thermoplastic composition, and method for forming a thermoplastic composition

专利摘要:
RENEWABLE POLYESTER COMPOUNDS WITH LOW DENSITY. Presentation of a thermoplastic compost that contains a renewable rigid polyester and presents a structure with voids and low density. To obtain such a structure, the renewable polyester is mixed with a polymeric curing additive to form a precursor material, in which the curing additive can be dispersed as discrete physical domains, within a continuous matrix of the renewable polyester. The precursor material is then stretched or pulled at a temperature below the glass transition temperature of the polyester (i.e., cold drawn). This creates a network of voids, located in a position adjacent to the discrete domains, which, as a result of their close locations, can form a bridge between the borders of the voids and act as? Hinges? structural elements that help stabilize the network and increase its energy dissipation capacity. These inventors also found that voids can be distributed quite evenly throughout the compound.
公开号:BR112014019493B1
申请号:R112014019493-9
申请日:2013-01-28
公开日:2020-12-22
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:

History of the Invention
[001] Molding processes are normally used to form plastic items that are relatively rigid in nature, including containers, medical devices, etc. For example, containers for batteries or wipes are usually made using injection molding techniques. However, a problem associated with these containers is that the molding material is often made up of synthetic polyolefins (for example, polypropylene or HDPE) that are not renewable. Several attempts to use renewable polyesters (for example, polylactic acid (“PLA”)) have been made in this and other applications. However, penetration in the renewable polyester market has been limited due to their density, which is approximately 30% higher than conventional polyolefins, making them considerably more expensive. To help reduce the density of these polyesters, it is possible to use gaseous blowing agents to help create a “foamy” cell structure with a determined degree of porosity. Unfortunately, the stress properties and processing power of the resulting cell structure are often compromised by the uncontrolled pore size and distribution. There are other problems as well. Renewable polyesters, for example, have a high glass transition temperature and usually demonstrate very high stiffness and modulus of elasticity, while having relatively low impact resistance 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 stress elongation (at break) for PLA materials is only approximately 5%, and the resistance to impact deformation is only approximately 0.22 J / cm. These low values of impact resistance and stress elongation considerably limit the use of these polymers in injection molded parts, in which a good balance between the rigidity and impact resistance of the material is necessary.
[002] Thus, there is a need for a low density renewable polyester compound that can also have a high resistance to failure when subjected to stress. Summary of the Invention
[003] According to an embodiment of the current invention, a thermoplastic compound is disclosed which includes at least one renewable rigid polyester with a glass transition temperature of about 0 ° C or more, and at least one polymeric curing additive . The thermoplastic compound has a morphology in which several discrete and empty primary domains are dispersed within a continuous phase, with the domains containing the polymeric curing additive and with the continuous phase containing the renewable polyester. The thermoplastic compound has a density of approximately 1.4 grams per cm3 or less. The average percentage volume of the compound that is occupied by the voids is approximately 20% to 80% per cubic centimeter.
[004] In accordance with another embodiment of the current invention, a method for forming a low density thermoplastic compound for use in a molded article is disclosed. The method consists of forming a mixture containing a renewable rigid polyester and a polymeric curing additive, in which the renewable rigid polyester has a glass transition temperature of about 0 ° C or more. The mixture is applied in the form of a precursor material. The precursor material is stretched below the glass transition temperature of the renewable polyester in order to form a thermoplastic compound that contains several voids and has a density of about 1.4 grams per cubic centimeter or less.
[005] Other properties and aspects of the present invention will be discussed in more detail below. Brief description of the illustrations
[006] 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:
[007] Fig. 1 is a schematic illustration of a configuration of an injection molding apparatus for use in the current invention;
[008] Fig. 2 is a SEM photomicrograph of a sample from Example 7 after cold drawing and recording of oxygen plasma;
[009] Fig. 3 is a SEM photomicrograph of a sample from example 8 after cold drawing and the impact test;
[010] Fig. 4 is a SEM photomicrograph of a sample from example 11 before cold drawing; and
[011] Fig. 5 is a SEM photomicrograph of a sample from example 11 before cold drawing; and
[012] Fig. 6 is a SEM photomicrograph of a sample from Example 11 after cold drawing and recording of oxygen plasma.
[013] The repeated use of reference characters in this specification and in the drawings is intended to represent the same characteristics or elements, or analogues, of the present invention. Detailed Description of Representative Forms of Realization
[014] Detailed references will be made to various configurations of the invention, with one or more examples described below. Each example is provided for purposes of explaining the invention, and not as limitations on 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, the features illustrated or described as part of a configuration can be used in another configuration, to obtain a third configuration. Thus, it is intended that the present invention covers modifications and variations that are within the scope of the attached claims and their equivalents.
[015] In general, the present invention is directed to a thermoplastic compound that contains a renewable rigid polyester and presents a structure with empty areas and low density. To obtain such a structure, the renewable polyester is mixed with a polymeric curing additive to form a precursor material, in which the curing additive can be dispersed as discrete physical domains, within a continuous matrix of the renewable polyester. The precursor material is then stretched or pulled at a temperature below the glass transition temperature of the polyester (ie, "cold drawn"). Without the intention of being limited by theory, the present inventors believe that the deformation force and the stretching tension of the stretching process causes the disintegration of the renewable polyester matrix, in the areas adjacent to the discrete domains. This creates a network of voids, (for example, voids, nano-voids or a combination of them) located adjacent to discrete domains, which, as a result of this proximity, can form a bridge between the void boundaries and act as “ internal structural hinges that help to stabilize the network and increase its energy dissipation capacity.
[016] The average percentage volume occupied by the empty spaces within a given volume unit of the thermoplastic compound is relatively high, such as from about 20% to about 80% per cm3, in some embodiments from about 30% to about 70%, and in some embodiments, from about 40% to about 60% per cubic centimeter of the compound. This high volume of empty spaces can considerably reduce the density of the material. For example, the compound may have a density of about 1.4 grams per cubic centimeter ("g / cm3") or less, in some embodiments about 1.1 g / cm3 or less, in some embodiments from 0.4 g / cm3 to approximately 1.0 g / cm3, and in other embodiments from 0.5 g / cm3 to approximately 0.95 g / cm3. These inventors also found that voids can be distributed quite evenly throughout the compound. For example, voids can be distributed in columns oriented in a direction normally perpendicular to the direction in which the tension is applied. These columns can generally be parallel to each other over the entire width of the compound. Without the intention of imposing theoretical limitations, it is believed that the presence of this network of homogeneously distributed empty spaces can result in a considerable dissipation of energy under load and considerably greater resistance. There is a stark contrast to conventional techniques for creating empty spaces that involve the use of swelling agents to initiate the formation of pores, which tends to result in an uncontrolled pore distribution and low quality mechanical properties.
[017] We will now describe several embodiments of this invention in more detail.
[018] I. Thermoplastic compound
[019] A. Renewable polyester
[020] Renewable polyesters typically comprise approximately 70% by weight to approximately 99% by weight, in some configurations, approximately 75% by weight to approximately 98% by weight and, in other configurations, approximately 80% by weight to approximately 95% by weight of the thermoplastic compound. Various renewable polyesters can normally be employed in the thermoplastic compound, such as those such as aliphatic polyesters such as polycaprolactone, polyesteramides, polylactic acid (PLA) and their copolymers, polyglycolic acid, polyalkylene carbonates (for example, polyethylene carbonate), poly-3- hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, copolymers of poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3-hydroxybutyrate-co -3-hydroxyhexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxydecanoic, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and succinate-based aliphatic polymers example, polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (for example, 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.
[021] Typically, the thermoplastic compound 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 approximately 0 ° C or more, in some embodiments, from approximately 5 ° C to approximately 100 ° C, in some embodiments, approximately 30 ° C to approximately 80 ° C and, in some embodiments, from approximately 50 ° C to approximately 75 ° C. Renewable polyester can also have a melting temperature of approximately 140 ° C to approximately 260 ° C, in some embodiments, from approximately 150 ° C to approximately 250 ° C and, in some embodiments, approximately 160 ° C at approximately 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.
[022] 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 (“D-lactic acid”) , meso-lactic acid or combinations of these. Monomer units can also be formed by anhydrides of any isomer of lactic acid, 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 extension agent can also be employed (for example, a diisocyanate compound, an epoxy compound or acid anhydride). The polylactic acid can be a homopolymer or a copolymer, such as one that contains monomeric units derived from L-lactic acid and monomeric units derived from D-lactic acid. Although not required, the content ratio of one of the monomeric units derived from L-lactic acid and the monomeric unit derived from D-lactic acid is preferably approximately 85% per mol or more, in some embodiments, approximately 90% per mol or more and, in other embodiments, approximately 95% per mol or more. Various polylactic acids, each with a different ratio between the monomeric unit derived from L-lactic acid and the monomeric unit derived from D-lactic acid, can be mixed in any random percentage. Of course, polylactic acid can be mixed with other types of polymers (for example, polyolefins, polyesters, etc.).
