THERMOPLASTIC COMPOSITION MIXED BY FUSION, AND, MOLDED ARTICLE BY INJECTION

专利摘要:
Renewable rigid polyester composites with high impact strength and tensile elongation. presentation of a thermoplastic compound containing a rigid renewable polyester and a polymeric hardening additive. the hardening additive can be dispersed as physical domains within a continuous matrix of the renewable polyester. an increase in the deformation force and elongation stress causes the decomposition of the renewable polyester matrix in the areas located adjacent to the discrete domains. this can result in the formation of several void areas adjacent to discrete domains, which can help dissipate energy under load and increase impact strength. to further increase the ability to dissipate this form of energy from the composite, an interphase modifier can be employed, which reduces the degree of friction between the hardening additive and the renewable polyester, and thus increases the degree of uniformity of decomposition.
公开号:BR112014019541B1
申请号:R112014019541-2
申请日:2013-01-28
公开日:2021-06-29
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Neil T. Scholl；Tom Eby
申请人:Kimberly-Clark Worldwide, Inc；
IPC主号:

专利说明:

Invention history
[1] Injection molding is commonly used to form plastic items that are relatively rigid in nature, including containers, medical devices, etc. For example, containers for piles or rolls of wet wipes are generally formed by injection molding techniques. However, a problem associated with these containers is that the molding material is often formed from a synthetic polymer (eg, polypropylene or HDPE) that is not renewable. The use of renewable polymers in an injection molded article presents problems due to the difficulty involved with thermally processing these polymers. Renewable polyesters, for example, have a high glass transition temperature and typically demonstrate very high stiffness and modulus of elasticity, while having relatively low impact strength and low malleability/low elongation at break. As an example, polylactic acid has a glass transition temperature of approximately 59°C and an elastic modulus of approximately 2 GPa or more. However, the tensile elongation (at break) for PLA materials is only approximately 5%, and the resistance to impact deformation (notched) is only approximately 0.22 J/cm. These low impact strength and tensile elongation values considerably limit the use of these polymers in injection molded parts where a good balance between material stiffness and impact strength is required.
[2] As such, there is currently a need for a renewable polyester composition that is capable of exhibiting relatively high impact strength and stress elongation so that it can be readily employed in injection molded articles. Summary of the invention
[3] According to one embodiment of the present invention, a melt blended thermoplastic composition comprising at least one rigid and renewable polyester having a glass transition temperature of approximately 0°C or more of approximately 1% is disclosed. of mass to approximately 30% by mass of at least one polymeric hardening additive, based on the mass of the renewable polyester, and from approximately 0.1% by mass to approximately 20% by mass of at least one interphase modifier based on the renewable polyester mass. The thermoplastic composition has a morphology in which several distinct primary domains are dispersed within a continuous phase, with the domains containing the polymeric hardening additive and the continuous phase containing the renewable polyester. In addition, the composition exhibits an Izod strength of approximately 0.3 J/cm or more, measured at 23°C, in accordance with ASTM D256-10 (Method A) and a stress elongation at break of approximately 10% or more , measured at 23°C, in accordance with ASTM D638-10. In addition, the ratio of the glass transition temperature of the thermoplastic composition to the glass transition temperature of the renewable polyester is from approximately 0.7 to approximately 1.3.
[4] According to another embodiment of the present invention, a molded article formed from a thermoplastic composition has been disclosed. The thermoplastic composition comprises approximately 70% by mass or more of at least one polylactic acid with a glass transition temperature of approximately 0°C or more, from approximately 0.1% by mass to approximately 30% by mass, of at least one polymeric hardening additive, and from approximately 0.1% by mass to approximately 20% by mass of at least one interphase modifier. The molded article exhibits an Izod strength of approximately 0.3 J/cm or more, measured at 23°C, in accordance with ASTM D256-10 (Method A) and a tensile elongation at break of approximately 10% or more, measured at 23°C, in accordance with ASTM D63810.
[5] Other features and aspects of the present invention are discussed in more detail below. Brief description of the illustrations
[6] A complete and clarifying description of the present invention, including its best mode, directed to people with technical knowledge in the area, is demonstrated in more detail in the rest of the specification, which makes reference to the attached figures in which: Fig. 1 is a schematic illustration of an embodiment of an injection molding apparatus for use in the present invention; Fig. 2 is an SEM photomicrograph of a sample from Example 1 prior to testing; Fig. 3 is an SEM photomicrograph of a sample from Example 1 after the impact test; Fig. 4 is an SEM photomicrograph of a sample from Example 3 prior to testing; Fig. 5 is an SEM photomicrograph of a sample from Example 3 after the impact test; and Fig. 6 is an SEM photomicrograph of a sample from Example 3 after stress testing and recording of the oxygen plasma.
[7] The repeated use of reference characters in this specification and drawings is intended to represent the same or similar features or elements of the present invention. Detailed description of representative embodiments
[8] Detailed references will be made to various configurations of the invention, with one or more examples described below. Each example is provided for the purpose of explaining the invention and not as a limitation of it. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one configuration can be used in another configuration to obtain a third configuration. Thus, it is intended that the present invention cover such modifications and variations as are within the scope of the appended claims and their equivalents.
[9] In general, the present invention is directed to a thermoplastic composition that contains a rigid and renewable polyester and a polymeric hardening additive. The present inventors have found that the specific nature of the components can be carefully controlled in order to achieve a composition with the desired morphological characteristics. More specifically, the hardening additive can be dispersed as distinct physical domains within a continuous matrix of the renewable polyester. During the initial application of an external force with low elongation stress, the composition can behave like a monolithic material that exhibits high stiffness and high modulus of stress. However, an increase in the deformation force and in the elongation stress causes the decomposition of the renewable polyester matrix in the areas adjacent to the distinct domains. This can result in the formation of several void areas adjacent to discrete domains, which can help dissipate energy under load and increase impact strength. To further increase the composition's ability to dissipate this form of energy, the present inventors have found that an interface modifier can be employed in the composition, which reduces the degree of friction and connectivity between the hardening additive and the renewable polyester, and thus , increases the degree of uniformity of decomposition. In this way, the resulting voids can be distributed in a substantially homogeneous way throughout the composition. For example, voids can be distributed in columns that are oriented in a direction normally perpendicular to the direction in which the stress is applied. Without intending to impose theoretical limitations, it is believed that the presence of this homogeneously distributed space system can result in a significant dissipation of energy under load and a significantly higher resistance.
[10] The resulting thermoplastic composition, as well as the articles formed therefrom, typically have a high level of strength due to the unique morphology achieved by the present invention. The composition mode can, for example, process an Izod (notched) resistance of approximately 0.3 Joules per centimeter (“J/cm”) or more, in some configurations of approximately 0.5 J/cm or more, and in some configurations from approximately 0.8 J/cm to approximately 2.5 J/cm, measured at 23°C, per ASTM D256-10 (Method A). Stress elongation at break can also be relatively high, such as approximately 10% or more, in some compositions, approximately 50% or more, and in some compositions, approximately 100% to approximately 300%. By achieving a high level of tensile strength and elongation, the present inventors have found that other mechanical properties are not adversely affected. For example, the composition may have a peak voltage of approximately 10 to approximately 65 Megapascals (“MPa”), in some configurations, from approximately 15 to approximately 55 MPa, and in some configurations, from approximately 25 to approximately 50 MPa; a tensile strength of approximately 10 to approximately 65 MPa, in some compositions, from approximately 15 to approximately 60 MPa, and in some compositions, from approximately 20 to approximately 55 MPa; and/or a voltage modulus of approximately 500 to approximately 3800 MPa, in some compositions, from approximately 800 MPa to approximately 3400 MPa, and in some compositions, from approximately 1000 MPa to approximately 3000 MPa. Stress properties can be determined in accordance with ASTM D638-10 at 23°C.
[11] Various embodiments of the present invention will now be described in more detail. 1. Thermoplastic composition A. Renewable polyester
[12] Renewable polyesters typically constitute from approximately 70% by mass to approximately 99% by mass, in some embodiments from approximately 75% by mass to approximately 98% by mass, and in other embodiments from approximately 80% by mass to approximately 95% by mass of the thermoplastic composition. Various renewable polyesters can normally be employed in the thermoplastic composition, such as those such as aliphatic polyesters such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (eg, polyethylene carbonate), poly-3- hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, copolymers of poly-3-hydroxybutyrate-co3-hydroxyvalerate (PHBV), poly-3-hydroxybutyrate-co-3 -hydroxyhexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxydecanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and succinate-based aliphatic polymers (eg, polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (eg polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene adipate isophthalate, polybutylene adipate isophthalate etc.); aromatic polyesters (for example polyethylene terephthalate, polybutylene terephthalate etc.); and so on.
[13] Typically, the thermoplastic composition contains at least one renewable polyester that is rigid in nature and thus has a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be about 0°C or more, in some embodiments from about 5°C to 100°C, in some embodiments from about 30° C to about 80°C, and in some embodiments, from about 50°C to 75°C. Renewable polyester can also have a melting temperature of from about 140°C to 260°C, in some embodiments from about 150°C to about 250°C, and in some embodiments, from about from 160°C to 220°C. The melting temperature can be determined using Differential Scanning Calorimetry (“DSC”) in accordance with ASTM D-3417. The glass transition temperature can be determined by dynamic-mechanical analysis in accordance with ASTM E1640-09.
