Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

• thermoplastic polyamide articles having improved aging characteristics.
• High temperature resins based on polyamides possess desirable chemical resistance, processability and heat resistance. This makes them particularly well suited for demanding high performance automotive and electrical/electronics applications.
• temperatures higher than 150 ° C, even higher than 200 ° C are often reached in under-hood areas of automobiles.
• the mechanical properties When plastic parts are exposed to such high temperatures for a prolonged period, such as in automotive under-tbe-bood applications or in electrical/electronics applications, the mechanical properties generally tend to decrease due to the thermo-oxidation of the polymer. This phenomenon is called heat aging.
• polyhydric alcohols have been found to give significantly improved heat aging characteristics as disclosed in US patent application publication US 2010-0029819 A1 (Palmer et al).
• molded articles derived from the polyamide compositions comprising the polyhydric alcohols have a tendency to undergo surface whitening upon aging at high humidity; which is an undesirable feature for many applications.
• thermoplastic compositions that are suitable for manufacturing articles, that exhibit good mechanical properties after long-term high temperature exposure; and have desirable visual properties; that is, exhibit no whitening or a low degree of whitening, upon aging at high humidity.
• EP 1041 109 discloses a polyamide composition
• a polyamide composition comprising a polyamide resin, a polyhydric alcohol having a melting point of 150 to 280 °C, that has good fluidity and mechanical strength and is useful in injection welding techniques.
• poly(ethy!ene glycol) diester as a plasticizer.
• US 2012/0029133 discloses a polyamide resin comprising a styrene block copolymer as a plasticizer.
• _ r _. nt application abstract CN 2011 -102000646 discloses a flameproof material comprising a polymer, magnesium hydroxide, triorthocresoi phosphate, and a toughener selected from a group including styrene-isoprene- styrene block copolymer.
• thermoplastic po!yamide composition comprising
• anti-whitening agents selected from the group consisting of poly(ethylene glycol), poly(ethy!ene glycol) diesters, polypropylene glycol), poly(propylene glycol) diesters; and styrene- isoprene-styrene block copolymers; and mixtures of these;
• thermoplastic composition comprises less than 15 weight percent magnesium hydroxide and less than 0.20 weight percent zinc compounds selected from the group consisting of zinc borate and zinc oxide; and with the further proviso that at least 2 weight percent of styrene-isoprene-styrene block copolymers are present when no other anti-whitening agents selected from the group are present; and wherein all weight percentages are based on the total weight of the polyamide composition.
• thermoplastic polyamide composition Also disclosed are molded or extruded articles made from the thermoplastic polyamide composition disclosed above.
• melting points and glass transitions are as determined with differential scanning ca!orimetry (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 ca!orimetry
• high- temperature means a temperature at or higher than 170 °C, preferably at or higher than 210 °C, and most preferably at or higher than 230 °C.
• long-term refers to an aging period equal or longer than 500 hrs.
• the term "high heat stability" refers to the retention of physical properties (for instance, tensile strength) of 2 mm thick molded test bars consisting of the polyamide composition that are exposed to air oven aging (AOA) conditions at a test temperature at 210 °C or 230 °C for a test period of at least 500 h, in an atmosphere of air, and then tested according to ISO 527-2/1 BA method.
• AOA air oven aging
• the physical properties of the test bars are compared to that of unexposed controls that have identical composition and shape, and are expressed in terms of "% retention".
• the test temperature is at 210 °C
• the test period is at 500 hours
• the exposed test bars have a % retention of tensile strength of at least 50 %.
• high heat stability means that said molded test bars, on average, meet or exceed a retention for tensile strength of 50 % when exposed at a test temperature at 210 °C for a test period of at least 500 h.
• compositions exhibiting a higher retention of physical properties for a given exposure temperature and time period have better heat stability.
• At 170 °C refers to the nominal temperature of the environment to which the test bars are exposed; with the understanding that the actual temperature may vary by +/- 2 °C from the nominal test temperature.
• thermoplastic polyamide compositions of various embodiments of the invention comprise a polyamide resin.
• the polyamide resins are condensation products of one or more dscarboxylic acids and one or more diamines, and/or one or more aminocarboxylic acids, and/or ring-opening polymerization products of one or more cyclic lactams. Suitable cyclic lactams are capro!actam and lauro!actarn.
• Polyamides may be fully aliphatic or semi-aromatic.
• Fully aliphatic polyamides are formed from aliphatic and alicyclic monomers such as diamines, dicarboxylic acids, lactams, aminocarboxylic acids, and their reactive equivalents.
• a suitable aminocarboxylic acid is 11 -aminododecanoic acid. e capro!actam and !auro!actam.
• the term "fully aliphatic polyamide” also refers to copolymers derived from two or more such monomers and blends of two or more fully aliphatic polyamides. Linear, branched, and cyclic monomers may be used.
