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    FUSION MIXED THERMOPLASTIC COMPOSITION AND METHOD FOR PROVIDING A FUSION MIXED THERMOPLASTIC COMPOSITION The present invention relates to a mixed fusion thermoplastic composition comprising: (A) a polyamide composition comprising (a) 55 to 90% by weight of semi-aromatic copolyamide and semicrystalline; wherein the semi-aromatic copolyamide has a peak Tan Delta value per DMA greater than or equal to 0.23; and heat of the melt of at least 20 J / g, and (b) 10 to 45% by weight of aliphatic homopolyamide; and wherein the aliphatic homopolyamide has a peak Tan Delta value per DMA less than or equal to 0.21, and heat of fusion of at least 30 J / g; (B) 0 to 45% by weight of polymeric stiffener; (C) 0 to 20% by weight, preferably 0 to 12% by weight, of plasticizers, and (D) 0 to 45% by weight of reinforcing agent; and wherein said mixed melt composition has a glass transition and has a peak Tan Delta (E? / E?) value of 0.21 or less at said glass transition. The present invention also relates to a method for providing the melt blended thermoplastic composition.
    公开号:BR112013019343B1
    申请号:R112013019343-3
    申请日:2012-01-31
    公开日:2021-02-09
    发明作者:Shailesh Doshi；Annakutty Mathew
    申请人:E.I. Du Pont De Nemours And Company；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to the field of polyamide compositions that have improved properties at elevated temperatures. BACKGROUND OF THE INVENTION
    [002] Thermoplastic polymeric materials are used extensively in automotive vehicles and for other purposes. They are light and relatively easy to mold into complex parts, and therefore are preferred over metals in many cases. However, a problem with some metal alloys and some polymers is the cracking by corrosion (induced) of salt stress (SSCC), where a stressed part undergoes accelerated corrosion when it is stressed and in contact with inorganic salts. This often results in cracking and premature part failure.
    [003] US patent publication 2010 / 0.233.402, entitled “Salt Resistant Polyamide Compositions” describes certain semi-aromatic copolyamides that exhibit improved chemical resistance especially for metal halides and salts compared to the corresponding aliphatic homopolyamides. In these copolyamides, at least 15 mol% of repeating units are derived from monomers that comprise an aromatic structure. Accordingly, semi-aromatic 612 / 6T copolyamides comprise 20 to 30 mol% of 6T units which exhibit improved salt resistance compared to the corresponding PA 612 homopolyamide.
    [004] The presence of two or more types of the repeat units of a copolyamide, however, has a negative consequence. These copolyamides have a reduced degree of crystallinity. As a result, they exhibit lower high temperature properties compared to the corresponding homopolyamides. These properties include mechanical properties, such as resistance to stiffness, strength and deformation at elevated temperature, which are important in many of its end uses. As the content of the aromatic repeating units increases to approximate 50 mol%, the polymer becomes increasingly amorphous and, correspondingly, exhibits greater loss in properties at elevated temperature.
    [005] When the content of the molar aromatic repetition unit exceeds 55%, as in the case of polyphthalamides, copolyamide is able to develop crystallinity and exhibits improved properties at elevated temperatures. However, these copolyamides have many high melting points, often above 300 ° C. They are less desirable for applications that require extrusion processing, such as hoses and tubes, cable and filament sheathing. For these applications, it is desirable to have polyamides that have melting points below about 290 ° C.
    [006] Salt resistance and high temperature mechanical properties are, therefore, two conflicting aspects influenced by the content of the aromatic repetition unit of semiaromatic copolyamides. It is desirable to develop formulations of semiaromatic copolyamides that simultaneously exhibit good salt resistance and high temperature properties, and are processable at temperatures below 300 ° C. BRIEF DESCRIPTION OF THE INVENTION
    [007] A thermoplastic melt blended composition is described herein comprising: (A) a polyamide composition comprising (a) 55 to 90% by weight of semi-aromatic and semicrystalline copolyamide having a melting point, at which said semi-aromatic copolyamide comprises: a-1) about 15 to 50 mol% of aromatic repeating units derived from: (i) one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and a first aliphatic diamine with 4 to 20 carbon atoms; and a-2) 50 to 85 mol% of aliphatic repeating units derived from: (ii) a first aliphatic dicarboxylic acid with 8 to 20 carbon atoms and said first aliphatic diamine with 4 to 20 carbon atoms; or (iii) a first aliphatic amino acid or lactam with 8 to 20 carbon atoms; wherein the semi-aromatic copolyamide has a peak Tan Delta value per DMA greater than or equal to 0.23; and heat of fusion of at least 20 J / g, as measured in the first DSC thermal cycle; (b) 10 to 45% by weight of aliphatic homopolyamide which has a melting point, wherein said aliphatic homopolyamide comprises repeating units derived from: (iv) a second aliphatic dicarboxylic acid with 8 to 20 carbon atoms and a second diamine aliphatic with 4 to 20 carbon atoms, or (v) a second aliphatic amino acid or lactam with 8 to 20 carbon atoms, and where the aliphatic homopolyamide has a peak value of Tan Delta per DMA less than or equal to 0.21 , and heat of fusion of at least 30 J / g, as measured in the first DSC thermal cycle; wherein the weight percent of a) and b) are based on the total weight of a) and b) and said first and second aliphatic diamines can be the same or different; (B) 0 to 45% by weight of the polymeric stiffener; (C) 0 to 20% by weight, preferably 0 to 12% by weight, of plasticizers; and (D) 0 to 45% by weight of reinforcing agent; wherein the weight percent of (B), (C) and (D) are based on the total weight of the melt-mixed thermoplastic composition, the melt-mixing is carried out at a melting temperature above the melting point of said semi-aromatic copolyamide and semicrystalline and said aliphatic homopolyamide and less than or equal to about 290 ° C, preferably less than or equal to 280 ° C, to provide said melt-mixed thermoplastic composition, and wherein said melt-mixed composition has a glass transition and has a peak Tan Delta (E ”/ E ') value of 0.21 or less at said glass transition.
    [008] Also described is a method for providing a melt blended thermoplastic composition, comprising: the components of (A) to (D) melt blended as described above, wherein the weight percentages of (B), (C ) and (D) are based on the total weight of the melt blended thermoplastic composition, and in which said melt blended composition has a glass transition and has a Tan Delta peak value (E ”/ E ') of 0.21 or least to said glass transition. BRIEF DESCRIPTION OF THE FIGURES
    [009] Figure 1 shows a dynamic mechanical analysis of a semicrystalline copolymer. DETAILED DESCRIPTION OF THE INVENTION
    [010] In this document, melting points are as determined by differential scanning calorimetry (DSC) at a scan rate of 10 ° C / min in the first heating scan, where the melting point is taken at the maximum level of the endothermic peak, and the heat of fusion, in Joules / gram (J / g) is the area within the endothermic peak.
    [011] Dynamic mechanical analysis (DMA) is currently used to determine the storage module (E ') and the loss module (E ”), and the glass transition, as a function of temperature. Tan Delta is a curve resulting from the loss module divided by the storage module (E ”/ E ') as a function of temperature.
    [012] Dynamic mechanical analysis is discussed in detail in “Dynamic Mechanical Analysis: A practical Introduction”, Menard K.P., CRC Press (2008) ISBN is 978-1-4200-5312-8. The curves of the storage module (E '), loss module (E ”) show the specific changes in response to the molecular transitions that occur in the polymeric material, in response to the increase in temperature. A key transition is called a glass transition. It characterizes a temperature range in which the amorphous phase of the polymer transitions from the vitreous to the elastic state, and exhibits large-scale molecular movement. The glass transition temperature is, therefore, a specific attribute of a polymeric material and its morphological structure. For the melt-mixed polyamide compositions described herein, the glass transition occurs over a temperature range of about 10 to about 90 ° C. The Tan Delta curve shows a prominent peak in this temperature range. This peak temperature of Tan Delta is defined in the prior art as the glass transition temperature of Tan Delta, and the height of the peak is a measure of the crystallinity of the polymeric material. A polymeric sample with low or no crystallinity exhibits a high Tan Delta peak due to the wide contribution of the molecular motion of the amorphous phase, while a sample with a high crystallinity level exhibits a lower peak, since the molecules in the crystalline phase are not capable of exhibiting such elastic movement on a large scale. Therefore, in this document, the Tan Delta glass transition peak value is used as a comparative indicator of the level of crystallinity in the melt blended thermoplastic polyamide composition.
    [013] Figure 1 shows a dynamic mechanical analysis of a crystalline copolymer, showing the curves of the storage module (E '), the loss module (E ”) and the computerized Tan Delta curve (E” / E') . An upper Tan Delta peak corresponds to lower crystallinity and, conversely, a lower Tan Delta peak corresponds to higher crystallinity, as discussed in “Thermal Analysis of Polymers”, Sepe MP, Rapra Review Reports, Vol. 8, No. 11 ( 1977).
    [014] The polyamides described herein are homopolymers or copolymers in which the term copolymer refers to polyamides that have two or more molecular repeating units of amide and / or diamide. Homopolymers and copolymers are identified by their respective repetition units. For copolymers described herein, the repetition units are listed in descending order of the percentage (%) in mol of repetition units present in the copolymer. The following list exemplifies the abbreviations used to identify the monomers and repeating units in the homopolymer and copolymer (PA) polyamides:


