• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    polyamide compositions showing improved thermal stability. the present invention relates to polyamide compositions having improved thermal stability comprising at least one semiaromatic polyamide, pa 6 and / or pa 6,6, and elemental iron. these new compositions are very well suited for the manufacture of articles exposed to high temperature environments such as articles used in automotive applications.
    公开号:BR112013030906B1
    申请号:R112013030906-7
    申请日:2012-06-08
    公开日:2021-04-06
    发明作者:Linda M. Norfolk
    申请人:Solvay Specialty Polymers Usa, Llc；
    IPC主号:
    专利说明:

    [0001] [0001] This order claims priority for US provisional order No. 61/495024 filed on June 9, 2011 and European order No. 11176634.1 filed on August 4, 2011, with the entire contents of each of these requests being incorporated here by reference for all purposes.
    [0002] [0002] The present invention relates to polyamide compositions having improved thermal stability. These new compositions are very well suited for the manufacture of articles exposed to high temperature environments such as articles used in automotive applications. BACKGROUND
    [0003] [0003] Semi-aromatic polyamides are a class of high-performance polyamides with remarkable properties such as excellent creep and fatigue resistance, good mechanical properties, low moisture absorption, improved dimensional stability, very high strength and rigidity at elevated temperatures, as well as good resistance to a wide range of chemicals.
    [0004] [0004] Some demanding applications require high resistance to very high temperatures. Semi-aromatic polyamides are candidates of choice for these applications, typically due to their high intrinsic melting temperatures. However, the thermal stability of these materials still needs to be improved, especially in the long term. When molded compositions are subjected to relatively high temperatures for an extended period, as is the case with objects that serve in automotive under-the-hood applications and in various electrical or electronic applications, the compositions generally tend to show a decrease in mechanical properties (such as tensile properties) due to the thermal degradation of the polymer. This effect is called heat aging.
    [0005] [0005] Thermal stabilizers are typically added to polymer compositions to better retain the properties of the polymers after exposure to elevated temperature. When using a thermal stabilizer, the service life of the molded material can be significantly extended, depending on the type of material, conditions of use and type and amount of heat stabilizer. Examples of heat stabilizers typically used in polyamides are organic stabilizers, such as phenolic antioxidants and aromatic amines, and a combination of potassium iodide or copper iodide. Unfortunately, semi-aromatic polyamide compositions comprising such stabilizers do not achieve acceptable heat aging performances that are required in some demanding applications.
    [0006] [0006] It is, therefore, an object of the present invention to provide semi-aromatic polyamide compositions showing very good heat aging performance while maintaining all other semi-aromatic polyamide properties at a good level.
    [0007] [0007] WO 2005/007727 discloses a process for preparing heat-stabilized molding compositions comprising melt blending of a thermoplastic polymer, in non-metallic inorganic filler and elemental iron having a weighted average particle size of a maximum of 450 μm for form a composition in which the thermoplastic polymer forms a continuous phase and the use of these compositions in applications where they are exposed to elevated temperature. WO 2005/007727 claims a significant improvement in the heat aging properties, exhibited by a much better retention of mechanical properties at elevated temperature, with respect to compositions containing copper salt / potassium iodide or elementary copper of the prior art. WO 2005/007727 discloses aliphatic polyamide compositions (such as PA 6, PA 6.6, and PA 4.6) comprising an elemental iron thermal stabilizer. It also discloses in its example IV a composition comprising PA 6,6 / 6T and elementary iron.
    [0008] [0008] WO 2011/051123 relates to thermoplastic molding compounds comprising a polyamide and powdered iron having a particle size not greater than 10 μm that can be obtained by thermal disintegration of iron pentacarbonyl.
    [0009] [0009] However, the use and handling of powders having a very fine particle size should preferably be avoided for health and safety reasons. The risk of inhaling fine particles raises major health concerns since it has been shown to cause lung cancer, while the presence of fine particles in the air poses a number of safety concerns. the most dangerous being a risk of explosion.
    [0010] [0010] The Applicant has surprisingly found that the addition of PA 6 and / or PA 6.6 to compositions comprising semi-aromatic polyamides and elemental iron having a weighted average particle size of at least 10 μm leads to remarkable results with respect to performance aging by heat while maintaining all other properties of semi-aromatic polyamides at a very good level and without the health and safety risk associated with the prior art. BRIEF DESCRIPTION OF THE FIGURE
    [0011] [0011] Figure 1 is a graph showing the tensile strength in MPa of example E1 (according to the invention) and comparative examples EC1 and EC2 as a function of the oxidative heat treatment time they have been subjected to in hours. DETAILED DESCRIPTION
    [0012] [0012] It is a first object of the present invention to provide a polymer composition comprising at least one semi-aromatic polyamide, at least one aliphatic polyamide selected from PA 6 and PA 6.6, and elemental iron having a weighted average particle size of at least 10μm.
    [0013] [0013] It is another object of the present invention to provide a process for preparing the polymer composition as described above in which it comprises melt blending of at least one semi-aromatic polyamide, at least one aliphatic polyamide selected from PA 6 and PA 6.6, and elemental iron having a weighted average particle size of at least 10 μm.
    [0014] [0014] Yet another object of the present invention relates to the use of the aforementioned composition for the preparation of a molded part and with the molded part itself.
