BR112012010494B1 - biodegradable aliphatic-aromatic polyester, combination comprising polyester, films, injection molding articles, coatings and polyester application - Google Patents

Abstract

Biodegradable Aliphatic-Aromatic Polyester The present invention relates to biodegradable aliphatic-aromatic polyesters obtained from aliphatic dicarboxylic acids, polyfunctional aromatic acids and diols, with polyfunctional aromatic acids consisting of mixtures of acids of renewable and synthetic origin.

Description

FIELD OF THE INVENTION [001] The present invention relates to biodegradable aliphatic-aromatic polyesters comprising units derived from aliphatic dicarboxylic acids, polyfunctional aromatic acids and diols, with units derived from polyfunctional aromatic acids comprising units derived from at least one phthalic diacid and at least one heterocyclic aromatic diacid of renewable origin.

[002] The present invention also relates to mixtures of polyesters with other biodegradable polymers of both natural and synthetic origin.

BACKGROUND OF THE INVENTION [003] Biodegradable aromatic aliphatic polyesters obtained from terephthalic acid, aliphatic diacids and 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 with adequate crystallization rates.

[004] Although an increase in the content of terephthalic acid improves the thermal and mechanical properties of such polyesters, a high content in it decreases the percentage of biodegradation of the polyesters.

[005] Furthermore, terephthalic acid is of synthetic origin and any production of it from renewable sources is too complex. This limits the ability of polyesters currently commercialized of this type to reduce, to any great extent, the environmental impact in terms of non-renewable carbon raw material regardless of its biodegradability.

[006] If it were possible to maintain suitable biodegradation properties and performances in use, the presence of an aromatic acid of renewable origin in the chain would therefore be desirable since it would allow a polymer to be obtained by breaking

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2/33 of raw material from a renewable source for a very high percentage of total carbon. The use of monomers of plant origin, in fact, contributes to the reduction of CO2 in the atmosphere and to the decrease in the use of non-renewable sources.

[007] All the limits mentioned above are now overcome through the polyesters according to the present invention.

BACKGROUND OF THE INVENTION [008] The present invention, in fact, relates to biodegradable aliphatic-aromatic polyesters comprising units derived from at least one diol, at least one aliphatic dicarboxylic acid and at least two polyfunctional aromatic acids, characterized by the fact that that units derived from polyfunctional aromatic acids comprise:

- from 1 to 99 mol%, preferably from 5 to 95 mol%, and more preferably from 10 to 85 mol%, of units from at least one aromatic phthalic diacid;

- from 99% to 1 mol%, preferably from 95% to 5 mol%, and more preferably from 90% to 15 mol%, of units from at least one heterocyclic aromatic diacid of renewable origin .

[009] 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 future generations, are considered to be of renewable origin. A typical example of a renewable source is plant crops. With respect to aliphatic dicarboxylic acids, C2-C22 dicarboxylic acids are taken into account here.

[010] Of the aliphatic diacids, those with a number of carbon atoms in the main chain between 2 and 22, esters and mixtures thereof, C4 (succinic acid), C6 (adipic acid), C7 (pyelic acid), C8 are preferred (submeric acid), C9 (azelaic acid), C10 (sebacic acid), C11 (undecanedioic), C12 (dodecanedioic) and C13 (acid

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3/33 brassyl), C18 (octadecanedioic) being particularly preferred. Of these, aliphatic diacids from renewable sources and, preferably, C6 (adipic acid), C8 (submeric acid), C9 (azelaic acid), C10 (sebacic acid), C11 (undecanedioic), C12 (dodecanedioic) are particularly preferred and C13 (brassylic acid), its esters and mixtures. Even more preferred are the aliphatic diacids from renewable sources C9 (azelaic acid) and C10 (sebacic acid) and their esters. Mixtures of these acids are also particularly interesting.

[011] Deacids with unsaturation, such as itaconic acid and maleic acid, are also included.

[012] The total content of aliphatic dicarboxylic acids in the biodegradable polyesters according to the present invention is between 95% and 10%, preferably between 80% and 15%, more preferably between 60% and 20%, and, even more preferably, between 50% and 25 mol%, with respect to the total molar content of dicarboxylic acids.

[013] In the polyesters according to the invention, polyfunctional aromatic acids are made up of mixtures of at least one phthalic diacid and at least one heterocyclic aromatic diacid of renewable origin.

[014] It is intended that the phthalic aromatic diacids, for the purposes of the present invention, are aromatic compounds of the phthalic acid type and their esters, preferably terephthalic acid, its esters and / or mixtures thereof.

[015] It is intended that the heterocyclic aromatic diacids of renewable origin, for the purposes of the present invention, are aromatic compounds of the type furanodicarboxylic acid and its esters, preferably 2,5-furan-dicarboxylic acid, its esters and / or mixtures thereof.

[016] Examples of diols, for the purposes of the present invention, are 1,2-ethane-diol, 1,2-propane-diol, 1,3-propane-diol, 1,4-butane-diol, 1,5 -pentano-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,

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4/33

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 -manitol, dianidroiditol, cyclohexane-diol, cyclohexane-methane-diol, aromatic diols, such as phenols, furan-diol, isosorbide and their derivatives.

[017] C2-C10 type diols are particularly preferred. C2-C4 diols are even more preferred. Among these, 1,2-ethane-diol, 1,3-propane-diol, 1,4-butane-diol and mixtures thereof are particularly preferred. Advantageously, the diols consist of at least 50%, preferably at least 80% by mol, of 1,4-butane-diol, with respect to the total diol content.

[018] The molecular weight, Mn, of the polyester according to the present invention is greater than 15,000. The polydispersity index Mw / Mn is between 1.5 and 10.