    [015] Note that in the state of the art the term “6”, when used alone designates a polymer repetition unit formed from € -prolactam. Alternatively, the term "6", when used in combination with a diacid, such as T, for example, 6T, the term "6" refers to HMD. In the repetition units that comprise a diamine and a diacid, the diamine is designated first. In addition, when the term "6" is used in combination with a diamine, for example 66, the first "6" refers to the HMD diamine, and the second "6" refers to adipic acid. Likewise, repeating units derived from other amino acids or lactams are designated as unique numbers that designate the number of carbon atoms.
    [016] The copolymer repeating units are separated by a slash (ie, /). For example, poly (decamethylene decanediamide / decamethylene terephthalamide) is abbreviated PA1010 / 10T (75/25), and the values in parentheses are the percentage (%) in mol of the repeat unit in each repeat unit in the copolymer.
    [017] Semicrystalline and semi-aromatic copolyamides useful in the melt-mixed thermoplastic composition comprise: a-1) about 15 to 50 mol%, and preferably 15 to 40 mol%, of aromatic repeating units derived from: ( i) one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and a first aliphatic diamine with 4 to 20 carbon atoms; and a-2) 50 to 85 mol%, preferably 60 to 85 mol%, of aliphatic repeating units derived from: (ii) a first aliphatic dicarboxylic acid with 8 to 20 carbon atoms and said first aliphatic diamine with 4 to 20 carbon atoms, or (iii) an aliphatic amino acid or lactam with 8 to 20 carbon atoms, where the semi-aromatic copolyamide has a peak value of Tan Delta per DMA greater than or equal to 0.23, and heat of the melt of at least 20 J / g, as measured in the first DSC thermal cycle.
    [018] Aromatic dicarboxylic acid with 8 to 20 carbon atoms includes terephthalic acid, isophthalic acid and 2,6-naphthalenedioic acid. Terephthalic acid and isophthalic acid are preferred.
    [019] The first aliphatic dicarboxylic acid with 8 to 20 carbon atoms can include decanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid. Dodecanedioic acid and decanedioic acid are the preferred aliphatic dicarboxylic acids.
    [020] The first aliphatic diamine with 4 to 20 carbon atoms can have 4 to 12 carbon atoms and, most preferably, is selected from the group consisting of hexamethylenediamine (HMD), 1,10-decanediamine, 1,12-dodecanediamine and 2-methyl-1,5-pentamentylenpiamine.
    [021] The aliphatic amino acid or lactam with 8 to 20 carbon atoms can be 11-aminoundecanoic acid, 12-aminododecanoic acid, or their respective lactams. Semicrystalline and semi-aromatic copolyamides useful in melt-mixed thermoplastic compositions include those selected from the group consisting of: PA 612 / 6T (85/15) to (55/45) and, preferably, PA 612 / 6T (75 / 25), PA 612 / 6T (70/30) and PA 612 / 6T (60/40); PA 610 / 6T (85/15) to (55/45) and, more preferably, PA 610 / 6T (80/20), PA 610 / 6T (75/25) and PA 610 / 6T (60/40) ; PA 1010/10 (85/15) to (55/45) and, even more preferably, PA 1010 / 10T (80/20), PA 612 / 6I (90/10) to (70/30), and, even more preferably, PA 612 / 6I (85/15); and PA 612 / 6T / 6I which has a percentage (mol%) of 6T + 6I from 15 to 45 mol% and the ratio of T to I is about 4: 1 to 1: 1 and, most preferably also, PA 612 / 6T / 6I (80/10/10) and (75/20/5).
    [022] Aliphatic homopolyamides useful in the melt-mixed thermoplastic composition comprise repeating units derived from: (iv) a second aliphatic dicarboxylic acid with 8 to 20 carbon atoms and a second aliphatic diamine with 4 to 20 carbon atoms; or (v) a second aliphatic or lactam amino acid with 8 to 20 carbon atoms, where the aliphatic homopolyamide has a peak value of Tan Delta per DMA less than or equal to 0.21, and heat of fusion of at least 30 J / g, in the first thermal cycle as measured with the DSC.
    [023] The second aliphatic dicarboxylic acid with 8 to 20 carbon atoms can be the same as described above for the first aliphatic dicarboxylic acid. The second aliphatic diamine with 6 to 20 carbon atoms can be the same as described above for the first aliphatic diamine. The second aliphatic or lactam with 8 to 20 carbon atoms can be the same as described above for the first aliphatic or lactam. The second preferred aliphatic diamines are HMD, decanediamine and dodecanediamine.
    [024] Preferably, the second aliphatic dicarboxylic acid, the second aliphatic diamine and / or the second aliphatic amino acid or lactam present in the aliphatic homopolyamide are the same as the first aliphatic dicarboxylic acid, the first aliphatic diamine, and the first aliphatic or lactam, present in semiaromatic and semicrystalline copolyamide.
    [025] Aliphatic homopolyamides useful in the melt blended thermoplastic composition include PA 612, PA 610, PA 1010 and PA 614.
    [026] The thermoplastic composition mixed by fusion can be, in which the composition (A) of polyamide is selected from the group consisting of those listed in Table 1. TABLE 1 PREFERRED COMBINATIONS OF SEMIAROMATIC AND HOMOPOLIAMID POLYAMIDE