    [0015] [0015] Finally, a final object of the present invention relates to the use of such a molded part on a machine, a motor, an electrical or electronic installation and in particular with a motor vehicle, general means of transport, domestic utensil, or installation general industrial system, comprising said molded part.
    [0016] [0016] Semi-aromatic polyamide
    [0017] [0017] The term "polyamide" is generally understood to indicate a polymer comprising units derived from at least one diamine and at least one dicarboxylic acid and / or at least one carboxylic acid or amino lactam.
    [0018] [0018] The semi-aromatic polyamide of the composition according to the present invention is intended to denote any polyamide comprising more than 35 mol. % of recurrent aromatic units. It advantageously comprises more than 55 mol. %, preferably more than 65 mol% of recurrent aromatic units, more preferably more than 70 mol%, even more preferably more than 80 mol%, even more preferably more than 85 mol% and most preferably more than 90 mol%. In a specific embodiment, the semi-aromatic polyamide of the composition according to the present invention comprises 100 mol% of recurrent aromatic units. For the purpose of the present invention, the term "recurrent aromatic unit" is intended to denote any recurring unit that comprises at least one aromatic group. Recurrent aromatic units can be formed by the polycondensation of at least one aromatic dicarboxylic acid and at least one diamine or by the polycondensation of at least one dicarboxylic acid and at least one aromatic diamine.
    [0019] [0019] Non-limiting examples of aromatic dicarboxylic acids are notably phthalic acids, including isophthalic acid, terephthalic acid and orthophthalic acid, naphthalenedicarboxylic acids (including 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4- naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid and 1,2-naphthalene dicarboxylic acid), 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2 , 2-bis (4-carboxyphenyl) propane, bis (4-carboxyphenyl) methane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) ketone, 4,4'-bis ( 4-carboxyphenyl) sulfone, 2,2-bis (3-carboxyphenyl) propane, bis (3-carboxyphenyl) methane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) ketone, bis (3-carboxyphenoxy) benzene. Phthalic acids, including isophthalic acid, terephthalic acid and orthophthalic acid, are the preferred aromatic dicarboxylic acids. Terephthalic acid and isophthalic acid are even more preferred.
    [0020] [0020] Non-limiting examples of aromatic diamines are notably meta-phenylene diamine, meta-xylylene diamine and para-xylylene diamine. Para-xylylene diamine is the most preferred.
    [0021] The semi-aromatic polyamide of the composition according to the present invention may additionally comprise at least one aromatic dicarboxylic acid and / or at least one aromatic diamine described above recurrent units derived from at least one aliphatic dicarboxylic acid and / or at least one aliphatic diamine and / or at least one lactam.
    [0022] [0022] Non-limiting examples of aliphatic dicarboxylic acids are notably oxalic acid (HOOC-COOH), malonic acid (HOOC-CH2-COOH), succinic acid [HOOC- (CH2) 2-COOH], glutaric acid [HOOC- (CH2 ) 3-COOH], 2,2-dimethyl-glutaric acid [HOOC-C (CH3) 2- (CH2) 2-COOH], adipic acid [HOOC- (CH2) 4-COOH], 2,4,4 -trimethyl-adipic [HOOC-CH (CH3) -CH2-C (CH3) 2-CH2-COOH], pyelic acid [HOOC- (CH2) 5-COOH], submeric acid [HOOC- (CH2) 6-COOH] , azelaic acid [HOOC- (CH2) 7-COOH], sebacic acid [HOOC- (CH2) 8-COOH], undecanedioic acid [HOOC- (CH2) 9-COOH], dodecanedioic acid [HOOC- (CH2) 10- COOH], tetradecanedioic acid [HOOC- (CH2) 11-COOH] and 1,4-cyclohexane dicarboxylic acid, are non-limiting examples of aliphatic dicarboxylic acids. Sebaceic acid, adipic acid and 1,4-cyclohexane dicarboxylic acid are preferred.
    [0023] [0023] Non-limiting examples of aliphatic diamines are notably 1,2-diaminoethane, 1,2-diaminopropane, propylene-1,3-diamine, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 2 -methyl-1,5-diaminopentane, 1,6-hexamethylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, 1,8-diaminooctane, 2-methyl-1,8-diaminooctane, 1,9 nonanediamine, 5-methyl-1,9-nonanediamine, 1,10-diaminodecane, 1,11-diaminodecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,16-diaminohexadecane, 1,18- diaminooctadecane and 1-amino-3-N-methyl-N- (3-aminopropyl) -aminopropane. Among these, 1,6-hexamethylenediamine, 2-methyl-1,8-diaminooctane, 1,9 nonanediamine, 5-methyl-1,9-nonanediamine, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12- diaminododecane are preferred, and 1,6-hexamethylenediamine, 1,9 nonanediamine, 1.10-diaminodecane are even more preferred.
    [0024] [0024] In a first embodiment, the semi-aromatic polyamide of the composition according to the present invention is preferably a polyphthalamide (PPA). For the purpose of the present description, the term "polyphthalamides" is to be understood as defining any polymer of which more than 70 mol. %, preferably more than 80 mol. %, more preferably more than 90 mol. % of recurrent units are formed by the polycondensation reaction between at least one phthalic acid and at least one diamine. Phthalic acid can be notably o-phthalic acid, isophthalic acid or tereflactic acid. The diamine can be notably 1,6-hexamethylenediamine, 1,9-nonanediamine, 1,10-diaminodecane 2-methyl-octanediamine, 2-methyl-1,5-pentanediamine or 1,4-diaminobutane; a C6 and / or C10 diamine, especially 1,6-hexamethylenediamine and 1,10-diaminodecane are preferred. Suitable polyphthalamides are notably available as AMODEL® polyphthalamides from Solvay Advanced Polymers, L.L.C.