[019] The molecular weights Mn and Mw can be measured using Gel Permeation Chromatography (acronym, in English, GPC). The determination can be carried out with the chromatography system maintained at 40 ° C, using a set of three columns in series (particle diameter of 5 pm and porosities, respectively, of 500 Angstrom, 1,000 Angstrom and 10,000 Angstrom), a detector of refractive index, chloroform as eluent (flow rate 1 mL / min) and using polystyrene as a reference standard.

[020] The polyester according to the present invention has an inherent viscosity (measured with Ubbelhode viscometer for solutions in CHCl3 with concentrations of 0.2 g / dL at 25 ° C) greater than 0.3 dL / g.

[021] The polyesters according to the present invention may contain, in addition to the basic monomers, at least one hydroxy acid in an amount between 0-49%, preferably between 0-30% by mol, with respect to moles of aliphatic dicarboxylic acid. 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

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5/33 can be inserted into the chain as such or can also be subjected to the reaction, first, with diacids or diols. Such hydroxy acids can be present with a distribution of repetitive units or at random or in blocks.

[022] Long bifunctional molecules also with function not in the terminal position can also be added in quantities not exceeding 10%. Examples are dimeric acids, ricinoleic acid and acids with epoxide functions.

[023] Amines, amino acids and amino alcohols can also be present in percentages of up to 30 mol%, with respect to all other components.

[024] In the process of preparing the polyester according to the invention, 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-ethanetetracarboxylic acid, 1,3,5 pentatricarboxylic acid, 1,2,3,4-cyclopentatetracarboxylic acid, malic acid, tartaric acid, 3-hydroxy-glutaric acid, mucoic acid, trihydroxyglutaric acid , hydroxy-isophthalic acid, hexane-triol, sorbitol, trimethyl-ethane, mannitol, 1,2,4-butane-triol, xylitol, 1,2,4,4-tetrakis (hydroxy-methyl) cyclohexane, arabitol, adonitol , iditol.

[025] Although the polymers according to the present invention achieve high performances without the need to add chain extenders, such as isocyanates and isocyanurates, epoxides and, in particular, polyepoxides, oxazolines or carbodiimides, it is nevertheless possible to modify the properties according to need.

[026] The increase in molecular weight of polyesters can be advantageously obtained, for example, through the addition of various organic peroxides during their extrusion processing. The increase in molecular weight of biodegradable polyesters

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6/33 can be easily detected by observing the increase in viscosity values following the processing of the polyesters with peroxides.

[027] The polyester production process according to the present invention can take place according to any of the processes known in the art. In particular, polyester can be advantageously obtained with a polycondensation reaction.

[028] Advantageously, the polyester polymerization process according to the present invention can be carried out in the presence of a suitable catalyst. By way of example, suitable catalysts can be organo-metallic tin compounds, i.e., derivatives of stanoic acid, titanium compounds, such as orthobutyl titanate, aluminum compounds, such as Al-triisopropyl, and antimony compounds and zinc compounds.

[029] Preferably, the polyester according to the present invention is obtainable by reacting at least one PP of precursor polyester, having at least one acid component and at least one diol component with compounds bearing groups that can react with groups OH and / or COOH, such as, for example, polyepoxides and polycarbodiimides, or with free radical initiators.

[030] Such compounds can also be used in a mixture.

[031] The at least one precursor polyester PP can be of the aliphatic, aromatic or aliphatic-aromatic type.

[032] The person skilled in the art will be able to easily identify the actual molar ratios required with respect to the nature of the precursor polyester PP in order to obtain the desired polyester.

[033] Preferably, the polyester according to the present invention is obtainable by a reactive extrusion process.

[034] Among the free radical initiators, peroxides are preferred and, among peroxides, organic peroxides are particularly preferred. Organic peroxides

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7/33 can be advantageously selected from the group consisting of: benzoyl peroxide, lauroyl peroxide, isononanoyl peroxide, di (t-butyl-peroxy-isopropyl) benzene, t-butyl peroxide, peroxide dicumila, alfa, alfa'-di (t-butyl-peroxy) -di-isopropylbenzene, 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hexane, t-butyl peroxide and cumila, peroxide di-t-butyl, 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hex-3-yn, di (4-tbutyl-cyclohexyl) peroxy-dicarbonate, peroxy-dicarbonate of dicetyl, dimyristyl peroxydicarbonate, 3,6,9triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di (2-ethylhexyl) peroxydicarbonate and mixtures thereof.

[035] Preferably, such peroxides are added to at least one precursor polyester PP in an amount of less than 0.1%, more preferably, 0.05% and, even more preferably, 0.02% in Weight.

[036] Examples of polyepoxides, which can be used advantageously, are all polyepoxides from epoxidized oils and / or from styrene - glycidyl ether methyl methacrylate, such as the 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 of the group comprising: 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.

[037] 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.

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8/33 [038] Catalysts can also be used to increase the reactivity of reactive groups. In the case of polyepoxides, for example, fatty acid salts can be used. Calcium and zinc stearates are particularly preferred.