    [027] The polymeric stiffener is a polymer, usually an elastomer that has a melting point and / or glass transition points below 25 ° C, or an elastic type, that is, it has a melting heat (measured by the ASTM method D3418-82) less than about 10 J / g, more preferably less than about 5 J / g, and / or has a melting point of less than 80 ° C, more preferably less than about 60 ° Ç. Preferably, the polymeric stiffener has a weighted average molecular weight of about 5,000 or more, more preferably, about 10,000 or more, when measured by gel permeation chromatography using polyethylene standards.
    [028] The polymeric stiffener can be a functionalized stiffener, a non-functionalized stiffener, or a mixture of the two.
    [029] A functionalized stiffener has reactive functional groups attached to it, which can react with the polyamide. Such functional groups, in general, are "linked" to the polymeric stiffener by grafting small molecules into an existing polymer or by copolymerizing a monomer that contains the desired functional group when the most stiffening polymer molecules are produced through copolymerization. As an example of grafting, maleic anhydride can be grafted onto hydrocarbon rubber (such as, an ethylene / α-olefin copolymer, an α-olefin being a linear chain with a terminal double bond, such as a propylene or 1- octene) using free radical grafting techniques. The resulting grafted polymer has the carboxylic anhydride and / or carboxyl groups attached to it.
    [030] Ethylene copolymers are an example of a polymeric cooling agent in which the functional groups are copolymerized in the polymer, for example, an ethylene copolymer and a (meth) acrylate monomer containing the appropriate functional group. In this document, the term "(meth) acrylate" means that the compound can be an acrylate, a methacrylate, or a mixture of the two. Useful (meth) acrylate functional compounds include (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and 2-isocyanatoethyl (meth) acrylate. In addition to ethylene and a functionalized (rnet) acrylate monomer, other monomers can be copolymerized to such a polymer, such as vinyl acetate, non-functionalized (rnet) acrylate esters, such as ethyl (meth) acrylate , n-butyl (meth) acrylate, i-butyl (meth) acrylate and cyclohexyl (meth) acrylate. Polymeric stiffeners include those listed in US patent 4,174,358, which is hereby incorporated by reference.
    [031] Another functionalized stiffener is a polymer that has the metal salts of carboxylic acid. Such polymers can be prepared by grafting or copolymerizing a carboxyl or carboxylic anhydride that contains the compound to bind it to the polymer. Useful materials of this type include the Surlyn® ionomers available from E.I. DuPont of Nemours & Co. Inc., Wilmington, DE 19898, USA, and the metal-neutralized maleic anhydride grafted with the ethylene / α-olefin polymer described above. Preferred metal cations for these carboxylate salts include Zn, Li, Mg and Mn.
    [032] The polymeric stiffeners useful in the present invention include those selected from the group consisting of linear low density polyethylene (LLDPE), or linear low density polyethylene grafted with unsaturated carboxylic anhydride ethylene copolymers; ethylene / α-olefin or ethylene / α-olefin / diene copolymer grafted with an unsaturated carboxylic anhydride; core-coating polymers, and non-functionalized stiffeners, as defined herein.
    [033] In this document, the term "ethylene copolymers" includes ethylene terpolymers and ethylene multipolymers, that is, which have more than three different repeat units. Ethylene copolymers useful as polymeric stiffeners in the present invention include those selected from the group consisting of ethylene copolymers of Formula E / X / Y in which: (c) E is the radical formed from ethylene; (d) X is selected from the group consisting of radicals formed from CH2 = CH (R1) -C (O) -OR2 where R1 is H, CH3 or C2H5, R2 is an alkyl group containing from 1 to 8 carbon atoms; vinyl acetate; and their mixtures; wherein X comprises from 0 to 50% by weight of the E / X / Y copolymer; (e) Y is one or more radicals formed from the monomers selected from the group consisting of carbon monoxide, sulfur dioxide, acrylonitrile, maleic anhydride, maleic acid diesters, (meth) acrylic acid, maleic acid, monoesters of maleic acid, itaconic acid, fumaric acid, fumaric acid monoesters and potassium, sodium and zinc salts of said previous acids, (meth) glycidyl acrylate, (meth) 2-hydroxyethyl acrylate, (meth) 2-acrylate isocyanatoethyl and vinyl glycidyl ether, where Y is from 0.5 to 35% by weight of the E / X / Y copolymer, preferably from 0.5 to 20% by weight of the E / X / Y and E copolymer is the percentage by weight remaining and preferably comprises 40 to 90% by weight of the E / X / Y copolymer.
    [034] It is preferable that the functionalized stiffener contains a minimum of about 0.5, more preferably, 1.0, most preferably, about 2.5% by weight of the repeating units and / or molecules grafts containing the functional groups, or carboxylate salts (including the metal), and a maximum of about 15, more preferably, about 13, and most preferably, about 10% by weight of the monomers that contain functional groups, or carboxylate salts (including metal). It is to be understood that any preferred minimum amount can be combined with any preferred maximum amount to form a preferred range. There may be more than one type of functional monomer present in the polymeric stiffener, and / or more than one polymeric stiffener. In one embodiment, the polymeric stiffener comprises from about 2.5 to about 10% by weight of the repeating units and / or grafted molecules that contain the functional groups, or carboxylate salts (including the metal).
    [035] It has been found that often the stiffness of the composition is increased, increasing the functionalized stiffening amount and / or the amount of the functional groups and / or the metal carboxylate groups. However, these amounts should preferably not be increased to the point where the composition can cross-link (thermostabilize), especially before the final shape of the part is reached, and / or the first cast stiffener can cross-link between itself. Increasing these amounts can also increase the melt viscosity, and the melt viscosity should preferably also not be increased so that molding is difficult.
    [036] Non-functionalized stiffeners can also be present in addition to a functionalized stiffener. Non-functionalized stiffeners include polymers, such as ethylene / α-olefin / diene rubber (EPDM), polyophyllines that include polyethylene (PE) and polypropylene, and ethylene / α-olefin (EP), and rubbers ethylene / α-olefin, such as ethylene / 1-octene copolymer and the like, such as commercial copolymers under the trademark ENGAGE® of Dow Chemical, Midland Michigan. Other non-functional stiffeners include styrene-containing polymers that include the acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-styrene-copolymer-styrene-isoprene copolymer. -styrene, styrene-hydrogenated styrene-butadiene copolymer, styrene block copolymer, polystyrene (not the block polymers or random polymers listed above). For example, acrylonitrile-butadiene-styrene, or ABS, is a terpolymer produced through the polymerization of styrene and acrylonitrile in the presence of polybutadiene. The proportions can vary from 15 to 35% acrylonitrile, from 5 to 30% butadiene and from 40 to 80% styrene. The result is a long polybutadiene chain crossed with the shorter poly (styrene acrylonitrile) chains.
    [037] Other polymeric hardeners useful in the present invention have a core (aromatic vinyl comonomer) comprising an ethylene copolymer, as described above, the core optionally cross-linking and optionally containing an aromatic vinyl comonomer , for example, styrene, and a coating comprising another polymer which may include polymethyl methacrylate and optionally contains functional groups, including epoxy, or amine. The coated core polymer can be composed of several layers, prepared using a multistage sequential polymerization technique of the type described in US patent 4,180,529. Each successive stage is polymerized in the presence of previously polymerized stages. Therefore, each layer is polymerized as a layer on top of the immediately previous stage.
