WO2011072203A2 - Compositions de polyamide résistantes au sel - Google Patents

Compositions de polyamide résistantes au sel Download PDF

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Publication number
WO2011072203A2
WO2011072203A2 PCT/US2010/059842 US2010059842W WO2011072203A2 WO 2011072203 A2 WO2011072203 A2 WO 2011072203A2 US 2010059842 W US2010059842 W US 2010059842W WO 2011072203 A2 WO2011072203 A2 WO 2011072203A2
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WO
WIPO (PCT)
Prior art keywords
polyamide composition
repeat units
formula
mole percent
semi
Prior art date
Application number
PCT/US2010/059842
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English (en)
Other versions
WO2011072203A3 (fr
Inventor
Anna Kutty Mathew
Original Assignee
E. I. Du Pont De Nemours And Company
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Publication date
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Publication of WO2011072203A2 publication Critical patent/WO2011072203A2/fr
Publication of WO2011072203A3 publication Critical patent/WO2011072203A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass

Definitions

  • the present invention relates to the field of polyamide compositions having improved salt resistance.
  • thermoplastics and thermosets are used extensively in automotive vehicles and for other purposes. They are light and relatively easy to fashion into complex parts, and are therefore preferred instead of metals in many instances.
  • SSCC salt stress (induced) corrosion cracking
  • Polyamides such as polyamide 6,6, polyamide 6, polyamide 6,10 and polyamide 6,12 have been made into and used as vehicular parts and other types of parts. While it has been reported that polyamides 6,10 and 6,12 are more resistant to SSCC (see for instance Japanese Patent 3271325B2), all of these polyamides are prone to SSCC in such uses, because for instance, various sections of vehicles and their components are sometimes exposed to salts, for example salts such as sodium chloride or calcium chloride used to melt snow and ice in colder climates. Corrosion of metallic parts such as fittings and frame components made from steel and various iron based alloys in contact with water and road salts can also lead to formation of salts. These salts, in turn, can attack the polyamide parts making them susceptible to SSCC. Thus polyamide compositions with better resistance to SSCC are desired.
  • US Patent 4,076,664 discloses a terpolyamide resin that has favorable resistance to zinc chloride.
  • European patent application 0272503 discloses a molding polyamide resin comprising poiy(m-xylylenesebacamide) (PA MXD10) and a crystalline polyamide having a melting point about 20-30 °C higher than that of PA MXD10.
  • US 6,841 ,651 discloses a polyamide resin including a diamine component comprising 70 mol % or more of m-xylylene diamine and a dicarboxylic acid component comprising 70 mol % or more of a C4-C20 aliphatic dicarboxylic acid.
  • a polyamide composition comprising at least one semi- aromatic copolyamide, said semi-aromatic copolyamide consisting essentially of 40 to 60 mole percent repeat units of the formula
  • Ar is a meta-substituted benzene ring.
  • a molded article comprising the polyamide composition disclosed above.
  • (meth)acrylic and “(meth)acrylate” encompass acrylic acid and methacrylic acid, and esters of acrylic acid and methacrylic acid, respectively.
  • melting points and glass transitions are as determined with differential scanning calorimetry (DSC) at a scan rate of 10 "C/min in the first heating scan, wherein the melting point is taken at the maximum of the endothermic peak and the glass transition, if evident, is considered the mid-point of the change in enthalpy.
  • DSC differential scanning calorimetry
  • the polyamide composition disclosed herein comprises at least one semi- aromatic copolyamide, said semi-aromatic copolyamide consisting essentially of 40 to 60 mole percent repeat units of the formula
  • Ar is a meta-substituted benzene ring.
  • said copolyamide has a melting point equal to or less than 225 °C.
  • Preferred copolyamides are wherein said semi-aromatic copolyamide has about 45 to about 55 mole percent repeat units of formula (1 ) and about 45 to about 55 mole percent repeat units of formula (II).
  • the semi-aromatic copolyamide is formed from polycondensation of a mixture of adipic acid, hexamethylene diamine, and meta-xylylene diamine
  • aliphatic dicarboxylic acids and aliphatic diamines may be present in the semi-aromatic copolyamide, but only to the extent that they do not affect the salt resistant properties of the copolymer. For instance in one embodiment other aliphatic dicarboxylic acids and aliphatic diamines may be present at about 0.1 to 3 weight percent based on the total mole percent of diamine and/or dicarboxylic acid.
  • dicarboxylic acid monomers include decanedioic acid (C10), dodecanedioic acid (C12), and tetradecanedioic acid (C14).
  • Other aliphatic diamines include decamethylene diamine, and dodecamethylene diamine.
  • PA semi-aromatic copolyamides
  • HMD hexamethylene diamine or 6 when used in combination with a
