by weight, 5-45% by weight, or 5-50% by weight.

[0068] In some embodiments, the amount of at least one additive is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

[0069] In some embodiments, the PVOH is present in an amount of 73-96.5, 68.5-89.8, 77.5-96.3, 67.5-91.5, 72-95, 71-85, 81-90, 68-81, 75-84, 60-78, 91.5-99.3, 87.5-98.7, 94.6-82.5, 87-93.3, 83-98.7, 78.5-94.3, 79.5-93.8, 68-93.5, 81.5-93.7, 73.5-93.3, 82-98.6, or 77.5-98.2 wt.%. wherein the at least one crosslinking compound is present in an amount of 0.1-1.5, 1.5-2.5, 1-2.5, 1.5-4, 1, 1.5-2, 1.5-2, 5, 0.1-0.5, 0.5-2, 0.1-0.5 or 1-2 wt. % and / or the at least one bioplastic is present in an amount of 1.5-10, 5-10, 1.5-5, 1.5-4, 5, 2, 10, 0-1, 1-5, 5-10, 0.1-1 or 0.1-1 wt. % and the composition optionally comprises at least one additive.

[0070] In some embodiments, the compositions of the present invention comprise PVOH, PAA, and PEO, respectively, in an amount selected from the following: 73 to 96.5% by weight, 0.1 to 1.5% by weight, and 1.5 to 10% by weight, -68.5 to 89.8% by weight, 0.1 to 1.5% by weight, and 5 to 10% by weight, -77.5 to 96.3% by weight, 1.5 to 2.5% by weight, and 1.5 to 5% by weight, -67.5 to 91.5% by weight, 1 to 2.5% by weight, and 1.5 to 5% by weight, 72 to 95% by weight, 1.5 to 4% by weight, and 1.5 to 4% by weight, 71 to 85% by weight, 1% by weight and 5% by weight, 81 to 90% by weight, 1.5 to 2% by weight and 2% by weight, 68 to 81% by weight, 1.5 to 2% by weight and 5% by weight, 75 to 84% by weight, 5% by weight and 5% by weight, 60 to 78% by weight, 5% by weight and 10% by weight, -91.5 to 99.3% by weight, 0.1 to 0.5% by weight, and 0 to 1% by weight, -87.5 to 98.7% by weight, 0.1 to 0.5% by weight, and 1 to 5% by weight, -94.6 to 82.5% by weight, 0.1 to 0.5% by weight, and 5 to 10% by weight, -87 to 93.3% by weight, 0.5 to 2% by weight, and 0 to 1% by weight, -83 to 98.7% by weight, 0.5 to 2% by weight, and 1 to 5% by weight, -78.5 to 94.3% by weight, 0.5 to 2% by weight, and 5 to 10% by weight, -79.5 to 93.8% by weight, 0.1 to 0.5% by weight and 5 to 10% by weight (optionally containing PCL in an amount ranging from 1 to 5% by weight); -68 to 93.5 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt% (optionally containing PCL in an amount ranging from 5 to 10 wt%); -81.5 to 93.7% by weight, 0.1 to 1.5% by weight and 0 to 1% by weight (optionally containing PCL in an amount ranging from 5 to 10% by weight); - 73.5 to 93.3 wt%, 0.5 to 1.5 wt% and 5 to 10 wt% (optionally containing PCL in an amount ranging from 1 to 5 wt%); -82 to 98.6 wt%, 1 to 2 wt%, and 0.1 to 1 wt%, optionally containing PCL in an amount ranging from 1 to 5 wt%, or - 77.5 to 98.2 wt%, 0.5 to 1.5 wt% and 0.1 to 1 wt% (optionally further comprising PCL in an amount in the range of 5 to 10 wt%).

[0071] The compositions exemplified herein demonstrate and embody a novel method for modifying at least one property of a solid composite material derived from a material combination disclosed herein, such as a combination comprising poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), and poly(acrylic acid) (PAA).

[0072] The composite materials of the present invention are considered to be solids and, as disclosed herein, can be produced with one or more enhanced properties, which properties can be imparted based on the intended use of the composite material. The composite materials of the present invention can be produced in a variety of shapes, sizes, and forms, and can be produced by a variety of processing techniques known in the art of polymeric materials.

[0073] Thus, the present invention further contemplates composite materials of non-specific form, including: at least one material chosen among polymeric materials that are amenable to crosslinking in combination (these polymers may be chosen from poly(vinyl alcohol), poly(acrylic acid) and glutaraldehyde); at least one additional bioplastic material selected to be insoluble in water (the material is also selected to be biodegradable. By including such a material, the amount of materials such as poly(vinyl alcohol), poly(acrylic acid), glutaraldehyde, etc. can be reduced. The combination of the poly(vinyl alcohol), poly(acrylic acid) or glutaraldehyde material with the biodegradable material selected from the water-insoluble material is designed to fine-tune the sensitivity to water. In some embodiments, the water-insoluble material is selected from among hydroxypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC), hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC) and / or cellulose-derived materials such as chitosan); at least one material selected from among hygroscopic materials (such a material may be an ionic material such as a calcium salt, e.g. CaCl2), and - at least one material selected from bioplastics (non-limiting examples include PEO);

[0074] Further provided is a polymeric composition in the form of a solid composite material comprising, in some embodiments, a combination of poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) (herein the core combination), optionally with at least one material selected from inorganic salts, cellulose-derived materials, and chitosan.

[0075] The present invention further provides a feedstock comprised of poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) and at least one material selected from inorganic salts, cellulose-derived materials, chitosan and formaldehyde.

[0076] In some embodiments, the composite material of the present invention comprises poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA) and at least one material selected from inorganic salts, cellulose-derived materials, chitosan, and formaldehyde.

[0077] The composite material of the present invention can be made into any shape and form, as a substantially one-dimensional object, such as a fiber, a two-dimensional object, such as a sheet or film, or a three-dimensional object. In some embodiments, the composite material is in the form of a sheet or film of material. In other embodiments, the composite material is a three-dimensional product, which can be made by manipulating the composite sheet or film, or by any one of the methods selected from casting, blowing, pouring and injection molding, extrusion, and the like. Non-limiting examples of three-dimensional products that can be made include storage chambers and containers, boxes, tubes, liners, advertising stands and billboards, exhibition fixtures and panels, automotive components, bags, accessories, clothing parts, pipes, rods, and the like.