[023] In a specific embodiment, polylactic acid has the following general structure:

[024] In a specific example of a suitable polylactic acid polymer that can be used in the current invention is marketed by Biomer, Inc. of Krailling, Germany) under the name BIOMER ™ L9000. Other suitable polylactic acid polymers are marketed by Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEA®). Other suitable polylactic acids can be described in U.S. Patent No. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254 and 6,326,458, which are an integral part of this in its entirety by reference for all purposes.
[025] Polylactic acid normally has an average molecular weight in number ("Mn") that ranges from approximately 40,000 to 160,000 grams per mol; in some embodiments, from 50,000 to 140,000 grams per mol approximately, and in other embodiments, from 80,000 to 120,000 grams per mol approximately. Likewise, the polymer typically has an average molecular weight in number ("Mn") that ranges from approximately 80,000 to 200,000 grams per mol; in some embodiments, from 100,000 to 180,000 grams per mol approximately, and in other embodiments, from 110,000 to 160,000 grams per mol approximately. The relationship between the average molecular weight by weight and the average molecular weight in number (“Mw / Mn”), that is, the "polydispersity index", is also relatively low. For example, the polydispersity index usually ranges from approximately 1.0 to 3.0; in some embodiments from 1.1 to 2.0 approximately, and in other embodiments, from 1.2 to 1.8 approximately. The average molecular masses in number and weight can be determined by methods known to those of skill in the art.
[026] Polylactic acid may also have an apparent viscosity of approximately 50 to 600 Pascal-seconds (Pa-s); in some embodiments, approximately 100 to 500 Pa ^ s and, in other embodiments, approximately 200 to 400 Pa ^ s, as measured at a temperature of 190 ° C and a shear rate of 1,000 sec-1 . The fluidity index of polylactic acid (on a dry basis) can also vary from about 0.1 to 40 grams for 10 minutes; in some embodiments, from about 0.5 to 20 grams for 10 minutes, and, in other embodiments, from about 5 to about 15 grams for 10 minutes, measured at a load of 2,160 grams and 190 ° C.
[027] Some types of pure polyester (eg polylactic acid) can absorb water from an environment in a way that has a moisture content of approximately 500 to 600 parts per million (“ppm”), or even higher, based on dry weight of the initial polylactic acid. The moisture content can be determined in several ways, as is known in the art, in accordance with ASTM D 7191-05, as described below. Since 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 mixing it. In most embodiments, for example, it is best for renewable polyester to have a moisture content of approximately 300 parts per million ("ppm") or less, in some embodiments, approximately 200 ppm or less, in some forms of approximately 1 to approximately 100 ppm, before mixing with the curing additive. Drying of the polyester can take place, for example, at a temperature of approximately 50 ° C to 100 ° C and, in some embodiments, from 70 ° C to approximately 80 ° C.
[028] B. Polymeric Hardening Additive
[029] As indicated above, the thermoplastic compound of the present invention also contains a polymeric curing additive. Due to its polymeric nature, the curing additive has a relatively high molecular weight that can help to improve the melting capacity and stability of the thermoplastic compound. Although not required, the polymeric curing additive can be immiscible with renewable polyester. In this way, the curing additive can be better spread as discrete phase domains within a continuous phase of the renewable polyester. The discrete domains are able to absorb energies resulting from an external force, which increase the stiffness and the total resistance of the resulting material. Domains can have several different shapes, for example, elliptical, spherical, cylindrical, etc. In one embodiment, for example, 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 shear zones in the inclusion of particles or at the around them.
[030] Although the polymers may be immiscible, the curing 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 the discrete and continuous phase boundaries and thus reduce the likelihood of the compound breaking. For this, the ratio of the renewable polyester solubility parameter to the hardener additive parameter is normally approximately 0.5 to approximately 1.5 and, in some embodiments, approximately 0.8 to approximately 1.2. For example, the polymeric curing additive may have a solubility parameter of approximately 15 to approximately 30 MJoules1 / 2 / m3 / 2 and, in some embodiments, approximately 18 to approximately 22 MJoules1 / 2 / m3 / 2, while polylactic acid can have a solubility parameter of approximately 20.5 MJoules1 / 2 / m3 / 2. The term "solubility parameter", as used in this document, refers to the "Hildebrand Solubility Parameter", which is the square root of the cohesive energy density, calculated using the following equation:
in which:
[031] Δ Hv = heat of vaporization
[032] R = Ideal gas constant
[033] T = Temperature
[034] Vm = Molecular volume
[035] Hildebrand's solubility parameters for many polymers are also found in Wyeych's Solubility Handbook of Plastics (2004), included in this document as a reference.
[036] The polymeric curing additive can also have a fluidity index (or viscosity) to ensure that the resulting discrete domains and voids can be maintained properly. For example, if the curing rate of the curing additive is too high, it tends to flow and disperse uncontrollably during the continuous phase. This results in lamellar or plaque-like domains that are difficult to maintain and are likely to rupture prematurely. On the other hand, if the flow rate of the curing additive is too low, it will tend to agglutinate and form very large elliptical domains, which are difficult to disperse during mixing. This can cause an irregular distribution of the curing additive throughout the continuous phase. Accordingly, the present inventors have found that the ratio of the curing index flow rate to the renewable polyester flow rate is normally approximately 0.2 to approximately 8, in some embodiments, approximately 0.5 to approximately 6 and, in other embodiments, from approximately 1 to approximately 5. The curing additive may, for example, have a melt index of 0.1 to 250 grams for approximately 10 minutes, in some embodiments of 0, 5 to 200 grams for approximately 10 minutes and, in other embodiments, 5 to 150 grams for approximately 10 minutes, determined at a load of 2,160 grams and at 190 ° C.
[037] In addition to the properties noted above, the mechanical characteristics of the polymeric curing additive can also be selected to achieve the desired increase in stiffness. For example, when a mixture of the renewable polyester and the curing additive is applied with an external force, shear flow and / or plastic flow zones can be initiated in and around the discrete phase domains as a result of stress concentrations. arising from a difference in the modulus of elasticity of the curing additive and the renewable polyester. Higher concentrations of stress promote a more intense localized plastic flow in the domains, allowing them to undergo considerable elongation when subjected to stress. These elongated domains allow the compound to behave more flexibly and softly than rigid polyester resin. To improve stress concentrations, the hardening additive is selected in a way 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 curing additive is normally approximately 1 to approximately 250, in some embodiments, approximately 2 to approximately 100 and, in other embodiments, approximately 2 to approximately 50. The modulus of elasticity of the curing additive can, for example, vary from 2 to 500 megapascals (MPa) approximately, in some embodiments from 5 to 300 MPa approximately, and in other embodiments, from 10 to 200 MPa approximately. On the other hand, normally the modulus of elasticity of polylactic acid is from about 800 MPa to about 2000 MPa.
[038] In order to provide the desired increase in stiffness, the polymeric curing additive may also exhibit an elongation at break (that is, the percentage of elongation of the polymer at its pour point) greater than renewable polyester. For example, the polymeric curing additive of the present invention may exhibit an elongation at break of approximately 50% or more, in some embodiments, from approximately 100% or more, in some embodiments, from approximately 100% to about 2,000% and, in other embodiments, from 250% to 1,500% approximately.
[039] Although a wide variety of polymeric additives with the properties identified above can be employed, especially suitable examples of such polymers (for example, polyethylene, polypropylene, polybutylene, etc.); styrenic copolymers (for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-butadiene-styrene, etc.); polytetrafluoroethylenes; polyesters (for example, recycled polyester, polyethylene terephthalate, etc.); polyvinyl acetates (for example, poly (ethylene vinyl acetate), polyvinyl chloride acetate, etc.); polyvinyl alcohols (for example, 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 (for example, low density polyethylene (“PE-LD”), high density polyethylene (“HDPE”), linear low density polyethylene (“PELBD”), etc. .), propylene homopolymers (for example, syndiotactic, atactic, isotactic, etc.), propylene copolymers and so on.
[040] In a given embodiment, the polymer is a propylene polymer, such as homopolypropylene, or a propylene copolymer. The propylene polymer can, for example, be formed by an isotactic polypropylene homopolymer or a copolymer containing an amount equal to or less than approximately 10% of the mass of another monomer, that is, at least approximately 90% of the mass of propylene. Such polymers can have a melting point of about 160 ° C to about 170 ° C.
[041] In yet another embodiment, 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 substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The especially desired comonomers of α-olefin are 1-butene, 1-hexene and 1-octene. The ethylene or propylene content of such copolymers can vary from about 60% per mol to about 99% per mol, in some embodiments from 80% per mol to about 98.5% and in other embodiments of 87% by mol to about 97.5% by mol. The content of α-olefin can vary from 1% per mole to about 40% per mole, in some embodiments from about 1.5% per mole to about 15% per mole and in some forms of making 2.5% per mol to about 13% per mol.