• Carboxylic acid monomers comprised in the fully aliphatic polyamides include, but are not limited to aliphatic carboxylic acids, such as for example adipic acid (C6), pimeiic acid (C7), suberic acid (C8), azelaic acid (C9), decanedioic acid (C10), dodecanedioic acid (C12), tridecanedioic acid (C13), tetradecanedioic acid (C14).
• aliphatic carboxylic acids such as for example adipic acid (C6), pimeiic acid (C7), suberic acid (C8), azelaic acid (C9), decanedioic acid (C10), dodecanedioic acid (C12), tridecanedioic acid (C13), tetradecanedioic acid (C14).
• Diamines can be chosen among diamines having four or more carbon atoms, including, but not limited to tetramethylene diamine, hexamethylene diamine, octamethyiene diamine, decamethylene diamine, dodecamethylene diamine, 2- methylpentamethylene diamine, 2-ethyltetrarnetbylene diamine, 2- methyioctamethylenediamine; trimethylhexamethylenediamine, me a-xylylene diamine, and/or mixtures thereof.
• the semi-aromatic polyamide is a homopolymer, a copolymer, a terpolymer or more advanced polymers formed from monomers containing aromatic groups.
• One or more aromatic carboxylic acids may be terephthalate or a mixture of terephthalate with one or more other carboxylic acids, such as isophthalic acid, phthalic acid, 2- methyl terephthalic acid and naphthalic acid.
• the one or more aromatic carboxylic acids may be mixed with one or more aliphatic dicarboxylic acids, as disclosed above.
• an aromatic diamine such as meta-xylylene diamine (MXD) can be used to provide a semi-aromatic polyamide, an example of which is MXD6, a homopolymer comprising MXD and adipic acid.
• MXD meta-xylylene diamine
• Preferred polyamides disclosed herein are homopolymers or copolymers wherein the term copolymer refers to polyamides that have two or more amide and/or diamide molecular repeat units.
• the homopolymers and copolymers are identified by their respective repeat units.
• the repeat units are listed in decreasing order of mole % repeat units present in the copolymer. The following list exemplifies the abbreviations used to identify monomers and repeat units in the homopolymer and copolymer polyamides (PA): HMD hexamethylene diamine (or 6 when used in combination with a diacid)
• the term "6" when used alone designates a polymer repeat unit formed from €-caprolactam.
• “8" when used in combination with a diacid such as T, for instance 8T the “8” refers to HMD.
• the diamine is designated first.
• the first "8” refers to the diamine HMD
• the second "8” refers to adipic acid.
• repeat units derived from other amino acids or lactams are designated as single numbers designating the number of carbon atoms.
• the po!yamide composition comprises a one or more poiyamides selected from the group consisting of
• PA512 poly(8-caprolactam/hexamethylene hexanediamide) (PA6/66), poly(e-caproiactam/hexamethylene decanediamide) (PA6/610), poly(e- caprolactam/hexamethyiene dodecanediamide) (PA6/612), poly ⁇ hexamethy!ene tridecanediamide) (PA613), poly(hexamethy!ene pentadecanediamide) (PA615), poiy(s-caprolactam/tetramethyiene terephthaiamide) (PA6/4T), poly ⁇ s- caprolactam/hexamethy!ene terephthaiamide) (PA6/6T), poly(s- caprolactam/decamethylene terephthaiamide) (PA6/10T), poiy(s- caprolactam/dodecamethylene ter
• PA614/6T poly(s-caprolactam/ hexamethylene isophthaiamide/hexamethylene terephthaiamide)
• PA6/6I/6T poly(8-caprolactam/hexamethyIene
• PA6/66/610 poly(e- caprolactam/hexamethyiene hexanediamide/hexamethylene dodecanediamide)
• PA6/66/612 poly(e-caprolactam/hexamethy!ene hexanediamide/hexamethylene decanediamide/hexamethylene dodecanediamide)
• PA6/66/610/612 po!y(2- methylpentamethylene hexanediamide/hexamethylene
• PA D6/66/6T poly(2- methy!pentamethylene hexanediamide/hexamethylene hexanediamide/)
• PA D6/66 poly(decamethylene decanediamide)
• PA1010 poly(decamethy!ene
• PA1012 dodecanediamide
• PA1010/10T poly(decamethyiene
• PA1 terephthaiamide PA1 1/ 6T
• PA1 1./10T poly(1 1 -aminoundecanamide/decamethylene terephthaiamide)
• poiy(1 1-aminoundecanamide/dodecamethylene , x PA1 1/ 6T
• PA1 1./10T poly(1 1 -aminoundecanamide/decamethylene terephthaiamide)
• poiy(1 1-aminoundecanamide/dodecamethylene x .
