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    • 专利摘要:
    Mixtures of biodegradable polyesters with at least one naturally occurring polymer.The present invention relates to mixtures comprising biodegradable polyesters comprising at least one polymer of natural origin and at least two aliphatic-aromatic polyesters of the diacid-diol type, of which at least one with a high content of long chain aliphatic diacids, of origin renewable, exhibiting excellent mechanical properties, sufficiently high melting temperatures, adequate crystallization rates, improved biodegradability properties, as well as stability of physical properties over time.
    公开号:BR112012010358A2
    申请号:R112012010358-0
    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:

    t o | 1 1/27 ”Mixtures of biodegradable polyesters with at least one polymer of natural origin.
    DESCRIPTION The present invention relates to mixtures comprising at least one polymer of natural origin and at least two biodegradable aliphatic-aromatic polyesters of the diacid-diol type, of which at least one with a high content of long-chain aliphatic diacids of renewable origin.
    Polyesters — biodegradable aliphatic-aromatics, obtained from aliphatic diacids, such as adipic acid, aromatic diacids, such as! 10 terephthalic acid, and aliphatic diols, are known in the literature and on the market.
    A limit of these polymers is that monomers, of which they are composed, come mainly from non-renewable sources. This causes them to have an environmental impact regardless of their biodegradability.
    In addition, currently commercially available polyesters of this type have amounts of aromatic acid of less than 48 mol%, since, above this threshold, even the percentage of biodegradation of these polyesters significantly decreases. 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 collecting 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 constitute the humus, Ú which, therefore, represents an important food supplement for plants, given its ability to release the nutritive elements (nitrogen, phosphorus, potassium, etc.),: slowly, but constantly, ensuring the constant fertility of the soil. Industrial composting is, therefore, a process, in which structures are provided for 'rational management of microbiological activities that occur spontaneously in the. nature, in order to reduce the time needed to obtain a type of humus, that is, the compost, and to improve the quality of the final product with respect to the product! 35 - obtained in a natural way.
    Similarly, domestic composting is a process in which organic matter from food scraps from kitchens and gardens is accumulated in compost containers, or holes dug in the soil, and degraded
    > = & rt aerobically under milder conditions than those of industrial composting. Particularly, aerobic biodegradation in domestic composting processes occurs at room temperature, typically between 10 and 45ºC.
    Regarding the aliphatic aromatic polyesters of the S mentioned above, the presence of aromatic monomers, such as terephthalic acid, i in the chain is relevant to obtain aliphatic-aromatic polyesters with temperatures of! sufficiently high melt rates, adequate crystallization rates, relevant mechanical properties, such as final strength, puncture energy and elastic modulus, and excellent industrial processability characteristics. However, the synthetic origin of the monomers limits the possibility that these polyesters significantly reduce the consumption of resources (raw materials) from non-renewable carbon, regardless of their biodegradability.
    On the other hand, a high content of aliphatic monomers of + synthetic origin, such as adipic acid, although it is desirable to achieve an ô * 15 adequate level of biodegradability, not only increases the environmental impact of these r polyesters, but also worsens its mechanical properties. Also, one high content of aliphatic monomers significantly decreases the melting temperature of the polyester and decreases its rate of crystallization at high temperature, thus requiring the use of more refrigeration and longer cooling times during industrial processing of the polyester. These limits have a negative influence on the industrial processability of these polyesters.
    Biodegradable compositions of natural polymers with polyesters are known in the market. Due to their mechanical properties and biodegradability, such compositions are particularly suitable for - applied in the production of films for packaging and bags, particularly for collection: organic waste. It is also 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 and chemical entities. The problem underlying the present invention is, therefore, if: to develop a biodegradable material capable of combining improved biodegradability properties, 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.
    Starting from this problem, it has now been surprisingly found that, by mixing specific quantities of a first biodegradable aromatic aliphatic polyester, obtained from adipic acid, aromatic diacids and diols, a second aliphatic polyester- aromatic with a high content of long chain aliphatic diacids, from a renewable source, and of at least one polymer of natural origin, there is a range of compositions that allows a material with excellent mechanical properties to be obtained, sufficiently high melting temperatures , adequate crystallization rates, biodegradability in composting, as well as stability of physical properties over time.
    In particular, the present invention relates to a mixture comprising: (A) at least a first biodegradable aliphatic-aromatic polyester (A) of the diacid-diol type, obtainable by a mixture comprising: a) at least one acid component having the following composition: a) 51 95% by mol of aliphatic dicarboxylic acids, composed of at least 50%, preferably 60% and, more preferably 75, 70% by mol of long-chain diacids of renewable origin; 'a 2) 5- 49 mol% of polyfunctional aromatic acids; b) at least one diol; (B) At least a second biodegradable aromatic aliphatic polyester! (B), obtainable from a mixture comprising adipic acid, terephthalic acid and at least one aliphatic diol; (C) at least one polymer of natural origin (C); the concentration of (A) varies, with respect to (A + B), in the range between 5 and 95%, preferably between 20 and 70%, and more preferably between 30 and 60% by weight, being —Which (C) is present in an amount lower than 50%, preferably more than 1 lower than 45%, more preferably lower than 40% by weight, with respect to (A + B + C) , the mixture having a Melting Mass Flow Index '(EMI) of 1.5 - 109/10 min, preferably 2 - 7 g / 10 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 | 'in relation to its Melting Mass Flow Index (MFI). In the meaning of the present invention, “high stability” | of MFI means that, after 6 months under normal storage conditions (ie 23ºC, 55% RH), the MFI of the mixture is less than 12 g / 10 min, preferably | less than 10 9/10 min, more preferably less than 7 g / 10 min.
    pN i 4/27 | . | In the meaning of the present invention, products obtained from | from sources that, due to their intrinsic characteristics, are naturally regenerated or are not exhaustible in the time scale of human life and, by extension, whose use Í: does not compromise natural resources for future generations, are considered as - being of renewable source.
    The use of products from renewable sources also contributes | to decrease CO in the atmosphere and to decrease the use of non-renewable resources.
    A typical example of renewable sources is vegetable crops.