[0078] In some embodiments, the compositions of the invention comprise: A - Poly(vinyl alcohol) (PVOH) in an amount ranging from 30 to 99% by weight In some embodiments, the amount of PVOH in the composition is 30-40%, 30-45%, 30-50%, 30-55%, 30-60%, 30-65%, 30-70%, 30-75%, 30-80%, 30-85%, 30-90%, 40-45%, 40-50%, 40-60%, 40-70%, 40-85%, 4 ...85%, 40-95%, 40-85%, 40-95%, 40-95%, 40-85%, 40-95%, 40-95%, 40-95%, 40-100%, 40-105%, 40-105%, 40-105%, 40-105%, 40-105%, 40-105%, 40-105%, 40-10 80% by weight, 40 to 90% by weight, 50 to 60% by weight, 50 to 70% by weight, 50 to 80% by weight, 50 to 90% by weight, 60 to 70% by weight, 60 to 80% by weight, 60 to 90% by weight, 70 to 80% by weight, 70 to 90% by weight, 80 to 85% by weight, 80 to 90% by weight, 80 to 99% by weight, 85 to 99% by weight, 90 to 99% by weight, 78 to 85% by weight, or 78 to 90% by weight. B - at least one cross-linking compound selected from polymers, copolymers and non-polymeric materials in an amount ranging from 0.1 to 20% by weight. In some embodiments, the amount of this component in the compositions of the present invention is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%. C - at least one bioplastic in an amount ranging from 0.1 to 50% by weight In some embodiments, the amount of bioplastic is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-19 wt%, 0.1-20 wt%, 0.1-22 wt%, 0.1-25 wt%, 0.1-27 wt%, 0.1-30 wt%, 0.1-32 wt%, 0.1-35 wt%, 0.1-37 wt%, 0.1-40 wt%, 0.1-43 wt%, 0.1-45 wt%, 0.1-47 wt%, 1-5 wt%, 1-7 wt%, 1-2 wt%, 1-3 wt%, 1-4 wt%, 1-5 ... % by weight, 1 to 12% by weight, 1 to 15% by weight, 1 to 17% by weight, 1 to 20% by weight, 1 to 22% by weight, 1 to 25% by weight, 1 to 27% by weight, 1 to 30% by weight, 1 to 32% by weight, 1 to 35% by weight, 1 to 37% by weight, 1 to 40% by weight, 1 to 42% by weight, 1 to 45% by weight, 1 to 47% by weight, 3 to 20% by weight, 5 to 20% by weight, 7 to 20% by weight, 9 to 20% by weight, 10 to 20% by weight, 12 to 20% by weight, 15 to 20% by weight, 17 to 20% by weight, 5 to 20% by weight, 5 to 25% by weight, 5 to 30% by weight, 5 to 35% by weight, 5 to 40% by weight, 5 to 45% by weight, or 5 to 50% by weight. D - at least one additive in an amount ranging from 0.1 to 20% by weight In some embodiments, the amount of additive in the composition of the present invention is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

[0079] In some embodiments, the compositions of the present invention comprise an amount of PVOH of 73-96.5, 68.5-89.8, 77.5-96.3, 67.5-91.5, 72-95, 71-85, 81-90, 68-81, 75-84, 60-78, 91.5-99.3, 87.5-98.7, 94.6-82.5, 87-93.3, 83-98.7, 78.5-94.3, 79.5-93.8, 68-93.5, 81.5-93.7, 73.5-93.3, 82-98.6, or 77.5-98.2 weight percent, or 0.1-1. 5, 1.5-2.5, 1-2.5, 1.5-4, 1, 1.5-2, 1.5-2, 5, 0.1-0.5, 0.5-2, 0.1-0.5 or 1-2 wt. % of at least one crosslinking compound disclosed herein, and / or 1.5-10, 5-10, 1.5-5, 1.5-4, 5, 2, 10, 0-1, 1-5, 5-10, 0.1-1 or 0.1-1 wt. % of at least one bioplastic, wherein the total amounts of the components (including additives, if present) add up to 100%.

[0080] In some embodiments, the compositions of the present invention further comprise at least one additive.

[0081] In some embodiments, the compositions of the present invention include materials from groups (A), (B), and (C) above, such as PVOH, PAA, and PEO, respectively, as follows: 73 to 96.5% by weight, 0.1 to 1.5% by weight, and 1.5 to 10% by weight, -68.5 to 89.8% by weight, 0.1 to 1.5% by weight, and 5 to 10% by weight, -77.5 to 96.3% by weight, 1.5 to 2.5% by weight, and 1.5 to 5% by weight, -67.5 to 91.5% by weight, 1 to 2.5% by weight, and 1.5 to 5% by weight, 72 to 95% by weight, 1.5 to 4% by weight, and 1.5 to 4% by weight, 71 to 85% by weight, 1% by weight and 5% by weight, 81 to 90% by weight, 1.5 to 2% by weight and 2% by weight, 68 to 81% by weight, 1.5 to 2% by weight and 5% by weight, 75 to 84% by weight, 5% by weight and 5% by weight, 60 to 78% by weight, 5% by weight and 10% by weight, -91.5 to 99.3% by weight, 0.1 to 0.5% by weight, and 0 to 1% by weight, -87.5 to 98.7% by weight, 0.1 to 0.5% by weight, and 1 to 5% by weight, -94.6 to 82.5% by weight, 0.1 to 0.5% by weight, and 5 to 10% by weight, -87 to 93.3% by weight, 0.5 to 2% by weight, and 0 to 1% by weight, -83 to 98.7% by weight, 0.5 to 2% by weight, and 1 to 5% by weight, -78.5 to 94.3% by weight, 0.5 to 2% by weight, and 5 to 10% by weight, -79.5 to 93.8% by weight, 0.1 to 0.5% by weight and 5 to 10% by weight (optionally containing PCL in an amount ranging from 1 to 5% by weight); -68 to 93.5 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt% (optionally containing PCL in an amount ranging from 5 to 10 wt%); -81.5 to 93.7% by weight, 0.1 to 1.5% by weight and 0 to 1% by weight (optionally containing PCL in an amount ranging from 5 to 10% by weight); - 73.5 to 93.3 wt%, 0.5 to 1.5 wt% and 5 to 10 wt% (optionally containing PCL in an amount ranging from 1 to 5 wt%); -82 to 98.6% by weight, 1 to 2% by weight, and 0.1 to 1% by weight (optionally containing PCL in an amount ranging from 1 to 5% by weight); -77.5 to 98.2% by weight, 0.5 to 1.5% by weight, and 0.1 to 1% by weight (optionally containing PCL in an amount ranging from 5 to 10% by weight)

[0082] The present invention further provides a method for manufacturing an object or a composite material according to the invention, the method being adapted according to the manufacturing rules described herein, comprising: forming a core composition comprising PAA and PEO; and treating said core composition with a composition comprising PVOH and any of the additional materials described herein; All ingredients are compounded into a single homogenous composition and contained under conditions that allow the composition to be processed to obtain 1D, 2D or 3D objects.

[0083] The present invention further comprises: forming a core composition comprising, for example, PVOH, PEO and PAA; - treating said core composition with at least one additional material, for example selected from inorganic salts, cellulose-derived substances, chitosan and formaldehyde, as described above, Compounding all of the components into a single homogenous composition under conditions that allow processing of said composition to obtain 1D, 2D or 3D objects. The present invention provides a method including:

[0084] As previously described herein, for example, to adjust the rate of water decomposition, composites containing amounts of PAA in the range of 0.1-2 wt% can be tailored to be more or less susceptible to water decomposition. The more PAA present (i.e., amounts closer to the 2 wt% limit), the slower the observed water decomposition. A smaller amount of PAA (i.e., amounts closer to the 0.1 wt% limit) allows for faster water decomposition. Similarly, composites containing amounts of PEO in the range of 1-10 wt% can be tailored to be more or less susceptible to water decomposition. The more PEO present (i.e., amounts closer to the 10 wt% limit), the faster the observed water decomposition. A smaller amount of PEO (i.e., amounts closer to the 1.5 wt% limit) allows for slower water decomposition at a constant PAA concentration.