[14] An especially suitable rigid polyester is polylactic acid, which can be derived from monomeric units of any lactic acid isomer, such as levorotatory lactic acid ("L-lactic acid"), dextrorotatory lactic acid ("Dlactic acid"), meso-lactic or combinations of these. Monomeric units can also be formed from anhydrides of any lactic acid isomer, including L-lactide, D-lactide, meso-lactide or combinations thereof. Cyclic dimers of these lactic acids and/or lactides can also be used. Any known polymerization method, such as polycondensation or ring opening polymerization, can be used to polymerize lactic acid. A small amount of a chain-extending agent (for example, a diisocyanate compound, an epoxy compound, or an acid anhydride) may also be employed. The polylactic acid can be a homopolymer or a copolymer, such as one containing monomeric units derived from lactic acid and monomeric units derived from D-lactic acid. Although not necessary, the content ratio of an L-lactic acid derived monomer unit and D-lactic acid derived monomer unit is preferably about 85% mol or more, in some embodiments about 90% mol or more, and in some embodiments, about 95% mol or more. Various polylactic acids, each with a different ratio between the L-lactic acid-derived monomer unit and the D-lactic acid-derived monomer unit, can be mixed at any random percentage. Of course, polylactic acid can be blended with other types of polymers (eg polyolefins, polyesters, etc.).
[15] In a specific embodiment, polylactic acid has the following general structure:

[16] A specific example of a suitable polylactic acid polymer that can be used in the present invention is marketed by Biomer, Inc. of Krailling, Germany) under the name BIOMER™ L9000. Other suitable polylactic acid polymers are commercially available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEA™). Other suitable polylactic acids can be described in U.S. Patent Nos. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254; and 6,326,458, which are incorporated herein in their entirety by reference for all purposes.
[17] Polylactic acid typically has a number average molecular weight ("Mn") ranging from about 40,000 to 160,000 grams per mole, in some embodiments from about 50,000 to 140,000 grams per mole, and in some embodiments some embodiments, from about 80,000 to 120,000 grams per mol. Likewise, the polymer also typically has an average molecular weight ("Mw") ranging from about 80,000 to 200,000 grams per mole, in some embodiments from about 100,000 to 180,000 grams per mole, and in some embodiments embodiments, from about 110,000 to 160,000 grams per mol. The relationship between the weight average molecular mass and the number average molecular mass ("Mw/Mn"), i.e. the "polydispersity index", is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to about 3.0, in some embodiments from about 1.1 to about 2.0, and in some embodiments from about from 1.2 to about 1.8. The weight and weight average molecular mass numbers can be determined by methods known to those skilled in the art.
[18] Polylactic acid may also have an apparent viscosity of from about 50 to about 600 Pascal seconds (Pa's), in some embodiments, from about 100 to about 500 Pa's, and in some embodiments, from about 200 to about 400 Pas, as determined at a temperature of 190°C and a shear rate of 1000 sec-1. The melt flow index of polylactic acid (on a dry basis) can also range from about 0.1 to about 40 grams per 10 minutes, in some embodiments, from about 0.5 to about 20 grams per 10 minutes and, in some embodiments, from about 5 to about 15 grams per 10 minutes, determined at a load of 2160 grams and at 190°C.
[19] Some types of pure polyester (eg, polylactic acid) can absorb water from an environment in such a way that it has a moisture content of approximately 500 ppm to 600 parts per million (“ppm”), or even higher, based on in the dry weight of the starting polylactic acid. Moisture content can be determined in various ways, as is known in the art, in accordance with ASTM D 7191-05, as described below. As the presence of water during melt processing can hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes better to dry the polyester before blending it. In most embodiments, for example, it is best for the renewable polyester to have a moisture content of about 300 parts per million ("ppm") or less, in some embodiments about 200 ppm or less, in some embodiments from about 1 to about 100 ppm prior to mixing with the curing additive. Drying of polyester can occur, for example, at a temperature of from about 50°C to about 100°C, and in some embodiments, from about 70°C to about 80°C. B. Polymeric Hardening Additive
[20] As indicated above, the thermoplastic composition of the present invention also contains a polymeric hardening additive. Due to its polymeric nature, the hardening additive has a relatively high molecular weight which can help to improve the meltability and stability of the thermoplastic composition. Although not required, the polymeric hardening additive can be immiscible with the renewable polyester. In this way, the hardening additive can best be spread as distinct phase domains within a continuous phase of the renewable polyester. The distinct domains are able to absorb energies arising from an external force, which increases the rigidity and total strength of the resulting material. Domains can have a variety of different shapes such as elliptical, spherical, cylindrical etc. In one embodiment, the domains are quite elliptical in shape. The physical dimension of an individual domain is usually small enough to minimize the propagation of cracks in the polymeric material by applying an external stress, but large enough to initiate microscopic plastic deformation and allow for shear zones in particle inclusions or the around them.
[21] Although polymers can be immiscible, the hardening additive can still be selected having a solubility parameter that is relatively similar to that of renewable polyester. This can improve the interfacial compatibility and physical interaction of distinct and continuous phase boundaries and thus reduce the likelihood of composition disruption. For that, the ratio of the solubility parameter of the renewable polyester to the setting additive parameter is typically from about 0.5 to about 1.5, and in some embodiments, from about 0.8 to about 1.2. For example, the polymeric hardening additive can have a solubility parameter of from about 15 to about 30 MJoules1/2/m3/2, and in some embodiments, from about 18 to about 22 MJoules1/2/m3 /2, while polylactic acid can have a solubility parameter of about 20.5 MJoules1/2/m3/2. The term “solubility parameter”, as used herein, refers to the “Hildebrand Solubility Parameter”, which is the square root of the cohesive energy density, calculated using the following equation:
where: 4Hv = heat of vaporization R = Constant of perfect gases T = Temperature Vm = Molecular volume
[22] Hildebrand solubility parameters for many polymers are also found in Wyeych's Solubility Handbook of Plastics (2004), which is incorporated herein by reference.
[23] The polymeric hardening additive may also have a melt index (or viscosity) to ensure that the distinct domains and resulting voids can be properly maintained. For example, if the melt index of the hardening additive is too high, it tends to flow and disperse uncontrollably during the continuous phase. This results in lamellar or plaque-shaped domains that are difficult to maintain and likely to rupture prematurely. On the other hand, if the melt index of the hardening additive is too low, it will tend to clump together and form very large elliptical domains, which are difficult to disperse during mixing. This can cause uneven distribution of the hardening additive throughout the continuous phase. In this regard, the present inventors have found that the ratio of the melt flow rate of the hardening additive to the melt flow rate of the renewable polyester is typically from about 0.2 to 8, in some embodiments from about 0.5 to 6, and in some embodiments from about 1 to 5. The hardening additive may, for example, have a melt index of 0.1 to about 250 grams per 10 minutes, in some forms from about 0.5 to about 200 grams per 10 minutes and, in other embodiments, from about 5 to about 150 grams per 10 minutes, determined at a load of 2160 grams and at 190°C.
[24] In addition to the properties noted above, the mechanical characteristics of the polymeric hardening additive can also be selected to achieve the desired increase in stiffness. For example, when a mixture of the renewable polyester and the hardening additive is applied with an external force, shear and/or plastic flow zones may be initiated in and around distinct phase domains as a result of stress concentrations that arise from a difference in the modulus of elasticity of the hardening additive and the renewable polyester. Higher stress concentrations promote a more intense localized plastic flux in the domains, allowing them to undergo considerable elongation when subjected to stress. These elongated domains allow the composition to exhibit a more flexible and softer behavior than rigid polyester resin. To improve stress concentrations, the hardening additive is selected so that it has a relatively low Young's modulus of elasticity compared to renewable polyester. For example, the ratio of the modulus of elasticity of the renewable polyester to that of the hardening additive is typically from about 1 to about 250, in some embodiments from about 2 to about 100, and in some embodiments. , from about 2 to about 50. The modulus of elasticity of the hardening additive can, for example, range from about 2 MPa to about 500 megapascals (MPa), in some embodiments of about 5 MPa to about 300 MPa, and in some embodiments, from about 10 MPa to about 200 MPa. In contrast, the modulus of elasticity of polylactic acid is typically approximately 800 MPa to approximately 2000 MPa.
[25] To provide the desired increase in stiffness, the polymeric hardening additive may also exhibit greater elongation at break (ie, the percentage of polymer elongation at its pour point) than renewable polyester. For example, the polymeric curing additive of the present invention may exhibit an elongation at break of about 50% or more, in some embodiments from about 100% or more, in some embodiments from about 100% to about from 2,000%, and in some embodiments, from about 250% to about 1,500%.
