Copolyetherester formulation with improved heat-stability

Abstract

To provide a copolyetherester resin composition having excellent retention of mechanical properties during prolonged heat exposure.SOLUTION: A copolyetherester resin composition comprises: at least one copolyetherester; at least one phenolic antioxidant; at least one thioester antioxidant; at least one phosphite and / or phosphonite antioxidant; and at least one epoxy compound or a reaction product of the epoxy compound. Further provided are articles comprising the composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. §365 to U.S. Provisional Patent Application No. 62 / 724,908, filed August 30, 2018, which is incorporated herein by reference in its entirety.

[0002] The present invention relates to the field of polymer resin formulations, specifically copolyetherester resin formulations having good thermal stability. [Background technology]

[0003] Copolyetheresters are increasingly being used to replace metal and rubber, especially in automotive applications.

[0004] In many such applications, for example in automotive fluid ducts, copolyetherester parts are exposed to high temperatures during use, which are generally detrimental to the mechanical properties of the copolyetherester, resulting, for example, in reduced tensile strength and reduced strain to break over time, which can lead to part failure.

[0005] The use of antioxidants in copolyetheresters to impart improved thermal stability is known. Nevertheless, as engine operating temperatures increase, there is an increasing need for copolyetherester compositions that have improved retention of mechanical properties over extended heat exposure. Summary of the Invention [Means for solving the problem]

[0006] In a first aspect, the present invention provides a method for producing a method for treating a cancer cell comprising: (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; and (E) at least one epoxy compound.

[0007] In a second aspect, the present invention provides a method for producing a method for treating a cancer cell comprising: (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; and (E) at least one epoxy compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] All documents mentioned herein are incorporated by reference.

[0009] The inventors have surprisingly found that copolyetherester resin compositions comprising at least one phenolic antioxidant, at least one thioester antioxidant, at least one phosphite and / or phosphonite antioxidant, and at least one epoxy compound improve the retention of mechanical properties, especially the breaking strain, during heat aging. This property makes such resin formulations particularly suitable for use in high temperature environments. For example, the formulations may be useful as fluid ducts for carrying air, gas, or liquid, especially in automotive applications, such as the airflow system of a vehicle engine.

[0010] At least one copolyetherester The one or more copolyether-esters suitable for use in the compositions of the present invention are preferably present in the compositions of the present invention in an amount from at or about 50 weight percent to at or about 98 weight percent, the weight percentages being based on the total weight of the polymer composition.

[0011] The copolyetheresters used in the compositions of the present invention have a plurality of repeating long chain ester units and short chain ester units joined head to tail through ester bonds, the long chain ester units having the formula (A):

[0012] [ka]

[0013] and the short chain ester unit is represented by formula (B):

[0014] [ka]

[0015] wherein G is a divalent radical remaining after removal of the terminal hydroxyl groups from a poly(alkylene oxide) glycol having a number average molecular weight of from about 400 to about 6000 Da, or preferably from about 400 to about 3000 Da; R is a divalent radical remaining after removal of a carboxyl group from a dicarboxylic acid having a molecular weight of less than about 300 Da; D is a divalent radical remaining after removal of a hydroxyl group from a diol having a molecular weight of less than about 250 Da.

[0016] As used herein, the term "long chain ester unit" as applied to units in a polymer chain refers to the reaction product of a long chain glycol with a dicarboxylic acid. Suitable long chain glycols are poly(alkylene oxide) glycols having terminal (or as close to terminal as possible) hydroxy groups and having a number average molecular weight of about 400 to about 6000 Da, preferably about 600 to about 3000 Da. Preferred poly(alkylene oxide) glycols include poly(tetramethylene oxide) glycol, poly(trimethylene oxide) glycol, poly(propylene oxide) glycol, poly(ethylene oxide) glycol, copolymer glycols of these alkylene oxides, and block copolymers such as ethylene oxide-capped poly(propylene oxide) glycol. Mixtures of two or more of these glycols can be used.