[0085] In some embodiments, the methods of the present invention include providing a formulation comprising PVOH.

[0086] In some embodiments, a formulation containing PVOH is added to or combined with a pre-made formulation containing PEO, and in some embodiments, the combined formulations can be mixed to obtain a homogenous formulation.

[0087] In some embodiments, the PVOH-PEO formulation is added to or mixed with a preformed formulation of PAA under conditions that allow crosslinking of the PAA with PVOH. In some embodiments, crosslinking is allowed by adding at least one acid at a temperature between room temperature (RT, 23-30° C.) and 230° C. (or between 120-150° C. or between 150-230° C.). In some embodiments, the temperature is between 50-150° C. or between 150-230° C. In some embodiments, the acid can be selected from mineral acids and organic acids. In some embodiments, the acid is selected from sulfuric acid, HCl, nitric acid, and the like. In some embodiments, the combination of PVOH, PEO, and PAA is further treated with or mixed with at least one inorganic salt. In some embodiments, the inorganic salt is as defined herein above.

[0088] In some embodiments, the combination of PVOH, PEO and PAA is further treated with or mixed with PVOH and at least one cellulose-based material selected as detailed herein above.

[0089] Compounding the components together into a single homogenous composition can be carried out under mixing at temperatures between room temperature (23° C.-30° C.) and 120° C.-230° C. or 150° C.-230° C. Once the homogenous composition is formed, it can then be manipulated and processed under industrially acceptable conditions to obtain the final composite product. Such methods include one or more of casting, blowing, injection and extrusion.

[0090] The present invention further provides exemplary composite materials as prepared and characterized herein, which composite materials are formed of the compositions listed in Tables 1 and 3. Accordingly, the present invention further contemplates the compositions listed in Tables 1 and 3, designated herein as Compositions 1-22.

[0091] Also provided are composite materials incorporating the aforementioned compositions, designated Compositions 1-22, as defined.

[0092] In the method of the present invention, the final product produced from the raw materials including PVOH, PEO, and PAA, and optionally one or more additional materials selected from, for example, inorganic salts, cellulose-derived materials, chitosan, and glycerol, can be given a desired property or set of properties by modifying, fine tuning, or tweaking the method for its production. The method of the present invention can be modified by changing the amount of material ratio between two or more components included in the core combination (i.e., PVOH, PEO, and PAA) or between any component of the core combination and any other component of the material combination (e.g., inorganic salts, cellulose-derived materials, chitosan, and glycerol), by changing the additional components added to the core combination, by changing or modifying the processing conditions of the method for making the solid product, or by selecting a particular sequence of steps. Examples of the effect of these modifications on the properties of the final solid product are given herein below.

[0093] The method of the present invention includes a step of controlling the weight / weight ratio (w / w) between (a) two or more materials selected from PVOH, PEO and PAA, or (b) between at least one material selected from PVOH, PEO and PAA and at least one other material selected from inorganic salts, cellulose derived materials, chitosan and formaldehyde, providing the option to modify the properties of the solid composite material by selecting the material ratio between any two materials of the core combination comprising PVOH, PEO and PAA, for example, the ratio between PVOH and PEO, or PVOH and PAA, or PEO and PAA, or between any one of PVOH, PEO and PAA and any of inorganic salts, cellulose derived materials, chitosan and formaldehyde. Non-limiting pairs of materials whose relative weight amounts (in grams or weight percent) affect at least one property of the solid end product include PVOH and PEO, PVOH and PAA, PEO and PAA, PVOH and inorganic salts, PVOH and cellulose-containing materials, PVOH and chitosan, PVOH and formaldehyde, PEO and inorganic salts, PEO and cellulose-derived materials, PEO and chitosan, PEO and formaldehyde, PAA and inorganic salts, PAA and cellulose-derived materials, PAA and chitosan, and PAA and formaldehyde.

[0094] As shown in the examples described herein, increasing the amount of an inorganic salt (such as a calcium salt, e.g., calcium chloride) relative to at least one component of the core combination results in improved extensibility of the solid product obtained from a composition comprising the core combination and at least one inorganic salt.

[0095] Similarly, increasing the amount of PVOH relative to PAA increases the OTR, and increasing the amount of PAA relative to PVOH increases stiffness.

[0096] Varying the relative amount of PEO also affects the stability of the product in water: increasing the amount of PEO relative to either PAA or PVOH increases water solubility (or decreases water resistance and increases water degradability) and increases the flexibility of the material. Similarly, increasing the amount of cellulose derivatives (such as HPMC) relative to either of the core components decreases the water solubility of the solid final product.

[0097] An embodiment of the invention illustrating the ability to modulate some of the properties detailed herein is shown in FIG.

[0098] As used herein, the terms "ratio", "material ratio" or "weight / weight (w / w) ratio" refer to the amount of material of one component of the combination (out of the total weight of the combination) relative to the amount of material of another component of the combination (out of the total weight of the combination). For example, a ratio between PVOH and PEO refers to the relative amount of PVOH compared to the amount of PEO in the combination. The ratio is given in absolute weight values. For example, a ratio of 1:1 PVOH:PEO indicates the same amount of each component of the combination. An increase in the ratio stated for one component means an increase in the amount of that particular component relative to the other component. For example, an increase in the amount of PVOH relative to PEO can result in a stated ratio greater than 1:1, such as 2:1 or higher. When the term "about" is used with respect to a stated ratio or amount, it is meant to mean a ratio or amount ±10% of the stated value. For example, a ratio of about 1:1 is a ratio between (0.9 and 1.1):(1.1 and 0.9).

[0099] Thus, in another aspect of the present invention, there is provided a method for producing a solid composite material having a predefined rate of water decomposition, the method comprising: - in the process of producing a solid composite material, (a) between two or more materials selected from poly(vinyl alcohol) (PVOH), poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA); or (b) between at least one material selected from PVOH, PEO and PAA and at least one other material selected from inorganic salts, cellulose-derived substances, chitosan and formaldehyde. Control the weight / weight ratio (wt / wt).

[0100] In some embodiments, the "predefined water degradation rate" is the rate at which the composite material of the present invention degrades upon contact with water. The rate may be measured in grams per minute or simply by the time it takes for the article to begin to degrade. As previously described herein, composite materials containing amounts of PAA in the range of 0.1-2 wt. % can be tailored to be more susceptible or less susceptible to water degradation. The more PAA present (i.e., amounts closer to the 2 wt. % limit), the slower the observed water degradation. A lower amount of PAA (i.e., amounts closer to the 0.1 wt. % limit) allows for faster water degradation. Similarly, composite materials containing amounts of PEO in the range of 1.5-10 wt. % can be tailored to be more susceptible or less susceptible to water degradation. The more PEO present (i.e., amounts closer to the 10 wt. % limit), the faster the observed water degradation. A lower amount of PEO (i.e., amounts closer to the 1.5 wt. % limit) allows for slower water degradation.

