Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/10—Silicon-containing compounds

Definitions

• the present disclosure relates to methods of forming polyester nanocomposites comprising a fibrous clay nanofiller and a polyester.
• Nanocomposites are polymers reinforced with nanometer sized
• particles i.e., particles with a dimension on the order of 1 to several hundred nanometers.
• Polymer-layered silicate nanocomposites incorporate a layered clay mineral filler in a polymer matrix.
• Layered silicates are made up of several
• Each of these platelets is characterized by a large aspect ratio (diameter/thickness on the order of 100-1000). Accordingly, when the clay is dispersed homogeneously and exfoliated as individual platelets
• a method for preparing a polyester nanocomposite composition from a masterbatch comprising melt-compounding a mixture of: fibrous clay, at least one polyester oligomer, and at least one polyester polymer to produce a nanocomposite composition containing a greater concentration of fibrous clay than is desired in the final resin composition; optionally, subjecting said nanocomposite composition to solid state polymerization to increase the polyester molecular weight; and further melt compounding said nanocomposite composition with polyester polymer and, optionally, additional ingredients.
• a process is desired for producing polyester/fibrous clay
• nanocomposite materials with improved mechanical properties.
• the invention is directed a method for preparing a polyester nanocomposite, comprising melt-mixing a mixture of:
• nanocomposite composition to produce a nanocomposite composition; and, optionally, subjecting said nanocomposite composition to solid state polymerization to increase polyester molecular weight.
• the invention is further directed to a method for preparing a polyester nanocomposite composition from a masterbatch, comprising melt-compounding a mixture of: fibrous clay, at least one sodium salt, optionally at least one polyester oligomer, and at least one polyester polymer to produce a nanocomposite composition containing a greater concentration of fibrous clay than is desired in the final resin composition; optionally, subjecting said nanocomposite composition to solid state polymerization to increase the polyester molecular weight; and further melt compounding said nanocomposite composition with polyester polymer and, optionally, additional ingredients.
• nanocomposite means a polymeric material which contains particles, dispersed throughout the polymeric material, having at least one
• nanoparticles The polymeric material in which the nanoparticles are dispersed is often referred to as the "polymer matrix.”
• polymer matrix The term “polyester composite” refers to a
• nanocomposite in which the polymeric material includes at least one polyester includes at least one polyester.
• fibrous clay refers to naturally-occurring and synthetic clays which are predominantly characterized by long, slender fibers (which can be hollow), as opposed to plates or grainy structures.
• exfoliate literally refers to casting off in scales, laminae, or splinters, or to spread or extend by or as if by opening out leaves.
• exfoliation refers to the separation of platelets from the smectic clay and dispersion of these platelets throughout the polymer matrix.
• fibrous clays for fibrous clays, "exfoliation" or
• exfoliated means the separation of fiber bundles or aggregates into nanometer diameter fibers which are then dispersed throughout the polymer matrix.
• TSPP tetrasodium
• TSPP decahydrate refers specifically to
• TSPP is also available in an anhydrous form, Na 4 P 2 O 7 .
• polyester means a condensation polymer in which more than 50 percent of the groups connecting repeat units are ester groups.
• polyesters may include polyesters, poly(ester-amides) and poly(ester-imides), so long as more than half of the connecting groups are ester groups.
• at least 70% of the connecting groups are esters, more preferably at least 90% of the connecting groups are ester, and especially preferably essentially all of the connecting groups are esters.
• the proportion of ester connecting groups can be estimated to a first approximation by the molar ratios of monomers used to make the polyester.
• PET means a polyester in which at least 80, more preferably at least 90, mole percent of the diol repeat units are from ethylene glycol and at least 80, more preferably at least 90, mole percent of the dicarboxylic acid repeat units are from terephthalic acid.
• oligomer means a molecule that contains 2 or more identifiable structural repeat units of the same or different formula.
• linear polyester oligomer means oligomeric material, excluding macrocyclic polyester oligomers, which by itself or in the presence of monomers can polymerize to a higher molecular weight polyester.
• polyester component refers to the total of all polyester moieties present in the nanocomposite, i.e., linear oligomers plus polymer(s).
• resin means a composition comprising a polymer and at least one additional ingredient (for example, a filler, flame retardant, toughener, plasticizer, etc.).
• melt mixing means applying shear stress to a melt to mix the ingredients comprising the melt.
• ingredients e.g., clay, glass fiber
• melting means applying shear stress to a melt to mix the ingredients comprising the melt.
• One or more ingredients e.g., clay, glass fiber
• melting may remain unmelted during the melt mixing process as long as at least one ingredient is molten.
• compounding and “melt compounding” as used herein are synonymous.
• dry blend means to mix together unmelted ingredients, typically prior to melt mixing.
• staged feeding indicates that ingredients are separately fed at different stages of a melt mixing process. For example, two different ingredients may be fed into one feed port of an extruder and a third ingredient into a second feed port downstream of the first one.
• split feeding indicates that the total amount of an ingredient has been split into two or more portions and the portions are separately fed at different stages of a melt mixing process.
• an ingredient may be split into three portions, each of which is fed into a different feed port of an extruder.
• One aspect of the invention described herein is directed to a method for preparing a polyester nanocomposite, comprising melt- compounding a mixture of: fibrous clay, at least one sodium salt, optionally at least one polyester oligomer, and at least one polyester polymer to produce a nanocomposite composition; and, optionally, subjecting said nanocomposite composition to solid state polymerization to increase the polyester molecular weight.