[0017] As used herein, the term "short chain ester units" as applied to units in the polymer chain of a copolyetherester means low molecular weight compounds or polymer chain units having a molecular weight less than about 550 Da. They are prepared by reacting a low molecular weight (less than about 250 Da molecular weight) diol or mixture of diols with a dicarboxylic acid to form the ester units represented by formula (B) above.

[0018] Among the low molecular weight diols that react to form short chain ester units suitable for use in preparing copolyetheresters are acyclic, alicyclic and aromatic dihydroxy compounds. Preferred compounds are diols having about 2 to 15 carbon atoms, such as ethylene, propylene, isobutylene, tetramethylene, 1,4-pentamethylene, 2,2-dimethyltrimethylene, hexamethylene and decamethylene glycols, dihydroxycyclohexane, cyclohexanedimethanol, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, and the like. Particularly preferred diols are aliphatic diols containing 2 to 8 carbon atoms, and the more preferred diol is 1,4-butanediol. Among the bisphenols that can be used are bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)methane, and bis(p-hydroxyphenyl)propane. Equivalent ester forming derivatives of the diols are also useful (for example, ethylene oxide or ethylene carbonate can be used in place of ethylene glycol, or resorcinol diacetate can be used in place of resorcinol).

[0019] As used herein, the term "diol" includes equivalent ester-forming derivatives such as those mentioned, however any molecular weight requirements refer to the corresponding diols and not their derivatives.

[0020] The dicarboxylic acids that can be reacted with the aforementioned long chain glycols and low molecular weight diols to prepare copolyetheresters are aliphatic, cycloaliphatic or aromatic dicarboxylic acids with low molecular weight, i.e., less than about 300 Da. The term "dicarboxylic acid" as used herein includes functional equivalents of dicarboxylic acids having two carboxyl functional groups that function substantially like dicarboxylic acids in the reaction with glycols and diols to form copolyetherester polymers. These equivalents include esters and ester-forming derivatives such as acid halides and acid anhydrides. The molecular weight requirement relates to the acid and not to its equivalent ester or ester-forming derivatives.

[0021] Thus, esters of dicarboxylic acids having a molecular weight greater than 300 Daltons or functional equivalents of dicarboxylic acids having a molecular weight greater than 300 Daltons are included, provided that the corresponding acids have a molecular weight less than about 300 Daltons. The dicarboxylic acids may contain any substituents or combinations that do not substantially interfere with copolyetherester polymer formation.

[0022] As used herein, the term "aliphatic dicarboxylic acid" refers to a carboxylic acid having two carboxyl groups, each attached to a saturated carbon atom. If the carbon atom to which the carboxyl groups are attached is saturated and in a ring, the acid is cycloaliphatic. Aliphatic or cycloaliphatic acids with conjugated unsaturation often cannot be used for homopolymerization. However, some unsaturated acids, such as maleic acid, can be used.

[0023] As used herein, the term "aromatic dicarboxylic acid" refers to a dicarboxylic acid having two carboxyl groups, each attached to a carbon atom in a carbocyclic aromatic ring structure. It is not necessary that both functional carboxyl groups are attached to the same aromatic ring, and when more than one ring is present, they can be linked by an aliphatic or aromatic divalent radical, or a divalent radical such as -O- or -SO2-. Representative useful aliphatic and cycloaliphatic acids that can be used include sebacic acid; 1,3-cyclohexanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; adipic acid; glutaric acid; 4-cyclohexane-1,2-dicarboxylic acid; 2-ethylsuberic acid; cyclopentanedicarboxylic acid, decahydro-1,5-naphthalenedicarboxylic acid; 4,4'-bicyclohexyldicarboxylic acid; decahydro-2,6-naphthalenedicarboxylic acid; 4,4'-methylenebis(cyclohexyl)carboxylic acid; and 3,4-furandicarboxylic acid. Preferred acids are cyclohexanedicarboxylic acid and adipic acid.