[0101] Thus, in some embodiments, a method for producing a solid composite material having a predefined water decomposition rate includes: (a) varying the amount of PAA to be between 0.1 and 2 wt % (higher amounts of PAA in the composite (1-2 wt %) lead to slower water decomposition, whereas lower amounts of PAA (0.1-1 wt %) lead to faster water decomposition), or (b) Varying the amount of PEO to be between 1.5 and 10 wt % (higher amounts of PEO in the composite (3–10 wt %) lead to faster water decomposition, whereas lower amounts of PEO (1.5–3 wt %) lead to slower water decomposition).

[0102] In some embodiments, composites containing 0.4-0.55 wt% PAA in PVOH have a molecular weight of ∼1 mg / (min × cm2 ) decomposition rate. Composites containing 0.6–1.4 wt% PAA in PVOH showed decomposition rates of ∼0.2 mg / (min × cm 2 The rate of water decomposition of ) was shown.

[0103] Also provided is a method for modifying at least one property of a solid composite material formed with a composition according to the present invention, the method comprising treating a composition comprising an amount of PAA and an amount of PEO with a composition comprising an amount of PVOH and optionally at least one additive, wherein the amount of PAA, the amount of PEO and the amount of optionally PVOH are selected to modify the at least one property under conditions that enable compounding of the PAA, PEO and PVOH, and optionally the at least one additive, into a solid composite material having the at least one property.

[0104] In some embodiments, the at least one property is water degradation.

[0105] In some embodiments, the amount of PAA and the amount of PEO, respectively, are in a ratio of about 1:5.

[0106] In some embodiments, the amount of PAA and the amount of PEO are in a ratio of about 2:8. In some embodiments, the ratio is PAA:PEO, 2:8.

[0107] In some embodiments, the ratio of the sum of the amount of PEO and the amount of PAA to the amount of PVOH is 2:98, respectively.

[0108] In some embodiments, the ratio of the sum of the amount of PEO and the amount of PAA to the amount of PCL and the amount of PVOH is PEO / PAA:PCL:PVOH, 2:5:93.

[0109] In some embodiments, the amount of PAA is 0.4-0.5% by weight.

[0110] In some embodiments, the amount of PAA is 0.9-1.1 wt %.

[0111] In some embodiments, the amount of PVOH is 80-85 wt%, 80-90 wt%, 80-99 wt%, 85-99 wt%, 90-99 wt%, 78-85 wt%, or 78-90 wt%.

[0112] In some embodiments, the amount of PAA is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

[0113] In some embodiments, the amount of PEO is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-19 wt%, 0.1-20 wt%, 0.1-22 wt%, 0.1-25 wt%, 0.1-27 wt%, 0.1-30 wt%, 0.1-32 wt%, 0.1-35 wt%, 0.1-37 wt%, 0.1-40 wt%, 0.1-43 wt%, 0.1-45 wt%, 0.1-47 wt%, 1-5 wt%, 1-7 wt%, 1-10 wt%, 1-20 wt%, 1-30 wt%, 1-40 wt%, 1-50 wt%, 1-20 wt%, 1-20 wt%, 1-30 wt%, 1-4 ... %, 1 to 12 weight%, 1 to 15 weight%, 1 to 17 weight%, 1 to 20 weight%, 1 to 22 weight%, 1 to 25 weight%, 1 to 27 weight%, 1 to 30 weight%, 1 to 32 weight%, 1 to 35 weight%, 1 to 37 weight%, 1 to 40 weight%, 1 to 42 weight%, 1 to 45 weight%, 1 to 47 weight%, 3 to 20 weight%, 5 to 20 weight%, 7 to 20 weight%, 9 to 20 weight%, 10 to 20 weight%, 12 to 20 weight%, 15 to 20 weight%, 17 to 20 weight%, 5 to 20 weight%, 5 to 25 weight%, 5 to 30 weight%, 5 to 35 weight%, 5 to 40 weight%, 5 to 45 weight%, or 5 to 50 weight%.

[0114] In some embodiments, the PVOH is 73-96.5, 68.5-89.8, 77.5-96.3, 67.5-91.5, 72-95, 71-85, 81-90, 68-81, 75-84, 60-78, 91.5-99.3, 87.5-98.7, 94.6-82.5, 87-93.3, 83-98.7, 78.5-94.3, 79.5-93.8, 68-93.5, 81.5-93.7, 73.5-93.3, 82-98.6, or 77.5- 98.2 wt%, PAA is present in an amount of 0.1-1.5, 1.5-2.5, 1-2.5, 1.5-4, 1, 1.5-2, 1.5-2, 5, 0.1-0.5, 0.5-2, 0.1-0.5 or 1-2 wt%, and / or PEO is present in an amount of 1.5-10, 5-10, 1.5-5, 1.5-4, 5, 2, 10, 0-1, 1-5, 5-10, 0.1-1 or 0.1-1 wt%, and the composition optionally comprises at least one additive.

[0115] In some embodiments, the composition comprises PVOH, PAA, and PEO, each in an amount selected from the following: 73 to 96.5% by weight, 0.1 to 1.5% by weight, and 1.5 to 10% by weight, -68.5 to 89.8% by weight, 0.1 to 1.5% by weight, and 5 to 10% by weight, -77.5 to 96.3% by weight, 1.5 to 2.5% by weight, and 1.5 to 5% by weight, -67.5 to 91.5% by weight, 1 to 2.5% by weight, and 1.5 to 5% by weight, 72 to 95% by weight, 1.5 to 4% by weight, and 1.5 to 4% by weight, 71 to 85% by weight, 1% by weight and 5% by weight, 81 to 90% by weight, 1.5 to 2% by weight and 2% by weight, 68 to 81% by weight, 1.5 to 2% by weight and 5% by weight, 75 to 84% by weight, 5% by weight and 5% by weight, 60 to 78% by weight, 5% by weight and 10% by weight, -91.5 to 99.3% by weight, 0.1 to 0.5% by weight, and 0 to 1% by weight, -87.5 to 98.7% by weight, 0.1 to 0.5% by weight, and 1 to 5% by weight, -94.6 to 82.5% by weight, 0.1 to 0.5% by weight, and 5 to 10% by weight, -87 to 93.3% by weight, 0.5 to 2% by weight, and 0 to 1% by weight, -83 to 98.7% by weight, 0.5 to 2% by weight, and 1 to 5% by weight, -78.5 to 94.3% by weight, 0.5 to 2% by weight, and 5 to 10% by weight, -79.5 to 93.8% by weight, 0.1 to 0.5% by weight and 5 to 10% by weight (optionally containing PCL in an amount ranging from 1 to 5% by weight); -68 to 93.5 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt% (optionally containing PCL in an amount ranging from 5 to 10 wt%); -81.5 to 93.7% by weight, 0.1 to 1.5% by weight and 0 to 1% by weight (optionally containing PCL in an amount ranging from 5 to 10% by weight); - 73.5 to 93.3 wt%, 0.5 to 1.5 wt% and 5 to 10 wt% (optionally containing PCL in an amount ranging from 1 to 5 wt%); -82 to 98.6 wt%, 1 to 2 wt%, and 0.1 to 1 wt%, optionally containing PCL in an amount ranging from 1 to 5 wt%, or -77.5 to 98.2% by weight, 0.5 to 1.5% by weight, and 0.1 to 1% by weight (optionally containing PCL in an amount ranging from 5 to 10% by weight)

[0116] Thus, the degradation profile, i.e., the pace or rate at which the composite material degrades upon contact with water, and possibly even how the degradation proceeds, will depend on any of the factors described herein. In some embodiments, water degradation is controlled by increasing the amount of PEO relative to PAA, thereby increasing water degradation. In some embodiments, water degradation is controlled by increasing the amount of PEO relative to PEO, thereby decreasing water degradation. In other embodiments, water degradation is controlled by decreasing the amount of PEO relative to PAA, thereby decreasing water degradation. In other embodiments, water degradation is controlled by decreasing the amount of PAA relative to PEO, thereby increasing water degradation.