    Long chain diacids in the present invention are intended to be dicarboxylic acids with more than 6 carbon atoms in the main chain.
    Such long chain acids are preferably selected from the group consisting of aliphatic dicarboxylic acids with a number of carbon atoms in the main chain between 7 and 22, esters and mixtures thereof, submeric acid, azelaic acid, sebacic acid, dodecanedioic, brassylic acid, octadecanedioic, their esters and mixtures thereof, being particularly preferred * 15.
    In polyester (A), polyfunctional aromatic acids are intended to be aromatic dicarboxylic compounds, of the phthalic acid type, and aromatic heterocyclic dicarboxylic compounds of renewable origin, mixtures and esters thereof.
    Particularly preferred are terephthalic acid and its esters and 2,5-furan-dicarboxylic acid and its esters, and mixtures thereof.
    The content of polyfunctional aromatic acids in polyester (A) is between 5 and 49%, preferably between 30 and 48.5%, and more preferably between 40 and 48% by mol, with respect to the total mole content of the acids dicarboxylics.
    Examples of diols in the polyester (A) 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-decane-diol, 1,11-undecane-diol,: 1 , 12-dodecan-diol, 1,13-tridecan-diol, 1,4-cyclohexane-dimethanol, propylene glycol, neopentyl-glycol, 2-methyl-1,3-propane-diol, dianhydro-sorbitol, dianhydro- mannitol, dianhydro-iditol, cyclohexane-diol, cyclohexane-methane-diol, and mixtures thereof.
    Among these, 1,4-butane-diol, 1,3-propane-diol, 1,2-ethane-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.
    The polyester (A) may contain, in addition to the basic monomers 1, at least one hydroxy acid in an amount between O - 49%, | preferably between 0 - 30 mol%, with respect to the moles of the aliphatic dicarboxylic acid.
    Examples of suitable hydroxy acids are glycolic acid, hydroxy-butyric acid, | i 1
    Rom ia ga "ee sc [" 22225 22296]. â € “iiuui Ú 527: hydroxy-capranoic acid, hydroxy-valeric acid, 7-hydroxy-heptanoic acid, 8-hydroxy-capranoic 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 distribution of repetitive units or at random or in blocks.
    Long bifunctional molecules also with function, not in a 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 polyester (A), one or more polyfunctional molecules can be advantageously added, in amounts between 0.01 and 3 mol%, with respect to the amount of acids - dicarboxylic (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 glutaric, hydroxy-isophthalic acid, esantriol, sorbitol, trimethyl-ethane, mannitol, 1,2,4-butanotriol, xylitol, 1,2,4,4-tetrakis (hydroxy-methyl) cyclohexane, arabitol, adonitol, iditol.
    The molecular weight M, of the polyester (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.
    Polyester (A) has an inherent viscosity (measured with an Ubbelhode viscometer for CHCI solutions; with concentrations of 0.2 g / dL —à25ºC) greater than 0.5 dL / g, preferably greater than 0, 6 dL / g, even more preferably, greater than 0.7 dL / g.
    The polyester production process (A) can take place according to any of the processes known in the art. In particular,
    ] 6127 the polyester can be advantageously obtained with a polycondensation reaction. Advantageously, the polymerization process of! polyester can be carried out in the presence of a suitable catalyst. Among the 'suitable catalysts, mention may be made, for example, of tin-organo-metallic compounds, for example, those derived from stanoic acid, titanium compounds, such as ortho-butyl titanate, aluminum compounds, such as such as Al-I tri-isopropyl, and antimony compounds and zinc compounds. | Preferably, polyester (A) is obtainable by reacting at least one precursor polyester PP, having at least one acid component of the type mentioned above and at least one diol component of the type mentioned above, with compounds bearing groups that may 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. = 15 Such at least one precursor polyester PP can be of the aliphatic, aromatic or aliphatic-aromatic type. "The person skilled in the art will easily be able to identify the actual molar ratios required with respect to the nature of the precursor polyester PP in order to obtain the desired polyester (A). Preferably, the polyester (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 , lauroyl peroxide, isononanoyl peroxide, di (t- - butyl-peroxy-isopropyl) -benzene, t-butyl peroxide, dicumyl peroxide, alpha, alpha'-di (t-butyl-peroxy) -di-isopropyl -benzene, 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hexane, t- "butyl and cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5 -di (t-butyl-peroxy) -hex-3-ino, peroxy-dicarbonate of di (4-t-butyl-cyclohexyl), peroxy-dicarbonate of dicetyl, peroxy-dicarbonate ode dimiristila, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, peroxydicarbonate of di (2-ethylhexyl) 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 from | advantageously, are all polyepoxides from epoxidized oils and / or from styrene - glycidyl ether - methyl methacrylate, such as products distributed by BASF Resins B.V., under the trademark Joncryl & ADR, glycidyl ether methacrylate ether Í
    = 727 methyl 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: diglicidyl ether of diethylene glycol, diglycidyl poly (ethylene glycol!), glyceryl poly (glycidyl ether), —diglycerol poly (glycidyl ether), 1,2-epoxy-butane, polyglycerol poly (glycidyl ether), isoprene diepoxide , and cycloaliphatic diepoxide, diglycidyl ether of 1,4-cyclohexane-dimethanol, glycidyl 2-methyl-phenyl-ether, triglycidyl ether of glycerol propoxylate, diglycidyl ether of 1,4-butane-diol, poly (glycidyl ether) of sorbitol, diglycidyl ether of glycerol, tetraglycidyl ether of meta-xylene diamine and diglycidyl ether of bisphenol A, 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, * 15 fatty acid salts can be used. Calcium and zinc stearates are particularly preferred.