[0024] Representative aromatic dicarboxylic acids include phthalic acid, terephthalic acid, and isophthalic acid; dibenzoic acid; substituted dicarboxy compounds with two benzene nuclei, such as bis(p-carboxyphenyl)methane; p-oxy-1,5-naphthalenedicarboxylic acid; 2,6-naphthalenedicarboxylic acid; 2,7-naphthalenedicarboxylic acid; 4,4'-sulfonyldibenzoic acid and its ring-substituted derivatives, such as C1-C12 alkyl and halo, alkoxy, and aryl derivatives. Hydroxy acids, such as p-(beta-hydroxyethoxy)benzoic acid, can also be used, provided that an aromatic dicarboxylic acid is also used.

[0025] Aromatic dicarboxylic acids are a preferred class for preparing the copolyetherester elastomers useful in the present invention. Among the aromatic acids, those with 8 to 16 carbon atoms are preferred, especially terephthalic acid, either alone or in mixtures with phthalic and / or isophthalic acid.

[0026] The copolyetherester elastomer preferably contains from 15 or about 15 weight percent to 99 or about 99 weight percent short chain ester units corresponding to formula (B) above, with the remainder being long chain ester units corresponding to formula (A) above, based on the total weight of the copolyetherester. The sum of the weight percentages of all copolymerized units in the copolyetherester is 100 weight percent. More preferably, the copolyetherester elastomer contains from 20 or about 20 weight percent to 95 or about 95 weight percent, and even more preferably from 50 or about 50 weight percent to 90 or about 90 weight percent short chain ester units, with the remainder being long chain ester units. More preferably, at least about 70 mole percent of the groups represented by R in formulas (A) and (B) above are 1,4-phenylene radicals, at least about 70 mole percent of the groups represented by D in formula (B) above are 1,4-butylene radicals, and the sum of the percentages of R groups that are not 1,4-phenylene radicals and D groups that are not 1,4-butylene radicals does not exceed 30 mole percent. When a second dicarboxylic acid is used to prepare the copolyetherester, isophthalic acid is preferred, and when a second low molecular weight diol is used, ethylene glycol, 1,3-propanediol, cyclohexanedimethanol, or hexamethylene glycol are preferred.

[0027] Blends or mixtures of two or more copolyetherester elastomers can be used. The copolyetherester elastomers used in the blend do not have to be individually within the values ​​disclosed above for the elastomers. However, blends of two or more copolyetherester elastomers must, on a weighted average basis, conform to the values ​​set forth herein for the copolyetheresters. For example, equal amounts of two copolyetheresters For a weighted average short-chain ester unit of 45 weight percent in a mixture containing polyetherester elastomers, one copolyetherester elastomer contains 60 weight percent short-chain ester units and the other resin contains 30 weight percent short-chain ester units.

[0028] Preferred copolyetheresters include, but are not limited to, copolyetherester elastomers prepared from monomers comprising: (1) poly(tetramethylene oxide) glycol; (2) a dicarboxylic acid selected from isophthalic acid, terephthalic acid, and mixtures thereof; and (3) a diol selected from 1,4-butanediol, 1,3-propanediol, and mixtures thereof; or from monomers comprising: (1) poly(trimethylene oxide) glycol; (2) a dicarboxylic acid selected from isophthalic acid, terephthalic acid, and mixtures thereof; and (3) a diol selected from 1,4-butanediol, 1,3-propanediol, and mixtures thereof; or from monomers comprising: (1) ethylene oxide-capped poly(propylene oxide) glycol; (2) a dicarboxylic acid selected from isophthalic acid, terephthalic acid, and mixtures thereof; and (3) a diol selected from 1,4-butanediol, 1,3-propanediol, and mixtures thereof.