[26] Although a wide variety of polymeric additives with the properties identified above can be employed, especially suitable examples of such polymers (eg, polyethylene, polypropylene, polybutylene etc.); styrenic copolymers (for example, styrene-butadiene-styrene, styrene-styrene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-butadiene-styrene etc.); polytetrafluoroethylenes; polyesters (eg recycled polyester, polyethylene terephthalate etc.); polyvinyl acetates (for example, poly(ethylene vinyl acetate), polyvinyl chloride acetate etc.); polyvinyl alcohols (eg polyvinyl alcohol, poly(ethylene vinyl alcohol), etc.); polyvinyl butyral; acrylic resins (for example, polyacrylate, polymethylacrylate, polymethylmethacrylate etc.); polyamides (for example nylon); polyvinyl chlorides; polyvinylidene chlorides; polystyrenes, polyurethanes etc. Suitable polyolefins may, for example, include ethylene polymers (eg, low density polyethylene ("PE-LD"), high density polyethylene ("HDPE"), linear low density polyethylene ("LDPE") etc. ), propylene homopolymers (eg syndiotactic, atactic, isotactic etc.), propylene copolymer and so on.
[27] In a given composition, the polymer is propylene, such as homopolypropylene or a copolymer of propylene. The propylene polymer can, for example, be formed of an isotactic polypropylene homopolymer or a copolymer containing an amount equal to or less than approximately 10% by mass of another monomer, i.e. at least approximately 90% by mass of propylene. These polymers can have a melting point of approximately 160°C to approximately 170°C.
[28] In yet another composition, the polyolefin can be a copolymer of ethylene or propylene with another α-olefin, such as C3-C20 α-olefin or C3-C12 α-olefin. Specific examples of suitable α-olefins are 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substitutes; 1-hexene with one or more methyl, ethyl or propyl substitutes; 1-heptene with one or more methyl, ethyl or propyl substitutes; 1-octene with one or more methyl, ethyl or propyl substitutes; 1-nonene with one or more methyl, ethyl or propyl substitutes; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. Especially desired α-olefin comonomers are 1-butene, 1-hexene and 1-octene. The ethylene and propylene content of these copolymers can range from 60% to 99% mol, in some embodiments from 80% to 98.5% mol, and in some embodiments, from 87% to 97.5% mol. Aolefin content can similarly range from approximately 1% by mol to approximately 40% by mol, in some embodiments, from approximately 1.5% by mol to approximately 15% by mol, and in other embodiments, from approximately 2.5% by mol to approximately 13% by mol.
[29] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers, available under the EXACT™ designation, from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are available as ENGAGE™, AFFINITY™, DOWLEX™ (LLDPE) and ATTANE™ (ULDPE) from the Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patents 4,937,299 to Ewen et al.; 5,218,071 to Tsutsui et al.; 5,272,236 to Lai et al.; and 5,278,272 to Lai et al., which are included in their entirety herein by reference for all purposes. Exemplary propylene copolymers are commercially available under the designations VISTAMAXX™ from ExxonMobil Chemical Co. of Houston, Texas; FINA™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER™ available from Mitsui Petrochemical Industries; and VERSIFY™, available from Dow Chemical Co. of Midland, Michigan. Other examples of suitable propylene polymers are described in U.S. Patents 6,500,563 to Datta et al.; 5,539,056 to Yang et al.; and 5,596,052 to Resconi et al., which are included in their entirety herein as a reference for all purposes.
[30] Any of several known techniques can be employed to form olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordination catalyst (eg Ziegler-Natta). Typically, the olefin polymer is formed from a single-site coordination catalyst such as a metallocene catalyst. This catalyst system produces ethylene copolymers, in which the comonomer is randomly distributed within a molecular chain and evenly distributed among the different molecular weight fractions. Metallocene catalyzed polyolefins are described, for example, in U.S. Patents 5,571,619 to McAlpin et al.; 5,322,728 to Davis et al.; 5,472,775 to Obijeski et al.; 5,272,236 to Lai et al.; and 6,090,325 to Wheat et al., which are incorporated in their entirety herein by reference for all purposes. Examples of metallocene catalysts include bis(nbutylcyclopentadienyl)titanium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)scandium chloride, bis(indenyl)zirconium dichloride, bis(methylcyclopentadienyl) titanium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafniocene dichloride, isopropyl(cyclopentadienyl,-1-fluorenyl)zirconium dichloride, molybdocene dichloride, nickelocene, titanium dichloride, titanium dichloride, titanium dichloride zirconocene hydroxide, zirconocene dichloride, etc. Polymers created using the metallocene catalyst typically have a narrow molecular mass range. For example, metallocene catalyzed polymers can have polydispersity numbers (Mw/Mn) below 4, controlled short chain branching distribution, and controlled isotacticity.
[31] Regardless of the materials used, the relative percentage of polymeric hardening additive in the thermoplastic composition is selected in order to achieve the desired properties without considerably affecting the renewability of the resulting composition. For example, the hardening additive is typically employed in the amount of from about 1% to about 30% by weight, in some embodiments from about 2% to about 25% by weight, and in other embodiments from about 5% to about 20% by weight of the thermoplastic compositions, based on the weight of the renewable polyesters employed in the compound. The concentration of the setting additive throughout the thermoplastic composition can also form from about 0.1% to about 30% by weight, in some embodiments from about 0.5% to about 25% by weight and , in other embodiments, from about 1% to about 20% by weight. C. Interface modifier
[32] An interphase modifier is also employed in the thermoplastic composition to alter the interaction between the hardening additive and the renewable polyester matrix. Typically, the modifier form is liquid or semi-solid at room temperature (eg, 25°C) so it has a relatively low viscosity, allowing it to be more quickly incorporated into the thermoplastic composition and easily migrated to polymer surfaces. In this regard, the kinematic viscosity of the interphase modifier is typically from about 0.7 cs to about 200 centistokes ("CS"), in some embodiments from about 1 cs to about 100 cs, and in some embodiments, from about 1.5 cs to about 80 cs, determined at 40°C. In addition, the interphase modifier is also typically hydrophobic, such that it has an affinity for the polymer's hardening additive, which results in a change in interfacial tension between the polyester and the renewable hardening additive. By reducing the physical forces at the interfaces between the polyester and the hardening additive, it is believed that the hydrophobic and low viscosity nature of the modifier can help facilitate the peeling of the polyester matrix until an external force is applied. As used herein, the term "hydrophobic" typically refers to material that has a contact angle of water and air of approximately 40° or more and, in some cases, approximately 60° or more. In contrast, the term “hydrophilic” usually refers to material that has a contact angle of water and air less than approximately 40°. A suitable test for measuring contact angle is ASTM D5725-99 (2008).
[33] Some suitable hydrophobic and low viscosity interphase modifiers are, for example, silicones, silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (eg, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol etc.), alkanes diols (eg 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol , etc.), amine oxides (eg octyldimethylamine oxide), fatty acid esters, etc. An especially suitable interphase modifier is polyester polyol, such as those sold under the trade name PLURIOL® WI by BASF Corp. Another particularly suitable modifier is the partially renewable ester, such as that sold under the trade name HALLGREEN® IM by Hallstar.
[34] Although the actual amount may vary, the interphase modifier is typically employed in the amount of from about 0.1% to about 20% by weight, in some embodiments from about 0.5% to about 15 % by weight and, in other embodiments, from about 1% to about 10% by weight of the thermoplastic compounds, based on the weight of the renewable polyesters employed in the compound. The concentration of interphase modifiers throughout the thermoplastic composition can likewise be formed from about 0.05% to about 20% by weight, in some embodiments from about 0.1% to about 15 % by weight and, in other embodiments, from about 0.5% to about 10% by weight.
[35] When using the amounts noted above, the interphase modifier has a characteristic that will allow it to rapidly migrate to the interfacial surface of the polymers and facilitate debonding without damaging the melting properties of the thermoplastic composition. For example, the interphase modifier normally does not have a plasticizing effect on the polymer by reducing its glass transition temperature. Rather, the present inventors have found that the glass transition temperature of the thermoplastic composition can be the same as that of the initial renewable polyester. In this regard, the ratio of the glass temperature of the composition to that of the polyester is typically from about 0.7 to about 1.3, in some embodiments from about 0.8 to about 1. 2, and in some embodiments, from about 0.9 to about 1.1. The thermoplastic composition can be, for example, have a glass transition temperature between about 35°C to about 80°C, in some embodiments from about 40°C to 80°C, and in some embodiments , from about 50°C to 65°C. The melt flow rate of the thermoplastic composition may also be similar to that of renewable polyester. For example, the melt flow index of the composition (on a dry basis) can be from about 0.1 to about 70 grams per 10 minutes, in some embodiments from about 0.5 to about 50 ranges per 10 minutes and, in other embodiments, from about 5 to about 25 grams per 10 minutes, determined at a load of 2160 grams and a temperature of 190°C. D. Compatibilizer
[36] As noted above, the polymeric hardening additive is typically selected so that it has a solubility parameter relatively close to that of renewable polyester. Among other things, this can improve phase compatibility and increase the overall distribution of distinct domains within the continuous phase. However, in certain embodiments, a compatibilizer can optionally be employed to further increase the degree of compatibility between the renewable polyester and the polymeric curing additive. This may be desirable especially when the polymeric hardening additive has a polar part such as polyurethanes, acrylic resins etc. When employed, compatibilizers are typically formed from approximately 0.5% by mass to approximately 20% by mass; in some embodiments, from approximately 1% by mass to approximately 15% by mass, and in other embodiments, from approximately 1.5% by mass to approximately 10% by mass of the thermoplastic composition. An example of a suitable compatibilizer is functionalized polyolefin. The polar component can, for example, be provided by one or more functional groups, and the non-polar component can be provided by an olefin. The olefin component of the compatibilizer typically can be formed from any branched or linear α-olefin monomer, oligomer or polymer (including copolymers) derived from an olefin monomer as described above.