    'Examples of carbodiimides, which can be used advantageously, are selected from the group comprising: poly (carbodiimide cyclooctylene), = poly (1,4-dimethylene - cyclohexylene - carbodiimide) , - poly (cyclohexylene carbodiimide, polyethylene 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-triisopropyl-1,3-phenylene carbodiimide) (Stabaxolº P-100), poly (1,3,5-triisopropyl-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), polyimphenylene carbodiimide), poly (3,3'-dimethyl-4,4'-diphenyl - carbodiimide methane), poly naphthlene carbodiimide), polyphisophorone carbodiimide), polycycene 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 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. And Particularly - preferred are polyester PP - precursors with terminal unsaturation. Among unsaturated chain terminators, those with the formula are preferred: T- (CH2) .- CH = CH, in which "T" is a group capable of reacting with carboxylic and / or hydroxy groups and "No. is an integer comprised 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 groups, with 7 particularly being hydroxyl 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, omega-undecenoic acid, omega-undecylenic alcohol and mixtures thereof being particularly preferred, in order to maximize compatibility with at least one naturally occurring polymer.
    Also after the preparation process, the biodegradable polyester (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 that derive from their reaction with free radical initiators can be 'determined by different methods well known to those skilled in the art, such as NMR spectroscopy or by methanolysis reactions. of the chain of Í, polymer coupled with chromatographic methods combined with spectroscopy of | pasta. The person skilled in the art will readily be able to identify referable structures or their unsaturation or the reacted facility after the reaction. Preferably, the biodegradable polyester (A) is obtainable through a reactive extrusion process starting from a precursor polyester PP having a content in terminal acid groups in amounts of 35 - 150 meq KOH / Kg of the precursor polyester.
    The measurement of the terminal acid groups can be carried out 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 indicator suitable for determining the equivalence point of the titration, 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) = - [4 = Y7,) - T) 1000 | P | where: Í 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 blank titration; . T = concentration in moles / L of the KOH / ethanol solution; P = g of sample.
    Among the biodegradable aliphatic-aromatic polyesters (B), polyesters with a melting point between 50 and 170 ° C are preferred, preferably between 55 and 130 ° C, and more preferably between 60 and 110 ° C.
    With respect to the acid component of the biodegradable aliphatic-aromatic polyesters (B), it preferably comprises 5 - 65% in | mol, preferably 15 -60%, even more preferably 46 - 55% terephthalic acid or derivatives thereof. . 25 Sulfonate compounds can be comprised between 0 and 5 mol%, considering the sum of the percentages of the different components of 100%. Such sulfonate compounds are preferably selected from the group consisting of alkali metal or alkaline earth metal salt of a dicarboxylic acid containing sulfonate groups, or their ester-forming derivatives, more preferably, alkali metal salts of the S5-sulfo-isophthalic acid or mixed with them, particularly preferably the sodium salt.
    The presence of corresponding isocyanates or compounds is also possible, containing two, three or four functional groups capable of reacting with terminal groups of the aliphatic-aromatic polyesters, or mixtures - corresponding isocyanatosis compounds.
    Among these, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, 4.4 "diisocyanate - and 2,4'-diphenylmethane, 1,5-diisocyanate naphthylene, xylylene diisocyanate, hexamethylene diisocyanate, di-
    | i 10/27; . Isophorone isocyanate and methylenebis (4-isocyanate-cyclohexane) are preferred.
    Preferably, such polyesters (B) comprise at least one diol selected from the group consisting of C, 2-C; s-alkene-diols and Cs-Cao-cycloalkane-diols and mixtures thereof. Among these, 1,4-butane-diol, 1,3-propane-diol, 1,2-ethane-diol and mixtures thereof are particularly preferred. Advantageously, such diols consist of at least 50%, preferably at least 80 mole%, of 1,4-butane-diol with respect to the total diol content.
    With respect to aliphatic-aromatic polyesters (B), the teaching of document 96/15173 has to be understood as incorporated in this specification. Preferably, aliphatic-aromatic polyesters (B) may contain 0.01 - 5 mol%, based on the total content of the repetitive units, of a polyfunctional compound.
    Such a polyfunctional compound is preferably selected from the group consisting of glycerol, pentatritol, trimethylol-propane, citric acid, 7 "15 dipentaerythritol, monoanhydro-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, music acid, tri acid -hydroxy-glutaric, hydroxy-isophthalic acid, esantriol, sorbitol, trimethyl-ethane, mannitol, 1,2,4-butanotriol, xylitol, 1,2,4,4-tetrakis (hydroxy-methyl) cyclohexane, arabitol , adonitol, iditol.
    The polyester (B) may contain, in addition to the basic monomers, at least one hydroxy acid in an amount between O - 49%, preferably between O - 30% by mol with respect to the moles of aliphatic dicarboxylic acid. Examples of suitable hydroxy acids are glycolic acid, hydroxy-butyric acid, hydroxy-ccaproic acid, hydroxy-valeric acid, 7-hydroxy-heptanoic, 8-hydroxy-capranoic, "* acid, 9-hydroxy-nonanoic, 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 distribution of repetitive units either randomly or in The at least one polymer of natural origin (C) is advantageously selected from starch, cellulose, chitin, chitosan: alginates, proteins, such as gluten, zein, casein, collagen, gelatin, natural rubbers , rosinic acid and its 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 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.
    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 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 the blocks. 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 portion of the sample, 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 coater".
    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 particle size (d) is calculated according to the following formula:
    d =. d, -d, where d is the smallest diameter and d, is the largest diameter of the ellipse, in which the particle can be inscribed or approximated.
    The selective pickling of the dispersed starch phase can be advantageously carried out with HCI 5 N as pickling, with a pickling time of 20 minutes, at a pickling 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.
    The use of corn and potato starch is particularly preferred.
    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 optical microscope in polarized light and any “phantoms” 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 a high resistance to tearing even in a low humidity condition. : 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 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, poly (ethylene 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 dimensions of the dispersed particles. Compatibilizers can also be added to the mix. They can belong to the following classes: - Additives, such as esters that have hydrophilic / lipophilic balance index (EHL) values greater than 8, and which are obtained from polyols and from mono- or polycarboxylic acids with constants pK dissociation levels 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 of refers to the pK of the first carboxyl group in the case of polycarboxylic acids); - Esters with EHL values lower than 5.5, obtained from polyols and from fatty acids with 12 - 22 carbon atoms; These —compatibilities can be used in amounts of 0.2 to 40% by weight and, preferably, from 1 to 20% by weight, with respect to starch. Starch combinations may also contain polymeric-compatible 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 function as 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. Aliphatic-aromatic polymers with extended chains can also be used, with diisocyanates or di- and poliepoxides or isocyanurates or with oxazolines, aliphatic or aromatics, with intrinsic viscosities higher than 1 dL / g or, in any case, aliphatic polyesters -articles 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.