  • the copolyamide may be prepared by any means known to those skilled in the art, such as in a batch process using, for example, an autoclave or using a continuous process. See, for example, Kohan, M.l. Ed. Nylon Plastics Handbook, Hansen Kunststoff, 1995; pp. 13-32. Additives such as lubricants, antifoaming agents, and end-capping agents may be added to the polymerization mixture.
  • the polyamide composition may optionally comprise additives including additives selected from the group consisting of polymeric tougheners, plasticizers, and reinforcing agents.
  • the polyamide composition optionally, comprises 0 to 50 weight percent of a polymeric toughener comprising a reactive functional group and/or a metal salt of a carboxylic acid.
  • the molded or extruded thermoplastic article comprises 2 to 20 weight percent polymeric toughener selected from the group consisting of: a copolymer of ethylene, giycidyl (meth)acrylate, and optionally one or more (meth)acrylate esters; an ethylene/a-olefin or ethylene/a- olefin/diene copolymer grafted with an unsaturated carboxylic anhydride; a copolymer of ethylene, 2-isocyanatoethyl (meth)acrylate, and optionally one or more (meth)acrylate esters; and a copolymer of ethylene and (meth)acrylic acid reacted with a Zn, Li, Mg or Mn compound to form the corresponding ionomer.
  • polymeric toughener selected from the group consisting of: a copolymer of ethylene, giycidyl (meth)acrylate, and optionally one or more (meth)acrylate esters;
  • the polyamide composition may optionally comprise at least one plasticizer.
  • the plasticizer will preferably be miscible with the copolyamide.
  • suitable plasticizers include sulfonamides, preferably aromatic sulfonamides such as benzenesulfonamides and toluenesulfonamides.
  • Suitable sulfonamides include W-alkyl benzenesulfonamides and toluenesulfonamides, such as N-butylbenzenesulfonamide, N-(2- hydroxypropyl)benzenesulfonamide, N-ethyi-o-toluenesulfonamide, W-ethyl-p- toluenesulfonamide, o-toluenesulfonamide, p-to!uenesulfonamide, and the like.
  • Preferred are /V-butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, and N- ethyl-p-toluenesutfonamide.
  • the plasticizer may be incorporated into the composition by melt-blending the polymer with plasticizer and, optionally, other ingredients, or during polymerization. If the plasticizer is incorporated during polymerization, the copolyamide monomers are blended with one or more plasticizers prior to starting the polymerization cycle and the blend is introduced to the
  • the plasticizer can be added to the reactor during the polymerization cycle.
  • the plasticizer When used, the plasticizer will be present in the composition in about 1 to about 20 weight percent, or more preferably in about 6 to about 18 weight percent, or yet more preferably in about 8 to about 15 weight percent, wherein the weight percentages are based on the total weight of the composition.
  • the poiyamide composition may optionally comprise 0 to about 60 weight percent, and preferably about 10 to 60 weight percent, and 15 to 50 weight percent, of one or more reinforcement agents.
  • the reinforcement agent may be any filler, but is preferably selected from the group consisting of calcium carbonate, glass fibers with circular cross-section, glass fibers with noncircular cross-section, glass flakes, glass beads, carbon fibers, talc, mica, wollastonite, calcined clay, kaolin, diatomite, magnesium sulfate, magnesium silicate, barium sulfate, titanium dioxide, sodium aluminum carbonate, barium ferrite, potassium titanate and mixtures thereof. Glass fibers, glass flakes, talc, and mica are preferred reinforcement agents.
  • the poiyamide composition may optionally comprise additional additives such as thermal, oxidative, and/or light stabilizers; colorants; lubricants; mold release agents; and the like.
  • additional additives such as thermal, oxidative, and/or light stabilizers; colorants; lubricants; mold release agents; and the like.
  • additives can be added according to the desired properties of the resulting material, and the control of these amounts versus the desired properties is within the knowledge of the skilled artisan.
  • the poiyamide composition is a mixture by melt-blending, in which all polymeric ingredients are adequately mixed, and all non-polymeric ingredients are adequately dispersed in a polymer matrix.
  • Any melt-blending method may be used for mixing polymeric ingredients and non-polymeric ingredients of the present invention.
  • polymeric ingredients and non-polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches.
  • the present invention relates to a method for
  • an article by shaping the polyamide composition of the invention.
  • articles are films or laminates, automotive parts or engine parts or electrical/electronics parts.
  • shaping it is meant any shaping technique, such as for example extrusion, injection molding, thermoform molding, compression molding or blow molding.
  • the article is shaped by injection molding or blow molding.
  • the molded or extruded thermoplastic articles disclosed herein may have application in many vehicular components that meet one or more of the following requirements: high impact requirements; significant weight reduction (over conventional metals, for instance); resistance to high temperature; resistance to oil environment; resistance to chemical agents such as coolants and road salts; and noise reduction allowing more compact and integrated design.