[0029] Preferably, the copolyetherester is prepared from an ester or mixture of esters of terephthalic acid and / or isophthalic acid, 1,4-butanediol and poly(tetramethylene ether) glycol or poly(trimethylene ether) glycol or ethylene oxide-capped polypropylene oxide glycol, or from an ester of terephthalic acid, such as dimethyl terephthalate, 1,4-butanediol and polyethylene oxide) glycol. More preferably, the copolyetherester is prepared from an ester of terephthalic acid, such as dimethyl terephthalate, 1,4-butanediol and poly(tetramethylene ether) glycol.

[0030] In a preferred embodiment, the composition according to the present invention comprises a copolyetherester elastomer prepared from monomers comprising: (1) poly(tetramethylene oxide) glycol or poly(trimethylene oxide) glycol and mixtures thereof; (2) a dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures thereof; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol, and mixtures thereof.

[0031] More preferably, the composition according to the present invention comprises a copolyetherester elastomer prepared from monomers comprising: (1) poly(tetramethylene oxide) glycol; (2) terephthalic acid; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol, and mixtures thereof, wherein the concentration of poly(tetramethylene oxide) glycol is greater than about 25 weight percent, based on the total weight of the copolyetherester.

[0032] More particularly preferably, the compositions according to the present invention comprise a copolyetherester elastomer prepared from monomers comprising: (1) poly(tetramethylene oxide) glycol; (2) terephthalic acid; and (3) 1,4-butanediol, with the concentration of poly(tetramethylene oxide) glycol preferably being greater than about 15 weight percent, based on the total weight of the copolyetherester.

[0033] Particularly preferred is an elastomeric copolyether-ester having a hard segment composed of polybutylene terephthalate and approximately 40% by weight of a soft segment composed of polyether terephthalate. The proportion of hard segments is approximately 60% by weight. The polyether blocks are derived from polytetramethylene glycol and have a molecular weight of approximately 1000 g / mol. The copolyether-ester has a tensile modulus of approximately 180 MPa at 23° C. according to ISO standard 527 / 2.

[0034] In a particularly preferred embodiment, the copolyetherester has a Shore D hardness of 40 to 72, more preferably 50 to 63, and especially preferred 55D, measured with a Type D durometer according to ISO 7619-1, after conditioning at 23° C. for at least 1 hour before testing. The hardness value corresponds to the maximum force that can be applied to a 6 mm thick injection molded flat surface.

[0035] The copolyetheresters may be blended with other polymers such as polyesters (PET, PBT, etc.), ionomers, styrenic copolymers (ABS, SEBS, SEPS, etc.), polyamides, polycarbonates, PVC, or PMMA.

[0036] At least one phenolic antioxidant The composition of the present invention comprises at least one phenolic antioxidant. The phenolic antioxidant is not particularly limited, provided that it is a hindered phenol that can act as a radical scavenger. For example, phenols whose hydroxyl functional group is adjacent to fe / f-butyl groups are common and suitable.

[0037] Phenolic antioxidants may be selected from mono-phenols, di-phenols, tri-phenols, and molecules with more than three phenolic groups.

[0038] Di- and tri-phenols in which the hydroxyl group is adjacent to two alkyl groups, especially tertiary butyl groups, are especially preferred.