[039] Examples of carbodiimides, which can be used advantageously, are selected from the group comprising: poly (carbodiimide cyclooctylene), poly (1,4dimethylene cyclohexylene carbodiimide), poly ( cyclohexylene carbodiimide, poly (ethylene carbodiimide), poly (butylene carbodiimide), poly (isobutylene carbodiimide), poly (nonylene carbodiimide), poly (dodecylene carbodiimide), poly (neopentylene carbodiimide), poly (1,4dimethylene phenylene carbodiimide), poly (2,2 ', 6,6', tetraisopropyl-diphenylene carbodiimide), (Stabaxol® D), poly (2,4, 6-triisopropyl-1,3-phenylene carbodiimide) (Stabaxol® P-100), poly (1,3,5-triisopropyl-phenylene-2,4-carbodiimide), poly (2, 6-diisopropyl-1,3-phenylene carbodiimide) (Stabaxol® P), poly (tolyl carbodiimide), poly (4,4'-diphenylmethane carbodiimide), poly (3,3'-dimethyl -4,4'-biphenylene carbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide), poly (3,3'-dimethyl-4,4'-diphenyl-methane carbodi -imide), poly (naphthylene c arbodiimide), poly (carbodiimide isophorone), poly (cumene carbodiimide), pphenylene 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.

[040] 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.

[041] 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%.

[042] Such unsaturations 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.

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9/33 [043] Particularly preferred are PP polyester precursors with terminal unsaturation.

[044] Among unsaturated chain terminators, those with the formula are preferred:

T- (CH2) n-CH = CH2 [045] in which T is a group capable of reacting with carboxylic and / or hydroxy groups and n is an integer between 0 and 13.

[046] Such unsaturated chain terminators can also be used in admixture.

[047] 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.

[048] Preferably, the integer n is between 1 and 13, more preferably between 3 and 13, even more preferably 8 or 9, with omega-undecenoic, omega-undecyl alcohol and mixtures thereof being particularly preferred, in order to maximize compatibility with naturally occurring polymers.

[049] Also after the preparation process, the polyester according to the present invention may have double bonds and / or addition products that are derived from the reaction of unsaturation with the free radical initiators.

[050] The presence of unsaturation and / or addition products 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 metanolysis coupled with chromatographic methods combined with mass spectroscopy.

[051] The technician specialized in the subject will be promptly able to identify structures referable to either their unsaturation or to the reacted installation after the reaction.

[052] Preferably, the polyester according to the present invention is obtainable through a reactive extrusion process using a precursor polyester PP

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10/33 showing a content of terminal acid groups in amounts of 35 - 150 meq KOH / Kg of the precursor polyester.

[053] 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 of terminal acid groups is calculated from the consumption of the KOH / ethanol solution, based on the following equation:

[CVeç -Vb) .η.1000 Content in terminal acid groups (meq KOH / Kg of polymer) = --------? ------- in which:

- Veq = mL of KOH / ethanol solution at the equivalence point for sample titration;

- Vb = 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.

[054] The polyester according to the present invention is biodegradable in industrial composting according to the EM 13432 standard.

[055] The polyester according to the invention and combinations thereof have properties and viscosity values that make them suitable for use, modulating the relative molecular weight appropriately, for numerous practical applications, such as films, articles injection molding, extrusion coatings, fibers, foams, thermoformed articles, rubbers, glues, coatings,

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11/33 lacquers, thermosetting resins, etc.

[056] In particular, the polyesters according to the invention 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 adherent 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 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;

- 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 consists of

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12/33 rigid polymers, such as PLA, PET, PTT, and the wrap consists of the material of the invention, composite composite fibers, fibers with different sections, from circular to multilobulated, staple fibers, woven and non-woven or bonded textile materials spinning or thermocouples for application in sanitary and hygiene products, and in the agriculture and clothing sectors.

[057] They can also be used in applications in place of plasticized PVC.

[058] The polyesters of the present invention can also be used to produce biodegradable spandex-like elastomers, hot melt glue and other glues, paint polyesters, paper treatment coatings, paint matrices.

[059] The polyester 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.

[060] In the meaning of this invention, biodegradable polymers are understood to mean biodegradable polymers according to the standard EN 13432.

[061] In particular, the polyester according to the invention can be combined with biodegradable polyesters of the diacid-diol, hydroxy-acid or polyester-ether type.

[062] As far as biodegradable polyesters of the diacid-diol type are concerned, they can be either aliphatic or aliphatic-aromatic.

[063] Aliphatic polyesters biodegradable from diacid-diols comprise units that are derived from aliphatic diacids and aliphatic diols, while biodegradable aliphatic-aromatic polyesters have an aromatic part comprising mainly polyfunctional aromatic acids, of both synthetic and renewable origin , the aliphatic part comprising aliphatic diacids and aliphatic diols.

[064] Aromatic aliphatic biodegradable polyesters from diacids-diols are preferably characterized by an aromatic acid content of between 30% and 90% by mol, preferably between 45% and 70% by mol, with respect to the acid component.

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13/33 [065] Preferably, polyfunctional aromatic acids of synthetic origin are dicarboxylic aromatic compounds of the phthalic acid type and their esters, preferably terephthalic acid.

[066] Polyfunctional aromatic acids of renewable origin are preferably selected from the group comprising 2,5-furan-dicarboxylic acid and its esters.

[067] 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 and dodecanic acid brassylic acid, octadecanedicarboxylic acid, its esters and mixtures. Among these, adipic acid and dicarboxylic acids from renewable sources are preferred, and among these, dicarboxylic acids from renewable sources are particularly preferred, such as succinic acid, sebacic acid, azelaic acid, undecanedioic, dodecanedioic and brassyl acid. and their mixtures.

[068] 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, 1,10decane-diol, 1,11-undecane- diol, 1,12-dodecane-diol, 1,13-tridecan-diol, 1,4-cyclohexane-dimethanol, neopentylglycol, 2-methyl-1,3-propane-diol, dianhydro-sorbitol, dianhydromanitol, dianhydro-iditol, cyclohexane-diol, cyclohexane-methane-diol and mixtures thereof. Of these, 1,4-butane-diol, 1,3-propane-diol and 1,2-ethane-diol and mixtures thereof are particularly preferred.