• PA12 po!y(12-aminododecanamicle)
• PA12 poly(12- aminododecanamide/tetramethylene ierephthalamide)
• PA12/6T poly(12- aminododecanamide/hexamethyiene terephthalamide)
• PA12/10T po!y(12- aminododecanamide/decamethy!ene terephthalamide)
• PA616 poly(hexamethy!ene octadecanediamide)
• PA618 poly(hexamethy!ene octadecanediamide)
• PA46 poly(8-caprolactam)
• PA 8 poly(hexamethylene hexanediamide/(8-caproiactam/)
• PA 66/8 polyihexamethylene hexanediamide
• PA 68 poly(hexamethylene hexanediamide/hexamethylene decanediamide)
• PA66/610 polyihexamethylene hexanediamide/hexamethylene dodecanediamide) (PA88/612), polyihexamethylene hexanediamide/decamethylene decanediamide) (PA66/1010), polyihexamethylene decanediamide) (PA610), polyihexamethylene dodecanediamide) (PA612), polyihexamethylene tetradecanediamide) (PA814), and poly(tetramethylene hexanediamide/2-methylpentamethy!ene hexanediamide) (PA46/D6);
• Group (ill) po yamides having a melting point of at least 210 °C, and comprising (aa) about 20 to about 35 mole percent semiaromatic repeat units derived from monomers selected from one or more of the group consisting of:
• aromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms; and 5 to about 50 mole percent aliphatic repeat units derived from monomers selected from one or more of the group consisting of:
• Group (!) polyamides may have semiaromatic repeat units to the extent that the melting point is less than 210 °C and generally the semiaromatic polyamides of the group have less than 40 mole percent semiaromatic repeat units.
• Semiaromatic repeat units are defined as those derived from monomers selected from one or more of the group consisting of: aromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.
• Another embodiment is a molded or extruded thermoplastic article wherein said poiyamide resin is selected from Group (III) polyamides selected from the group consisting of poIy(tetramethyiene hexanediamide/tetramethylene terephthalamide) (PA46/4T), po!y(tetramethyiene hexanediamide/hexamethylerie terephthalamide) (PA46/6T), poIy(tetramethyIene hexanediamide/2-methylpentamethylene
• PA66/6T poly(hexamethylene hexanedsamide/hexamethyiene terephthalamide)
• PA66/6I poiy(hexamethyIene hexanediamide/hexamethylene isophthalamide/hexamethylene terephthalamide PA66/6I/6T
• PA66/6I/6T poiy(hexamethylene hexanediamide/2- ⁇ e hexanediarrside /hexamethyiene terephtha!amide
• PA66/D6/6T a most preferred Group (III) polyamide Is PA 66/6T.
• polyamide resin is selected from Group (IV) polyamides selected from the group consisting of poiy(tetramethylene terephthalamide/hexamethylene hexanediamide) (PA4T/68), poly(tetramethylene terephtha!amide/s-caprolactam) (PA4T/6), poly(tetramethylene terephthalamide/hexamethylene dodecanediamide) (PA4T/612), poly(tetramethylene terephthalamide/2-methyIpentamethyIene
• PA4T/68 poiy(tetramethylene terephthalamide/hexamethylene hexanediamide)
• PA4T/6 poly(tetramethylene terephthalamide/hexamethylene dodecanediamide)
• PA4T/612 poly(tetramethylene terephthalamide/2-methyIpentamethyIene
• PA6T/DT/66 poly(hexamethylene terephthalamide/hexamethylene hexanediamide) PA6T/66, poiy(hexamethylene terephthalamide /hexamethyiene decanediamide) (PA6T/610), poly(hexamethylene terephthalamide/hexamethylene tetradecanediamide) (PA6T/614), poIy(nonamethyiene
• PA9T/910 terephthalamide/nonamethylene decanediamide
• PA9T/912 poiy(nonamethylene terephthalamide/nonamethyiene dodecanediamide)
• PA9T/912 poiy(nonamethylene terephthalamide/nonamethyiene dodecanediamide)
• PA9T/1 1 poly(nonamethylene terephthalamide/11 -aminoundecanamide)
• PA9T/12 poly(nonamethylene terephthalamide/12-aminododecanamide)
• PA9T/12 poiy(decamethyIene terephthalamide/1 1 -aminoundecanamide)
• PA 10T/1 1 poiy(decamethyIene terephthalamide/1 1 -aminoundecanamide)
• PA10T/66 poly(dodecamethylene terephtha!amide/dodecamethylene dodecanediamide)
• PA12T/1212 poly(dodecamethylene terephtha!amide/dodecamethylene dodecanediamide)
• PA12T/66 a most preferred Group (IV) polyamide is PA8T/66.
• polyamide resin is selected from Group (V) polyamides selected from the group consisting of poly(tetramethylene terephthaiamide/2-methyIpentamethyIene terephthalamide) PA4T/DT, poly(tetramethy!ene terephthalamide/ hexamethyiene , .