[0039] Examples of suitable phenolic antioxidants include, but are not limited to, the following: 1,3,5-tris(3,5-di-fe / f-butyl-4-hydroxybenzyl)-s-triazine-2,4,6(1 / - / ,3 / - / ,5 / - / )-trione (AO-20), pentaerythritol tetrakis(3,5-di-fe / f-butyl-4-hydroxyhydrocinnamate) (AO-60), 1,3,5-trimethyl-2,4,6-tris(3,5-di-fe / f-butyl-4-hydroxyhydrocinnamate) (AO-60), dibenzyl)benzene (AO-330), octadecyl 3-(3,5-di-fe / f-butyl-4-hydroxyphenyl)propionate (EVERNOX-76), octyl-3,5-di-fe / f-butyl-4-hydroxy-hydrocinnamate (EVERNOX-1135), 1,2-bis(3,5-di-fe / f-butyl-4-hydroxyhydrocinnamoyl)hydrazine (EVERNOX MD-1024), 3,3'-bis(3,5-di-fe / f-butyl-4-hydroxyphenyl)-N,N'-hexamethylenedipropionamide (EVERNOX-1098), N,N'-propane-1,3-diylbis[3-(3,5-di-fe / f-butyl-4-hydroxyphenyl)propionamide], 1,1,3-tris(2-methyl-4-hydroxy-5-fe / f-butylphenyl)butane (AO-30), 4,4'-butylidene-bis(6-fe / f-butyl- / 77-cresol) (AO-40), octadecyl 3-(3,5-di-fe / f-butyl-4-hydroxyphenyl)propanoate (AO-50).

[0040] The phenolic antioxidants may be used alone or in combinations of two, three or more in the copolyetherester resin compositions described herein.

[0041] Particularly preferred are (a) N,N'-propane-1,3-diylbis[3-(3,5-di-fe / f-butyl-4-hydroxyphenyl)propionamide] and (b) a mixture with N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], In particular, the total amount [(a)+(b)] is 0.10-1.0 wt%, more preferably 0.20-0.4 wt%, and even more preferably 0.3 wt% or about 0.3 wt%, based on the total weight of the copolyetherester resin composition. Preferably, the ratio of (a):(b) is 1:1 by weight.

[0042] The at least one phenolic antioxidant is preferably present in an amount of 0.10 to 0.6 wt %, more preferably 0.10 to 0.3 wt %, and especially preferably 0.20 to 0.30 wt %, based on the total weight of the copolyetherester resin composition.

[0043] At least one thioester antioxidant The composition of the present invention comprises at least one thioester antioxidant. Thioesters having a melting point between 30 and 60° C. are particularly preferred.

[0044] Non-limiting examples of suitable thioester antioxidants include: Dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], 3,3'-thiodipropionic acid dioctadecyl ester, 4,4'-thiobis(2-tert-butyl-5-methylphenol)bis(3-(dodecylthio)propionate), neopentanetetrayl 3-(dodecylthio)propionate, di(tridecyl)thiodipropionate, dimyristyl thiodipropionate, and mixtures of two or more thereof. Dilauryl thiodipropionate is the most preferred.

[0045] The thioester antioxidants may be used alone or in combinations of two, three or more.

[0046] The at least one thioester antioxidant is preferably present at 0.1 to 2.0 wt %, more preferably 0.2 to 1.0 wt %, and especially more preferably 0.3 to 0.5 wt %, based on the total weight of the copolyetherester resin composition.

[0047] If the at least one thioester antioxidant is present at more than 2.0 wt%, based on the total weight of the composition, deposits may appear on the surface of the composition ("blooming"), which may be aesthetically unpleasing in some applications. To avoid blooming, it is preferred to use less than 1.0 wt%, more preferably 0.5 wt% or less of the thioester antioxidant, based on the total weight of the copolyetherester resin composition.

[0048] At least one phosphite and / or phosphonite antioxidant The composition of the present invention comprises at least one phosphite and / or phosphonite antioxidant. The phosphite compounds that may be used in the composition according to the present invention may be monophosphites, diphosphites, and polyphosphites, with diphosphites being preferred.

[0049] Suitable monophosphites are, for example, trialkylphosphites, dialkylarylphosphites, alkyldiarylphosphites, and triarylphosphites. The alkyl groups in these phosphites may be linear and branched, may contain cyclic and / or aromatic groups, and may contain heteroatom-containing substituents. The aryl groups in these phosphites may be unsubstituted aryl groups as well as substituted aryl groups, where the substituted aryl groups may contain, for example, alkyl groups and / or heteroatom-containing substituents.