• Another aspect of the invention described herein is a method for preparing a polyester nanocomposite composition from a masterbatch, comprising melt-compounding a mixture of: fibrous clay, at least one sodium salt, optionally at least one polyester oligomer, and at least one polyester polymer to produce a nanocomposite composition containing a greater concentration of fibrous clay than is desired in the final resin composition; optionally, subjecting said nanocomposite composition to solid state polymerization to increase the polyester molecular weight; and further melt compounding said nanocomposite composition with polyester polymer and, optionally, additional ingredients.
• the nanocomposite composition contains about 0.1 to about 40 wt% of fibrous clay.
• Fibrous clays include naturally-occurring and synthetic clays which are predominantly characterized by long, slender fibers (which can be hollow), as opposed to plates or grainy structures.
• the individual fibers generally range from about 0.2 to 5 micrometers in length and have a diameter ranging from about 5 to 200 nanometers.
• Such fibrous clays generally occur as aluminosilicates, magnesium silicates and aluminomagnesium silicates.
• Examples of fibrous clays include but are not limited to: attapulgite (palygorskite), sepiolite, halloysite, endellite, chrysotile asbestos, and imogolite. Sepiolite and attapulgite, separately or as a mixture, are attractive because of a combination of high length-to-diameter ratio, ready availability, and low cost.
• Sepiolite is a hydrated magnesium silicate filler that exhibits a high aspect ratio due to its fibrous structure.
• sepiolite is composed of long lath-like crystallites in which the silica chains run parallel to the axis of the fiber.
• the material has been shown to consist of two forms, an ⁇ and a ⁇ form.
• the ⁇ form is known to be long bundles of fibers and the ⁇ form is present as
• Attapulgite also known as palygorskite
• fibrous clay includes
• Fibrous clays are layered fibrous materials in which each layer is made up of two sheets of tetrahedral silica units bonded to a central sheet of octahedral units containing magnesium ions (see, e.g., Figures 1 and 2 in L. Bokobza et al., Polymer International, 53, 1060-1065 (2004)).
• the fibers stick together to form fiber bundles, which in turn can form
• agglomerates agglomerates. These agglomerates can be broken apart by industrial processes such as micronization or chemical modification (see, e.g., European Patent 170,299 to Tolsa, S.A.) to produce nanometer diameter fibers, i.e., exfoliated fibrous clay.
• the amount of fibrous clay used in the present invention ranges from about 0.1 to about 40 wt% based on the fibrous clay and polyester component of the composition.
• the specific amount chosen will depend on the intended use of the nanocomposite, as is well understood in the art.
• Fibrous clays are available in a high purity (“rheological grade"), uncoated form (e.g., PANGEL® S9 sepiolite clay from the Tolsa Group, Madrid, Spain) or, more commonly, treated with an organic material to make the clay more "organophilic," i.e., more compatible with systems of low-to-medium polarity (e.g., PANGEL® B20 sepiolite clay from the Tolsa Group).
• An example of such a coating for fibrous clay is a quaternary ammonium salt such as dimethylbenzylalkylammonium chloride, as disclosed in European Patent Application 221 ,225.
• the fibrous clay used in the process described herein is typically unmodified; i.e., the surface of the fibrous clay has not been treated with an organic compound (such as an onium compound, for example, to make its surface less polar).
• an organic compound such as an onium compound, for example, to make its surface less polar.
• onium compounds tend to degrade at the temperatures used to process polyesters such as PET.
• the fibrous clay is rheological grade, such as described in European patent applications EP-A-0454222 and EP-A- 0170299 and marketed under the trademark Pangel® by Tolsa, S.A., Madrid, Spain.
• rheological grade denotes a fibrous clay with a specific surface area greater than 120 m 2 /g (N 2 , BET), and typical fiber dimensions: 200 to 2000 nm long, 10-30 nm wide, and 5-10 nm thick.
• Rheological grade sepiolite is obtained from natural sepiolite by means of special micronization processes that substantially prevent breakage of the sepiolite fibers, such that the sepiolite disperses easily in water and other polar liquids, and has an external surface with a high degree of irregularity, a high specific surface, greater than 300 m 2 /g and a high density of active centers for adsorption, that provide it a very high water retaining capacity upon being capable of forming, with relative ease, hydrogen bridges with the active centers.
• the microfibrous nature of the rheological grade sepiolite nanoparticles makes sepiolite a material with high porosity and low apparent density.
• rheological grade sepiolite has a very low cationic exchange capacity (10-20 meq/100 g) and the interaction with electrolytes is very weak, which in turn causes rheological grade sepiolite not to be practically affected by the presence of salts in the medium in which it is found, and therefore, it remains stable in a broad pH range.
• rheological grade sepiolite can also be attributed to rheological grade attapulgite with particle sizes smaller than 40 microns, such as for example the range of ATTAGEL goods (for example ATTAGEL 40 and ATTAGEL 50) manufactured and marketed by the firm Engelhard Corporation, United States, and the MIN- U-GEL range of Flohdin Company.
• ATTAGEL goods for example ATTAGEL 40 and ATTAGEL 50
• the amount of fibrous clay used in the present invention ranges from about 0.1 to about 40 wt% based on the fibrous clay and polyester component of the composition.
• the specific amount chosen will depend on the intended use of the nanocomposite composition, as is well understood in the art. For example, in film, it may be advantageous to use as little fibrous clay as possible, so as to retain desired optical properties.