[37] The functional group of the compatibilizer can be any group that provides a polar segment to the molecule. Especially suitable functional groups are maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a reaction product of maleic anhydride and diamine, methylnadic anhydride, dichloromaleic anhydride, maleic acid amide etc.
[38] Maleic anhydride-modified polyolefins are especially suitable for use in this invention. These modified polyolefins are typically formed by grafting maleic anhydride onto a polymeric backbone material. These maleated polyolefins are marketed by EI du Pont de Nemours and Company under the name FUSABOND® as the P series (chemically modified polypropylene), the E series (chemically modified polyethylene), the C series (chemically modified vinyl acetate ethylene) , the A series (chemically modified ethylene acrylate copolymers or terpolymers) or the N series (chemically modified ethylene-propylene, ethylene-propylene diene ("EPDM") or ethylene-octene monomer). Alternatively, maleated polyolefins are also marketed by Chemtura Corp. under the name Polybond® and by Eastman Chemical Company under the name Eastman G series.
[39] In certain embodiments, the compatibilizer can also be reactive. An example of this reactive compatibilizer is the polyepoxide modifier that contains, on average, at least two oxirane rings per molecule. Without intending to be bound by theory, it is believed that these polyepoxide molecules can induce a reaction of the renewable polyester under certain conditions, thus improving their meltability without greatly reducing the glass transition temperature. The reaction may involve chain extension, side chain branching, grafting, copolymer formation, etc. Chain extension, for example, can occur through a variety of different reactive pathways. For example, the modifier may allow a nucleophilic ring-opening reaction via a carboxyl end group of the renewable polyester (esterification) or via a hydroxyl group (etherification). Reactions on the oxazoline side can occur and form organic stearamide functions. Through these reactions, the molecular mass of the renewable polyester can be increased to combat the degradation often observed during the melting process. While it is desirable to induce a reaction with the renewable polyester as described above, the present inventors have found that too much reaction can cause crosslinking between the polyester structures. If this crosslinking is allowed to proceed to a considerable extent, the resulting polymer blend can become brittle and difficult to mold into a material with the desired strength and elongation properties.
[40] In this regard, the present inventors have found that polyepoxide modifiers with a relatively low epoxy resource are especially effective, which can be quantified by their "epoxy equivalent weight". The epoxy equivalent weight reflects the amount of resin that contains a molecule of an epoxy group, and can be calculated by dividing the number average molecular mass of the modifier by the number of epoxy groups in the molecule. The polyepoxide modifier of the present invention typically has a number average molecular weight of from about 7,500 g/mol to 250,000 grams per mol, in some embodiments from about 15,000 g/mol to 150,000 grams per mol, and in some forms of embodiment, from about 20,000 g/mol to 100,000 grams per mol, with a polydispersity index typically ranging from 2.5 to 7. The polyepoxide modifier may contain less than 50, in some embodiments from 5 to 45, and in some embodiments, from 15 to 40 epoxy groups. On the other hand, the equivalent weight of epoxy can be less than 15,000 grams per mol approximately; in some embodiments, 200 to 10,000 grams per mole approximately, and in other embodiments, 500 to 7,000 grams per mole approximately.
[41] Polyepoxide can be a linear or branched homopolymer or copolymer (eg, random, graft, block, etc.) containing terminal epoxy groups, skeletal oxirane units, and/or pendant epoxy groups. The monomers used to form these polyepoxides can vary. In a specific embodiment, for example, the polyepoxide modifier contains at least one epoxy-functional (meth)acrylic monomeric component. As used herein, the term "(meth)acrylic" includes acrylic and methacrylic monomers, as well as salts or esters thereof, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meth)acrylic monomers can include, but are not limited to, those containing 1,2-epoxy groups such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate and glycidyl itoconate.
[42] Polyepoxide typically has a relatively high molecular mass, as indicated above, so it may not only result in chain extension of the renewable polyester, but also help achieve the desired blend morphology. Thus, the resulting melt flow rate of the polymer ranges from about 10 g to about 200 grams per 10 minutes, in some embodiments from about 40 g to 150 grams per 10 minutes, and in some embodiments from about 60 g to 120 grams for 10 minutes, determined at a load of 2,160 grams and a temperature of 190°C.
[43] If desired, other monomers can also be employed in the polyepoxide to help achieve the desired molecular mass. Such monomers can vary and include, for example, ester monomers, (meth)acrylic monomers, olefin monomers, amide monomers, etc. In a certain embodiment, for example, the polyepoxide modifier includes at least one linear or branched α-olefin monomer, such as those with 2 to 20 carbon atoms and preferably with 2 to 8 carbon atoms. Specific examples are ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substitutes; 1-hexene with one or more methyl, ethyl or propyl substitutes; 1-heptene with one or more methyl, ethyl or propyl substitutes; 1-octene with one or more methyl, ethyl or propyl substitutes; 1-nonene with one or more methyl, ethyl or propyl substitutes; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. Specifically desired α-olefin comonomers are ethylene and propylene.
[44] Another suitable monomer may include a (meth)acrylic monomer that is not epoxy-functional. Examples of such (meth)acrylic monomers may be methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, tbutyl acrylate , n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, nhexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-methacrylate amyl, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate, cyclohexyl methacrylate, methacrylate of cyclopentyl, 2-ethoxyethyl methacrylate, d methacrylate and isobornyl etc., as well as combinations of these.
[45] In a particularly desirable composition of the present invention, the polyepoxide modifier is a terpolymer formed from an epoxy-functional monomeric (meth)acrylic component, an α-olefin monomeric component and a non-functional (meth)acrylic monomeric component. epoxy-functional. For example, the polyepoxide modifier can be poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate), with the following structure:
where x, y and z are 1 or greater.
[46] The epoxy-functional monomer can be formed into a polymer using several known techniques. For example, a monomer containing polar functional groups can be grafted onto a polymer backbone to form a grafted copolymer. Such grafting techniques are well known in the art and are described, for example, in U.S. patent no. 5,179,164, which is incorporated herein in its entirety by reference for all purposes. In other embodiments, a monomer containing epoxy functional groups can be copolymerized with a monomer to form a random block or copolymer using known free radical polymerization techniques such as high pressure reactions, ZieglerNatta catalysis reaction systems, single-site catalysis reaction systems (eg metallocene), etc.
[47] The relative part of the monomeric components can be selected in order to achieve a balance between epoxy reactivity and melt index. More specifically, high epoxy monomer contents can result in good reactivity with the renewable polyester, but too high a content can reduce the melt index to such an extent that the polyepoxide modifier negatively affects the melt strength of the polymer blend. Thus, in most embodiments, the epoxyfunctional (meth)acrylic monomers are formed from approximately 1% to 25% by mass; in some embodiments; from 2% to 20% of the mass approximately e; in other embodiments; 4% to 15% of the approximate mass of the copolymer. The α-olifine monomers can also constitute from about 55% to 95% by weight, in some embodiments from about 60% to 90% by weight, and in some embodiments, from about 65% to 85% by weight. When used, other monomeric components (eg, non-epoxyfunctional (meth)acrylic monomers) may constitute approximately 5% to 35% of the mass; in some embodiments from approximately 8% to 30% by mass and in other embodiments from approximately 10% to 25% by mass of the copolymer. A specific example of a suitable polyepoxide modifier that can be used in this invention is marketed by Arkema under the name LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a pour rate of 70 to 100 g/10 min and an amount of glycidyl methacrylate monomer from 7% by weight to 11% by weight, an amount of methyl acrylate monomer from 13% of mass at 17% mass, and an amount of ethylene monomer from 72% mass to 80% mass.
[48] In addition to controlling the type and relative content of the monomers used to form the polyepoxide modifier, the overall mass percentage can also be controlled in order to achieve the desired benefits. For example, if the modification level is too low, the desired increase in melt strength and mechanical properties may not be obtained. The present inventors have also discovered, however, that if the level of modification is too high, molding may be restricted due to strong molecular interactions (eg, cross-linking) and physical network formation by epoxy-functional groups. Thus, the polyepoxide modifier is normally employed in an amount of from about 0.05% to about 10% by weight; in some embodiments, from about 0.1% to about 8% by weight, in other embodiments, from about 0.5% to about 5% by weight, and in other embodiments, from about 1% to about 3% by weight, based on the weight of the renewable polyesters employed in the composition. The polyepoxide modifier can also constitute from about 0.05% to about 10% by weight; in some embodiments, from about 0.05% to about 8% by weight, in other embodiments, from about 0.1% to about 5% by weight, and in other embodiments, from about 0.5% to about 3% by weight, based on the total weight of the compound.