    [0025] [0025] The polyphthalamide (PPA) of the invented composition is more preferably a polyetherphthalamide. For the purpose of the present description, the term "polytherephthalamide" is to be understood as defining any polymer of which more than 70 mol. %, preferably more than 80 mol. %, more preferably more than 90 mol. % of recurrent units are formed by the polycondensation reaction between at least terephthalic acid with at least one diamine. The diamine can be aliphatic or aromatic. It is preferably an aliphatic diamine selected from the group consisting of 1,6-hexamethylenediamine, 1,9-nonanediamine, 1,10-diaminodecane, 2-methyl-octanediamine, 2-methyl-1,5-pentanediamine or 1,4-diaminobutane.
    [0026] [0026] Obviously, more than one semi-aromatic polyamide can be used in the composition according to the invention.
    [0027] [0027] In a second embodiment, the semi-aromatic polyamide of the composition according to the invention is preferably a class of polyamides consisting of PXDAs, ie aromatic polyamides comprising more than 50 mole% of recurring units formed by the polycondensation reaction between at least minus an aliphatic diacid and paraxylylene diamine. The aliphatic diacid can be chosen notably from oxalic acid (HOOC-COOH), malonic acid (HOOC-CH2-COOH), succinic acid [HOOC- (CH2) 2-COOH], glutaric acid [HOOC- (CH2) 3-COOH ], 2,2-dimethyl-glutaric acid [HOOC-C (CH3) 2- (CH2) 2-COOH], adipic acid [HOOC- (CH2) 4-COOH], 2,4,4-trimethyl-adipic acid [HOOC-CH (CH3) -CH2-C (CH3) 2-CH2-COOH], pyelic acid [HOOC- (CH2) 5-COOH], submeric acid [HOOC- (CH2) 6-COOH], azelaic acid [ HOOC- (CH2) 7-COOH], sebacic acid [HOOC- (CH2) 8-COOH], undecanedioic acid [HOOC- (CH2) 9-COOH], dodecanedioic acid [HOOC- (CH2) 10-COOH], acid tetradecanedioic [HOOC- (CH2) 11-COOH] and 1,4-cyclohexane dicarboxylic acid. Sebaceic acid, adipic acid and 1,4-cyclohexane dicarboxylic acid are preferred. Adipic acid or sebacic acid are even more preferred, and PXDAs derived from adipic acid or sebacic acid with paraxylylenediamine are usually referred to as PXD6 and PXD10 respectively.
    [0028] [0028] Excellent results have been obtained when polyphthalamide is selected from the group consisting of PA 6T, PA9T, PA10T, PA11T, PA12T, PA6T / 6I, PA6T / 6I / 10T / 10I, PA6T / 10T / 6,10 / 10,10 , PA6T / 11 and PA10T / 11.
    [0029] [0029] The semi-aromatic polyamide can be semicrystalline or amorphous.
    [0030] [0030] When the semi-aromatic polyamide is semicrystalline, it has a melting point advantageously greater than 220 ° C, preferably greater than 270 ° C, more preferably greater than 280 ° C, and even more preferably greater than 320 ° C . In addition, semiaromatic polyamide has a melting point advantageously below 350 ° C, preferably below 340 ° C and more preferably below 330 ° C.
    [0031] [0031] The melting point of the semi-aromatic polyamide was measured by Differential Scanning Calorimetry using ASTM D3418 with the following heating / cooling cycle: 1st heating from room temperature to 350 ° C at a rate of 10 ° C / min, followed by cooling from 350 ° C to room temperature at a rate of 20 ° C / min, followed by 2 ° heating from room temperature to 350 ° C at a rate of 10 ° C / min. The melting point was measured during the 2nd heating.
    [0032] [0032] The semi-aromatic polyamide is preferably present in the polymer composition in an amount of at least 30% by weight, preferably at least 35% by weight, more preferably at least 40% by weight, even more preferably at least 45 % by weight and most preferably at least 50% by weight, based on the total weight of the composition. In addition, semiaromatic polyamide is preferably present in the polymer composition in an amount of a maximum of 85% by weight, preferably of a maximum of 80% by weight, more preferably of a maximum of 75% by weight, even more preferably of a maximum of 70 % by weight and most preferably at most 65% by weight, based on the total weight of the composition.
    [0033] [0033] The elementary iron
    [0034] [0034] The inventive composition additionally comprises elemental iron. Elemental iron is preferably in the form of particles, most of which have a small particle size, such as a powder. In general, elemental iron has a weighted average particle size of a maximum of 450 μm, preferably a maximum of 200 μm. It is additionally preferred that elemental iron having a small particle size has a weighted average particle size of a maximum of 200 μm, more preferably a maximum of 100 μm, and even more preferably a maximum of 50 μm. On the other hand, elemental iron has a weighted average particle size of at least 10 μm, preferably at least 13 μm. It is additionally preferred that elemental iron having a small particle size has a weighted average particle size of at least 15 μm, more preferably at least 18 μm, and even more preferably at least 20 μm.
