MXPA00012018A

MXPA00012018A - High barrier polyester / phenylenedi (oxyacetic acid) polyester blends

Info

Publication number: MXPA00012018A
Application number: MXPA/A/2000/012018A
Authority: MX
Inventors: David R Fagerburg; Martin E Rogers; Robert B Barbee; Timothy E Long
Original assignee: Eastman Chemical Company
Priority date: 1998-06-15
Filing date: 2000-12-04
Publication date: 2001-11-21

Abstract

The invention concerns polyester blend compositions comprising:(1) from about 5 to about 85 weight%of a polyester which is the reaction product of:(A) a repeat unit of phenylenedi(oxyacetic acid) represented by formula (I), wherein R1, R2, R3 and R4 each independently represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a phenyl group, a chlorine atom, a bromine atom, or a fluorine atom, or an ester derivative of phenylenedi(oxyacetic acid) of the formula (I);(B) a repeat unit of a diol containing up to 24 carbon atoms;and (2) from about 95 to about 15 weight%of a thermoplastic polyester of poly(ethylene terephthalate), a copolyester of poly(ethylene terephthalate) modified with from greater than 0 to about 70 mole%of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1,4-cyclohexanedimethanol, and/or a dicarboxylic acid comprising isophthalic acid or naphthalenedicarboxylic acid, or a mixture of the poly(ethylene terephthalate)copolyesters with poly(ethylene terephthalate);from about 95 to about 15 weight%of a polyester of poly(ethylene naphthalate), a poly(ethylene naphthalate) copolyester modified with from greater than 0 to about 30 mole%of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1, 4-cyclohexanedimethanol, and/or a dicarboxylic acid comprising isophthalic acid or terephthalic acid, or a mixture of the poly(ethylene naphthalate) copolyester with poly(ethylene naphthalate);from about 95 to about 15 weight%of poly(butylene terephthalate);from about 95 to about 15 weight%of poly(trimethylene terephthalate);or from about 95 to about 15 weight%of poly(butylene naphthalate).

Description

HIGH BARRIER / POLYESTER POLYESTER MIXTURES FENILENEDI (OXYACTIC ACID) This application claims the benefit of ..as Provisional Applications of the United States of America number 60 / 089,220, filed June 15, 1998, 60 / 089,221, filed June 15, 1998, and 60 / 089,391, filed June 15, 1998. This invention relates to polyester compositions which have improved barrier properties. These novel polyester blends comprise repeated units of phenylendi (oxyacetic acid). Such polyesters with improved gas barrier properties are useful in packaging applications where low gas permeability is required for the protection or preservation of the contents. Phenylendi (oxyacetic acid) can be prepared by several methods. U.S. Patent Nos. 4,238,625 and 4,935,540 describe a method for preparing phenylendi (oxyacetic acid) through the oxidation of aploxyethanols. Japanese Patents 3204833, 4091052 and 4173765 describe the preparation of phenylendi (oxyacetic acid) from resorcmol and chloroacetic acid. U.S. Patent 4,440,922 describes polyester homopolymers made from phenylendi (oxyacetic acid). However, homopolymers made from phenylendi (oxyacetic acid) are amorphous and have low glass transition temperature making these polyesters difficult to dry. These polyesters have low elongation and are therefore brittle. In general, homopolymers made from phenylendi (oxyacetic acid) are not suitable for use as monolayers in rigid containers. U.S. Patent Nos. 4,440,922, 4,552,948, 4,663,426 and 5,030,705 describe the use of copolyesters containing phenylendi (oxyacetic acid) for containers. These copolyester has low permeability. However, due to their high level of modification, these copolyesters are difficult to crystallize. The poor crystallization behavior of these copolyesters makes them difficult to dry and limits the amount of crystallization induced by the deformation that occurs during the manufacture of the container. The low levels of crystallinity in the containers very often result in poorer mechanical properties and a lower gas barrier. U.S. Patent 5,239,045 discloses copolyesters containing terephthalic acid, ethylene glycol and 0.5 to 4.5 mol% of phenylendi (oxyacetic acid). The gas barrier properties of these of these copolyesters are not sufficient to meet the requirements of many container applications including small soft drink and beer containers. U.S. Patent 4,959,421 discloses mixtures of PET with copolyesters containing isophthalic acid, naphthalenedicarboxylic acid and phenylendi (oxyacetic acid). In these gas barrier materials described in the aforementioned specification, the barrier level is low and to be able to produce a vessel having a sufficient gas barrier property, it is thus necessary to make the barrier layer 1 thick. The total thickness of the container, therefore, is inconveniently increased. The aforementioned prior art references comprising phenylendi (oxyacetic acid) exhibit deficient gas barrier and / or crystallinity properties. The present invention solves the problems of poor gas barrier and crystallization properties by providing a novel polyester blend comprising phenylendi (oxyacetic acid) with improved barrier properties The present invention provides polyester blend compositions, Methods and articles of manufacture In one embodiment, the invention provides a polyester blend composition comprising: 1. From about 5 to about 85% by weight of a polyester which is the product of the reaction of: (A) a unit of phenylenylene (oxyacetic acid) represented by formula (I). ) wherein R1, R2, R3 and R4 each independently represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy groups having de. ' to 6 carbon atoms, a phenyl group, a chlorine atom, a bromine atom, or a fluorine atom, or an ester derived from phenylendi (oxyacetic acid) of the formula I; (B) a repeating unit of a diol containing up to 24 carbon atoms; and II. from about 95 to about 15% by weight of a poly (ethylene terephthalate) thermoplastic polyester, a modified poly (ethylene terephthalate) copolyester of from greater than 0 to about 70 mol% of a glycol comprising diethylene glycol, propanediol, butanediol , hexanediol or 1,4-cyclohexanedimethanol, and / or dicarboxylic acid comprising isophthalic acid or naphthalenedicarboxylic