    [038] When used, the minimum amount of polymeric stiffener is 0.5, preferably 6, and more preferably, about 8% by weight of the thermoplastic composition mixed by melting, while the maximum amount of the polymeric stiffener it is about 45% by weight, preferably about 40% by weight. It is to be understood that any minimum amount can be combined with any maximum amount to form a preferred weight range.
    [039] Useful polymeric hardeners include: (f) an ethylene copolymer, glycidyl (meth) acrylate, and optionally one or more (meth) acrylate esters. (g) an ethylene / α-oiefin or ethylene / α-oiefin / diene copolymer (EPDM) grafted with an unsaturated carboxylic anhydride, such as maleic anhydride. (h) an ethylene copolymer, 2-isocyanatoethyl (meth) acrylate and, optionally, one or more (meth) acrylate esters. (i) a copolymer of ethylene and acrylic acid reacted with a compound of Zn, Li, Mg or Mn to form the corresponding ionomer.
    [040] The polyamide composition used in the present invention can comprise the copolyamide alone or can optionally comprise additives. A preferred additive is at least a plasticizer. The plasticizer, preferably, will be miscible with the polyamide. Examples of suitable plasticizers include sulfonamides, preferably aromatic sulfonamides, such as benzenesulfonamides and toluenesulfonamides. Examples of suitable sulfonamides include N-alkyl benzenesulfonamides and toluenesulfonamides, such as N-butylbenzenesulfonamide, N- (2-hydroxypropyl) benzenesulfonamide, N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, p-toluenesulfonamide, and the like. Preferably, N-butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, and N-ethyl-p-toluenesulfonamide
    [041] The plasticizer can be incorporated into the composition by mixing by melting the polymer with the plasticizer and, optionally, other components, or during polymerization. If the plasticizer is incorporated during polymerization, the polyamide monomers are mixed with one or more plasticizers, before starting the polymerization cycle and the mixture is introduced into the polymerization reactor. Alternatively, the plasticizer can be added to the reactor during the polymerization cycle.
    [042] When used, the plasticizer is present in the composition in about 1 to about 20% by weight, or more preferably, in about 6 to about 18% by weight, or even more preferably, in about 8 to about 15% by weight, where the weight percentages are based on the total weight of the composition.
    [043] The reinforcing agent can be any excipient, but is preferably selected from the group consisting of calcium carbonate, glass fibers with a circular or non-circular cross section, glass flakes, glass spheres, carbon fibers, talc, mica, wollastonite, calcined clay, kaolin, diatomite, magnesium sulfate, magnesium silicate, barium sulfate, titanium dioxide, aluminum and sodium carbonate, barium ferrite, potassium titanate and mixtures thereof.
    [044] Fiberglass with a non-circular cross section refers to fiberglass that has a cross section that has a larger axis that is perpendicular to a longitudinal direction of the fiberglass and that corresponds to the longest linear distance in the transversal section. The non-circular cross section has a smaller axis that corresponds to the longest linear distance from the cross section in the direction perpendicular to the major axis. The non-circular cross section of the fibers has a variety of shapes including a cocoon-shaped shape (Figure 8), a rectangular shape, an elliptical shape, an almost triangular shape, a polygonal shape and an oblong shape. As will be understood by the technicians of the subject, the cross section can have other formats. The ratio of the length of the major axis to the minor axis is preferably between about 1.5: 1 and about 6: 1. The most preferred ratio is between about 2: 1 and 5: 1 and, even more preferably, between about 3: 1 to about 4: 1. Suitable glass fiber is described in EP 0.190.001 and EP 0.196.194.
    [045] Preferred reinforcing agents include glass fibers and minerals of kaolin, clay, mica and talc. Glass fiber is preferably a reinforcing agent.
    [046] The polyamide composition used in the present invention can optionally comprise additional additives, such as impact modifiers; thermal, oxidative and / or light stabilizers, colorants, lubricants, mold release agents and the like. Such additives can be added in conventional amounts according to the desired properties of the resulting product, and the control of these amounts versus the desired properties is within the skill of the art.
    [047] When present, additives can be incorporated into the polyamide composition used in the present invention through melt mixing using any known methods. Component materials can be mixed until homogeneous using a melt mixer, such as a twin or single screw extruder, mixer, kneader, Banbury mixer, and so on, to give a polyamide composition. Or, part of the material can be mixed in a melt mixer, and the rest of the materials can then be added and further mixed by melting until smooth.
    [048] In addition, the present invention relates to a method for providing a melt blended thermoplastic composition, comprising: melt blending of: (A) a polyamide composition comprising: a) 55 to 90% by weight of semi-aromatic and semicrystalline copolyamide which has a melting point, wherein said semi-aromatic copolyamide comprises: a-1) about 15 to 50 mol%, preferably 15 to 40 mol%, of aromatic repeating units derived from: ( i) one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and a first aliphatic diamine with 4 to 20 carbon atoms; and a-2) 50 to 85 mol%, preferably 60 to 85 mol%, of aliphatic repeating units derived from: (ii) an aliphatic dicarboxylic acid with 8 to 20 carbon atoms and said first aliphatic diamine with 4 to 20 carbon atoms; or (iii) an aliphatic amino acid or lactam with 8 to 20 carbon atoms; b) 10 to 45% by weight of aliphatic homopolyamide which has a melting point, wherein said aliphatic homopolyamide comprises repeating units derived from: c) v) an aliphatic dicarboxylic acid with 8 to 20 carbon atoms and a second aliphatic diamine with 4 to 20 carbon atoms, or v)) an aliphatic amino acid or lactam with 8 to 20 carbon atoms; and wherein the weight percent of a) and b) are based on the total weight of a) and b) and said first and second aliphatic diamines can be the same or different. (B) 0 to 45% by weight, preferably 10 to 40% by mol, of polymeric hardeners; (C) 0 to 20% by weight, preferably 0 to 12% by weight, of plasticizers; and (D) 0 to 45% by weight of reinforcing agent; wherein the weight percent of (B), (C) and (D) are based on the total weight of the thermoplastic composition mixed by melting; wherein the melt mixing is carried out at a melting temperature above the melting point of said semiaromatic and semicrystalline copolyamide and said aliphatic homopolyamide and less than or equal to about 290 ° C, preferably less than or equal to 280 ° C , to provide said melt-mixed thermoplastic composition, and wherein said melt-mixed composition has a glass transition and has a Tan Delta peak value (E ”/ E ') of 0.21 or less to said glass transition. All the preferences and attributes described herein mentioned for the melt blended thermoplastic composition also apply to the method for providing a melt blended thermoplastic composition.
    [049] The term "melting temperature" means the highest melting temperature of the melt-mixed thermoplastic composition during the melt mixing process, as determined at the end of the melt mixing process. Preferably, the melting temperature is 290 ° C or less and, more preferably, less than or equal to 280 ° C.
    [050] In another aspect, the present invention relates to a method for the manufacture of an article by molding the mixed compositions by melting. Examples of articles are films, laminates, filaments, fibers, monolayer tubes, hoses, pipes, multilayer tubes, hoses and pipes with one or more layers formed from the above composition, and automotive parts, including engine parts . The term "shaping" means any shaping technique, such as, for example, extrusion, injection molding, thermoforming molding, compression molding, blow molding, filament spinning, sheet molding or film blowing. Preferably, the article is shaped by extrusion or injection molding.