• the method described herein is particularly useful in preparing
• masterbatches of the nanocomposite composition, which contain relatively high concentrations of fibrous clay, typically 15 to 30 wt%.
• the masterbatch can then be mixed with additional polyester (let down), and optionally other ingredients to produce a resin composition that contains a desired lower concentration of fibrous clay. Let-down ratios are selected so that the desired level of dispersed filler particles is present in the final product. For example, a nanocomposite composition masterbatch containing 30% by weight of the fibrous clay may be used.
• the composition containing the 3 weight percent may be made by melt mixing 1 part by weight of the 30% masterbatch with 9 parts by weight of the "pure" polyester, i.e., a let-down ratio of 9 parts additional polymer to 1 part masterbatch.
• a let-down weight ratio of from about 0.5-20 parts of additional polymer or polymerizable material to 1 part masterbatch, especially about 1-10:1 or even about 2-6:1 is often convenient. This is conveniently done by melting the components and mixing them, or by forming a dry blend followed by heating and melt mixing. During melt mixing, other ingredients can also be added to form a final desired composition.
• the amount of fibrous clay in the nanocomposite is preferably about 0.1 to about 35 wt% based on the weight of fibrous clay plus polyester component. In some embodiments, the, fibrous clay is present in the amount between (and optionally including) any two of the following weight percentages: 0.1 , 5, 10, 15, 20, 25, 30, 35 and 40.
• At least one sodium salt is added in an amount ranging from about 0.5 to about 12 wt% based on the weight of fibrous clay, where "wt% based on the weight of fibrous clay" is defined as 100 times the weight of sodium salt divided by the weight of fibrous clay; e.g., 4 grams sodium salt plus 50 grams fibrous clay would be 2 wt% sodium salt based on the weight of fibrous clay.
• the sodium salt is present in the amount between (and optionally including) any two of the following weight percentages: 0.5, 1 , 3, 5, 7, 9, 11 , and 12 weight percent of the weight of the fibrous clay.
• Suitable sodium salts include without limitation: tetrasodium pyrophosphate ("TSPP"), trisodium phosphate (“TSP", Na 3 PO 4 ), sodium carbonate (Na 2 CO 3 ), and mixtures thereof.
• TSPP tetrasodium pyrophosphate
• TSP trisodium phosphate
• Na 2 CO 3 sodium carbonate
• the TSPP may be the anhydrous form, Na 4 P 2 O 7 [CAS Reg. No. 7722-88-5], or the hydrated form, "TSPP decahydrate,” Na 4 P 2 O 7 -I OH 2 O [CAS Reg. No. 13472-36-1]. It may be used as-received (flake) or ground to a powder as desired.
• Linear polyester oligomers and polyester polymers suitable for use in the process described herein are described below.
• the molecular weight of the polyester polymer will depend on the eventual use of the final composition. Typically, the number average molecular weight (M n ) will be from about 12,000 to about 50,000.
• Linear polyester oligomers include, for example, oligomers of linear polyesters and oligomers of polymerizable polyester monomers.
• reaction of dimethyl terephthalate or terephthalic acid with ethylene glycol when carried out to remove methyl ester or carboxylic groups, usually yields a mixture of bis(2-hydroxyethyl) terephthalate and a variety of oligomers: oligomers of bis(2-hydroxyethyl) terephthalate, oligomers of mono(2-hydroxyethyl) terephthalate (which contain carboxyl groups), and polyester oligomers capable of being further extended.
• Such oligomers will have an average degree of polymerization (average number of monomer units) of about 20 or less, more typically about 10 or less.
• the linear polyester oligomers may be obtained as a byproduct of a polyester polymer manufacturing process (see, e.g., S. Hansen and K. B. Atwood, "Polyester Fibers,” Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, A. Seidel ed., 5 th edition, vol. 20, 1 -31 (2006)). Alternatively, they may be produced by degrading ("cracking") polyester polymer, for example, by alcoholysis as described by David E. Nikles, Medhat S. Farahat in "New Motivation for the
• Linear polyester oligomers obtained by these processes are likely to have a broad molecular weight distribution and to contain measurable amounts of monomeric species.
• Linear polyester oligomer could also be produced in situ in the process described herein by adding monomeric species (e.g., ethylene glycol, bis-hydroxyterephthalic acid) to a mixture of polyester polymer and fibrous clay and then melt mixing.
• monomeric species e.g., ethylene glycol, bis-hydroxyterephthalic acid
• Polyesters which have mostly or all ester linking groups are normally derived from one or more dicarboxylic acids and one or more diols. They can also be produced from polymerizable polyester monomers or from macrocyclic or linear polyester oligomers as described in copending U. S. Patent Application 11/312068 herein incorporated by reference in its entirety.
• Polyesters for use in practicing the invention described herein may be amorphous, crystalline, semicrystalline, anisotropic (i.e., liquid crystalline), or isotropic or may contain a mixture of these morphologies.
• Polyesters most suitable for use in practicing the invention comprise isotropic thermoplastic polyester homopolymers and copolymers (both block and random). The production of polyesters from reaction mixtures containing diols and hydrocarbyl diacids or esters of such diacids is well known in the art, as described by A. J. East, M. Golden, and S. Makhija in the Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, J. I.
• suitable diacids are those selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, cyclohexane dicarboxylic acids, succinic acid, glutaric acid, adipic acid, sebacic acid, 1 ,12-dodecane dioic acid fumaric acid, maleic acid, and the derivatives thereof, such as, for example, the dimethyl, diethyl, or dipropyl esters.