[0117] Increasing the amount of PEO or PAA relative to the amount of PAA or PEO does not necessarily mean increasing the amount of PEO / PAA over the amount of PAA / PEO, but the increase in the amount should be sufficient to increase / decrease the water degradation. The degree of increase / decrease in the amount depends, among other things, on the initial amount of PEO / PAA in the composition, the further effects of increasing / decreasing the amount of PEO / PAA, the degradation profile desired, and other factors.

[0118] The present invention also provides a method for adjusting the water degradation profile of a solid composite material formed with a composition according to the present invention, the method comprising treating a composition comprising an amount of PAA and an amount of PVOH and optionally at least one additive, together with an effective amount of PEO, the effective amount being selected to increase or decrease the water degradation of said solid composite material, the method being carried out under conditions that allow compounding of the PAA, PEO and PVOH, and optionally at least one additive, into a solid composite material having a water degradation profile.

[0119] Also provided is a method for setting the onset of water degradation of a solid composite material comprising PVOH, the method comprising: - selecting an amount of the at least one crosslinking material and an amount of the at least one additional bioplastic that, in combination, accelerates or retards the water degradation of the solid composite material when preparing a composition comprising PVOH, at least one crosslinking material and at least one additional bioplastic; and - Thermally treating said composition to form a solid composite material.

[0120] As used herein, the expression "setting the onset of water degradation" means to predetermine the rate at which the composite will degrade, or in other words, whether it will degrade quickly, slowly, or not degrade in water. By selecting the components of the composition from which the composite is made, the onset of degradation can be predetermined in advance by a simple experimental protocol, as disclosed herein. By determining the rate of degradation, as disclosed herein, the earliest time point at which the composite will degrade and degrade can be determined. Without being bound by theory or degradation mechanism, depending on the morphology of the composite, e.g., film or granules, a cascade of degradation can be completed and the onset of degradation can be determined. For example, in the degradation of a composite in the form of a film, after the initial deformation, the film can break and crumble into particles, followed by dissolution. Thus, the onset of degradation can be considered as the initial deformation stage.

[0121] The method of the present invention is therefore adapted to produce a polymer composite material according to the present invention. The composite material has a molecular weight of about 1 mg / (min×cm 2 ), or about 0.2 mg / (min × cm 2 ) or 0.001mg / (min×cm 2 )~5mg / (min×cm 2 ) or greater. Some composites are configured to degrade immediately, others are configured to degrade days, weeks, or months after manufacture, and even some are designed not to degrade at all.

[0122] As mentioned above, the method of the present invention can include forming the composite material into a desired form, for example, in the form of granules, in the form of a masterbatch, in the form of a 1D, 2D or 3D object.

[0123] Also provided are objects comprising or constructed from the inventive composite materials as disclosed herein and uses thereof. [Brief description of the drawings]

[0124] In order that the subject matter disclosed herein may be better understood and to illustrate how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which: [Figure 1] FIG. 1 is a schematic diagram of an embodiment of the present invention illustrating the ability to tailor the properties of composite materials. [Diagram 2] FIG. 2 shows the effect of PAA on the dissolution of PVOH. [Diagram 3] FIG. 3 shows the effect of PEO on the dissolution of PVOH. EXAMPLES

[0125] Example 1 PAA and ground thermoplastic PVOH were mixed in a ratio of 1:99 and extruded through a 3 mm diameter die at 50 rpm and 190-210 °C using a twin-screw co-rotating extruder with L / D of 40, and the emerging polymer chains were passed through an air cooling system and a pelletizer.

[0126] Example 2 PAA, HPMC and ground thermoplastic PVOH were mixed in a ratio of 1:10:89 and extruded through a die with a diameter of 3 mm using a twin-screw co-rotating extruder with L / D 40 at 50 rpm and 190-210 °C, and the emerging polymer strands were passed through an air cooling system and a pelletizer.

[0127] Example 3 PEO and PAA were mixed together in a ratio of 8:2 and extruded through a 3 mm diameter die using a twin-screw co-rotating extruder with L / D 40 at 50 rpm and 80°C, with the exiting polymer strands passing through an air cooling system and a pelletizer. The resulting PEO / PAA pellets were further mixed with PVOH in a ratio of 2:98 and extruded through a 3 mm diameter die using a twin-screw co-rotating extruder with L / D 40 equipped with a devolatilizing system at 150 rpm and 190-210°C, with the exiting polymer strands passing through an air cooling system and a pelletizer.

[0128] Example 4 PEO and PAA were mixed together in a ratio of 8:2 and extruded through a 3 mm diameter die using a twin-screw co-rotating extruder with L / D 40 at 50 rpm and 80°C, with the exiting polymer chains passing through an air cooling system and a pelletizer. The resulting PEO / PAA pellets were further mixed with PCL and PVOH in a ratio of 2:5:93 and extruded through a 3 mm diameter die using a twin-screw co-rotating extruder with L / D 40 equipped with a devolatilizing system at 150 rpm and 190-210°C, with the exiting polymer chains passing through an air cooling system and a pelletizer.

[0129] Figure 2 shows the effect of PAA on the dissolution of PVOH. Compounds containing 0%, 0.5%, 1%, 1.5% and 2% PAA in PVOH were produced by reactive extrusion. Samples were then pressed to 200 microns from each compound and the dissolution was examined with stirring at room temperature. The time for initial deformation (D), tearing of the film (T), fracture into particles in water (P) and dissolution (S) are recorded. In general, as the concentration of PAA in the compound increases, the deformation, tearing, fracture into particles and dissolution slow down.

[0130] Figure 3 shows the effect of PEO on the dissolution of PVOH. Compounds containing 0%, 1%, 5% and 10% PEO in PVOH at a constant concentration of PAA (0.5%) were produced by reactive extrusion. Samples were then pressed to 200 microns from each compound and the dissolution was investigated with stirring at room temperature. The time of initial deformation (D), tearing of the film (T), fragmentation into particles in water (P) and dissolution (S) were recorded. In general, as the PEO concentration in the compound increased, the deformation, tearing, fragmentation into particles and dissolution were promoted.