    The mixtures according to the present invention exhibit good properties also in the case of starch combinations, in which the starch is not strongly complexed. With regard to the starch complexation, it must be intended that the teachings contained in document EP-O 965 615 are incorporated into this specification. 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 2 theta scale. According to the present invention, with the compositions of the statement, in which the starch - is not strongly complexed, the compositions are intended, in which the HH 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 mixtures according to the invention contain at least one plasticizer for the starch to provide suitable rheological properties. This plasticizer can be simply water (even the water 'contained in the native starch alone without the need for further additions), or. high boiling points or polymeric plasticizers of the type mentioned above. | Mixtures of different plasticizers are also preferred.
    The amount of plasticizer is, in general, chosen based on the rheological requirements 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.
    In the meaning of the present invention, plasticizers with high boiling points are understood to be plasticizers with boiling points higher than 250 ° C. Among these, those described in WO 92/14782, glycerol, diglycerol, triglycer | and tetraglycer | and mixtures thereof.
    Mixtures of high boiling point plasticizers containing at least 75% by weight, preferably 90% by weight of diglycerol, triglycerides are also particularly preferred. and tetraglycerol. Such mixtures contain | more than 50% by weight, preferably more than 80% by weight of diglycerol with | regarding the total weight of diglycerol, triglycerol and tetraglycerol. The use of this type of high boiling point plasticizers is particularly preferred, as they | they avoid problems with fumes in processing environments and there are no frequent interruptions that are necessary to clean the machines during the processing of the composition.
    In the meaning of this specification, with the word “diglycerol”, here are understood all compounds that are derived from condensation reactions of two glycerol molecules, such as alpha-alpha'-diglycerol, alpha-beta-diglycerol, beta -beta'-diglycerol, its 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.
    Mixtures according to the present invention are also preferred, containing water as the only plasticizer. Among these, mixtures containing the water present in the native starch as the only plasticizer are particularly preferred.
    The mixtures according to the invention can be used, in combinations, which can also be obtained by reactive extrusion processes, with one or more polymers, which may or may not be biodegradable.
    In particular, the mixtures according to the invention can be combined with biodegradable polyesters of the type diacid-diol, hydroxy-acid] or polyester-ether. Preferably, biodegradable polyesters are biodegradable polymers according to the EN 13432 standard.
    As far as biodegradable polyesters are concerned — diptycodiacid-diol, these can be either aliphatic or aliphatic-aromatics.
    Biodegradable aliphatic polyesters from diacid-diols comprise aliphatic diacids and aliphatic diols, while biodegradable aliphatic-aromatic polyesters have an aromatic part comprising mainly polyfunctional aromatic acids, the aliphatic part consisting of aliphatic diacids and aliphatic diols. The aromatic aliphatic biodegradable polyesters from diacids-diols are preferably characterized by an aromatic acid content of between 30 and 590 mol%, preferably between 45 and 70% mol, with respect to the acid component.
    Preferably, the polyfunctional aromatic acids can advantageously be aromatic dicarboxylic compounds of the phthalic acid type and their esters, preferably terephthalic acid.
    Polyfunctional aromatic acids can also be selected from the group comprising heterocyclic dicarboxylic aromatic acids, 2,5-furan-dicarboxylic acid and its esters being preferred.
    Aliphatic-aromatic polyesters biodegradable from diacids-diols, in which the aromatic diacid component comprises a mixture | of aromatic dicarboxylic compounds of the type phthalic acid and aromatic acids | heterocyclic dicarboxylics 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, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanoic and brass , its esters and mixtures. Among these, adipic acid and dicarboxylic acids from renewable sources are preferred, and among these, dicarboxylic acids from renewable sources, such as —succinic acid, sebacic acid, azelaic acid, undecanedioic, dodecanedioic acid and acid, are particularly preferred. "brassyl and mixtures thereof. Examples of aliphatic diols, in biodegradable polyesters" 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- —nano-diol, 1,10 -decane-diol, 1,11-undecane-diol, 1,12-dodecan-diol, 1,13-tridecane-diol, 1,4-cyclohexane-dimethanol, neopentylglycol, 2-methyl-1,3-propane -diol, dianhydro- 'sorbitol, diahydro-mannitol, dianhydro-iditol, cyclohexane-diol, cyclohexane-methane-dioles. mixtures, of which 1,4-butane-diol, 1,3-propane-diol and 1,2-ethane-diol and mixtures thereof are particularly preferred.
    Among the biodegradable polyesters of the diacid-diol type, aliphatic / aromatic copolyesters are particularly preferred, such as, for example, poly (butylene terephthalate-co-sebacate), poly (butylene terephthalate-co-azelate), poly (terephthalate- butylene co-brassylate), poly (butylene terephthalate-co-adipate),
    poly (butylene terephthalate-co-succinate) and poly (butylene terephthalate-co-glutarate), and aliphatic polyesters, such as, for example, poly (alkylene succinates) and, particularly, poly (butylene succinate) and their compounds copolymers with adipic acid and lactic acid.
    Preferably, the combinations of the mixtures according to the invention, with biodegradable polyesters, from the diacids-diols described above, are characterized by a content in the biodegradable polyesters from diacids-diols, 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 mixtures 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-DL-lactic acid esterocomplex, poly-and-caprolactone, poly-hydroxy-butyrate, poly-hydroxy-butyrate -valerate, polyhydroxy-butyrate-propanoate, polyhydroxy-butyrate-hexanoate, polyhydroxy-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 mixtures according to the invention, with the biodegradable polyesters, from the hydroxy acids described above, are characterized by a content in the biodegradable polyesters from hydroxy acids, 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 mixtures according to the invention and the first, respectively. The mixtures according to the invention can also be combined with polyolefins, non-polyesters biodegradable, polyester- and polyether- 7 urethanes, —polyurethanes, polyamides, polylamino acids), polyethers, polyureas, polycarbonates and mixtures thereof.