• glycols that can be utilized as the diol component include ethylene glycol, 1 ,3-propylene glycol, 1 ,2- propylene glycol, 2,2-diethyl-1 ,3-propane diol, 2,2-dimethyl-1 ,3-propane diol, 2-ethyl-2-butyl-1 ,3-propane diol, 2-ethyl-2-isobutyl-1 ,3-propane diol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,5-pentane diol, 1 ,6-hexane diol, 2,2,4- trimethyl-1 ,6-hexane diol, 1 ,2-cyclohexane dimethanol, 1 ,3-cyclohexane dimethanol, 1 ,4-cyclohexane dimethanol, 2,2,4,4-tetramethyl-i ,3- cyclobutan
• Polyesters suitable for use in the present invention can also be produced directly from reaction mixtures containing polymerizable polyester monomers.
• polymerizable polyester monomers hydroxyacids such as hydroxybenzoic acids, hydroxynaphthoic acids and lactic acid; bis(2-hydroxyethyl) terephthalate, bis(4-hydroxybutyl) terephthalate, bis(2- hydroxyethyl)naphthalenedioate, bis(2-hydroxyethyl)isophthalate, bis[2-(2- hydroxyethoxy)ethyl]terephthalate, bis[2-(2- hydroxyethoxy)ethyl]isophthalate, bis[(4- hydroxymethylcyclohexyl)nnethyl]terephthalate, and bis[(4- hydroxymethylcyclohexyl)nnethyl]isophthalate, mono(2- hydroxyethyl)terephthalate, bis(2-hydroxyethyl)sulfoisophthalate, and lactide. Alkyl-substituted and chloro-substituted versions of these species may
• Polyester polymers can also be produced directly from reaction mixtures containing macrocyclic polyester oligomers.
• suitable macrocyclic polyester oligomers include without limitation macrocyclic polyester oligomers of 1 ,4-butylene terephthalate (CBT); 1 ,3- propylene terephthalate (CPT); 1 ,4-cyclohexylenedimethylene
• CCT ethylene terephthalate
• CEN 1 ,2-ethylene 2,6- naphthalenedicarboxylate
• CPEOT the cyclic ester dimer of terephthalic acid and diethylene glycol
• macrocyclic co-oligoesters comprising two or more of the above structural repeat units. Alkyl- substituted and chloro-substituted versions of these species may also be used.
• the polyesters may be branched or unbranched, and may be homopolymers or copolymers or polymeric blends comprising at least one such homopolymer or copolymer.
• polyesters examples include without limitation
• PET poly(ethylene terephthalate)
• PPT poly(1 ,3-propylene terephthalate)
• PBT poly(1 ,4-butylene terephthalate)
• thermoplastic elastomeric polyester having poly(1 ,4-butylene terephthalate) and poly(tetramethylene ether)glycol blocks (available as HYTREL® from E. I. du Pont de Nemours & Co., Inc., Wilmington, DE 19898 USA)
• PCT poly(1 ,4-cylohexyldimethylene terephthalate)
• PLA polylactic acid
• the polyester component is about 0 to about 99 wt% linear oligomer and about 100 to about 1 wt% polyester polymer.
• the linear oligomer is present in the amount between (and optionally including) any two of the following weight percentages of the polyester component: 0, 5, 10, 13, 15, 17, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 99.
• the polyester polymer is present in the amount between (and optionally including) any two of the following weight percentages of the polyester component: 100, 95, 90, 87, 85, 83, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, and 1.
• a mixture comprising fibrous clay, at least one sodium salt, at least one polyester polymer, and optionally at least one linear polyester oligomer.
• the mixture is melt- mixed (i.e., a shear stress is applied to the molten mixture) and, optionally, subjected to solid phase polymerization to raise the polyester molecular weight.
• Process equipment typical for melt-mixing thermoplastics in a batchwise or continuous fashion may be used.
• kneaders e.g., a Buss Co-Kneader from Buss AG, Pratteln, Switzerland
• extruders single screw, twin-screw, multi-screw
• Banbury® Mixers e.g., Banbury® Mixers
• Farrel® Continuous Mixers e.g., Banbury® and Farrel® are registered trademarks of Farrel Corporation, Ansonia, Connecticut, USA
• Twin-screw extruders such as ZSK machines from Werner & Pfleiderer (now part of Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart, Germany) are commonly used.
• the screw design encompasses the typical polyester processing operations of conveying, melting, mixing, homogenization, dispersion, devolatilization (i.e., off-gassing), stranding, and peptization.
• the optimum mixing intensity depends on the
• the ingredients of the nanocomposite may be introduced to an extruder in a number of different ways.
• a mixture of the ingredients may be fed at once into a rear feed port.
• separate ingredients may be fed into separate feed ports ("staged feeding"; for example, one ingredient fed into one port, two other ingredients into a second).
• feeds of any single component may be split into two or more streams and fed into multiple feed ports ("split feeding").
• split feeding both staged feeding and split feeding processes may be used.
• two or more extruders in series can be employed, each to perform one or more compounding steps.
• extruded composition also, known as "output" of an extruder can be re-fed one or more times through the same extruder to produce the final composition.
• Extrusion conditions are adjusted depending on the specific composition, i.e., specific materials and relative amounts. For example, extrusion temperatures may need to be adjusted to maintain adequate melt strength depending on the concentration of linear polyester oligomer and whether the oligomer is solid or molten when added. Such
• the molecular weight of the polymer material in the resulting nanocomposite may be increased by any of a number of known
• SSP solid phase polymerization
• solid phase polymerization is typically used (see, e.g., A. East, “Polyesters, Thermoplastic,” Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, A. Seidel ed., 5 th edition, vol. 20, 31 -95 (2006)).
