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    • 专利摘要:
    Biodegradable composition comprising polymers of natural origin and aliphatic-aromatic copolyesters.The present invention relates to a compositionbiodegradable material comprising at least one polymer of natural origin and at leasta cupAliphatic-aromatic iester obtained from mixtures comprising diolsaliphatic, polyfunctional aromatic acids and at least two dicarboxylic acidsaliphatic, at least one of which is long chain. Such a composition combinesimproved biodegradability, excellent mechanical properties, a high levelindustrial processability, (imitated environmental impact, as well as stability ofphysical properties under the influence of environmental factors.
    公开号:BR112012010341A2
    申请号:R112012010341-5
    申请日:2010-11-04
    公开日:2020-09-15
    发明作者:Catia Bastioli
    申请人:Novamont S.P.A.；
    IPC主号:
    专利说明:

    Biodegradable composition comprising polymers of natural origin and aliphatic-aromatic copolyesters.
    DESCRIPTION The present invention relates to the biodegradable composition comprising at least one polymer of natural origin and at least one aliphatic-aromatic copolyester obtained from mixtures comprising aliphatic diols, polyfunctional aromatic acids and at least two aliphatic dicarboxylic acids, at least one of the which is long chain, | Biodegradable aliphatic-aromatic polyesters *, obtained | 10 - starting from aliphatic diacids, such as adipic acid, aromatic diacids, such as terephthalic acid, and aliphatic diols, are known in the literature and on the market. The presence of the aromatic component in the chain is relevant to obtain polymers with sufficiently high melting temperatures and adequate crystallization rates. i However, polyesters currently commercialized of this type have amounts of aromatic acid of less than 48 mol%, since, above this threshold, the percentage of biodegradation of these polyesters decreases significantly.
    This markedly limits the possibility of using such polyesters for applications, in which high mechanical properties associated with compostability are necessary, such as, for example, for the production of bags for the collection of organic waste.
    Composting is the industrial process that mimics processes, reproducing them in a controlled and accelerated way, which, in nature, return organic substances to the life cycle. In nature, the organic substance produced and no longer “useful” for life (dry leaves, branches, animal waste, etc.) is. decomposed by microorganisms present in the soil, which brings it back to the natural cycle. The least degradable components that remain are humus, which, therefore, represents an important dietary supplement for plants, given its ability to release nutritive elements (nitrogen, phosphorus, potassium, etc.), slowly, but constantly, ensuring fertility soil constant. "Industrial composting is, therefore, a process, in which structures are provided for the rational management of microbiological activities that occur spontaneously in nature, with the aim of reducing the time necessary to obtain a type of humus, that is, the and improve the quality of the final product with respect to the product - obtained naturally.
    In fact, it is known in the literature (Muller et al., Angew. Chem,., Int. Ed. (1999), 38, 1438-1441) that copolymers of the poly (butylene adipate-co- a 42% molar fraction of terephthalate, completely biodegrades in the 12-week compost, while products, with a 51% molar fraction of terephthalate, present biodegradation percentages below 40%. This difference was attributed to the formation of a more elevated number of poly (butylene terephthalate) sequences with a length greater than or equal to 3, which are less readily biodegradable.
    If it were possible to maintain suitable biodegradation properties, however, an increase in the percentage of aromatic acid in the chain would be desirable, since it would allow an increase in the melting point of the polyester, an increase in, or at least the maintenance of, important mechanical properties, such as the final strength and the elastic modulus, and would also allow an increase in the crystallization rate of the polyester, thereby improving its industrial processability.
    Biodegradable compositions of natural polymers with aliphatic-aromatic polyesters are also known in the market. Due to their mechanical and biodegradable properties, such compositions are particularly suitable for use in the production of films for food packaging and bags, particularly for waste collection. organic In addition, it is known that these compositions suffer a deterioration of physical properties and, particularly, of mechanical and rheological properties, under the influence of one or more environmental factors, such as heat, light or chemical beings.
    The problem underlying the present invention is, therefore, that of developing a biodegradable composition comprising at least one polymer of natural origin and at least one aliphatic-aromatic polyester of the type: diacid-diol, with a high percentage of aromatic acid in the chain and capable overcome the disadvantages mentioned above.
    . Starting from this problem, it has now been found, surprisingly, that, by mixing specific amounts of at least one polymer of natural origin with at least one aliphatic-aromatic polyester Í presenting a molar fraction of the aromatic acid component above 48 %, and . supplied with a specific composition ratio of at least two aliphatic dicarboxylic acids, one of which is long-chain, it is possible to obtain a composition that combines excellent mechanical properties, a high level of —industrial processability, limited environmental impact, as well as stability of physical properties under the influence of environmental factors, without compromise, but, instead, with improvement, of its biodegradation properties.
    The present invention relates to a composition comprising: (A) at least one biodegradable aliphatic-aromatic copolyester, obtainable from mixtures comprising at least one diol, at least one polyfunctional aromatic acid and at least two aliphatic dicarboxylic acids, characterized by the fact that the content of such aromatic acids is between 48 and 70 mol%, with respect to the total molar content of dicarboxylic acids and that the dicarboxylic acids comprise: i5S1 to 95% mol of at least one C4-Cs diacid ; ii from 5 to 49 mol%, preferably from 30 to 49%, of at least one long chain diacid having more than 6 atoms of: carbon in the main chain, (B) at least one polymer of natural origin; the concentration of (A), with respect to (A + B), being> 40%, preferably> 50% and more preferably> 60% by weight, the composition having a Mass Flow Index at Fusion (EMI) of 1.5-10 g / 10 min, preferably 2-7 g 110 min.
    With respect to MFI, it is measured at 160ºC and 5 Kg according to the ASTM 1238-89 standard “Standard Test Method for Mass Flow Rates in Fusion of Thermoplastics by Extrusion Plastometer”.
    Advantageously, the mixture according to the present invention exhibits a high stability of physical properties, particularly in relation to its Melt Flow Index (MFI).
    In the meaning of the present invention, "high stability" of MFlI means that, after 6 months under normal storage conditions (ie BR, 23ºC, 55% RH), the MFI of the mixture is less than 12 g / 10 min preferably less than 10 g / 10 min, more preferably less than 7 9/10 min s Long chain diacids in the present invention are intended to be dicarboxylic acids with more than 6 carbon atoms Such long-chain diacids are preferably selected from the group consisting of aliphatic dicarboxylic acids with a number of C atoms in the main chain from 7 to 22, esters and mixtures thereof, submeric acid, azelaic acid, sebacic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, its esters and mixtures thereof, being particularly preferred.
    In the meaning of the present invention, products obtained from sources that, due to their intrinsic characteristics, are regenerated in a natural way or are not exhaustible in the time scale of human life and, by extension, whose use does not compromise natural resources for people. future generations, are considered to be of renewable origin. The use of products of renewable origin also contributes to the reduction of CO, in the atmosphere and to the reduction of the use of non-renewable resources. A typical example of renewable sources is made up of vegetable cultures. In copolyester (A), it is intended that polyfunctional aromatic acids are dicarboxylic aromatic compounds, of the phthalic acid type, and heterocyclic aromatic dicarboxylic compounds of renewable origin, mixtures and esters thereof. Particularly preferred are terephthalic acid and its esters and 0,5-furan-dicarboxylic acid and its esters, and mixtures thereof.