    Among the polyolefins, polyethylene, polypropylene, their copolymers, poly (vinyl alcohol), polyvinyl acetate), polyacetate: ethyl vinyl) and polyethylene - vinyl alcohol are preferred. Among the non-biodegradable polyesters, are preferred: PET, PBT, PTT, in particular with a renewable content> 30%, and poly (furan-alkylene dicarboxylates). 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 and 9.9, 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), polit (propylene carbonates), butyl polycarbonates) 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 blends according to the invention with the polymers described above (polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, polyurethanes, polyamides, polyamino acids), polyethers, polyureas, polycarbonates and mixtures thereof) 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 mixtures of - according to the invention and the former, respectively .
    The mixtures 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 accordingly - with the measurement method described above for starch particles.
    'Among rigid polymers, poly (hydroxy alkanoates), such as poly (lactic acid) and glycolic polyacid) are particularly preferred, and, more preferably, polymer or copolymers of poly (lactic acid) containing at least 75% acid L-lactic 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 5 minutes, at a pickling temperature of 25ºC.
    Combinations of the mixtures according to the present invention, with one or more polymers of the type mentioned above, are particularly suitable for the production of films. Advantageously, the films obtained with such combinations exhibit excellent mechanical properties, as well as high thermal resistance.
    Combinations of the mixtures according to the present invention with PLA are of particular interest because of their high compatibility with PLA polymers and copolymers allows to cover materials with a wide range of rigidity - which makes these combinations particularly suitable for injection molding and extrusion.
    To improve the transparency of the strength of such combinations and to decrease or avoid a lamellar structure of polylactic polymers, it is possible to introduce other polymers as compatibilizers or resistance-promoting agents, such as: poly (butylene succinate) and copolymers with adipic acid and / or lactic acid and / or hydroxy-caprylic acid, polycaprolactone, aliphatic polymers of C, 2 to C13 diols and C, C13, polyhydroxy-alkanoates), poly (vinyl alcohol) in the degree range hydrolysis between 75 and 99% and its copolymers, poly (vinyl acetate) in a range of hydrolysis degree between 0 and 70%, preferably between 0 and 60%. Particularly preferred are diols, ethylene glycol, propane-diol, butane-diol, and, as acids: azelaic acid, sebacic acid, undecanedioic, dodecanedioic, brassic acid and combinations thereof.
    In order to maximize the compatibility between the mixtures of the invention and the poly (lactic acid), it is very useful to introduce copolymers with blocks showing affinity for the aliphatic-aromatic copolyesters of the invention, and blocks with affinity for the polymers or lactic acid copolymers. Particularly preferred examples are block copolymers of aliphatic-aromatic copolyesters with poly (lactic acid). Such block copolymers can be obtained by taking the two original polymers terminated with hydroxyl groups and then reacting such polymers with chain extenders, capable of reacting with hydroxyl groups, such as diisocyanates. Examples are 1,6-hexamethylene diisocyanate, isophorone diisocyanate, methylene diphenyl diisocyanate, toluene diisocyanate or the like. It is also possible to use chain extenders capable of reacting with carboxylic groups, such as di- and poliepoxide divinyl derivatives (eg, diglycidyl ethers of bisphenols, —diglycidyl ethers of glycerol), if the polymers of the combination are terminated with groups of acid, It is also possible to use carbodiimides, bis-oxazolines, isocyanurates, etc., as chain extenders. . The intrinsic viscosity of such block copolymers can be between 0.3 and 1.5 dL / g, more preferably between 0.45 and 1.2 dL / g. The amount of compatibiizer in the combination of aliphatic-aromatic and poly (lactic acid) copolyesters can be in the range between 0.5 and 50%, more preferably between 1 and 30%, more preferably between 2 and 20% by weight.
    The mixtures according to the present invention can be advantageously combined with nucleating agents and fillers, both organic and inorganic in nature. | Examples of nucleating agents include talc, sodium saccharin salt, calcium silicate, sodium benzoate, calcium titanate, boron nitride, 1 zinc salts, porphyrin, chlorine, florin, porphodimetine, porphomethamine, bacterioclorin, | isobacteriochlorine, porphyrinogen, forbine, isotactic polypropylene, low molecular weight PLA and PBT.
    The preferred amount of fillers is in the range of 0.5 - 70% by weight, preferably 5 - 50% by weight. | With regard to organic fillers, wood powder, proteins, cellulose powder, grape residues, bran, corn husks, compost, other natural fibers, cereal cracks with or without plasticizers, such as polyols, may be mentioned.
    With regard to inorganic fillers, substances that are capable of being dispersed and / or reduced to slides with submicron dimensions, preferably less than 500 nm, more preferably less than 300 nm, may be mentioned, and, even more preferably, of less than | than 50 nm.
    Particularly preferred are zeolites and silicates of various types, such as! wolastonites, montmorillonites, hydrotalcites, also functionalized with molecules! capable of interacting with starch and / or the specific polyester.
    The use of such charges Í can improve stiffness, permeability to water and gases, dimensional stability and | maintain transparency. | The mixtures according to the invention can be | prepared by means of an extruder or any other machine capable of supplying | - temperature and shear conditions, allowing a homogeneous mixture of! 7 components. | The mixtures according to the present invention are: advantageously obtainable by reactive extrusion process with compounds containing groups that can react with OH and / or COOH groups, such as, for example, —polypoxides and polycarbodiimides or with unsaturated bonds, such as, for example, peroxides. In a preferred embodiment, the first polyester (A) and the: second polyester (B) can also be present in the mixtures according to the present invention in the form of a block copolymer.
    Such a block copolymer is advantageously obtained | by reaction of the first polyester (A) with the second polyester (B), by means of! above compounds bearing groups that can react with OH and / or COOH groups or with unsaturated bonds.
    Such block copolymer can be prepared in a separate step or can be prepared in situ, during the reactive extrusion process.