    [0035] [0035] The elemental iron of the present invention preferably has a weighted average particle size of 10 to 50 μm, more preferably 15 to 45 μm, even more preferably 20 to 40 μm and most preferably 25 to 35 μm.
    [0036] [0036] The weighted average particle size is determined as Dm according to ASTM standard D1921-89, method A. Preferably, the size, to be understood as the largest dimension, of at least 99% by weight of the elementary iron particles it is at most 450 μm and preferably at most 200 μm, more preferably at most 100 μm, even more preferably at most 90 μm, even more preferably at most 80 μm and most preferably at most 70 μm.
    [0037] [0037] Preferably, the size, to be understood as the smallest dimension, of at least 99% by weight of the elementary iron particles is at least 10 μm and preferably at least 15 μm, more preferably at least 20 μm and most preferably at least 25 μm.
    [0038] [0038] The elemental iron in the polymer composition according to the present invention can be used in any amount, which can be varied over a wide range. Elemental iron has been shown to be a very effective stabilizer, showing an effect even at very low amounts.
    [0039] [0039] Elemental iron is preferably present in the polymer composition in an amount of at least 0.1% by weight, preferably at least 0.2% by weight, more preferably at least 0.5% by weight, still more preferably at least 0.9% by weight and most preferably at least 1.0% by weight, based on the total weight of the composition. In addition, elemental iron is preferably present in the polymer composition in an amount of a maximum of 10% by weight, based on the total weight of the composition. Higher amounts of elemental iron can be used, however without any additional effect on the heat-aging properties of the composition. More preferably, elemental iron is generally present in the polymer composition in an amount of a maximum of 5% by weight, more preferably of a maximum of 4% by weight, even more preferably of a maximum of 3% by weight and most preferably of no. maximum 2.5% by weight, based on the total weight of the composition.
    [0040] [0040] Excellent results were obtained when elemental iron was used in an amount ranging from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight and most preferably from 0.9 to 2.5% by weight, based on the total weight of the polymer composition.
    [0041] [0041] Aliphatic polyamide
    [0042] [0042] The Applicant has surprisingly found that the presence of an aliphatic polyamide selected from PA 6 and PA 6.6 in combination with elemental iron improves the heat aging performance of semi-aromatic polyamides.
    [0043] [0043] The aliphatic polyamide of the composition according to the present invention is selected from PA 6 and PA 6.6. Excellent results were obtained with PA 6.
    [0044] [0044] PA 6 is a polyamide synthesized by polymerization with caprolactam ring opening.
    [0045] [0045] PA 6.6 is a polyamide synthesized by the polycondensation of 1,6-hexamethylene diamine and adipic acid.
    [0046] [0046] The at least one aliphatic polyamide is generally present in the polymer composition in an amount of at least 1% by weight, preferably at least 2% by weight, more preferably at least 2.5% by weight, even more preferably at least 3% by weight and most preferably at least 4% by weight, based on the total weight of the composition. In addition, at least one aliphatic polyamide is generally present in the polymer composition in an amount of a maximum of 20% by weight, preferably of a maximum of 18% by weight, more preferably of a maximum of 16% by weight, even more preferably of at most 14% by weight and most preferably at most 12% by weight, based on the total weight of the composition.
    [0047] [0047] Other optional additives
    [0048] [0048] The composition according to the invention can optionally comprise additional additives / components such as fillers, pigments, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants and antioxidants etc.
    [0049] [0049] Fillers
    [0050] [0050] A large selection of reinforcement fillers can be added to the composition according to the present invention. They are preferably selected from fibrous and particulate fillers. A fibrous reinforcement filler is considered here to be a material having length, width and thickness, where the average length is significantly greater than the width and thickness. Generally, such a material has an aspect ratio, defined as the average ratio between length and greatest width and thickness, of at least 5. Preferably, the aspect ratio of the reinforcing fibers is at least 10, more preferably at least 20, even more preferably at least 50.
    [0051] [0051] Preferably, the reinforcement filler is selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), fiberglass, carbon fibers, synthetic polymeric fiber, fiber aramid, aluminum fiber, titanium fiber, magnesium fiber, boron carbide fibers, glass wool fiber, steel fiber, wollastonite etc. Even more preferably, it is selected from mica, kaolin, calcium silicate, magnesium carbonate and fiberglass etc.
    [0052] [0052] Among fibrous fillers, glass fibers are preferred; they include glass fibers A, E, C, D, S and R of cut yarns, as described in chapter 5.2.3, p. 43-48 from Additives for Plastics Handbook, 2nd edition, John Murphy. Preferably, the filler is chosen from fibrous fillers. It is most preferably a reinforcing fiber that is able to withstand high temperature applications.
    [0053] [0053] In a preferred embodiment of the present invention, the reinforcement filler is chosen from wollastonite and fiberglass. Excellent results were obtained when glass fibers were used. Glass fibers can have a round cross section or a non-circular cross section.
    [0054] [0054] Excellent results were obtained when the reinforcement filler was used in an amount of 20-60% by weight, preferably 30-50% by weight, based on the total weight of the composition.
    [0055] [0055] The fillers are contained in the polymer composition in a total amount of advantageously more than 15% by weight, preferably more than 20% by weight, even more preferably more than 25% by weight, and most preferably more than 30% by weight, based on the total weight of the polymer composition. On the other hand, the reinforcement fibers are contained in the polymer composition in a total amount of advantageously less than 65% by weight, preferably less than 60% by weight, even more preferably less than 55% by weight, and the more preferably less than 50% by weight, based on the total weight of the polymer composition.