[042] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers, marketed under the name EXACT®, from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are marketed under the name ENGAGE®, AFFINITY®, DOWLEX® (PELBD) and ATTANE ™ (PEUBD) from Dow Chemical Company of Midland, Michigan. Other suitable propylene polymers are described in U.S. Patent No. 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 in this document, by reference, for all purposes. Propylene copolymers are marketed under the name VISTAMAXX® from ExxonMobil Chemical Co. of Houston, Texas; FINA® (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER® marketed by Mitsui Petrochemical Industries; and VERSIFY®, marketed by Dow Chemical Co. of Midland, Michigan. Other examples of suitable propylene polymers are described in U.S. Patent No. 6,500,500 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 in this document by reference for all purposes.
[043] A wide variety of known techniques can be employed to form the olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordinating catalyst (for example, Ziegler-Natta). Typically, the olefin polymer is formed by 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 uniformly distributed among the different molecular weight fractions. Metallocene-catalyzed polyolefins are described, for example, in U.S. Patent No. 5,571,619 to McAlpin et al .; 5,322,728 for Davis et al .; 5,472,775 to Obijeski et al .; 5,272,236 to Lai et al .; and 6,090,325 for Wheat, et al., which are included in their entirety in this document, by reference, for all purposes. Examples of metallocene catalysts include bis (n-butylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) scandium chloride, bis (indenyl) zirconium dichloride, methyl (dichloride) bis (methylene chloride) dichloride , bis (methylcyclopentadienyl) dichloride, zirconium, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl dichloride (cyclopentadienyl, -1-flourenyl) zirconium, molybdenum, dichloride, dichloride, nichloride, nickel zirconocene chloride hydride, zirconocene dichloride and so on. Polymers created using the metallocene catalyst usually have a narrow molecular weight range. For example, metallocene-catalyzed polymers may have polydispersity numbers (Mw / Mn) below 4, controlled short chain branch distribution and controlled isotacticity.
[044] Regardless of the materials used, the relative percentage of the polymeric curing additive in the thermoplastic compound is selected in order to achieve the desired properties without considerably affecting the resulting compound's ability to renew. For example, the curing additive is normally employed in the amount of 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 compounds, based on the weight of the renewable polyesters employed in the compound. The concentration of the curing additive in the entire thermoplastic compound can also be formed 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.
[045] C. Interphasic modifier
[046] An interphasic modifier can also be used in the thermoplastic compound to reduce the degree of friction and connectivity between the hardening additive and the renewable polyester and, thus, increase the degree and uniformity of the take-off. In this way, the empty spaces can be distributed in a very homogeneous way throughout the compound. Typically, the form of the modifier is liquid or semi-solid at room temperature (for example, 25 ° C), so that it has a relatively low viscosity, allowing it to be incorporated more quickly into the thermoplastic compound and easily migrated to the polymer surfaces. In this regard, the kinematic viscosity of the interphasic modifier is usually approximately 0.7 to approximately 200 centistokes ("cs"), in some compositions, approximately 1 to approximately 100 cs and, in other compositions, approximately 1.5 to approximately 80 cs, determined at 40 ° C. In addition, the interphasic modifier is also normally hydrophobic, so that it has an affinity with the polymeric curing additive, resulting in a change in the interfacial tension between the renewable polyester and the curing additive. By reducing the physical forces at the interfaces between the polyester and the curing additive, it is believed that the hydrophobic and low viscosity nature of the modifier can help facilitate the detachment of the polyester matrix. As used here, the term "hydrophobic" usually 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 the contact angle is ASTM D5725-99 (2008).
[047] Some suitable, low-viscosity hydrophobic 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 polypropylene glycol, polybutylene glycol, etc.), alkanes diols, (for example, Propane-1,3-diol, 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 the one sold under the trade name HALLGREEN® IM by Hallstar.
[048] Although the actual amount may vary, the interphasic modifier is usually employed in the amount of 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 interphasic modifiers in the entire thermoplastic compound 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.
[049] When the amounts observed above are used, the interphasic modifier will have a characteristic that allows it to migrate quickly to the interfacial surface of the polymers and facilitate the detachment without damaging the melting properties of the thermoplastic compound. For example, the interphasic modifier does not normally have a plasticizing effect on the polymer by reducing its glass transition temperature. In contrast, the present inventors have found that the glass transition temperature of the thermoplastic compound can be the same as that of the initial renewable polyester. In this regard, the ratio of the glass transition temperature of the compound to that of the polyester is normally about 0.7 to about 1.3, in some forms and carrying out from about 0.8 to about 1.2 and , in other embodiments, from about 0.9 to about 1.1. The thermoplastic compound can, for example, have a glass transition temperature of about 35 ° C to about 80 ° C, in some embodiments of about 40 ° C to about 80 ° C and, in other forms of from about 50 ° C to about 65 ° C. The fluidity index of the thermoplastic compound can also be similar to that of renewable polyester. For example, the fluidity index of the compound (on a dry basis) can be about 0.1 to about 70 grams for 10 minutes, in some embodiments from about 0.5 to about 50 ranges for 10 minutes and, in other embodiments, from about 5 to about 25 grams for 10 minutes, determined at a load of 2,160 grams and at a temperature of 190 ° C.
[050] D. Compatibilizer
[051] As indicated above, the polymeric curing additive is normally selected in a way 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 discrete domains within the continuous phase. However, in some embodiments, a compatibilizer can be used to further improve the compatibility between the renewable polyester and the polymeric curing additive. This may be desirable especially when the polymeric curing additive has a polar part, such as polyurethanes, acrylic resins, etc. When used, compatibilizers generally form from about 0.5% to about 20% by weight, in some embodiments, from about 1 to about 15% by weight and, in other embodiments, from about 1.5% to about 10% by weight of the thermoplastic compound. An example of a suitable compatibilizer is the functionalized polyolefin. The polar compound can, for example, be provided by one or more functional groups, and the non-polar component can be provided by an olefin. The compatibilizer olefin compound can normally be formed from any branched or linear α-olefin monomer, oligomer or polymer (including copolymers) derived from an olefin monomer, as described above.
[052] The compatibilizer functional group 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. Maleic anhydride modified polyolefins are especially suitable for use in the present invention. These modified polyolefins are usually formed by grafting maleic anhydride into a material of the polymeric structure. These maleated polyolefins are marketed by EI du Pont de Nemours and Company under the name of FUSABOND®, as the P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified satin vinyl foam), A series (chemically modified ethylene acrylate copolymers or terpolymers), or the N series (chemically modified ethylene-propylene diene monomer ("EPDM") or ethylene-octene). As an alternative, maleated polyolefins are also marketed by Chemtura Corp. under the name of Polybond® and by the Eastman Chemical Company under the name of Eastman G series.
[053] 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 axirane rings per molecule. Without the intention of being limited by theory, it is believed that these polyepoxide molecules can induce a reaction of the renewable polyester under certain conditions, thus improving its melting capacity 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 can allow a nucleophilic reaction for ring opening through a renewable polyester carboxyl end group (esterification) or through a hydroxyl group (etherification). Reactions on the oxazoline side can occur to form amide ester parts. Through these reactions, the molecular weight of the renewable polyester can be increased to combat the degradation often seen during the fusion process. Although 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 mixture may become brittle and difficult to mold into a material with the desired strength and elongation properties.
[054] In this sense, 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 in an epoxy group, and can be calculated by dividing the average molecular weight in number of the modifier by the number of epoxy groups in the molecule. The polyepoxide modifier of the present invention usually has an average molecular weight in number ranging from about 7,500 to about 250,000 grams per mole; in some embodiments, from about 15,000 to about 150,000 grams per mole, and in other embodiments, from about 20,000 to about 100,000 grams per mole, with a polydispersity index ranging from 2.5 to 7 The polyepoxide modifier may contain less than 50, in some embodiments, from 5 to 45 and, in other embodiments, from 15 to 40 epoxy groups. In turn, the epoxy equivalent weight can be less than about 15,000 grams per mol; in some embodiments, from about 200 to about 10,000 grams per mole, and in other embodiments, from about 500 to about 7,000 grams per mole.
[055] The polyepoxide can be a linear or branched homopolymer or copolymer (for example, 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 monomeric (meta) acrylic component. As used here, the term “(meta) acrylic” includes acrylic and methacrylic monomers, as well as salts or esters thereof, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meta) acrylic monomers can include, without limitation, 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.
[056] Poliepoxide usually has a relatively high molecular mass, as indicated above, so it can not only result in the extension of the renewable polyester chain, but also help to achieve the desired blend morphology. Thus, the resulting flow rate of the polymer can thus vary from about 10 to about 200 grams for 10 minutes; in some embodiments, from about 40 to about 150 grams for 10 minutes and, in other embodiments, from about 60 to about 120 grams for 10 minutes, determined at a load of 2,160 grams and a temperature 190 ° C.
