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    • 专利摘要:
    aliphatic-aromatic copolyester, mixture of aliphatic-aromatic copolyester and use of copolyester and the mixture this invention refers to an aliphatic-aromatic copolyester characterized by the fact that it has appreciable functionality properties, even when mixed with other polymers, appreciable strength and high values for ultimate tensile strength and elastic modulus. this invention also relates to the mentioned copolyester with other polymers.
    公开号:BR112012028012B1
    申请号:R112012028012
    申请日:2011-05-24
    公开日:2020-06-09
    发明作者:Bastioli Catia；Borsotti Giampietro；Capuzzi Luigi；Vallero Roberto；Milizia Tiziana
    申请人:Novamont Spa；
    IPC主号:
    专利说明:

    ALIPHATIC-AROMATIC COPOLIESTER, MIXTURE OF ALIPHATIC-AROMATIC COPOLYSTER AND USE OF COPOLIESTER AND MIXTURE
    DESCRIPTION
    [001] The present invention relates to an aliphatic-aromatic copolyester characterized by appreciable properties of functionality, even when mixed with other polymers, strength and high values for tensile maintaining adequate values of elastic modulus and elongation at break and ability to crystallize under stretching, which makes it particularly useful for the production of mono- and bioriented films, as well as meltblown spunbondou fibers.
    [002] This invention also relates to mixtures of copolyesters with other polymers. [003] Over the years, polymeric materials have become increasingly widespread because of their versatility, their ability to be easily processed and their low cost.
    [004] Among the polymeric materials, isotactic polypropylene is used in a wide range of applications, such as, for example, for the production of mono- and bioriented films, as well as meltblown spunbond or fibers.
    [005] Also, because of its low surface tension, polypropylene is not compatible with most known polymers and it is also difficult to paint or color. For example, polypropylene fibers are generally colored in bulk and cannot be dyed after production, giving rise to notable storage management problems. In addition, because of the fossil origin of the monomer of which it is made, polypropylene also contributes to the emptying of non-renewable raw materials. Polypropylene from renewable resources, on the other hand, needs much higher energy sources than polypropylene from non-renewable sources.
    [006] Therefore, there is a demand for suitable polymeric material to overcome the problems mentioned above.
    [007] Among the thermoplastic polymer materials, the development of new
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    2/31 polyesters became particularly significant. Polymer materials of this type have, in fact, found considerable uses in the field of fibers, molded and blown articles and films.
    [008] The increasing use of polymer materials in progressively more technologically advanced application sectors, however, requires that new materials, capable of ensuring progressively better use performance, have to be developed.
    [009] The problem underlying this invention is, therefore, that the development of a new polymer exhibiting a range of applicability comparable to that of polypropylene, capable of providing high performance when in use, such as high strength values, tensile strength, elastic modulus with elongation at break and elasticity, as well as the ability to crystallize under stretching, together with good functionality characteristics, even when mixed with other polymers.
    [010] Starting from this problem, it has now been surprisingly found that, by properly selecting the type and monomer ratios, it is possible to obtain a copolyester with appreciable functionality properties, even when mixed with other polymers and resistance and improved tensile strength, as well as the ability to crystallize under stretching, while maintaining high values for elastic modulus and elongation at break.
    [011] Thanks to its characteristics, copolyester is particularly suitable for the production of mono- and bioriented films, as well as spunbond and meltblown fibers.
    [012] In particular, the present invention relates to an aliphatic-aromatic copolyester formed by a dicarboxylic component and a diol component, comprising the following structural units:
    Formula 1:
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    3/31 - [- 0— (R ,,) - Ο — C (O) - (R ] 3 ) —C (O) -] - - [- O— (R] 2 ) —O — C (OHR ] 4 ) —C (O) -] - in which the diol component comprises units of -O- (R11) -0- and -0- (R12) -0 that are derived from diols, where R11 and R12 are the same or different and are selected from the group consisting of C2-C14-alkylenes, C5-C10-cycloalkylenes, C2-C12oxyalkylenes, heterocyclic groups and mixtures thereof, in which the dicarboxylic component comprises units of -C (0) - ( R13) -C (0) - which are derived from aliphatic diacids and units of -C (0) - (R14) -C (0) - which are derived from aromatic diacids, where R13 is selected from of the group consisting of C0-C20-alkenes and mixtures thereof, in which the aromatic diacids comprise at least one aromatic diacid of renewable origin and in which the molar percentage of the aromatic diacids is greater than 90% and less than 100% of the component dicarboxylic.
    [013] Among the aliphatic diacids, those with a number of C atoms in the main chain between 2 and 22, esters and mixtures thereof are preferred, C4 (succinic acid), C6 (adipic acid), C7 (pyelic acid), C8 (submeric acid), C9 (azelaic acid), C10 (sebacic acid), Cll (undecanedioic acid), C12 (dodecanedioic acid) and C13 (brassic acid), C18 (octadecanedioic acid). Of these, aliphatic diacids from renewable sources are particularly preferred and, preferably, C6 (adipic acid), C8 (submeric acid), C9 (azelaic acid), C10 (sebacic acid), C12 (dodecanedioic acid) and C13 (acid brassyl), its esters and mixtures thereof. Even more preferred are aliphatic acids, from renewable sources C9 (azelaic acid), C10 (sebacic acid) and their esters. Mixtures of these acids are also particularly interesting.
    [014] Dacids that show unsaturation within the chain, such as, for example, itaconic acid and maleic acid, are also included.
    [015] As far as the -C- (O) - (R14) -C (O) - unit of the copolyester according to this invention is concerned, aromatic diacids contain at least one aromatic diacid of
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    4/31 renewable origin and, preferably, comprise mixtures of aromatic diacids of synthetic and renewable origin. Preferably, in the case of mixtures of aromatic diacids of synthetic and renewable origin, they comprise up to 40 mol% of aromatic diacids of synthetic origin.