[49] When employed, a polyepoxide modifier can also influence the morphology of the thermoplastic composition in a way that further increases its reactivity with the renewable polyester. More especially, the resulting morphology can have several distinct domains of the polyepoxide modifier, distributed throughout a continuous polyester matrix. These "secondary" domains can have many different shapes, for example, elliptical, spherical, cylindrical, etc. However, regardless of shape, the size of an individual secondary domain after mixing is small to provide a larger surface area for the reaction with the renewable polyester. For example, the size of a secondary domain (eg, length) typically ranges from approximately 10 to 1000 nanometers; in some embodiments, approximately 20 to 800 nanometers; in some embodiments, approximately 40 to 600 nanometers, and in other embodiments, approximately 50 to 400 nanometers. As indicated above, the hardening additive also forms distinct domains within the polyester matrix, which are considered to be among the “primary” domains of the composition. It should also be understood that domains can be formed by a combination of polyepoxide, hardening additive and/or other blend components.
[50] In addition to polyepoxides, other reactive compatibilizers can also be used in the present invention, such as polymers functionalized with oxazoline, polymers functionalized with cyanide, etc. When employed, these reactive compatibilizers can be employed within the concentrations indicated above for the polyepoxide modifier. In a specific composition, an oxazoline grafted polyolefin can be employed, that is, a polyolefin grafted with a monomer containing an oxazoline ring. Oxazoline may include 2-oxazolines such as 2-vinyl-2-oxazoline (eg 2-isopropenyl-2-oxazoline), 2-fatty acid-alkyl-2-oxazoline (eg obtained from oleic acid ethanolamide, linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and/or arachidonic acid) and combinations thereof. In another composition, oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soy-2-oxazoline, ricino-2-oxazoline and combinations thereof, for example. In yet another embodiment, the oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof. E. Other components
[51] A beneficial aspect of this invention is that quality mechanical properties (eg elongation) can be achieved without the need for conventional plasticizers such as solid or semi-solid polyethylene glycol, marketed by Dow Chemical under the name Carbowax™). The thermoplastic composition can be substantially free of these plasticizers. However, it should be understood that plasticizers can be used in certain embodiments of the present invention. When used, however, plasticizers are typically present in an amount less than about 10% by weight, in some embodiments from about 0.1% to 5% by weight, and in some embodiments, from from about 0.2% to 2% by weight of the thermoplastic composition. Obviously, other ingredients can be used for a number of different reasons. For example, materials that can be used include, but are not limited to, catalysts, pigments, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents (eg, titanium dioxide, calcium carbonate, etc.), particulates and other added materials in order to improve the processability of the thermoplastic composition. When employed, it is preferable that the amounts of these additional ingredients are kept to a minimum in order to ensure the highest compatibility and cost-effectiveness. Thus, for example, it is normally preferred that such ingredients constitute less than about 10% by weight; in some embodiments less than about 8% by weight and in other embodiments less than about 5% by weight of the thermoplastic composition. II. Mix
[52] The raw materials (eg renewable polyester, hardening additive and interphase modifiers can be blended using a variety of known techniques. In a composition, for example, the raw materials can be supplied separately or as a combination For example, the raw materials can first be dry blended to form an essentially homogeneous dry mixture. The raw materials can also be supplied simultaneously or sequentially to a melt processing device, which dispersively mixes the materials Batch and/or continuous melt processing techniques can be employed, for example, a mixer/kneader, Banbury mixer, Farrel continuous mixer, single screw extruders, twin screw extruders, rolling mills etc. can be used to mix and melt processing the materials. Especially suitable melt processing apparatus may be a double screw extruder. o-rotation (for example, the ZSK-30 extruder marketed by Werner & Pfleiderer Corporation of Ramsey, New Jersey or a Thermo Prism™ USALAB 16 extruder marketed by Thermo Electron Corp., Stone, England). These extruders can include feed and vent ports and provide high intensity distributive and dispersive mixing. For example, raw materials can be introduced into the same or different ports of the twin screw extruder and melt blended to form a very homogeneous molten mixture. If desired, other additives can also be injected into the molten polymer and/or separately introduced into the extruder at a different point along its length. Alternatively, the additives can be pre-mixed with the renewable polyester, the hardening additive and/or the interphase modifier.
[53] Regardless of the specific processing technique chosen, raw materials are mixed under sufficient shear/pressure and heat to ensure sufficient dispersion, but not so high as to negatively reduce the size of the distinct domains, rendering them incapable to achieve the desired firmness and stretch. For example, mixing normally takes place at a temperature of 180°C to approximately 260°C; in some embodiments from approximately 185°C to 250°C and in other embodiments from approximately 190°C to 240°C. Likewise, the apparent shear rate during the melting process can range from 10 s-1 to approximately 3000 seconds-1; in some embodiments, from 50 s-1 to 2000 seconds-1 approximately, and in other embodiments, from 100 s-1 to 1200 seconds-1 approximately. The apparent shear rate is equal to 4Q/ÕR3, where Q is the volumetric flow rate (“m3/s”) of the polymer melt and R is the radius (“m”) of the capillary (eg matrix of extrusion) through which the molten polymer flows. Obviously, other variables, such as the residence time during the melting process, which is inversely proportional to the throughput, can also be controlled in order to achieve the desired degree of homogeneity.
[54] To achieve the desired shear conditions (eg rate, residence time, shear rate, melt processing temperature, etc.), the speed of the extruder rotations can be selected within a certain range. Generally, an increase in product temperature is observed with increasing rotational speed due to the additional input of mechanical energy into the system. For example, the rotation speed can range from approximately 50 rpm to approximately 500 revolutions per minute (“rpm”); in some embodiments, from approximately 70 rpm to approximately 300 rpm, and in other embodiments, from approximately 100 rpm to approximately 200 rpm. This can result in a temperature high enough to disperse the hardening additive and interphase modifier without negatively affecting the size of the resulting domains. The melt shear rate and, in turn, the degree to which the polymers are dispersed, can also be increased during the use of one or more distributive and/or dispersive mixing elements within the mixing section of the extruder. Among the single screw distributive mixers are, for example, the Saxon, Dulmage, Cavity Transfer etc. mixers. Likewise, suitable dispersive mixers may include bubble ring mixers, Leroy/Maddock, CRD, etc. As is known in the art, blending can be further enhanced by using pins on the barrel that create a bend, reorienting the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin (VIP) mixers . III. formed articles
[55] Due to its unique and beneficial properties, the thermoplastic composition of the present invention is suitable for use in formed articles and especially those that have a relatively small thickness. For example, the article may have a thickness of approximately 100 micrometers to approximately 50 millimeters; in some embodiments, from approximately 200 micrometers to approximately 10 millimeters, in some embodiments, from approximately 400 micrometers to approximately 5 millimeters, and in other embodiments, from approximately 500 micrometers to approximately 2 millimeters.
[56] The formed article can be configured using any of several techniques known in the art, such as profile extrusion, extrusion blow molding, injection molding, rotational molding, compaction molding, etc., and combinations of these. Regardless of the process selected, the thermoplastic composition of the present invention can be used exclusively to form the article, or in combination with other polymeric components to form formed articles. For example, one thermoplastic composition may be extruded in profile as a core, while other polymer(s) may be extruded as a "skin" or outer layer. In another embodiment, other polymer(s) may be injected or transferred into a mold during an injection molding process to form a surface layer around the core. Examples of machines suitable for co-injection, sandwich, or two-component molding are machines produced by Presma Corp., by Northeast Mold & Plastics, Inc. Although not mandatory, the core of the formed article is usually made up of thermoplastic composition of the present invention and the surface layer is usually formed from a different polymer (eg polyolefins, polyesters, polyamides etc.) which improves the surface, batch and bond properties for the intended use.
[57] Referring to Fig. 1, for example, a specific embodiment of a single-component injection molding apparatus or tool 10 that can be employed in this invention is shown in more detail. In that embodiment, apparatus 10 includes a first mold base 12 and a second mold base 14, which together define a component-defining article or mold cavity 16. Each of mold bases 12 and 14 includes one or more cooling lines 18 through which a coolant, such as water, flows to cool the device 10 during use. The molding apparatus 10 also includes a resin flow path that runs from an outer surface 20 of the first mold half 12 to an inlet channel 22 to the mold cavity 16 defining the article. The resin flow path can also include a channel and port, both of which are hidden away for simplicity. The molding apparatus 10 also includes one or more ejector pins 24 slidably secured in the half of the second mold 14, helping to define the cavity 16 defining the article in the closed position of the apparatus 10, as shown in Fig. 1 The ejector pin 24 operates in a well-known manner to remove a molded article or component from the cavity 16 defining the article in the open position of the molding apparatus 10.