    The content of polyfunctional aromatic acids in the copolyester (A) is between 48 and 70%, preferably between 49 and 60%, more preferably between 49 and 58%, and even more preferably between 49 and 53% by mol, with respect to the total molar content of dicarboxylic acids.
    Examples of diols in the copolyester according to the invention are 1,2-ethane-diol, 1,2-propane-diol, 1,3-propane-diol, 1,4-butane-diol, 1,5-pentane-diol , 1,6-hexane-diol, 1,7-heptane-diol, 1,8-octane-diol, 1,9-nonano-diol, 1,10-decano-diol, 1,11-undecane-diol, 1 , 12-dodecan-diol, 1,13-tridecan-diol, 1,4-cyclohexane-dimethane] |, propylene glycol, neopentyl-glycol, 2-methyl-1,3-propane-diol, dianhydro-sorbitol, dianhydro-mannitol, dianhydro-editol, cyclohexane-diol, cyclohexane-methane-diol, and mixtures thereof. Among the diols, 1,2-ethane-diol, 1,4-butane-diol and mixtures thereof are particularly preferred. Advantageously, such diols consist of at least 50%, preferably at least 80% by mol, of 1.4 butane-diol with respect to the total diol content.
    Copolyester (A) can contain, in addition to monomers. basic, at least one hydroxy acid in an amount between O - 49%, preferably between O - 30% by mol, with respect to the moles of dicarboxylic acid - aliphatic. Examples of suitable hydroxy acids are glycolic acid, hydroxy-butyric acid, hydroxy-caprylic acid, hydroxy-valeric acid, 7-hydroxy-heptanoic acid, 8-hydroxy-caprylic acid, 9-hydroxy-nonanoic acid, lactic acid or milk acid . Hydroxy acids can be inserted into the chain as such or they can also be subjected to reaction: first, with diacids or diols, Such hydroxy acids can be present with a repetitive unit distribution or in a random or block way.
    Long bifunctional molecules also with function, not in terminal position, can also be added in quantities not exceeding 10%. Examples are dimeric acids, ricinoleic acid and acids with epoxide functions.
    Amines, amino acids and amino alcohols can also be present in percentages of up to 30 mol%, with respect to all other components.
    In the process of preparing the copolyester (A), one or more polyfunctional molecules can be advantageously added, in amounts between 0.01 and 3 mol%, with respect to the amount of dicarboxylic acids (and any hydroxy acids) in order to obtain branched products. Examples of these molecules are glycerol, pentatritol, trimethylol-propane, citric acid, dipentaerythritol, monohydro-sorbitol, monohydro-mannitol, acid triglycerides, undecylenic acid, triethanol-amine, 1,1,2-ethane-tricarboxylic acid; 1,1,2,2-ethane-tetracarboxylic acid, 1,3,5-pentatricarboxylic acid, 1,2,3,4-cyclopentatetracarboxylic acid, malic acid, tartaric acid, 3-hydroxy-glutaric acid, mucoic acid, trihydroxy acid agglutaric acid, hydroxy-isophthalic acid, esantriol, sorbitol, trimethyl-ethane, mannitol, 1.24 butanotriol, xylitol, 1,2,4-4 tetrakis (hydroxy-methyl) cyclohexane, arabitol, adonitol, iditol.
    The molecular weight M of the copolyester (A) is greater than
    Preferably 15,000 greater than 30,000, more preferably greater than 40,000.
    The polydispersity index M, / M, is between 1.5 and 10, preferably between 1.6 and 5 and more preferably between 1.7 and 3. The molecular weights M, and M, can be measured using Gel Permeation Chromatography (acronym, in English, GPC). The determination can be carried out with the chromatography system maintained at 40ºC, using a set of three columns in series (particle diameter of 5 µm and —porosities, respectively, 500 Angstrom, 1,000 Angstrom and 10,000 Angstrom), an index detector of refraction, chloroform as eluent (flow rate 1 mL / min) and using polystyrene as a reference standard.
    Copolyester (A) has an inherent viscosity (measured with Ubbelhode viscometer for CHCl solutions; with concentrations of 0.2g / dlà25ºC) greater than 0.5 dL / g, preferably greater than 0.6 dL / ge, yet. more preferably, greater than 0.7 dL / g. The copolyester production process (A) can take place according to any of the processes known in the art. In particular, copolyester can be obtained, advantageously with a "polycondensation" reaction.
    Advantageously, the copolyester (A) polymerization process can be carried out in the presence of a suitable catalyst. By way of example, suitable catalysts can be organo-metallic tin compounds, that is, derivatives of stanoic acid, titanium compounds, such as ortho-butyl titanate, aluminum compounds, such as Al-tri-isopropyl, compounds antimony and zinc compounds.
    Preferably, copolyester (A) is obtainable by reacting at least PP of precursor polyester, having at least one component of pr MM oo —i 6/21 acid and at least one component of diol, with compounds bearing groups that can react with OH and / or COOH groups, such as, for example, polyepoxides and polycarbodiimides or with free radical initiators.
    Such compounds can also be used in a mixture.
    Such at least one precursor polyester PP may be of the aliphatic, aromatic or aliphatic-aromatic type.
    The person skilled in the art will be easily able to identify the actual molar ratios required with respect to the nature of polyester PP in order to obtain the desired copolyester (A).
    Preferably, copolyester (A) is obtainable by a reactive extrusion process Among the free radical initiators, peroxides are preferred and, among peroxides, organic peroxides are particularly preferred. Organic peroxides can be advantageously selected from the group consisting of: benzoyl peroxide, lauryl peroxide, isononanoyl peroxide, di (t-butyl-peroxy-isopropyl) -benzene, t-butyl peroxide, peroxide dicumila, alfa, alfa'-di (t-butyl-peroxy) -di-isopropyl-benzene, 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hexane, t-butyl peroxide and cumila , di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hex-3-yne, peroxy-dicarbonate - di (4-t-butyl-cyclohexyl) , dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di (2-ethylhexyl) peroxydicarbonate and mixtures thereof .
    Preferably, such peroxides are added to at least one PP of precursor polyester in an amount of less than 0.1%, more preferably, 0.05% and, even more preferably, 0.02% by weight.
    Examples of polyepoxides, which can be used to advantage, are all polyepoxides from epoxidized oils and / or from styrene - glycidyl ether - methyl methacrylate, such as products distributed by. BASF Resins BV, under the trademark Joncryl & ADR, glycidyl ether methyl methacrylate included in a molecular weight range between 1,000 and 10,000 and with a number of epoxides per molecule ranging from 1 to 30 and preferably from 5 to '25 , and epoxides selected from the group consisting of: diglycidyl diethylene glycol ether, polyethylene glycol diglycidyl ether, glycerol poly (glycidyl ether), diglycerol poly (glycidyl ether), 1,2-epoxy-butane, poly ( glycidyl ether) of polyglycerol, isoprene diepoxide, and cycloaliphatic diepoxide, 1,4-cyclohexane-dimethanol diglycidyl ether, glycidyl 2-methyl-phenyl ether, glyceryl propoxylate ether triglycidyl, 1,4- butane diol, sorbitol poly (glycidyl ether), glycerol diglycidyl ether, meta-xylene diamine tetraglycidyl ether and bisphenol A diglycidyl ether, and mixtures thereof.