• PA4T/6T/DT poiy(hexamethylene terephthaiamide/2-methyIpentamethyIene terephthalamide)
• PA8T/DT poly(hexamethylene hexanediamide/hexamethylene isophthaiamide)
• PA 6TY6I poly(hexamethylene terephthalamide/decamethylene terephthalamide)
• PA8T/10T poly(hexamethylene terephthalamide/dodecamethylene terephthalamide) (PA6T/12T), poly(hexamethy!ene terephtha!amide/2-methyiperitamethylene terephthalamide/poiy(decamethyIene terephthalamide) (PA6T/DT/10T),
• PA12T/6T poiy(dodecamethylene terephthaiamide)/decamethylene
• PA12T/10T poly(dodecamethylene terephthalamide)/2- methylpentamethylene terephthalamide)
• PA12T/DT poly(dodecamethylene terephthalamide)/2- methylpentamethylene terephthalamide)
• a most preferred_Group (V) Polyamide is PA6T/DT.
• the polyamide is a Group (I) Polyamide, Group (N) Polyamide, Group (III) Polyamide, Group (IV) Polyamide, Group (V) Polyamide or Group (VI) Polyamide, respectively.
• the polyamide resin is selected from the group consisting of poly(E-caprolactam), poly(hexamethyiene hexanediamide), poly(hexamethylene hexanediamide/hexamethylene , _.nd poly(hexamethylene terephthalamide/ hexamethy!ene hexanediamide).
• the polyamides may also be blends of two or more polyamides.
• Preferred blends include those selected from the group consisting of Group (I) and Group (I!) Polyamides; Group (I) and Group (III) Polyamide, Group (I) and Group (VI)
• a preferred blend includes Group ( ⁇ ) and (V) Polyamides, and a specific preferred blend includes poly(hexamethylene hexanediamide) (PA 86) and poiy(hexamethylene terephthaiamide/2-methyIpentamethyIene terephthalamide) (PA 6T/DT).
• Another preferred blend includes Group (II) and Group (III) Polyamides and a specific preferred blend includes poly(e-caprolactam) (PA8) and poly(hexamethylene hexanediamide/hexamethylene terephthalamide (PA66/6T).
• PA8 poly(e-caprolactam)
• PA66/6T poly(hexamethylene hexanediamide/hexamethylene terephthalamide
• thermoplastic polyamide composition comprises 0.1 to 10 weight percent of one or more po!yhydric alcohols having more than two hydroxy! groups and a number average molecular weight (M n ) of less than 2000, as determined for polymeric materials with gel permeation chromatography (GPC)
• Po!yhydric alcohols may be selected from aliphatic hydroxylic compounds containing more than two hydroxyl groups, aliphatic-cycloa!iphatic compounds containing more than two hydroxyl groups, cycloa!iphatic compounds containing more than two hydroxyl groups, and saccharides.
• An aliphatic chain in the polyhydric alcohol can include not only carbon atoms but also one or more hetero atoms which may be selected, for example, from nitrogen, oxygen and sulpher atoms.
• a cycloa!iphatic ring present in the polyhydric alcohol can be monocyclic or part of a bicyclic or polycyc!ic ring system and may be carbocyclic or heterocyclic.
• a heterocyclic ring present in the polyhydric alcohol can be monocyclic or part of a bicyclic or polycyclic ring system and may include one or more hetero atoms which may be selected, for example, from nitrogen, oxygen and sulphur atoms.
• the one or oho!s may contain one or more substituents. such as ether, carboxylic acid, carboxy!ic acid amide or carboxylic acid ester groups.
• poiyhydric alcohol containing more than two hydroxy! groups include, without limitation, triols, such as glycerol, trirnethy!olpropane, 2,3-di-(2'- hydroxyethyl)-cyclohexan-1 -ol, hexane-1 ,2,6-triol, 1 ,1 ,1 -tris-(hydroxymethyi)ethane, 3-(2'-hydroxyethoxy)-propane-1 ,2-diol, 3-(2'-hydroxypropoxy)-propane-1 ,2-diol, 2-(2 ' - hydroxyethoxy)-hexane-1 ,2-diol, 6-(2'-hydroxypropoxy)-hexane-1 ,2-diol, 1 ,1 ,1 -tris- [(2"-hydroxyethoxy)-methyl]-ethane, 1 ,1 ,1 -tris-[(2'-hydroxyl
• Preferred po!yhydric alcohols include those having a pair of hydroxyl groups which are attached to respective carbon atoms which are separated one from another by at least one atom.
• Especially preferred poiyhydric alcohols are those in which a pair of hydroxyl groups is attached to respective carbon atoms which are separated one from another by a single carbon atom.