[58] The thermoplastic composition can be directly injected into the molding apparatus 10 using techniques known in the art. For example, molding material can be supplied in the form of grains in a feed hopper attached to a barrel that contains a swivel screw (not shown). As the screw turns, the beans are pushed through and undergo extreme pressure and friction, which generates heat to melt the beans. Electric heating strips (not shown) attached to the outside of the keg can also aid in heating and temperature control during the fusion process. For example, the strips can be heated to a temperature of approximately 200°C to approximately 260°C; in some embodiments, from approximately 230°C to approximately 255°C, and, in embodiments, from approximately 240°C to approximately 250°C. Upon entering molding cavity 16, the molding material is solidified by the coolant flowing through lines 18. The coolant may, for example, have a temperature (the "molding temperature") of approximately 5°C at approximately 50°C; in some embodiments, from approximately 10°C to approximately 40°C, and in some embodiments, from approximately 15°C to approximately 30°C.
[59] Formed articles can be of varying sizes and shapes. For example, the article can be used to form dispensers (eg for paper towels), packaging materials (eg food, medicine packaging, etc.), medical devices such as surgical instruments (eg scalpels, scissors, retractors, suction tubes, probes, etc.); implants (eg bone plates, prostheses, plates, threads, etc.); containers or bottles, etc. The article can also be used to form various pieces used in “personal care” applications. For example, in a special embodiment, the article is used to form a wet tissue container. The embodiment of the container may vary, as is known in the art and described in U.S. Patent No. 5,687,875 to Watts et al.; 6,568,625 to Faulks et al.; 6,158,614 to Haines et al.; 3,973,695 to Ames; 6,523,690 to Buck et al.; and 6,766,919 to Huang et al., which are incorporated herein in their entirety by reference for all purposes. Tissues to be used with the container, eg baby wipes, can be arranged in a way that provides convenient and reliable release and helps them not to get too dry. For example, the baby wipes can be arranged in the container as a number of individual sheets arranged in a stacked embodiment to provide a stack of baby wipes that may or may not be individually folded. Wet wipes can be individual wipes folded in c, z, connected to adjacent wipes by a faded line or other non-interleaved embodiments known in the art. Alternatively, the individual wet wipes can be folded so that the leading and trailing edge edges of successive wipes overlap in the stacked embodiment. In each of these folded and unfolded embodiments, the leading edge edge of the next wet wipe is slackened into the stack by the trailing edge edge when the wet wipe is removed by the user from the dispenser or package. For example, representative wet wipes for use with the invention are described in U.S. Patent No. 6,585,131 to Huang et al and 6,905,748 to Sosalla, which are incorporated herein in their entirety by reference for all purposes.
[60] The present invention can be better understood by referring to the following examples. Test Methods Fluidity Index:
[61] The melt flow index ("MFR") is the mass of a polymer (in grams) forced through the orifice of a rheometer by extrusion (diameter 0.0825 inch) when subjected to a load of 2160 grams for 10 minutes, usually at 190°C or 230°C. Unless otherwise noted, the melt flow index is measured in accordance with ASTM test method D1239, with an extrusion plastomer from Tinius Olsen. Thermal properties:
[62] The glass transition temperature (Tg) can be determined by dynamic mechanical analysis (DMA) in accordance with ASTM E1640-09. Instrument A Q800 of TA instruments can be used. Experimental runs can be performed in stress/stress geometry, in a temperature range mode in the range of -120°C to 150°C with a heating rate of 30C/min. The voltage amplitude frequency can be kept constant (2 Hz) during the test. Three (3) independent samples can be tested to obtain an average glass transition temperature, which is defined by a peak value of the tan S curve, where tan S is defined as the ratio of the loss modulus to the storage modulus. (tan S = E”/E').
[63] Melting temperature can be determined using differential scanning calorimetry (DSC). The differential scanning calorimetry equipment can be a DSC Q100 Differential Scanning Calorimeter, prepared with a liquid nitrogen cooling accessory and UNIVERSAL ANALYSIS 2000 analysis software (version 4.6.6), both marketed by TA Instruments Inc. of New Castle, Delaware. To avoid direct handling of samples, tweezers and other tools are used. The samples are placed on an aluminum dish and weighed to 0.01 milligram accuracy on an analytical balance. A lid is placed over the sample material in the dish. Grains are normally placed directly on the weighing pan.
[64] The differential scanning calorimetry equipment is calibrated using an indium metal standard and a base correction is made, as described in the equipment's operating manual. The sample of material is placed in the test chamber of the differential scanning calorimetry equipment to be tested, and an empty plate is used as a reference. All tests are performed by purging 55 cubic centimeters per minute of nitrogen (industrial grade) in the test chamber. For resin grain samples, the heating and cooling program is a two-cycle test, which started with chamber equilibration at -30°C, followed by a first heating period at a rate of 10°C per minute to a temperature of 200°C, followed by a sample equilibration at 200°C for 3 minutes, followed by a first cooling period of 10°C per minute to a temperature of -30°C, followed by a sample equilibration at -30°C for 3 minutes, then a second heating period at a rate of 10°C per minute to a temperature of 200°C. All tests are performed by purging 55 cubic centimeters of nitrogen (industrial grade) in the test chamber.
[65] The results are evaluated using the UNIVERSAL ANALYSIS 2000 analysis software, which identified and quantified the glass transition temperature (Tg) of the inflection, the endothermic and exothermic peaks, and the areas under the peaks in the DSC traces. The glass transition temperature has been identified as the region of the drawn line where a clear change in the curve has occurred, and the melting temperature is determined using an automatic bending calculation. Izod deformation resistance test (notched):
[66] The deformation strength of injection molded (notched) Izod bars was determined following ASTM D256 - 10 Method A (Standard Test Methods for Determining Izod Pendulum Strength of Plastics (notched)). Izod bars were conditioned for more than 40 hours at 23°C ± 2°C with a relative humidity of 50% ±10% before testing under the same conditions. The pendulum has a 2 ft-lb capacity. The injection molded Izod test specimens have a height of 12.70 mm ± 0.20 mm and a thickness of 3.2 mm ± 0.05 mm. Izod deformation resistance test (not notched):
[67] The Deformation Strength of Injection Molded Izod Bars (Not Notched) was determined following ASTM D 4812 -06 (Deformation Strength of Plastics Cantilever Beam (Not Notched)). Izod bars have been conditioned for more than 40 hours at 23°C ± 2°C with a relative humidity of 50% ±10% before being tested under the same conditions. The pendulum has a capacity of 2 ftlb or 5 ftlb. The injection molded Izod test specimens have a height of 12.70 mm ± 0.20 mm and a thickness of 3.2 mm ± 0.05 mm. Stress properties:
[68] The modulus was determined using an MTS 810 hydraulic tension frame to extract Type I injection molded dog bones as described in ASTM D638-10. The specimens were conditioned at 23°C ± 2°C and with a relative humidity of 50% ± 10% for a minimum period of 40 hours. Conditions were 23°C ± 2°C and a relative humidity of 50% ± 10%. The tension frame fixings were, at a nominal jig length, of 115 mm. Specimens were extracted at a rate of 50 mm/min (87.7%.min strain). Five (5) specimens were tested for each composition. A computer program called TestWorks 4 was used to collect data during the test and generate a stress curve against a strain curve, from which the modulus of the average of five specimens was determined.
[69] Peak stress, stress at break, elongation at break, and energy per volume at break were determined using an MTS Synergie 200 Stress Frame for removal of injection-molded Type V dog bones as described in ASTM D638 -10. The specimens were conditioned at 23°C ± 2°C and with a relative humidity of 50% ± 10% for a minimum period of 40 hours. Conditions were 23°C ± 2°C and a relative humidity of 20% ± 10%. The tension frame fixings were, at a nominal jig length, of 25.4 mm. The specimens were extracted at a rate of 8.4 mm/min (87.7%.min of deformation). Five (5) specimens were tested for each composition. A computer program called TestWorks 4 was used to collect the data during the test and generate a stress curve against a deformation curve, from which the mean stress peak, rupture stress, elongation at break were determined. and energy per volume at break. High Speed Punching Property
[70] Total Energy Average High Speed Punching Property was determined by the following ASTM D3763 - 10 Standard Test Method for High Speed Punching Properties of Plastics Using Load and Displacement Sensors. The specimens were prepared by forming an injection molded disc with a diameter of 63.5 mm ± 0.5 mm, with a thickness of 1.09 mm ± 0.2 mm. Injection molding was performed by the overflow feed grains inside a Spritzg i esseuto mate n BOY 22D injection molding device at a barrel temperature of 225°C to 195°C, mold temperature of approximately 27°C, and a cycle time of approximately 40 seconds. ASTM D3763 test speed was 3.3 meters/second, test conditions were 23°C ± 2°C / 50% ± 10% RH, using Intron Dynatup 8250 with Impulse Data Acquisition System v 2.2.1, 12.7 mm tup diameter, with a 40 mm diameter base and top support bracket assembly. Total energy averages (in Joules) for examples 1, 4, 5, 7, 11, and 16 are reported.