    [016] By aromatic diacids of synthetic origin, within the meaning of this invention, are meant aromatic compounds of the phthalic acid type and their esters, preferably terephthalic acid, its esters and / or mixtures thereof.
    [017] Among aromatic diacids of renewable origin, within the meaning of this invention, aromatic heterocyclic compounds are preferred and, particularly preferred, are the compounds of the furan-dicarboxylic acid type and their esters, preferably the 2,5-furan-dicarboxylic acid, their esters and / or mixtures thereof, are even more preferred.
    [018] Those products obtained from sources that, because of their intrinsic characteristics, regenerate or are not exhaustible over the scale of a human lifetime, and, by extension, whose use does not harm natural resources for generations future, are considered to be of renewable origin. The use of products of renewable origin, even from biomass, also helps to reduce CO2 in the atmosphere, and to reduce the use of non-renewable resources. Typical examples of renewable sources are plant crops and residual biomass for the production of sugars. The content of units derived from aromatic diacids in the copolyester according to this invention is greater than 90% and less than 100%, preferably between 91 and 99%, and more preferably between 92 and 98% in mol, with respect to the total content of diacids in moles.
    [019] As far as you tell the units -O- (R11) -O- and -O- (R12) -O-, in the copolyester according to this invention, the diols are preferably selected from 1.2 -ethanediol, 1,2propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -decanediol, 1,11-undecanediol, 1,12dodecanediol, 1,13-tridecanediol, 1,4-cyclohexane-dimethanol, propylene glycol, neo-pentylglycol, 2-methyl-1,3-propanediol, dianhydro-sorbitol, dianhydro-mannitol, dianhydro-iditol, cycle
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    5/31 hexanediol, cyclohexane-methanediol, isosorbide and its derivatives, aromatic diols such as phenols, furanediol. Type C2-C10 diols are particularly preferred. C2C4 diols are even more preferred.
    [020] Among the diols, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and mixtures thereof are particularly preferred. Advantageously, said diols consist of at least 50%, preferably at least 80 mol% by 1.4 butanediol, with respect to the total diol content.
    [021] In addition to the base monomers, the copolyester may contain at least one hydroxy acid in an amount between 0-49%, preferably between 0-30% by mol, with respect to the moles of aliphatic dicarboxylic acid. Examples of suitable hydroxy acids are glycolic acid, hydroxy-caprylic acid, hydroxy-valeric acid, 7-hydroxy-heptanoic acid, 8-hydroxy-capranoic, 9-hydroxy-nonanoic acid, lactic acid or lactides. Hydroxy acids can be inserted into a chain as such or they can also be caused to react first with diacids or diols. Said hydroxy acids can be present with a distribution of repetitive units either random or in blocks.
    [022] Long molecules with two functional groups, including functional groups that are not in the terminal position, can also be added in amounts not exceeding 10%. Examples are dimeric acids, ricinoleic acid and acids incorporating epoxy groups and also polyoxyethylenes having a molecular weight between 200 and 10,000. [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 copolyester according to this invention, one or more molecules with multiple functional groups can also be advantageously added in amounts between 0.1 and 3 mol%, with respect to the amount of dicarboxylic acids (including hydroxy acids) in order to obtain branched products. Examples of these molecules are glycerol, pentaerythritol, trimethylol-propane, citric acid, dipentaerythritol, monoanhydrous-sorbitol, monoanhydro-mannitol, acid triglycerides,
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    6/31 polyglycerols, undecylenic acid, triethanolamine, 1,1,2-ethane-tricarboxylic acid; acid
    1,1,2,2-ethane-tetracarboxylic acid, 1,3,5-pentane-tricarboxylic acid, 1,2,3,4-cyclopentane-tetracarboxylic acid, malic acid, tartaric acid, 3-hydroxy-glutaric acid, musclic acid, trihydroxy-glutaric acid, hydroxy-isophthalic acid, hexanotriol, trimethyl-ethane, sorbitol, mannitol, 1,2,4-butanotriol, xylitol, 1,2,4,4-tetrakis (hydroxy-methyl) cyclohexane, arabitol, adonitol, iditol.
    [025] Although the copolyester according to the present invention achieves high performances without the need to add chain extenders, such as isocyanates and isocyanurates, epoxides and, in particular, oxazolines or carbodiimides polyepoxides, it is nevertheless possible to modify its properties according to need. [026] The increase in molecular weight of the copolyester can be obtained, advantageously, for example, through the addition of various organic peroxides during its extrusion processing. The increase in molecular weight of the copolyester can be easily detected by observing the increase in viscosity values following the processing of the polyesters with peroxides.
    [027] The molecular weight Mn of the copolyester according to this invention is preferably greater than 30,000. As far as the polydispersity index of the molecular weights, Mw / Mn, is concerned, it is preferably between 1.5 and 10, more preferably between
    1.5-7 and, more preferably, between 1.6 and 5, and, even more preferably, between 1.7 and 3.
    [028] The molecular weights Mn and Mw can be measured using Gel Permeation Chromatography (acronym, in English, GPC). The determination can be carried out with a chromatographic 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 the reference standard. [029] In the case of use for typical applications in plastic materials (such as, for example, bubble plastics, injection molding, foams, etc.), The Flow Rate of
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    7/31
    Fusion Mass (acronym, in English, MFR) of the copolyester according to the present invention is preferably between 1 and 500 g / 10 min, more preferably between 3 and 100 g / 10 min, and even more preferably , between 5 and 50 g / 10 min (measurement made at 190 ° C / 2.16 Kg according to ASTM D1238-89 Standard Test Method for Mass Flow Rates in Fusion of Thermoplastics by Extrusion Plastomer).
