• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    compositions, methods and articles produced by combining polyamides with olefin-maleic anhydride polymers. the disclosure of the present application provides compositions and methods of combining polyamides comprising the steps of forming a polyamide mixture, which comprises a polyamide with a maleic anhydride olefin copolymer, and combining the polyamide mixture at its processing temperature. recycled nylon-derived combined polyamides and methods for preparing the combined polyamides are described.
    公开号:BR112013003774B1
    申请号:R112013003774
    申请日:2011-08-16
    公开日:2020-04-22
    发明作者:M Adur Ashok；Tarbit Brian
    申请人:Vertellus Holdings Llc；Vertellus Specialties Inc；
    IPC主号:
    专利说明:

    (54) Title: COMBINED POLYAMIDE UNDERSTANDING POLYAMIDE AND A COPPERYL OF OLEFINE-MALEIC ANIDIDE, THERMOPLASTIC PELETIZABLE POLYMER COMPOSITION, METHOD OF COMBINED POLYMER AND 51 METHOD.
    (30) Unionist Priority: 06/03/2011 US 61 / 493,058; 05/13/2011 US 61 / 485,826; 08/18/2010 US 61 / 374,817.
    (73) Holder (s): VERTELLUS HOLDINGS LLC.
    (72) Inventor (s): BRIAN TARBIT; ASHOK M. ADUR.
    (86) PCT Application: PCT US2011047872 of 16/08/2011 (87) PCT Publication: WO 2012/024268 of 02/23/2012 (85) Date of Beginning of the National Phase: 02/18/2013 (57) Summary: COMPOSITIONS, METHODS AND ARTICLES PRODUCED BY COMBINING POLYAMIDES WITH POLYMERS OF OLEFINE-MALÉIC ANYTHRID. The disclosure of the present application provides compositions and methods of combining polyamides comprising the steps of forming a polyamide mixture, which comprises a polyamide with a maleic anhydride olefin copolymer, and combining the polyamide mixture at its processing temperature. Combined polyamides derived from recycled nylon and methods for preparing the combined polyamides are described.
    1/35 “COMBINED POLYAMIDE UNDERSTANDING POLYAMIDE AND A COPOLYMER OF OLEFINE-MALEIC ANIDIDE, THERMOPLASTIC PELETIZABLE POLYMER COMPOSITION, GROSS POLYMER COMPOSITION AND METHOD FOR PREPARING THAT COMBINED POLYAMIDE”
    CROSS REFERENCE TO RELATED APPLICATIONS [001] This application claims priority under 35 U.S.C. § 119 (e) for U.S. Provisional Applications Nos. Series 61 / 374,817, filed on August 18, 2010; 61 / 485,826, deposited on May 13, 2011; and 61 / 493,058, filed on June 3, 2011. The totality of the disclosures of each of these requests is incorporated in this document by reference.
    [002] A polyamide is a polymer containing repeating units of amides. These polymers can occur both naturally, with examples being proteins, such as wool and silk, as they can be artificially prepared through polymerization in stages of development, with examples being nylon, aramid, and poly (aspartate) ) sodium. Currently, polyamides are commonly used in fabrics, automobiles, carpet and sportswear due to their extreme durability and resistance.
    [003] A subgroup of polyamides, nylon, is one of the most commonly created subgroups of synthetic polymers. Nylons are typically condensation copolymers formed by reacting dicarboxylic acids with diamines or by opening a lactam ring. Several nylon polymers can be created by adjusting the number of carbons. Conventional nomenclature designations on these various nylon and polyamides specify diamine first and diacid second. Therefore, the most commercially common variant of nylon, nylon 66, has six carbons donated by the diamine, and six carbons from the diacid, and nylon 612 would have six carbons donated by the diamine and twelve carbons donated from the diacid. Unlike nylon 6-6, nylon-6 is a homopolymer formed through a poly
    Petition 870190112428, of 11/04/2019, p. 12/54
    2/35 merization by ring opening. An example of this is nylon-6 produced by polymerization of caprolactam. Because each variant has a different chemical structure, the physical properties of nylon differ with respect to impact resistance, stress resistance, elasticity, tear resistance, melting temperature, color stability, and other properties.
    [004] Olefin maleic anhydride polymers (OMAP) are formed by copolymerizing maleic anhydride with olefin monomers. Examples of such olefins include ethylene, propylene, isobutylene, butene-1, octene, butadiene, styrene, isoprene, hexene, long chain alkenes (eg, dodecene, dodecene- 1, tetradecene), and the like. Some of these olefins are derived from natural gas and / or crude oil, while others are derived from natural substances or by biosynthesis. Examples of such copolymers include, but are not limited to, copolymers of ethylene-maleic anhydride, propylene-maleic anhydride, isobutylene-maleic anhydride, and terpolymers, such as ethylene-propylene-maleic anhydride terpolymer.
    [005] It will be appreciated that products that are prepared from polyamides are exposed to considerable stresses during manufacture and processing, and that a method for producing nylon or other polyamides with increased durability would be appreciated in the art, and that formulations of Specific nylon having increased durability would be highly appreciated in the art.
    BRIEF DESCRIPTION OF THE DRAWINGS [006] FIG. 1 shows the reduction in high shear viscosity resulting from the combination of a nylon (eg, nylon-6) with the EMA.
    DESCRIPTION [007] The disclosure of the present application provides compositions comprising polyamides with such olefin-maleic anhydride polymers (OMAP).
    [008] The disclosure of this application also provides several methods
    Petition 870190112428, of 11/04/2019, p. 13/54
    3/35 to produce polyamide compounds with ethylene maleic anhydride (EMA) copolymers. Specifically, at least one embodiment of the present disclosure relates to methods for the reaction of nylon-like materials with maleic anhydride ethylene copolymers. At least one embodiment of the present disclosure involves processing methods, such as combining by extrusion using equipment known to one skilled in the art. In the plastics industry, blending is a process that mixes one or more polymers with one or more additives to produce plastic compounds in one or more steps. The feeds can be granules, powder and / or liquids, however the product is usually in the form of granules, to be used in other plastics forming processes, such as extrusion and injection molding. The size of the machine ranges from very small laboratory machines to the largest extruders in the industry, running as much as 20 tonnes per hour. Twin screw extruders are usually preferred because they give better mixing at lower melting temperatures. Most of these have threads and cylinders made up of smaller segments (mixing, transport, ventilation and feeding of additives), so that the design and the sequence of addition of each of the ingredients in the formulation can be changed to meet production needs and product. Other equipment, such as single screw extruders, oscillating screw extrusion, continuous mixers, Banbury mixers, and planetary extruders, can also be used for the combination. Additional components to be mixed and / or combined (viscosity modifiers, additive vehicles, and the like) and processing parameters, such as temperature of each zone, feed rates, residence time and thread speed, can modified by the person skilled in the art for each application. The method of producing the polyamide compounds according to at least one embodiment of the present application results in a polymer combined with perfection
    Petition 870190112428, of 11/04/2019, p. 14/54
    4/35 steels in properties and performance, such as increased extend performance, impact resistance, resistance to slow deformation, and resistance to anti-freeze degradation due to hydrolysis, of the compound formed by reaction of the polyamide with the olefin-anhydride polymer maleic.
    [009] According to at least one embodiment of the method of producing the combined polyamides of the present disclosure, the method comprises the step of combining a polyamide with a maleic anhydride ethylene copolymer in a twin screw extruder or other processing method listed in previous paragraph. Such granules are subsequently processed by a plastic processing method, such as injection molding, blown or molten film, sheet extrusion, thermoforming, or blow molding, into a finished article, such as vial, molded part, film, sheet , fabric, filament, fiber, etc.
    [0010] Another modality includes directly extruding such reaction mixture into a finished article, such as a filament, fiber, film, sheet, and molded part.
    [0011] In the production of the compounds of the present disclosure, a polyamide can be any suitable polyamide, as described in this document. For example, in an illustrative embodiment, the polyamide can be a nylon, such as nylon-6 or nylon 6-6. In addition, the polyamides used in at least one embodiment of the method of producing a polyamide compound can be aliphatic, alicyclic and aromatic polyamides, such as one or more of nylon 6-12, nylon 4-6, nylon 9 nylon 10, nylon 6 -9, nylon 11, nylon 12, nylon 5-10, nylon-meta-xylene diamine (nylon-MXD6), Kevlar® (DuPont), Nomex® (DuPont), Ixef® (Solvay Advanced Polymers), Trogamid® (Evonik Degussa), and Amodel® (Solvay Advanced Polymers). In addition, according to at least one illustrative embodiment of the method of producing a combined polyamide, olefin-maleic anhydride as an alternating copolymer of ethylene maleic anhydride (EMA) can be used in the method of treatment in a molar ratio of ethylene to maleic anhydride about 1: 1.
    Petition 870190112428, of 11/04/2019, p. 15/54
    5/35
    In alternative embodiments, olefin-maleic anhydride as an alternating copolymer of ethylene maleic anhydride (EMA) can be used in the treatment method in a molar ratio of ethylene to maleic anhydride from about 1:99 to about 99: 1 . The additional alternative embodiments employ non-alternating copolymers or random copolymers with a range of molar ratio of ethylene to maleic anhydride from about 1:50 to about 50: 1; about 1:20 to about 20: 1; about 1:10 to about 10: 1; about 1: 5 to about 5: 1; and about 1: 2 to about 2: 1. In yet another embodiment, non-alternating copolymers or random copolymers can be used.