    [0056] [0056] Pigments and dyes
    [0057] [0057] The composition according to the present invention can additionally comprise pigments and dyes. It can remarkably comprise black pigments such as carbon black and nigrosine.
    [0058] [0058] Lubricants
    [0059] [0059] The composition according to the present invention can additionally comprise lubricants such as linear low density polyethylene, calcium or magnesium stearate, sodium montanate etc.
    [0060] [0060] Additional stabilizers
    [0061] [0061] The composition according to the present invention further comprises in another preferred embodiment, in addition to the elemental iron thermal stabilizer, at least one well-known thermal stabilizer other than elemental iron which further promotes the properties of aging by heat. They can typically be one or more selected of phenolic thermal stabilizers (such as Irganox 1098 or Irganox 1010, available from Ciba Specialty Chemicals), organic phosphites (such as Irgafos 168, available from Ciba Specialty Chemicals), aromatic amines, metal salts of elements of group IB, IIB, III and IV of the Periodic Table and metal halides of alkali and alkaline earth metals.
    [0062] [0062] Preferably, the composition according to the present invention further comprises a combination of copper salt and an alkali metal halide. More preferably, it comprises a copper halide and an alkali metal halide, such as CuI and KI. Most preferably, CuI and KI are used in a ratio ranging from 1/6 to 1/10, preferably 1/7 to 1/9.
    [0063] [0063] This additional thermal stabilizer may be present in an amount of 0.1 to 5% by weight, preferably from 0.2 to 2.5% by weight.
    [0064] [0064] Light stabilizers such as blocked amine light stabilizers (HALS) can also be in the composition.
    [0065] [0065] Flame Retardants
    [0066] [0066] The composition according to the present invention may further comprise flame retardants such as halogen and halogen-free flame retardants.
    [0067] [0067] Another aspect of the present invention relates to a process for preparing the polymer composition as described above, wherein it comprises melt blending of at least one semi-aromatic polyamide, at least one aliphatic polyamide selected from PA 6 and / or PA 6 , 6, and elemental iron.
    [0068] [0068] The process according to the invention can be carried out by any well-known melt-mixing process that is suitable for preparing thermoplastic molding compositions. Such a process is typically carried out by heating the thermoplastic polymer above the melting temperature or in the case that the thermoplastic polymer is an amorphous polymer above the glass transition temperature, the thermoplastic polymer thereby forming a melt of thermoplastic polymer. The process according to the invention can be carried out in a melt mixing device, for which any melt mixing device known to the person skilled in the art of preparing melt polymer compositions can be used. Suitable melt mixing devices are, for example, kneaders, Banbury mixers, single screw extruders and double screw extruders. Preferably, an extruder equipped with means is used to dose all the desired components to the extruder, either to the neck of the extruder or to the melt. In the process according to the invention, the constituent components for forming the composition are fed to the melt mixing device and mixed by melting in that device. The constituent components can be fed simultaneously as a powder mixture or granule mixer, also known as a dry combination, or they can be fed separately. The process according to the invention is not limited in the way in which elemental iron is added. It can be added, for example, as a powder, a dry or premixed combination comprising the thermoplastic polymer in the form of granules and the elemental iron in the form of powder, or as a main mixture of elemental iron finely dispersed in a carrier polymer. Advantageously, elementary iron is added in the form of a master mixture, as this allows for better control of the dosing accuracy of elementary iron when elemental iron is added in small amounts to the thermoplastic polymer. The carrier polymer that can be used in the main mixture can be the same as the thermoplastic polymer, as well as another polymer, such as a low melting thermoplastic polymer, an elastomer or a rubber. Non-limiting examples of such carriers include SBS rubber, EPDM rubber, polyethylene, polypropylene and ethylene / propylene copolymers.
    [0069] [0069] The advantage of the inventive composition is that it shows a noticeable improvement in the heat aging properties, exhibited by a much better retention of the mechanical properties at elevated temperature, with respect to the known copper salt / potassium iodide compositions. Another advantage is that the composition could be prepared with a lower percentage mass of heat stabilizer, relative to the total mass of the composition, to achieve the same or even higher level of heat aging properties.
    [0070] [0070] Preferred embodiments of the composition according to the invention relate directly to preferred embodiments of the process according to the invention and specific components used in them, as described above, and their reported advantages.
    [0071] [0071] The invention also relates to the use of a polymer composition according to the invention for the preparation of a molded part, as well as to a molded part comprising a composition according to the invention.
    [0072] [0072] An additional object of the present invention relates to the use of a molded part comprising the polymer composition mentioned above in a machine, a motor, an electrical or electronic installation, such as motor vehicles, general means of transport, utensils domestic, oil and gas exploration equipment or general industrial facilities.