acid, or a mixture of the poly (ethylene terephthalate) copolyethers with polyethylene terephthalate; from about 95 to about 15% by weight of a poly (ethylene naphthalate) polyester, a modified poly (ethylenic naphthalate) copolyester with more than 0 to about 30 mol% of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1,4-cyclohexanedimethanol, and / or a dicarboxylic acid comprising isophthalic acid or terephthalic acid, or a mixture of the copolyester poly (ethylene naphthalate) with poly (ethylene naphthalate); from about 95 to about 15% by weight of poly (butylene terephthalate); from about 95 to about 15% by weight of poly (trimethylenic terephthalate); or from about 95 to about 15% by weight poly (butylene) naphthalate. In another embodiment the invention provides a method for producing a polyester blend comprising: mixing from about 5 to about 85% by weight of a polyester I and from about 95 to about 15% by weight of the polyester II, wherein the polyester I comprises: (A) a repeated unit of phenylendi (oxyacetic acid) m wherein R1, R2, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a chlorine atom, a bromine atom, or a fluorine atom, or an ester derived from phenylendi (oxyacetic acid) of the formula I; (B) a repeating unit of a diol containing up to 24 carbon atoms; and the polyester II comprises a poly (ethylene terephthalate) thermoplastic polyester, a copolyether of poly (ethylene terephthalate) modified with more than 0 to about 70 mol% of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1,4 -cyclohexanedimethanol, and / or dicarboxylic acid comprising isophthalic acid or naphthalenedicarboxylic acid, or a mixture of the copolyester poly (ethylene terephthalate) with poly (ethylene terephthalate); a poly (ethylene naphthalate) polyester, a copolyether of polyethylene naphthalate modified with more than 0 to about 30 mol% of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1/4-cyclohexanedimethanol, and / or a dicarboxylic acid comprising isophthalic acid or terephthalic acid, to a mixture of the copolyester poly (ethylene naphthalate) with poly (ethylene naphthalate); a poly (butylene terephthalate); a poly (trimethylenic terephthalate); or a poly (butylenic naphthalate). Additional advantages of the invention will be established in the following description, and in part will be obvious from the description or can be learned by practicing the invention. The advantages of the invention will be obtained by means of the elements and combinations particularly mentioned in the appended claims. It will be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and should not be taken as restrictive of the invention., as claimed. The present invention can be more easily understood by reference to the following detailed description of the preferred embodiments of the invention and the examples thereof. It should be noted that, as used in the specification and appended claims, the singular forms "a" and "an" and "the" include plural references unless the context clearly dictates otherwise. Ranges are very often expressed here as "approximately" a particular value, and / or as "approximately" another particular value. When such a range is expressed, another modality includes from a particular value and / or up to the other particular value. Similarly, when the values are expressed as approximations, by using the "approximately" antecedent, it should be understood that the particular value forms another modality. A weight percent of a component, unless otherwise specified, is based on the total weight of the formulation or composition in which the component is included. With respect to polyesters,% mol is based on 100 mol% of diacid and 100 mol% of diol, for a total of 200 mol%. "Optional" or "optionally" means that the c = iso or circumstance subsequently described may or may not occur, and that the description includes examples where said case or circumstance occurs and cases where it does not. For example, the phrase "optionally substituted lower alkyl" means that the alkyl group can or can not be substituted and that the description includes both unsubstituted lower alkyl and lower alkyl where there is a substitution. The term "adjacent" means that the layers in multilayer structures are close to one another, and may or may not imply that the layers are in direct contact with each other. The term "contact" means that the layers in the multilayer structure touch each other, and are not separated by an intermediate layer. Preferred phenylenyl (oxyacetic acids) of the formula (I) include 1,2-phenylendi (oxyacetic acid), 1,3-phenylendi (oxyacetic acid), 1,4-phenylendi (oxyacetic acid), 2-methyl-1, 3-Phenylenylene (oxyacetic acid), 5-methyl-1,3-phenylendi (oxyacetic acid), 4-methyl-1,3-phenylenedia (oxyacetic acid), 5-ethyl-1, 3-phenylenedia (oxyacetic acid ), 4-eti.l-1, 3-phenylendi (oxyacetic acid), 5-methoxy-l, 3-phenylendi (oxyacetic acid), 4-methoxy-1, 3-phenylendi (oxyacetic acid), 4- chloro-1, 2-phenylendi (oxyacetic acid), or 4-chloro-l, 3-phenylendi (oxyacetic acid), or an ester thereof. An even more preferred phenylenylene (oxyacetic acid) of the formula (I) includes a 1,2-phenylenedi derivative (oxyacetic acid), 1,3-phenylendi (oxyacetic acid), or 1,24-phenylendi (oxyacetic acid), or an ester of these. The phenylendi (oxyacetic acids) as the dicarboxylic acid component (IA) in the present invention can be used as a raw material of a polyester of the present invention in the form of an acid itself or in the form of an ester which forms a derivative as an acid halide and an ester, in particular, an ester forming a derivative such as the alkyl ester of C? _4 phenylendi (oxyacetic acid). Alternatively, an oligomer obtained by the reaction of a phenylendi (oxyacetic acid) with a glycol can be used for the polymerization. The polyester component I is present in the range of from about 5 to about 85% by weight of the blend composition, more preferably from about 5 to about 60% by weight of the blend composition, and more preferably from about 5 to about 40% by weight of the blend composition. As the diol component (IB) for the polyester of the present invention, typical diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, clohexanedimethanol , 1,3-bis (2-hydroxyethoxy) benzene, or