    [0012] Additionally, according to at least one illustrative modality, the olefin maleic anhydride selected for the reaction with a polyamide has an average molecular weight in the range of about 300 to about 10 million; about 10,000 to about 1 million; about 20,000 to about 800,000; about 40,000 to about 600,000; about 50,000 to about 500,000; or about 60,000 to about 400,000. For example, according to at least one illustrative embodiment, the selected EMA can have a molecular weight of around 60,000, such as that sold under the trademark ZeMac® E-60 (E60), or the selected EMA can have a weight molecular weight of about 400,000, such as that sold under the trademark ZeMac® E-400 (Vertellus Specialties Inc.) (E400). In addition, EMA can be used in an illustrative embodiment of the method of producing a combined polyamide in a concentration of between about 0.01% to about 20.0% w / w; about 0.02% to about 0.5%; about 0.05% to about 7.0% w / w; about 0.1% to about 5.0% w / w; or about 0.5% to about 3.0% w / w.
    [0013] According to at least one optional embodiment, a stabilizer package is added to the formulation, the stabilizer package comprising additives used individually or in combination with each other. According to such modality, the additives can comprise phenolic antioxidants, phosphites, iodide
    Petition 870190112428, of 11/04/2019, p. 16/54
    6/35 cuprous (CuI), potassium iodide (KI), and / or other stabilizers. Optionally, the stabilizer package can comprise about 0.01% to about 5.0% w / w of the overall reaction mixture; about 0.1% to about 2.0% w / w; or about 0.5% to 1.0% w / w.
    [0014] Several illustrative modalities of the invention are described by the following sentences listed:
    1. A thermoplastic pelletizable polymer composition comprising:
    (a) a polyamide; and (b) a polymer polymerized from maleic anhydride and an olefin; where the polyamide and the polymer are combined.
    2. The thermoplastic pelletizable polymer composition of clause 1, where the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, nylon-9, nylon -10, nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides, and mixtures thereof.
    3. The thermoplastic pelletizable polymer composition of clause 2, where the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, and mixtures thereof.
    4. The thermoplastic pelletizable polymer composition of clause 1, where the olefin is selected from the group consisting of ethylene, propylene, isobutylene, butene-1, octene, butadiene, styrene, isoprene, hexene, dodecene, dodecene-1, and tetradecene.
    5. The thermoplastic pelletizable polymer composition of clause 1, where the olefin is ethylene.
    6. A cross-linked polymer composition comprising:
    (a) a polyamide, and (b) a polymer polymerized from maleic anhydride and an olefin; where the polyamide and the polymer are combined at a processing temperature
    Petition 870190112428, of 11/04/2019, p. 17/54
    7/35 to, where the processing temperature is sufficient to promote crosslinking.
    7. The crosslinked polymer composition of clause 6, where the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, nylon-9, nylon- 10, nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides, and mixtures thereof.
    8. The crosslinked polymer composition of clause 6, where the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, nylon-11, and their mixtures.
    9. The crosslinked polymer composition of clause 6, where the olefin is selected from the group consisting of ethylene, propylene, isobutylene, butene-1, octene, butadiene, styrene, isoprene, hexene, dodecene, dodecene-1, and tetradecene.
    10. The cross-linked polymer composition of clause 6, where the olefin is ethylene.
    11. A method of preparing a combined polyamide comprising the steps of:
    forming a polyamide reaction mixture by contacting the polyamide with an olefin-maleic anhydride copolymer; and combining the polyamide reaction mixture at a processing temperature.
    11a. A method of preparing a combined polyamide comprising:
    combining a polyamide mixture comprising a polyamide and an olefin-maleic anhydride copolymer at a processing temperature.
    12. The clause 11 or 11a method, where the olefin is selected from the group consisting of ethylene, propylene, isobutylene, butene-1, octene, butadiene, styrene, isoprene, hexene, dodecene, dodecene-1, and tetradecene .
    13. The clause 11 method, where the olefin is ethylene.
    Petition 870190112428, of 11/04/2019, p. 18/54
    8/35
    14. The clause 11 or 11a method, where polyamide is nylon.
    15. The clause 11 or 11a method, where polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, nylon-9, nylon-10 , nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides, and mixtures thereof.
    16. The method of clause 11 or 11a, where polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, and mixtures thereof.
    17. The method of clause 13, where the olefin-maleic anhydride copolymer has an ethylene to maleic anhydride ratio of 1: 1.
    18. The method of clause 17, where the olefin-maleic anhydride copolymer has a molecular weight of about 300 to 1,000,000.
    19. The method of clause 17, where the olefin-maleic anhydride copolymer has a concentration of about 0.01% to about 0.5%, about 0.5% to about 1.0%, about 1.0% to about 1.5%, or 1.5% to about 3.0% w / w.
    20. The clause 11 or 11a method, where the processing temperature is about 230 ° C to about 300 ° C.
    21. The method of clause 11 or 11a, where the step of forming the polyamide reaction mixture additionally comprises the step of combining a polyamide with a glass fiber.
    22. The clause 21 method, where the glass fiber has a concentration of about 0.1% to about 30%.
    23. The method of clause 11 or 11a, where the step of forming a polyamide reaction mixture additionally comprises the step of contacting a polyamide with one or more stabilizing agents.
    24. The clause 23 method, where each of the one or more stabilizing agents is independently selected from a group consisting of
    Petition 870190112428, of 11/04/2019, p. 19/54
    9/35 cuprous iodide, potassium iodide, tris (2,4-di-tert-butylphenyl) phosphite, and N, N'hexane-1,6-diylbis (3- (3,5-di-tert-butyl) -4-hydroxyphenylpropionamide)).
    25. The clause 23 method, where each of the one or more stabilizing agents independently has a concentration of about 0.01 to about 1.0% w / w.
    26. A method of producing a combined polyamide, comprising the steps of:
    providing a polyamide mixture, where the polyamide mixture comprises an olefin-maleic anhydride copolymer; a glass fiber and; one or more stabilizing agents; and combining the polyamide reaction mixture between about 230 ° C and about 300 ° C.
    26a. A method of producing a combined polyamide, comprising combining a polyamide mixture, where the polyamide mixture comprises an olefin-maleic anhydride copolymer; a glass fiber and; one or more stabilizing agents, at a temperature of between about 230 ° C and about 300 ° C.
    27. A combined polyamide produced by a process comprising the steps of:
    forming a polyamide reaction mixture, comprising a polyamide and an olefin-maleic anhydride copolymer;
    combine the polyamide reaction mixture at a processing temperature.
    27a. A combined polyamide, produced by a process comprising combining a polyamide mixture, comprising a polyamide and an olefinic maleic anhydride copolymer, at a processing temperature.
    28. The combined polyamide of clause 27 or 27a, where the olefin-maleic anhydride polymer is an ethylene-maleic anhydride polymer.
    Petition 870190112428, of 11/04/2019, p. 20/54
    10/35
    29. The combined polyamide of clause 27 or 27a, where the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, nylon-9, nylon- 10, nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides, and mixtures thereof.
    30. The combined polyamide of clause 27 or 27a, where the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, and mixtures thereof.
    31. The combined polyamide of clause 27 or 27a, where the polyamide is selected from the group consisting of nylon-6 and nylon 6-6.
    32. The combined polyamide of clause 28, where the ethylene maleic anhydride copolymer has an ethylene to maleic anhydride ratio of 1: 1.
    33. The combined polyamide of clause 28, where the ethylene maleic anhydride copolymer has a molecular weight of about 300 to 1,000,000.
    34. The combined polyamide of clause 27 or 27a, where ethylene-maleic anhydride has a concentration of about 0.01% to about 0.5%, about 0.5% to about 1.0%, about from 1.0% to about 1.5%, or 1.5% to about 3.0% w / w.
    35. The combined polyamide of clause 27 or 27a, where the processing temperature is about 230 ° C to about 300 ° C.
    36. The combined polyamide of clause 27 or 27a, where the polyamide reaction mixture additionally comprises a glass fiber.
    37. The combined polyamide of clause 36, where the glass fiber has a concentration of about 0.1% to about 30%.
    38. The combined polyamide of clause 27 or 27a, where the polyamide reaction mixture additionally comprises one or more stabilizing agents.
    39. The combined polyamide of clause 38, where the one or more stabilizing agents are each independently selected from the group consisting of cuprous iodide, potassium iodide, tris (2,4-di-tert-butylphenyl phosphite) ),
    Petition 870190112428, of 11/04/2019, p. 21/54
    11/35 and N, N'-hexane-1,6-diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)).
    40. The combined polyamide of clause 39, where the one or more stabilizing agents each independently have a concentration of about 0.01% w / w to about 1.0% w / w.
    41. The combined polyamide of clause 33, where the ethylene maleic anhydride copolymer has a molecular weight of about 60,000 to about 400,000.
    42. The combined polyamide of clause 13, where the ethylene maleic anhydride copolymer has a molecular weight of about 60,000 to about 400,000.
    43. The combined polyamide or polymer composite of any of the preceding clauses, where the polyamide is a recycled nylon.