    Preferably, such polyepoxides are added to at least one PP of precursor polyester in an amount of less than 2%, more preferably 1%, and even more preferably 0.75% by weight.
    Catalysts can also be used to increase the reactivity of the reactive groups. In the case of polyepoxides, for example, fatty acid salts can be used. Calcium and zinc stearates are particularly preferred.
    Examples of carbodiimides, which can be used to advantage, are selected from the group comprising: poly (carbodiimide cyclooctylene), = poly (1,4-dimethylene - cyclohexylene - carbodiimide), - poly (cyclohexylene — carbodiimide, polyphethylene carbodiimide), poly (butylene carbodiimide), polyphisobutylene carbodiimide), poly (nonylene carbodiimide), poly (dodecylene carbodiimide), poly (neopentylene carbodiimide), poly (1,4-dimethylene phenylene carbodiimide), poly (2,2 ', 6,6', tetraisopropyl-diphenylene carbodiimide), (Stabaxolº D), poly (2,4 , 6-tri-isopropyl-1,3-phenylene carbodiimide) (Stabaxol ™ P-100), poly (1,3,5-tri-isopropyl-phenylene-2,4-carbodiimide), poly (2 , 6-diisopropyl-1,3-phenylene carbodiimide) (Stabaxolº P), poly (tolyl carbodiimide), poly (4,4'-diphenylmethane - carbodiimide), = poly (3, 3'-dimethyl-4.4 "-biphenylene-carbodiimide), poly (p-phenylene carbodiimide), poly-phenyl carbodiimide), poly (3,3'-dimethyl-4,4" -diphenyl - carbodiimide methane), polyin phenyl carbodiimide), polylisophorone carbodiimide), polycycene carbodiimide), p-phenylene bis (ethyl-carbodiimide), 1,6-hexamethylene bis (ethyl- | 20 - carbodiimide), 1,8-octamethylene bis (ethyl-carbodiimide), 1,10-decamethylene-bis (ethyl-carbodiimide), 1.12 dodecamethylene bis (ethyl-carbodiimide) and mixtures the same.
    Preferably, such carbodiimides are added to at least one PP of precursor polyester in an amount of less than 1.5%, more preferably 0.75% and, even more preferably, 0.5% by weight .
    Such at least one precursor polyester PP preferably has an installation content of 0.1 - 0.8 and, more preferably, 0.2 - 0.7 mole%.
    . Such unsaturation can be generated in situ during the polymerization phase or during the processing of at least one precursor polyester PP, by adding suitable unsaturated monomers or suitable unsaturated chain terminators. Particularly preferred are PP polyesters precursors with terminal unsaturation.
    Among unsaturated chain terminators, preferred are those with the formula: T- (CH3), .- CH = CH, in which "T" is a group capable of reacting with carboxylic and / or hydroxy groups and “number is a number integer between 0 and 13,
    Such unsaturated chain terminators can also be used in admixture.
    With respect to "T", it is preferably selected from the group consisting of hydroxyl, carboxylic, amine, amide or ester group, particularly hydroxy or carboxylic groups.
    Preferably, the whole number "No. is between 1 and 13, more preferably between 3 and 13, even more preferably 8 or 9, with omega-undecenoic acid, omega-undecylenic alcohol and mixtures thereof being particularly preferred in order to to maximize compatibility with at least one naturally occurring polymer.
    Also after the preparation process, copolyester (A) may have double bonds and / or addition products that are derived from the reaction of unsaturation with the free radical initiators. The presence of unsaturation and / or addition products: 15 that are derived from their reaction with free radical initiators can be determined with different methods well known to those skilled in the art, such as NMR spectroscopy or by reactions of polymer chain methanolysis coupled with chromatographic methods combined with mass spectroscopy.
    The person skilled in the art will readily be able to identify referable structures or their unsaturation or the reacted installation after the reaction.
    Preferably, the polyester (A) is obtainable through a reactive extrusion process starting from a precursor polyester PP having a content of terminal acid groups in amounts of 35 - 150 meq KOH / kg of the precursor polyester. The measurement of the terminal acid groups can be performed BR as follows: 1.5 - 3 g of the polyester according to the invention are placed in a 100 ml Erlenmeyer flask. 60 mL of chloroform is added to dissolve the resin. After complete dissolution, 25 ml of 2-propanol are added and, just before determination, 1 ml of deionized water is added. The solution thus obtained is titrated with a previously standardized KOH / ethanol solution using an i indicator suitable for determining the titration equivalence point, such as, for example, a glass electrode designed for use with non-aqueous acid-base titrations . The content in terminal acid groups is calculated from the consumption of the KOH / ethanol solution, based on the following equation: Content in terminal acid groups (meq KOH / Kg of polymer) =
    —L, = W,): 7) -1000
    P in which; Ve = mL of KOH / ethanol solution at the equivalence point for sample titration; V, = mL of KOH / ethanol solution needed to reach pH = 9.5 during the blank titration; T = concentration in moles / L of the KOH / ethanol solution; P = g of sample. Copolyester (A) is biodegradable in industrial composting according to the EM 13432 standard.
    The at least one polymer of natural origin (B) is advantageously selected from starch, cellulose, chitin, chitosan, alginates, proteins, such as gluten, zein, casein, collagen, gelatin, natural rubbers, rosinic acid and their derivatives, lignins and their derivatives. Starches and cellulose can be modified and, among these, it is possible to mention, for example, starch or cellulose esters with a degree of substitution between 0.2 and 2.5, hydroxy-propylated starches, modified starches with fatty chains.
    Among the polymers of natural origin mentioned above, starch is particularly preferred. .
    The word "starch" is understood here as all types of starch, for example, potato starch, corn starch, tapioca starch, pea starch, rice starch, wheat starch and also starch with a high content of amylose - preferably, containing more than 30% by weight of amylose - and waxy starches. Mixtures of starches are also particularly preferred.
    Starch can be used in an unstructured or gelatinized form or as a filler. Such starch can represent the continuous or dispersed phase or it can be in co-continuous form.
    Ú In general, to obtain co-continuous structures, it is possible to work either on the selection of starch with a high content of amylopectin and / or to add block copolymers with hydrophobic and hydrophilic units to the - 30 starch-polyester compositions. Possible examples are poly (vinyl acetate) / polyfalco copolymers | 'vinyl) and polyester / polyether, in which the length of the blocks, the balance between the hydrophilicity and the hydrophobicity of the blocks and the quality of the used compatibilizer can be modified accordingly, in order to fine-tune the - microstructure of starch-polyester compositions.
    In the case of dispersed starch, the starch preferably represents a phase of homogeneously dispersed particles, with average dimensions of less than 1 µm, preferably less than 8 µm.
    - The dimensions of the starch particles are measured in the cross section, with respect to the flow direction of the extrusion or, in any case, with respect to the direction of the material outlet. For this purpose, a sample of the mixture, which must be examined, is immersed in liquid nitrogen and subsequently fractured, in order to obtain a fracture surface along a cross section of the sample. The sample portion, which must be examined, is then subjected to selective pickling, dried and a thin layer of metal is deposited on it, for example, a gold / platinum mixture, using a "hot coat".