  • Specific molded or extruded thermoplastic articles are selected from the group consisting of charge air coolers (CAC); cylinder head covers (CHC); oil pans; engine cooling systems, including thermostat and heater housings and coolant pumps; exhaust systems including mufflers and housings for catalytic converters; air intake manifolds (AIM); and timing chain belt front covers.
  • thermoplastic articles disclosed herein are selected from the group consisting of pipes for transporting liquids and gases, inner linings for pipes, fuel lines, air break tubes, coolant pipes, air ducts, pneumatic tubes, hydraulic houses, cable covers, cable ties, connectors, canisters, and push-pull cables.
  • melting points were as determined with DSC at a scan rate of 10 °C/min in the first heating scan, wherein the melting point is taken at the maximum of the endothermic peak.
  • Inherent Viscosity Inherent Viscosity (IV) was measured on a 0.5% solution of copolyamide in m-cresol at 25 °C.
  • Copolyamides obtained from multiple preparation batches (2 to 3 batches) were cube blended, dried and then injection molded into test bars.
  • the tensile and flexural properties were measured as per ASTM D638 and ASTM D790 test procedures, respectively. Yield stress was measured using 115 mm (4.5 in) long and 3.2 mm (0.13 in) thick type IV tensile bars per ASTM D638-02a test procedure with a crosshead speed of 50 mm/min (2 in/min).
  • Flexural modulus was measured using 3.2 mm (0.13 in) thick test pieces per ASTM D790 test procedure with a 50 mm (2 in) span, 5 mm (0.2 in) load and support nose radii and 1.3 mm/min (0.05 in/min) crosshead speed.
  • the method for stress crack resistance is based on ASTM D1693 which provides a method for determination of environmental stress-cracking of ethylene plastics in presence of surface active agents such as soaps, oils, detergents etc. This procedure was adapted for determining salt stress cracking resistance of copolyamides to salt solutions as follows.
  • Rectangular test pieces measuring 50 mm X 12 mm X 3.2 mm were used for the test.
  • a controlled nick was cut into the face of each molded bar as per the standard procedure, the bars were bent into U-shape with the nick facing outward, and positioned into brass specimen holders as per the standard procedure. At least five bars were used for each copolymer.
  • the holders were positioned into large test tubes.
  • test fluid used was 50 weight percent zinc chloride solution prepared by dissolving anhydrous zinc chloride into water in 50:50 weight ratio.
  • the test tubes containing specimen holders were filled with freshly prepared salt solution fully immersing the test pieces such that there was at least 12 mm of fluid above the top test piece.
  • the test tubes were positioned upright in a circulating air oven maintained at 50 °C. Test pieces were periodically examined for development of cracks.
  • PA MXD6 is nylon MXD6 Grade S60 1 , available from Mitsubishi Gas Chemical America Inc. 655 Third Avenue, 24 th Floor, New York, NY 10017.
  • This Example discloses the preparation of PA66/MXD6 (50/50 mole ratio).
  • a 10L autoclave was charged with adipic acid (2093 g), meta-xylylene diamine (983 g), an aqueous solution containing 81.93 weight % of
  • HMD hexamethylene diamine
  • the autoclave agitator was set to 5 rpm and the contents were purged with nitrogen at 10 psi for 10 minutes. The agitator was then set to 50 rpm, the pressure control valve was set to 1.72 MPa (250 psi), and the autoclave was heated. The pressure was allowed to rise to 1.72 MPa at which point steam was vented to maintain the pressure at 1 .72 Mpa. The temperature of the contents was allowed to rise to 240 °C. The pressure was then reduced to 0 psig over about 45 minutes. During this time, the temperature of the contents rose to 260°C. The autoclave pressure was reduced to 5 psia by applying vacuum and held there for 20 minutes. The autoclave was then pressurized with 65 psia nitrogen and the molten polymer was extruded into strands, quenched with cold water and cut into pellets.
  • the copolyamide obtained had an IV of 1.21 dl/g and a melting point of 213 °C.
  • PA MXD6 A commercial sample of PA MXD6 was used in preparation of test samples.
  • Comparative Examples C-2 (PA 66/MXD6, 70/30) and C-3 (PA 66/MXD6, 30/70) were prepared similarly to Example 1 by adjusting the amount of HMD and MXD to achieve the desired mole ratio.
  • the physical testing and salt stress crack resistance properties of the Example and Comparative Examples are listed in Tables 1.
  • Examples 1 shows no failure after up to 168 h exposure to the ZnCI 2 solution; whereas Comparative Examples C-1 - C-3 exhibit significant failures after 4 hours.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne une composition de polyamide comprenant au moins un copolyamide semi-aromatique, ledit copolyamide semi-aromatique étant essentiellement constitué d'unités de répétition de formule -C(O)(CH2)4C{O)NHCH2ArCH2NH- (I) de 40 à 60 % en pourcentage molaire et d'unités de répétition de formule -C(O)(CH2)4C(O)NH(CH2)6NH- (II) de 40 à 60 % en pourcentage molaire, Ar étant un cycle benzénique métasubstitué. L'invention concerne également des articles moulés comprenant ladite composition de polyamide.
PCT/US2010/059842 2009-12-11 2010-12-10 Compositions de polyamide résistantes au sel WO2011072203A2 (fr)