    44. An article comprising the combined polyamide or polymer composite of any one of clauses 1 to 42, where the article is selected from the group consisting of carpet fiber, clothing, an airbag, a tire, a rope, a conveyor belt, a hose, luggage, a molded auto part, a molded gun holder, a molded electrical part, a molded tool handle, a toothbrush, a comb, a hairbrush, a food wrap film, a oil resistant gasket, and bullet resistant materials.
    [0015] In addition, according to the additional illustrative modalities, halogenated or non-halogenated flame retardant additives are included in the reaction mixture; reinforcers, such as a mineral or fibers, fabrics, strand filaments, tubes and threads, made of glass, carbon, graphite, cellulose and other natural materials; and / or high fusion aromatic polymers (sometimes referred to as aramides). Plasticizers, lubricants, rheology modifiers, friction modifiers, and other additives known to someone skilled in the art can also optionally be added to the mixture, depending on application requirements.
    Petition 870190112428, of 11/04/2019, p. 22/54
    12/35 [0016] According to at least one step of forming a polyamide reaction mixture, the component parts can be combined by any type of applicable extruder, such as a single or twin screw extruder, or a applicable extruder used in conjunction with a mixer.
    [0017] While conducting the step of combining in one embodiment of the method of producing a combined polyamide of the present disclosure, the first temperature can be any temperature sufficient to melt the polyamide and promote the combination of a polyamide with the EMA. In an illustrative embodiment, with nylon-6, the temperature settings on the extruder and the processing temperature can be about 230 ° C to about 300 ° C. In other embodiments, the temperature settings and the combination temperature can be from about 230 ° C to about 260 ° C or from about 220 ° C to 260 ° C. For nylon 6-6, this temperature can vary from 250 ° C to 310 ° C or from 240 ° C to 280 ° C. However, for higher melting polyamides, such as the Nomex® polymer, such processing temperatures are likely to be in the range of 280 ° C to 380 ° C. For elastomeric polyamides, such as nylon-9, nylon-10, nylon-6,10, nylon-11 and nylon-12, the range can be considerably smaller, in the range of 150 ° C to 250 ° Ç. It is recognized that the upper value of the combination temperature may be linked by the temperature at which the degradation of the nylon being combined becomes significant, the lower value may be linked by the melting point or softening of the nylon.
    [0018] Without being bound by theory, it is believed that nylon (also called polyamides) requires the presence of a free amine group to react with the anhydride groups of the olefin-maleic anhydride copolymer (see formula below). Illustratively, the Ultramid B3S grade, which has free amine groups and is not capped at the end, reacts, while Ultramid B27, which is capped at the end, has no free amine group available for the reaction.
    Petition 870190112428, of 11/04/2019, p. 23/54
    13/35
    R- (CH 2 -CH 2 -MAh) n -R '' + H 2 N-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CO (HN-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CO) m -R 'polymer of maleylene anhydride an nylon-6 polyamide
    - m H 2 O '<
    CO-NH-CH2-CH2-CH2-CH2-CH2-CO (HN-CH2-CH2-CH2-CH2-CH2-CO) m-R '
    R- (CH 2 -CH 2 -CH-CH) n -R ''
    CO-NH-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CO (HN-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CO) m -R 'a polyamide compound [0019 ] In at least one embodiment of the method of combining a polyamide, the step of forming a polyamide reaction mixture can additionally comprise the step of contacting a polyamide with a glass fiber. The introduction of fiberglass can occur before or after the combination of the polyamide with the EMA. The glass fiber can have a concentration of about 0.1% to about 60%; about 10% to about 50%. In addition, in an illustrative embodiment of the present disclosure, a glass fiber can have an applicable degree and size with the combination of nylon.
    [0020] According to other illustrative modalities, other reinforcements can be combined with polyamide, including carbon nanotubes, mica, talc, calcium carbonate, wollastonite, carbon fibers, Kevlar® fibers, nano-particles made of clay and other materials. Other modalities include fabrics, weft filaments, tubes and threads, made of glass, cellulose and other natural materials, carbon, graphite, high-fusion aromatic polymers (sometimes referred to as aramids) and ceramics . A specific example is Kevlar® fibers, with a diameter of 12 microns and fiber length of 1.27 cm (0.5 inch). Another example is a biaxially oriented fiberglass fabric, such as VECTORPLY® E-LTM 3610.
    [0021] An illustrative embodiment of the method of producing a combined polyamide may also comprise the pulley injection molding step
    Petition 870190112428, of 11/04/2019, p. 24/54
    14/35 mida. Optionally, the polyamide can be combined with the EMA directly during injection molding.
    [0022] As a result of producing a combined polyamide by one embodiment of the method of the present disclosure, the treated polyamide (ie, the combined polyamide) has been found to exhibit increased impact resistance and / or increased tensile strength compared to non-polyamide combined. The increased impact resistance can be at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 28%, at least at least about 30%, at least about 33%, at least about 35%, at least about 40%, or at least about 50%, greater than unmatched polyamide.
    [0023] According to at least one embodiment of a combined polyamide of the present disclosure, a combined polyamide, formed by the process of combining the polyamide with an EMA, is disclosed. More optionally, the polyamide can be a nylon-6 or a nylon-6,6 and the EMA has a weight molecular weight of about 60,000 to about 400,000. The polyamide can also be nylon-9, nylon-12, nylon-11, nylon 4-6, or any of the polyamides listed in this document. In another illustrative embodiment, the polyamide combined with the EMA in any of the embodiments described in this document can be recycled nylon.
    [0024] Recycled nylon / polyamide can include many different types of materials of varying quality from different industries. The recycled polyamide can be from post-industrial sources or post-consumer sources or a combination of both. An example of a high quality recycled nylon is non-colored nylon that has sufficient molecular weight for injection molding. Another illustrative recycled nylon is polyamide / nylon Unspec or not superior that does not meet the specifications for its intended use or is a transition material
    Petition 870190112428, of 11/04/2019, p. 25/54
    15/35 tion that is produced during switching between the production of one grade of nylon and another grade in nylon. This type of product made from recycled nylon material is valued from about 2-5% below the price of the upper nylon to around 25% below the price of the upper nylon, depending on market conditions. Much of the lower quality recycled nylon that is currently available goes to landfills. Illustrative sources of substandard recycled nylon are the fabric or lingerie industry. Another source is recycled fishing nets. Much of this lower quality material is low viscosity nylon, which cannot normally be used for injection molding applications without modification, as described in this document. The automotive industry's recycled nylon is typically black and cannot be used for non-black applications. Recycled nylon can also contain one or more polymers other than polyamide. In an illustrative example, the carpet waste typically contains 80-85% polyamide, the remaining material being polyester, polypropylene and some polyurethane. Due to poor mechanical performance, such carpet waste is not typically reused and ends up in landfills. Depending on the performance and quality of the material, polyamide prices vary. By combining these types of recycled polyamides with EMA copolymers, as described in this document, these materials can be used for more value added applications.
    [0025] According to at least one additional embodiment of the combined polyamide of the present disclosure, a reacted or combined polyamide can be incorporated into any product where increased performance over the unmatched polyamide is desired. In an illustrative embodiment, the combined polyamide can be incorporated into any of carpet fiber, clothing, airbags, tires, ropes, conveyor belts, hoses, luggage, molded products (auto parts, gun holders, electrical parts, and tool handles) ), personal care products (such as toothbrushes), medical devices and
    Petition 870190112428, of 11/04/2019, p. 26/54
    16/35 surgical, food packaging films, oil resistant gaskets, defense and aerospace products, and bulletproof materials.
    [0026] According to at least one embodiment, the crosslinked compositions of this disclosure, prepared using relatively higher levels of an olefin-maleic anhydride polymer (OMAP) in a polyamide matrix, are used for fused nylon or thermally laminated applications. To achieve these goals, the OMAP ratio is in the range of about 10% to about 50% w / w, or about 10% to about 20%. Applications for a cross-linked composition of this variety are optionally processed by methods typically used for thermoset polymers, some of which use reinforcement with fabrics made of glass fibers. Such polymers can be useful for applications ranging from metal replacement (eg, mechanical parts, medical devices, and the like) to transport use. Other uses include applications in defense and aerospace. In other embodiments of these crosslinked compositions, the olefin polymer-maleic anhydride is an alternating polymer of ethylene-maleic anhydride 1: 1.
    [0027] As used in this document, the term combination in general refers to a process that mixes one or more polymers with one or more additives, to produce plastic compounds, in one or more steps. The materials to be mixed can be in the form of granules, powders and / or liquids. Typically, the product is in the form of granules for use in other plastic forming processes, such as extrusion and injection molding.
    METHODS AND EXAMPLES
    MATERIALS [0028] Polyamide 6 (Ultramid® B3S grade) and Polyamide 6.6 (Ultramid® A34 grade), both superior quality from BASF, were used as received, as was recycled polyamide 6. Care has been taken to ensure that all grades remain dry. An alternating ethylene-maleic anhydride copolymer
    Petition 870190112428, of 11/04/2019, p. 27/54
    17/35 to 1: 1 grade ZeMac® E60 (E60) from Vertellus Specialties Inc., with a weight average molecular weight (MW) of 60,000, was used in these illustrative examples. An alternating ethylene-maleic anhydride copolymer at 1: 1 grade ZeMac® E400 (E400) from Vertellus Specialties Inc., with a weight average molecular weight (MW) of 400,000, was also used in the illustrative examples. A stabilizer package, consisting of 0.09% potassium iodide (KI), 0.01% cuprous iodide (CuI), 0.4% Irgafos® 168 (phosphite stabilizer), and 0.5% Irganox ® 1098 (hindered phenol antioxidant), was used with all samples combined.