    [051] The molded or extruded thermoplastic articles described herein can be applied to various components of vehicular, industrial and consumer products that satisfy one or more of the following requirements: resistance against road salts, hydrolysis through water and refrigerants, such as solutions of glycol, fuels, alcohols, oils, chlorinated water; high impact resistance, especially in a cold environment, improved retention of mechanical properties at elevated temperatures, such as car temperatures under the hood, significant weight reduction (over conventional metals, for example), and noise reduction, allowing a more compact and integrated model. Specific molded or extruded thermoplastic items are selected from the group consisting of automotive coolant pipes, fuel pipes, oil pipes, truck air brake pipes, final radiator tanks, engine mounts, torque bars, filaments used for industrial and consumer applications, such as bushings and those used in the belts for paper machines and sporting goods, such as the lamination layers for skis and ski boots.
    [052] The present invention is further illustrated by the following Examples, it should be understood that the following Examples are for illustrative purposes only, and are not used to limit the present invention to them. METHODS MIXING BY FUSION
    [053] The melt blending was performed in a 25 mm W & P twin screw extruder with nine drum segments. The extruder was supplied with double screws that incorporate the elements for kneading and mixing in an upstream melting zone and a downstream melting zone. All polymer pellets and post-additives were premixed and fed into the main feed port of the extruder at a nominal rate of 250 g / min. The drums were heated to a desired temperature profile of 200 ° C at the feed port to a temperature in the range of 240 to 250 ° C, at the front end. The screw rpm, in general, was 300. The melt was extruded through a matrix with two holes and was pelleted in granules. MOLDING METHOD
    [054] The pellets of the melt-mixed compositions were molded into test pieces according to the ASTM D 638 standard for specification using a 180-ton Nissei injection molding machine. The mold cavity included type IV draw bars with 3.2 mm thickness and type V draw bars with 3.2 mm thickness according to the ASTM D638 standard. The temperature profile of the drum was 220 ° C at the feed port at 240 ° C at the nozzle. The mold temperature was 70 ° C. The melt-blended compositions were pre-dried at 65 ° C overnight in a dehumidifying dryer to provide a moisture level below 0.05% which is suitable for molding. The molded bars were ejected from the cavity and stored in dry-conformed-molded condition in vacuum-sealed aluminum foil bags until they were ready for testing. TEST TEST METHOD
    [055] The tensile properties at 23 ° C were measured according to the specification of the ASTM D638 standard with type IV bars using an Instron model 4469 tensile testing machine. The crosshead speed was 50 mm / min. The tensile properties at 125 ° C were measured using a heating oven installed on the test machine with claws located inside the oven. The smaller V-type bars in accordance with the ASTM D638 standard were used to accommodate the largest elongations inside the oven. The crosshead speed was 250 mm / min. The averages of the five samples are listed in the Tables. DSC TEST METHOD
    [056] In this document, melting points are as determined by differential scanning calorimetry (DSC) at a scan rate of 10 ° C / min in the first heating scan, where the melting point is taken at the maximum level of the endothermic peak, and the heat of fusion in Joules / gram (J / g) is the area within the endothermic peak. DMA TEST METHOD
    [057] The dynamic mechanical analysis (DMA) test was performed using the Q800 DMA equipment of TA instruments. The injection molded test bars nominally measuring 18 mm x 12.5 mm x 3.2 mm were used in the single balance mode by fixing their end. The bars were equilibrated at -140 ° C for 3 to 5 minutes, and then the DMA test was performed with the following conditions: the temperature rising from -140 ° C to + 160 ° C at a rate 2 ° C / min, the sinusoidal mechanical vibration imposed at an amplitude of 20 μm and different frequencies of 100, 50, 20, 10, 5, 3 and 1 Hz, with a response at 1 Hz selected for the determination of the storage module (E ') and the loss module (E ”), as a function of temperature. Tan Delta was calculated by dividing the loss module (E ”) by the storage module (E '). EXTRUSION TUBE AND BREAKING PRESSURE TEST METHOD
    [058] The impact-modified melt-blended compositions comprising polymeric stiffeners were dried overnight in a dehumidifying dryer at 65 ° C. They were extruded into tubes measuring 8.3 mm OD X 6.3 mm DI using a Davis Standard tube extrusion system. The system consisted of a 50 mm single screw extruder equipped with a tube matrix, a vacuum sizing tank with a plate-style calibrator, an extractor and a cutter. The matrix with 15.2 mm (0.600 ’) bushings and an 8.9 mm (0.350’) tip was used. The calibrator was 8.3 mm (0.327 ’). The temperature profile of the extruder drum was 210 ° C in the feed port, increasing to about 230 ° C in the die. The speed of the pipe was normally 4.6 m / min (15 feet / min). After establishing a stable process, the tubing was cut into pieces of 30 cm in length and used for the burst pressure measurements.
    [059] The burst pressure of the pipeline was measured using a hand operated hydraulic pump equipped with a pressure gauge. One end of the tubing was connected to a pump, using the Swagelok fitting, while the other end of the tubing was capped. The burst pressure was measured manually, increasing the fluid pressure, until failure. The burst pressure at 125 ° C was similarly measured by positioning the tubing in an oven with heated air circulation and allowing the temperature to equilibrate for several hours before the test. The means of the three samples are listed in the Tables. ZINC CHLORIDE RESISTANCE TEST
    [060] ASTM D1693, Condition A, provides a test method for determining the environmental stress cracking of ethylene plastics in the presence of surface active agents, such as soaps, oils, detergents, and so on. This procedure was adapted to determine the stress cracking strength of the polyamide compositions to 50% by weight of the aqueous ZnCI2 solution, as follows.
    [061] The rectangular test pieces measuring 37.5 mm x 12 mm X 3.2 mm were molded. A controlled cut was cut on the face of each bar molded according to the standard procedure, the bars were bent into a U shape with the cut out, and positioned on the bronze sample holders, according to the standard procedure. At least five bars were used for each composition. The supports were placed in large test tubes.
    [062] The test fluid used was a 50% by weight zinc chloride solution prepared by dissolving anhydrous zinc chloride in water in a 50:50 weight ratio. The test tubes containing the sample holders were filled with freshly prepared saline by fully immersing the test pieces in such a way that there was at least 12 mm of fluid above the upper test piece. The test tubes were positioned in an upright position in an air circulation oven maintained at 50 ° C. The test pieces were examined periodically for cracking development over a period of 24 hours of immersion followed by 24 hours of dry in ambient conditions without cleaning or continuous immersion of up to 200 hours, as indicated in the Tables below. The time for the first observation of the failure in any of the test pieces was recorded. MATERIALS
    [063] PA610 refers to the Zytel® RS3090 610 polyamide produced from 1,6-diaminohexane and 1,10-decanedioic acid which has a melting point of 224 ° C, available from EI DuPont de Nemours and Company, Wilmington, Delaware, USA.
    [064] PA612 refers to Zytel® 158 NC010 resin, which has a melting point of about 218 ° C, available from E.I. du Pont de Nemours and Company, Wilmington, Delaware.
    [065] PA1010 refers to the polyamide resin produced from 1,10-decanediamine acid and 1,10-decanedioic acid, which has a melting point of about 203 ° C, available from EI du Pont de Nemours and Company, Wilmington, Delaware. COPOLYAMID PREPARATIONS
    [066] The copolyamides PA612 / 6T with 15, 20, 25 and 30 mol% of PA6T repeating units, were prepared in autoclaves as follows. Two sizes of autoclaves were used, a small autoclave with 5 kg of nominal polymer capacity and a large autoclave with 1,200 kg of polymer nominal capacity. PA612 / 6T 85/15 and 80/20 were prepared in the small autoclave and PA612 / 6T 75/25 and 70/30 were prepared in the larger autoclave.
    [067] The procedure for performing copolyamide 612 / 6T PA 85/15 in the minor autoclave was as follows.