[057] Other monomers can also be used in the polyepoxide to help achieve the desired molecular mass, if desired. Such monomers may vary and include, for example, ester monomers, (meta) acrylic monomers, olefin monomers, amide monomers, etc. In a particular 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 substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1- heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The α-olefin comonomers specifically desired are ethylene and propylene.
[058] Another suitable monomer may include an (meta) acrylic monomer that is not epoxy-functional. Examples of such (meta) acrylic monomers can be methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-acrylate - butyl, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, acrylate methylcyclohexyl, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, methacrylate, methacrylate, methacrylate of n-amyl, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, methacrylate methacrylate , cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, methacrylate isobornyl, etc., good as combinations of these.
[059] In a particularly desirable embodiment of the present invention, the polyepoxide modifier is a terpolymer formed from an epoxy-functional monomeric (meta) acrylic component, an alphaolefin monomeric component and a non-epoxy acrylic monomeric (meta) component -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.
[060] The epoxy-functional monomer can be transformed into a polymer using several known techniques. For example, a monomer containing polar functional groups can be grafted onto a polymer structure 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, Ziegler-catalytic reaction systems Natta, single site catalytic reaction systems (eg metallocene), etc.
[061] The relative part of the monomeric components can be selected in order to achieve a balance between epoxy reactivity and fluidity index. More specifically, high levels of epoxy monomer can result in a good reactivity with the renewable polyester, but a very high content can reduce the flow rate in such a way that the polyepoxide modifier will negatively affect the melt resistance of the polymer mixture. Thus, in most embodiments, epoxy-functional (meta) acrylic monomers form about 1% to about 25% by weight, in some embodiments, from about 2% to about 20% by weight and , in other embodiments, from about 4% to about 15% by weight of the copolymer. Alphaolefin monomers can also comprise from about 55% to about 95% by weight; in some embodiments; from about 60% to about 90% by weight and; in other embodiments; from about 65% to about 85% by weight of the copolymer. When used, other monomeric components (for example, non-epoxy-functional (meta) acrylic monomers) can make up from about 5% to about 35% by weight, in some embodiments, from about 8% to about 30% % by weight and, in other embodiments, from about 10% to about 25% by weight 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 of LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a melt index of 70 to 100 g / 10 min and has a 7% to 11% by weight glycidyl methacrylate monomer content, a 13% methyl acrylate monomer content at 17% by weight, and an ethylene monomer content of 72% to 80% by weight.
[062] In addition to controlling the type and relative content of the monomers used to form the polyepoxide modifier, the overall weight percentage can also be controlled in order to achieve the desired benefits. For example, if the level of modification is very low, the desired increase in melt strength and mechanical properties may not be achieved. The present inventors have also found, however, that if the level of modification is too high, molding may be restricted due to strong molecular interactions (eg, crosslinking) and physical network formation by epoxy-functional groups. Thus, the polyepoxide modifier is normally employed in an amount of 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 used in the compound. The polyepoxide modifier can also constitute 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.
[063] In addition to polyepoxides, other reactive compatibilizers can also be employed in the present invention, such as polymers functionalized with oxazoline, polymers functionalized with cyanide, etc. When used, these reactive compatibilizers can be used within the concentrations indicated above for the polyepoxide modifier. In a specific embodiment, an oxazoline-grafted polyolefin can be employed, i.e., a polyolefin grafted with a monomer containing an oxazoline ring. Oxazoline may include 2-oxazolines, such as 2-vinyl-2-oxazoline (for example, 2-isopropenyl-2-oxazoline), 2-fatty acid-alkyl-2-oxazoline (for example, obtained from oleic acid ethanolamine, linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and / or arachidonic acid) and combinations thereof. In another embodiment, oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soy-2-oxazoline, castor-2-oxazoline and combinations thereof, for example. In yet another embodiment, oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof.
[064] E. Other Components
[065] A beneficial aspect of the current invention is that good mechanical properties can be provided without the need for various conventional additives, such as swelling agents (for example, chlorofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, carbon dioxide, etc.) and plasticizers (for example example, solid or semi-solid polyethylene glycol). In fact, the thermoplastic compound can be considerably free of swelling and / or plasticizing agents. For example, swelling and / or plasticizing agents may be present in an amount of no more than about 1% by weight, in some embodiments no more than about 0.5% by weight and, in other embodiments, from about 0.001% to about 0.2% by weight of the thermoplastic compound. In addition, due to the stress-bleaching properties, as described in more detail below, the resulting compound can achieve an opaque color (for example, white) without the need for conventional pigments, such as titanium dioxide. In certain embodiments, for example, pigments can be present in an amount of no more than about 1% by weight, in some embodiments no more than about 0.5% by weight, and in other embodiments from about 0.001% to about 0.2% by weight of the thermoplastic compound. Obviously, a wide variety of ingredients can be used in the compound for several different reasons. For example, materials that can be used include, without limitation, catalysts, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents (eg calcium carbonate, etc.), particulates and other materials added to in order to improve the processing capacity of the thermoplastic compound.
[066] II. Formation of precursor material
[067] As indicated above, the thermoplastic compound of the present invention is generally formed by a cold stretch of the precursor material containing the renewable rigid polyester, the polymeric curing additive and also other optional components. To form the precursor material, the components are usually mixed using one of several known techniques. In one embodiment, for example, the components can be supplied separately or as a combination. For example, the components can be mixed dry to form an essentially homogeneous dry mixture and can be supplied simultaneously or in sequence in a melt-processing apparatus that mixes materials dispersively. Batch and / or continuous fusion processing techniques can be employed. For example, a mixer / kneader, Banbury mixer, Farrel continuous mixer, single screw extruders, double screw extruders, laminators, etc. can be used to mix and process materials by melting. Especially suitable melt-processing apparatus can be a co-rotating twin screw extruder (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 supply and ventilation ports and provide a high intensity distributive and dispersive mixture. For example, components can be introduced into the same feed ports as the twin screw extruder, or into other ports, and mixed by melting to form a very homogeneous melt. If desired, other additives can also be injected into the molten polymer and / or introduced separately into the extruder at a different point along its length.
[068] Regardless of the specific processing technique chosen, the material resulting from the melt mixing typically contains domains of the curing additive with an axial dimension of a domain (eg length) of about 0.05 μm to about 30 μm , in some embodiments of 0.1 μm to approximately 25 μm, in some embodiments of 0.5 μm to approximately 20 μm, and in other embodiments of approximately 1 μm to 10 μm. When used, the polyepoxide modifier can also be in the form of discrete domains distributed throughout the continuous polyester matrix. These "secondary" domains can have several 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 (for example, length) typically ranges from approximately 10 to 1000 nanometers; in some embodiments, approximately 20 to 800 nanometers; in some embodiments, from 40 to 600 nanometers approximately, and in other embodiments, from 50 to 400 nanometers approximately. As indicated above, the curing additive also forms discrete domains within the polyester matrix, which are considered to be among the “primary” domains of the compound. It is also necessary to understand that the domains can be formed by a combination of polyepoxide, curing additive and / or other components of the mixture.
[069] The degree of shear / pressure and heat can be controlled to ensure sufficient dispersion, but not so high as to negatively reduce the size of the discrete domains, making them unable to achieve the desired firmness and elongation . For example, mixing normally takes place at a temperature of about 180 ° C to about 260 ° C; in some embodiments, from about 185 ° C to about 250 ° C and, in other embodiments, from about 190 ° C to about 240 ° C. Likewise, the apparent shear rate during the melting process can vary from about 10 seconds-1 to about 3,000 seconds-1, in some embodiments, from about 50 seconds-1 to about 2,000 seconds- 1 and, in other embodiments, from about 100 seconds-1 to about 1,200 seconds-1. The apparent shear rate is equal to 4Q / πR3, where Q is the volumetric flow rate (“m3 / s”) of the polymer fusion and D is the radius (“m”) of the capillary (for example, extrusion die) through which the molten polymer flows. Obviously, other variables, such as the residence time during the melting process, which is inversely proportional to the transfer rate, can also be controlled in order to achieve the desired degree of homogeneity.
[070] 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 with a certain interval. Generally, an increase in the temperature of the product is observed with increasing speed of rotation due to the additional input of mechanical energy into the system. For example, the speed of rotation can vary from about 50 to about 300 revolutions per minute ("rpm"), in some embodiments, from about 70 to about 500 rpm and, in other embodiments, from about 100 to about 300 rpm. This can result in a temperature high enough to disperse the curing additive without adversely 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 extruder mixing section. Among the single screw distributive mixers are, for example, the Saxon, Dulmage, Cavity Transfer, etc. Likewise, suitable dispersive mixers can include bubble ring mixers, Leroy / Maddock, CRD, etc. As is known in the art, mixing can be further enhanced by using pins in the cylinder that create a bend by reorienting the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers and Vortex Intermeshing Pin (VIP) mixers.