    [030] Preferably, the copolyester according to the invention has an inherent viscosity (measured with an Ubbelhode viscometer for o-cresol solutions at a content of 0.2 g / dL at 40 ° C), which is greater than than 0.4, preferably between 0.4 and 2, and more preferably 0.7 and 1.5 dL / g.
    [031] The copolyester according to the invention can be used in a mixture, which can also be obtained by reactive extrusion processes, with one or more polymers of synthetic or natural origin, which may or may not be biodegradable.
    [032] In the sense of this invention, biodegradable polymers are understood to mean biodegradable polymers according to the standard EN 13432.
    [033] In particular, the copolyester according to the invention can be used in admixture with diacid-diol, hydroxy-acid or polyester-ether type biodegradable polyesters. [034] As far as biodegradable polyesters of the diacid-diol type are concerned, they can be either aliphatic or aliphatic-aromatic.
    [035] Biodegradable aliphatic polyesters, from diacids-diols, comprise aliphatic diacids and aliphatic diols, while biodegradable aliphatic-aromatic polyesters have an aromatic part comprising mainly aromatic acids with multiple functional groups, of both synthetic and renewable origin, the aliphatic part being made up of aliphatic diacids and aliphatic diols.
    [036] Aliphatic-aromatic biodegradable polyesters from diacids-diols are preferably characterized by an aromatic acid content of between 30 and 90 mol%, preferably between 45 and 70 mol%, with respect to acid component.
    [037] Preferably aromatic acids with multiple functional groups of origin
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    Synthetic 8/31 are aromatic dicarboxylic compounds of the type of phthalic acid and its esters, preferably terephthalic acid.
    [038] Aromatic acids with multiple functional groups of renewable origin are preferably selected from the group comprising 2,5-furan-dicarboxylic acid and its esters.
    [039] Aliphatic-aromatic biodegradable polyesters from diacids-diols, where the aromatic diacid component comprises a mixture of aromatic acids with multiple functional groups of synthetic and renewable origin are particularly preferred. [040] 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, undecanoic acid, dodecanoic and brassic acid, their 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 acid, dodecanedioic acid and acid Brassyl and its mixtures are particularly preferred.
    [041] Examples of aliphatic diols in biodegradable polyesters, from diacids-diols, are: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,4-cyclo- hexane-dimethanol, neopentyl-glycol, 2-methyl-1,3-propanediol, dianhydro-sorbitol, dianhydro-mannitol, dianhydro-iditol, cyclohexanediol, cyclohexane-methanediol and mixtures thereof. Of these, 1,4-butanediol, 1,3propanediol and 1,2-ethanediol and mixtures thereof are particularly preferred.
    [042] Among biodegradable polyesters of the diacid-diol type, aliphatic / aromatic copolyesters, such as, for example, poly (butylene terephthalate co-sebacate), poly (butylene terephthalate co-azelate) copolymers, are particularly preferred, poly (butylene terephthalate-co-brassylate), poly (butylene terephthalate-co-adipate),
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    9/31 poly (butylene terephthalate-co-succinate) and poly (butylene terephthalate-co-glutarate), and aliphatic polyesters, such as, for example, poly (alkylene succinates) and succinate, and particularly poly (succinate) butylene) and its copolymers with adipic acid and lactic acid.
    [043] Preferably, the mixtures of copolymers according to the invention with biodegradable polyesters, from diacids-diols described above, are characterized by a content of said 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 copolyester according to the invention and the first, respectively.
    [044] In addition to this, the copolyester according to the invention can be mixed with more than one aliphatic-aromatic polyester having an aromatic part comprising mainly aromatic acids with multiple functional groups, of both synthetic and renewable origin or mixtures thereof.
    [045] Both binary and ternary mixtures of the copolyester according to the invention with said polyesters are also particularly preferred.
    [046] Preferred biodegradable polyesters from hydroxy acids include: poly (L-lactic acid), poly (D-lactic acid) and poly (DL-lactic acid) stereocomplexed, polyε-caprolactone, poly (hydroxy- butyrate), poly (hydroxy butyrate valerate), poly (hydroxy butyrate propanoate), poly (hydroxy butyrate hexanoate), poly (hydroxy butyrate decanoate), poly (hydroxybutyrate dodecanoate), poly (hydroxy butyrate hexadecanoate), poly (hydroxy-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 poly (L-lactic acid) and poly (Dlactic acid) stereocomplex.
    [047] Preferably, the mixtures of the copolyester according to the invention with the biodegradable polyesters from hydroxy acids described above are characterized by a content of said biodegradable polyesters, which varies within the range between 1 and 99%
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    10/31 by weight, more preferably between 5 and 95% by weight, with respect to the sum of the weights of the copolyester according to the invention and the first, respectively.
    [048] The copolyester according to the invention can also be used in a mixture with polymers of natural origin, such as, for example, starch, cellulose, chitin, chitosan, alginates, proteins, such as gluten, zein, casein, collagen , gelatine, natural rubbers, rosinic acid and its derivatives, lignins, such as purified, hydrolyzed and base treated lignins, etc., or their derivatives. Starches and celluloses can be modified and, among these, mention can be made, for example, of starch or cellulose esters having a degree of substitution between 0.2 and 2.5, hydroxy-propylated starches, modified starches with chains greases and cellophane. Starch mixtures are particularly preferred. Starch can also be used in either unstructured, gelatinized or filler forms. Starch can represent the continuous or dispersed phase and can be in a cocontinuous form. In the case of dispersed starch, the starch is preferably in the form of particles with an average diameter less than one micron and, more preferably, less than an average diameter of 0.5 pm.