• the poiyhydric alcohol used in the thermoplastic composition is pentaerythritol, dipentaerythritoi, tripentaerythritol, di-trimethylo!propane, D-mannitol, D-sorbitol and xylitol. More preferably, the poiyhydric alcohol used is
• dipentaerythritoi and/or tripentaerythritol are dipentaerythritoi and/or tripentaerythritol.
• a most preferred poiyhydric alcohol is dipentaerythritoi.
• the content of said poiyhydric alcohol in the thermoplastic composition is 0.25-10 weight percent, preferably 0.25-8 weight percent, more preferably 1 .0 - 8 weight percent and 1 .0 - 5 weight percent, and most preferably 1 - 4 weight percent, based on the total weight of the thermoplastic composition.
• the thermoplastic poiyamide composition comprises (c) 0.5 to 5 weight percent of one or more anti-whitening agents selected from the group consisting of po!y(ethylene glycol), poly(ethylene glycol) diesters, poly(propylene glycol), poly(propylene glycol) diesters; and styrene-isoprene-styrene block copolymers; and , ,/ith the proviso that at least 2 weight percent of styrene-isoprene- styrene block copolymer is present when no other anti-whitening agents selected from the group are present.
• the term poly(ethylene glycol) includes materials having n of about 400 and higher and includes those materials often referred to as polyethylene oxides having ⁇ ⁇ greater than 5,000 and preferably greater than 10,000.
• anti-whitening agents for the composition include Plasthall® 809, a polyethylene glycol 400 di-2-ethylhexoate available from C . Hall Company; PEG 6000J, a poly(ethylene glycol) manufactured by Lion Corporation, Japan; and Kraton D1 1 18AT, a styrene-butadiene-styrene block copolymer (SBS), available from Kraton Performance Polymers.
• anti-whitening agents are materials, that when present in the thermoplastic compositions in the presence of lubricants disclosed herein, significantly impede or prevent the whitening of molded or extruded parts upon ageing.
• ageing is performed at 85 °C and 85 % relative humidity for periods of time, typically 1 day and 7 days.
• anti-whitening agent In various embodiments 0.5 to 3.0 weight percent, 0.75 to 3.0 weight percent, and 0.75 to 2.0 weight percent of anti- whitening agent are present in the thermoplastic po!yamide composition.
• the anti-whitening agent is selected from the group consisting of po!y(ethylene glycol) diesters and styrene-isoprene-styrene block copolymers.
• the anti-whitening agent is selected from the group consisting of polyethylene glycol and po!y(ethyiene glycol) diesters.
• the thermoplastic polyamide composition comprises (d) 0.02 to 1 weight percent, and preferably 0.02 to 0.8 weight percent and 0.05 to 0.8 weight percent, of a lubricant.
• a lubricant is selected from the group consisting of fatty acids, fatty acid esters, fatty acid amides, fatty acid metal salts (e.g. aluminum stearate), and oxidized polyethylene wax.
• fatty acid herein means carboxyl groups with the fatty acids, fatty acid esters, fatty acid amides, and fatty acid metal salts have 10, and preferably 12 or 16, or more aliphatic carbon atoms linked in a linear or branched chain.
• fatty acid comprises 10 to 22 carbon atoms in a linear carbon chain.
• lubricant (d) is present, based on the total weight of the thermoplastic composition.
• fatty acids examples include stearic acid, oleic acid, erucic acid, and behenic acid.
• fatty acid esters include pentaerythritol tetrastearate, stearyl stearate, and montanic acid esters.
• fatty acid metal salts examples include aluminum stearate, sodium montanate, and calcium montanate.
• fatty acid amide examples include methyienebisstearylamide, methy!enebislaurylamide, ethy!enebissteary!amide, ethylenebislaurylamide, methyienebehenylamide, ethyienebisbehenylamide, dioctadecyladipamide, dioctadecylsuccinamide, dihexy!adipamide, dihexyisuccinamide, distearyladipamide, distearylsuccinamide, eruccamide, stearylamide, oleamide, oleyl palmitamide, erucyf stearamide, and N-stearylerucamide.
• N-stearylerucamide is a preferred fatty acid amide compound.
• Kemamide E180 lubricant is N-stearylerucamide, CAS No. [10094-45-8], available from Chemtura Corp., Philadelphia, PA; Crodamide® 212 lubricant, a stearyl erucamide available from Croda Chemicals, Hull UK; Licowax OP lubricant manufactured by Clariant Corp., Charlotte, NC; PED 191 lubricant, an oxidized polyethylene wax available from Clariant Corp., Charlotte, NC; Licomont ⁇ CaV 102 lubricant, a fine grain calcium montanate available from Clariant Corp.; Hostamont® NAV 101 lubricant, a sodium montanate manufactured by Clariant, Muttenz, Switzerland; aluminum distearate, a wax supplied by PMC Global, Inc. Sun Valley, CA, USA; and Loxiol® VPG 881 lubricant, a pentaerythritol tetrastearate, manufactured by C
• the thermoplastic polyamide composition comprises 10 to about 60 weight percent, and preferably about 12.5 to 55 weight percent and 15 to 50 weight percent, of one or more reinforcement agents.