[0050] Preferably, the phosphite stabilizer is a sterically hindered aryl phosphite compound, more preferably pentaerythritol diphosphite.

[0051] Preferably, the phosphites have good hydrolysis resistance. The order of hydrolysis resistance of phosphites is typically: sterically hindered aryl phosphites > unsubstituted aryl phosphites > araliphatic phosphites > aliphatic phosphites.

[0052] Sterically hindered aryl phosphites and hindered amine stabilizer (HAS) phosphites (those containing 2,2,6,6-tetramethyl or 1,2,2,6,6-pentamethylpiperidinyl groups) are particularly preferred.

[0053] Suitable diphosphites are, for example, biphenylene diphosphite, pentaerythritol diphosphite, 4,4'-iso-propylidenediphenol diphosphite, and dipropylene glycol diphosphite. The phosphite groups in these diphosphites preferably contain alkyl and / or aryl groups, where the alkyl and aryl groups are preferably selected from those mentioned above for the monophosphites.

[0054] An example of a suitable biphenylene diphosphite is tetrakis-(2,4-di-tert-butyl-phenyl)-4,4'-biphenylene diphosphite. An example of a suitable pentaerythritol diphosphite is bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite and bis-(2,4-dicumylphenyl)pentaerythritol diphosphite. An example of a suitable 4,4'-isopropylidenediphenol diphosphite is tetrakis(iso-decyl)isopropylidenediphenol diphosphite, and an example of a suitable dipropylene glycol diphosphite is tetraphenyl dipropylene glycol diphosphite.

[0055] If used, the preferred amount of phosphite present in the copolyetherester compositions of the present invention is from 0.05 to 2.0 wt %, more preferably from 0.1 to 1.0 wt %, and especially preferably from 0.2 to 0.5 wt %, based on the total weight of the copolyetherester resin composition.

[0056] If the phosphite antioxidant is present at more than 0.8 wt%, based on the total weight of the copolyetherester resin composition, deposits may appear on the surface of the composition ("blooming"), which may be aesthetically unpleasing in some applications. To avoid blooming, it is preferred to use the phosphite antioxidant at a concentration of less than 0.8 wt%, more preferably 0.5 wt% or less, based on the total weight of the composition.

[0057] When it is desired to avoid blooming, solid phosphites are preferred over liquid phosphites.

[0058] If used, the preferred amount of phosphonite present in the copolyetherester composition is from 0.05 to 3.0 wt%, more preferably from 0.1 to 1.5 wt%, and especially preferably from 0.2 to 0.75 wt%, based on the total weight of the copolyetherester resin composition.

[0059] Some specific examples of suitable phosphite and phosphonite antioxidants include, but are not limited to, the following: Tris(2,4-di-fe / f-butylphenyl)phosphite, 1,3,7,9-tetratert-butyl 1-1 1-(2-ethylhexoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocin, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, (bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite), bis(2,4-di-fe / f-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(nonylphenyl)phosphite, isodecyldiphenylphosphite, 4,4'-isopropylidenediphenol C1 2~15-alcohol phosphite, triisodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, diisodecyl phenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite (ADK STAB PEP-36), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (Ultranox 626), 2,2'2"-nitrilo[triethyl-tris[3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl]]phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'diylbisphosphonite (Songwon PQ), and mixtures of two or more thereof.

[0060] Tris(2,4-di-fe / f-butylphenyl)phosphite, 1,3,7,9-tetratert-butyl-11-(2-ethylhexoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocin, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, (bis(2,6-di-fe / f-butyl-4-methylphenyl)pentaerythritol-diphosphite), bis(2, More preferred are bis(2,4-di-fe / f-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, 2,2'2"-nitrilo[triethyl-tris[3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl]]phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'diylbisphosphonite (e.g., SONGNOX PQ), and mixtures of two or more thereof.