[71] The shrinkage of the dimensions of the injection mold cavity was determined by the following ASTM D955 - 08 Standard shrinkage test method of measuring the dimensions of thermoplastics. The injection mold cavity had a length dimension (Lm) of 126.78 mm and a width dimension (Wm) of 12.61 mm, which meets the ASTM D955-08 Type A specimen. The length (Ls) and the mean width (Ws) of 5 test specimens were measured after 24 ± 1 hours, 48 ± 1 hours, or 96 ± 1 hours after specimen removal from the mold. Lengthwise shrinkage (Sl) was calculated by Sl = (Lm-Ls) X 100/Lm. Shrinkage in the height direction (Sw) was calculated by SW = (Wm-Ws) X 100/Wm. moisture content
[72] Moisture content can be determined using the Arizona Instruments Computrac Vapor Pro Moisture Analyzer (Model No. 3100) in accordance with ASTM D 7191-05, incorporated herein by reference in its entirety. for all purposes. The test temperature (§X2.1.2) can be 130°C, the sample size (§X2.1.1) can be 2 g to 4 grams, and the vial emptying time (§X2.1.4) can be 30 seconds. In addition, the termination criterion (§X2.1.3) can be set to a “prediction” mode, which means that the test is terminated when the internally programmed criterion (which mathematically calculates the moisture content at the end point) is hit. EXAMPLE 1
[73] Polylactic acid (PLA 6201 D with a melt flow index of 10 g/10 min at 190°C, Natureworks®) was formed into an injection molded part as a control. The mold length dimension shrinkage after 24 hours and 48 hours was 0.2% and 0.2%, respectively. The shrinkage of the mold length dimension after 24 hours and 48 hours was -0.5% and 0.1%. EXAMPLE 2
[74] The ability to form injection molded parts from a polylactic acid blend of 88.7% by mass (PLA 6201 D with a melt flow index of 10 g/10 min at 190°C) has been demonstrated , Natureworks®) and 9.9% by mass of a hardening additive and 1.4% of polyepoxy modifier. The hardening additive was VISTAMAXX™ 2120 (ExxonMobil), which is a polyolefin copolymer/elastomer with a melt melt index of 29 g/10 min (190°C, 2160 g) and a density of 0.866 g/cm3 . The polyepoxy modifier was poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) (LOTADER® AX8950, Arkema) with a melt flow index of 70 g/10 min. at 100 g/10 min. (190°C/2160 g), a glycidyl methacrylate content of 7% to 11% by mass, a methyl acrylate content of 13% to 17% by mass, and an ethylene content of 72% to 80% by mass. pasta. The polymers were fed into a co-rotating twin screw extruder (ZSK-30, 30 mm diameter, 1328 mm long) for composites manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered consecutively from 1 to 14, from the feed funnel to the die. The first drum zone No. 1 received the resins via a gravimetric feeder, with a total yield of 6.8 kilograms per hour. The die used to expel the resin had 3 die openings (6 millimeters in diameter) 4 millimeters apart. After formation, the expelled resin was cooled on a fan-cooled conveyor belt and transformed into grains by a Conair granulator. The screw speed of the extruder was 200 revolutions per minute (“rpm”).
[75] The grains were then overflow fed into an injection molded device (Spritzg i esseuto mate n BOY 22D) and molded into one piece with a drum temperature of 210°C ± 25°C, mold temperature of approximately 20°C ± 13°C, and cycle time of approximately 45 ± 25 seconds. The mold length dimension shrinkage after 24 hours and 48 hours was 0.4% and 0.4%, respectively. The mold length dimension shrinkage after 24 hours and 48 hours was 0.0% and 0.2%. EXAMPLE 3
[76] The parts were injection molded as described in Example 2, except that the mixture contained 85.3% by mass of polylactic acid (PLA 6201 D, Natureworks®), 9.5% by mass of VISTAMAXX hardening additive ™ 2120 (ExxonMobil), 1.4 mass% polyepoxide modifier (LOTADER® AX8950, Arkema), and 3.8 mass% interphase modifier (PLURIOL® WI 285 from BASF). PLURIOL® WI-285 was added via the injection pump to drum zone #2. The shrinkage of the mold length and height dimensions after 96 hours was -0.4% and 0. 3%, respectively. EXAMPLE 4
[77] Parts were injection molded as described in Example 3, except that LOTADER® AX8900 (Arkema) was employed as a polyepoxide modifier. EXAMPLE 5
[78] The parts were injection molded as described in Example 2, except that the mixture contained 84.5% by mass of PLA 6201 D polylactic acid, Natureworks®), 9.4% by mass of VISTAMAXX™ hardening additive 2120 (ExxonMobil), 1.4 mass% polyepoxide modifier (LOTADER® AX8900, Arkema), and 4.7 mass% Hallstar HALLGREEN® IM-8830 interphase modifier. HALLGREEN® IM-8830 was added via the injection pump into drum zone #2. EXAMPLE 6
[79] The parts were injection molded as described in Example 4, except the hardening additive which was EXCEED™ 3512CB resin (ExxonMobil). EXAMPLE 7
[80] The parts were injection molded as described in Example 4, except the hardening additive which was ESCORENE™ UL EVA 7720 (ExxonMobil). EXAMPLE 8
[81] The parts were injection molded as described in Example 2, except that the mixture contained 88.7% by mass of polylactic acid (PLA 6201 D, Natureworks®), 9.9% by mass of the polypropylene additive. hardening, PP 3155 (ExxonMobil), 1.4% by mass of polyepoxide modifier (LOTADER® AX8950, Arkema). EXAMPLE 9
[82] The parts were injection molded as described in Example 8, except that the mixture contained 87.4% by mass of polylactic acid (PLA 6201 D, Natureworks®), 9.7% by mass of VISTAMAXX hardening additive ™ 2120 (ExxonMobil), and approximately 2.9% by weight of the maleic anhydride graft polypropylene, Fusabond 353D (ExxonMobil). EXAMPLE 10
[83] The parts were injection molded as described in Example 4, except that the hardening additive was INFUSETM 9507 olefin block copolymer resin (Dow Chemical Company). EXAMPLE 11
[84] The parts were injection molded as described in Example 4, except that the hardening additive was VECTOR* 4113A styrenic block copolymer resin (Dow Chemical Company). EXAMPLE 12
[85] The parts were injection molded as described in example 11, except that the interphase modifier was Hallstar's HALLGREEN® IM-8830. EXAMPLE 13
[86] The parts were injection molded as described in example 7, except that the interphase modifier was Hallstar's HALLGREEN® IM-8830. EXAMPLE 14
[87] The parts were injection molded as described in Example 2, except that the mixture contained 80.6% by weight of polylactic acid (PLA 6201 D, Natureworks®), 14.2% by weight of the ESCORENE hardening additive ™ UL EVA 7720 (ExxonMobil), 1.4 mass% polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8 mass% interphase modifier (PLURIOL® WI 285 from BASF). PLURIOL® WI-285 was added via the injection pump to drum zone #2. EXAMPLE 15
[88] The parts were injection molded as described in Example 14, except that the mixture contained 90.1% by mass of polylactic acid (PLA 6201 D, Natureworks®), 4.7% by mass of the ESCORENE hardening additive ™ UL EVA 7720 (ExxonMobil), 1.4 mass% polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8 mass% interphase modifier (PLURIOL® WI 285 from BASF). PLURIOL® WI-285 was added via the injection pump to drum zone #2. EXAMPLE 16
[89] The parts were injection molded as described in Example 2, except that LOTADER® AX8900 (Arkema) was employed as a polyepoxide modifier.
[90] The injection molded parts of Examples 1 through 16 were then tested for strength, high speed punching properties and tensile properties in the manner described above. The results are shown below.

[91] As noted above, samples containing an interphase modifier (Samples 3 to 7 and 10 to 15) typically exhibited much higher strength than Sample 1 (containing only polylactic acid), Samples 2, 8 to 9 and 16 (containing only polylactic acid, hardening additive and polyepoxide modifier). SEM photomicrographs were also taken of Sample 1 (containing only polylactic acid) and 3 (containing interphase modifier) before and after testing. The results are shown in Figs. 2 to 6. Figs. 2 to 3, for example, show the samples formed in Example 1 before and after the strength test. Fig. 4 shows a sample formed in Example 3, before the resistance/stress test. As shown, the PLA matrix of Example 3 underwent decomposition, which resulted in the formation of many empty areas adjacent to distinct domains of the Vistamaxx™ polymer. Figs. 5 to 6 similarly show the sample of Example 3, after the impact and stress test, respectively (Fig. 6 was obtained after the oxygen plasma pickling). As shown in Fig. 6, for example, nearly parallel linear openings are formed which are oriented perpendicular to the direction of stress application and extend through the height of material samples exposed to external stress. The openings have many characteristics of empty spaces, as well as many elongated ligaments that together help to dissipate tension. EXAMPLE 17
[92] Polyethylene terephthalate (Crystar 4434 from Du Pont) was extruded and then formed into an injection molded part as a control. EXAMPLE 18
[93] The ability to form injection molded parts from a blend of 88.7% by weight polyethylene terephthalate (Crystar 4434 from Du Pont) and 9.9% by weight of a hardening additive and 1 has been demonstrated. .4% polyepoxide modifier. The hardening additive was VISTAMAXX™ 2120 (ExxonMobil), which is a polyolefin copolymer/elastomer with a melt melt index of 29 g/10 min (190°C, 2160 g) and a density of 0.866 g/cm3. The polyepoxy modifier was poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) (LOTADER® AX8900, Arkema), with a melt flow index of 6 g/10 min (190°C/2160 g), a glycidyl methacrylate content of 8% by mass, a methyl acrylate content of 24% by mass, and an ethylene content of 68% by mass. The polymers were fed into a co-rotating twin screw extruder (ZSK-30, 30 mm diameter, 1328 mm long) for composites manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered consecutively from 1 to 14, from the feed funnel to the die. The first drum zone #1 received the resins via a gravimetric feeder, with a total yield of 6.8 kilograms per hour. The die used to expel the resin had 3 die openings (6 millimeters in diameter) 4 millimeters apart. After formation, the expelled resin was cooled on a fan-cooled conveyor belt and transformed into grains by a Conair granulator. The screw speed of the extruder was 200 revolutions per minute (“rpm”).