    [049] The dimensions of the starch particles are measured in the cross section, with respect to the direction of the extrusion flow or, in any case, with respect to the direction of exit of the material. 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 portion of the sample, which must be examined, is then subjected to selective chemical attack, dried and a thin layer of metal is deposited over it, for example, a gold / palladium mixture, using a sputter. coater). Finally, the fracture surface is examined under a scanning electron microscope (English acronym, SEM). [050] The size of starch particles is determined by measuring the dimensions of the holes in the fracture surface after the selective chemical attack of the starch.
    [051] The average size of the starch particles, that is, the holes detectable on the
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    11/31 The chemically attacked 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 that corresponds 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:
    Equation 1:
    d = yj d { · d 2 in which dl is the smallest diameter and d2 is the largest diameter of the ellipse, in which the particle can be inscribed or approximated.
    [052] The selective chemical attack of the dispersed starch phase can advantageously be carried out with HCI 5 N, chemical attacker, with a chemical attack time of 20 minutes, at a chemical attack temperature of 25 ° C. Combinations containing unstructured starch are preferred.
    [053] Starches, such as potato and corn starch, capable of being easily destructible and having high initial molecular weights, have proved to be particularly advantageous.
    [054] The use of corn and potato starch is particularly preferred.
    [055] For unstructured starch, the teachings contained in documents EP-0 118 240 and EP-0 327 505 are referred to here, this being intended to be processed as processed starch, so that it substantially does not show Maltese crosses under the light optical microscope polarized and do not show ghosts under the phase-contrast optical microscope.
    [056] In addition, physically and chemically modified starch grades can be used, such as ethoxylated starches, oxypropylated starches, starch acetates, starch butyrates, starch propionates, with a degree of substitution within the range of 0, 1 and 2, cationic starches, oxidized starches, cross-linked starches, gelled starches. [057] Starch combinations, in which the starch represents the dispersed phase, can form
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    12/31 biodegradable polymeric compositions with good resistance to aging and moisture. In fact, these polymeric compositions can maintain a high resistance to tearing, even in low humidity conditions.
    [058] 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 this case, starting from pre-dried and pre-plasticized starch.
    [059] It may also be useful to degrade starch at a low molecular weight, before or during the formation of the composition with the polyesters of the present invention, in order to have, in the final material or in the finished product, an inherent viscosity of the starch 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.
    [060] Unstructured starch can be obtained before or during mixing with the polyesters according to the present invention, in the presence of plasticizers, such as glycerol, water, di- and poly-glycerols, ethylene or propylene glycol, ethylene and propylene diglycol , poly (ethylene glycol), poly (propylene glycol), 1,2-propanediol, trimethylol ethane, trimethylol propane, pentaerythritol, dipentaerythritol, sorbitol, erythritol, xylitol, mannitol, sucrose, 1,3-propanediol, 1,2-butanediol ,
    1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,2,6hexanotriol, 1,3,5-hexanotriol, neopentylglycol and prepolymers and poly (vinyl alcohol) polymers, polyols acetates, ethoxylates and propoxylates, in particular sorbitol ethoxylate, sorbitol acetate and pentaerythritol acetate.
    [061] Water can be used as a plasticizer, in combination with plasticizers with high boiling points, alone during the plasticization phase of the starch, before or during mixing of the composition and can be removed, at the necessary level, by degassing in one or more steps during extrusion. Upon completion of the plasticization and mixing of the components, the water is removed by degassing, to give a final content of about 0.2-3% by weight.
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    13/31
    [062] Water, as well as high boiling point plasticizers, changes the viscosity of the starch phase and affects 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 values (acronym, in English, HLB) greater than 8, and that are obtained from polyols and mono- or polycarboxylic acids with pK dissociation constants more casualties than
    4.5 (the value refers to the pK of the first carboxyl group, in the case of polycarboxylic acids);
    - Esters with HLB 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 to the pK of the first carboxylic group, in the case of polycarboxylic acids);
    - Esters with HLB values less than 5.5, obtained from polyols and fatty acids with 12-22 carbon atoms.
    [063] These compatibilizers can be used in amounts from 0.2 to 40% by weight and, preferably, from 1 to 20% by weight, related 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.
    [064] Examples are starch / polyester copolymers via transesterification catalysts. Such polymers can be generated through reactive combination during the formation of the composition 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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    14/31
    [065] All of the above products can help to create the necessary microstructure.
    [066] 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 Mn and MFI 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.
    [067] Another method to improve the microstructure is to achieve the starch complexation in the starch-polyester mixture.
    [068] 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-0 965 615 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.
    [069] Advantageously, starch combinations contain at least one plasticizer for 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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    15/31 plasticizers are also preferred.
    [070] 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.
    [071] In addition to water, plasticizers, which can be used in the compositions according to the invention, are plasticizers with high boiling points or polymeric.
    [072] In the sense 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.
    [073] 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, which become necessary for cleaning the machines, during the processing of the composition.
    [074] In the sense of the present patent application, with the word diglycerol are understood here all compounds that are derived from condensation reactions of two glycerol molecules, such as alpha-alpha-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.
    [075] Combinations of water-containing starches are also preferred as the only
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    16/31 plasticizer. Among these, mixtures containing the water present in the native starch as the only plasticizer are particularly preferred.
    [076] Preferably, the copolyester mixtures according to the invention with the polymers of natural origin described above are characterized by a content of 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 copolyester according to the invention and the first, respectively.
    [077] The copolyester according to the invention can also be used in a mixture with polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, polyurethanes, polyamides, poly (amino acids), polyethers, polyureas, polycarbonates and mixtures of themselves.
    [078] Among polyolefins, polyethylene, polypropylene, their copolymers, poly (vinyl alcohol), poly (vinyl acetate), poly (ethyl vinyl acetate) and poly (ethylene - vinyl alcohol) are preferred.
    [079] 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 furanodicarboxylate), poly (furene-butylene dicarboxylate) and mixtures thereof are preferred.
    [080] 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.