[071] After mixing, the resulting material can be molded into a precursor material using one of several known techniques, such as extrusion, profile extrusion, film melting, swelling, thermoforming, injection molding, compression molding, rotational molding, etc. In one embodiment, for example, the precursor material is in the form of a sheet approximately 1 to 5,000 micrometers thick, in some embodiments of approximately 2 to 4,000 micrometers approximately, in some embodiments of about 5 to 2,500 micrometers approximately, in other embodiments of about 10 to 500 micrometers approximately.
[072] Regardless of the specific nature of the precursor material, a network structure of empty spaces is introduced by stretching the material to a temperature below the glass transition temperature of the renewable polyester. Stretching can occur in the longitudinal direction (for example, machine direction), transverse direction (for example, machine cross direction), or a combination of them. Although not required, the precursor material can be stretched on the line without having to remove it for separate processing. Various stretching techniques can be employed, such as stretching the tension frame, biaxial stretching, multi-axial stretching, profile stretching, cold air stretching, vacuum stretching, etc. For example, the precursor material can be stretched longitudinally by rollers rotating at different speeds of rotation.
[073] The degree of stretching is generally selected in the present invention to ensure that the desired network of voids is obtained, but not in such a way that the precursor material stretches significantly. In this regard, the precursor material is normally stretched (for example, in the machine direction) at a stretch rate of about 1.1 to about 3.0, in some embodiments of about 1.2 to about of 2.0 and, in other embodiments, from about 1.3 to about 1.8. The stretching rate is determined by dividing the length of the stretched material by its length before stretching. The stretch rate can also vary to help achieve the desired properties, for example, the variation of about 5% to about 1500% per minute of deformation, in some embodiments from about 10% to about 1,000% per minute of deformation and, in other embodiments, from about 100% to about 850% per minute of deformation. The precursor material is generally maintained at a temperature below the glass transition temperature of the renewable polyester during stretching. Among other things, this helps to ensure that the polyester chains are not altered in such a way that the web of voids becomes unstable. Usually, the precursor material is stretched to a temperature of at least about 10 ° C, in some embodiments of at least about 20 ° C and, in other embodiments of at least about 30 ° C below the glass transition temperature. For example, the precursor material can be stretched at a temperature of about 0 ° C to about 50 ° C, in some embodiments of about 15 ° C to about 40 ° C and, in other embodiments, from about 20 ° C to about 30 ° C. If desired, the precursor material can be stretched without the application of external heat (for example, heated rollers).
[074] Cold drawing in the manner described above generally results in the formation of empty spaces that have an axial dimension in the direction of stretching (for example, longitudinal or in the machine direction) relatively small. For example, in one embodiment, the axial dimension of the voids can be about 5 micrometers or less, in some embodiments about 2 micrometers or less and, in other embodiments, from about 25 nanometers to about 1 micrometer. In certain cases, voids can be “micro-voids” in the sense that at least one dimension of these voids is about 1 micrometer or more in size. For example, these micro-voids may have a dimension in a direction orthogonal to the axial dimension (i.e., machine's cross-sectional direction) of about 1 micrometer or more, in some embodiments about 1.5 micrometers or more and, in other embodiments about 2 micrometers to about 5 micrometers. This can result in an aspect ratio of the micro-voids (the ratio of the axial dimension to the orthogonal dimension to the axial dimension) of about 0.1 to about 1, in some embodiments of about 0.2 to about 0.9 and, in other embodiments, about 0.3 to about 0.8. Likewise, “nano-voids” can also be present, alone or in conjunction with micro-voids. Each dimension of the nano-voids is generally less than about 1 micrometer and, in some embodiments, about 25 to about 500 nanometers.
[075] In addition to forming a void network as described above, stretching can also significantly increase the axial dimension of the primary domains, so that they have a generally elongated and linear shape. For example, elongated domains can have an axial dimension of about 10% or more, in some embodiments from about 20% to about 500% and, in some embodiments, from about 50% to about 250% larger than the axial dimension of the domains before stretching. The axial dimension after stretching can, for example, vary from about 1 μm to about 400 μm, in some embodiments from about 5 μm to about 200 μm and, in some embodiments, from about 10 μm at about 150 μm. The domains can be relatively thin and thus have a small dimension in a direction orthogonal to the axial dimension (ie, transversal dimension). For example, the cross-sectional dimension can be from about 0.02 to about 75 micrometers, in some embodiments from about 0.1 to about 40 micrometers and, in other embodiments, from about 0.4 about 20 micrometers. This can result in an aspect ratio of the domains (the ratio of the axial dimension to the orthogonal dimension to the axial dimension) from about 2 to about 150, in some embodiments from about 3 to about 100, and in other embodiments, from about 4 to about 50.
[076] As a result of the elongated and empty space domain structure obtained with cold drawing, the present inventors have found that the resulting compound can expand uniformly in volume when drawn in the longitudinal direction, which is reflected by a low “coefficient of Poisson ”, as determined according to the following equation: Poisson's ratio = - Transversal / Elongitudinal in which Etransversal is the transversal deformation of the material and Elongitudinal is the longitudinal deformation of the material. More specifically, the Poisson's ratio of the material can be approximately 0 or even negative. For example, the Poisson's ratio may be approximately 0.1 or less, in some embodiments of approximately 0.08 or less and in other embodiments of approximately -0.1 to approximately 0.04. When the Poisson's ratio is zero, there is no contraction in the transverse direction when the material is expanded in the longitudinal direction. When the Poisson's ratio is negative, the transverse or lateral dimensions of the material also expand when the material is stretched in the longitudinal direction. Thus, materials with a negative Poisson's ratio can exhibit an increase in width when stretched in the longitudinal direction, which can result in increased energy absorption in the transverse direction.
[077] Even at the lowest densities achieved by the present invention, the resulting thermoplastic compound still has excellent mechanical properties due to its unique structure and morphology. In fact, the thermoplastic compound can have certain properties, such as impact resistance, considerably superior to conventional compounds. For example, the thermoplastic compound may have an Izod resistance to impact deformation of approximately 1 Joules per centimeter (“J / cm”) or more, in some embodiments of approximately 3 J / cm or more, and in some forms of 5 J / cm to approximately 15 J / cm, measured at 23 ° C, according to ASTM D256-10 (Method A). The stress elongation at break can also be relatively high, such as approximately 40% or more, in some compositions, approximately 60% or more and, in some compositions, from approximately 70% to approximately 300%. Upon reaching a high level of strength and tension elongation, the present inventors have found that other mechanical properties are not adversely affected. For example, the compound may exhibit a peak stress of approximately 10 to approximately 65 Megapascals ("MPa"), in some embodiments, from approximately 15 to approximately 55 MPa, and in some embodiments, from approximately 25 to approximately 50 MPa; a tensile strength of approximately 10 to approximately 65 MPa, in some embodiments, from approximately 15 to approximately 60 MPa, and in some embodiments, from approximately 20 to approximately 55 MPa; and / or a tension module of approximately 50 to approximately 3,800 MPa, in some embodiments, from approximately 100 MPa to approximately 1,500 MPa and, in some embodiments, from approximately 200 MPa to approximately 1,000 MPa. The tension properties can be determined according to ASTM D638-10 at 23 ° C.
[078] Another benefit of the present invention is that the void structure can have a higher surface roughness than the precursor material, which can increase the tactile sensation and the softness of the resulting article. For example, the void structure may have an average surface roughness of approximately 0.2 μm or more, in some embodiments of approximately 0.3 μm or more and in some embodiments of 0.5 to 1, 5 μm approximately. The average surface roughness can be determined from the surface topography profile as described below and is generally calculated as the arithmetic mean of the absolute values of the roughness profile values. Such measurements and calculations can be conducted according to ISO 25178.
[079] III. Formed articles
[080] Due to its unique and beneficial properties, the cold drawn thermoplastic compound of the present invention is suitable for use in formed articles and especially those having a relatively small thickness. For example, the article can 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.
[081] The formed article can be configured using any of the several techniques known in the field, such as profile extrusion, extrusion blow molding, injection molding, rotational molding, compacting molding, etc., in addition to combinations of these. Regardless of the process selected, the stretch compound can be used exclusively to form the article or in combination with other polymeric components to shape formed articles. For example, a thermoplastic compound can be profiled as a core, while other polymer (s) can be extruded as a "skin" or outer layer. In another embodiment, other polymer (s) can be injected or transferred to 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 include machines produced by Presma Corp., Northeast Mold & Plastics, Inc. Although not mandatory, the core of the formed article is usually composed of the cold drawing of the present invention and the surface layer is usually formed from a different polymer (for example, polyolefins, polyesters, polyamides, etc.) which improves the surface, batch and bonding properties for the intended use.