diethylene glycol, or a derivative of an aromatic dihydroxy compound. A preferable diol component is ethylene glycol, and typically aromatic hydroxy derivatives include resorcinol, hydroquinone, Bisphenol A, or Bisphenol S. The polyester component II is present in the range of about 95 to about 15% by weight of the composition of mixture, more preferably from about 95 to about 40% by weight of the blend composition, more preferably from about 95 to about 60% by weight of the blend composition. A polyester mixture of the present invention may contain a polyfunctional compound such as methylmethylolpropane, pentacptptopol, glycepna, trimellitic acid, trimesic acid, or pyromellitic acid, or a monofunctional compound such as o-benzoylbenzoic acid in the range not precluding the effect of the present invention. The polyfunctional or monofunctional compound can be added to the resulting polyester mixture comprising phenylendi (oxyacetic acid), or the polyfunctional or multifunctional compound can be used as an additional monomeric component to form the polyester phenylendi (oxyacetic acid). Such a polyfunctional or monofunctional compound is preferably used in the range of not more than 20 mol% of the diol component (IB). The preparation of the phenylenyl monomers (oxyacetic acid) is described in U.S. Patent 4,935,540, the teachings of which are incorporated herein by reference. The polyesters (I or II) of the present invention preferably have an intrinsic viscosity of 0.4 to 2.0, preferably 0.50 to 1.2 [measured at 25 ° C using a mixed solvent of phenol and tetrachloroethane (in a weight ratio of 60). : 40)]. If the viscosity is less than 0.4, the strength of the polyester obtained is so low that it is practically impossible to obtain the necessary physical properties when the polyester is taken out of the reaction vessel after the polymerization and cut into small pieces, on the other hand, if the intrinsic viscosity exceeds 2.0, the melt viscosity becomes so high as to make subsequent processing difficult. The polyesters (I or II) of the present invention can be produced by any polymerization method that is conventionally known for a polymerization method for polyethylene terephthalate. For example, a polycondensation method can be adapted, which comprises the steps of directly esterifying a phenylendi (oxyacetic acid) represented by the formula [I] such as 1,3-phenylendi (oxyacetic acid) and ethylene glycol under pressure. and thereafter gradually reducing the pressure while raising the temperature to polycondensen the reaction product. It is also possible to produce copolymerized polyester of the present invention by subjecting an ester derivative of a phenylendi (oxyacety acid) represented by the general formula [I] as dimethyl 1,3-phenylenediane (oxyacetate) and ethylene glycol to an exchange reaction of ester, and further polycondensing the reaction product. In the production of such polymer, (I or II) it is preferred to use an esterifying catalyst, ester exchange catalyst, polycondensation catalyst, stabilizer, etc. As the ester exchange catalyst, at least one known compound selected from calcium, manganese, zinc, sodium and lithium compounds can be used. From the transparency point of view, a manganese compound is more preferable. As the polycondensation catalyst, at least one known compound selected from an antimony, germanium, titanium and cobalt compound can be used. Preferably, antimony, germanium and titanium compounds are used. Polyester blends are prepared using conventional fusion mixing equipment, such as Brabender extruder equipment, single screw extruders, twin screw extruders and the like. The mixtures are generally processed at temperature in the range of about 240 ° C to about 330 ° C. The properties of the mixtures can be significantly altered depending on the mixing temperature and the mixing time. Usually, processing times in the range of 0.4 to about 5 minutes are useful to achieve the desired results. Conventionally known additives include, but are not limited to, an antioxidant additive, ultraviolet absorber, fluorescent brightener, mold release agent, antistatic agent, dispersant, auxiliary to enhance reheating, acetaldehyde reducing additive, nanoparticle, coloring agent as a dye or pigment, or a mixture of these can be added, if necessary, to a polyester blend in the present invention at any stage of manufacture. Alternatively, said additive can be added before molding by what is known as main batch formation. The additives may be added in any amount and combination insofar as they do not depart from the purposes of the present invention. The polyester mixture of the present invention can be subjected to heat treatment, if necessary, before use to reduce acetaldehyde or decrease the degree of oligomerization. Alternatively, a polyester mixture of the present invention may also be subjected to a solid state polymerization before being used to improve the degree of polymerization, reduce acetaldehyde or decrease the degree of oligomerization. The heat treatment is preferably carried out at 30 ° C at a temperature directly below the melting point, for several hundred hours. The polymerization of the solid state is preferably carried out at 120 ° C at a temperature directly below the melting point, preferably 140 ° to 230 ° C for less than ten hours, preferably 5 to 30 hours after the surface of the The small pieces are crystallized at a temperature of 80 ° to 200 ° C. Polyester blending compositions can be crystallized and dried before processing to remove moisture to prevent degradation during processing. The polyester blend compositions are crystallized at a temperature of 80 ° to 200 ° C. the polyester blending compositions are dried either in an inert atmosphere, an atmosphere of dry air or under reduced pressure at 30 ° to 200 ° C for several hundred hours. Preferably, the polyester blend compositions are dried at 80 ° to 180 ° c for 2 to 40 hours. To produce a hollow molded product of the polyester blend of the present invention, for example, a blow molding method such as a hot process or cold parison process is adopted, in which a first preform is produced or by ordinary extrusion blow molding, injection blow molding, injection molding or extrusion