    [081] Polycarbonates can be poly (ethylene carbonates), poly (propylene carbonates), butylene polycarbonates) and their mixtures and copolymers.
    [082] 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.
    Petition 870190130695, of 12/09/2019, p. 28/50
    17/31
    [083] Preferably, the mixtures of the copolyester according to the invention with the polymers described above (polyolefins, non-biodegradable polyesters, polyester- and polyetherurethanes, polyurethanes, polyamides, poly (amino acids), polyethers, polyureas, polycarbonates and mixtures are characterized by a content of the polymers ranging from 0.5% to 99% by weight, more preferably from 5% to 50% by weight, with respect to the sum of the copolyester weights according to invention and the first, respectively. [084] The copolyester 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 larger module 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.
    [085] 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.
    [086] The dimensions of such particles are measured according to the measurement method described above for starch particles.
    [087] Among the rigid polymers, poly (hydroxy alkanoates), such as poly (lactic acid) and poly (glycolic acid), and, more preferably, polymers or copolymers of poly (lactic acid) containing at least 75 are particularly preferred. % L-lactic or D-lactic acid or combinations thereof, advantageously, with molecular Mw greater than 70,000. Such rigid polymers can also be plasticized.
    [088] The selective chemical attack of dispersed phase of poly (lactic acid) can be advantageously carried out with acetone as the attacker, with a chemical attack time of 5 minutes, at a chemical attack temperature of 25 ° C.
    [089] The copolyesters according to the 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
    Petition 870190130695, of 12/09/2019, p. 29/50
    18/31 particularly preferred.
    [090] The combinations of the copolyester 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.
    [091] Combinations of the copolyester 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 stiffness - which makes these combinations particularly suitable for injection molding and extrusion.
    [092] In order to improve the transparency and 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, propanediol, butanediol, and, as acids: azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid and combinations thereof.
    [093] To maximize the compatibility between the copolyester 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 chain extenders, capable of reacting with hydroxyl groups, such as diisocyanates. Examples are 1.6 diisocyanate
    Petition 870190130695, of 12/09/2019, p. 30/50
    19/31 hexamethylene, 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 (e.g., 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.
    [094] 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.
    [095] The mixture according to the present invention can be advantageously combined also with nucleating agents and fillers, both organic and inorganic in nature.
    [096] 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, isobacteriodorine , porphyrinogen, forbine, isotactic polypropylene, low molecular weight PLA and PBT.
    [097] The preferred amount of fillers is in the range of 0.5% - 70% by weight, preferably 5% - 50% by weight.
    [098] 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.
    [099] 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, may be mentioned nm, and, even more preferably, less than 50 nm. They are particularly
    Petition 870190130695, of 12/09/2019, p. 31/50
    Preferred 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.
    [0100] The combinations comprising the copolyester according to the present invention can be prepared by means of an extruder or any other machine capable of providing temperature and shear conditions, which allow homogeneous mixing of the components.
    [0101] The combinations are advantageously obtainable by a process of reactive extrusion 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.
    [0102] 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, 2,5dimethyl-2,5-di (t-butyl-peroxy) -hexane, t-butyl peroxide and cumila, di-t-butyl peroxide,
    2,5-dimethyl-2,5-di (t-butyl-peroxy) -hex-3-yn, di (4-t-butyl-cyclohexyl) peroxy-dicarbonate, dicetyl peroxy-dicarbonate, peroxides dimyristyl dicarbonate, 3,6,9-triethyl-3,6,9-trimethyl1,4,7-triperoxonane, di (2-ethylhexyl) peroxydicarbonate and mixtures thereof.
    [0103] 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.
    [0104] 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 weight range
    Petition 870190130695, of 12/09/2019, p. 32/50
    21/31 molecular 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 comprising: diglycidyl diethylene glycol ether, diglycidyl polyether (ethylene glycol), glycerol poly (glycidyl ether), diglycerol poly (glycidyl ether), 1,2-epoxy-butane, polyglycerol poly (glycidyl ether), isoprene diepoxide, and cycloaliphatic diepoxide, diglycidyl ether of 1, 4cyclohexane-dimethanol, glycidyl 2-methyl-phenyl-ether, glycerol propoxylate triglycidyl ether, 1,4-butane-diol diglycidyl ether, sorbitol poly (glycidyl ether), glycerol diglycidyl ether, meta-tetraglycidyl ether -xylene-diamine and diglycidyl bisphenol A ether, and mixtures thereof.
    [0105] 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.
    [0106] 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.
    [0107] Examples of carbodiimides, which can be used advantageously, are selected from the group comprising: poly (carbodiimide acid-octylene), poly (1,4-dimethylene 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-tri-isopropyl-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 ^ S'-dimetM ^ '- diphenyl-methane carbodiimide), poly (carbodi-imi naphthylene da), poly (carbodiimide isophorone), poly (cumene carbodiimide), p
    Petition 870190130695, of 12/09/2019, p. 33/50
    22/31 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.
    [0108] 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.
    [0109] Thanks to its characteristics, the copolyester according to the invention is extremely suitable for the production of mono- and bi-oriented films, as well as fibers, whether spunbond or meltblown.
    [0110] The copolyester according to the present invention is also particularly suitable, alone or in a mixture with other polymers, for use in many practical applications, such as films, injection molded articles, extrusion coatings, fibers, foams, articles thermoformed, etc.
    [0111] In particular, copolyester and its mixtures 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;
    - cling films for use with foodstuffs, for bales in agriculture and for wrapping waste;
    - bags and liners for containers for organic collection, such as the collection of food waste and garden waste;
    - 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;
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    23/31
    - expanded or expandable accounts for the production of parts obtained by sintering;
    - expanded and semi-expanded products, including foam blocks formed using pre-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 constitutes rigid polymers, such as PLA, PET, PTT, and the outer skin constitutes the biodegradable polyester according to the invention, combined composite fibers, fibers with different cross sections, circular to multilobulated, staple fibers, woven and non-woven textile items or spunbond, meltblown or heat-bonded textile items for application in sanitary and hygiene products, and in the agriculture and clothing sectors.