    [0073] [0073] The advantage of the molded part according to the invention is that it has very good heat aging properties. The molded part can be mainly two-dimensional in shape, such as for engine covers. The mold can also have a more complex three-dimensional shape, as is the case with many parts used in high temperature applications. Generally, the part has a thickness of at least 0.5 mm, although the parts may have a lesser thickness as well. Preferably, the piece has a thickness of at least mm, more preferably at least 2 mm, and even more preferably at least 4 mm. The advantage of the piece having a greater thickness is that the mechanical properties are better retained under conditions of aging by heat at elevated temperature. More particularly, the molded part is a molded part for use in machines and engines, which can be applied, for example, in motor vehicles, such as personal cars, motorcycles, trucks and vans, general means of transport, including trains, aviation and ships, household items, such as lawn mowers and small engines, and general industrial facilities, such as pumps, compressors, conveyor belts, or a molded part for use in electrical and electronic installations, such as household electrical tools and electrical equipment portable. The part can be, for example, a bearing, a gearbox, an engine cover, an air duct, an intake manifold, an intercooler plug, a roller, or a trolley part.
    [0074] [0074] The invention relates further to products, including motor vehicles, general means of transport, household utensils, and general industrial installations, electrical and electronic installations, comprising a molded part according to the invention. The advantage is that the service life of said products with regard to the necessary replacement of said molded part due to deterioration of the molded part by exposure to high temperature is longer, and / or that the product can be operated at temperature higher compared to a corresponding product comprising a molded part made of the known composition comprising a copper iodide / potassium iodide stabilizing system.
    [0075] [0075] The invention is further illustrated with the following examples and comparative examples.
    [0076] [0076] EXAMPLES
    [0077] (1) PA 1: Vicnyl 600, PA10,T/10,6 (92/8) disponível da Kingfa; (2) PA 2: PA 6 Ultramid® 8202 HS da BASF; (3) PA 3: Amodel A-4002, PA 6,T/6,6 (65/35) disponível da Solvay Specialty Polymers; (4) Estabilizante: mistura de iodeto de cobre e iodeto de potássio em uma razão de 1/9 com um ligante de estearato; (5) Compatibilizante: Fusabond® MB226 da Dupont™ (LLDPE modificado por anidro); (6) Ferro elementar: SHELFPLUSTMO2 2400 da ALBIS Plastic Corporation, mistura principal contendo 20% em peso de partículas de ferro elementar em polietileno tendo um tamanho de partículas D99 de 63 μm; (7) Fibra de vidro 1: fios cortados OCV 983 com 10 microns de diâmetro comercializados pela Owens Corning®; (8) Fibra de vidro 2: fios cortados HP3540 com 10 mícrons de diâmetro comercializados pela PPG Industries; (9) Lubrificante: Polietileno linear de baixa densidade (LLDPE) GRSN-9820 comercializado pela Dow® Chemical. [0077] - Components and ingredients used: (1) PA 1: Vicnyl 600, PA10, T / 10.6 (92/8) available from Kingfa; (2) PA 2: PA 6 Ultramid® 8202 HS from BASF; (3) PA 3: Amodel A-4002, PA 6, T / 6.6 (65/35) available from Solvay Specialty Polymers; (4) Stabilizer: mixture of copper iodide and potassium iodide in a ratio of 1/9 with a stearate binder; (5) Compatibilizer: Fusabond® MB226 from Dupont ™ (anhydrous modified LLDPE); (6) Elemental iron: SHELFPLUSTMO2 2400 from ALBIS Plastic Corporation, main mixture containing 20% by weight of elementary iron particles in polyethylene having a D99 particle size of 63 μm; (7) Fiberglass 1: 10 micron diameter OCV 983 cut wires marketed by Owens Corning®; (8) Fiberglass 2: HP3540 cut threads with 10 microns in diameter marketed by PPG Industries; (9) Lubricant: Low density linear polyethylene (LLDPE) GRSN-9820 marketed by Dow® Chemical.
    [0078] [0078] Preparation of polymer compositions
    [0079] [0079] Examples E1, E2, E3 and comparative examples EC1, EC2 and EC3 were prepared by combining by melting the ingredients listed in Table 1 in a 26 mm twin screw extruder (ZSK 26 by Coperion) operating at about 290 ° C barrel setting using a screw speed of about 200 rpm, a flow rate of 13.6 kg / hour and a melting temperature of about 310325 ° C. Glass fibers 1 or 2 were added to the melt via a side screw feeder. The amounts of ingredients shown in Table 1 are given by weight% based on the total weight of the polymer composition.
    [0080] [0080] The composite mixture was extruded in the form of wires cooled in a water bath, cut into granules and placed in sealed aluminum lined bags in order to avoid the capture of moisture. Cooling and cutting conditions were adjusted to ensure that the materials were kept below 0.15% by weight of moisture level.
    [0081] [0081] Table 1: Nature and quantities of the ingredients of the prepared compositions
    [0082] [0082] Initial Properties of Polymer Compositions
    [0083] [0083] The initial mechanical tensile properties, ie stress at break (tensile strength) and break elongation (break elongation) were measured according to ISO 527-2 / 1A and are recorded in Tables 2 and 3 at the time of 0 hour aging. Measurements were made on injection molded ISO draw bars. The molding temperature for the test specimen ranged from 115-120 ° C and the melting temperature ranged from 315-330 ° C.
    [0084] [0084] The thickness of the test bars was 4 mm and their width was 10 mm. According to ISO 527-2 / 1A, the tensile strength and elongation were determined at a test speed of 5 mm / min.
    [0085] [0085] Aging from thermal oxidation
    [0086] [0086] The test bars were aged by heat in an oven with air recirculation (Blue M) at a temperature set to 230 ° C, according to the procedure detailed in ISO 2578. At various times of aging by heat, the Test bars were removed from the oven, allowed to cool to room temperature and sealed in aluminum lined bags until they were ready for testing. The mechanical tensile properties were then measured according to ISO 527 as described above. All values recorded in Tables 2 and 3 are average values obtained from 5 specimens.