[069] Among the biodegradable polyesters of the diacid-diol type, aliphatic / aromatic copolyesters, such as, for example, poly (butylene terephthalate-sebaçate), poly (butylene terephthalate-co-azelate), poly (terephthalate) are particularly preferred -butylene copper-silicate), poly (butylene terephthalate-co-adipate), poly (butylene terephthalate-cosuccinate) and poly (butylene terephthalate-co-glutarate), and aliphatic polyesters,

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14/33 such as, for example, poly (alkylene succinates) and, particularly, poly (butylene succinate) and its copolymers with adipic acid and lactic acid.

[070] Preferably, the combinations of the polyester according to the invention, with biodegradable polyesters, from the diacids-diols described above, are characterized by a content in the biodegradable polyesters, which varies within the range between 1% and 99% in 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.

[071] Preferred biodegradable polyesters from hydroxy acids include: poly-L-lactic acid, poly-D-lactic acid and the poly-DL-lactic acid esterocomplex, poly-εcaprolactone, poly-hydroxy-butyrate, poly -hydroxy-butyrate-valerate, polyhydroxy-butyratepropanoate, polyhydroxy-butyrate-hexanoate, polyhydroxy-butyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxy-butyrate-hexadecanoate, polyhydroxy-butyrate and polyadiene-polyadecane -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-Dlactic acid.

[072] Preferably, the combinations of the polyester 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 [073] Advantageously, the polyester according to the invention can be combined with at least one polymer of natural origin 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 .

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15/33

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.

[074] Among the polymers of natural origin mentioned above, starch is particularly preferred.

[075] 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.

[076] 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 the case of dispersed starch, the starch preferably represents a homogeneously dispersed phase of particles with average dimensions of less than 1 pm, preferably less than 0.8 pm.

[077] 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 combination, 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 / palladium mixture, using a hot coater. Finally, the fracture surface is examined under a scanning electron microscope (SEM).

[078] 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.

[079] The average size of the starch particles, that is, the detectable holes on the

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16/33 pickled surface of the fracture, is calculated as the numerical (or arithmetic) average 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 * 2 where d1 is the smallest diameter and d2 is the largest diameter of the ellipse, in which the particle can be inscribed or approximated.

[080] The selective pickling of the dispersed starch phase can be carried out advantageously with 5 N HCl as a pickling, with a pickling time of 20 minutes, at a pickling temperature of 25 ° C.

[081] Combinations containing unstructured starch are preferred.

[082] Starches, such as corn and potato starch, capable of being facially unstructured and having high initial molecular weights, have proven to be particularly advantageous.

[083] The use of corn and potato starch is particularly preferred.

[084] For unstructured starch, here refers to the teachings of 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. [085] In addition, physically and chemically modified grades of starch, such as ethoxylated starches, oxypropylated starches, starch acetates, starch butyrate, starch propionates, can be used with a degree of substitution within the range of from 0, 1 to 2, cationic starches, oxidized starches, cross-linked starches, gelled starches.

[086] Starch combinations, in which the starch represents the dispersed phase, can form biodegradable polymeric compositions with good resistance to aging and

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17/33 to humidity. In fact, these polymeric compositions can maintain high tear resistance even in low humidity conditions.

[087] 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.

[088] It may 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.

[089] 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, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, erythritol, xylitol, mannitol, sucrose, 1,3propane-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), acetates, ethoxylates and polyol propoxylates, particularly sorbitol ethoxylate, sorbitol acetate and pentaerythritol acetate.

[090] Water can be used as a plasticizer in combination with high boiling 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 the 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.

[091] Water, as well as plasticizers with high boiling points, modify the

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18/33 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 lower pK dissociation constants than 4.5 (the 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 EHL values lower than 5.5, obtained from polyols and from fatty acids with 12 - 22 carbon atoms;

[092] These compatibilizers can be used in amounts of 0.2% to 40% by weight and, preferably, from 1% to 20% by weight, in relation to starch. Starch combinations may also contain polymeric compatibilizing agents having two components: one compatible with or soluble in starch and a second soluble in or compatible with polyester.

[093] 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 such as di- and polyepoxides, di- and polyisocyanates, isocyanurates, polycarbodiimides and peroxides can also be added. They can function as stabilizers as well as chain extenders.

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19/33 [094] All of the above products can help to create the necessary microstructure.

[095] 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 polyiepoxides or isocyanurates or with oxazolines, aliphatic or aromatic, with intrinsic viscosities higher than 1 dL / g or, in any case, aliphatic polyesters -articles with a ratio between Mn and EMI at 190 ° C, 2.16 kg, higher than 10,000, preferably higher than 12,500, and more preferably higher than 15,000, to achieve the microstructure needed.

[096] Another method to improve the microstructure is to achieve the starch complexation in the starch-polyester mixture.

[097] Such combinations exhibit good properties also in the case of starch combinations, in which the starch is not strongly complexed. With respect to starch complexation, it is intended that the teachings contained in EP-O 965 615 are incorporated into the present description. 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 13-14 ° on the theta scale. According to the present invention, with the above compositions, in which the starch is not strongly complexed, compositions are intended, in which the Hc / Ha ratio between the peak height (Hc) in the range of 13-14 ° of the complex and the peak height (Ha) of amorphous starch, which appears at about 20.5 °, is less than 0.15, and even less than 0.07.

[098] Advantageously, starch combinations 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 plasticizers with high boiling points or polymeric of the type mentioned above. Mixtures of different

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20/33 plasticizers are also preferred.

[099] The amount of plasticizer is, in general, chosen based on the rheological and mixing system needs. 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.

[0100] In addition to water, plasticizers, which can be used in the composition according to the invention, are plasticizers with high boiling points or polymeric.