[0061] Particularly preferred phosphites and / or phosphonites are selected from bis(2,4-di-fe / f-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]4,4'diylbisphosphonite, and (bis(2,6-di-fe / f-butyl-4-methylphenyl)pentaerythritol-diphosphite), most preferably bis(2,4-di-fe / f-butylphenyl)pentaerythritol diphosphite and bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0062] The phosphite or phosphonite antioxidants may be used alone or in combinations of two, three or more.

[0063] At least one epoxy compound The compositions of the present invention comprise at least one epoxy compound or a reaction product of an epoxy compound. For purposes of the present invention, the term "epoxy compound" includes any compound having one or more epoxide group functionalities, including polymers having multiple epoxy functionalities, such as copolymers of ethylene / n-butyl acrylate / glycidyl methacrylate.

[0064] Preferred epoxy compounds have a maximum of two epoxide groups per molecule.

[0065] Preferred epoxy compounds are prepared by reacting epichlorohydrin with diols such as diphenylolpropane, diphenylolmethane, diamines, diacids and polypropylene glycol, and polymers having glycidyl groups such as ethylene / n-butyl acrylate / glycidyl methacrylate, etc. Particularly preferred epoxy compounds are prepared by reacting epichlorohydrin with diols such as diphenylolpropane, diphenylolmethane, or polypropylene glycol.

[0066] Examples of suitable epoxy compounds include, but are not limited to: Included are poly(bisphenol A-co-epichlorohydrin) glycidyl endcaps, poly(bisphenol F-co-epichlorohydrin) glycidyl endcaps, 2,2-bis(4-hydroxyphenyl)propane-epichlorohydrin copolymers, tetraglycidyl ethers of tetraphenol ethane, diglycidyl ethers of polypropylene glycol, and combinations of two or more thereof. Most preferred are poly(bisphenol A-co-epichlorohydrin) glycidyl endcaps.

[0067] All of the epoxy compounds described herein may be used alone or in combinations of two, three or more.

[0068] To calculate the amount of epoxide groups in the composition, the -CFIOCFI2 group, which has a molecular weight of 43 g / mol, is used. The epoxide groups from the epoxy compounds are preferably present in an amount of 0.01 to 2.00 wt%, more preferably 0.05 to 1.00 wt%, and especially preferably 0.1 to 0.6 wt%, based on the total weight of the copolyetherester resin composition.

[0069] Optional Further Additives The copolyetherester resin composition of the present invention may further comprise additives including, but not limited to, one or more of the following: metal deactivators such as hydrazines and hydrazides; additional heat stabilizers; additional antioxidants; modifiers; colorants, lubricants, waxes, fillers, and reinforcing agents, impact modifiers, flow improver additives, antistatic agents, crystallization promoters, conductive additives, viscosity modifiers, nucleating agents, plasticizers, mold release agents, scratch and mar modifiers, drip suppressants, adhesion modifiers, and other processing aids known in the polymer compounding art; and combinations of two or more thereof. Preferably, the additives are selected from the group consisting of stabilizers, processing agents, metal deactivators, antioxidants, UV stabilizers, heat stabilizers, dyes, and / or pigments. If used, the additional additives are preferably present in an amount of about 0.05 weight percent to about 10 weight percent based on the total weight of the copolyetherester resin composition.

[0070] The copolyetherester resin compositions of the present invention may further comprise organic and inorganic fillers and reinforcing agents such as glass fibers, glass flakes, glass particles, carbon fibers, aramid fibers, mica, talc, and wollastonite.

[0071] The composition of the present invention may additionally comprise one or more arylamine antioxidants. For example, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine is a suitable arylamine antioxidant. When present, the one or more arylamine antioxidants are preferably present at 0.4 to 1.6 wt%, more preferably 0.6 to 1 wt%. In a preferred embodiment, the one or more arylamine antioxidants are 4,4'-bis(α,α-dimethylbenzyl)diphenylamine in an amount of 0.8 wt%, based on the total weight of the copolyetherester resin composition.