• the reinforcement agent may be any filler with the proviso that the thermoplastic composition comprises less than 15 weight percent magnesium hydroxide and preferably less than 10 weight percent, and more preferably less than 1 weight percent magnesium hydroxide.
• the reinforcement agent is preferably selected from the group consisting calcium carbonate, glass fibers with circular and noncircular cross-section, glass flakes, glass beads, carbon fibers, talc, mica, wollastonite, calcined clay, kaolin, diatomite, magnesium sulfate, , bariurrs sulfate, titanium dioxide, sodium aluminum carbonate, barium ferrite, potassium titanate and mixtures thereof.
• the reinforcing agent is selected from the group consisting of glass fiber and glass fiber with noncircular cross-section.
• the glass fiber may have sizing or coupling agents, organic or inorganic materials that improve the bonding between glass and the po!yamide resin.
• Glass fibers with noncircular cross-section refer to glass fiber having a cross section having a major axis lying perpendicular to a longitudinal direction of the glass fiber and corresponding to the longest linear distance in the cross section.
• the non- circular cross section has a minor axis corresponding to the longest linear distance in the cross section in a direction perpendicular to the major axis.
• the non-circular cross section of the fiber may have a variety of shapes including a cocoon-type (figure-eight) shape, a rectangular shape; an elliptical shape; a roughly triangular shape; a polygonal shape; and an oblong shape.
• the cross section may have other shapes.
• the ratio of the length of the major axis to that of the minor access is preferably between about 1 .5:1 and about 6:1.
• the ratio is more preferably between about 2:1 and 5:1 and yet more preferably between about 3:1 to about 4:1 .
• Suitable glass fiber are disclosed in EP 0 190 001 and EP 0 196 194.
• the thermoplastic 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 composition comprises 2 to 20 weight percent polymeric toughener selected from the group consisting of: a copolymer of ethylene, glycidyl (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-isocyanatoethy! (meth)acrylate, and optionally one or more
• (meth)acrylate esters and a copolymer of ethylene and acrylic acid reacted with a Na, Li, or !vln compound to form the corresponding ionomer.
• thermoplastic composition of the present invention may also comprise other additives commonly used in the art, such other heat stabilizers or antioxidants referred to as "co-stabilizers", antistatic agents, blowing agents, and colorant and pigments.
• co-stabilizers such as heat stabilizers or antioxidants referred to as "co-stabilizers", antistatic agents, blowing agents, and colorant and pigments.
• 0.1 to 3.0 weight percent of one or more colorants is present, wherein the weight percent colorant includes the weight of the carrier , colorant.
• the colorant is selected from the group of carbon black and nigrosine black pigment.
• thermoplastic polyamide of the present invention may further comprise halogenated flame retardants, preferably in the range of 2 to 30 weight percent based on the total weight of the polyamide composition.
• halogenated flame retardant is brominated polystyrene.
• thermoplastic polyamide composition consists of less than 15 weight percent, preferably less than 10 weight percent magnesium hydroxide; and less than 0.20 weight percent, preferably less than 0.10 weight percent, of zinc compounds selected from the group consisting of zinc borate and zinc oxide.
• Co-stabilizers include copper stabilizers, secondary aryl amines, hindered amine light stabilizers (HALS), hindered phenols, and mixtures thereof, that are disclosed in US patent application publication 2010/0029819, Palmer et al, herein incorporated by reference.
• HALS hindered amine light stabilizers
• Molded parts comprising the thermoplastic polyamide composition herein disclosed exhibit no whitening or only low levels of whitening upon ageing. For instance, molded parts, aged in an environmental chamber under conditions of 85% relative humidity and 85 °C for one to seven days show significantly less whitening than similar compositions absence the anti-whitening agents and lubricant. Although not met to be limiting the scope of the invention disclosed herein, whitening is thought to be related to the migration, (often referred to as blooming) and
• test plaques prepared from the thermoplastic polyamide composition when exposed at a test temperature at 85 °C and relative humidity of 85 %, for a test period of 7 days in an atmosphere of air, had a AL value, versus an untreated control of identical composition, determined at 110 ° reflection with a multi-angle spectrophotometer, of at least 25 percent less than that of the same composition absent the anti-whitening agent.
• thermoplastic composition is a mixture by me!t-blending, in which all polymeric ingredients are adequately mixed, and all non-polymeric ingredients are , 3d 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 manufacturing an article by shaping the thermoplastic po!yamide composition disclosed herein.