    GENERAL PREPARATION OF THE COMBINED POLYAMIDE [0029] The composite granules of polyamide combined with E60 or E400 were prepared in a double screw extruder with counter-rotating combination (Bertstroff 25 mm. 32D). The polyamide-6 and recycled polyamide-6 samples were run using the temperature settings of 235, 245, 255, 245, 240, 240, 240, 240 ° C, while the polyamide-6,6 samples were combined using the temperature settings of 250, 265, 275, 270, 270, 270, 270, 280 ° C. For GF reinforced runs, the fiberglass, at a load level of 30%, was fed downstream with a side feeder.
    GENERAL TEST METHODS [0030] Measurements of tensile strength, bending, toothed Izod impact and fluidity index were performed using standard ASTM methods D-638, D790, D-256 and D-1238, respectively, at 23 ° Ç. Charpy impact resistance was measured using the ISO-179-2 / 2 method at room temperature (23 ° C) and at -30 ° C. The deflection / distortion temperature was measured using the ASTM D-648 method. These mechanical and thermal tests were performed without additional drying, the samples were used as molded after conditioning the test sample according to the ASTM protocol. Water absorption tests were carried out after drying to equilibrium, to ensure that all absorbed water is removed and
    Petition 870190112428, of 11/04/2019, p. 28/54
    18/35 all samples are dry. The percentage of increases in the amount of water absorbed was determined after 24, 48 and 72 hours.
    SUPERIOR POLYAMIDE-6 [0031] Polyamide-6 was combined with 1% ethylene maleic anhydride copolymer, with and without 30% glass fiber. The tensile strength, elongation and resistance to toothed Izod impact of the resulting combined materials are shown in TABLE 1 below.
    TABLE 1
    Formulation Nylon-6 + without additive Nylon-6 +1% E60 Nylon-6 + 30% Fiberglass + without additive Nylon-6 + 30% Fiberglass dro + 1%E60 in Stress Tensile Strength (MPa) 50 70.5 69 79 Stretching byRupture Traction(%) 5.9 8.0 4.9 9.2 Stretching byYield Traction (%) 5.2 7.9 4.9 8.8 Voltage Module(MPa) 1150 1200 2250 2400 Toothed Izod [J / m.(ft-lb./pol.)] 0.6942(1.30) 0.8277(1.55) 0.801 (1.50) 1.068 (2.00) Toothed Izod (J / m.) 69 83 80 107
    [0032] The results of tensile strength, elongation and resistance to toothed Izod impact shown in TABLE 1 demonstrate that the copolymer alter
    Petition 870190112428, of 11/04/2019, p. 29/54
    19/35 nado increases all three properties, with and without 30% fiberglass. Typically, when the tensile strength is increased in most plastics with some type of modification, the elongation decreases and vice versa. It was found that the combination of polyamide and EMA results in increases in both tensile strength and elongation, simultaneously. These observations are believed to show that the basic structure of at least some of the polyamide is being modified to a highly branched structure, with very high molecular weight, which results in a stronger and harder combined polyamide.
    [0033] During the combination, an increase in both viscosity and torque is observed. When a grade of polyamide was used without any end groups, no increase in viscosity or mechanical properties was observed. This is believed to indicate that no amidation reaction can occur in the absence of amine end groups on the polyamide. It has also been observed that crosslinking can occur at high EMA loads (> 10%) and the combined material does not flow. The use of other materials that have a reactive group, ie, an anhydride (for example, polyethylene grafted with maleic anhydride) or a modifier with a reactive group at each end, shows only a slight increase in viscosity and little increase in mechanical properties , compared to the use of the EMA copolymer (unique structures with thousands of reactive groups on each molecular chain) disclosed in this document. This increase in viscosity also results in a reduction in the flow rate of polyamide-6, as shown in TABLE 2.
    TABLE 2
    Additive Flow Rate at 235 ° C and 1 kg(g / 10 min) not combined 9.7 0.1% E60 4.3
    Petition 870190112428, of 11/04/2019, p. 30/54
    20/35
    0.3% of E60 1.7 0.5% E60 1.0
    SUPERIOR POLYAMIDE-6.6 [0034] It was observed during the combination that the polyamide 6.6 generated higher viscosity and torque increase at the same load levels as the EMA. This can be partially attributed to the higher temperature at which polyamide-6,6 is processed, compared to polyamide-6, but also because polyamide-6,6 is known to typically have amine end groups in both ends. Similar to the results for polyamide-6, the mechanical properties of polyamide-6,6 are also improved, while the flow rate decreases. In addition, we observed an increase in thermal deflection temperature, as shown in TABLE 3 below.
    TABLE 3
    Additive Flow Rate at 275 ° C and 5 kg (g / 10 min) Temp. Heat Deflection ° C at 1.82 Mpa (264 psi) not combined 142.05 59.6 without additive 29.06 70.5 0.1% E60 21.12 74.1 0.3% of E60 8.98 71.0 0.5% E60 2.27 71.3
    RECYCLED Nylon-6 [0035] The recycled polyamide, used for this study, was mainly nylon-6 from an industrial source. Due to the presence of some nylon-6,6 in this recycled polyamide, the flow rate is less than what would typically be expected from a stream recycled with only polyamide-6. During the combination, it generated less torque than the corresponding upper nylon-6. Without being linked by theory, it is believed that the lower torque is due to the degradation caused by
    Petition 870190112428, of 11/04/2019, p. 31/54
    21/35 history of additional heat from recycled nylon-6 compared to superior nylon-6. TABLE 4 shows the decrease in the flow rate in recycled polyamide combined with E60. It is believed that this decrease in the flow rate is due to the expansion of the chain and the resulting branching. The resulting shear dilution enabled excellent injection molding, contrary to what might be expected from the fractional flow rates obtained when the ASTM test samples were molded.
    TABLE 4
    Additive Flow Rate (ASTM D-1238)235 ° C w / 1 kg (g / 10 min) without E60 13 without additive 6.2 0.1% E60 1.17 0.3% of E60 0.80 0.5% E60 0.44 1% E60 0.5 3% E60 1.6 Superior nylon-6 9.65
    [0036] The tensile strength of injection molded samples was measured as described in the ASTM D638 protocol. The results are shown in TABLE 5. The various commercial grades of the upper polyamide-6 grades differ slightly in terms of tensile strength values, as indicated in the specification data sheets provided by the supplier.
    [0037] As shown in TABLE 5, after the reactive combination of the recycled polyamide with the alternating ethylene-maleic anhydride copolymer to produce the combined recycled polyamide, the tensile strength values are equal to, or close to, value range of the upper polyamide grades (75 to
    Petition 870190112428, of 11/04/2019, p. 32/54
    22/35
    MPa). The other properties of the combined recycled polyamide are also improved. TABLE 6 shows the flexural modulus properties of recycled polyamide as a function of adding low charges of the same alternating copolymer of ethylene and maleic anhydride.
    [0038] This increase in the flexural modulus of the combined recycled polyamide is equal to, or exceeds, the similar range of flexural modulus of the various grades of superior polyamide-6 available from different suppliers. An increase in flexural strength at break is also observed for the combined recycled polyamide, as shown in TABLE 6. It is seen from the values for both the flexural module and the flexural strength at break that the values increase as a function of the amount of alternating copolymer added from 0.1 to 0.5%. The values do not seem to increase further when the percentage of added E60 is increased further.
    TABLE 5 Increased tensile strength of recycled polyamide due to reaction with E60 ._______________________________________________________
    Recycled PolyamideCombined TRACTION PROPERTIES(ASTM D638) Additive Yield Tensile Strength (MPa) Stretching onBreak (%) without E60 61.1 19.47 without additive 78.2 18.24 0.1% E60 78.5 12.66 0.3% of E60 80.2 17.58 0.5% E60 79.5 12.79 1% E60 82.0 29.17 3% E60 80.4 15.91 Superior nylon-6 83.6 12.41
    Petition 870190112428, of 11/04/2019, p. 33/54
    23/35
    TABLE 6 Increase in the flexural modulus and strength of recycled polyamide due to the reaction with E60 .____________________________________
    Additive FLEX ASTM D790 Flex module.(Mpa) Flex resistance. atBreak (Mpa) without E60 2385 77.2 without additive 2632 102.5 0.1% E60 2689 105.7 0.3% of E60 2749 114.0 0.5% E60 3016 121.1 1% E60 2867 110.8 3% E60 2866 113.3 Nylon-6 Sup-rior 2796 113.8
    [0039] The Izod impact strength for the combined recycled polyamide was measured according to the ASTM D256 protocol. The results measured at room temperature (23 ° C) and -30 ° C are shown in TABLE 7. The results show an increase as a function of the alternating copolymer addition level at both room temperature and -30 ° C. What is surprising, however, is that the values measured at low temperature are unexpectedly greater than the values measured at room temperature and are greater than the values measured for the upper nylon-6.