[082] With reference to Fig. 1, for example, a specific configuration of an injection molding apparatus or tool 10 with a single component 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 16 defining article or mold cavity. Each of the mold bases 12 and 14 includes one or more more cooling lines 18 through which a cooling liquid, such as water, flows in order to cool the device 10 during use. The molding apparatus 10 also includes a resin flow path that extends from an outer surface 20 of the half of the first mold 12 to an inlet channel 22 to the mold cavity 16 that defines the article. The resin flow path can also include a channel and a door, both hidden for simplicity. The molding apparatus 10 also includes one or more ejector pins 24 attached to the middle of the second mold 14 which help to define the cavity 16 that defines the article in the closed position of the apparatus 10, as indicated in Fig. 1. The ejector pin 24 operates in a well-known manner in order to remove a molded article or component from the cavity 16 that defines the article in the open position of the molding apparatus 10.
[083] The cold drawn compound can be directly injected into the molding apparatus 10 using techniques known in the art. For example, the compost can be supplied in sheet form in a feed hopper attached to a barrel that contains a rotating thread (not shown). As the thread rotates, the sheet is pushed through and undergoes extreme pressure and friction, which generates heat to melt the polymer. Electric heating strips (not shown) attached to the outside of the barrel can also assist in heating and temperature control during the melting 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 other embodiments, from approximately 240 ° C to approximately 250 ° C. After entering the molding cavity 16, the compound is solidified by the coolant flowing through lines 18. The coolant can, for example, be at 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.
[084] If desired, the molded article can also be annealed to help ensure maintenance of the desired shape. Annealing normally occurs at temperatures above the glass transition temperature of the renewable polyester, such as temperatures of approximately 65 ° C to 120 ° C, in some embodiments of approximately 70 ° C to 110 ° C, and in other embodiments of 80 ° C to approximately 100 ° C. Articles can also be surface treated using any of several known techniques in order to improve their properties. For example, high energy beams (for example, plasma, x-rays, electron beams, etc.) can be used to remove or reduce any surface layers that form on the molded article, in order to change the polarity of the surface, porosity, surface layer, etc. If desired, this surface treatment can be used alternatively before molding and before and / or after cold drawing the precursor material.
[085] The resulting formed articles can have different sizes and configurations. For example, the article can be used to form dispensers (for example, for paper towels), packaging materials (for example, food packaging, medicines, etc.), medical devices, such as surgical instruments (for example, scalpels, scissors, retractors, suction tubes, probes, etc.); implants (for example, bone plates, prostheses, plates, threads, etc.); containers or bottles, etc. The article can also be used to form various parts used in “personal care” applications. For example, in a special configuration, the article is used to form a wet tissue container. The configuration 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 for Huang et al., which are an integral part of this in its entirety, as a reference, for all purposes. Tissues for use with the container, for example, wet wipes, can be arranged in a way that provides a convenient and reliable release and helps them not to get too dry. For example, wet wipes can be arranged in the container as several individual sheets arranged in a stacked configuration to provide a stack of wet wipes that may or may not be folded individually. Wet wipes can be individual wipes folded in c, z, connected to adjacent wipes by a weakened line or other non-interleaved configurations known in the art. Alternatively, the individual wet wipes can be folded so that the edges of the front and rear ends of successive wipes are overlapped in the stacked configuration. In each of these folded and unfolded configurations, the leading edge of the next wipe is loosened in the stack by the leading edge when the 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 and others and 6,905,748 to Sosalla, which are an integral part of this in its entirety, by reference, for all purposes. .
[086] The present invention can be better understood with reference to the following examples. Testing methods
[087] Fusion flow rate:
[088] The melt flow rate ("MFR") is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.0825 inch diameter) when subjected to a load of 2,160 grams in 10 minutes, typically 190 ° C or 230 ° C, unless otherwise stated, the melt flow rate is measured according to the ASTM D1239 test method with a Tinius Olsen extrusion plastomer.
[089] Thermal properties:
[090] The glass transition temperature (Tg) can be determined by means of dynamic-mechanical analysis (DMA), according to the ASTM E1640-09 standard. A TA Instruments Q800 instrument can be used. Experimental tests can be performed on voltage / voltage geometry, in a temperature sweep mode in the range of -120 ° C to 150 ° C with a heating rate of 3 ° C / min. The frequency of the voltage amplitude 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 the peak value of the tangent curve δ, where the tangent δ is defined as the ratio of the loss module to the storage module. (tangent δ = E ”/ E ').
[091] The melting temperature can be determined by means of differential scanning calorimetry-DSC. The differential scanning calorimeter can be a DSC Q100 calorimeter, which has been equipped with a liquid nitrogen cooling accessory and UNIVERSAL ANALYSIS 2000 analysis software (version 4.6.6), which are available from TA Instruments Inc. of New Castle , Delaware. To avoid handling samples directly, tweezers or other instruments are used. The samples are placed in an aluminum pan and weighed to the nearest 0.01 milligram on an analytical balance. A lid is folded over the sample material over the pan. Usually, the resin grains are placed directly on the weighing pan.
[092] The calorimetry differential scanning equipment is calibrated using an Indian metal standard, and a basic correction is made, as described in the equipment's operation manual. The material sample is placed in the test chamber of the calorimetry differential scanning equipment to be tested and an empty plate is used as a reference. All tests are performed with the application of 55 cubic centimeters per minute of nitrogen (industrial grade) on the test chamber. For resin grain samples, the heating and cooling program is a 2-cycle test, which started with chamber equilibration at -30 °° C, followed by a first heating period to a rate of 10 ° C per minute to a temperature of 200 ° C, followed by a sample equilibrium 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 the sample equilibrium at -30 ° C for 3 minutes, and then a second heating period, at a rate of 10 ° C per minute to a temperature of 200 ° C. All tests are carried out with the discharge of 55 cubic centimeters of nitrogen per minute (industrial scale) in the test chamber.
[093] The results are evaluated using the UNIVERSAL ANALYSIS 2000 analysis software, which identifies and quantifies the inflection glass transition temperature (Tg), the endothermic and exothermic peaks and the areas under the peaks in the DSC graphs. The glass transition temperature is identified as the region in the narrative line where a clear change in slope has occurred, and the melting temperature is determined through an automatic inflection calculation.
[094] Izod resistance to impact deformation:
[095] The resistance to impact deformation of injection molded Izod bars was determined by the following ASTM D256 - 10 Method A (Standard Test Methods for Determination of Izod Pendulum Strength of Plastics). 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 capacity of 2 feetdb. The injection molded Izod test specimens have a height of 12.70 ± 0.20 mm and a thickness of 3.2 ± 0.05 mm.
[096] Voltage properties:
[097] The module was determined using an MTS 810 hydraulic tension frame to extract bones from Type I injection molded dogs, 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. The conditions were 23 ° C ± 2 ° C and a relative humidity of 50% ± 10%. The fixings of the tension frame were, in a nominal length of the template, 115 mm. The specimens were extracted at a rate of 50 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 data during the test and generate a stress curve in relation to a strain curve, from which the modulus of the average of five specimens was determined.
[098] Peak tension, rupture stress, elongation at break and energy by volume at break were determined using an MTS Synergie 200 tension board, for removing bone from Type V dogs, injection molded, 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. The conditions were 23 ° C ± 2 ° C and a relative humidity of 20% ± 10%. The fixings of the tension frame were, in a nominal length of the gauge, 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 in relation to a strain curve, from which the mean peak stress, breaking stress, elongation at break were determined and energy per volume at break.
[099] Expansion ratio, density and percentage of empty volume.
[100] To determine the expansion ratio, density and percentage of empty volume, the width (Wi) and thickness (Ti) of the specimen were initially measured before cold drawing. The length (Li) before stretching was also determined by measuring the distance between two marks on the specimen's surface. Consequently, the specimen was cold drawn to begin emptying. Specimen width (Wf), thickness (Tf) and length (Lf) were measured to the nearest 0.01 mm using a Digimatic Caliper caliper (Mitutoyo Corporation). The volume (Vi) before cold drawing was calculated by Wi x Ti x Li = Vi. The volume (Vf) after cold drawing was calculated by Wf x Tf x Lf = Vf. The expansion rate (Φ) was calculated by Φ = Vf / Vi; density (Pf) was calculated by: Pf = Pi / Φ, where Pi is the density of the precursor material; and the percentage of empty volume (% Vv) was calculated by:% Vv = (1 - 1 / Φ) x 100.
[101] Surface roughness
[102] Clean surfaces (air blowing) of the material were analyzed. The samples were analyzed using a FRT MicroProf® non-contact white light profilometer. The optical head used was the 100 μm z-range unit, calibrated before use. The Z sensitivity of this head was approximately 6 nanometers. Areas of 500 μm x 500 μm and 1 mm x 1 mm in each were analyzed. The 500-μm fields were sampled with 250 lines x 250 points / line generating a sampling resolution of = 2-microns. 1 mm scans were made using 400 lines x 400 dots / line for a sampling resolution of 2.5 microns. The resulting topographic maps were processed using the FRT Mark III software in order to obtain the average surface roughness parameter, sPa.