• Nanocomposites may contain additional ingredients, including but not limited to stabilizers, antioxidants, tougheners, pigments, other fillers, plasticizers, lubricants, mold release agents, flame retardants, and other polymers.
• Nanocomposite compositions containing ingredients in addition to polyester and fibrous clay can be prepared in a variety of ways.
• a polyester nanocomposite masterbatch with a high concentration of fibrous clay could be prepared using the process described herein, then let down by melt mixing with additional polyester, then melt mixed with the desired added ingredients (process A). Alternatively, and more economically, the masterbatch could simply be melt-mixed with the additional polyester and desired additional ingredients at once (process B).
• a polyester nanocomposite could be prepared at the desired final fibrous clay concentration and melt-mixed in a separate step with the desired additional ingredients, or (process D) the final composition could be prepared by including all ingredients when the nanocomposite is made.
• Other variations might combine these approaches; for example, a stabilizer might be included when a nanocomposite masterbatch is prepared and flame retardant added when the masterbatch is let down with additional polyester. Which of these or other processes is used will depend on factors such as economics and the nature of the additional ingredients and is readily determined by one of ordinary skill in the art. For example, process B is more economical than process A because it has two processing steps while A has three. Process D may be
• Process C allows the manufacturer some flexibility in composition formulation, while use of a masterbatch in process A or B is more flexible by allowing easy variation of clay content over a wide range.
• ingredients may be added at one or more downstream points in the extruder instead of into a rear feed port for one or more of a variety of reasons, for example, to decrease attrition of solids such as fillers, improve dispersion, decrease equipment wear, decrease the thermal history of relatively thermally unstable ingredients, and/or decrease losses by evaporation of volatile ingredients.
• Solid particulate fillers exclusive of the fibrous clay are examples of solids such as fillers, improve dispersion, decrease equipment wear, decrease the thermal history of relatively thermally unstable ingredients, and/or decrease losses by evaporation of volatile ingredients.
• solid fillers can be added during the extrusion of the fibrous clay/sodium salt/polyester mixture or melt mixed with a formed
• nanocomposite composition in a separate step.
• the solid particulate filler will be a material which may already be used in thermoplastic compositions, such as pigments, reinforcing agents, and fillers.
• the solid particulate filler may or may not have a coating on it, for example, a sizing and/or a coating to improve adhesion of the solid particulate filler to the polymers of the composition.
• the solid particulate filler may be organic or inorganic.
• Useful solid particulate fillers include minerals such as clay (other than sepiolite and attapulgite), talc, wollastonite, mica, and calcium carbonate; glass in various forms such as fibers, milled glass, solid or hollow spheres; carbon as carbon black, carbon fiber, graphene sheets (exfoliated graphite, graphite oxide), carbon nanotubes or nano-diamond; titanium dioxide; aramid in the form of short fibers, fibrils or fibrids; and flame retardants such as antimony oxide, sodium antimonate, and appropriate infusible organic compounds.
• minerals such as clay (other than sepiolite and attapulgite), talc, wollastonite, mica, and calcium carbonate
• glass in various forms such as fibers, milled glass, solid or hollow spheres
• carbon as carbon black, carbon fiber, graphene sheets (exfoliated graphite, graphite oxide), carbon nanotubes or nano-diamond
• titanium dioxide aramid in
• the solid particulate material may be conventionally melt mixed with the nanocomposite, for example in a twin-screw extruder or Buss kneader.
• the particulate material may also be added to the process for forming the polyester nanocomposite, i.e., added as part of the formation of the polymer/fibrous clay/linear oligomer/sodium salt mixture. It may be added at the same time as the fibrous clay, although if a great deal of particulate material is added it may increase the viscosity of the material undergoing the melt mixing process, and care should be taken not to increase the viscosity so much that the material is difficult to process.
• Plasticizers can be added during the extrusion of the fibrous clay/linear polyester oligomer/polyester polymer or melt mixed with a formed nanocomposite composition in a separate step.
• a plasticizer is a compound that, when added to a polymer, makes it more pliable, typically by lowering its glass transition temperature.
• a plasticizer is typically a compound or mixture of compounds with a melting point of about 5O 0 C or less with a(n) (average) molecular weight of 2000 or less. Typically, the plasticizer is 0 to about 5 weight percent of the weight of polyester in the composition.
• Specific useful plasticizers include poly(ethylene glycol 400) di-2-ethylhexanoate and poly(ethylene glycol) dilaurate with a number average molecular weight of approximately 946. Toughening Agents
• Toughening agents can be added during the extrusion of the fibrous clay/linear polyester oligomer/polyester polymer or melt mixed with a formed nanocomposite composition in a separate step.
• a polymeric toughening agent is a polymer, typically which is an elastomer or has a relatively low melting point, generally ⁇ 200°C, preferably ⁇ 150°C, which has attached to it functional groups which can react with the polyester (and optionally other polymers present), as described in copending U. S. Patent Application 11/312065, herein incorporated by reference in its entirety.
• the amount of polymeric toughening agent containing functional groups present is about 1 to about 20 percent based on the weight of the polyester.
• suitable tougheners include those listed in U.S. Patent 4,753,980, which is hereby incorporated by reference, such as copolymers of ethylene, ethyl acrylate or n-butyl acrylate, and glycidyl methacrylate.