[0101] 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, triglycerol and tetraglycerol and mixtures thereof are preferred.

[0102] Mixtures of plasticizers with high boiling points containing at least 75% by weight, preferably 90% by weight of diglycerol, triglycerol and tetraglycerol are also particularly preferred. Such mixtures contain more than 50% by weight, preferably more than 80% by weight of diglycerol with respect to the total weight of diglycerol, triglycerol and tetraglycerol. The use of this type of plasticizer with high boiling points is particularly preferred, since 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.

[0103] In the meaning of the present patent application, with the word diglicerol, 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.

[0104] Combinations of water-containing starches are also preferred as the only

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21/33 plasticizer. Among these, mixtures containing the water present in the native starch as the only plasticizer are particularly preferred.

[0105] Preferably, combinations with polymers of natural origin are characterized by a content in the polymers of natural origin, which varies within the range between 1% and 99% by weight, more preferably between 5% and 95% by weight, and , more preferably, between 10% and 40% by weight, with respect to the sum of the weights of the polyester according to the invention and the first, respectively.

[0106] The polyester according to the invention can also be combined with polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, polyurethanes, polyamides, poly (amino acids), polyethers, polyureas, polycarbonates and mixtures thereof.

[0107] Among polyolefins, polyethylene, polypropylene, their copolymers, poly (vinyl alcohol), poly (vinyl acetate), poly (ethyl vinyl acetate) and poly (ethylene vinyl alcohol) are preferred.

[0108] Among non-biodegradable polyesters, PET, PBT, PTT are preferred, in particular with a renewable content> 30%, and poly (alkylene furan-dicarboxylates). Among the latter, poly (ethylene furan-dicarboxylate), poly (propylene furanedicarboxylate), poly (furene-butylene dicarboxylate) and mixtures thereof are preferred.

[0109] 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.

[0110] Polycarbonates can be poly (ethylene carbonates), poly (propylene carbonates), poly (butylene carbonates) and their mixtures and copolymers.

[0111] 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.

[0112] Preferably, combinations of the composition according to the invention with the

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22/33 polymers described above (polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, polyurethanes, polyamides, poly (amino acids), polyethers, polyureas, polycarbonates and mixtures thereof) are characterized by a content in 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.

[0113] The polyester according to the invention can be advantageously used in combinations of 5% - 30% by weight, preferably 7% - 25% by weight of at least one rigid polymer with a module greater than than 1,500 Mpa. Such at least one rigid polymer can be present as an additional dispersed phase, as well as in lamellar structures or mixtures thereof.

[0114] 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 pm, preferably less than 1 pm.

[0115] The dimensions of such particles are measured according to the measurement method described above for starch particles.

[0116] Among the rigid polymers, poly (hydroxyalkanoates), such as poly (lactic acid) and poly (glycolic acid), are particularly preferred, and, more preferably, polymers or copolymers of poly (lactic acid) containing at least 75% of L-lactic or D-lactic acid or combinations thereof, advantageously, with molecular Mw greater than 70,000. Such rigid polymers can also be plasticized.

[0117] The selective stripping of the dispersed phase of poly (lactic acid) can be carried out advantageously with acetone as a stripping agent, with a stripping time of 5 minutes, at a stripping temperature of 25 ° C.

[0118] The polyesters according to the present invention can also be used in combinations with the polymers of synthetic origin and polymers of natural origin mentioned above. Mixtures of polyesters with starch and poly (lactic acid) are

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Particularly preferred.

[0119] The combinations of the polyester 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.

[0120] Combinations of polyester according to the present invention with PLA are of particular interest because 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.

[0121] To improve the transparency of the resistance 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 C2 to C13 diols and C4 to C13 diacids, poly (hydroxy alkanoates), poly (vinyl alcohol) in the grade 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.

[0122] In order to maximize the compatibility between the polyester of the invention and the poly (lactic acid), it is very useful to introduce copolymers with blocks showing high affinity for the aliphatic-aromatic copolyesters of the invention, and blocks with affinity for polymers or acid copolymers lactic. 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

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24/33 chain, 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 polyepoxide 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.

[0123] 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 compatibilizer 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% in Weight.

[0124] The mixture according to the present invention can be advantageously combined also with nucleating agents and fillers, both organic and inorganic in nature.

[0125] Examples of nucleating agents include talc, sodium saccharin salt, calcium silicate, sodium benzoate, calcium titanate, boron nitride, zinc salts, porphyrin, chlorine, florin, porphodimetine, porphomethamine, bacterioclorin, isobacterioclorin , porphyrinogen, forbine, isotactic polypropylene, low molecular weight PLA and PBT.

[0126] The preferred amount of fillers is in the range of 0.5% - 70% by weight, preferably 5% - 50% by weight.

[0127] Regarding organic loads, wood dust, proteins, cellulose powder, grape residues, bran, corn husks, compost, other natural fibers, cereal cracks with or without plasticizers, such as polyols.

[0128] 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

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25/33 than 300 nm, and, even more preferably, less 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 with the specific polyester. The use of such fillers can improve rigidity, permeability to water and gases, dimensional stability and maintain transparency.

[0129] The compositions comprising the polyester 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 a homogeneous mixing of the components.

[0130] The combinations are advantageously obtainable by a 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 unsaturated bonds, such such as peroxides.

[0131] 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) -di-isopropyl-benzene, 2,5-dimethyl-2,5-di (t-butyl- peroxy) -hexane, t-butyl and cumyl peroxide, di-tbutyl peroxide, 2,5-dimethyl-2,5-di (t-butyl-peroxy) -hex-3-yne, di (peroxy-dicarbonate) 4-t-butyl-cyclohexyl), dicetyl peroxy-dicarbonate, dimyristyl peroxy-dicarbonate, 3,6,9-triethyl-3,6,9trimethyl-1,4,7-triperoxonane, di (2 peroxy-dicarbonate) -ethylhexyl) and mixtures thereof.