    [0087] [0087] The tensile strength results of examples E1, EC1 and EC2 are also shown in Figure 1.
    [0088] [0088] Table 2: Results of tensile strength in Mpa
    [0089] [0089] Table 3: Results of elongation to traction in%
    [0090] [0090] EC1 and EC2 do not appear to withstand high heat treatment in the long term or even in the short term. On the other hand, the example E1 according to the invention shows a very surprising response to the treatment by the extreme heat applied to it. Its tensile strength is somewhat reduced in the short term but returns to the initial level after 2000 hours of heat treatment at 230 ° C. Even more surprisingly, the tensile strength is even improving to reach higher levels after 4000 hours of heat treatment.
    [0091] [0091] Comparison of the results obtained with examples EC3, E2 and E3 demonstrates that the presence of aliphatic polyamide in the composition also improves the heat aging performance of semi-aromatic polyamide comprising lower amounts of recurrent aromatic units. In this case, the benefit of the presence of the aliphatic polyamide is observed in the long term, i.e. by comparing the tensile properties at 5000 hours.
    [0092] [0092] These examples demonstrate the benefit of the presence of an aliphatic polyamide selected from PA 6 and PA 6.6 in semi-aromatic polyamides that are heat stabilized with elemental iron. This effect is even greater when the semi-aromatic polyamide has a high aromatic content (compare example E1 completely aromatic with E2 and E3 which have a lower aromatic content).
    [0093] [0093] The advantage of the polymer composition having good retention of tensile strength and / or elongation at break, tested after aging by heat, is that it can be used for molded parts and applications of molded parts made of them, in which the part Molded mold has a long life span or can be used at a higher temperature than a molded part not having such good retention of mechanical properties after heat aging. An additional advantage is that the polymer composition having good retention of tensile strength and / or elongation at break can be used at the highest continuous use temperature, and / or that it can be used for a longer time at the same temperature. continuous use.
    [0094] [0094] If the disclosure of any patents, patent applications, and publications that are incorporated herein by reference conflict with the description of the present application to the extent that it may make an unclear term, the present description shall prevail.
    权利要求:
    Claims (12)
    [0001]
    Polymer composition, characterized by the fact that it comprises: - 30% by weight to 85% by weight with at least one semi-aromatic polyamide; - 1% by weight to 20% by weight of at least one aliphatic polyamide selected from PA 6 and PA 6.6; and - 0.1% by weight to 10% by weight of elementary iron having a weighted average particle size of at least 10 μm, where the proportions are based on the total weight of the composition ..
    [0002]
    Polymer composition according to claim 1, characterized in that the at least one semi-aromatic polyamide comprises more than 70 mol% of recurrent aromatic units.
    [0003]
    Polymer composition according to claim 1, characterized in that the at least one semi-aromatic polyamide is a polyphthalamide.
    [0004]
    Polymer composition according to any one of claims 1 to 3, characterized in that the elemental iron has a weighted average particle size of a maximum of 100 μm, measured according to ASTM standard D1921-89, method A.
    [0005]
    Polymer composition according to any one of claims 1 to 4, characterized in that the elemental iron has a weighted average particle size of at least 15 pm, measured according to ASTM standard D1921-89, method A.
    [0006]
    Polymer composition according to any one of claims 1 to 5, characterized in that the semi-aromatic polyamide has a melting point greater than 220 ° C.
    [0007]
    Process for preparing the polymer composition as defined in any one of claims 1 to 6, characterized in that it comprises melt blending of at least one semi-aromatic polyamide, at least one aliphatic polyamide selected from PA 6 and / or PA 6.6 , and elemental iron having a weighted average particle size of at least 10 pm, measured according to ASTM standard D1921-89, method A.
    [0008]
    Process according to claim 7, characterized in that the at least one semi-aromatic polyamide comprises more than 70 mol% of recurrent aromatic units.
    [0009]
    Use of the polymer composition as defined in any one of claims 1 to 6, characterized in that it is for the preparation of a molded part.
    [0010]
    Molded-part polymer, characterized in that it comprises a composition as defined in any one of claims 1 to 6.
    [0011]
    Use of a molded part as defined in claim 10, characterized by the fact that it is on a machine, a motor, an electrical or electronic installation.
    [0012]
    Motor vehicle, general means of transport, domestic utensil, or general industrial installation, characterized by the fact that it comprises a molded part as defined in claim 10.