    Examples of peroxides, which can be used advantageously, are selected from the group of dialkyl peroxides, such as: benzoyl peroxide, lauroyl 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, t-butyl peroxide and 'cumila, di-t-butylay peroxide 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hex-3-yn, peroxide; di (4-t-butyl-cyclohexyl) dicarbonate, dicetyl peroxy-dicarbonate, peroxy-1 10 —dimyristyl dicarbonate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane , peroxi- | di (2-ethylhexyl) dicarbonate and mixtures thereof.
    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 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 in: diglycidyl ether of diethylene glycol, diglycidyl ether of poly (ethylene glycol!), poly (glycidyl ether) of glycerol, poly (glycidyl ether) of diglycerol, 1,2-epoxy-butane, poly (glycidyl ether) of polyglycerol, isoprene diepoxide, and cycloaliphatic diepoxide, 1,4-cyclohexane-dimethanol diglycidyl ether, glyceryl-2-methyl-phenyl-ether, glycerol-propoxylate-triglycidyl, 1,4-butane-diol-diglycidyl ether, poly ( glycidyl ether) of sorbitol, diglycidyl ether of glycerol, tetraglycidyl ether of meta-xylene-diamine and diglycidyl ether of bisphenol A, and mixtures thereof.
    Preferably, such polyepoxides are added to the 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 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 advantageously, are selected from the group comprising: poly (carbodiimide cyclooctylene), poly (1,4-dimethylene - cyclohexylene - carbodiimide), - poly (cyclohexylene carbodiimide, poly (ethylene 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-triisopropyl-1,3-phenylene carbodiimide) (Stabaxolº P-100), poly (1,3,5-tricisopropyl-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), polyimphenylene carbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethane carbodi -imide), poly (naft lene carbodiimide), polyphisophorone carbodiimide), polycycene carbodiimide), p-phenylene bis (ethyl-carbodiimide), 1,6-hexamethylene bis (ethyl-carbobodiimide), 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 mixtures, several additives can also be incorporated, such as antioxidants, UV stabilizers, heat and hydrolysis stabilizers, chain extenders, flame retardants, slow release agents, inorganic and organic fillers, such such as natural fibers, antistatic agents, wetting agents, dyes, lubricants or agents! 20 compatibility between the various phases.
    The mixtures according to the invention are biodegradable in industrial composting! according to the EN 13432 standard. In the mixture according to the present invention, a! concentration of at least first aliphatic-aromatic biodegradable polyester (A) | 25 varies with respect to (A + B), in the range between 5 and 95%, preferably between 20 and 70%: by weight.
    In a particularly preferred embodiment of the invention, "the concentration of the at least first aliphatic-aromatic biodegradable polyester (A) varies between 30 and 60% by weight, with respect to the total weight of the polyesters (A) and (B). surprisingly, it was found that, in this range, mixtures according to the present invention are liable to domestic composting in accordance with Italian Standard UNI 11355: 2010. Preferably, mixtures according to the present invention exhibit a puncture energy, measured in films having thicknesses of 10-50 µm, greater than 7 J / mm, more preferably, more than 9 J / mm, and, more preferably, more than 12 J / mm.
    Preferably, the mixtures according to the present invention exhibit a higher melting temperature (T,) than the T, of the biodegradable aromatic aliphatic-polyester (A).
    With respect to the melting temperature (Tr), it is advantageously determined by means of differential scanning calorimetry (CVD), with a Perkin Elmer Diamond differential scanning calorimeter operating with the following thermal profile: - 30 seconds of thermal equilibration at -20ºC; - first sweep from -20 to 200ºC at 20ºC / min; - 30 seconds of thermal equilibration at 200ºC; - second sweep from 200 to -20ºC at 10ºC / min; - 30 seconds of thermal equilibration at -20ºC; - third sweep from -20 to 200ºC at 20ºC / min; - 30 seconds of thermal equilibration at 200ºC; Tn is measured as the maximum of the endothermic peak during the third scan.
    Regarding the measurement of puncture energy, it is performed according to the ASTM D5748-95 standard (2001), using a triangular pyramid-shaped probe (edges = 35 mm; vertex angles = 90º) at a speed of 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 punching energy of 9.2 J / mm, while an LDPE film, with a thickness of 40 µm, exhibits an energy punch of 10 J / mm.
    The mixtures according to the invention, have properties and viscosity values, which make them suitable for use, appropriately modulating the relative molecular weight, for numerous practical applications, such as films, injection molding articles, extrusion coatings, fibers, foams, thermoformed articles, etc., with specific attention to applications, in which compostability or domestic biodegradation in non-aggressive environments is desirable.
    In particular, such mixtures and combinations thereof are therefore 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;
    - seed coatings; - glues, such as hot melt adhesives; - bags and linings for containers for the collection of organic waste, such as the collection of scrap and garden waste; S - 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; - 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 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 wrapper is 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 or spun-bonded or thermally bonded textile materials for use in sanitary and hygiene products, and in the agriculture and clothing sectors.
    ] They can also be used in applications instead of plasticized PVC.
    The invention is now illustrated by describing various modalities, which will be intended as non-limiting examples of the inventive concept protected by the present patent.
    Example 1 '40 parts by weight of a poly (butylene sebaceous butylene terephthalate) with 47 mol% of butylene terephthalate units and TEM at: 2.16 Kg, 190ºC, 6 g / 10 min and Tr = 116ºC, were combined with 40 parts of butylene polyladipate-butylene co-terephthalate) with 53 mol% of butylene terephthalate units and TEM at 2.16 kg, 190ºC, 2 g / 10 min and Tr = 132ºC, 16 parts of starch, 2 parts of water, 2 parts of glycerol and 0.5 part of a copolymer of styrene - glycidyl ether - methyl methacrylate. 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 0.8%.
    The granules exhibited an EMI of 3.5 g / 10 min (determined - according to ASTM at 160ºC and 5 Kg, according to the ASTM 1238-89 standard) and Tr = 132ºC.
    The granules were filmed in a 40 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 (traction at 23ºC and 55% relative humidity and V = 50 mm / min), and according to the ASTM D5748-95 standard (triangular pyramid-shaped probe with edges = 35 mm and apex angles = 90º; crosshead speed of 500 mm / min, temperature of 23ºC, relative humidity of 55%, film specimen diameter of 125 mm).