    [0112] They can also be used in applications as a substitute for plasticized PVC.
    [0113] The copolyester production process according to this invention takes place according to any of the processes known in the art. In particular, copolyester can be advantageously obtained by means of a polycondensation reaction.
    [0114] Advantageously, the copolyester polymerization process can be carried out in the presence of a suitable catalyst. Among such suitable catalysts, mention may be made, for example, of organo-metallic tin compounds, for example, those derived from stanoic acid, titanium compounds, such as ortho-butyl titanate, aluminum compounds, such as Al-triisopropyl, and antimony and zinc compounds.
    [0115] Although the copolyester according to the present invention exhibits properties
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    24/31 high mechanics, the technician specialized in the subject will be easily able to even improve them, for example, increasing its percentage of crystallinity. For example, such an increase can be achieved by stretching annealing or simply modulating the cooling rate of the polymer after its preparation.
    [0116] Generally, the polymers of the invention are characterized by a glass transition temperature between 0 ° C and + 60 ° C, preferably between 5 ° C and 40 ° C, and more preferably between 10 ° C and 30 ° C; melting points between 150-170 ° C are preferred. After annealing for 12 to 18 hours, in a temperature range of 60-80 ° C, the tensile properties are preferably as follows: tensile strength> 50MPa, elongation at break> 200%, Young's modulus included between 1,000 MPa 1,900 MPa, measured according to the ASTM D638 standard.
    [0117] Preferably, the copolyester according to the present invention is obtainable by reacting at least one precursor polyester, having at least one acid component and at least one diol component, with compounds bearing groups that can react with OH groups and / or COOH, such as, for example, polyepoxides and polycarbodiimides or with free radical initiators.
    [0118] Said compounds can also be used in a mixture.
    [0119] The at least one precursor copolyester can be of the aliphatic, aromatic or aliphatic-aromatic type.
    [0120] 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 copolyesters in order to obtain the desired copolyester.
    [0121] Preferably, the copolyester according to the present invention is obtainable by a reactive extrusion process.
    [0122] Among the free radical initiators, peroxides are preferred and, among peroxides, organic peroxides are particularly preferred. Organic peroxides can be selected, advantageously, from the group consisting of: peroxide
    Petition 870190130695, of 12/09/2019, p. 36/50
    25/31 benzoyl, lauroyl peroxide, isononanoyl peroxide, di (t-butyl-peroxy-isopropyl) benzene, t-butyl peroxide, dicumyl peroxide, alpha z alpha , -di (t-butyl-peroxy) - diisopropylbenzene, 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-yn, di (4-t-butylcyclohexyl) peroxy-dicarbonate, dicetyl peroxy-dicarbonate, dimyristyl peroxy-dicarbonate, 3,6,9-triethyl -
    3,6,9-trimethyl-l, 4,7-triperoxonane, di (2-ethylhexyl) peroxydicarbonate and mixtures thereof.
    [0123] Preferably, such peroxides are added to at least one precursor polyester in an amount of less than 0.1%, more preferably, 0.05% and, even more preferably, 0.02% by weight.
    [0124] Examples of polyepoxides, which can be used advantageously, are all polyepoxides from epoxidized oils and / or from styrene - glycidyl ether methyl methacrylate, such as products distributed by BASF Resins BV, under the trademark Joncryl® ADR, glycidyl ether methyl methacrylate included in a range of molecular weights 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, diglycidyl ether of 1,4cyclohexane-dimethanol, glycidyl 2-methyl-phenyl-ether, triglycidyl glycerol propoxylate ether, diglycidyl 1,4-butane-diol ether, poly (glycidyl ether) of sorbitol, diglycidyl ether glycerol, tetraglycidyl ether of meta-xylene-diamine and diglycidyl ether of bisphenol A, and mixtures thereof.
    [0125] Preferably, such polyepoxides are added to at least one precursor polyester in an amount of less than 2%, more preferably 1%, and even more preferably 0.75% by weight.
    [0126] Catalysts can also be used to increase the reactivity of groups
    Petition 870190130695, of 12/09/2019, p. 37/50
    26/31 reactive. In the case of polyepoxides, for example, fatty acid salts can be used. Calcium and zinc stearates are particularly preferred.
    [0127] Examples of carbodiimides, which can be used to advantage, are selected from the group comprising: poly (carbodiimide acid-octylene), poly (1,4-dimethylene 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-tri-isopropyl-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 carb diimide), 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.
    [0128] Preferably, such carbodiimides are added to at least one precursor polyester in an amount of less than 1.5%, more preferably, 0.75% and, even more preferably, 0.5% in Weight.
    [0129] Such at least one precursor copolyester preferably has an installation content of 0.05 - 0.8 and, more preferably, 0.1 - 0.7 mole%.
    [0130] Such unsaturations can be generated in situ during the polymerization phase or during the processing of at least one precursor copolyester, through the addition of suitable unsaturated monomers or suitable unsaturated chain terminators. [0131] Particularly preferred are precursor polyesters with terminal unsaturation. [0132] Among unsaturated chain terminators, those presenting the
    Petition 870190130695, of 12/09/2019, p. 38/50
    27/31 formula:
    Formula 2:
    T- (CH2) n-CH = CH2 in which T is a group capable of reacting with carboxylic and / or hydroxy groups and n is an integer between 0 and 13.
    [0133] Such unsaturated chain terminators can also be used in admixture.
    [0134] 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.
    [0135] Preferably, the integer n 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 naturally occurring polymers.
    [0136] Also after the preparation process, the copolyester 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.