[94] The grains were then overflow fed into an injection molded device (Spritzg i esseuto mate n BOY 22D) and molded into a drum part with a temperature of 285°C ± 45°C, mold temperature of approximately 27°C ± 10°C, and cycle time of approximately 35 s ± 10 seconds. EXAMPLE 19
[95] The parts were injection molded as described in Example 18, except that the mixture contained 85.3% by mass of polyethylene terephthalate (Crystar 4434 from Du Pont), 9.5% by mass of VISTAMAXX hardening additive ™ 2120 (ExxonMobil), 1.4 mass% polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8 mass% internal interphase modifier (PLURIOL® WI 285 from BASF). PLURIOL® WI-285 was added via the injection pump to drum zone #2. EXAMPLE 20
[96] The parts were injection molded as described in Example 19, except the hardening additive which was ESCORENE™ UL EVA 7720 (ExxonMobil).
[97] The injection molded parts of Examples 17 to 20 were then tested for strength, high speed punch properties and tensile properties in the manner described above. The results are shown below.
EXAMPLE 21
[98] The parts were injection molded as described in Example 2, except that the mixture contained 96.2% by weight of polylactic acid (PLA 6201 D, Natureworks®) and 3.8% by weight of PLURIOL® WI 285 of BASF. PLURIOL® WI-285 was added via the injection pump to drum zone #2. EXAMPLE 22
[99] The parts were injection molded as described in Example 2, except that the mixture contained 95.2% by mass of polylactic acid (PLA 6201 D, Natureworks®) and 4.7% by mass of HALLGREEN® IM- 8830 from Hallstar. HALLGREEN® IM-8830 was added via the injection pump into drum zone #2. EXAMPLE 23
[100] The parts were injection molded as described in Example 2, except that the mixture contained 96.2% by weight of polylactic acid (PLA 6201 D, Natureworks®) and 3.8% by weight of polyethylene glycol CarbowaxTM PEG 3350 of Dow Chemical.
[101] The glass transition temperature was determined for Examples 1, 21 to 23, 16, 4 and 5 as described above. The results are shown below.

[102] The above data demonstrate that the ratio of the glass transition temperature of the thermoplastic composition to the glass transition temperature of the renewable polyester is between 0.7 to approximately 1.3.

权利要求:
Claims (15)
[0001]
1. Melt-blended thermoplastic composition, characterized by the fact that it comprises: at least one renewable rigid polyester with a glass transition temperature of 0 °C or higher as determined by dynamic-mechanical analysis (DMA) in accordance with ASTM E1640- 09; from 1% by weight to 30% by weight of at least one polymeric hardening additive, based on the weight of the renewable polyester; from 0.1 wt% to 20 wt% of at least one interphase modifier, based on the weight of the renewable polyester; and wherein the thermoplastic composition exhibits a morphology in which a plurality of discrete primary domains are dispersed within a continuous phase, with the domains containing the polymeric hardening additive and the continuous phase containing the renewable polyester, wherein the composition still exhibits strength. Izod at impact of 0.3 Joules per centimeter or greater, measured at 23°C, per ASTM D256-10 (Method A) and stress elongation at break of 10% or greater, measured at 23°C, of according to ASTM D638-10, and where the ratio between the glass transition temperature of the thermoplastic composition and the glass transition temperature of the renewable polyester is 0.7 to 1.3.
[0002]
2. Thermoplastic composition according to claim 1, characterized in that the renewable polyester is a polylactic acid.
[0003]
3. Thermoplastic composition according to claim 1 or 2, characterized in that the renewable polyester and the thermoplastic composition have a glass transition temperature of 50°C to 75°C, as determined by dynamic-mechanical analysis (DMA) in conformance to ASTM E1640-09.
[0004]
4. Thermoplastic composition according to any one of the preceding claims, characterized in that the ratio of the solubility parameter of the renewable polyester to the solubility parameter of the polymeric hardener additive is 0.5 to 1.5; and wherein the polymeric hardening additive has a solubility parameter of 15 to 30 MJoules1/2/m3/2; where the solubility parameter is the Hildebrand Solubility Parameter.
[0005]
5. Thermoplastic composition according to any one of the preceding claims, characterized in that the ratio of the melt index of the renewable polyester to the melt index of the polymeric hardener additive is from 0.2 to 8, where the index of fluidity is determined according to ASTM test method D1239; and/or wherein the ratio of the Young's modulus of elasticity for the renewable polyester to the Young's modulus of elasticity of the polymeric hardener additive is from 2 to 500; wherein Young's modulus is determined in accordance with ASTM D638-10 at 23°C.
[0006]
6. Thermoplastic composition according to any one of the preceding claims, characterized in that the polymeric hardening additive includes a polyolefin, such as a propylene homopolymer, propylene/α-olefin copolymer, ethylene/α-olefin copolymer, or a combination of these.
[0007]
7. Thermoplastic composition according to any one of the preceding claims, characterized in that the interphase modifier has a kinematic viscosity of 0.7 to 200 centistokes, determined at a temperature of 40°C.
[0008]
8. Thermoplastic composition according to any one of the preceding claims, characterized in that the interphase modifier is hydrophobic; and/or wherein the interphase modifier is a silicone, silicone-polyether copolymer, aliphatic polyester, aromatic polyester, alkylene glycol, alkane diol, amine oxide, fatty acid ester or a combination thereof.
[0009]
9. Thermoplastic composition according to any one of the preceding claims, characterized by the fact that the discrete domains have a length of 0.05 micrometers to 30 micrometers.
[0010]
10. Thermoplastic composition according to any one of the preceding claims, characterized in that it further comprises a compatibilizer, a polyepoxide modifier or both.
[0011]
11. Thermoplastic composition according to any one of the preceding claims, characterized in that the composition comprises a polyepoxide modifier that includes an epoxy-functional (meth)acrylic monomeric component, such as poly(ethylene-co-methacrylate-co-glycidyl methacrylate ).
[0012]
12. Thermoplastic composition according to any one of the preceding claims, characterized in that the renewable polyester constitutes 70% by weight or more of the thermoplastic composition.
[0013]
13. Thermoplastic composition according to any one of the preceding claims, characterized in that the composition has Izod resistance to deformation by impact (notched) from 0.8J/cm to 2.5J/cm, measured at a temperature of 23° C, according to ASTM D256-10 (Method A); and/or wherein the composition exhibits stress elongation at break of 100% to 300%, measured at 23°C, in accordance with ASTM D638-10.
[0014]
14. Injection molded article characterized by the fact that it comprises the thermoplastic composition as defined in any one of the preceding claims.
[0015]
15. Injection molded article characterized in that it is formed from a thermoplastic composition, wherein the thermoplastic composition comprises: 70% or more by weight of at least one polylactic acid with a glass transition temperature of 0°C or higher, as determined by dynamic mechanical analysis (DMA) in accordance with ASTM E1640-09; from 1% by weight to 30% by weight of at least one polymeric hardener additive, based on the weight of the renewable polyester, and from 0.1% by weight to 20% by weight of at least one interphase modifier based on weight the renewable polyester, wherein the thermoplastic composition has a morphology in which a plurality of discrete primary domains are dispersed within a continuous phase, with the domains containing the polymeric hardening additive and the continuous phase containing the renewable polyester; wherein the molded article further exhibits Izod impact deformation resistance of 0.3J per centimeter or greater, measured at 23°C, in accordance with ASTM D256-10 (Method A), and stress elongation at break of 10% or upper, measured at 23°C in accordance with ASTM D638-10 and where the ratio of the glass transition temperature of the thermoplastic composition to the glass transition temperature of the renewable polyester is 0.7 to 1.3.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-15| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-29| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-05-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/370,869|US8975305B2|2012-02-10|2012-02-10|Rigid renewable polyester compositions having a high impact strength and tensile elongation|

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US13/370,869|2012-02-10|

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PCT/IB2013/050730|WO2013118020A1|2012-02-10|2013-01-28|Rigid renewable polyester compositions having a high impact strength and tensile elongation|

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