molding, and of this mode the preform obtained is reheated and biaxially as such or after processing the mouth portion and the lot of background. It is also possible to form a uniaxially or biaxially stretched film of a polyester of the present invention or a container in the form of a can, a tray or the like by means of vacuum formation or air pressure formation after it has been formed on a sheet by injection molding. It is also possible to form a polyester mixture of the present invention in a multi-layer sheet of the polyester mixture and the polyethylene terephthalate, for example, by means of a multi-layer extruder and thereafter to form the sheet to a film. stretched uniaxially or biaxially, a container in the form of a can or a tray. A polyester blend composition of the present invention can be formed into a film, sheet, container, bottle or other packaging material by a melt molding method that is generally used to mold polyethylene terephthalate. The polyester composition can be used as a material having a high barrier gas property in a non-stretchable state. By stretching the polyester composition at least uniaxially, it is possible to improve the gas barrier property and the mechanical strength. A stretched sheet of a polyester blend composition of the present invention is produced by stretching the polyester blend composition of the present invention that has been formed into a sheet by injection molding or extrusion molding. The adopted stretching method can be freely selected from this a uniaxial stretch, a sequential biaxial stretch and a simultaneous biaxial stretch. It is also possible to form a stretched sheet of a polyester composition of the present invention to form a cup or tray by means of air pressure formation. When a stretched sheet of a polyester blend composition of the present invention is produced, the stretching temperature is established between the glass transition point (Tg) of the polyester and a temperature of 70 ° C higher than the transition point of the polyester. glass (Tg) as it is in the case of producing a fluted sheet of a copolymerized polystyrene of the present invention. The stretch ratio is ordinarily 1.1 to 10 times, preferably 1.1. to 8 times in the case of a uniaxial stretch, and 1.1 to 8 times, preferably to 1.1. to 5 times both in the transversal and machine directions in the case of biaxial stretching. The stretched sheet of this embodiment obtained from a polyester blend composition of the present invention has excellent mechanical strength and gas barrier property and is useful as a packaging material in the form of a film, cup or tray. A hollow molded polyester product of the present invention is produced by stretching and blowing the preform produced from the polyester blend composition of the present invention. Therefore, it is possible to use an apparatus conventionally used in the blow molding of poly (ethylene terephthalate). More specifically, a blow molding method is adopted as a hot parison process to a cold parison process in which a preform is first produced by ordinary extrusion blow molding, injection blow molding, molding by injection or extrusion molding, and the preform thus obtained is biaxially heated and stretched. The stretching temperature is 70 ° to 120 ° C, preferably 80 ° to 110 ° C, and the stretch ratio is 1.5 to 3.5 times in the machine direction and 2 to 5 times in the direction of the ring. In another embodiment, the invention provides a multilayer structure comprising a first layer, and a barrier layer of the polyester blend composition of phenylendi (oxyacetic acid). in this embodiment, the barrier layer is adjacent to, preferably in contact with, the first layer. The first layer may also be referred to as the main layer, inner layer or innermost layer, and the barrier layer is also referred to as the intermediate or inner layer. In a multi-layered structure, the first layer is typically formed from a polyester or copolyester of polyethylene terephthalate, and the barrier layer is formed from a mixture of polyester of phenylendi (oxyacetic acid). the additional layers in the cap structure > as multiple may contain the same composition as the first layer, and may be referred to as the second, third, fourth, etc. , cap . Additional bar layers in the multi-layer structure may contain the same phenylenedia-polyester mixture (oxyacetic acid) as the first barrier layer, and may be referred to as the second, third, fourth, etc., barrier layer. Additional layers in the multilayer structure may include an outermost layer and / or a protective layer, the outermost layer is formed from a polyester polyethylene terephthalate, or the polyester mixture of phenylendi (oxyacetic acid) ). the protective layer is adjacent to the outermost layer of the multilayer structure. The protective layer may be formed of a polymer, an organic coating or an inorganic coating, preferably polypropylene, and a toxic coating, or a coating based on silica or aluminum or the like. When a hollow molded polyester product is produced, it is possible first to form a preform of a laminate comprising a layer of polyester blend composition of the present invention and a layer of poly (alkylene terephthalate) mainly containing poly (ethylene terephthalate) , and biaxially blowing the preform thus obtained in order to produce a hollow container of multiple capias. In this case, the structure of the multiple layer is not restricted, but a multilayer of three to five layers is preferable. Especially, a multilayer structure of at least one layer of polyester blend composition of the present invention and at least one polyester layer containing polyethylene terephthalate as the main component (hereinafter referred to as the PET layer) or first layer) is preferable. The polyester of the polyester layer in the present invention may be polyethylene terephthalate, polyethylene naphthalate modified with from 0 to about 20 mol% of terephthalic acid or polycarbonate. Preferably the polyester of the polyester layer in the present invention is a poly (ethylene terephthalate). It is preferred that at least 80 mol% of the structural unit of the polyester are ethylene terephthalate units, and it is possible to use a dicarboxylic acid with a phthalic acid, isophthalic