    [0137] The presence of unsaturation and / or addition products that are derived from their reaction with free radical initiators can be determined with different methods well known to those skilled in the art, such as NMR spectroscopy or by reactions of polymer chain methanolysis coupled with chromatographic methods combined with mass spectroscopy.
    [0138] The technician specialized in the subject will be easily able to identify structures referable to either their unsaturation or to the reacted installation after the reaction.
    [0139] Preferably, the copolyester according to the present invention is obtainable through a reactive extrusion process starting from a precursor polyester having a content in terminal acid groups in amounts of 35 -150 meq KOH / Kg of precursor polyester.
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    28/31
    [0140] 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 50 ml flask. 35 mL of a 70% cresol / 30% chloroform mixture is added to dissolve the resin. After complete dissolution, the solution is allowed to cool and then 5-6 drops of a 0.1% solution in a-naphtholphthalein ethanol are added.
    [0141] The solution thus obtained is titrated with a previously standardized KOH / benzyl alcohol solution, using an α-naphtholphthalein indicator for determining the titration equivalence point.
    [0142] The content in terminal acid groups is calculated from the consumption of the KOH / benzyl alcohol solution, based on the following equation:
    Equation 2:
    Content in terminal acid groups (meq KOH / Kg of polymer) .ίΚ- ^ Μ'ΟΟΟ
    P in which:
    Veq = mL of KOH / benzyl alcohol solution at the equivalence point for sample titration;
    Vb = mL of KOH / benzyl alcohol solution at the equivalence point of the blank titration;
    T = concentration in moles / L of the KOH / benzyl alcohol solution;
    P = g of sample.
    [0143] The invention will now be illustrated by some modalities provided by way of example and without restricting the scope of protection of this patent application.
    Example 1
    [0144] Synthesis of polybutylene (furan-dicarboxylate-co-sebacate) containing 92 mol% of butylene-furan dicarboxylate units.
    [0145] Next, they were placed in a two-way glass reaction vessel equipped with a Teflon propellant stirrer, a nitrogen connection and a condenser
    Petition 870190130695, of 12/09/2019, p. 40/50
    29/31 water connected to a distillate collection test tube:
    2,5-furan-dicarboxylic acid dimethyl ester (DMFD): 60.4 g (0.328 moles)
    Sebacic acid: 5.8 g (0.028 moles)
    Butanediol: 45.0 g (0.5 moles)
    Esterification stage
    [0146] The flask was immersed in a thermostatic oil bath up to a temperature of 180 ° C, maintaining agitation at 400 rpm.
    [0147] Water and methanol are distilled off during the reaction. The distillation was allowed to proceed for 30 minutes, after which 100 ppm of tetraorto-butyl titanate (Tyzor® TnBT, marketed by DuPont) was added as an esterification catalyst and the temperature of the oil bath was gradually increased to 235 ° C over the course of two hours and 30 minutes. The conversion achieved, calculated from the ratio between the amount of distillates recovered during the reaction and the amount that could theoretically be obtained from them, was> 95%.
    Polycondensation Stage
    [0148] The water cooler was subsequently replaced by an air cooler equipped with a graduated conical bottom test tube for the collection of distillates and an additional 1,000 ppm of Tyzor® TnBT was added as a polycondensation catalyst. The pressure was reduced to 1 mbar over a period of approximately 10 minutes.
    [0149] The reaction was then continued for 4 hours, raising the oil temperature to 245 ° C.
    [0150] A product with an MFR (190 ° C, 2.16 Kg) = 12.6 g / 10 minutes was obtained.
    [0151] The product was analyzed using a PerkinElmer DSC differential scanning calorimeter, obtaining the following results:
    Tm = 154 ° C,
    AHf = 19.0 J / g,
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    Tg = 21 ° C.
    [0152] The polymer was subsequently characterized with respect to its mechanical properties according to the ASTM D638 standard (see Table 1).
    Example 2
    [0153] Using the equipment and operating conditions according to Example 1, a polybutylene (furan-dicarboxylate-co-sebacate) was prepared, containing 97 mol% of butylene-furan dicarboxylate units.
    [0154] The polymer was characterized with respect to its mechanical properties according to the ASTM D638 standard (see Table 1).
    Comparative Example 1
    [0155] Using the equipment and operating conditions according to Example 1, a polybutylene (furan-dicarboxylate-co-sebacate) was prepared, containing 85 mol% of butylene-furan dicarboxylate units.
    [0156] The polymer was characterized with respect to its mechanical properties according to the ASTM D638 standard (see Table 1).
    Table 1
    Mole% of butylene-furan dicarboxylate units 85 92 97 Yield resistance (MPa) 15 24.5 19 Tensile strength (MPa) 51 52 60 Elongation at break (%) 420 380 380 Elastic modulus (MPa) 240 610 600
    Example 3
    [0157] The copolyesters according to Examples 1 and 2 and Comparative Example 1 were annealed for 18 hours at 80 ° C. After annealing, copolyesters were characterized with respect to their mechanical properties according to the ASTM D638 standard (see Table 2).
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    Table 2
    Mole% of butylene-furan dicarboxylate units 85 92 97 Yield resistance (MPa) 23 30 60 Tensile strength (MPa) 57 54 59 Elongation at break (%) 440 360 275 Elastic modulus (MPa) 490 1,550 1,850
    Petition 870190130695, of 12/09/2019, p. 43/50
    权利要求:
    Claims (15)
    [1]
    Claims
    1. Aliphatic-aromatic copolyester, characterized by comprising the following repetitive units, which comprise a dicarboxylic component and a dihydroxy component:
    - [- O— (Ri i) —O — C (O) - (Rb) —C (O) -] - - [- O— (R 12 ) —O — C (O) - (R ] 4 ) —C (O) -] - in which the dihydroxy component comprises units of -O- (R11) -O- and -O- (R12) 0- which are derived from diols, where R11 and R12 are equal or different and are selected from the group comprising C2-C14-alkylene, C5-C10-cycloalkylene, C2-C12-oxyalkylene, heterocyclics and mixtures thereof, said diols comprising at least 50 mol% of 1,4 butanediol, with respect to the total content of diols, the dicarboxylic component comprising units of -C (0) - (R13) -C (0) - which are derived from aliphatic diacids and units of -C (O) - (R14 ) -C (O) - which are derived from aromatic diacids, with R13 being selected from the group comprising C0-C20 alkylene and mixtures thereof, with aromatic diacids comprising acid
    [2]
    2,5-furan-dicarboxylic of renewable origin and the molar percentage of aromatic diacids is greater than 90% and less than 100% of the dicarboxylic component.