• the polymeric toughener typically will contain about 0.5 to about 20 weight percent of monomers containing functional groups, often about 1.0 to about 15 weight percent, or even about 7 to about 13 weight percent of monomers containing functional groups.
• polymers can be added during the extrusion of the fibrous clay/linear polyester oligomer/polyester polymer or melt mixed with a formed nanocomposite composition in a separate step.
• polyester nanocomposites can be blended with a wide variety of other polymers, as described in copending U. S. Patent Application 11/642182, herein incorporated by reference in its entirety.
• other polymers include olefin homopolymers and copolymers, thermoplastic polyurethanes, polyvinyl chloride, polyvinylidene chloride copolymers, liquid crystalline polymers, fluohnated polymers, polyamides, polyimides, polyphenylene sulfide, polyphenylene oxide, polysulfones,
• Another type of other ingredient is an epoxy compound or resin. It is believed that in some instances the epoxy compound or resin stabilizes melt viscosity and/or improves color stability of the composition. Typically such a compound or resin has an average molecular weight of less than about 1000. This epoxy material is normally present at a level of 0 to about 1.0 weight percent of the entire composition. It can be added during the extrusion of the fibrous clay/linear polyester oligomer/polyester polymer or melt mixed with a formed nanocomposite composition in a separate step.
• Examples of useful epoxy compounds or resins include without limitation Epon® 1002F, 1009F or 1031 (Resolution Performance
• Hydrolysis stabilizers can be added during the extrusion of the fibrous clay/linear polyester oligomer/polyester polymer or melt mixed with a formed nanocomposite composition in a separate step.
• the polyester nanocomposites can be stabilized with an effective amount of any hydrolysis stabilization additive, particularly when it is to be used to form monofilament.
• the hydrolysis stabilization additive can be any known material that enhances the stability of the polyester
• hydrolysis stabilization additive can include: diazomethane, carbodiimides, epoxides, cyclic carbonates, oxazolines, aziridines, keteneimines, isocyanates, alkoxy end-capped polyalkylene glycols, and the like, as described in copending U. S. Patent Application 11/642182, herein incorporated by reference in its entirety.
• the amount of hydrolysis stabilization additive used is from 0.1 to 10.0 weight percent based on the polyester nanocomposite. Typically the amount of the hydrolysis stabilization additive used is in the range of 0.2 to 4.0 weight percent.
• ingredients can be added during the extrusion of the fibrous clay/linear polyester oligomer/polyester polymer or melt mixed with a formed nanocomposite composition in a separate step. Such ingredients may be added to the present composition in amounts commonly used in thermoplastics as needed for the desired end use.
• Such materials include without limitation antioxidants, lubricant, mold release agents, flame retardants, (paint) adhesion promoters, thermal stabilizers, UV absorbers, UV stabilizers, processing aids, waxes, color stabilizers, pigments, nucleants, dyes, delusterants such as titanium dioxide and zinc sulfide, antiblocks such as silica, antistats, brighteners, silicon nitride, metal ion sequestrants, anti-staining agents, silicone oil, surfactants, soil repellants, viscosity modifiers, and zirconium acid. It is to be understood that any ingredient and/or ingredient amount may be combined with any other ingredient and/or ingredient amount herein.
• polyester nanocomposite compositions can also be integrated with additional forming processes, for example, by feeding the product, or co-feeding with an additional polymer stream, directly into an additional forming device, such as an extruder, extruder to form shaped articles, including but not limited to monofilament, multifilament yarn, film, sheet, pellets, and tubing.
• additional forming device such as an extruder, extruder to form shaped articles, including but not limited to monofilament, multifilament yarn, film, sheet, pellets, and tubing.
• One example is an integrated continuous process for making monofilament in which the output of the extruder is fed directly into a filament extruder or co-fed into a filament extruder with an additional polymer stream.
• Articles comprising the nanocomposite compositions produced by the present invention may be prepared by any means known in the art, such as, but not limited to, methods of injection molding, extrusion, blow molding, thermoforming, solution casting, or film blowing. They are particularly useful in appearance parts, packaging, monofilament, and other applications in which engineering plastics are typically used.
• compositions described herein are particularly useful as "appearance parts", that is parts in which the surface appearance is important.
• Such parts include automotive body panels such as fenders, fascia, hoods, tank flaps and other exterior parts; interior automotive panels; automotive lighting fixtures (e.g., bezels); parts for appliances (e.g., refrigerators,
• dishwashers washing machines, clothes driers, food mixers, hair driers, coffee makers, toasters, and cameras
• handles control panels, chassis (cases), washing machine tubs and exterior parts, interior or exterior refrigerator panels, and dishwasher front or interior panels
• power tool housings such as drills and saws
• electronic cabinets and housings such as personal computer housings, printer housings, peripheral housings, server housings
• exterior and interior panels for vehicles such as trains, tractors, lawn mower decks, trucks, snowmobiles, aircraft, and ships
• decorative interior panels for buildings furniture such as office and/or home chairs and tables
• telephones and other telephone equipment As mentioned above these parts may be painted or they may be left unpainted in the color of the composition.
• Nonappearance parts may also be made with these compositions.
• Such parts include those now made with so-called engineering thermoplastics, especially those which are filled with materials which are designed to enhance the composition's physical properties, such as stiffness, toughness, and tensile strength.