    [0040] Resistance to Charpy impact, measured at 23 ° C and -30 ° C, is shown in TABLE 8. Increases in resistance to Charpy impact are observed compared to without adding the alternating copolymer. However, the increase is not progressive at the 0.5% load level, at 23 ° C. When compared to the values for the upper polyamide, they are exceeded at 23 ° C for all three loads, however only
    Petition 870190112428, of 11/04/2019, p. 34/54
    24/35 at 0.5%, at -30 ° C.
    TABLE 7 Increased resistance to Izod impact from recycled polyamide, combined with E60, measured at 23 ° C and -30 ° C.
    Additive IZOD IMPACT [J / cm (ft-lb / in)]ASTM D256 at 23 ° C at -30 ° C without E60 0.277 (0.52) 0.224 (0.42) (CB) without additive 0.465 (0.87) 0.24 (0.45) (CB) 0.1% E60 0.512 (0.96) 0.539 (1.01) (CB) 0.3% of E60 0.561 (1.05) 0.694 (1.30) (CB) 0.5% E60 0.705 (1.32) 0.742 (1.39) (CB) Superior nylon-6 0.71 (1.33) (CB) 0.246 (0.46) (CB)
    TABLE 8 Increased impact resistance Charpy from recycled polyamide, combined with E60, measured at room temperature (23 ° C) and -30 ° C.
    Additive IMPACT CHARPY ISO-179-2 / 2 (KJ / m 2 ) at 23 ° C at -30 ° C without E60 33.8 24.7 without additive 46.9 19.9 0.1% E60 40.3 23.7 0.3% of E60 48.4 29.2 0.5% E60 40.1 39.4 Prime Nylon-6 32.2 22.3
    [0041] It is appreciated that the addition of polar E60 as an additive can result in increased water absorption from the combined polyamide samples. Water absorption measurements were performed after drying the sample to equilibrium, to ensure that they were dry. The amount of water absorbed
    Petition 870190112428, of 11/04/2019, p. 35/54
    25/35 was determined after 24, 48 and 1'2 hours. As shown in TABLE 9, there is only a small increase in water absorption observed in polyamide samples combined with copolymer E60.
    TABLE 9
    Additive WATER ABSORPTION (%) 24 h 48 h 72 h without E60 1.03 1.48 1.79 without additive 1.02 1.42 1.77 0.1% E60 1.28 1.69 2.24 0.3% of E60 0.88 1.32 1.56 0.5% E60 0.69 1.10 1.97 1% E60 1.09 1.50 1.8 3% E60 0.87 1.38 1.82
    EXAMPLE [0042] In determining the effect of ethylene maleic anhydride (EMA) copolymers on nylon-6 and nylon 6-6, both types of nylon were combined with 30% glass fiber, 1.4% EMA , and a stabilizer package comprising the combination of compounds disclosed in TABLE 2. The combined nylon granules were then molded into ASTM test samples and the following properties were tested: Impacted Izod Impact Resistance, Impacted Izod Impact Not Dented, as well as for the properties of traction, effort in the rupture and effort in the yield. The combination of nylon, fiberglass, EMA and the stabilizer package was performed on a twin screw extruder, with all components added to a collector. According to the illustrative embodiment, the processing melting temperature of the nylon mixture was 260 ° C for the nylon-6.6 compounds and 240 ° C for the nylon-6 compounds. The illustrative results of the analysis of the properties of the combined nylon, in comparison with the
    Petition 870190112428, of 11/04/2019, p. 36/54
    26/35 non-combined nylon, are shown in TABLE 10. The grade of the fiberglass used in the mixture was a high performance E-glass cut wire, with a diameter of 10 μ and a length of 4.5 mm, typically used in combination by extrusion with polyamide resin systems.
    TABLE 10
    Comparison of Properties Physics of Compounds Nylon Formulation(all with 30% E-Glass Fiber *) Nylon-6 without EMA Nylon-6 with E400 Nylon-6 with E60 Tensile Strength (MPa) 94 14 (176 3) 33 16 (162 1) 85 92 (160 9) Elongation by Traction (%) 1 98 (3 70) 2 60 (4 86) 2 94 (5 50) Izod Dentato [J / cm (ft-lb./pol.)l 0.96 (1.80) 0.87 (1.62) 1.23 (2.30) Izod Not Toothed [J / cm (ft-lb./pol.)l 10.95 (20.5) 9.35 (17.5) 12.34 (23.1)
    TABLE 11
    Composition of the Stabilizer as a Function of the Total Weight of the Compound
    Compound % w / w to 100% total Cuprous Iodide 0.01% Potassium iodide 0.09% Irgafos 168 (phosphite) 0.40% Irganox 1098 (hindered phenol) 0.50%
    [0043] In each of the TABLES 12-15 below, except for the first entry, each polymer was combined with the stabilizer composition shown in TABLE 11.
    TABLE 12 - Flow Rate of Nylon-6 Recycled at 235 ° C and 1 kg (g / 10 min)
    Not with- Without 0.1% of 0.3% of 0.5% of 1 of 3% of bino additive E60 E60 E60 E60 E60 13.0 6.2 1.2 0.8 0.4 0.5 1.6
    Petition 870190112428, of 11/04/2019, p. 37/54
    27/35
    TABLE 13 - Tensile Strength of Recycled Nylon-6 (MPa) *
    Not with- Without 0.1% of 0.3% of 0.5% of 1 of 3% of bino additive E60 E60 E60 E60 E60 61.1 78.2 78.5 80.2 79.5 82.0 80.4
    * The values for Superior Nylon are in the range of about 65-71 MPa
    TABLE 14 - Flex module. of Nylon-6 Recycled. (MPa) *
    Not with-bino Without additive 0.1% ofE60 0.3% ofE60 0.5% ofE60 1 ofE60 3% ofE60 1%E400 2385 2632 2689 2749 3016 2867 2866 3000 * Values for Superior Nylon are in the range of about 2600-2800MPa TABLE 15 - Flex Resistance. in the Rup structure of recycled nylon-6 (M Pan) Not combined Without additive 0.1% ofE60 0.3% ofE60 0.5% ofE60 1 ofE60 3% ofE60 1%E400 77.24 102.52 105.70 113.95 121.09 110.78 113.3 119.15
    * The values for Superior Nylon are in the range of about 100-108 MPa
    TABLE 16 [0044] In 0.1% ZeMac E-60 in Nylon 6-6 Superior (Ultramid A34 from
    BASF),. the combined polyamide shows improvement of several. properties.
    Traction Properties Flexional ImpactIzod ImpactCharpy HDT MFI DensityASTM D638 ASTMD790 ASTMD256 ISO-179-2 / 2 ASTMD648 ASTMD1238 ASTMD792 Additive Mó- Voltage Ten- Esdulo in Ren-são force Mó- Tendulo são Temp. -Ambi- 30 ° Temp. -30 ° CAmbi- (KJ / m 6.89 kPa 275 °C e (g / ml)
    Petition 870190112428, of 11/04/2019, p. 38/54
    28/35
    (MPThe) diment(MPa) atBreak (MPa) atRup-ture(%) (MPThe) atBreak (MPa) ente[J / cm(ftlb / in)] C [J / c m (ftlb / p ol)] ent (KJ / m A 2) A 2) (264psi)(° C) 5 kg(g / 10min)not combined 2653 75.4 56.9 33.6 2787 100.8 0.29(0.54)(CB) 0.26(0.48)(CB) 36.00(NB) 33.6(NB) 59.6 142,1 1.14 0.1%from E60 2719 84.8 66.1 13.1 2781 112.3 0.57(1.07)(CB) 0.22(0.42)(CB) 35.0(NB) 35.8(NB) 74.1 21.1 1.14
    MFI - fluidity index, HDT - Thermal Deflection Temperature, NB - without rupture, CB - complete rupture, HB - half rupture
    TABLE 17 [0045] The superior nylon-6 (Ultramid B3S from BASF), combined with E60, shows improvement in the following properties:
    Properties ofTraction Flexional Izod Impact Charpy Impact HDT MFIASTM D638 ASTM D790 ASTM ISO-179-2 / 2 AST ASTMD256 M D123 D648 8 Additive Voltage in Effort Modu- Tension -30 ° C 23 ° C -30 ° C 6.89 235 ° CYield at it at [J / cm (KJ / m A 2 (KJ / m A 2 kPa w / 1to Ruptu- (MPa) Ruptu- (ft- ) ) (264 kg
    Petition 870190112428, of 11/04/2019, p. 39/54
    29/35
    (MPa) ra (%)frog(MPa) lb / in)] psi)(° C) (g / 10min) not with-bino 83.6 12.4 2796.1 113.8 0.25(0.46)(CB) 32.2(NB) 22.3(CB) 62.1 9.65 0.1% ofE60 78.4 11.4 2680.2 105.4 0.20(0.38)(CB) 42.9(NB) 24.4(CB) 59.1 4.34 0.3% ofE60 78.8 14.5 2747.6 106.9 0.25(0.46)(CB) 44.6(NB) 23.9(CB) 55.3 1.73 0.5% ofE60 85.4 15.0 2992.0 121.3 0.33(0.61)(CB) 49.7 (NB) 27.0(CB) 56.5 0.97
    TABLE 18 [0046] Properties of upper nylon-6 (Ultramid B3S from BASF) combined with 30% glass fiber and E60
    Traction Properties Flexional ImpactIzod ImpactCharpy HDTASTM D638 ASTM D790 ASTM D256 ISO-179-2 / 2 ASTMD648 Additive Module (MPa) Yield Stress (MPa) Voltage onRup- Effort inRup- Module (MPa) Voltage onRup- Yield Stress (MPa) Temp.Environment [J / cm 30 ° C[J / cm Temp. Environment (KJ / m A -30 ° C (KJ / m Λ 2) 6.89 kPa(264psi)
    Petition 870190112428, of 11/04/2019, p. 40/54
    30/35
    ture(MPa) ture(%)ture(MPa)(ftlb / in)] (ftlb / po l)] 2)(° C) 0.3% inE60 5586 78.8 78.6 3.17 7263 112.6 24.6 0.60(1.13)(CB) 0.41(0.77)(CB) 6.24(CB) 5.80(CB) 198,8 0.5% inE60 5547 82.9 82.5 3.34 6744 122.9 130.9 0.60(1.13)(CB) 0.39(0.73)(CB) 7.09(CB) 7.62(CB) 192,3
    TABLE 19 [0047] Properties of upper 6.6 nylon (BASF Ultramid A-34) with
    30% fiberglass.