[0132] 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% in Weight.

[0133] Examples of polyepoxides, which can be used to advantage, are

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26/33 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: diglicidyl ether, diethylene glycol, diglicidyl 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, diglycidyl ether 1,4-cyclohexane-dimethanol, glycidyl 2-methyl-phenyl-ether, glycerol propoxylate triglycidyl ether, 1,4-butane-diol diglycidyl ether, sorbitol poly (glycidyl ether), glyceryl diglycidyl ether, tetraglycidyl ether of meta-x ileno-diamine and diglycidyl ether of bisphenol A, and mixtures thereof.

[0134] 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.

[0135] Catalysts can also be used to increase the reactivity of reactive groups. In the case of polyepoxides, for example, fatty acid salts can be used. Calcium and zinc stearates are particularly preferred.

[0136] Examples of carbodiimides, which can be used advantageously, are selected from the group comprising: poly (carbodiimide cyclooctylene), poly (1,4dimethylene cyclohexylene carbodiimide), poly ( cyclohexylene carbodiimide, poly (ethylene carbodiimide), poly (butylene carbodiimide), poly (isobutylene carbodiimide), poly (nonylene carbodiimide), poly (dodecylene carbodiimide), poly (neopentylene carbodiimide), poly (1,4dimethylene phenylene carbodiimide), poly (2,2 ', 6,6', tetraisopropyl-diphenylene carbodiimide), (Stabaxol® D), poly (2,4, 6-triisopropyl-1,3-phenylene carbodiimide) (Stabaxol® P-100), poly (1,3,5-triisopropyl-phenylene-2,4-carbodiimide), poly (2, 6-diisopropyl-1,3-phenylene carbodiimide) (Stabaxol® P), poly (tolyl carbodiimide), poly (4,4'-diphenylmethane carbodi

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27/33 imide), poly (3,3'-dimethyl-4,4'-biphenylene carbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide), poly (3, 3'-dimethyl-4,4'-diphenyl-methane carbodiimide), poly (naphthylene carbodiimide), poly (carbodiimide isophorone), poly (cumene carbodiimide), pphenylene 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.

[0137] 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% in weight.

[0138] The invention is now illustrated by description of various modalities, which will be intended as non-limiting examples of the inventive concept protected by the present patent.

Examples

Example 1 [0139] Synthesis of Poly (Butylene Furan-Dicarboxylate -co- Butylene Terephthalate -co Butylene Sheep) with 60 mol% of Butylene Furan-Dicarboxylate Units, 10 mol% of Butylene Terephthalate Units and 30% by mol of Butylene Sebaceous Units.

[0140] The following were loaded into a 1 L glass reactor with two mouths equipped with a sealed mechanical stirrer and a water cooler connected to a graduated test tube for collecting the distillate:

2,5-furan-dicarboxylic acid dimethyl ester (DMFD): 49.11 g (0.267 moles)

Terephthalic acid dimethyl ester (DMT): 8.63 g (0.044 moles)

Sebacic acid: 26.96 g (0.133 moles)

1,4-Butane-diol: 55.94 g (0.622 moles)

Esterification [0141] The glass reactor was immersed in a controlled oil bath

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28/33 thermostatic, at a temperature of 200 ° C, and stirred continuously at 400 rpm. [0142] Water and methanol are distilled during the reaction. The distillation was allowed to proceed for one hour, after which 100 ppm of tetra-butyl titanate (Tyzor®, marketed by DuPont) was added as an esterification catalyst and the temperature of the oil bath was gradually raised to 235 ° C over the course of three hours. The achieved conversion, calculated as the ratio between the amount of distillates recovered during the reaction, vis-à-vis, the amount theoretically obtainable, was approximately 87%.

[0143] Polycondensation Phase [0144] The water cooler was subsequently replaced by an air cooler equipped with a coded and graduated test tube for the collection of the distillates and an additional 1,000 ppm of Tyzor® was added as the catalyst polycondensation. The pressure was reduced to 1 mbar over a period of approximately 10 minutes.

[0145] The reaction was protruded for 4 hours, bringing the oil temperature to 240 ° C. A product was obtained with an inherent viscosity, measured in chloroform at 25 ° C (2 g / L), according to the ASTM D 2857-89 standard, equal to 0.76 dL / g.

[0146] The product thus obtained was subjected to the determination of the melting temperature (Tm).

[0147] Regarding the melting temperature (Tm), it was determined in a 3-6 mg sample using Differential Scanning Calorimetry (CVD) with a Perkin Elmer Diamond differential scanning calorimeter operating with the following thermal profile:

- 30 seconds of thermal equilibration at -20 ° C;

- Sweep from -20 to 200 ° C at 20 ° C / min;

[0148] Tm was measured as the maximum of the endothermic peak during the scan, obtaining the following results:

Melting temperature (Tm) = 102 ° C,

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29/33 [0149] The polymer has been characterized as far as concerns the mechanical properties according to the ASTM D638 standard.

[0150] Mechanical properties:

Breaking stress (MPa) 43

Elongation at break (%) 750

Elastic modulus (MPa) 105

Example 2 [0151] Synthesis of Poly (Butylene Furan-Butane Dicarboxylate -co- Butylene Terephthalate -co Butylene Sheep) with 25 mol% of Butylene Furan-Dicarboxylate Units, 45 mol% of Butylene Terephthalate Units and 30% by mol of Butylene Sebaceous Units.