• engineering thermoplastics especially those which are filled with materials which are designed to enhance the composition's physical properties, such as stiffness, toughness, and tensile strength. Examples include but are not limited to electrical connectors, covers for switchboxes or fuses, radiator grille supports, printed circuit boards, plugs, switches, keyboard components, small electric motor components, distributor caps, bobbins, coil-formers, rotors, windshield wiper arms, headlight mountings, other fittings, and conveyor-belt links.
• the nanocomposites will find use in applications that involve some type of repeated mechanical movement, such as bending, flexing, pushing, rotating, pulsing, impacting, or recoiling, since they have a desirable combination of they have an excellent combination of strength, toughness, flexibility and recovery from deformation (see East, op. cit.).
• Examples of uses include but are not limited to hydraulic hosing, rail car couplers, release binders, auto vacuum control tubing, door lock bumpers, railroad car shock absorbers, headphones; specialty fibers, films, and sheets; jacketing, automotive shock absorbers, diaphragms for railroad cars, corrugated plastic tubing, railroad draft gear, auto electric window drive tapes, CVJ boots, recreational footwear, conductive rubbers, wire coatings, energy management devices, telephone handset cords, compression spring pads, wire clamps, gun holsters, drive belts, run-flat tire inserts, and medical films.
• Nanocomposite compositions made by the process described herein can be formed into shaped articles useful in packaging applications, such as film, sheet, container, membrane, laminate, pellet, coating, and foam.
• Articles may be prepared by any means known in the art, such as, but not limited to, methods of injection molding, (co)extrusion, blow molding, thermoforming, solution casting, lamination, and film blowing.
• the article may be an injection stretch blow molded bottle.
• Examples of articles comprising nanocomposite compositions prepared by the process described herein include without limitation packaging for food, personal care (health and hygiene) items, and cosmetics.
• Packaging refers to either an entire package or a component of a package.
• packaging components include, but are not limited, to packaging film, liners, shrink bags, shrink wrap; trays such as but not limited to "CPET" (crystalline polyethylene terephthalate) trays, including but not limited to frozen food trays; tray/container assemblies, replaceable and nonreplaceable caps, lids, and drink bottle necks.
• the package may be in any form appropriate for the particular application, such as a can, box, bottle, jar, bag, cosmetics package, or closed-ended tube.
• Other examples of packaging for food include without limitation hot fill bottles and jars for, e.g., juices and sports drinks; and plastic cans for, e.g., vegetables, soup, canned stews, meats, and beans.
• the packaging may be fashioned by any means known in the art, such as, but not limited to, extrusion, coextrusion, thermoforming, injection molding, lamination, or blow molding.
• packaging for personal care items and cosmetics include, but are not limited to, bottles, jars, and caps for food and for prescription and non-prescription capsules and pills; solutions, creams, lotions, powders, shampoos, conditioners, deodorants, antiperspirants, and suspensions for eye, ear, nose, throat, vaginal, urinary tract, rectal, skin, and hair contact; and lip product.
• Polymeric monofilaments are used as reinforcements for rubber articles, fishing lines, toothbrush bristles, paintbrush bristles and the like.
• woven fabrics produced from monofilaments are used, for example, in industrial belts and paper machine clothing.
• Poly(ethylene terephthalate) (“PET”) filaments are also employed in industrial applications such as tire cords, composites, belts, and textiles.
• Multifilament yarns can be produced comprising the polyester nanocomposites described herein using any of the typical processes well known in the art for making multifilament polyester yarns (see, e.g., Reese, Glen, "Polyesters, Fibers” in Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc. (2002), vol. 3, 652-678; U. S. Patents 3,409,496, 4,933,427, 4,929,698, 5,061 ,422, 5,277.858; British Patent 1 ,162,506). Textile filament yarns are continuous yarns produced at high speeds and are used for fabrics with silk-like esthetics. Industrial filament yarns are used for rubber reinforcement and high strength industrial fabrics.
• pyrophosphate and "wt%" means weight percent(age),.
• Linear PET oligomer was obtained from E I. du Pont de Nemours & Co., Inc. (Wilmington, Delaware, USA) as a byproduct of a PET
• the material contained 5.2% free glycol, as determined by extraction in acetone and gas chromatography.
• TSP and TSPP decahydrate were obtained from Aldrich Chemical Company (Milwaukee, Wisconsin, USA). Anhydrous TSPP was obtained from BHS Marketing (Salt Lake City, Utah, USA). Sodium carbonate was obtained from EMD Chemicals (Gibbstown, New Jersey, USA).
• Pangel® S-9 sepiolite was purchased from EM Sullivan Associates, Inc. (Paoli, Pa, USA), a distributor for the manufacturer, Tolsa S.A.
• Pangel® S-9 is a rheological grade of sepiolite that has an unmodified surface.
• Licowax® PE520 polyethylene wax, a mold release agent, was obtained from Clahant (Muttenz, Switzerland).
• Irganox® 1010 antioxidant was obtained from Ciba Specialty Chemicals (Basel, Switzerland). Characterization Methods.
• Intrinsic viscosity of polyester polymers was determined at a concentration of 0.5 g/100 ml_ of a 50:50 weight % thfluoroacetic acid:dichloromethane acid solvent system at room temperature by a Goodyear R-103B method .
• ISO 1A multipurpose bars (4 mm thick) were molded from dried polyester nanocomposite resins on a Nissei 3000 injection molding machine with temperatures of 265-280 0 C and a mold temperature of 120 0 C. Tensile properties of the molded bars were measured according to the procedures of ISO 527 with an extension rate of 5 mm/min. A minimum of 5 bars per condition were tested.