    Finally, the fracture surface is examined under a scanning electron microscope (SEM).
    The size of the starch particles is determined by measuring the dimensions of the holes in the fracture surface, after the selective stripping of the starch.
    The average size of the starch particles, that is, the detectable holes on the blasted surface of the fracture, is calculated as the numerical (or arithmetic) mean of the particle dimensions. In the case of a spherical particle, the particle size corresponds to the diameter of a circle corresponding to the two-dimensional shape resulting from the cross section. In the case of a non-spherical particle, the dimension (d) of the particle is calculated according to the following formula: d = dd, in which d, is the smallest diameter and d, is the largest diameter of the ellipse, in which the particle can be entered or approximated.
    The selective stripping of the dispersed starch phase can be advantageously carried out with HCI 5 N as a stripping agent, with a stripping time of 20 minutes, at a stripping temperature of 25ºC.
    Mixtures containing unstructured starch are preferred.
    - Starches, such as corn and potato starch, capable of being facially unstructured and having high initial molecular weights, have proven to be particularly advantageous.
    'It is particularly preferred to use cornstarch and. potato.
    For unstructured starch, this refers to the teachings contained in documents EP-O 118 240 and EP-O 327 505, which is intended as processed starch, so that it substantially does not show any “Maltese crosses” under the light microscope. polarized and any “ghosts” under the phase-contrast optical microscope.
    In addition, physically and chemically modified grades of starch can be used, such as ethoxylated starches, oxypropoxylated starches, starch acetates, starch butyrate, starch propionates, with a degree of substitution ranging from 0.1 to 2 , cationic starches, oxidized starches, cross-linked starches, gelled starches.
    Mixtures according to the present invention, in which the starch represents the dispersed phase can form biodegradable polymeric compositions with good resistance to aging and moisture. In fact, these polymeric compositions can maintain high tear resistance even in low humidity conditions.
    Such characteristics can be achieved when the water content of the composition during mixing of the component is preferably maintained between 1% and 15% by weight. However, it is also possible to operate with a content of less than 1% by weight, in that case, starting with previously dried and previously plasticized starch.
    It should also be useful to degrade starch at a low molecular weight before or during composting with the polyesters of the present invention, in order to have, in the final material or in the finished product, an inherent starch viscosity between 1 and 0.2 dL / g, preferably between 0.6 and 0.25 dL / g, more preferably between 0.55 and 0.3 dL / g.
    Unstructured starch can be obtained before or during mixing with the polyesters according to the present invention, in the presence of plasticizers, such as water, glycerol, di- and poly glycerols, ethylene or propylene glycol, ethylene and propylene diglycol, polyphethylene glycol), poly (propylene glycol), 1,2-propane-diol, trimethylol-ethane, trimethylol-propane, pentaerythritol, dipentaerythritol, sorbitol, erythritol, xylitol, —manitol, sucrose, 1,3-propane-diol, 1,2-butane -diol, 1,3-butane-diol, 1,4-butane-diol, 1,5- 'pentane-diol, 1,5-hexane-diol, 1,6-hexane-diol, 1,2,6- hexane-triol, 1,3,5-hexane-triol, neopentyl glycol and prepolymers and polymers of poly (vinyl alcohol), polyol acetates,. ethoxylates and propoxylates, particularly sorbitol ethoxylate, sorbitol acetate and pentaerythritol acetate.
    Water can be used as a plasticizer in combination with high boiling point plasticizers or alone during the plasticization phase of the starch, before or during mixing of the composition, and can be removed to the required level by degassing in one or more steps during extrusion. When plasticization and mixing of the components are complete, the water is removed by "degassing, to give a final content of about 0.2 - 3% by weight.
    Water, as well as plasticizers with high boiling points, modify the viscosity of the starch phase and affect the rheological properties of the starch / polymer system, helping to determine the particle sizes
    "12/21 dispersed. Compatibilizers can also be added to the mixture. They can belong to the following classes: - Additives, such as esters that have hydrophilic / lipophilic balance index (EHL) values greater than 8, and that are obtained at from polyols and —part from mono- or polycarboxylic acids with pK dissociation constants lower than 4.5 (values refer to the pK of the first carboxyl group in the case of polycarboxylic acids); - esters with EHL values between 5 , 5 and 8, obtained from polyols and mono- or polycarboxylic acids with less than 12 carbon atoms and with pK values greater than 4.5 (this value refers to the pK of the first carboxyl group in the case of polycarboxylic acids); - Esters with lower EHL values than 5.5, obtained from polyols and from fatty acids with 12 - 22 carbon atoms; These —compatibizers can be used in 15th quantities of 0.2 to 40% by weight and preferably from 1 to 20% by weight, based on starch. Starch combinations can also contain polymeric compatibilizing agents having two components: one compatible with or soluble in starch and a second soluble in or compatible with polyester. Examples are starch / polyester copolymers via transesterification catalysts. Such polymers can be generated through reactive combination during composting or they can be produced in a separate process and then added during extrusion. In general, block copolymers of a hydrophilic unit and a hydrophobic unit are particularly suitable. Additives can also be added, such as di- and polyepoxides, di- and poly-isocyanates, isocyanurates, polycarbodiimides and peroxides. They can work like. stabilizers as well as chain extenders. All of the above products can help to create the 'necessary microstructure. It is also possible to promote reactions in situ, to create links between the starch and the polymeric matrix. Bi-aliphatic-aromatic polymers with extended chains can also be used, with diisocyanates or di- and polyiepoxides or isocyanurates or with oxazolines, aliphatic or aromatics, with intrinsic viscosities U greater than 1 dL / g or, in any case, aliphatic-aromatic polyesters with a ratio between M, and EMI at 190ºC, 2.16 Kg, higher than 10,000, preferably higher than 12,500, and more preferably higher than
    15,000 to achieve the necessary microstructure. Another method to improve the microstructure is to achieve the starch complexation in the starch-polyester mixture.
    The composition according to the present invention exhibits good properties also in the case of starch combinations, in which the starch does not | is highly complex.
    With regard to the complexation of starch, the teachings contained in EP-O 965 615 must be intended to be incorporated into the present invention.
    The presence of starch complexes with a hydrophobic polymer incompatible with starch can be demonstrated, by the presence in the X-ray diffraction spectra, of a peak in the range of 13-14º on the theta scale.
    According to the present invention, with the compositions of the statement, in which the starch is not strongly complexed, compositions are intended, in which the H./H ratio, between the height of the peak (H.) in the range of 13 -14º of the complex and the peak height (H.) of amorphous starch, which appears at about 20.5º, is less than 0.15, and even less than 0.07. Advantageously, the composition according to the invention contains at least one plasticizer of the starch to provide suitable 15 rheological properties.
    This plasticizer can be simply water (even the water contained in the native starch evenly without the need for further additions), or plasticizers with high boiling points or polymeric.
    Mixtures of different plasticizers are also preferred.