acid, and hexahydrophthalic acid, naphthalene dicarboxylic acid, succinic acid, adipic, or cebasic acid or a polyfunctional carboxylic acid such as trimellitic acid or pyromellitic acid as an acid component in the range of more than 0 to about 20 mol% of the total acid component. It is possible to use a glycol such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycoltriethylene glycol, or cyclohexanedimethanol, or a polyvalent alcohol such as trimethylol propane, triethylol propane or pentaerythritol in the range of more than 0 to about 40 mol% of the total alcohol component. The intrinsic viscosity of the polyester containing polyethylene terephthalate as the first layer is preferably 0.6 to 1.2 [measured at 30 ° C using a mixed solver.te of phenol and tetrachloroethane (in one provides weight of 60:40)] , and the glass transition point (Tg) of this is preferably 70 ° to 80 ° C. The polyester can be mixed with another polyester used as a polyester layer. In this case, the content of the polyethylene terephthalate in the polyester layer is preferably not less than 50%. The polyester layer containing polyethylene terephthalate as the first layer can be produced by a polymerization method known as the polyester blend of the present invention. The polyester can be subjected to a solid state polymerization, if necessary. The polymerization of this solid is ordinarily carried out at 170 ° C at a temperature directly below the melting point of the polyester., preferably 183 ° to 230 ° C for less than 10 hours, preferably not less than 5 hours. A multi-ply hollow polyester container according to the present invention is produced by forming a multi-ply hollow container preform from a polyester blend composition and a polyester containing poly (ethylene terephthalate) as the first layer which epitopes are obtained by the method described above, and stretching the preform thus obtained from the glass transition point (Tg) of the polyester at least in the biaxial direction. The multiple layer may be composed of either two layers or not less than three layers. A multiple layer of 3 to 5 layers is preferable. In this case, it is preferable that the inner layer of the hollow container is a polyester layer. The outermost layer of the hollow container may be the polyester mixture composition containing phenylendi (oxyacetic acid) or poly (ethylene terephthalate); however, polyethylene terephthalate is preferable in terms of surface strength. When the outermost layer is composed of the polyester mixture composition containing phenylendi (oxyacetic acid), a protective layer on the outside of the outermost layer 1 can be provided for the purpose of protecting the surface, the protective layer can be formed to a stage to form the preform of the hollow container. Alternatively, the protective layer may be formed after the preform is stretched to produce the hollow labeling container or the like. The thickness of the polyester layer and the thickness of the polyester blend layer are not specified. Generally, the total body thickness of the bottle is 200 to 700 μ, preferably 250 to 600 μ. The thickness of the polyester blend composition layer is different depending on the desired barrier property, but is generally 5 to 300 μ, preferably 10 to 200 μ. A container in the present invention is produced by blow molding by extrusion or blow molding with biaxial orientation which is conventionally known. The blow model with biaxial orientation is more advantageous. In the case of using a blow molded by biaxial orientation, the preform c.the hollow container is formed, after the preform has been heated up to the stretching temperature, is drawn into a blow mold. In order to form a preform of the hollow container having a multi-layer structure, a bottom preform can be formed by injection molding, or after a multi-layer tube has been formed, one end thereof can be formed to obtain a background. When a preform of a hollow container having a multilayer structure or a multilayer tube is not produced, the layers can be formed sequentially from the innermost layer by an ordinary injection molding machine or a molding machine having a plurality of melt injection apparatuses, or the respective layers can be extruded from a plurality of injection apparatuses to form a single mold one by one, so that the first injected polyethylene terephthalate resin can constitute the innermost layer and the outermost layer, and the phenylenediane (oxyacetic acid) polyester blend composition injected afterwards constitutes a barrier or intermediate layer. By selecting the injection time, it is possible to design the preform to obtain three layers, circus layers or more. The preform of the obtained hollow container is generally heated in a heating zone having a heater as a block heater and an infrared heater for the subsequent stretching process. The heating temperature for the preform for a multi-layer hollow polyester container of the present invention is determined by the glass transition temperature (hereinafter referred to as "Tg") of the polyester layer. The heating temperature is preferably in the range of Tg + 5 ° C to Tg + 80 ° C. If the heating temperature is too low, microspaces are produced due to a cold stretch and the container unfavorably presents the appearance of a pearl or nebula. On the other hand, if the heating temperature is too high, the preform becomes too soft to obtain a hollow container having a sufficient stretching effect. When the preform of a multi-layer hollow polyester container is stretched to form the hollow container, the preform is preferably stretched one to four times in the machine direction and two or six times in the transverse direction (direction of the container rim) by moving a rod in the machine direction and blowing pressurized air. to be able to improve the heat resistance of the container, it is possible to heat fix the container by additionally heating the drawn hollow container within the mold to the same temperature or higher than the stretching temperature for a short time. The polyester blend composition of the present invention is useful as a packaging material and can also be widely used as a container, sheet, film, bottle, etc., in the form of a mixture or a laminate with other thermoplastic