    2. Aliphatic-aromatic copolyester according to claim 1, characterized in that the molar percentage of the aromatic diacids is between 91 and 99%.
    [3]
    3. Aliphatic-aromatic copolyester, according to claim 2, characterized in that the molar percentage of the aromatic diacids is between 92 and 98%.
    [4]
    4. Aliphatic-aromatic copolyester according to any one of the preceding claims, characterized in that the aliphatic diacid has a number of C atoms in the main chain, between 2 and 22.
    [5]
    5. Aliphatic-aromatic copolyester according to claim 4,
    Petition 870190130695, of 12/09/2019, p. 44/50
    2/4 characterized by the aliphatic diacids being selected from the group comprising succinic acid, adipic acid, pyelic acid, submeric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassyl acid and octadecanedioic acid.
    [6]
    Aliphatic-aromatic copolyester according to any one of the preceding claims, characterized in that the aromatic diacids are mixtures of phthalic acid and its esters and 2,5-furan-dicarboxylic acid.
    [7]
    7. Aliphatic-aromatic copolyester according to any one of the preceding claims, characterized in that it is used in admixture with one or more polymers.
    [8]
    8. Mixture of aliphatic-aromatic copolyester, according to claim 7, characterized in that the polymer is biodegradable.
    [9]
    Mixture according to claim 8, characterized in that the biodegradable polymer is a biodegradable polyester of the diacid-diol type, from hydroxy acid or of the poly (ester-ether) type.
    [10]
    Mixture according to claim 9, characterized in that the biodegradable polyester of the diacid-diol type is aliphatic.
    [11]
    Mixture according to claim 9, characterized in that the biodegradable polyester of the diacid-diol type is aliphatic-aromatic.
    [12]
    Mixture according to claim 9, characterized in that the biodegradable polyester from hydroxy acid is poly (L-lactic acid), poly (D-lactic acid) and poly (DL-lactic acid) stereocomplexed, ροΐϊ-ε- caprolactone, poly (hydroxybutyrate), poly (hydroxy-butyrate valerate), poly (hydroxy-butyrate propanoate), poly (hydroxybutyrate hexanoate), poly (hydroxy-butyrate decanoate), poly (hydroxy-butyrate dodecanoate), poly (hydroxy-butyrate) hexadecanoate), poly (hydroxy-butyrate octadecanoate) and poly (3-hydroxybutyrate-4-hydroxy-butyrate).
    [13]
    13. Mixture according to claim 8, characterized in that the
    Petition 870190130695, of 12/09/2019, p. 45/50
    3/4 polymer be starch, cellulose, chitin, chitosan, alginates, proteins, natural rubbers, rosinic acid and its derivatives, lignins, such as purified, hydrolyzed, basified lignins or their derivatives.
    [14]
    Mixture according to claim 8, characterized in that the polymer is a polyolefin, a non-biodegradable polyester, a polyester- and polyetherurethane, a polyurethane, a polyamide, a poly (amino acid), a polyether, a polyurea, a polycarbonate and mixtures thereof.
    [15]
    15. Use of the copolyester according to any one of claims 1 to 7 and the mixture according to any one of claims 8 to 14, 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, such as films for use in vegetation cover;
    - cling films for use with foodstuffs, for bales in agriculture and for wrapping waste;
    - bags and liners for containers for collecting organic waste, such as the collection of food waste and garden waste;
    - 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;
    Petition 870190130695, of 12/09/2019, p. 46/50
    4/4
    - expanded and semi-expanded products, including foam blocks formed using pre-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 and the wrap is made up of biodegradable polyester according to the invention, combined composite fibers, fibers with different sections, staple fibers, woven and non-woven textile items or textile items spunbond, meltblown or heat-bonded for application in sanitary and hygiene products, and in the agriculture and clothing sectors.
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    同族专利:
    公开号 | 公开日
    CN102933635B|2016-11-09|
    CN102933635A|2013-02-13|
    IT1400121B1|2013-05-17|
    CA2797945C|2018-12-18|
    CA2797945A1|2011-12-01|
    ES2574307T3|2016-06-16|
    ITMI20100932A1|2011-11-25|
    US20130071588A1|2013-03-21|
    BR112012028012A2|2018-05-15|
    EP2576653A1|2013-04-10|
    KR20180063907A|2018-06-12|
    KR20130118221A|2013-10-29|
    US9676902B2|2017-06-13|
    EP2576653B1|2016-03-02|
    WO2011147806A1|2011-12-01|
    KR102103095B1|2020-04-22|
    PL2576653T3|2016-08-31|
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    法律状态:
    2018-05-29| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-04-07| B09A| Decision: intention to grant|
    2020-06-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI2010A000932|2010-05-24|
    ITMI2010A000932A|IT1400121B1|2010-05-24|2010-05-24|ALIPHATIC-AROMATIC COPOLIESTERE AND ITS BLENDS.|
    PCT/EP2011/058422|WO2011147806A1|2010-05-24|2011-05-24|Aliphatic-aromatic copolyesters and their mixtures.|
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