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US28568509P 2009-12-11 2009-12-11
US61/285,685 2009-12-11

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WO2011072203A2 true WO2011072203A2 (fr) 2011-06-16
WO2011072203A3 WO2011072203A3 (fr) 2011-10-13

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120053294A1 (en) * 2010-09-01 2012-03-01 E. I. Du Pont De Nemours And Company Semi-aromatic copolyamide compositions with improved salt resistance and high temperture properties
FR3071503B1 (fr) * 2017-09-25 2020-06-19 Arkema France Utilisation d'une composition de copolyamide comme matrice de materiau charge avec des fibres de verre a section circulaire pour limiter le gauchissement

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5283282A (en) * 1987-12-08 1994-02-01 Asahi Kasei Kogyo Kabushiki Kaisha Polyamide composition
US20020142179A1 (en) * 2001-02-01 2002-10-03 Mitsubishi Gas Chemical Company, Inc. Stretched polyamide film
US6841651B2 (en) * 2002-04-19 2005-01-11 Mitsubishi Gas Chemical Company, Inc. Polyamide resin
US20080193691A1 (en) * 2005-04-14 2008-08-14 Arkema France Mxd. 10 Polyamide-Based Barrier Structures

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076664A (en) * 1975-11-13 1978-02-28 E. I. Du Pont De Nemours And Company 612 OR 610/6I or 6T/636 Polyamide terpolymer
EP0272503B1 (fr) 1986-12-01 1991-06-26 Mitsubishi Gas Chemical Company, Inc. Composition de moulage en résine polyamide
JPH03271325A (ja) 1990-03-22 1991-12-03 Nippon Steel Corp 磁気特性に優れた高強度電磁厚板の製造法
JP3271325B2 (ja) 1992-09-21 2002-04-02 東レ株式会社 ガラス繊維強化ポリアミド樹脂組成物およびその成形品
BE1006314A3 (fr) * 1992-11-04 1994-07-19 Solvay Procede de synthese de polyamides.
AU2003268631A1 (en) * 2002-08-30 2004-04-30 Toyo Boseki Kabushiki Kaisha Method for continuous production of polyamide
JP4444723B2 (ja) * 2004-04-20 2010-03-31 豊田合成株式会社 樹脂成形品
JP4857634B2 (ja) * 2005-07-22 2012-01-18 三菱瓦斯化学株式会社 ポリアミド樹脂

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5283282A (en) * 1987-12-08 1994-02-01 Asahi Kasei Kogyo Kabushiki Kaisha Polyamide composition
US20020142179A1 (en) * 2001-02-01 2002-10-03 Mitsubishi Gas Chemical Company, Inc. Stretched polyamide film
US6841651B2 (en) * 2002-04-19 2005-01-11 Mitsubishi Gas Chemical Company, Inc. Polyamide resin
US20080193691A1 (en) * 2005-04-14 2008-08-14 Arkema France Mxd. 10 Polyamide-Based Barrier Structures

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WO2011072203A3 (fr) 2011-10-13
US8487039B2 (en) 2013-07-16
US20110144257A1 (en) 2011-06-16

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