• 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 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.
• a charge air cooler is a part of the radiator of a vehicle that improves engine combustion efficiency. Charge air coolers reduce the charge air temperature and
• the temperature of the incoming air can be more than 200 ° C when it enters the charge air cooler, it is required that this part be made out of a composition maintaining good mechanical properties under high temperatures for an extended period of time. Also it is very desirable to have a shaped article that exhibits no whitening or very little whitening upon aging.
• compositions using a screw speed of about 300 rpm, a throughput of 13.8 kg/hour and a melt temperature measured by hand of about 320 - 355°C for the all compositions.
• the glass fibers were added to the melt through a screw side feeder.
• Ingredient quantities shown in the Tables are given in weight percent on the basis of the total weight of the thermoplastic composition.
• the compounded mixture was extruded in the form of laces or strands, cooled in a water bath, chopped into granules and placed into sealed aluminum lined bags in order to prevent moisture pick up.
• Examples and Comparative examples listed in Tables 9 and 12 were prepared by melt blending the ingredients listed in the Tables in a 40 mm twin screw extruder (Berstorif ZE40) operating at barrel settings of about 285 ° C using a screw speed of about 200 rpm, a throughput of 125 kg/hour and a melt temperature measured by hand of about 31 OX for all compositions.
• the glass fibers were added to the melt through a screw side feeder.
• Liquid plasticizer (Plasthall 809 and Uniplex 214) was added through a liquid injection pump to the final barrel section.
• Ingredient ⁇ the Tables are given in weight percent on the basis of the total weight of the thermoplastic composition.
• the compounded mixture was extruded in the form of laces or strands, cooled in a water bath, chopped into granules and placed into sealed aluminum lined bags in order to prevent moisture pick up.
• the cooling and cutting conditions were adjusted to ensure that the materials were kept below 0.15 wt % of moisture level.
• Examples and comparative examples listed in Table 10 were prepared by melt blending the ingredients listed in the Table in a 58 mm twin screw extruder operating at barrel settings of about 260 " C using a screw speed of about 300 rpm, a throughput of 600 lbs/hour and a melt temperature of about 315 for all
• compositions The glass fibers were added to the melt through a screw side feeder. Liquid p!asticizer (Plastha!l 809) was added through a liquid injection pump to the final barrel section. Ingredient quantities shown in the Table are given in weight percent on the basis of the total weight of the thermoplastic composition.
• the compounded mixture was extruded in the form of laces or strands, cooled in a water bath, chopped into granules and placed into sealed aluminum lined bags in order to prevent moisture pick up.
• the cooling and cutting conditions were adjusted to ensure that the materials were kept below 0.15 wt % of moisture level.
• Examples and comparative examples listed in Table 13 were prepared by melt blending the ingredients listed in the Table in a 58 mm twin screw extruder (ZSK58 by Coperion) operating at barrel settings of about 270 ° C using a screw speed of about 300 rpm, a throughput of 275 kg/hour and a melt temperature of about 315°C for all compositions.
• the glass fibers were added to the melt through a screw side feeder.
• Liquid plasticizer (Plasthall 809) was added through a liquid injection pump to a spacer plate between the final two barrel sections.
• Ingredient quantities shown in the Table are given in weight percent on the basis of the total weight of the thermoplastic composition.
• the compounded mixture was extruded in the form of laces or strands, cooled in a water bath, chopped into granules and placed into sealed polyethylene lined boxes in order to prevent moisture pick up. The cooling and cutting conditions were adjusted to ensure that the materials were kept below 0.15 wt % of moisture level.
• test specimens (2 mm thick tensile bars) were heat aged in a recirculating air ovens (Heraeus type UT6060) according to the procedure detailed in ISO 2578. At various heat aging times, the test specimens were removed from the oven, allowed to cool to room temperature and sealed into aluminum lined bags until ready for testing. The tensile mechanical properties were then measured according to ISO 527 using a Zwick tensile instrument. The average values obtained from 5 specimens are given in the Tables.
• Retention of tensile strength (TS) and elongation at break (EL) corresponds to the percentage of the tensile strength and elongation at break after heat aging for 500 or 1000 hours in comparison with the value of specimens non-heat-aged control specimens considered as being 100%.
• Two 5 in x 3 in X 3 mm plaques were treated by placing in an environmental chamber under conditions of 85% relative humidity and 85 °C. After one day one plaque was removed from the chamber and visually inspected. The L value, determined at 1 10 ° reflection was measured with a ChromaVision MA100 Multi- Angle Spectrophotometer (manufactured by X-Rite, Incorporated, Grandville, Michigan). L is a common measure of whiteness on the CIELAB colorspace. The L value was measured at 4 places on the plaque, both front and back and the L values averaged. A determination of L also was performed on an untreated plaque. A AL value was determined by subtracting the average of the four L measurements of the untreated plaque from the average of the four measurements from the treated plaque. After 7 days, the second plaque was removed from the chamber and the L value and AL value determined.