    30% GF in Nylon6-6(UltramidA34) Traction Properties ImpactIzod Charpy Impact Charpy ASTM D638 ASTMD790 ASTM D256 ISO-179-2 / 2 Additive Ten module Tensile Strength in Effort ofTra Traction Effort (Alon-_ Module Flex resistance. at 23 ° C -30 ° C 23 ° C 30 ° C
    Petition 870190112428, of 11/04/2019, p. 41/54
    31/35
    are Yield tion inRupture Rupture)Break(M (MPa) (MP (%) (M (MPa) [J / cm [J / cm (KJ / (KJ /Pan)The)Pan)(ft- (ft- m A 2) m A 2) lb / in)] lb / in)] 0.3% 654 97.1 97, 2.86 747 140.6 0.50 0.38 5.50 5.68 in 871(0.94) (0.71) (CB) (CB) E60 (CB) (CB) 0.5% 572 102.8 102 3.36 687 144.6 0.49 0.36 6.79 6.82 in 3, 53(0.93) (0.67) (CB) (CB) E60 (CB) (CB)
    EXAMPLE [0048] According to this example, the effect of reacting recycled nylon with varied maleic anhydride ethylene (EMA) copolymers was evaluated. According to at least one illustrative embodiment, the recycled nylon was processed with the EMA as discussed in more detail below, and the reaction product was evaluated for resistance to anti-freeze degradation due to hydrolysis and impact resistance, compared to untreated recycled nylon. The results indicate that the processing of nylon and other polyamides with EMA can improve both the resistance to anti-freeze degradation due to the hydrolysis properties and the resistance to the impact of the composition on non-combined polyamides.
    [0049] The combined nylon-6 exhibited an increase in the resistance to toothed Izod impact of 1.602 J / cm (3 ft-lb / in) for the non-combined nylon-6 to between 2.02 J / cm and 2.52 J / cm (3.78 ft-lb / in and 4.72 ft-lb / in). In addition to the increase in resistance
    Petition 870190112428, of 11/04/2019, p. 42/54
    32/35 due to antifreeze degradation due to hydrolysis and impact resistance, it is expected that the combined nylon will show an increase in tear resistance, a reduction in slow deformation, and a decrease in the coefficient of linear thermal expansion.
    EXAMPLE [0050] The properties of the various mixtures of nylon-6 (PA6) (as shown in TABLE 20) were tested with and without the copolymer of ethylene maleic anhydride (EMA), to determine the effect that the treatment of nylon-6 with the EMA has on the physical characteristics of nylon-6. When carrying out the treatment of nylon-6, the mixture of nylon-6 / EMA was combined in a corrective double screw extruder (Leistritz, ZSE, 27 HP, D = 40 mm), and then injection molded with a molding machine by injection (Cincinnati Milacron-Fanuc, Roboshot, 55USTON, 0.06 L (1.95 oz)) in standard traction and impact bars. The combination conditions in which nylon-6 was mixed are shown in TABLE 21. In addition, the injection molding conditions are shown in TABLE 22. In addition, before mixing, all nylon-6 was pre-dried at 85 ° Ç. during the night. The properties of the various mixtures of nylon-6 with the EMA are shown in TABLES 12-15.
    TABLE 20
    Components of the Nylon Blend
    Mixture Polymer Content [hr] Load Content [hr] EMA content [hr] Nylon-6 100 0 0 Nylon-6 + EMA ** 100 0 10 Nylon-6 + EMA 100 0 1 Nylon-6 + GF 67 33 0 Nylon-6 + GF + EMA ** 70 30 10 Nylon-6 + GF + EMA * 70 30 1
    TABLE 21 - PA6 Combination Conditions
    Petition 870190112428, of 11/04/2019, p. 43/54
    33/35
    Temp. [° C] RPM Torque [%] Pressure [kPa (psi)] Food [%] Nylon-6 + GF 200-230-240 50 60 551.58 (80) 20 Nylon-6 + GF + EMA 200-230-240 65 30 2137.38 20 Nylon-6 + EMA 200-230-240 65 30 2413.17 25 Nylon-6 200-220-230 50 40 206.84 (30) 25
    TABLE 22
    Injection Molding Conditions
    Temp. Barrel [° C (° F)] Temp. Mold [° C (° F)] Cooling Time[s] Nylon-6 + GF 226.67-240.56 (440-465) 65.56 (150) 30 Nylon-6 + GF + EMA 226.67-240.56 (440-465) 65.56 (150) 30 Nylon-6 + EMA 226.67-240.56 (440-465) 65.56 (150) 30 Nylon-6 226.67-240.56 (440-465) 65.56 (150) 30
    GF - fiberglass [0051] All samples were tested for impact properties according to ASTM D256, with a 2.71 J (2 lb-ft) pendulum, and tensile properties according to ASTM D638 in a crosshead speed of 50 mm / min. In determining these properties, the Stress Module (as shown in TABLE 1) indicates the force to bend. It will be appreciated that as the results increase, the stiffness of the sample increases, while as the results decrease, the flexibility increases. As shown in TABLE 1, the stress at break was calculated as a percentage, where the high numbers indicate the ability to stretch before the samples break. The yield effort, shown in TABLE 1, was calculated for each sample, indicating the strength at the peak before the reduction. In other words, as the material stretches, it requires more force to stretch, until it reaches a bottleneck, where the sample decreases enough to require less force to stretch. In general, it will be appreciated that rigid materials do not narrow. Furthermore, as shown in TABLE
    Petition 870190112428, of 11/04/2019, p. 44/54
    34/35 which indicates the effort in yield, showing the percentage of change in length, where a larger value indicates that the sample must stretch longer before it finally breaks. Finally, the samples were tested for impact resistance, which is the force required to break the sample. This is a high speed impact test, in which the higher the number, the greater the impact resistance. Each of these tests was run 4-5 times and the average reported.
    EXAMPLE [0052] 40 g of nylon-6 granules and 4 g of ZeMac® E-60 (E60) were mixed to melt in a Brabender lab-sized mixing vessel, preheated to 245 ° C, and mixed until all the granules were melted and the mixture well melted. At a ratio of a and above 10%, the ethylene maleic anhydride copolymer did not flow, and appeared to crosslink the polyamide.
    EXAMPLE [0053] Molded draw bars are immersed in radiator fluid (commercially available Prix® Ready-to-Use Pre-mixed Antifreeze) at 125 ° C for up to 3000 hours (500 hour intervals). A group of 5 samples for each formulation is removed from the test fluid at 500 hour intervals, washed with water, dried by rubbing and tested for tensile properties. Resistance to hydrolysis is demonstrated by comparing the tensile properties of treated bars with untreated bars.
    [0054] Although various modalities of the methods of producing compositions and the methods of using the compositions have been described in considerable detail in this document, the modalities are merely offered by way of non-limiting examples of the invention described here. Many variations and modifications to the modalities described in this document will be apparent considering the disclosure. It will, therefore, be understood that several changes and modifications can be made, and equivalents can replace its elements, without leaving the scope
    Petition 870190112428, of 11/04/2019, p. 45/54
    35/35 of the invention. In fact, this disclosure is not intended to be exhaustive or limit the scope of the invention. The scope of the invention is to be defined by the appended claims, and their equivalents.
    [0055] Furthermore, in the description of the representative modalities, the disclosure may have presented a method and / or a process as a particular sequence of steps. However, to the extent that the method or process is not based on the particular order of steps described in this document, the method or process should not be limited to the particular sequence of steps described. It will be appreciated that other sequences of steps may be possible. Therefore, the particular order of the steps disclosed here should not be interpreted as limitations on the claims. In addition, claims directed to a method and / or process should not be limited to the performance of its steps in the written order, and it will readily be appreciated that the sequences can be varied and still remain within the spirit and scope of the present invention.
    [0056] It is therefore intended that the invention includes, and this description and the appended claims will include, all apparent modifications and changes based on this disclosure.