    [068] Salt Preparation: The autoclave was loaded with dodecanedioic acid (2,266 g), terephthalic acid (288 g), an aqueous solution containing 78% by weight of hexamethylenediamine (1,751 g), an aqueous solution containing 1% in weight of sodium hypophosphite (35 g), an aqueous solution containing 28% by weight of acetic acid (34 g), an aqueous solution containing 1% by weight of Carbowax 8000 (10 g) and water (2,190 g).
    [069] Process conditions: The autoclave agitator was set to 5 rpm and the contents were purged with nitrogen at 69 kPa (10 psi) for 10 min. The agitator was set to 50 rpm, the pressure control valve was set to 1.72 MPa (250 psi), and the autoclave was heated. The pressure reached 1.72 MPa at the point where the steam was vented to maintain the pressure at 1.72 MPa. The temperature of the contents was allowed to rise to 250 ° C. The pressure was then reduced to 0 psig for about 60 min. During this time, the temperature of the autoclave rose to 270 ° C. The pressure of the autoclave was reduced to 34.5 kPa (absolute) (5 psia) through the application of vacuum and maintained for 15 min. The autoclave was then pressurized with 480 kPa (70 psi) of nitrogen and the molten polymer was modeled from the autoclave. The polymer filaments obtained were quickly cooled with cold water and pelleted.
    [070] The copolyamide obtained had an inherent viscosity (IV) of 1.16 dL / g, and in this case, the IV was measured in a solution of 0.5% in m-cresol, at 25 ° C.
    [071] For the production of another PA612 / 6T 80/20 composition, the amounts of dodecanedioic acid and terephthalic acid were adjusted to achieve the desired molar ratio.
    [072] The procedure for the production of PA 612 / 6T 75/25 in the larger autoclave was as follows.
    [073] The polyamide 612 salt solution of about 45% by weight of the concentration was prepared from hexamethylenediamine and dodecanoic acid in water and adjusted to a pH of 7.6 to about 0.1. The polyamide 612 salt solution of about 25% by weight was prepared from hexamethylenediamine and terephthalic acid in water and adjusted to a pH of 8.7 to about 0.1. A polyamide 612 salt solution of about 45% by weight (1,927 kg), a polyamide 6T salt solution of 25% by weight (937 kg), 8,300 g of an aqueous solution containing 80% by weight of hexamethylenediamine, 248 g of an aqueous solution containing 10% by weight of Carbowax 8000 and 3,106 g of glacial acetic acid, were loaded onto an evaporator. The salt solution was then concentrated to about 70% by weight and then loaded into an autoclave. The sodium hypophosphite (34 g) was dissolved in 3 liters of water and was also added to the autoclave through an additive pot container. The salt solution in the autoclave was then heated, while the pressure was allowed to rise to 1.72 MPa (250 psi) at the point where the steam was vented to maintain the pressure at 1.72 MPa, and heating continued. until the batch temperature reached 250 ° C. The pressure was then slowly reduced until it reached the range of 55 to 69 kPa (absolute) (8 to 10 psia), while the batch temperature was still allowed to rise to 265 to 275 ° C. The pressure was then maintained for about 69 kPa (absolute) (10 psia) and the temperature was maintained at 265 to 275 ° C for about 20 min. Finally, the molten polymer was extruded into filaments, cooled and cut into pellets. Copolyamides had an IV in the range of 1.2 to 1.4.
    [074] For the production of another PA612 / 6T 70/30 composition, the amounts of polyamide 612 and the salt solutions of polyamide 6T were adjusted to achieve the molar ratio of the desired acid.
    [075] PA610 / 6T copolyamides that have 20 mol% and 40 mol% of PA6T repeat units were prepared in size 10L autoclaves as follows. PA610 / 6T 80/20
    [076] Salt Preparation: The 10L autoclave was loaded with sebacic acid (2,028 g), terephthalic acid (416 g), an aqueous solution containing 78% by weight of hexamethylenediamine (1,880 g), an aqueous solution containing 1% by weight of sodium hypophosphite (35 g), an aqueous solution containing 28% by weight of acetic acid (30 g), an aqueous solution containing 1% by weight of Carbowax 8,000 (10 g) and water (2,180 g).
    [077] Process conditions: The autoclave agitator was set to 5 rpm and the contents were purged with nitrogen at 69 kPa (10 psi) for 10 min. The agitator was set to 50 rpm, the pressure control valve was set to 1.72 MPa (250 psi), and the autoclave was heated. The pressure reached 1.72 MPa at the point where the steam was vented to maintain the pressure at 1.72 MPa. The temperature of its content was allowed to rise to 250 ° C. The pressure was then reduced to 0 psig for about 60 min. During this time, the temperature of the autoclave increased to 270 ° C. The pressure of the autoclave was reduced to 34.5 kPa (absolute) (5 psia) through the application of vacuum and maintained for 15 min. The autoclave was then pressurized with 480 kPa (70 psi) of nitrogen and the molten polymer was modeled from the autoclave. The polymer filaments obtained were quickly cooled with cold water and pelleted.
    [078] The copolyamide obtained had an inherent viscosity (IV) of 1.17 dL / g, in this case the IV was measured in a 0.5% solution in m-cresol at 25 ° C. The polymer had a melting point of 204 ° C, as measured by DSC. PA610 / 6T 80/40
    [079] Salt Preparation: The 10L autoclave was loaded with sebacic acid (1,557g), terephthalic acid (852g), an aqueous solution containing 78.4% by weight of hexamethylenediamine (1,914 g), an aqueous solution containing 1% by weight of sodium hypophosphite (35 g), an aqueous solution containing 28% by weight of acetic acid (30 g), an aqueous solution containing 1% by weight of Carbowax 8,000 (10 g) and water (2,165 g ).
    [080] Process conditions: The autoclave agitator was set to 5 rpm and the contents were purged with nitrogen at 69 kPa (10 psi) for 10 min. The agitator was set to 50 rpm, the pressure control valve was set to 2.07 MPa (300 psi), and the autoclave was heated. The pressure reached 2.07 MPa at the point where the steam was vented to maintain the pressure at 2.07 MPa. The temperature of its content was allowed to rise to 280 ° C. The pressure was then reduced to 0 psig for about 45 min. During this time, the temperature of the autoclave increased to 285 ° C. The pressure of the autoclave was reduced to 34.5 kPa (absolute) (5 psia) through the application of vacuum and maintained for 30 min. The autoclave was then pressurized with 480 kPa (70 psi) of nitrogen and the molten polymer was modeled from the autoclave. The polymer filaments obtained were quickly cooled with cold water and pelleted.
    [081] The copolyamide obtained had an inherent viscosity (IV) of 1.18 dL / g, in this case the IV was measured in a 0.5% solution in m-cresol at 25 ° C. The polymer had a melting point of 243 ° C, as measured by DSC. POLYMERIC ENRIJECEDORES
    [082] PT-1 refers to a linear low density polyethylene (LLDPE) with a specific gravity of 0.918 and a melting index of 2 gm / 10 min at 190 ° C, commercially available as Exxon LLDPE 1002.09.
    [083] TP-2 refers to an LLDPE grafted with maleic anhydride, available as MB226D Fusabond® resin, available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
    [084] PT-3 refers to an ethylene-octene copolymer consisting of 72% by weight of ethylene and 28% by weight of 1-octene, commercially available as Engage 8180 from Dow Chemicals.
    [085] PT-4 refers to an ethylene-octene copolymer grafted with maleic anhydride available as Fusabond® N493, available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
    [086] PT - 5 refers to an ethylene-propylene-norbornene octene grafted with 0.9 wt% maleic anhydride consisting of ethylene, propylene and norbornene (70: 29.5: 0 weight ratio, 5), commercially available as Nordel 3745P. ADDITIONS
    [087] Akrochem 383 SWP refers to an impaired phenol antioxidant from Akron Chemicals.
    [088] The Nauqard 445 stabilizer refers to 4,4'di (α = dimethylbenzyl) diphenylamine commercially available from the Chemtura Chemical Company, Middlebury, Connecticut.
    [089] The stabilizer Irqafos 188 e is a phosphite antioxidant from BASF.
    [090] HS 7: 1: 1 refers to a copper based heat stabilizer with 7: 1: 1 parts by weight of KI distearate: Cul: Al.
    [091] C-Black refers to a black colored concentrate consisting of 45% by weight of carbon black in an ethylene / methacrylic acid copolymer, available from Ampacet Corporation, Tarrytown, New York.
    [092] n-BBSA is a benzene n-butyl sulfonamide plasticizer. EXAMPLES
    [093] Tables 2 and 3 list the properties of the aliphatic homopolyamides and the semi-aromatic copolyamides used in the Examples. TABLE 2
    TABLE 3