resins. Particularly, a laminate of the polyester mixture of the present invention with polyethylene terephthalate has a low gas permeability, so that it can be used very advantageously. Said laminate can also be used in conjunction with a gas barrier material such as vinylidene chloride or a saponified ethylene-vinyl acetate copolymer. A hollow molded polyester product of the present invention, which has a high mechanical strength as well as an excellent gas barrier and transfer property, can be widely used for fresh drinks, flavoring material, oil, alcoholic beverages such as beer, wine and serve and cosmetics. Particularly, the hollow molded polyester product of the present invention can be used as a small size container for carbonated beverages, beer, wine or the like, which would not be conserved for a predetermined guaranteed period due to the insufficient gas barrier property mediating a bottle of ordinary biaxially stretched poly (ethylene terephthalate). Especially, a multi-layer hollow polyester container of the present invention has an excellent gas barrier property, a high mechanical strength free of bending separation and excellent transparency in external appearance. A multi-layer hollow polyester container of the present invention can therefore be widely used for fresh drinks, flavoring material, oil, alcoholic beverages such as beer, wine and serve and cosmetics.

Molded articles, such as, but not limited to, a bottle, sheet, fiber, film, paper, preforms or containers formed of any of the mixtures described above are also described herein. EXAMPLES The following examples are shown to provide those of ordinary skill in the art with a complete description of how the polyester blends claimed herein are made and evaluated, and are intended to limit the scope of what the inventors consider to be their invention. Efforts have been made to ensure accuracy with respect to figures (eg, quantities, temperature, etc.) but some errors and deviations must be taken into account. Unless otherwise indicated, the parts are parts by weight, the temperature is in ° C or at room temperature, and the pressure is close to atmospheric. The present invention will be explained in detail with reference to the following non-limiting examples. Inherent viscosity (IhV) measurements were made at 25 ° C in a 60/40 phenol / tetrachloroethane (w / w) solvent system. The polyester oxygen transmission rates were determined in cubic centimeters having a permeability to a thickness of 1 thousand, 10 square inches, over a period of 24 hours under a partial pressure difference of oxygen of one atmosphere at 30 ° C using a MOCON Oxtran 100 instrument. The film currently used to measure permeability was 3-8 mil thick, but the permeability was converted to a base of 1 mil using conventional calculations. In a similar manner, the permeability of polyester carbon dioxide was determined using a MOCON Permatran C instrument. The tensile properties were measured on an Instron Universal Testing Machine. The test method used was an ASTM of 882 modified to measure the tensile properties of thin films. Example 1 Poly (ethylene 1,4-phenylendi (oxyacetatc)) was made as follows. A reaction vessel was charged with 22.42 grams of 1,4-phenylendi (oxyacetic acid), 24.60 grams of ethylene glycol and 100 ppm of titanium tetraisopropoxide titanium. The reaction mixture was heated and stirred under nitrogen at 210 ° C for 60 minutes, then the temperature was increased to 220 ° C for 120 minutes until all the water had been distilled from the reaction mixture, the temperature was then raised to 260 ° C; the nitrogen was evacuated from the reaction system and vacuum was applied. The melting condensation was continued at 260 ° C for 75 minutes under 0.5 mm Hg pressure. The heating was discontinued, the reaction mixture was raised to atmospheric pressure with nitrogen, and the polymer was collected. The polymer had an inherent viscosity of 0.88 dl / g. Example 2 A melt mixture of polyethylene terephthalate (IhV = 0.66 dl / g) and 5% by weight of poly (ethylene 1,4-phenylenedia (oxyacetic)) was prepared in a Brabender single-screw extruder. the mixture was extruded to form a 5 mil and 20 mil film. The amorphous 5 mil film was characterized by IhV, Tg values, melting point, tensile properties in the machine direction and gas transmission speeds. The data is shown in Table 1. Example 3 The 20 mil film made in Example 2 was oriented biaxially 4x by 4x on a T.M. machine. Long at 90 ° C. the oriented film was characterized by IhV, Tg values, melting point, tensile properties in the machine direction and gas transmission speeds. The data is shown in Table 1. Example 4 The same as in Example 2, except that 10% by weight of poly (ethylene 1,4-phenylendi (oxyacetic)) was used. Example 5 The 20 mil film made in Example 4 was oriented biaxially 4x by 4x on a T.M. machine. Long at 90 ° C. The oriented film was characterized by IhV, Tg values, melting point, traction properties in the machine direction and gas transmission speeds. The data is shown in Table 1. Example 6 The same as in Example 2, except that 20% by weight of poly (ethylene 1,4-phenylendi (oxyacetic)) was used. Example 7 The 20 mil film made in Example 6 was oriented biaxially 4x by 4x on a T.M. machine. Long at 90 ° C. The oriented film was characterized by IhV, Tg values, melting point, traction properties in the machine direction and gas transmission speeds. The data is shown in Table 1. Comparative Example 8 Poly (ethylenic terephthalate) was extruded to form a film and characterized as described in Example 2. Comparative Example 9 A film of poly (ethylene terephthalate) of 20 mil was oriented and was characterized as described in Example 3. Comparative Example 10 Poly (ethylene 1,4-phenylendi (oxyacetate)) was extruded to form a film. The IhV, Tg values, melting point, tensile properties in the machine direction and gas transmission velocities of the amorphous film are shown in the following Table 1. TABLE 1 1 nd - not detected The present invention provides a thermoplastic polyester with reduced permeability to gases such as oxygen and carbon dioxide. The polyester blend compositions disclosed in this invention unexpectedly have a lower gas permeability and improved crystallization behavior.