    Petition 870190112428, of 11/04/2019, p. 46/54
    1/4
    权利要求:
    Claims (22)
    [1]
    1. Combined polyamide CHARACTERIZED by the fact that it is produced by a process that comprises combining a polyamide mixture comprising a polyamide and an olefin-maleic anhydride copolymer, at a processing temperature, in which the olefin-maleic anhydride polymer is copolymerized from maleic anhydride and an olefin selected from the group consisting of ethylene, propylene, isobutylene, butene-1, octene, butadiene, isoprene, hexene, dodecene, dodecene-1 and tetradecene, in which the olefin-anhydride copolymer maleic has a maleic anhydride to olefin molar ratio of about 1:10 to about 10: 1, and the olefin-maleic anhydride copolymer is present in a concentration of about 0.01% to about 5% w / p of the combined polyamide.
    [2]
    2. Combined polyamide according to claim 1, CHARACTERIZED by the fact that the polyamide is selected from the group consisting of nylon-6, nylon 6-6, a copolymer of nylon-6 and nylon 6-6, nylon -9, nylon-10, nylon-11, nylon-12, nylon 6-10, aromatic polyamides, elastomeric polyamides and mixtures thereof.
    [3]
    3. Combined polyamide according to claim 1,
    CHARACTERIZED by the fact that the olefin is ethylene.
    [4]
    4. Combined polyamide according to claim 3,
    CHARACTERIZED by the fact that the olefin-maleic anhydride polymer has a 1: 1 ethylene to maleic anhydride ratio.
    [5]
    5. Combined polyamide, according to claim 1, CHARACTERIZED by the fact that the olefin-maleic anhydride polymer has a molecular weight of about 300 to 1,000,000.
    [6]
    6. Combined polyamide according to claim 5,
    Petition 870190112428, of 11/04/2019, p. 47/54
    2/4
    CHARACTERIZED by the fact that the olefin polymer-maleic anhydride has a molecular weight of about 60,000 to about 400,000.
    [7]
    7. Combined polyamide, according to claim 1, CHARACTERIZED by the fact that the olefin polymer-maleic anhydride is present in a concentration of about 0.01% to about 0.5%, about 0.5% about 1.0%, about 1.0% to about 1.5% or 1.5% to about 3.0% w / w.
    [8]
    8. Combined polyamide according to claim 1, CHARACTERIZED by the fact that the processing temperature is about 230 ° C to about 300 ° C.
    [9]
    9. Combined polyamide according to claim 1, CHARACTERIZED by the fact that the polyamide mixture additionally comprises a glass fiber.
    [10]
    10. Combined polyamide according to claim 1, CHARACTERIZED by the fact that the polyamide mixture additionally comprises one or more stabilizing agents.
    [11]
    11. Composition of thermoplastic pelletizable polymer CHARACTERIZED by the fact that it comprises:
    (a) a polyamide, and (b) a polymer polymerized from maleic anhydride and an olefin;
    wherein the polyamide and the polymer are combined;
    wherein said olefin is selected from the group consisting of ethylene, propylene, isobutylene, butene-1, octene, butadiene, isoprene, hexene, dodecene, dodecene-1 and tetradecene;
    wherein the polymer polymerized from maleic anhydride and an olefin has a maleic anhydride to olefin molar ratio of about 1:10 to about 10: 1; and wherein the polymer polymerized from maleic anhydride and an olefin
    Petition 870190112428, of 11/04/2019, p. 48/54
    3/4 is present in a concentration of about 0.01% to about 5% w / w of the polymer composition.
    [12]
    12. Composition of cross-linked polymer CHARACTERIZED by the fact that it comprises:
    (a) a polyamide, and (b) a polymer polymerized from maleic anhydride and an olefin;
    wherein the polyamide and the polymer are combined at a processing temperature, where the processing temperature is sufficient to promote cross-linking;
    wherein said olefin is selected from the group consisting of ethylene, propylene, isobutylene, butene-1, octene, butadiene, isoprene, hexene, dodecene, dodecene-1 and tetradecene;
    wherein the polymer polymerized from maleic anhydride and an olefin has a maleic anhydride to olefin molar ratio of about 1:10 to about 10: 1; and wherein the polymer polymerized from maleic anhydride and an olefin is present in a concentration of about 0.01% to about 5% w / w of the polymer composition.
    [13]
    13. Method for preparing a combined polyamide CHARACTERIZED by the fact that it comprises:
    combine a polyamide mixture comprising a polyamide and an olefin-maleic anhydride copolymer at a processing temperature, wherein said olefin is selected from the group consisting of ethylene, propylene, isobutylene, butene-1, octene, butadiene, isoprene, hexene, dodecene, dodecene-1 and tetradecene;
    wherein the olefin-maleic anhydride copolymer has a maleic anhydride to olefin molar ratio of about 1:10 to about 10: 1; and
    Petition 870190112428, of 11/04/2019, p. 49/54
    4/4 wherein the olefin-maleic anhydride copolymer is present in a concentration of about 0.01% to about 5% w / w of the combined polyamide.
    [14]
    14. Method according to claim 13, CHARACTERIZED by the fact that the olefin is ethylene.
    [15]
    15. Method according to claim 14, CHARACTERIZED by the fact that the olefin-maleic anhydride copolymer has a molecular weight of about 60,000 to about 400,000.
    [16]
    16. Method, according to claim 13, CHARACTERIZED by the fact that the polyamide is a nylon.
    [17]
    17. Method according to claim 14, CHARACTERIZED by the fact that the olefin-maleic anhydride copolymer has an ethylene to maleic anhydride ratio of 1: 1.
    [18]
    18. Method according to claim 17, CHARACTERIZED by the fact that the olefin-maleic anhydride copolymer has a molecular weight of about 300 to 1,000,000.
    [19]
    19. Method, according to claim 17, CHARACTERIZED by the fact that the olefin-maleic anhydride copolymer has a concentration of about 0.01% to about 0.5%, about 0.5% to about 1.0%, about 1.0% to about 1.5% or 1.5% to about 3.0% w / w.
    [20]
    20. Method according to claim 13, CHARACTERIZED by the fact that the processing temperature is about 230 ° C to about 300 ° C.
    [21]
    21. Method according to claim 13, CHARACTERIZED by the fact that the polyamide mixture additionally comprises a glass fiber.
    [22]
    22. The method of claim 13, characterized by the fact that the polyamide mixture additionally comprises one or more stabilizing agents.
    Petition 870190112428, of 11/04/2019, p. 50/54
    1/1
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112013003774B1|2020-04-22|combined polyamide comprising polyamide and an olefin-maleic anhydride copolymer, thermoplastic pelletizable polymer composition, crosslinked polymer composition and method for preparing said combined polyamide
    KR102194403B1|2020-12-24|Impact-modified polyamide compositions
    JP6328554B2|2018-05-23|Use of polyamide chain extension compounds as stabilizers
    JP2004352794A|2004-12-16|Polyamide composition
    BRPI0807187A2|2014-05-27|POLYAMIDE AND LACTIC ACID-BASED COMPOSITE MATERIAL, MANUFACTURING PROCESS AND USE
    JP6261575B2|2018-01-17|Olefin-maleic anhydride copolymer composition and method of use thereof
    KR101472650B1|2014-12-15|High-viscosity polyamide composition
    Kristofic et al.2012|Compatibilisation of PP/PA blends
    KR20210102934A|2021-08-20|polyamide composition
    同族专利:
    公开号 | 公开日
    BR112013003774A2|2017-10-24|
    PT2606083T|2018-08-03|
    ES2682058T3|2018-09-18|
    JP6218604B2|2017-10-25|
    AR082719A1|2012-12-26|
    MY179520A|2020-11-09|
    IL224762A|2018-04-30|
    KR20130100286A|2013-09-10|
    US9353262B2|2016-05-31|
    WO2012024268A1|2012-02-23|
    HUE040349T2|2019-03-28|
    EP2606083B1|2018-06-27|
    JP2014503003A|2014-02-06|
    TWI529212B|2016-04-11|
    EP2606083A1|2013-06-26|
    CN103261271A|2013-08-21|
    PL2606083T3|2018-12-31|
    SG188510A1|2013-04-30|
    RU2013111836A|2014-09-27|
    EP2606083A4|2014-05-14|
    US20130150517A1|2013-06-13|
    KR101822547B1|2018-01-26|
    CA2808431A1|2012-02-23|
    CN103261271B|2016-11-09|
    RU2586324C2|2016-06-10|
    TW201211156A|2012-03-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4351931A|1961-06-26|1982-09-28|E. I. Du Pont De Nemours And Company|Polyethylene copolymers|
    US3375219A|1964-11-23|1968-03-26|Gulf Oil Corp|Pigmenting polycarbonamide by means of an ethylene copolymer carrier resin|
    US3388186A|1965-03-02|1968-06-11|Allied Chem|Carboxy terminated graft copolymers of amino-carboxylic acids or lactams on acrylic copolymers|