• the ingredients were added simultaneously using two separate calibrated weight-loss feeders (K-Tron T-35 Twin-Screw for sodium salt, sepiolite, and oligomer flake; and K-Tron S-200 for PET pellets, K-Tron International, Pitman, New Jersey, USA) into a rear feed port of the extruder.
• K-Tron T-35 Twin-Screw for sodium salt, sepiolite, and oligomer flake
• K-Tron S-200 for PET pellets, K-Tron International, Pitman, New Jersey, USA
• the appropriate quantities of sodium salt as indicated in the tables, sepiolite (20 wt%), and, where present, oligomers (16 wt%) were first blended together in a polyethylene bag and then added to the K-Tron T-35 feeder. Barrel temperatures ranged from 240 to 280°C and the screw speed was 300 RPM. A 45-degree-1 /8 inch (3.2 mm) single hole die was
• the resins were then solid-phase polymerized in an oven with circulating nitrogen (Blue M Model 336, General Signal Co.). The temperature was increased from room temperature to 235°C over 3 h and then held constant for 24 h. The heaters then turned off and the pellets were removed after cooling. Let-down with additional PET to achieve desired resin composition
• Barrel temperatures ranged were set at 270 0 C. A 3/16 inch (4.8 mm) single hole die was used. The resulting strand was quenched in a water bath and pelletized with a Conair 304 pelletizer. The resulting pellets were then dried.
• EXAMPLES 1-2 COMPARATIVE EXAMPLE A
• Examples 1 and 2 demonstrate the preparation of polyester nanocomposites from masterbatches containing sepiolite and TSPP decahydrate powder.
• Comparative Example A a control polyester nanocomposite was prepared from a masterbatch containing no TSPP decahydrate.
• Nanocomposite resins and test bars were prepared as described above using Crystar® 3905 PET for both masterbatch and let-down and TSPP decahydrate as the sodium salt.
• the TSPP decahydrate was introduced as ground powder, having been ground from as-received flake with a Reitz Hammer Mill (12,000 RPM, 1/16 inch (1.59 mm) die hole screen).
• the masterbatch contained 16 wt% linear oligomer and 20 wt% sepiolite.
• the total masterbatch compounding rate for the examples was 20 Ib/h (9.1 kg/h) and 30 Ib/h (13.6 kg/h) for Comparative Example A.
• Compositions and tensile properties of test bars are presented in Table 1. The tensile testing results show a significant monotonic increase in both tensile strength and elongation-to-break, with no significant change in modulus, upon the addition of TSPP decahydrate.
• Resins and test bars were prepared as described above, using Crystar® 3905 PET for both masterbatch and let-down and TSPP decahydrate as the sodium salt, except that the TSPP decahydrate was introduced as the as-received larger flake, rather than as ground powder.
• the masterbatch contained 16 wt% linear oligomer and 20 wt% sepiolite,
• the masterbatch compounding extruder used a die with a screen pack, employing screens of 20 and 40 mesh surrounding a
• Examples 5-10 COMPARATIVE EXAMPLE C
• Examples 5 through 10 are additional examples of the preparation of polyester nanocomposites from masterbatches containing sepiolite and TSPP decahydrate flake (i.e., unground) or powder.
• Comparative Example C a control polyester nanocomposite was prepared from a masterbatch containing no TSPP decahydrate.
• Resins and test bars were prepared as described above using Crystar® 3905 PET for both masterbatch and let-down and TSPP decahydrate as the sodium salt.
• TSPP decahydrate was introduced at levels of 5, 7.5, or 10 wt% (based on sepiolite) as either ground powder or flake, as indicated in Table 3.
• the masterbatch contained 16 wt% linear oligomer and 20 wt% sepiolite.
• the total masterbatch compounding rate was 40 pph (18.2 kg/h).
• Example 11 illustrates the improved properties resulting from adding TSPP decahydrate to a polyester nanocomposite composition without added linear oligomer.
• Comparative Example D a control polyester nanocomposite was prepared from a masterbatch containing no TSPP decahydrate and no added linear oligomer. The same procedures as above were followed. The total masterbatch compounding rate was 40 pph (18.2 kg/h).
• Examples 12 through 20 demonstrate the effects of PET molecular weight and sodium salt type on nanocomposite properties.
• Resins and test bars were prepared as described above, except that TSPP decahydrate when used was introduced as as-received flake, the oligomers were introduced at either 0 or 16 wt.%, as indicated in Table 5, the total masterbatch compounding rate was 40 pph (18.2 kg/h), a range of sodium salts was used, as indicated in Table 5: TSPP
• Comparative Example E a control polyester nanocomposite was prepared from a masterbatch containing Crystar® 5005, 16 wt% linear oligomer, and no sodium salt.
• Comparative Example E a control polyester nanocomposite was prepared from a masterbatch containing Crystar® 5005, 16 wt% linear oligomer, and no sodium salt.
• Example F a control polyester nanocomposite was prepared from a masterbatch containing Crystar® 5005, no added linear oligomer, and no sodium salt.
• strains-to-break are reported in two ways: an average strain-to-break for the bars that broke in a brittle fashion (i.e., when the stress decreased to zero because the specimen broke as the testing machine continued to increase the jaw distance; the strains in this0 case were measured with an extensometer) and an average nominal
• Examples 22 through 33 demonstrate the effects of PET molecular weight and sodium salt type on nanocomposite properties.
• PET molecular weights can be used in either masterbatch production or
• nanocomposites were prepared from masterbatches containing no sodium
• the range is nevertheless bounded on its lower end by a non-zero

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