Claims

CLAIMS 1. A polyester blend composition comprising: from about 5 to about 85% by weight of a polyester which is the product of the reaction of: (A) a repeating unit of phenylendi (oxyacetic acid) represented by the formula ( I). 0) wherein R1, R2, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a chlorine atom, a bromine atom, or a fluorine atom, or an ester derived from phenylendi (oxyacetic acid) of the formula I; (B) a repeating unit of a diol containing up to 24 carbon atoms; and II. from about 95 to about 15% by weight of a poly (ethylene terephthalate) thermoplastic polyester, a modified poly (ethylene terephthalate) copolyester of from greater than 0 to about 70 mol% of a glycol comprising diethylene glycol, propanediol, butanediol , hexanediol or 1,4-cyclohexanedimethanol, and / or dicarboxylic acid comprising isophthalic acid or naphthalenedicarboxylic acid, or a mixture of co-polyester, poly (ethylene terephthalate) with poly (ethylene terephthalate); from about 95 to about 15% by weight of a polyester poly (ethylene naphthalate), a copolyester poly (ethylene terephthalate) modified with more than 0 to about 30 mol% of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1,4-cyclohexanedimethanol, and / or a dicarboxylic acid comprising isophthalic acid or terephthalic acid, or a mixture of the copolyester poly (ethylene naphthalate) with poly (ethylene naphthalate); from about 95 to about 15% by weight of poly (butylene terephthalate); from about 95 to about 15% by weight of poly (trimethylenic terephthalate) -; or from about 95 to about 15% by weight poly (butylene) naphthalate.
2. The polyester mixture composition according to claim 1, characterized in that formula 1 is 1,2-phenylendi (oxyacetic acid), 1,3-phenylendi (oxyacetic acid), 1,4-phenylendi (oxyacetic acid) , 2-methyl-l, 3-phenylendi (oxyacetic acid), 5-methyl-l, 3-phenylendi (oxyacetic acid), 4-methyl-1,3-phenylendi (oxyacetic acid), 5-ethyl-1, 3 phenylenendi (oxyacetic acid), 4-ethyl-1,3-phenylendi (oxyacetic acid), 5-methoxy-l, 3-phenylendi (oxyacetic acid), 4-methoxy-l, 3-phenylendi (oxyacetic acid), -chloro-1, 2-phenylendi (oxyacetic acid), or 4-chloro-l, 3-phenylendi (oxyacetic acid), or an ester thereof.
3. The polyester mixture composition according to claim 1, characterized in that formula 1 is 1,2-phenylendi (oxyacetic acid), 1/3-phenylendi (oxyacetic acid), 1,4-phenylendi (oxyacetic acid) or an ester of these.
The polyester blend according to claim 1, characterized in that the component II comprises the polyester or poly (ethylene terephthalate) copolyester.
5. The polyester blend composition according to claim 1, characterized in that the component II comprises a polyester or copolyester of poly (ethylene naphthalate).
6. The polyester blend composition according to claim 1, characterized in that component II comprises poly (butylene terephthalate).
The polyester blend composition according to claim 1, characterized in that the component II comprises poly (trimethylenic terephthalate).
8. The polyester blend composition according to claim 1, characterized in that component II comprises poly (butylenic naphthalate).
9. The polyester blend composition according to claim 1, characterized in that the component (IA) is an alkyl ester of C? _ Phenylendi (oxyacetic acid).
10. The polyester blend composition according to claim 1, characterized in that the component gave (IB) comprises ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, clohexanedimethanol, 1,3-bis (2-hydroxyethoxy) benzene, or diethylene glycol, or a derivative of a aromatic dihydrcxy compound comprising resorcinol, hydroquinone, Bisphenol.
The polyester blend composition according to claim 10, characterized in that the component (IB) is ethylene glycol
12. The polyester blend composition according to claim 1, characterized in that the mixture further comprises a polyfunctional compound it comprises trimethylol propane, pentacritritol, glycerin, trimellitic acid, trimesic acid, or pyrolectric acid.