    Example 2 43 parts by weight of a poly (butylene sebaceous butylene terephthalate) with 47 mol% of butylene terephthalate units and TEM at 2.16 kg, 190ºC, 6 g / 10 min and Tr = 116ºC, were combined with 30 parts of —butylene butyl polytadipate (butylene co-terephthalate) with 53 mol% of butylene terephthalate units and TEM at 2.16 kg, 190ºC, 2 g / 10 min and Tr = 132ºC , 7 parts by weight of poly-L-lactic polymer showing an M, of 130,000, TEM at 2.16 kg, 190ºC, of 3.5 g / 10 min, a lactic residue of less than 0.2% and a D content of about 6%, 16 parts of starch, 2 parts of water, 2 parts of glycerol and 0.5 part of a - styrene polymer - glycidyl ether - methyl methacrylate. 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%. ; The granules exhibited an EMI of 4.2 g / 10 min (determined - according to the ASTM 1238-89 standard) and T ,, = 126ºC. The granules were filmed in a 40 '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 (traction at 23ºC and 55% relative humidity and V, = 50 mm / min), and according to the ASTM D5748 standard -95 (triangular pyramid-shaped probe with edges = 35 mm and apex angles = 90º; crosshead speed of 500 mm / min, temperature of 23ºC, relative humidity of 55%,
    diameter of 125 mm film specimen). The results are shown in Table 1, below.
    TABLE 1. MECHANICAL PROPERTIES Oh Ep E Energy of (Mpa) (%) (Mpa) | En punch, (JImm) [1 | are | 40 | 20 | 15 | - Determination of size of starch particles The granules of the mixtures according to Examples 1 and 2, were immersed in liquid nitrogen and subsequently fractured, in order to obtain a fracture surface along the cross section of samples of cross section.
    A portion of such samples was then subjected to pickling with 5 N HCl (25ºC, 20 minutes), dried and a thin layer of a gold / palladium mixture was deposited on them by means of a "hot coater". 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.
    At the 15th average size of the starch particles it was calculated as the numerical (or arithmetic) average of the particle dimensions.
    The results are shown in Table 2, below. ; TABLE 2. DIMENSION OF STARCH PARTICLES | Example | Average particle size of dispersed starch (um) - | 'a ag | Biodegradation test Biodegradation tests, as well as domestic compostability tests, were carried out, respectively, according to the 'EN 13432 standard and the Italian Standard UNI 11355: 2010 on film samples obtained from BR from the mixtures of Examples 1 and two.
    s 27/27 The results are shown in Table 3 below.
    TABLE 3. BIODEGRADATION TESTS EN 13432 UNI 11355: 2010 150 days degradation 1> 90% According to> 90 UNI 11183 time 90 days disintegration 2> 90% According to> 90 UNI time 11183 110 day time disintegration - Example of Comparison1 As a reference test, 80 parts by weight of a poly (butylene adipate-butylene co-terephthalate) with 53 mol% of butylene terephthalate units and TEM at 2.16 Kg, 190ºC, 2 g / 10 min, were combined with 16 parts of starch, 2 parts of water, 2 parts of glycerol and 0.5 part of a copolymer of styrene - glycidyl ether - methyl methacrylate.
    The extrusion conditions were the same as in Example 1. The final water content of the granules was 0.8%. The granules were filmed in a 40 mm Ghioldi machine, mold interval = 1 mm, flow rate of 20 Kg / h, to obtain a 15º film with a thickness of 20 µm. "The 20 µm film was then subjected to the biodegradation tests reported above.
    The film obtained was not compostable: domestic according to the Italian Standard UNI 11355: 2010, but not even biodegradable according to the standard EN 13432 for industrial composting.
    权利要求:
    Claims (27)
    [1]
    1. Mixture, characterized by the fact that it comprises: (A) at least one first biodegradable aliphatic-aromatic polyester (A) of the diacid-diol type, obtainable by a mixture comprising: - a) at least one acid component having the following composition : a1) 51- 95 mol% of aliphatic dicarboxylic acids, composed of at least 50 mol% of long-chain diacids of renewable origin; a2) 5-49 mol% of polyfunctional aromatic acids; b) at least one diol; (B) at least a second biodegradable aromatic aliphatic polyester (B), obtainable from a mixture comprising adipic acid, terephthalic acid and at least one aliphatic diol; (C) at least one polymer of natural origin (C); the concentration of (A) varies, with respect to (A + B), in the range between 5 and 95% by weight, with (C) being present in an amount lower than 50% by weight, with respect a (A + B + C), the mixture showing a Melting Mass Flow Index of 1.5 - 109/10 min.
    [2]
    2. Mixture, according to claim 1, characterized by the fact that it is biodegradable in industrial composting according to the EN standard
    13432.
    [3]
    3. Mixture, according to claim 1, characterized by the fact that the concentration of at least the first biodegradable aliphatic-aromatic polyester (A) varies, with respect to (A + B), in the range between 30 and 60% in Weight. 1
    [4]
    4. Mixture, according to claim 3, characterized by the fact that it can be composted in accordance with Italian Standard 'UNI 11355: 2010.
    [5]
    5. Mixture, according to claim 1, characterized by the fact that the long chain diacids, of at least the first biodegradable aromatic aliphatic polyester (A), are selected from the group consisting of 'aliphatic dicarboxylic diacids, with number of carbon atoms in the main chain between 7 and 22, and mixtures thereof. 6. Mixture according to claim 1, characterized - by the fact that the polyfunctional aromatic acids, of the at least first aliphatic-aromatic biodegradable polyester (A), are dicarboxylic aromatic compounds of the phthalic acid type, and heterocyclic aromatic dicarboxylic compounds of renewable origin, mixtures and esters thereof.
    [6]
    : 2/4
    [7]
    7. Mixture, according to claim 1, characterized by the fact that the at least second biodegradable aromatic aliphatic polyester (B) has a melting point between 50 and 170ºC.
    [8]
    8. Mixture according to claim 1, characterized by the fact that the acid component, of at least second biodegradable aromatic aliphatic polyester (B), comprises from 5 - 65 mol% of terephthalic acid or its derivatives.