    TABLE 4


    [094] The compositions mixed by melting E1 to E3 show the peak values of Tan Delta below 0.21, the enhanced modulus of high temperature and the highest crystallinity in the mixtures versus Comparative Example C7. TABLE 5


    [095] The compositions mixed by melting E4 to E6 show the peak values of Tan Delta below 0.21, the enhanced modulus of high temperature and the highest crystallinity in the mixtures versus Comparative Example C8. EXAMPLES E7 TO E12
    [096] Examples E7 to E12 show the compositions prepared from a 25 screw twin extruder as described above, but with a drum temperature profile of 210 to 230 ° C or 260 to 285 ° C, used from automatic feeding into the matrix, resulting in a melt mixing temperature of less than 260 ° C or greater than 280 ° C. The resulting mixtures were analyzed using dynamic mechanical analysis, as shown in Table 6. TABLE 6


    [097] Compositions E7, E9 E1 and 1 produced at a melting temperature below 280 ° C exhibit lower values of Tan Delta and storage modulus greater than 125 ° C, compared to compositions E8, E10 and E12, respectively, produced at a melting temperature above 280 ° C. TABLE 7


    [098] Compositions mixed by melting E13 and E14 show peak values Tan Delta shows less than 0.21 and the enhanced high temperature module, and the burst pressure of the high temperature tube, compared to C9. TABLE 8


    [099] The E15 melt blended composition shows the peak values of Tan Delta below 0.21, and improved high temperature modulus, and the best burst pressure of the high temperature pipeline compared to C10. TABLE 9

    [100] The E16 and E17 melt blended compositions show the peak values of Tan Delta equal to or less than 0.21, and the enhanced high temperature modulus, and the best burst pressure of the high temperature pipeline compared to the C11. TABLE 10

    [101] The E18 melt blended composition shows the Tan Delta peak value of 0.21, and the enhanced high temperature modulus, and the best burst pressure of the high temperature pipeline compared to C12. TABLE 11

    [102] E19 and E20 melt blended compositions show Tan Delta peak values less than 0.21 and the enhanced high temperature modulus, and the best high temperature pipe burst pressure compared to C13. TABLE 12


    [103] The E21 fusion mixed composition shows peak values of Tan Delta below 0.21, and the enhanced high temperature modulus, and the best burst pressure of the high temperature pipeline compared to C14.
    [104] Table 13 lists the properties of PA 610 / 6T semi-aromatic copolyamides in various molar ratios. TABLE 13

    TABLE 14


    [105] The E22 melt blended composition shows the Tan Delta peak value less than 0.21, the enhanced modulus of high temperature and better crystallinity in the mixture versus Comparative Example C15. TABLE 15 PA 610 / 6T (60/40) AND MIXED COMPOSITIONS BY FUSING WITH PA 610, PA 1010 AND PA 612

    [106] E23, E24 and E25 melt blended compositions show the Tan Delta peak value less than 0.21 and the enhanced high temperature modulus versus Comparative Example C16. TABLE 16

    [107] The E26 melt blended composition shows the Tan Delta peak value of 0.21 and the enhanced high temperature module.