[0131] In addition to the dissolution kinetics, some further physico-mechanical parameters of the compounds were characterized (data not shown). The polymer pellets were processed into 100 μm films at 200 °C using a cast extruder. The cast films were conditioned for 48 h at 23 ± 2 °C and 50 ± 5% RH according to ASTM E171 / 71M-11 (reaffirmed in 2015) Standard Practice for Conditioning and Testing Flexible Barrier Packaging. Testing was performed under the same temperature / humidity conditions as above. The tensile properties of the films were measured according to ASTM D882-18 Standard Test Method for Tensile Properties of Thin Plastic Sheeting. For this purpose, strip specimens measuring 25.4 mm wide and 250 mm long were cut from the films using a dual blade shear cutter, following procedure B as specified in ASTM D6287-17 Standard Practice for Cutting Film and Sheeting Tests Specimens. Five specimens were tested for each film. A LLOYD INSTRUMENTS (UK) LRX 5K tensile tester equipped with a 500 N load cell and line grips according to ASTM D882 was used for the tests. The initial distance between the grips was 100 mm. All specimens were tested along the Machine Direction (MD) of the film with a grip separation speed of 500 mm / min. According to these measurements, increasing the content of PAA in the compound increased the tensile strength, break stress and Young's modulus, while the break elongation decreased.

[0132] The exemplary composites containing 1% PAA exhibited greater tensile strength, break stress and Young's modulus than the composites containing 0.5% PAA, and the elongation to break of the composites containing 1% PAA was less than the elongation to break of the composites containing 0.5% PAA.

[0133] Another exemplary composite containing 1% PAA exhibited a lower tensile strength, break stress and Young's modulus than the composite containing 1.5% PAA, and the break elongation of the composite containing 1% PAA was higher than the break elongation of the composite containing 1.5% PAA.

[0134] Another exemplary composite containing 0.5% PAA exhibited greater tensile strength, break stress and Young's modulus than the composite without PAA, and the elongation at break of the composite with 0.5% PAA was less than the composite without PAA.

Claims

1. 1. A composition comprising: A--poly(vinyl alcohol) (PVOH) in an amount ranging from 30 to 99 wt. %; B - at least one cross-linking compound present in an amount ranging from 0.1 to 20% by weight; C - at least one additional bioplastic in an amount ranging from 0.1 to 50 wt. %, and D-Optionally, at least one additive in an amount ranging from 0.1 to 20% by weight. A composition comprising:

2. The composition of claim 1 , wherein the at least one crosslinking compound is selected from polymers, copolymers, and non-polymeric materials and has functional groups capable of bonding to PVOH.

3. 3. The composition of claim 2, wherein the at least one crosslinking compound is a polymer or oligomer having functional groups selected from alcohol, epoxide, anhydride, carboxylic acid, amine, amide, glycidyl functional groups, aldehyde functional groups, or esters.

4. The composition of claim 2 , wherein the polymer is selected from ionomers.

5. The composition of claim 2 wherein the polymer is a polyacid.

6. 6. The composition of claim 5, wherein the polyacid is poly(acrylic acid) (PAA) or poly(methacrylic acid) (PMAA).

7. The composition of claim 1 , wherein the at least one cross-linking compound is PAA.

8. The composition of claim 1 , wherein the at least one cross-linking compound is an anhydride-grafted polymer.

9. 9. The composition of claim 8, wherein the polymer is selected from polyethylene (PE), poly(lactic acid) (PLA), polycaprolactone (PCL), polyhydroxybutyrate (PHB) and poly(butylene adipate-co-terephthalate) (PBAT), the polymer being optionally grafted with maleic anhydride.

10. 10. The composition of claim 9, wherein said at least one cross-linking compound is polyethylene-graft-maleic anhydride.

11. The composition of claim 1 , wherein the at least one cross-linking compound is a polymer having carboxylic acid functional groups.

12. 12. The composition of claim 11, wherein the polymer is selected from poly(ethylene-co-acrylic acid) (PE-co-AA), poly(ethylene-co-methacrylic acid) (PE-co-MAA), poly(lactide-block-acrylic acid) (PLA-block-AA), carboxyl-functionalized PVOH, and carboxymethylcellulose (CMC).

13. The composition of claim 12, wherein the polymer is poly(ethylene-co-acrylic acid).

14. The composition of claim 1 , wherein the at least one additional bioplastic is selected from aliphatic or aromatic polyesters, copolyesters, and polyesteramides.

15. 2. The composition of claim 1, wherein the at least one additional bioplastic is selected from poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polycaprolactone (PCL), poly(lactic acid) (PLA), cellulose and cellulose derivatives, starch, thermoplastic starch (TPS), chitosan, and polyhydroxyalkanoates (PHAs).

16. The composition of claim 15, wherein the PHA is polyhydroxybutyric acid (PHB).

17. 16. The composition of claim 15, wherein the cellulose derivative is selected from nanocrystalline cellulose (NCC), microfibril cellulose, bacterial cellulose, hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) and carboxymethyl cellulose (CMC).

18. 20. The composition of claim 1 or 15, wherein the at least one additional bioplastic is PEO.

19. 20. The composition of claim 1 or 15, wherein the at least one additional bioplastic is PCL.

20. 20. The composition of claim 1 or 15, wherein the at least one additional bioplastic is PEG.

21. 20. The composition of claim 1 or 15, comprising PEO and PCL.

22. The composition of any one of claims 1 to 15, comprising PVOH, PAA, PEO and optionally PCL.

23. 10. The composition of claim 1, wherein the at least one additive is selected from inorganic additives, fillers, reinforcing agents, processing aids, slip agents, light stabilizers, UV absorbers, flame retardants, antibacterial agents, antiviral agents, foaming agents, nucleating agents, antioxidants, antiblocking agents, and antistatic agents.

24. The composition of claim 1 , wherein the at least one additive is a moisture absorbent.

25. The moisture absorbent is CaO, CaCl ２ , LiCl, NaCl, CaI ２ , MgCl ２ , TiO ２ , CaCO ３ , alumina silicate filler and SiO ２ 25. The composition of claim 24, wherein said compound is selected from

26. 26. The composition of claim 1 or 25, wherein the at least one additive is CaO.

27. 27. The composition of claim 26, further comprising one or more additives selected from inorganic salts, cellulose-derived materials, and chitosan.

28. 28. The composition of any one of claims 1 to 27, wherein the amounts of the PVOH, at least one crosslinking compound, and at least one additional bio-plastic are selected to control water degradation of a composite material formed with the composition.

29. 30. The composition of claim 28, wherein water degradation increases with increasing amount of said at least one additional bio-plastic relative to the amount of said at least one cross-linked material.

30. 30. The composition of claim 28, wherein water degradation stops or slows or retards with a decrease in the amount of said at least one additional bio-plastic relative to the amount of said at least one cross-linked material.

31. 31. The composition of claim 30, wherein the at least one additional bioplastic is PEO.

32. 30. The composition of claim 28, wherein the at least one cross-linking material and the at least one additional bio-plastic are present in a ratio of about 1:5, respectively.

33. 33. The composition of claim 32, wherein the ratio is PAA:PEO, 1:

5.

34. 33. The composition of claim 32, wherein the ratio is 2:

8.

35. 35. The composition of claim 34, wherein the ratio is PAA:PEO, 2:

8.

36. 30. The composition of claim 28, wherein the ratio of the combined amount of PEO and PAA to PVOH is 2:98, respectively.

37. 30. The composition of claim 28, wherein the ratio of the sum of PEO and PAA to PCL and PVOH is PEO / PAA:PCL:PVOH, 2:5:

93.