    The amount of plasticizer is, in general, chosen based on the rheological needs of the mixing system. In any case, the plasticizers are advantageously added in an amount of less than 30%, preferably less than 20%, even more preferably, less than 10% and weight, relative to the starch on a dry basis.
    In addition to water, plasticizers, which can be used in the composition according to the invention, are high-boiling or polymeric plasticizers. i In the meaning of the present invention, plasticizers with. high boiling points are understood to be plasticizers with boiling points higher than 250ºC.
    Among those, those described in WO92 / 14782, glycerol, diglycerol, triglycerides are preferred! and tetraglycerol and mixtures thereof. Particularly preferred are mixtures of high boiling plasticizers containing at least 75% by weight, preferably 90% by weight of diglycerol, triglycerol and tetraglycerol.
    Such mixtures contain more than 50% by weight, preferably more than about 80% by weight of diglycerol with respect to the total weight of diglycerol, triglyceride! and tetraglycerol.
    The use of this type of plasticizers with high boiling points is particularly preferred, as they avoid problems with fumes in processing environments and there are no frequent interruptions that are necessary for cleaning the machines during the processing of the composition.
    In the meaning of the present patent application, with the word "diglycerol" are understood here all compounds that are derived from condensation reactions of two glycerol molecules, such as alpha-alpha'-diglycer |, —alpha-beta- diglycerol, beta-beta'-diglycerol, their various cyclic isomers and mixtures thereof As far as diglycerol is concerned, mixtures comprising at least 70% by weight of alpha-alpha'-diglycerol are particularly preferred.
    Compositions according to the present invention, containing water as the only plasticizer, are also preferred. Among these, compositions containing water present in native starch as the only plasticizer are particularly preferred.
    The compositions according to the present invention are biodegradable in industrial composting, according to the EM 13432 standard.
    The composition according to the invention can be used 15º in combinations, which can also be obtained by reactive extrusion processes, with one or more polymers, which may or may not be biodegradable.
    In the meaning of this invention, biodegradable polymers are understood to mean biodegradable polymers according to the EN standard
    13432.
    In particular, the composition according to the invention can be combined with biodegradable polyesters of the diacid-diol, hydroxy-acid or polyester-ether type.
    As far as biodegradable polyesters of the diacid-diol type are concerned, they can be either aliphatic or aliphatic-aromatics.
    Biodegradable aliphatic polyesters from diacid-R diols comprise aliphatic diacids and aliphatic diols, while biodegradable aliphatic-aromatic polyesters have an aromatic part comprising. mainly aromatic acids with multiple functional groups, the aliphatic part being made up of aliphatic diacids and aliphatic diols.
    The aromatic aliphatic biodegradable polyesters from] diacid-diols are preferably characterized by an aromatic acid content of between 30 and 90 mol%, preferably between 45 and 70 mol%, with respect to the Ú component of acid.
    Preferably, aromatic acids having multiple functional groups, advantageously, may be dicarboxylic aromatic compounds of the phthalic acid type and their esters, preferably terephthalic acid.
    Aromatic acids with multiple functional groups can also be selected from the group comprising aromatic heterocyclic dicarboxylic acids, among which 2,5-furanicicarboxylic acid and its esters are preferred.
    Aliphatic-aromatic polyesters biodegradable from diacids-diols, in which the aromatic diacid component comprises a mixture of aromatic dicarboxylic compounds of the phthalic acid type and heterocyclic aromatic dicarboxylic acids are particularly preferred.
    The aliphatic diacids of the biodegradable aliphatic-aromatic polyesters are aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glucaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid, sebacic acid, undecanedioic, dodecanoic and brass acid yours | esters and their mixtures. Among these, adipic acid and acids are preferred | dicarboxylic acids from renewable sources, and among these, dicarboxylic acids from renewable sources are particularly preferred, such as succeinic acid, sebacic acid, azelaic acid, undecanedioic, dodecanedioic and brassic acid and mixtures thereof.
    Examples of aliphatic diols, in polyesters biodegradable from diacids-diols, are: 1,2-ethane-diol, 1,2-propane-diol, 1,3-propane-diol, 1,4-butane-diol, 1 , 5-pentane-diol, 1,6-hexane-diol, 1,7-heptane-diol, 1,8-octane-diol, 1,9-nonano-diol, 1,10-decano-diol, 1,11 -undecan-diol, 1,12-dodecan-diol, 1,13-tridecan-dioli 1,4-cyclohexane-dimethanol, neopentylglycol, 2-methyl-1,3-propane-diol, dianhydrosorbitol, diahydro- mannitol, dianhydro-editol, cyclohexane-diol, cyclohexane-methane-dioles and mixtures. Of these, 1,4-butane-diol, 1,3-propane-diol and 1,2-ethane-diol and mixtures thereof are particularly preferred.
    Preferably, the combinations of the composition according to the invention, with biodegradable polyesters, from the diacid-diols described above - are characterized by a content in the biodegradable polyesters, which varies within the range between 1 and 99% by weight, more preferably , between 5 and 95% by weight, with respect to the sum of the weights of the composition according to the invention and the former, respectively.
    Preferred biodegradable polyesters from hydroxy-acids include: poly-L-lactic acid, poly-D-lactic acid and poly-D-L- acid ester complex. lactic acid, poly-s-caprolactone, poly-hydroxy-butyrate, poly-hydroxy-butyrate-valerate, poly-hydroxy-butyrate-propanoate, poly-hydroxy-butyrate-hexanoate, poly-hydroxy-butyrate-decanoate, polyhydroxy- butyrate-dodecanoate, polyhydroxy-butyrate-hexadecanoate, polyhydroxy-butyrate-octadecanoate and poly-3-hydroxy-butyrate-4-hydroxy-butyrate. Among the polyesters biodegradable from hydroxy acids, those particularly preferred are poly-L-lactic acid, poly-D-lactic acid and the stereocomplex of poly-L-lactic acid and poly-D-lactic acid,
    Preferably, the combinations of the composition according to the invention, with the biodegradable polyesters, from the hydroxy acids described above, are characterized by a content in the biodegradable polyesters, which varies within the range between 1 and 99% by weight, more preferably between 5 and 95% by weight, with respect to the sum of the weights of the composition according to the invention and the former, respectively The composition according to the invention can also be combined with polyolefins, non-biodegradable polyesters, polyester- and polyether - urethanes, —polyurethanes, polyamides, polyamino acids), polyethers, polyureas, - polycarbonates and mixtures thereof.
    Among polyolefins, polyethylene, polypropylene, their copolymers, poly (vinyl alcohol), polyvinyl acetacetate), polyacetate are preferred | ethyl-vinyl) and poly (ethylene-vinyl alcohol). ! Among non-biodegradable polyesters, PET, PBT, PTT are preferred, in particular with a renewable content> 30%, and alkylene polyururanidicarboxylates). Among the latter, poly (ethylene furan-dicarboxylate), polypropylene-propylene dicarboxylate), polyene-butylene dicarboxylate) and mixtures thereof are preferred.
    Examples of polyamides are: polyamide 6 and 6.6, polyamide 9 e8 & 989 polyamide 10 and 10.10, polyamide 11 and 11.11, polyamide 12 and 12.12 and their combinations of types 6/9, 6/10, 6/11 and 6/12. Polycarbonates can be poly (ethylene carbonates), poly (propylene carbonates), polycarbonates of butylene) and their mixtures and copolymers.