13. The polyester blend composition according to claim 12, characterized in that the polyfunctional compound is present in a concentration of not more than 20 mol% of the diol component (IB).
The polyester blend composition according to claim 1, characterized in that the composition has an intrinsic viscosity of about 0.4 to about 2.0 as measured at 25 ° C in a 60:40 phenol tetrachloroethane solvent.
15. The polyester blend composition according to claim 1, characterized in that the composition has an intrinsic viscosity of about 0.5 to about 1.2 measured at 25 ° C in a 60:40 phenol tetrachloroethane solvent.
16. The article comprising the polyester blend composition according to claim 1.
17. The article according to claim 16, characterized in that the article is a container.
18. The article according to claim 17, characterized in that the container is a bottle.
19. The article according to claim 16, characterized in that the article is a film, packing material or a sheet.
20. The article according to claim 16, characterized in that the article is a hollow article.
21. The article according to claim 16, characterized in that the article is a uniaxially or biaxially stretched film.
22. A method for producing a polyester blend comprising: mixing from about 5 to about 5% by weight of a polyester I and from about 95 to about 15% by weight of polyester II, wherein the polyester I comprises: ( A) a repeated unit of phenylendi (oxyacetic acid) represented by the formula (I). ) wherein R1, R2, R3 and R4 each independently represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy groups having from 1 to 6 carbon atoms, a phenyl group, an atom of chlorine, a bromine atom, or a fluorine atom, or an ester derived from phenylendi (oxyacetic acid) of the formula I; and (B) a repeating unit of a diol containing up to 24 carbon atoms; and the polyester II comprises a poly (ethylene terephthalate) thermoplastic polyester, a copolyether of poly (ethylene terephthalate) modified with more than 0 to about 70 mol% of a glycol comprising diethylene glycol, propanediol, bitanodiol, hexanediol or 1,4 -cyclohexanedimethanol, and / or dicarboxylic acid comprising isophthalic acid or naphthalenedicarboxylic acid, or a mixture of the copolyester poly (ethylene terephthalate) with poly (ethylene terephthalate); a poly (ethylene naphthalate) polyester, a copolyether of poly (ethylene naphthalate) modified with more than 0 to about 30 mol% of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1,4-cyclohexanedimethanol, and / or a dicarboxylic acid comprising isophthalic acid or terephthalic acid, to a mixture of the copolyester poly (ethylene naphthalate) with poly (ethylene naphthalate); a poly (butylene terephthalate); a poly (trimethylenic terephthalate); or a poly (butylenic naphthalate).
23. The method according to claim 22, characterized in that the step of mixing is carried out in an extruder, or during injection molding.
24. The method according to claim 22, characterized in that the step of mixing is carried out at a temperature of about 240 ° to about 330 ° C for a period of about 0.4 minutes to about 5 minutes.
25. The method according to claim 22, characterized in that it also comprises adding an additive, an antioxidant, ultraviolet absorber, fluorescent brightener, molting agent, antistatic agent, dispersant, auxiliary to improve reheating, reducing additive of acetaldehico, nanoparticle , or coloring agent, or a mixture of these.
26. The article characterized in that it is made of a polyester mixture produced according to claim 22
27. The article according to claim 26, characterized in that the article is a container.
28. The article according to claim 78, characterized in that the container is a bottle.
29. The article according to claim 26, characterized in that the article is a film packing material or a sheet.
30. The article according to claim 26, characterized in that the article is a hollow article.
31. The article according to claim 26, characterized in that the article is a uniaxially or biaxially stretched film. SUMMARY The invention relates to polyester blend compositions comprising: I. From about 5 to about 85% by weight of a polyester which is the product of the reaction of: (A) a repeating unit of phenylenedia (oxyacetic acid) depicted by the formula (I) wherein R1, R2, R3 and R4 each independently represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy groups having from 1 to 6 carbon atoms, a phenyl group, a chlorine atom, a bromine atom, or a fluorine atom, or an ester derived from phenylendi (oxyacetic acid) of the formula I; (B) a repeating unit of a diol containing up to 24 carbon atoms; and II. from about 9-5 to about 15% by weight of a poly (ethylene terephthalate) thermoplastic polyester, a copolyether of polyethylene terephthalate modified with from greater than 0 to about 70 mol% of a glycol cue comprises diethylene glycol, propanediol , butanediyl, hexanediol or 1,4-cyclohexanedimethanol, and / or dicarboxylic acid comprising isophthalic acid or naphthalenedicarboxylic acid, or a mixture of poly (ethylene terephthalate) copolyethers with polyethylene terephthalate; from about 95 to about 15% by weight of a poly (ethylene naphthalate) polyester, a modified poly (ethylenic naphthalate) copolyester with more than 0 to about 30 mol% of a glycol comprising diethylene glycol, propanediol, butanediol, hexanediol or 1,4-cyclohexanedimethanol, and / or a dicarboxylic acid comprising isophthalic acid or terephthalic acid, or a mixture of polyester poly (ethylene naphthalate) copolymer with poly (ethylenic naphthalate); from about 95 to about 15% by weight of poly (butylene terephthalate); from about 95 to about 15% by weight of poly (trimethylenic terephthalate); or from about 95 to about 15% by weight of poly (butylenic naphthalate)