• Polyamide A refers to PA 6T/66, a Zytel® HTN502HNC010 copolyamide, made from terephthaiic acid, adipic acid, and hexamethylenedsamine; wherein the two acids are used in a 55:45 molar ratio; having a melting point of about 310 °C and an inherent viscosity (IV), according to AST D2857 method, typically about 1 .07, available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
• Polyamide B refers to PA66/6T (75/25 molar ratio repeat units) with amine ends approximately 80 meq/kg, having a typical relative viscosity (RV) of 41 , according to ASTM D-789 method, and a typical melt point of 268 °C, that was provided according to the following procedure:
• Polyamide 68 salt solution 3928 lbs. of a 51 .7 percent by weight with a pH of 8.1
• 2926 lbs of a 25.2% by weight of polyamide 6T salt solution with a pH of 7.6 were charged into an autoclave with 100 g of a conventional antifoam agent, 20g of sodium hypophosphite, 220g of sodium bicarbonate, 2476 g of 80% HMD solution in water, and 1584 g of glacial acetic.
• the solution was then heated while the pressure was allowed to rise to 265 psia at which point, steam was vented to maintain the pressure at 265 psia and heating was continued until the temperature of the batch reached 250°C.
• the pressure was then reduced slowly to 6 psia, while the batch temperature was allowed to further rise to 280-290 °C. The pressure was then held , mperature was held at 280-290 °C for 20 minutes. Finally, the polymer melt was extruded into strands, cooled, and cut into pellets.
• PA 66 refers to an aliphatic po!yamide made of 1 ,6-hexanedioic acid and 1 ,6- hexamethy!enediamine having an relative viscosity in the range of 46 - 51 and a melting point of about 263 °C, commercially available from E.L DuPont de Nemours and Company, Wilmington, Delaware, USA under the trademark ZyteP 101 NC010.
• PA 6-1 refers to Ultramid® B27 polyamide 6 resin (poiycaprolactam) available from BASF Corporation, Florham Park, NJ, 07932.
• PA6 -2 refers to Durethan B29 poly(e-caprolactam) available from Lanxess Germany.
• Glass fiber B refers to CPIC 301 HP chopped glass fiber available from
• Glass fiber C refers to PPG 3610 chopped glass fiber available from PPG Industries, Pittsburgh, PA.
• Glass fibers D refer NEG 262H glass fibers manufactured by Nippon Electric Glass, Osaka, Japan.
• Black Pigment A refers to ZYTEL® FE3786 BK031 C black concentrate, a 40 wt % nigrosine black pigment concentrate in a PA66 carrier.
• Pigment B refers ZYTEL ® FE3779 BK031C black concentrate, a 25 wt % carbon black in a PA6 carrier.
• Cu heat stabilizer refers to a mixture of 7 parts of potassium iodide and 1 part of copper iodide in 0.5 part of aluminum stearate wax binder.
• Plasthall 809 is a polyethylene glycol 400 di-2-ethyihexoate available from CP. Hal! Company, Chicago, Illinois 60606.
• Loxiol HOB 7119 lubricant is a pentaerythritol tetrastearate manufactured by Cognis, Dusseldorf, Germany.
• PEG 6000J is a poly(ethylene glycol) manufactured by Lion Corporation
• PEG refers to a polyethylene glycol of MW about 18,500 from Po!ysciences Inc. Warrington, PA, 18976, USA.
• Uniplex 214 p!asticizer refers to N-buty!benzenesulfonamide available from Unitex Chemical Corp., Greensboro, NC.
• Kraton D1 161 PT is a styrene-isoprene-styrene block copolymer (SIS), available from Kraton Performance Polymers, Houston, TX, USA.
• 8AT is a styrene-butadiene-styrene block copolymer (SBS), available from Kraion Performance Polymers, Houston, TX, USA.
• Kemamide E180 lubricant is N-stearylerucamide, CAS No. [10094-45-8], available from C emtura Corp., Philadelphia, PA.
• Saytex 701 QG is brominated polystyrene used as a flame retardant manufactured by Albermarle.
• Thermoguard S PE80/20 is antimony oxide [CAS 1309-64-4] masterbatch in polyethylene, manufactured by Chemtura.
• Comparative Example C1 having no DPE, exhibits no whitening.
• Comparative Examples C3 and C4 having DPE but absent an anti-whitening agent, exhibits severe whitening.
• Comparative Example C2 having DPE and an anti-whitening agent, but absent a lubricant shows moderate whitening.
• the Examples comprising a polyhydric alcohol, anti-whitening agent, and lubricant, show significantly less whitening than the Comparative Examples.

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