38. The composition of claim 28, wherein the amount of the at least one cross-linking material is 0.4 to 0.5 wt.%.

39. The composition of claim 28, wherein the amount of the at least one cross-linking material is from 0.9 to 1.1 wt.%.

40. 2. The composition of claim 1, wherein the amount of PVOH is 80-85 wt%, 80-90 wt%, 80-99 wt%, 85-99 wt%, 90-99 wt%, 78-85 wt%, or 78-90 wt%.

41. 2. The composition of claim 1, wherein the amount of the at least one cross-linking component is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

42. the amount of said at least one bioplastic is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-19 wt%, 0.1-20 wt%, 0.1-22 wt%, 0.1-25 wt%, 0.1-27 wt%, 0.1-30 wt%, 0.1-32 wt%, 0.1-35 wt%, 0.1-37 wt%, 0.1-40 wt%, 0.1-43 wt%, 0.1-45 wt%, 0.1-47 wt%, 1-5 wt%, 1-7 wt%, 1-10 wt%, 2. The composition of claim 1, wherein the total weight of the composition is 1-12%, 1-15%, 1-17%, 1-20%, 1-22%, 1-25%, 1-27%, 1-30%, 1-32%, 1-35%, 1-37%, 1-40%, 1-42%, 1-45%, 1-47%, 3-20%, 5-20%, 7-20%, 9-20%, 10-20%, 12-20%, 15-20%, 17-20%, 5-20%, 5-25%, 5-30%, 5-35%, 5-40%, 5-45%, or 5-50% by weight.

43. 2. The composition of claim 1, wherein the amount of the at least one additive is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

44. 73.5-93.7, 82-98.6, or 77.5-98.2 weight percent of the PVOH; % by weight and / or the at least one bioplastic is present in an amount of 1.5-10, 5-10, 1.5-5, 1.5-4, 5, 2, 10, 0-1, 1-5, 5-10, 0.1-1 or 0.1-1 wt. %, and optionally comprising at least one additive.

45. PVOH, PAA and PEO, respectively. -73 to 96.5% by weight, 0.1 to 1.5% by weight, and 1.5 to 10% by weight, -68.5 to 89.8% by weight, 0.1 to 1.5% by weight, and 5 to 10% by weight, -77.5 to 96.3% by weight, 1.5 to 2.5% by weight, and 1.5 to 5% by weight, -67.5 to 91.5% by weight, 1 to 2.5% by weight, and 1.5 to 5% by weight, 72 to 95% by weight, 1.5 to 4% by weight and 1.5 to 4% by weight, 71 to 85% by weight, 1% by weight and 5% by weight, -81 to 90% by weight, 1.5 to 2% by weight and 2% by weight, -68 to 81% by weight, 1.5 to 2% by weight and 5% by weight, 75 to 84% by weight, 5% by weight and 5% by weight, 60 to 78% by weight, 5% by weight and 10% by weight, - 91.5 to 99.3% by weight, 0.1 to 0.5% by weight and 0 to 1% by weight, -87.5 to 98.7% by weight, 0.1 to 0.5% by weight and 1 to 5% by weight, - 94.6 to 82.5% by weight, 0.1 to 0.5% by weight and 5 to 10% by weight, -87 to 93.3% by weight, 0.5 to 2% by weight, and 0 to 1% by weight, -83 to 98.7% by weight, 0.5 to 2% by weight, and 1 to 5% by weight, - 78.5 to 94.3% by weight, 0.5 to 2% by weight and 5 to 10% by weight, - 79.5 to 93.8 wt%, 0.1 to 0.5 wt% and 5 to 10 wt% (optionally containing PCL in an amount ranging from 1 to 5 wt%); -68 to 93.5 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt% (optionally containing PCL in an amount ranging from 5 to 10 wt%); -81.5 to 93.7 wt%, 0.1 to 1.5 wt%, and 0 to 1 wt% (optionally containing PCL in an amount ranging from 5 to 10 wt%); - 73.5 to 93.3 wt%, 0.5 to 1.5 wt% and 5 to 10 wt% (optionally containing PCL in an amount ranging from 1 to 5 wt%); -82 to 98.6 wt%, 1 to 2 wt%, and 0.1 to 1 wt%, optionally including PCL in an amount ranging from 1 to 5 wt%, or - 77.5 to 98.2 wt%, 0.5 to 1.5 wt%, and 0.1 to 1 wt% (optionally including PCL in an amount ranging from 5 to 10 wt%) The composition of claim 1 comprising an amount selected from:

46. 46. ​​A method of modifying at least one property of a solid composite material formed with the composition of any one of claims 1-45, comprising processing a composition comprising an amount of PAA and an amount of PEO with a composition comprising an amount of PVOH and optionally at least one additive, wherein the amount of PAA, the amount of PEO and optionally the amount of PVOH are selected to modify the at least one property, and conducted under conditions that allow compounding of the PAA, PEO and PVOH, and optionally at least one additive, into the solid composite material having the at least one property.

47. 47. The method of claim 46, wherein the at least one characteristic is water degradation.

48. 48. The method of claim 46 or 47, wherein the amount of PAA and the amount of PEO are about 1:5, respectively.

49. 48. The method of claim 46 or 47, wherein the amount of PAA and the amount of PEO are in a ratio of about 2:

8.

50. 50. The method of claim 49, wherein the ratio is PAA:PEO, 2:

8.

51. 48. The method of claim 46 or 47, wherein the ratio of the sum of the amount of PEO and the amount of PAA to the amount of PVOH is 2:98, respectively.

52. 48. The method of claim 46 or 47, wherein the ratio of the sum of the amount of PEO and the amount of PAA to the amount of PCL and the amount of PVOH is PEO / PAA:PCL:PVOH, 2:5:

93.

53. 48. The method of claim 46 or 47, wherein the amount of PAA is 0.4-0.5 wt%.

54. 48. The method of claim 46 or 47, wherein the amount of PAA is 0.9-1.1 wt%.

55. 48. The method of claim 46 or 47, wherein the amount of PVOH is 80-85 wt%, 80-90 wt%, 80-99 wt%, 85-99 wt%, 90-99 wt%, 78-85 wt%, or 78-90 wt%.

56. 48. The method of claim 46 or 47, wherein the amount of PAA is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-0.2 wt%, 0.1-0.3 wt%, 0.1-0.4 wt%, 0.1-0.5 wt%, 0.1-0.6 wt%, 0.1-0.7 wt%, 0.1-0.8 wt%, 0.1-0.9 wt%, 1-20 wt%, 3-20 wt%, 5-20 wt%, 7-20 wt%, 9-20 wt%, 10-20 wt%, 12-20 wt%, 15-20 wt%, or 17-20 wt%.