    [108] E27 and E28 melt blended compositions show the improved high temperature modulus, the best burst pressure of the high temperature pipeline compared to C19 and C20, respectively. TABLE 18


    [109] Although both C21 and E29 compositions show Tan Delta peak values less than 0.21, when the plasticizer is present, the E29 melt blended composition shows the enhanced high temperature module, the best burst pressure high temperature compared to C21.
    权利要求:
    Claims (10)
    [0001]
    1. FUSION-MIXED THERMOPLASTIC COMPOSITION, characterized by comprising: (A) a polyamide composition comprising: (a) 55 to 90% by weight of semiaromatic and semicrystalline copolyamide which has a melting point, in which said semiaromatic copolyamide comprises: ( a-1) about 15 to 50 mol% of aromatic repeating units derived from: (i) one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and a first aliphatic diamine with 4 to 20 carbon atoms; and a-2) 50 to 85 mol% of aliphatic repeating units derived from: (ii) a first aliphatic dicarboxylic acid with 8 to 20 carbon atoms and said first aliphatic diamine with 4 to 20 carbon atoms; or (iii) a first aliphatic amino acid or lactam with 8 to 20 carbon atoms; wherein the semi-aromatic copolyamide has a peak Tan Delta value per DMA greater than or equal to 0.23; and heat of fusion of at least 20 J / g, as measured in the first DSC thermal cycle; (b) 10 to 45% by weight of aliphatic homopolyamide having a melting point, wherein said aliphatic homopolyamide comprises repeating units derived from: (c)) a second aliphatic dicarboxylic acid with 8 to 20 carbon atoms and a second aliphatic diamine with 4 to 20 carbon atoms; or (v) a second aliphatic amino acid or lactam with 8 to 20 carbon atoms; and wherein the aliphatic homopolyamide has a Tan Delta peak value (E "/ E ') less than or equal to 0.21; and heat of fusion of at least 30 J / g, as measured in the first DSC thermal cycle; wherein the weight percent of (a) and (b) are based on the total weight of (a) and (b) and said first and second aliphatic diamines can be the same or different; (B) 0 to 45% by weight of polymeric stiffener; (C) 0 to 20% by weight, preferably 0 to 12% by weight, of plasticizers; and (D) 0 to 45% by weight of reinforcing agent; wherein the weight percent of (B), (C) and (D) are based on the total weight of the melt mixed thermoplastic composition, and where said melt mixed composition has a glass transition and has a peak Tan value Delta (E ”/ E ') of 0.21 or less to said glass transition; and in which the semi-aromatic and semicrystalline copolyamide is selected from the group consisting of: PA 612 / 6T (85/15) to (55/45), PA 612 / 6I (90/10) to (70/30) and PA 612 / 6T / 6I, which has a mol percentage of 6T + 6I of 15 to 45 mol% and the ratio of T to I is about 4: 1 to 1: 1, and in which the peak value Tan Delta is determined by dynamic mechanical analysis (DMA).
    [0002]
    2. COMPOSITION, according to claim 1, characterized in that said aliphatic homopolyamide is selected from the group consisting of PA 612, PA 610, PA 1010 and PA 614.
    [0003]
    COMPOSITION according to any one of claims 1 to 2, characterized in that the semiaromatic and semicrystalline copolyamide is PA 612 / 6T (85/15) to (55/45), and said aliphatic homopolyamide is PA 612.
    [0004]
    COMPOSITION according to any one of claims 1 to 2, characterized in that the semiaromatic and semicrystalline copolyamide is PA 612 / 6T (85/15) to (55/45), and said aliphatic homopolyamide is PA 610.
    [0005]
    COMPOSITION according to any one of claims 1 to 2, characterized in that the semi-aromatic and semicrystalline copolyamide is PA 612 / 6T (85/15) to (55/45), and said aliphatic homopolyamide is PA 1010.
    [0006]
    6. METHOD TO PROVIDE A MIXED MIXED THERMOPLASTIC COMPOSITION, characterized by comprising: melting mixture of: (A) a polyamide composition comprising: (a) 55 to 90% by weight of semi-aromatic and semi-crystalline copolyamide that has a melting point , wherein said semi-aromatic copolyamide comprises: a-1) about 15 to 50 mol%, preferably 15 to 40 mol%, of aromatic repeating units derived from: (i) one or more aromatic dicarboxylic acids with 8 to 20 carbon atoms and a first aliphatic diamine with 4 to 20 carbon atoms; and a-2) 50 to 85 mol%, preferably 60 to 85 mol%, of aliphatic repeating units derived from: (ii) an aliphatic dicarboxylic acid with 8 to 20 carbon atoms and said first aliphatic diamine with 4 to 20 carbon atoms; or (iii) an aliphatic amino acid or lactam with 8 to 20 carbon atoms; (b) 10 to 45% by weight of aliphatic homopolyamide which has a melting point, wherein said aliphatic homopolyamide comprises repeating units derived from: (c)) an aliphatic dicarboxylic acid with 8 to 20 carbon atoms and a second diamine aliphatic with 4 to 20 carbon atoms; or (v) an aliphatic amino acid or lactam with 8 to 20 carbon atoms; and wherein the weight percent of (a) and (b) are based on the total weight of (a) and (b), and said first and second aliphatic diamines can be the same or different; (B) 0 to 45% by weight of polymeric stiffener; (C) 0 to 20% by weight, preferably 0 to 12% by weight, of plasticizers; and (D) 0 to 45% by weight of reinforcing agent; wherein the weight percent of (B), (C) and (D) are based on the total weight of the thermoplastic composition mixed by melting; and wherein the melt mixing is carried out at a melting temperature above the melting point of said semi-aromatic and semicrystalline copolyamide and said aliphatic homopolyamide and less than or equal to about 290 ° C, to provide the melt-mixed thermoplastic composition, and wherein said mixed melt composition has a glass transition and has a peak Tan Delta (E ”/ E ') value of 0.21 or less at said glass transition; and in which the semi-aromatic and semicrystalline copolyamide is selected from the group consisting of: PA 612 / 6T (85/15) to (55/45), PA 612 / 6I (90/10) to (70/30) and PA 612 / 6T / 6I, which has a percentage in mol of 6T + 6I of 15 to 45 mol% and the ratio of T to I is about 4: 1 to 1: 1, and in which the peak value Tan Delta is determined by dynamic mechanical analysis (DMA).
    [0007]
    7. METHOD, according to claim 6, characterized in that said aliphatic homopolyamide is selected from the group consisting of PA 612, PA 610, PA 1010 and PA 614.
    [0008]
    METHOD according to any one of claims 6 to 7, characterized in that the semiaromatic and semicrystalline copolyamide is PA 612 / 6T (85/15) to (55/45) and said aliphatic homopolyamide is PA 612.
    [0009]
    Method according to any one of claims 6 to 7, characterized in that the semiaromatic and semicrystalline copolyamide is PA 612 / 6T (85/15) to (55/45) and said aliphatic homopolyamide is PA 610.
    [0010]
    METHOD according to any one of claims 6 to 7, characterized in that the semiaromatic and semicrystalline copolyamide is PA 612 / 6T (85/15) to (55/45) and said aliphatic homopolyamide is PA 1010.
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    优先权:
    申请号 | 申请日 | 专利标题
    US201161437840P| true| 2011-01-31|2011-01-31|
    US61/437,840|2011-01-31|
    PCT/US2012/023276|WO2012106309A2|2011-01-31|2012-01-31|Melt-blended thermoplastic composition|
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