[103] Moisture content
[104] The moisture content can be determined using the Arizona Instruments Computrac Vapor Pro moisture analyzer (Model No. 3100) in accordance with ASTM D 7191-05, included in this document in its entirety, by reference to all purposes. The test temperature (§X2.1.2) can be 130 ° C, the sample size (§X2.1.1) can be 2 to 4 grams, and the emptying time of the bottle (§X2.1.4) can be 30 seconds. In addition, the final criteria (§X2.1.3) can be defined as a "prediction" mode, which means that the test ends when the internally programmed criteria (which mathematically calculate the final moisture point) are met. EXAMPLE 1
[105] A precursor material was formed from injection molded samples by extruding PLA 6201D (Natureworks®, 10 g / 10 minutes melt index at 190 ° C) in a canine bone shaped bar shaped by injection. When cold stretching was attempted at a stretch rate of 50 mm / min (87.7% / min), the bar failed at 3% elongation. EXAMPLE 2
[106] A precursor material was formed by injection molding a canine bone shaped bar from a mixture of 88.7% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.9% by weight of a hardening additive and 1.4% polyepoxide modifier. The hardening additive was VISTAMAXX ™ 2120 (ExxonMobil), which is a polyolefin copolymer / elastomer with a melt flow rate 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 rate of 70-100 g / 10 min (190 ° C / 2160 g) , a glycidyl methacrylate content of 7 to 11% by weight, a methyl acrylate content of 13 to 17% by weight, and an ethylene content of 72 to 80% by weight. The polymers were introduced into a co-rotating twin screw extruder (ZSK-30, diameter 30 mm, length 1,328 mm) for compounds manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered sequentially from 1 to 14, from the feed funnel to the die. The first zone of barrel # 1 received the resins through the gravimetric feeder at a total transfer rate of 15 pounds per hour. The die used to extrude the resin had 3 die openings (6 millimeters in diameter) separated by 4 millimeters. After forming, the extruded resin was cooled on a conveyor belt with ventilation and molded into pellets by a Conair pelletizer. The screw speed of the extruder was 200 revolutions per minute (“rpm”).
[107] The grains were then transferred in large volume in a Spritzgiessautomaten BOY 22D injection molding apparatus. The temperature zones for the injection molding process ranged from 185 ° C to 225 ° C, the injection molding pressure time was 10 sec to 14 sec, the cooling time from 25 sec to 50 sec, the cycle times varied from 35 sec to 65 sec and the mold temperature was set to approximately 21 ° C or 10 ° C. The injection molded bar in a canine bone shape (ASTM D638) was stretched at a stretch rate of 50 mm / min (87.7% strain / min). The material deformed non-uniformly with localized areas of stress bleached and showed elongation at failure of approximately 11% deformation. EXAMPLE 3
[108] A precursor material was formed by injection molding a canine bone shaped bar from a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of VISTAMAXX ™ 2120 (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8% by weight of internal interfacial modifier (BASF PLURIOL® WI 285 lubricant). PLURIOL® WI285 was added via an injection pump in barrel zone 2. The injection molded bars were formed from the mixture as described in Example 2. The injection molded bars were initially extended to failure and showed a deformation in the rupture of more than 120%, which was beyond the limits of the tester. During the extension test, initially the material showed white lines of tension in a uniform and homogeneous manner followed by bottlenecks located around the deformations of approximately 100% of the extension.
[109] After testing the extensibility of the precursor material to failure, the precursor material bar was stretched by 50% elongation at a stretch rate of 50 mm / min (87.7% strain / min) as described in Example 1. The material showed white lines uniformly in the functional length of the sample, demonstrating the formation of a homogeneous and uniform structure of empty spaces. The increase in volume due to the microvazio was estimated at approximately 57% and the expansion of total volume versus original volume was approximately 157%. The expansion rate was 1.57 resulting in an estimated percentage void volume of 36% and an estimated material density of approximately 0.76 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. The density of the material with empty spaces was also independently measured by the liquid displacement method. This measurement provided a material density of 0.78 g / cc, which is close to the estimated density based on the measurement of the volume expansion ratio. The longitudinal strain in the material with empty spaces was El = 60% (longitudinal stress of 0.60), the strain in the transversal direction was Et = -1% (transversal stress in the transversal direction of -0.01), and the Poisson's ratio was 0.017, which also indicated a considerable increase in the volume of the stretched material.
[110] Small samples of ASTM D638-10 Type V canine bone were also taken from the material with low density voids in order to conduct tensile tests according to the procedures of the ASTM D638-10 standard and as described above. The low density material presented a tensile modulus of approximately 340 Mpa, peak stress of 38.4 Mpa, stress at break of 38.4 Mpa and elongation at break of 131%. EXAMPLE 4
[111] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 85.91% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.55 % by weight of VISTAMAXX ™ 2120 (ExxonMobil), 0.72% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.82% by weight of PLURIOL® WI 285 (BASF). The injection-molded precursor material was stretched with approximately 76% tension, as described in Example 3. The material showed homogeneous and uniform white tension lines and empty spaces. The expansion rate was 1.95 resulting in an estimated percentage void volume of 49% and a material density of approximately 0.61 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. The Poisson's ratio was 0.06. EXAMPLE 5
[112] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 84.5% by weight of polylactic acid (PLA 6201D, Natureworks®), 9 , 4% by weight of VISTAMAXX ™ 2120 (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 4.7% by weight of Hallstar HALLGREEN® IM-8830 internal interfacial modifier. HALLGREEN® IM-8830 was added via the injection pump within zone # 2 of the barrel. Injection molded parts were formed from the mixture. The injection-molded precursor material was stretched at approximately 50% tension as described in Example 3, and showed homogeneous and uniform white tension lines and voids. The expansion rate was 1.26 resulting in an estimated percentage void volume of 21% and a material density of approximately 0.94 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. The Poisson's ratio was 0.01. EXAMPLE 6
[113] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5 % by weight of ESCORENE ™ UL EVA 7720 curing additive (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8% by weight of PLURIOL® WI 285 (BASF). The injection-molded precursor material was stretched at approximately 50% tension as described in Example 3, and showed homogeneous and uniform white tension lines and voids. The expansion rate was 1.67 resulting in an estimated percentage void volume of 40% and a material density of approximately 0.71 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. The Poisson's ratio was 0.03. The impact strain test was also carried out. Resistance to impact deformation was estimated at approximately 6.31 joules / cm. During the test, the notched sample resisted the propagation of the notch through folds, twists and plastic deformation. As a result of the complex response of the material, the notch was interrupted and the material did not fail during the test. On average, five samples were tested for impact resistance. Small samples of ASTM D638-10 Type V canine bone were also taken from the material with low density voids in order to conduct tensile tests according to the procedures of the ASTM standard. As a result of the test, the low density material showed a tensile modulus of approximately 522 Mpa, peak stress of 33.0 Mpa, tensile strength of 33.0 Mpa and elongation at break of 103%. EXAMPLE 7
[114] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9 , 5% by weight of VISTAMAXX ™ 2120 (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8% by weight of internal interfacial modifier (BASF PLURIOL® WI 285 lubricant). The injection-molded precursor material was stretched at approximately 110% tension at a rate of 5 mm / minute. The expansion rate was 2.01 resulting in an estimated percentage void volume of 50% and a material density of approximately 0.59 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. The Poisson's ratio was 0.04. SEM photomicrographs were also taken after the material was carved with cold drawing and oxygen plasma. The results are shown in Fig. 2. As shown, the material showed homogeneous and uniform white tension lines and empty spaces. The samples carved with oxygen plasma were also analyzed by a mercury intrusion method using an Autopore IV900 instrument in order to characterize the pore diameter, batch density and porosity. The samples had a median pore diameter of 0.0799 μm, an average pore diameter of 0.0398 μm, a batch density of 0.6888 g / mL and a porosity of 44.8957%. In addition, the BET surface area was 21.61 m2 / g, as determined via Micromeritics Instrument Services' Tristar II 3020 V1.03. EXAMPLE 8
[115] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9 , 5% by weight of VISTAMAXX ™ 2120 (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8% by weight of internal interfacial modifier (BASF PLURIOL® WI 285 lubricant). The injection-molded precursor material was stretched at approximately 50% tension at a rate of 5 mm / minute. The expansion rate was 1.53 resulting in an estimated percentage void volume of 35% and a material density of approximately 0.78 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. The Poisson's ratio was 0.01. The impact strain test was also performed on the material with low density voids. Resistance to impact deformation was estimated at approximately 5.75 joules / cm. During the test, the notched sample resisted the propagation of the notch through folds, twists and plastic deformation. As a result of this complex response of the material, the notch was interrupted and the material did not fail during the test. On average, five samples were tested for impact resistance.