57. The amount of the PEO is 0.1-1 wt%, 0.1-2 wt%, 0.1-4 wt%, 0.1-5 wt%, 0.1-7 wt%, 0.1-10 wt%, 0.1-12 wt%, 0.1-15 wt%, 0.1-17 wt%, 0.1-19 wt%, 0.1-20 wt%, 0.1-22 wt%, 0.1-25 wt%, 0.1-27 wt%, 0.1-30 wt%, 0.1-32 wt%, 0.1-35 wt%, 0.1-37 wt%, 0.1-40 wt%, 0.1-43 wt%, 0.1-45 wt%, 0.1-47 wt%, 1-5 wt%, 1-7 wt%, 1-10 wt%, 1-12 wt%, 1-20 wt%, 1-30 wt%, 1-40 wt%, 1-50 wt%, 1-60 wt%, 1-60 wt%, 1-70 wt%, 1-80 wt%, 1-90 wt%, 1-100 wt%, 1-120 wt%, 1-200 wt%, 1-300 wt%, 1-400 wt%, 1-50 wt%, 1-60 wt%, 1-100 wt%, 1-120 wt%, 1-200 wt%, 1-300 wt%, 1-400 wt%, 1-500 wt%, 1-600 wt%, 1-100 wt%, 1-120 wt%, 1-200 wt%, 1-300 wt%, 1-400 wt%, 1-400 wt%, 1-500 wt%, 48. The method of claim 46 or 47, wherein the weight percent of the hydroxyl group is up to 15%, 1-17%, 1-20%, 1-22%, 1-25%, 1-27%, 1-30%, 1-32%, 1-35%, 1-37%, 1-40%, 1-42%, 1-45%, 1-47%, 3-20%, 5-20%, 7-20%, 9-20%, 10-20%, 12-20%, 15-20%, 17-20%, 5-20%, 5-25%, 5-30%, 5-35%, 5-40%, 5-45%, or 5-50% by weight.

58. PVOH is present in an amount of 73 to 96.5, 68.5 to 89.8, 77.5 to 96.3, 67.5 to 91.5, 72 to 95, 71 to 85, 81 to 90, 68 to 81, 75 to 84, 60 to 78, 91.5 to 99.3, 87.5 to 98.7, 94.6 to 82.5, 87 to 93.3, 83 to 98.7, 78.5 to 94.3, 79.5 to 93.8, 68 to 93.5, 81.5 to 93.7, 73.5 to 93.3, 82 to 98.6, or 77.5 to 98.2 weight percent; 48. The method of claim 46 or 47, wherein AA is present in an amount of 0.1-1.5, 1.5-2.5, 1-2.5, 1.5-4, 1, 1.5-2, 1.5-2, 5, 0.1-0.5, 0.5-2, 0.1-0.5 or 1-2 wt % and / or the PEO is present in an amount of 1.5-10, 5-10, 1.5-5, 1.5-4, 5, 2, 10, 0-1, 1-5, 5-10, 0.1-1 or 0.1-1 wt %, and the composition optionally comprises at least one additive.

59. PVOH, PAA and PEO, respectively. -73 to 96.5% by weight, 0.1 to 1.5% by weight, and 1.5 to 10% by weight, -68.5 to 89.8% by weight, 0.1 to 1.5% by weight, and 5 to 10% by weight, -77.5 to 96.3% by weight, 1.5 to 2.5% by weight, and 1.5 to 5% by weight, -67.5 to 91.5% by weight, 1 to 2.5% by weight, and 1.5 to 5% by weight, 72 to 95% by weight, 1.5 to 4% by weight and 1.5 to 4% by weight, 71 to 85% by weight, 1% by weight and 5% by weight, -81 to 90% by weight, 1.5 to 2% by weight and 2% by weight, -68 to 81% by weight, 1.5 to 2% by weight and 5% by weight, 75 to 84% by weight, 5% by weight and 5% by weight, 60 to 78% by weight, 5% by weight and 10% by weight, - 91.5 to 99.3% by weight, 0.1 to 0.5% by weight and 0 to 1% by weight, -87.5 to 98.7% by weight, 0.1 to 0.5% by weight and 1 to 5% by weight, - 94.6 to 82.5% by weight, 0.1 to 0.5% by weight and 5 to 10% by weight, -87 to 93.3% by weight, 0.5 to 2% by weight, and 0 to 1% by weight, -83 to 98.7% by weight, 0.5 to 2% by weight, and 1 to 5% by weight, - 78.5 to 94.3% by weight, 0.5 to 2% by weight and 5 to 10% by weight, - 79.5 to 93.8 wt%, 0.1 to 0.5 wt% and 5 to 10 wt% (optionally containing PCL in an amount ranging from 1 to 5 wt%); -68 to 93.5 wt%, 0.1 to 0.5 wt%, and 1 to 5 wt% (optionally containing PCL in an amount ranging from 5 to 10 wt%); -81.5 to 93.7 wt%, 0.1 to 1.5 wt%, and 0 to 1 wt% (optionally containing PCL in an amount ranging from 5 to 10 wt%); - 73.5 to 93.3 wt%, 0.5 to 1.5 wt% and 5 to 10 wt% (optionally containing PCL in an amount ranging from 1 to 5 wt%); -82 to 98.6 wt%, 1 to 2 wt%, and 0.1 to 1 wt%, optionally including PCL in an amount ranging from 1 to 5 wt%, or - 77.5 to 98.2 wt%, 0.5 to 1.5 wt%, and 0.1 to 1 wt% (optionally including PCL in an amount ranging from 5 to 10 wt%) 48. The method of claim 46 or 47, comprising an amount selected from:

60. 48. The method of claim 46 or 47, wherein the at least one property is water degradation and the adjusting comprises increasing the amount of the PEO relative to PAA to increase water degradation.

61. 48. The method of claim 46 or 47, wherein the at least one property is water degradation and the adjusting comprises increasing the amount of the PAA relative to PEO to reduce water degradation.

62. 48. The method of claim 46 or 47, wherein the at least one property is water degradation and the adjusting comprises decreasing the amount of the PEO relative to PAA to decrease water degradation.

63. 48. The method of claim 46 or 47, wherein the at least one property is water degradation and the adjusting comprises decreasing the amount of the PAA relative to PEO to increase water degradation.

64. 46. ​​A method for adjusting the water degradation profile of a solid composite material formed with the composition of any one of claims 1 to 45, comprising treating a composition comprising an amount of PAA and an amount of PVOH and optionally at least one additive, together with an effective amount of PEO, said effective amount selected to increase or decrease water degradation of said solid composite material, under conditions that allow compounding of said PAA, PEO and PVOH, and optionally at least one additive, into a solid composite material having a water degradation profile.

65. 1. A method for setting the onset of water degradation of a solid composite material comprising PVOH, comprising: - when preparing a composition comprising PVOH, at least one cross-linking material and at least one additional bioplastic, selecting the amounts of said at least one cross-linking material and said at least one additional bioplastic that in combination accelerate or retard water degradation of said solid composite material; and - heat treating said composition to form said solid composite material; A method comprising:

66. A polymer composite formed from the composition of any one of claims 1 to 45.

67. The rate of water degradation is 1 mg / (min x cm ２ 67. The composite material of claim 66, wherein

68. The rate of water degradation is 0.2 mg / (min x cm ２ 67. The composite material of claim 66, wherein

69. A composite material produced according to the method of any one of claims 46 to 65.

70. 70. The composite material according to any one of claims 66 to 69, in the form of a granular material.

71. 70. The composite material of any one of claims 66 to 69 in the form of a masterbatch.

72. 70. The composite material of any one of claims 66 to 69, in the form of a 1D, 2D or 3D object.

73. 70. An object comprising a composite material according to any one of claims 66 to 69.

74. 74. The object of claim 73, which is a 1D, 2D or 3D object.

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