    [9]
    9. Mixture, according to claim 1, characterized by the fact that the diol component, of at least second aliphatic-aromatic biodegradable polyester (B), is selected from the group consisting of C7-Cs-alkane diols and Cs-C ,, - cycloalkane diols and mixtures thereof.
    [10]
    10. Mixture, according to claim 1, 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, 15º collagen, gelatin, natural rubbers, rosinic acid and its derivatives, lignins and their | derivatives.
    [11]
    11. Mixture according to claim 10, characterized by the fact that the starch is in an unstructured or gelatinized form or | in the form of cargo.
    [12]
    Mixture according to any one of claims 10 - 11, characterized in that the starch represents a homogeneously dispersed phase of particles with average dimensions of less than 1 µm.
    [13]
    13. Mixture according to any one of claims 1 - 12, characterized in that the mixture is combined with one or more polymers. l.
    [14]
    14. Combination, characterized in that it comprises the mixture according to claim 13, in which one or more polymers are 'selected from biodegradable polyesters of the diacid-diol, hydroxy-acid or polyester-ether type.
    [15]
    15. Combination according to claim 14, characterized by the fact that the polyesters of the diacid-diol type are aliphatic or 'aliphatic-aromatic.
    [16]
    16. Combination, according to claim 15,] characterized by the fact that the content of biodegradable polyesters, from diacid-diol, varies within the range between 1 and 99% by weight.
    [17]
    17. Combination according to claim 14, 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-D-L-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.
    [18]
    18. Combination, according to claim 17, characterized by the fact that the content of biodegradable polyesters, from hydroxy acid, varies within the range between 1 and 99% by weight.
    [19]
    19. Combination comprising the mixture according to claim 13, characterized by the fact that the one or more polymers are - selected from polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, -polyurethanes, polyamides, polyamino acids) , polyethers, polyureas, polycarbonates and mixtures thereof.
    [20]
    20. Combination according to claim 19, characterized by the fact that the content of polyolefins, non-biodegradable polyesters, 15th polyester- and polyether-urethanes, polyurethanes, polyamides, polyamino acids), polyethers, polyureas, polycarbonates and mixtures of varies within the range of 0.5 to 99% by weight.
    [21]
    21. Combination comprising the mixture according to claim 13, characterized by the fact that the one or more polymers are - selected from rigid polymers with a module greater than 1,500 Mpa.
    [22]
    22. Combination according to claim 21, characterized by the fact that the content in the rigid polymers varies within the range of 5 to 30% by weight.
    [23]
    23. Combination according to claim 22, characterized by the fact that the rigid polymers form a homogeneously 'dispersed phase of particles with average dimensions of less than 2 y.
    [24]
    24. Combination according to claim 23, "characterized by the fact 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 thereof .
    [25]
    25. Combination comprising the mixture according to. claim 13, characterized by the fact that it is obtained by a reactive extrusion process with compounds bearing groups that can react with groups OH and / or COOH, Ú or with unsaturated bonds.
    [26]
    26. Films, injection molding articles, extrusion coatings, fibers, foams, thermoformed articles, characterized in that they comprise the mixture according to any one of claims 1 - 13 or the combinations according to any one of claims 14 - 25.
    at 4/4 Lo
    [27]
    27. Application of the mixture according to any one of claims 1 - 13 or the combinations according to any one of claims 14 - 25, characterized in that it is for the production of: - mono and bi-oriented films, and films with multiple layers with other polymeric materials; - films for use in the agricultural sector; - films for cling films for use with foodstuffs, for 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; - 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; 7 - fibers, microfibers, composite microfibers, in which the core consists of rigid polymers, such as PLA, PET, PTT, composite fibers: combined, fibers with different sections, from circular to multilobulated, staple fibers, woven and non-woven fabrics woven or wired or thermally bonded for use in sanitary and hygiene products, and in the agriculture and clothing sectors. ,
    E 2 m1 à | Abstract Mixtures of biodegradable polyesters with at least: one polymer of natural origin.
    The present invention relates to mixtures comprising — biodegradable polyesters comprising at least one polymer of natural origin and at least two aliphatic-aromatic polyesters of the diacid-diol type, of which at least | least one with a high content of long chain aliphatic diacids, of origin | renewable, exhibiting excellent mechanical properties, sufficiently high melting temperatures, adequate crystallization rates, improved biodegradability properties, as well as stability of physical properties over time. *
    类似技术:
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    BR112012010358A2|2020-09-15|mixtures of biodegradable polyesters with at least one polymer of natural origin
    BR112012010341A2|2020-09-15|biodegradable composition, comprising polymers of natural origin and aliphatic-aromatic copolyesters.
    JP6267668B2|2018-01-24|Biodegradable aliphatic-aromatic polyester
    ES2574307T3|2016-06-16|Aliphatic-aromatic copolyesters and mixtures thereof
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    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
    WO2011054892A1|2011-05-12|
    EP2496644B1|2016-07-13|
    US8846825B2|2014-09-30|
    EP2496644A1|2012-09-12|
    JP2013510210A|2013-03-21|
    CN102597105B|2015-02-04|
    ES2596321T3|2017-01-05|
    IT1396597B1|2012-12-14|
    US9273207B2|2016-03-01|
    ITMI20091938A1|2011-05-06|
    CA2775176A1|2011-05-12|
    US20120322908A1|2012-12-20|
    EP3640300A1|2020-04-22|
    EP3085737B1|2020-01-01|
    CN102597105A|2012-07-18|
    JP5727497B2|2015-06-03|
    ES2768873T3|2020-06-23|
    EP3085737A1|2016-10-26|
    US20140364539A1|2014-12-11|
    CA2775176C|2018-09-11|
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    法律状态:
    2020-10-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-10-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-07-27| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-12-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-02-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/11/2010, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI2009A001938A|IT1396597B1|2009-11-05|2009-11-05|BIODEGRADABLE POLYESTER MIXTURES|
    ITMI2009A001938|2009-11-05|
    PCT/EP2010/066784|WO2011054892A1|2009-11-05|2010-11-04|Mixtures of biodegradable polyesters with at least one polymer of natural origin|
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