    US3845163A|1966-01-24|1974-10-29|Du Pont|Blends of polyamides and ionic copolymer|
    US3465059A|1966-11-28|1969-09-02|Allied Chem|Carboxy terminated graft copolymers of carbonamide group on acrylic copolymers|
    DE1769515C3|1968-06-05|1979-05-03|Veba-Chemie Ag, 4660 Gelsenkirchen- Buer|Moldings and coatings made from thermosetting plastics|
    US3668274A|1970-09-10|1972-06-06|Rohm & Haas|Acrylic modifiers for polycarbonamides|
    US4174358B1|1975-05-23|1992-08-04|Du Pont|
    US4448956A|1983-05-10|1984-05-15|The General Tire & Rubber Company|Polymerization of lactam with graft copolymer promoter|
    CA1290878C|1986-02-15|1991-10-15|Kentaro Mashita|Thermoplastic resin composition|
    JPS62250053A|1986-04-22|1987-10-30|Mitsubishi Petrochem Co Ltd|Polyamide resin composition|
    US5112908A|1986-12-23|1992-05-12|E. I. Du Pont De Nemours And Company|Tough polyamide compositions having high melt flow for complex moldings|
    BR8907868A|1987-12-14|1991-11-12|Du Pont|PERFECTED NAILON COMPOSITES FOR BLOW MOLDING|
    NL8801593A|1988-06-23|1990-01-16|Stamicarbon|POLYAMIDE COMPOSITIONS.|
    US5244971A|1991-07-22|1993-09-14|Exxon Chemical Patents Inc.|Graft polymers for use in engineering thermoplastic blends|
    DE4223864A1|1992-07-20|1994-01-27|Bayer Ag|Polyamide mixts. with scrap polyamide-polyolefin cpd. film - also contain special compatibiliser, esp. e.g. ethylene@]- maleic anhydride] copolymer or ethylene@]-butyl acrylate]-glycidyl acrylate] copolymer|
    US5346963A|1993-04-28|1994-09-13|The Dow Chemical Company|Graft-modified, substantially linear ethylene polymers and methods for their use|
    DE69412605T2|1993-05-28|1999-04-22|Du Pont|STAGE FEEDING METHOD FOR MIXING POLYMERS|
    DE4425615A1|1994-07-20|1996-01-25|Basf Ag|Recycled polyamide molding compounds for blow molding applications|
    AT185827T|1994-08-29|1999-11-15|Cabot Corp|UNIVERSAL PRE-MIX|
    SG66461A1|1997-05-16|1999-07-20|Mitsui Chemicals Inc|Polyamide resin composition and process for producing the same|
    JP3361249B2|1997-08-08|2003-01-07|アトフィナ・ジャパン株式会社|Method for producing thermoplastic resin composition and molded article|
    AU2003225961A1|2002-03-21|2003-10-08|Advanced Plastics Technologies, Ltd.|Compatibilized polyester/polyamide blends|
    US20060148988A1|2004-10-06|2006-07-06|Chou Richard T|Miscible blends of ethylene copolymers with improved temperature resistance|
    CA2483196A1|2002-05-23|2003-12-04|E. I. Du Pont De Nemours And Company|Toughened thermoplastic polyamide compositions|
    US20040242737A1|2003-04-14|2004-12-02|Georgios Topulos|Polyamide composition for blow molded articles|
    DE102004059241A1|2004-12-08|2006-06-14|Basf Ag|Impact-modified thermoplastic molding compositions based on vinylaromatic copolymers and polyamide|
    RU2419634C2|2005-12-16|2011-05-27|Эксонмобил Кемикэл Пейтентс Инк.|Substance for improving processing characteristics for elastomeric mixtures|
    US20070154697A1|2005-12-30|2007-07-05|Cossement Marc R|Two-part sizing composition for reinforcement fibers|
    FR2912150B1|2007-02-06|2009-04-10|Arkema France|FLEXIBLE THERMOPLASTIC COMPOSITION WITH ENHANCED OILS AND USE OF SUCH A COMPOSITION|
    CN101230193B|2007-12-28|2010-08-18|深圳市科聚新材料有限公司|High-strength basalt fibre reinforced nylon composition and preparation method thereof|
    RU2408630C2|2008-08-25|2011-01-10|Государственное научное учреждение "Институт механики металлополимерных систем имени В.А. Белого Национальной академии наук Беларуси"|Method of preparing mixed polyamide composition|
    TWI529212B|2010-08-18|2016-04-11|Vertellus Specialties Inc|Compositions, methods and articles produced by compounding polymides with olefin-maleic anhydride polymers|
    RU2648910C2|2012-07-06|2018-03-28|ВЕРТЕЛЛУС ХОЛДИНГЗ ЭлЭлСи|Olefin-maleic anhydride copolymer compositions and uses thereof|
    EP2970664A4|2013-03-15|2016-11-09|Vertellus Specialties Inc|Impact-modified polyamide compositions|TWI529212B|2010-08-18|2016-04-11|Vertellus Specialties Inc|Compositions, methods and articles produced by compounding polymides with olefin-maleic anhydride polymers|
    RU2648910C2|2012-07-06|2018-03-28|ВЕРТЕЛЛУС ХОЛДИНГЗ ЭлЭлСи|Olefin-maleic anhydride copolymer compositions and uses thereof|
    US20150203682A1|2012-07-26|2015-07-23|Invista North America S.A.R.L.|Thermoplastic composition for use inhigh impact applications|
    US9388312B2|2012-07-26|2016-07-12|Invista North America S.A.R.L.|Thermoplastic composition for use in high impact applications|
    US9109114B2|2012-09-27|2015-08-18|E I Du Pont De Nemours And Company|Polyamides having improved anti-delamination|
    US9193865B2|2012-09-27|2015-11-24|E I Du Pont De Nemours And Company|Polyamides having improved anti-delamination|
    US9023903B2|2012-09-27|2015-05-05|E I Du Pont De Nemours And Company|Reinforced polyamides having improved anti-delamination|
    CN103013097A|2012-11-22|2013-04-03|上海普利特复合材料股份有限公司|Ultra high-toughness glass fiber reinforcement nylon 6 composite material and preparation method thereof|
    CN102993744A|2012-11-22|2013-03-27|上海普利特复合材料股份有限公司|Glass fiber reinforced nylon 66 composite with super toughness and preparation method thereof|
    EP2970664A4|2013-03-15|2016-11-09|Vertellus Specialties Inc|Impact-modified polyamide compositions|
    FR3003575B1|2013-03-22|2015-03-27|Arkema France|NANOSTRUCTURED THERMOPLASTIC COMPOSITION OF POLYOLEFIN TYPE GRAFFEE POLYAMIDE|
    CN104086960B|2013-04-01|2016-04-27|中国石油化工股份有限公司|A kind of polylactic acid composition and preparation method thereof|
    CN105283508B|2013-06-20|2018-05-25|旭化成株式会社|Amilan polyamide resin composition and formed body|
    CN105086392B|2014-05-08|2017-05-31|中国石油化工股份有限公司|A kind of polydactyl acid and preparation method thereof|
    KR20170054382A|2014-07-14|2017-05-17|버텔러스 홀딩스 엘엘씨|Modification of engineering plastics using olefin-maleic anhydride copolymers|
    JP5954518B1|2014-11-19|2016-07-20|三菱瓦斯化学株式会社|Polyamide resin composition, molded product, and method for producing molded product|
    CN104788948A|2015-02-09|2015-07-22|上海金发科技发展有限公司|Polyamide composition suitable for extrusion molding, blow molding and foaming multi uses and preparation method thereof|
    CN104817841B|2015-02-09|2017-08-25|上海金发科技发展有限公司|A kind of daiamid composition and preparation method thereof|
    EP3260500A4|2015-02-20|2018-01-31|Asahi Kasei Kabushiki Kaisha|Polyamide resin composition, method for producing polyamide resin composition, and molded article|
    EP3439796A4|2016-04-04|2020-02-12|PPG Industries Ohio, Inc.|Fiberglass containing composites with improved retained glass fiber length, impact strength, and tensile properties|
    WO2018031564A1|2016-08-08|2018-02-15|Ticona Llc|Thermally conductive polymer composition for a heat sink|
    CN106751806A|2016-12-29|2017-05-31|上海普利特复合材料股份有限公司|A kind of reactive compatibilizer prepares the alloy material for reclaiming carpet PA66 resins and recycled PET|
    CN106751804B|2016-12-29|2019-11-19|上海普利特复合材料股份有限公司|A kind of high-performance composite materials as prepared by recycling waste carpet PA66 material and preparation method thereof|
    CN106751783A|2016-12-29|2017-05-31|上海普利特复合材料股份有限公司|High visocity nylon 6 composite prepared by a kind of melting extrusion chain extending reaction and preparation method thereof|
    WO2018185971A1|2017-04-07|2018-10-11|新生化学工業株式会社|Gasket for alkaline dry battery, and method for producing same|
    CN108047707A|2017-12-28|2018-05-18|南京聚隆科技股份有限公司|A kind of high-strength wearable injection-level nylon and preparation method|
    AU2019306552A1|2018-07-18|2021-02-18|INVISTA TextilesLimited|A modified polyamide fiber and articles made thereof|
    EP3914649A1|2019-10-24|2021-12-01|INVISTA TextilesLimited|Polyamide compositions and articles made therefrom|
    WO2021229922A1|2020-05-14|2021-11-18|東洋紡株式会社|Biaxially stretched polyamide film|
    法律状态:
    2018-03-13| B25A| Requested transfer of rights approved|Owner name: VERTELLUS HOLDINGS LLC (US) |
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-02-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-04-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US37481710P| true| 2010-08-18|2010-08-18|
    US201161485826P| true| 2011-05-13|2011-05-13|
    US201161493058P| true| 2011-06-03|2011-06-03|
    PCT/US2011/047872|WO2012024268A1|2010-08-18|2011-08-16|Compositions, methods and articles produced by compounding polyamides with olefin-maleic anhydride polymers|
    [返回顶部]