    Polyethers can be poly (ethylene glycols), poly (propylene glycols), poly (butylene glycols), their copolymers and mixtures, with molecular weights between 70,000 and 500,000. . Preferably, combinations of the composition according to the invention with the polymers described above (polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, polyurethanes, polyamides, poly (amino acids), polyethers, polyureas, polycarbonates and mixtures are characterized by a content of the polymers that varies within the range of 0.5 to 99% by weight, more: preferably from 5 to 50% by weight, with respect to the sum of the weights of the composition according to the invention and the former, respectively.
    The composition according to the invention can be used advantageously in combinations of 5 - 30% by weight, preferably 7 - 25% by weight of at least one rigid polymer with a module greater than 1500 Mpa.
    Such at least one rigid polymer can be present as an additional dispersed phase,
    as well as in lamellar structures or mixtures thereof.
    As far as this additional dispersed phase is concerned, the at least one rigid polymer forms a homogeneously dispersed phase of particles with average dimensions of less than 2 µm, preferably less than 1 µm.
    The dimensions of such particles are measured according to the measurement method described above for starch particles.
    Among the rigid polymers, poly (hydroxy alkanoates), such as lactic polyacid and glycolic polyacid) are particularly preferred, and, more preferably, poly (lactic acid) polymer or copolymers containing at least 75% L-lactic acid or D-lactic or combinations thereof, advantageously, with molecular hair M, greater than 70,000. Such rigid polymers can also be plasticized.
    | The selective pickling of dispersed phase of poly (lactic acid) can be carried out advantageously with acetone as pickling, with a pickling time of 15 minutes of 5 minutes, at a pickling temperature of 25ºC. The composition according to the present invention can be prepared by means of an extruder or any other machine capable of providing temperature and shear conditions, which allow homogeneous mixing of the components.
    The compositions according to the present invention are advantageously obtainable by reactive extrusion process with compounds bearing groups that can react with OH and / or COOH groups, such as, for example, polyepoxides and polycarbodiimides or with bonds unsaturated substances, such as, for example, peroxides.
    Examples of peroxides, which can be used advantageously, are selected from the group of dialkyl peroxides, such as: benzoyl peroxide, lauryl peroxide, isononanoyl peroxide, di (t-butyl-peroxy-isopropyl) - benzene, t-butyl peroxide, dicumyl peroxide, alpha, alpha'-di (t-butyl-peroxy) -. diisopropyl-benzene, 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hexane, tbutyl and cumyl peroxide, 2,5-dimethyl-2,5- di-t-butyl peroxide di (t-butyl-peroxy) -hex-3-yne, = peroxy-dicarbonate di (4-t-butyl-cyclohexyl), peroxy-dicarbonate, dicetyl, peroxy. dimyristyl dicarbonate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di (2-ethylhexyl) peroxydicarbonate and mixtures thereof.
    Ú Preferably, such peroxides are added to the polyesters according to the invention in an amount of less than 0.5%, more - preferably 0.2%, and even more preferably 0.1% by weight .
    Examples of polyepoxides, which can be used advantageously, are all polyepoxides from epoxidized oils and / or from styrene-glycidyl ether - methyl methacrylate, such as products distributed by i 18/21 BASF Resins BV, under the trademark Joncryl & ADR, glycidyl ether methyl methacrylate included in a molecular weight range between 1,000 and 10,000 and with a number of epoxides per molecule ranging from 1 to 30 and preferably from 5 to 25, and epoxides selected to from the group consisting of: diglycidyl diethyl ether — glycol, diglycidyl polyethylene glycol!), glycerol poly (alicyclic ether), diglycerol poly (glycidyl ether), 1,2-epoxy-butane, poly (glycidyl ether) polyglycerol, isoprene diepoxide, and cycloaliphatic diepoxide, 1,4-cyclohexane-dimethanol diglicidyl ether, glycidyl 2-methyl-phenyl ether, glycerol propoxylate triglycidyl ether, 1,4-butane-diol diglycidyl ether , sorbitol poly (glycidyl ether), diglycidi l glycerol ether, tetraglycidyl methaxylene diamine ether and —diglycidyl bisphenol A ether, and mixtures thereof.
    Preferably, such polyepoxides are added to the 1 polyesters according to the invention in an amount of less than 2%, more preferably 1%, and even more preferably 0.75% by weight.
    Catalysts can also be used to increase the 15th reactivity of the reactive groups.
    In the case of polyepoxides, for example, fatty acid salts can be used.
    Calcium and zinc stearates are particularly preferred.
    Examples of carbodiimides, which can be used to advantage, are selected from the group comprising: poly (cyclooctylene - carbodiimide), poly (1,4-dimethylene cyclohexylene carbodiimide), = polyifciclo -hexylene carbodiimide, polyphethylene carbodiimide), poly (butylene carbodiimide), polyphisobutylene carbodiimide), poly (nonylene carbodiimide), poly (dodecylene carbodiimide), poly (neopentylene carbodiimide), poly (1,4-dimethylene phenylene carbodiimide), poly (2,2 ', 6,6', tetraisopropyl-diphenylene carbodiimide), (Stabaxolº D), poly (2,4,6-trihydrate) isopropyl-1,3-phenylene — carbodiimide) (Stabaxolº P-100), poly (1,3, S5-triisopropyl-phenylene-2,4-carbodiimide), poly (2,6-diisopropyl- 1,3-phenylene carbodiimide) (Stabaxolº P), poly (tolyl carbodiimide), 'poly (4,4'-diphenylmethane - carbodiimide), = polyç3,3'-dimethyl-4,4 "-biphenylene carbodiimide),. poly (p-phenylene carbodiimide), polyvinyl-phenylene cearbodiimide), poly (3,3'-dimethyl-4,4'-diphenyl-methane carbodiimide), poly (in F ethylene carbodiimide), polyphisophorone carbodiimide), —polycumene carbodiimide), p-phenylene bis (ethyl-carbodiimide), 1,6-hexamethylene bis (ethyl- ”carbodiimide), 1,8- octamethylene - bis (ethyl carbodiimide), = 1.10-decamethylene bis (ethyl carbodiimide), 1.12 dodecamethylene bis (ethyl carbodiimide) and mixtures thereof. Preferably, such carbodiimides are added to the polyesters according to the invention in an amount of less than 1.5%, more preferably 0.75% and, even more preferably, 0.5% by weight .
    In the present biodegradable composition, several additives can also be incorporated, such as antioxidants, UV stabilizers, heat and hydrolysis stabilizers, chain extenders, 19/21 m flame retardants, slow release agents, inorganic fillers and organic, such as natural fibers, antistatic agents, wetting agents, dyes, lubricants or compatibility agents between the various phases.
    Preferably, the compositions according to the present invention exhibit a punching energy, measured in films having thicknesses of - 50 pum, greater than 7 J / mm, more preferably, more than 9 J / mm, and, more preferably, more than 12 J / mm.
    Regarding the measurement of puncture energy, it is carried out according to the ASTM D5748-95 (2001) standard, using a triangular pyramid-shaped probe 10 (edges = 35 mm; vertex angles = 90º) at a speed crosshead of 500 mm / min, temperature of 23ºC, Relative Humidity of 55%, in film specimens with a diameter of 125 mm.