[0152] The following were loaded into a 1 L glass reactor with two mouths equipped with a sealed mechanical stirrer and a water cooler connected to a graduated test tube for collecting the distillate:

2,5-furan-dicarboxylic acid (DMFD) dimethyl ester: 20.15 g (0.110 moles)

Terephthalic acid dimethyl ester (DMT): 38.24 g (0.197 moles)

Sebacic acid: 26.54 g (0.131 moles)

1,4-Butane-diol: 55.19 g (0.613 moles) [0153] Esterification Phase [0154] The glass reactor was immersed in a thermostatically controlled oil bath at a temperature of 200 ° C, and stirred continuously at 400 rpm.

[0155] Water and methanol are distilled during the reaction. The distillation was allowed to proceed for one hour, after which 100 ppm of tetra-butyl titanate (Tyzor®, marketed by DuPont) was added as an esterification catalyst and the temperature of the oil bath was gradually raised to 235 ° C over the course of three hours. The achieved conversion, calculated as the ratio between the amount of distillates recovered during the reaction, vis-à-vis, the amount theoretically obtainable, was

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30/33 of approximately 86%.

[0156] Polycondensation Phase [0157] The water cooler was subsequently replaced by an air cooler equipped with a coded and graded test tube for the collection of the distillates and an additional 1,000 ppm of Tyzor® was added as the catalyst polycondensation. The pressure was reduced to 1 mbar over a period of approximately 10 minutes.

[0158] The reaction was protruded for 2 hours, bringing the oil temperature to 240 ° C. A product was obtained with an inherent viscosity, measured in chloroform at 25 ° C (2 g / L), according to the ASTM D 2857-89 standard, equal to 0.87 dL / g.

[0159] The product was analyzed with a Perkin Elmer Diamond differential scanning calorimeter, using the procedure of Example 1, obtaining the following results: Melting temperature (Tm) = 97 ° C, [0160] The polymer was characterized in as far as concerns the mechanical properties according to the ASTM D638 standard.

[0161] Mechanical properties:

Breaking stress (MPa) 38

Elongation at break (%) 670

Elastic modulus (MPa) 60

Example 3 [0162] Synthesis of Poly (Butylene Furan-Butane Dicarboxylate-Butylene Terephthalate-Butylene Sheep) with 10 mol% of Butylene Furan-Dicarboxylate Units, 50 mol% of Butylene Terephthalate Units and 40% by mol of Butylene Sebaceous Units.

[0163] The following were loaded into a 1 L glass reactor with two mouths equipped with a sealed mechanical stirrer and a water cooler connected to a graduated test tube for collecting the distillate:

2,5-furan-dicarboxylic acid dimethyl ester (DMFD): 7.88 g (0.043 moles)

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31/33

Terephthalic acid dimethyl ester (DMT): 41.56 g (0.214 moles)

Sebacic acid: 34.62 g (0.171 moles)

1,4-Butane-diol: 53.93 g (0.599 moles) [0164] Esterification Phase [0165] The glass reactor was immersed in a thermostatically controlled oil bath at a temperature of 200 ° C, and stirred continuously at 400 rpm.

[0166] Water and methanol are distilled during the reaction. The distillation was allowed to proceed for one hour, after which 100 ppm of tetra-butyl titanate (Tyzor®, marketed by DuPont) was added as an esterification catalyst and the temperature of the oil bath was gradually raised to 235 ° C over the course of three hours. The achieved conversion, calculated as the ratio between the amount of distillates recovered during the reaction, vis-à-vis, the amount theoretically obtainable, was approximately 88%.

[0167] Polycondensation Phase [0168] The water cooler was subsequently replaced by an air cooler equipped with a coded and graduated test tube for the collection of the distillates and an additional 1,000 ppm of Tyzor® was added as the catalyst polycondensation. The pressure was reduced to 1 mbar over a period of approximately 10 minutes.

[0169] The reaction was protruded for 2 hours, bringing the oil temperature to 240 ° C. A product was obtained with an inherent viscosity, measured in chloroform at 25 ° C (2 g / L), according to the ASTM D 2857-89 standard, equal to 0.81 dL / g.

[0170] The product was analyzed with a Perkin Elmer Diamond differential scanning calorimeter, using the procedure of Example 1, obtaining the following results: Melting temperature (Tm) = 107 ° C, [0171] The polymer was characterized in as far as concerns the mechanical properties according to the ASTM D638 standard.

[0172] Mechanical properties:

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32/33

Breaking stress (MPa) 25

Elongation at break (%) 900

Elastic modulus (MPa) 65 [0173] The products according to Examples 1-3 showed mechanical and thermal properties making them particularly suitable for the production of films and products coated with high strength extrusion.

Example 4 [0174] Synthesis of Poly (Butylene Furan-Butane Dicarboxylate-Butylene Terephthalate-Butylene Sheep) with 30 mol% of Butylene Furan-Dicarboxylate Units, 30 mol% of Butylene Terephthalate Units and 40% by mol of Butylene Sebaceous Units.

[0175] The following were loaded into a 1 L glass reactor with two mouths equipped with a sealed mechanical stirrer and a water cooler connected to a graduated test tube for collecting the distillate:

2,5-furan-dicarboxylic acid (DMFD) dimethyl ester: 23.85 g (0.130 moles)

Terephthalic acid dimethyl ester (DMT): 25.15 g (0.130 moles)

Sebaceic acid: 34.92 g (0.173 moles)

1,4-Butane-diol: 54.56 g (0.606 moles) [0176] Esterification Phase [0177] The glass reactor was immersed in a thermostatically controlled oil bath at a temperature of 200 ° C, and stirred continuously at 400 rpm.