[116] SEM photomicrographs were also taken after cold stretching the material and performing the impact test. The results are shown in Fig. 3. As shown, the material showed homogeneous and uniform white lines of tension and microvazes. EXAMPLE 9
[117] A precursor material was formed from injection molded samples by extruding Crystar® 4434 polyethylene terephthalate (DuPont®) into an injection molded ASTM D638-10 Type I canine bone bar. When cold stretching was attempted at a stretch rate of 50 mm / min (87.7% / min), the bar failed at 3% elongation. EXAMPLE 10
[118] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 85.3% by weight of polyethylene terephthalate (Crystar® 4434, DuPont®) , 9.5% by weight of VISTAMAXX ™ 2120 (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 3.8% by weight of internal interfacial modifier (BASF PLURIOL® WI 285 lubricant) ). The injection-molded precursor material was stretched at approximately 50% tension at a rate of 5 mm / minute. The expansion rate was 1.49 resulting in an estimated percentage void volume of 33% and a material density of approximately 0.92 g / cc based on an estimated precursor material density of 1.37 g / cc. The Poisson's ratio was 0.06. EXAMPLE 11
[119] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 84.5% by weight of polylactic acid (PLA 6201D, Natureworks®), 9 , 4% by weight of VISTAMAXX ™ 2120 (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 4.7% by weight of Hallstar HALLGREEN® IM-8830 internal interfacial modifier. HALLGREEN® IM-8830 was added via the injection pump within zone # 2 of the barrel. Injection molded parts were formed from the mixture. The injection-molded precursor material was stretched at approximately 139% tension at 5 mm / min and presented homogeneous and uniform white tension lines and empty spaces. The expansion rate was 2.33 resulting in an estimated percentage void volume of 57% and a material density of approximately 0.51 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. Topographic surface analysis showed that the precursor material had an average roughness (sPA) of 0.134 μm. After cold drawing, the material had an average roughness of 0.907 μm. SEM photomicrographs were also taken after cold stretching the material and performing the impact test. The results are shown in Figs. 4 to 6. As shown, the material showed homogeneous and uniform white lines of tension and microvazes. EXAMPLE 12
[120] A precursor material was formed by injection molding a canine bone shaped bar ASTM D638-10 Type I from a mixture of 87.0% by weight of polylactic acid (PLA 6201D, Natureworks®), 9 , 7% by weight of VISTAMAXX ™ 2120 (ExxonMobil), 1.4% by weight of polyepoxide modifier (LOTADER® AX8900, Arkema) and 1.9% by weight of internal interfacial modifier (BASF PLURIOL® WI 285 lubricant). The injection-molded precursor material was stretched at approximately 50% tension at a rate of 5 mm / minute. The expansion rate was 1.47 resulting in an estimated percentage void volume of 32% and a material density of approximately 0.81 g / cc based on a precursor material density of 1.19 g / cc and a PLA density of 1.25 g / cc. The Poisson's ratio was 0.03. EXAMPLE 13
[121] Samples were formed as described in Example 2, except for the polyepoxide modifier that was LOTADER® AX8900. The injection-molded bar in an ASTM D638-10 Type I form was stretched at a stretch rate of 50 mm / min (87.7% strain / min). The material deformed in a non-uniform manner with localized white lines of stress and showed an elongation at failure of approximately 9% deformation.
[122] Although the invention has been described in detail with respect to its specific configurations, it would be good for experts in the field, after obtaining an understanding of the above, to be able to easily conceive changes, variations and equivalents to such configurations. Therefore, the scope of the present invention must be assessed as that of the appended claims and their equivalents.

权利要求:
Claims (15)
[0001]
1. 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, and preferably from 50 ° C to 75 ° C; and at least one polymeric curing additive; at least one interphasic modifier; and a polyepoxide modifier; in which the thermoplastic composition has a morphology in which several discrete and empty primary domains are dispersed within a continuous phase, with the domains containing the polymeric curing additive and with the continuous phase containing the renewable polyester, in which the thermoplastic composition has density 1.4 grams per cubic centimeter or less, and preferably 0.5 grams per cubic centimeter to 0.95 grams per cubic centimeter, and where the average percentage volume of the composition that is occupied by the voids is 20% to 80 % per cubic centimeter, and preferably 40% to 60% per cubic centimeter; wherein the glass transition temperature is determined according to ASTM E1640-09; wherein the volume of voids and the density of the composition are determined as defined herein.
[0002]
2. Thermoplastic composition according to claim 1, characterized by the fact that the void ratio is 0.1 to 1 and / or that the voids contain a combination of micro-voids and nano-voids.
[0003]
3. Thermoplastic composition according to any one of the preceding claims, characterized by the fact that the renewable polyester is a polylactic acid, and / or in which the renewable polyester makes up 70% by weight or more of the thermoplastic composition.
[0004]
4. Thermoplastic composition according to any one of the preceding claims, characterized by the fact that the ratio between the renewable polyester solubility parameter and the polymer hardening additive solubility parameter is 0.5 to 1.5, the ratio between the melt flow rate of the renewable polyester and the melt flow rate of the polymeric curing additive is 0.2 to 8, and the ratio between the Young's modulus of renewable polyester and the Young's modulus of the polymeric curing additive is 2 to 500; where the solubility parameter is Hildebrand's solubility parameter; wherein the melt flow rate is measured according to the ASTM D1239 test method; and where Young's modulus of elasticity is determined according to ASTM D638-10.
[0005]
5. Thermoplastic composition according to any of the preceding claims, characterized by the fact that the polymeric curing additive contains a polyolefin, such as a propylene homopolymer, α-olefin / propylene copolymer, ethylene / α-olefin copolymer, or a combination of these.
[0006]
6. Thermoplastic composition according to any one of the preceding claims, characterized by the fact that the interphasic modifier has a kinematic viscosity of 0.7 to 200 centistokes (7x10-7 to 2x10-4 m2 / s), determined at a temperature of 40 ° Ç.
[0007]
7. Thermoplastic composition according to claim 6, characterized by the fact that the interphasic modifier is hydrophobic and / or in which the interphasic modifier is a silicone copolymer, silicone-polyether, aliphatic polyester, aromatic polyester, alkylene glycol, alkane diol, amine oxide, fatty acid ester or a combination of these.
[0008]
8. Thermoplastic composition according to claim 6, characterized by the fact that the polymeric curing additive constitutes from 1% by weight to 30% by weight, based on the weight of the renewable polyester, and the interphasic modifier constitutes 0.1% by weight to 20% by weight based on the weight of the renewable polyester.
[0009]
9. Thermoplastic composition according to any one of the preceding claims, characterized by the fact that the composition comprises a polyepoxide modifier that contains an epoxy-functional monomeric (meta) acrylic component.
[0010]
10. Thermoplastic composition according to any one of the preceding claims, characterized by the fact that the composition has a Poisson's ratio of 0.1 or less, Izod resistance to impact deformation of 1 J / cm or higher, measured at a temperature of 23 ° C according to ASTM D256-10 (Method A), a stress elongation at break of 40% or higher, measured at a temperature of 23 ° C according to ASTM D638-10, and / or an average surface roughness of 0.2 μm or higher; wherein the average surface roughness is determined as described herein.
[0011]
11. Method for forming a low density thermoplastic composition for use in a molded article, characterized by the fact that the method comprises: the formation of a mixture containing a renewable rigid polyester, such as polylactic acid, and a polymeric curing additive, as a polyolefin, an interphasic modifier and a polyepoxide modifier in which the renewable rigid polyester has a glass transition temperature of 0 ° C or higher; forming a precursor material from the mixture; and stretching the precursor material at a temperature below the glass transition temperature of the renewable polyester, preferably at a temperature of at least 10 ° C below the glass transition temperature of the renewable polyester, to form a thermoplastic composition containing several voids and has a density of 1.4 grams or less per cubic centimeter, and preferably 0.5 grams per cubic centimeter to 0.95 grams per cubic centimeter; where the average percentage volume of the composition that is occupied by the voids is 20% to 80% per cubic centimeter; wherein the glass transition temperature is determined according to ASTM E1640-09; and wherein the volume of voids and the density of the composition are determined as defined herein.
[0012]
12. Method according to claim 11, characterized by the fact that it also comprises the molding of the thermoplastic composition in the article format.
[0013]
Method according to claim 12, characterized in that it further comprises the annealing of the composition after molding, at a temperature above the glass transition temperature of the renewable polyester.
[0014]
Method according to claim 11, characterized in that the polyepoxide modifier includes an epoxy-functional monomeric (meta) acrylic component.
[0015]
15. Method according to claim 11, characterized in that the mixture is free of gaseous swelling agents.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-09-29| B09A| Decision: intention to grant|

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2020-12-22| B16A| Patent or certificate of addition of invention granted|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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US13/370,883|2012-02-10|

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US13/370,883|US9040598B2|2012-02-10|2012-02-10|Renewable polyester compositions having a low density|

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PCT/IB2013/050731|WO2013118021A1|2012-02-10|2013-01-28|Renewable polyester compositions having a low density|

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