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    同族专利:
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    KR20140041685A|2014-04-04|
    BR112013030906A2|2017-03-21|
    US20140114005A1|2014-04-24|
    WO2012168442A1|2012-12-13|
    JP6088495B2|2017-03-01|
    KR101888721B1|2018-09-20|
    EP2718371B1|2019-08-14|
    CN103717675A|2014-04-09|
    JP2014516114A|2014-07-07|
    CN110079078A|2019-08-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1570369A1|1965-07-23|1970-03-05|Witten Gmbh Chem Werke|Process for the production of polyamides modified with finely divided fillers in powder form|
    JPS63258952A|1987-04-15|1988-10-26|Kishimoto Sangyo Kk|Polyamide composition filled with metallic powder or the like and production thereof|
    JPS6414271A|1987-07-07|1989-01-18|Showa Denko Kk|Resin composition|
    JPH05194842A|1992-01-21|1993-08-03|Toray Ind Inc|Flame-retarding polyamide resin composition|
    MY109225A|1992-10-12|1996-12-31|Kishimoto Sangyo Co|Flame retardant polyamide composition|
    JP3373872B2|1992-10-12|2003-02-04|岸本産業株式会社|Flame retardant polyamide resin composition|
    JPH11302539A|1998-04-21|1999-11-02|Kuraray Co Ltd|Resin composition|
    NL1013134C2|1999-09-24|2001-03-27|Dsm Nv|Flame retardant thermoplastic composition with improved properties.|
    JP4953519B2|2000-10-11|2012-06-13|名古屋油化株式会社|Masking material for painting|
    US20040022358A1|2000-12-01|2004-02-05|Hitoshi Tomita|Molded resin for radiation shielding|
    CA2386717A1|2001-05-21|2002-11-21|Kuraray Co., Ltd.|Polyamide composition|
    US7022776B2|2001-11-07|2006-04-04|General Electric|Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom|
    EP1498445A1|2003-07-18|2005-01-19|DSM IP Assets B.V.|Heat stabilized moulding composition|
    US7294661B2|2003-10-03|2007-11-13|E.I. Du Pont De Nemours And Company|Flame resistant aromatic polyamide resin composition and articles therefrom|
    US20060011892A1|2004-07-13|2006-01-19|Thomas Powers|Oxygen absorbing packaging material|
    EP1683830A1|2005-01-12|2006-07-26|DSM IP Assets B.V.|Heat stabilized moulding composition|
    EP1681313A1|2005-01-17|2006-07-19|DSM IP Assets B.V.|Heat stabilized moulding composition|
    US7999018B2|2007-04-24|2011-08-16|E. I. Du Pont De Nemours And Company|Thermoplastic resin composition having electromagnetic interference shielding properties|
    KR20110032001A|2008-07-30|2011-03-29|이 아이 듀폰 디 네모아 앤드 캄파니|Heat resistant thermoplastic articles including polyhydroxy polymers|
    US8293831B2|2008-10-30|2012-10-23|E I Du Pont De Nemours And Company|Thermoplastic composition including thermally conductive filler and hyperbranched polyesteramide|
    JP5555432B2|2009-02-16|2014-07-23|三菱エンジニアリングプラスチックス株式会社|Polyamide resin composition|
    WO2011010290A1|2009-07-24|2011-01-27|Ticona Llc|Thermally conductive thermoplastic resin compositions and related applications|
    ES2531430T3|2009-10-27|2015-03-16|Basf Se|Heat aging resistant polyamides|
    CN103201344B|2010-11-01|2015-07-01|东洋纺株式会社|Polyamide resin composition, expanded polyamide resin molding, and automotive resin molding|EP2666803B1|2012-05-23|2018-09-05|Ems-Patent Ag|Scratch-proof, transparent and ductile copolyamide moulding materials, moulded parts produced from same and use of same|
    US10143893B2|2012-09-07|2018-12-04|Acushnet Company|Golf balls having core structures with iron-containing centers|
    ES2527403T3|2012-12-18|2015-01-23|Ems-Patent Ag|Polyamide molding dough and molded bodies produced from it|
    EP2746341B2|2012-12-21|2018-11-14|Ems-Patent Ag|Stain-resistant articles and their use|
    EP2778190B1|2013-03-15|2015-07-15|Ems-Patent Ag|Polyamide moulding material and moulded body produced from the same|
    EP2902444B1|2014-01-31|2018-01-17|Ems-Patent Ag|Polyamide moulding compounds with flame retardant properties and very good long-term heat ageing resistance|
    ES2675213T3|2014-06-20|2018-07-09|Rhodia Operations|Polyamide molding compositions, molded parts obtained therefrom, and use thereof|
    EP3201273A1|2014-10-03|2017-08-09|DSM IP Assets B.V.|Chemically resistant thermoplastic compositions|
    EP3093312A1|2015-05-12|2016-11-16|LANXESS Deutschland GmbH|Thermoplastic moulding materials|
    CN105086442A|2015-08-25|2015-11-25|安徽安缆模具有限公司|High-temperature-resistant anti-aging nylon material for engine cover and preparation method of nylon material|
    JP2019515099A|2016-05-04|2019-06-06|エーエムエス−パテント アクチェンゲゼルシャフト|Polyamide molding material and molded article comprising the same|
    WO2018031564A1|2016-08-08|2018-02-15|Ticona Llc|Thermally conductive polymer composition for a heat sink|
    EP3615589A1|2017-04-25|2020-03-04|AdvanSix Resins & Chemicals LLC|Semi-aromatic copolyamides based on caprolactam|
    US20180237601A1|2018-04-23|2018-08-23|Solvay Specialty Polymers Usa, Llc|Heat stabilized long fiber polyamide polymer compositions and corresponding fabrication methods and articles|
    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-19| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-10-13| B09A| Decision: intention to grant|
    2021-01-05| B09X| Decision of grant: republication|
    2021-04-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161495024P| true| 2011-06-09|2011-06-09|
    US61/495,024|2011-06-09|
    EP11176634.1|2011-08-04|
    EP11176634|2011-08-04|
    PCT/EP2012/060919|WO2012168442A1|2011-06-09|2012-06-08|Polyamides compositions featuring improved thermal stability|
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