[0178] Water and methanol are distilled during the reaction. The distillation was allowed to proceed for one hour, after which 100 ppm of tetra-butyl titanate (Tyzor®, marketed by DuPont) was added as an esterification catalyst and the temperature of the oil bath was gradually raised to 235 ° C over the course of three hours. The achieved conversion, calculated as the ratio between the amount of distillates recovered during the reaction, vis-à-vis, the amount theoretically obtainable, was

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33/33 of approximately 89%.

[0179] Polycondensation Phase [0180] The water cooler was subsequently replaced by an air cooler equipped with a coded and graduated test tube for the collection of the distillates and an additional 1,000 ppm of Tyzor® was added as the catalyst polycondensation. The pressure was reduced to 1 mbar over a period of approximately 10 minutes.

[0181] The reaction was protruded for 2 hours, bringing the oil temperature to 240 ° C. A product was obtained with an inherent viscosity, measured in chloroform at 25 ° C (2 g / L), according to the ASTM D 2857-89 standard, equal to 0.65 dL / g.

[0182] The product was analyzed with a Perkin Elmer Diamond differential scanning calorimeter, using the procedure of Example 1, obtaining the following results: Melting temperature (Tm) = No melting point detectable in CVD analysis [0183] The polymer has been characterized as far as concerns mechanical properties according to the ASTM D638 standard.

[0184] Mechanical properties:

Breaking stress (MPa) 11.5

Elongation at break (%) 1,100

Elastic modulus (MPa) 13 [0185] The product according to example 4 exhibited mechanical and rheological properties making it particularly suitable for the production of elastic bands and elastic fibers.

[0186] The polyesters according to Examples 1-4 were subjected to a biodegradation test according to the EN 13432 standard. All polyesters exhibited a relative biodegradability with respect to cellulose greater than 90% after 150 days, resulting in thus, biodegradable in industrial composting.

Claims (17)

Claims 1. Biodegradable aliphatic-aromatic polyester comprising units derived from at least one diol, at least one aliphatic dicarboxylic acid and at least two polyfunctional aromatic acids, characterized in that the units derived from polyfunctional aromatic acids comprise: i. from 1 to 99 mol% of units from at least one aromatic phthalic diacid; ii. from 99% to 1 mol% of units from at least one heterocyclic aromatic diacid of renewable origin. Biodegradable polyester according to claim 1, characterized in that the aliphatic dicarboxylic acids are of the C2-C22 type. Biodegradable polyester according to claim 1 or 2, characterized in that at least one aromatic phthalic diacid is terephthalic acid, its esters and / or mixtures thereof. Biodegradable polyester according to any one of claims 1 to 3, characterized in that at least one aromatic heterocyclic diacid of renewable origin is 2,5-furan-dicarboxylic acid, its esters and / or mixtures thereof. Biodegradable polyester according to any one of claims 1 to 4, characterized in that the unit content from aliphatic dicarboxylic acids is between 95% and 10 mol% with respect to the total molar content of the units from acids dicarboxylics. A combination comprising the polyester as defined in any one of claims 1 to 5, characterized in that said polyester is combined with one or more polymers. Combination according to claim 6, characterized in that one or more polymers are selected from biodegradable polyesters of the type Petition 870190088603, of 09/09/2019, p. 40/45 2/4 diacid-diol, hydroxy-acid or polyester-ether. Combination according to claim 7, characterized in that the diacid-diol polyesters are aliphatic or aliphatic-aromatic. Combination according to claim 7, characterized in that said polyesters of the hydroxy-acid type are selected from poly-L-lactic acid, poly-D-lactic acid and the sterocomplex of poly-DL-lactic acid, poly-s-caprolactone, polyhydroxy-butyrate, polyhydroxy-butyrate-valerate, polyhydroxy-butyrate-propanoate, polyhydroxy-butyrate-hexanoate, polyhydroxy-butyrate-decanoate, polyhydroxy-butyrate -ododecanoate, polyhydro-hydroxy butyrate-hexadecanoate, polyhydroxy-butyrate-octadecanoate and poly-3-hydroxy-butyrate-4-hydroxy-butyrate. A combination comprising the polyester as defined in claim 6, characterized in that said one or more polymers are polymers of natural origin. Combination according to claim 10, characterized in that the polymers of natural origin are 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. Combination according to claim 11, characterized in that the starch is in an unstructured or gelatinized form or as a filler. Combination according to claim 11 or 12, characterized in that the starch represents a homogeneously dispersed phase of particles with average dimensions of less than 1 pm. Combination comprising polyester as defined in claim 6, characterized in that said one or more polymers are selected from polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, polyurethanes, polyamides, poly (amino acids), polyethers, polyureas, polycarbonates and mixtures thereof. Petition 870190088603, of 09/09/2019, p. 41/45 3/4 Combination comprising polyester as defined in claim 6, characterized by being obtained by a reactive extrusion process with binder groups that can react with OH and / or COOH groups, or with unsaturated bonds. 16. Films, injection molding articles, extrusion coatings, fibers, foams, thermoformed articles, rubbers, glues, coatings, lacquers, heat-resistant resins, characterized in that they comprise polyester as defined in any of claims 1 to 6 or the combinations as described in any of claims 7 to 15. 17. Application of the polyester as defined in any of claims 1 to 6 or combinations as described in any of claims 7 to 15, 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 bales in agriculture and for wrapping waste; - bags and linings for containers for the collection of organic waste; - seed coatings; - glues, such as hot melt adhesives; - thermoformed food packaging, both 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 Petition 870190088603, of 09/09/2019, p. 42/45 4/4 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 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 thermocoupled textile materials, for application in sanitary and hygiene products, and in the agriculture and clothing sectors.