    As a reference, under the same testing conditions, an HDPE film, with a thickness of 22 µm, exhibits a puncture energy of 9.2 J / mm, 15º while an LDPE film, with a thickness of 40 µm, exhibits a puncture energy of 10 J / mm.
    The composition according to the invention has properties and viscosity values, which make it suitable to be used, modulating, appropriately, the relative molecular weight, for numerous practical applications, such as films, injection molding articles, coatings by extrusion, fibers, foams, thermoformed articles, etc.
    In particular, such a composition and combinations thereof, therefore, are suitable for the production of: - mono- and bioriented films, and films with multiple layers with other polymeric materials; : - films for use in the agricultural sector, such as films for use in vegetation cover; . - films for cling films for use with foodstuffs, for bales in agriculture and for wrapping waste; - bags and liners for containers for the collection of organic waste, such. such as the collection of scrap and garden waste; - seed coatings; '- glues, such as hot melt adhesives; - thermoformed food packaging, both single and multiple layers, as well as containers for milk, yogurt, meat, drinks, etc; - coatings obtained using the extrusion coating method; - multilayer laminates, with layers of paper, plastic,
    aluminum or metallized films;
    - expanded or expandable accounts for the production of parts obtained by; sintering;
    í - expanded and semi-expanded products, including foam blocks - formed using expanded particles;
    - foam sheets, thermoformed foam sheets and containers obtained from them for use in food packaging;
    - containers for fruits and vegetables in general;
    - composites with gelatinized, unstructured and / or complexed starch,
    natural starch, flours or natural vegetable or inorganic fillers;
    - fibers, microfibers, composite microfibers, in which the core is | made up of rigid polymers, such as PLA, PET, PTT, and the wrapping made up of the material of the invention, combined composite fibers, fibers with different sections, from circular to multilobulated, staple fibers, woven and non-woven textile materials | 15 - woven or wired or thermally bonded for use in sanitary and bathroom products | hygiene, and in the agriculture and clothing sectors.
    They can also be used in applications instead of plasticized PVC.
    The composition according to the present invention is - biodegradable according to the standard EN 13432, The invention is now described with some examples of | modality provided purely by way of example not limiting the scope of protection of the present patent application.
    Example 1 '25 68 parts by weight of an aromatic aliphatic copolyester, | obtained from butanediol, and the following mixture of dicarboxylic acid:: 50 mol% of terephthalic acid. 26% by hand! adipic acid | 24% sebacic acid! 30 presenting a melt flow rate, TEM, of 3 g / 10 ',. were mixed with 10 parts of poly L-lactic polymer presenting TEM, at 190ºC, 2.16 Kg, of 3.5 9/10 min, a lactic residue of less than 0.2% and a D content of about 6%, 16.5 parts of starch, 2.5 parts of water, 3 parts of triglyceride! and 0.5 parts of a styrene - glycidyl ether - methyl methacrylate copolymer. The extruder used was a Haake Rheocord 90 Rheomex TW-100 twin screw extruder. The thermal profile was varying between 120 and 190ºC.
    The final water content of the granules was equal to 0.8%. S The granules were shot on a 40 1 mm Ghioldi machine, mold interval = 1 mm, flow rate of 20 kg / h, to obtain a film with a thickness of 20 µm.
    The 20 um films were then subjected to mechanical characterization according to the ASTM D882 standard (tensile at 23ºC and 55% relative humidity and V, = 50 mm / min), to measure Elmendorf tear strength according to with the ASTM D1922 standard (at 23ºC and 55% RH) and according to the ASTM D5748-95 standard (triangular pyramidal probe with edges = 35 mm and apex angles = 90º; crosshead speed of 500 mm / min , temperature of 23ºC, relative humidity of 55%, diameter of film specimen of 125 mm). The results are shown in Table 1, below.
    TABLE 1. MECHANICAL PROPERTIES Ex. O e & E Resistance to Energy of i (Mpa) (%) (Mpa) Puncture Tear En, Elmendorf (N / mm) (J / mMm) TD 151 Determination of starch particle size Os granules of the composition according to Example 1 15º were immersed in liquid nitrogen and subsequently fractured, in order to obtain a fracture surface along the cross section of cross section samples.
    A portion of such samples was, of course, blasted with HC! 5 N (25ºC, 20 minutes), dried and a thin layer of a gold / palladium mixture was deposited on them by means of a “hot coat”. Finally, the fracture surfaces thus obtained were - examined under a scanning electron microscope (SEM) (4,000 x magnification). For each sample, several microphotographs of the fracture surfaces were recorded.
    The - average starch particle size was calculated as the numerical (or arithmetic) mean of the particle dimensions.
    The composition according to Example 1 exhibited a "dispersed average particle size starch of 0.25 µm.
    BR Biodegradation test Biodegradation tests were performed according to the EN 13432 standard on film samples obtained from the composition of Example 1. The composition exhibited a higher relative biodegradability than 90% after 150 days.
    权利要求:
    Claims (22)
    [1]
    1. Composition comprising: (A) "at least one biodegradable aliphatic-aromatic copolyester, obtainable from mixtures comprising at least one diol, at least one polyfunctional aromatic acid and at least two aliphatic dicarboxylic acids, characterized by the fact that the The content of such aromatic acids is between 48 and 70 mol%, with respect to the total molar content of dicarboxylic acids and of which the dicarboxylic acids comprise: i deS1ag95 mol% of at least one C1-Cs diacid; 5 to 49 mol%, preferably 30 to 49%, of at least one | long-chain diacid having more than 6 carbon atoms in the main chain, (B) at least one polymer of natural origin; the concentration of (A), with respect to (A + B), is> 40% by weight, the composition having a Melting Mass Flow Index (EMI) of 1.5— 10g / 10 min, preferably 2—7 g / 10 min.
    [2]
    2. Composition according to claim 1, characterized by the fact that at least one long chain diacid, of at least one biodegradable aliphatic-aromatic copolyester, is selected from the group consisting of aliphatic dicarboxylic acids with number of atoms of carbon in the main chain of between 7 and 22, esters and mixtures thereof.
    [3]
    3. Composition according to claim 1, characterized by the fact that aromatic acids are aromatic compounds - dicarboxylic acids of the phthalic acid type and heterocyclic aromatic compounds of renewable origin, mixtures and esters thereof.
    [4]
    ] 4. Composition, according to claim 1, BR characterized by the fact that at least one polymer of natural origin is selected from starch, cellulose, chitin, chitosan, alginates, proteins, such as gluten, zein, casein, collagen, gelatin, natural rubbers, rosinic acid and their. derivatives, lignins and their derivatives.
    [5]
    Composition according to claim 4, | characterized by the fact that the starch is in an unstructured or gelatinized form or as a filler.
    [6]
    Composition according to any one of claims 4-5, characterized in that the starch represents a homogeneously dispersed phase of particles with average dimensions of less than 1 µm.
    [7]
    Composition according to any one of claims 1 - 6, characterized in that it is biodegradable according to the standard EN 13432.
    [8]
    8. Composition, according to any of the | claims 1 - 7, characterized by the fact that it is combined with one or more - polymers.
    [9]
    l 9. Combination, characterized by the fact that it comprises the composition according to claim 8, the one or more polymers being selected from biodegradable polyesters of the diacid-diol, hydroxy-acid or polyester-ether type,
    [10]
    10. Combination according to claim 9, characterized by the fact that diacid-diol polyesters are aliphatic or aliphatic-aromatic.
    [11]
    11. Combination according to claim 10, characterized by the fact that the content of biodegradable polyesters from diacid-15º diol varies within the range between 1 and 99% by weight.
    [12]
    12. Combination according to claim 9, characterized by the fact that polyesters of the hydroxy-acid type are selected from poly-L-lactic acid, poly-D-lactic acid and sterocomplex of poly-DL-lactic acid, poly-and-caprolactone, poly-hydroxy-butyrate, poly-hydroxy-butyrate-valerate, poly-hydroxy-butyrate- —propanoate, poly-hydroxy-butyrate-hexanoate, poly-hydroxy-butyrate-decanoate, poly-hydroxy-butyrate -dodecanoate, polyhydroxy-butyrate-hexadecanoate, polyhydroxy-butyrate-octadecanoate and poly-3-hydroxy-butyrate-4-hydroxy-butyrate.
    [13]
    13. Combination according to claim 12, characterized by the fact that the content of biodegradable polyesters from hydroxy-varic acid ranges between 1 and 99% by weight.
    [14]
    14. Combination, characterized by the fact that it comprises the 'composition according to claim 8, the one or more polymers being. selected from polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, —polyurethanes, polyamides, polyamino acids), polyethers, polyureas, —polycarbonates, polycarbonates and mixtures thereof.
    [15]
    - 15. Combination according to claim 14, characterized by the fact that the content of polyolefins, non-biodegradable polyesters, Ú polyester- and polyether-urethanes, polyurethanes, polyamides, poly (amino acids), polyethers, polyureas, polycarbonates , polycarbonates and mixtures thereof vary within the range of 0.5 to 99% by weight.
    [16]
    16. Combination, characterized by the fact that it comprises the composition according to claim 8, with one or more polymers being selected from rigid polymers with a module greater than 1,500 Mpa.
    [17]
    17. Combination according to claim 16, characterized by the fact that the content in the rigid polymers varies within the range of 5 to 30% by weight.
    [18]
    18. Combination according to claim 17, characterized in that the rigid polymers form a homogeneously dispersed phase of particles with average dimensions of less than 2 µm.
    [19]
    19. Combination according to claim 18, characterized in that the rigid polymers are polymers or copolymers of poly (lactic acid) containing at least 75% of L-lactic or D-lactic acid or combinations - of the same.
    [20]
    20. Combination, characterized by the fact that it comprises the composition according to claim 8, obtained by a reactive extrusion process with compounds bearing groups that can react with OH and / or COOH groups or with unsaturated bonds.
    [21]
    21. Films, injection molding articles, extrusion coatings, fibers, foams, thermoformed articles, characterized in that they comprise the composition according to any one of claims 1 - 8 or the combinations according to any one of claims 9 - 20.
    [22]
    22. Application of the composition according to any one of claims 1 - 8 or the combinations according to any one of claims 9 - 20, characterized in that it is for the production of: - mono and bioriented films, and films with multiple layers with other polymeric materials; - films for use in the agricultural sector; - films for adherent films for use with foodstuffs, for 'BR bales in agriculture and for wrapping waste; - seed coatings; . - glues; - bags and linings for containers for the collection of organic waste; - thermoformed food packaging, both with “single and multiple layers; - coatings obtained using the extrusion coating method; i - laminates with multiple layers, with layers of paper, plastic, aluminum or metallized films; - expanded or expandable accounts for the production of parts obtained by sintering; - expanded and semi-expanded products, including foam blocks formed using expanded particles;
    - foam sheets, thermoformed foam sheets and containers obtained from them for use in food packaging; - containers for fruits and vegetables; - composites with gelatinized, unstructured and / or complexed starch, natural starch, flours or natural vegetable or inorganic fillers; - fibers, microfibers, composite microfibers, in which the core consists of rigid polymers, such as PLA, PET, PTT, combined composite fibers, fibers with different sections, from circular to multilobulated, fibers: staple, woven and non-woven fabrics or wiring or thermocoupled for application in sanitary and hygiene products, and in the agriculture and clothing sectors.
    º m Summary
    Biodegradable composition comprising polymers of natural origin and aliphatic-aromatic copolyesters.
    The present invention relates to a composition - biodegradable comprising at least one polymer of natural origin and at least one aliphatic-aromatic copolyester obtained from mixtures comprising aliphatic diols, polyfunctional aromatic acids and at least two aliphatic dicarboxylic acids, at least one of which is long-chain.
    Such a composition combines improved biodegradability, excellent mechanical properties, a high level of industrial processability, limited environmental impact, as well as stability of physical properties under the influence of environmental factors.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012010341A2|2020-09-15|biodegradable composition, comprising polymers of natural origin and aliphatic-aromatic copolyesters.
    BR112012010358A2|2020-09-15|mixtures of biodegradable polyesters with at least one polymer of natural origin
    JP6267668B2|2018-01-24|Biodegradable aliphatic-aromatic polyester
    CA2797945C|2018-12-18|Aliphatic-aromatic copolyesters and their mixtures
    BRPI0611457A2|2010-09-14|biodegradable aliphatic-aromatic polyesters
    BR112012010494B1|2019-11-05|biodegradable aliphatic-aromatic polyester, combination comprising polyester, films, injection molding articles, coatings and polyester application
    同族专利:
    公开号 | 公开日
    EP2496631A1|2012-09-12|
    CN102639594A|2012-08-15|
    ES2589386T3|2016-11-14|
    WO2011054896A1|2011-05-12|
    US9156980B2|2015-10-13|
    US20120316257A1|2012-12-13|
    EP3284767B1|2019-06-19|
    IT1399031B1|2013-04-05|
    PL3070111T3|2018-04-30|
    EP3070111B1|2017-10-18|
    EP3070111A1|2016-09-21|
    EP3284767A1|2018-02-21|
    CA2775181C|2018-12-18|
    BR112012010341B1|2021-03-09|
    CA2775181A1|2011-05-12|
    ES2744481T3|2020-02-25|
    EP2496631B1|2016-06-08|
    JP2013510211A|2013-03-21|
    CN102639594B|2014-04-23|
    PL3284767T3|2020-02-28|
    JP5727498B2|2015-06-03|
    ES2655168T3|2018-02-19|
    ITMI20091941A1|2011-05-06|
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    法律状态:
    2020-10-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-10-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2021-01-26| B09A| Decision: intention to grant|
    2021-03-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 09/03/2021, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI2009A001941A|IT1399031B1|2009-11-05|2009-11-05|BIODEGRADABLE ALIPHATIC-AROMATIC COPOLIESTERE|
    ITMI2009A001941|2009-11-05|
    PCT/EP2010/066791|WO2011054896A1|2009-11-05|2010-11-04|Biodegradable composition comprising polymers of natural origin and aliphatic-aromatic copolyesters|
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