[0072] Preferred Compositions The following copolyetherester compositions are particularly preferred: (A) at least one copolyetherester; (B) a phenolic antioxidant selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) at least one epoxy compound or reaction product of an epoxy compound.

[0073] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) a thioester antioxidant selected from dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate]; (D) at least one phosphite and / or phosphonite antioxidant; (E) at least one epoxy compound or reaction product of an epoxy compound.

[0074] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) a phosphite antioxidant selected from sterically hindered aryl phosphite antioxidants and mixtures of two or more thereof; (E) at least one epoxy compound or reaction product of an epoxy compound.

[0075] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, diphenylolmethane, polypropylene glycol, and mixtures of two or more thereof, or a reaction product of one of these epoxy compounds.

[0076] (A) at least one copolyetherester; (B) a phenolic antioxidant which is a 1:1 mixture of N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide]; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) at least one epoxy compound or reaction product of an epoxy compound.

[0077] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) at least one epoxy compound or reaction product of an epoxy compound.

[0078] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) a phosphite antioxidant selected from bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and mixtures thereof; (E) at least one epoxy compound or reaction product of an epoxy compound.

[0079] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, polypropylene glycol, and combinations of two or more thereof, or at least one reaction product of one of these epoxy compounds.

[0080] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; (E) at least one epoxy compound or reaction product of an epoxy compound.

[0081] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) a poly(bisphenol A-co-epichlorohydrin) glycidyl endcap, or a reaction product thereof with an epoxy compound.

[0082] (A) at least one copolyetherester; (B) a phenolic antioxidant selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof; (C) a thioester antioxidant selected from dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], and mixtures thereof; (D) a phosphite antioxidant selected from sterically hindered aryl phosphite antioxidants, and mixtures of two or more thereof; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, polypropylene glycol, and a mixture of two or more thereof, or a reaction product of at least one of these epoxy compounds.

[0083] (A) at least one copolyetherester; (B) a phenolic antioxidant which is a 1:1 mixture of N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide]; (C) a thioester antioxidant selected from dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], and mixtures thereof; (D) a phosphite antioxidant selected from sterically hindered aryl phosphite antioxidants, and mixtures of two or more thereof; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, polypropylene glycol, and a mixture of two or more thereof, or a reaction product of at least one of these epoxy compounds.

[0084] (A) at least one copolyetherester; (B) a phenolic antioxidant which is a 1:1 mixture of N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide]; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) a phosphite antioxidant selected from sterically hindered aryl phosphite antioxidants, and mixtures of two or more thereof; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, polypropylene glycol, and a mixture of two or more thereof, or a reaction product of at least one of these epoxy compounds.

[0085] (A) at least one copolyetherester; (B) a phenolic antioxidant which is a 1:1 mixture of N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide]; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) a phosphite antioxidant selected from bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and mixtures thereof; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, polypropylene glycol, and a mixture of two or more thereof, or a reaction product of at least one of these epoxy compounds.

[0086] (A) at least one copolyetherester; (B) a phenolic antioxidant which is a 1:1 mixture of N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide]; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) a phosphite antioxidant selected from bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and mixtures thereof; (E) a copolyetherester resin composition comprising poly(bisphenol A-co-epichlorohydrin) glycidyl endcapped, poly(bisphenol F-co-epichlorohydrin) glycidyl endcapped, 2,2-bis(4-hydroxyphenyl)propane-epichlorohydrin copolymer, and an epoxy compound selected from epoxy compounds prepared by reaction of epichlorohydrin with a diol, such as polypropylene glycol, and combinations of two or more of these, or a reaction product of at least one of these epoxy compounds.

[0087] (A) at least one copolyetherester; (B) a phenolic antioxidant selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) a phosphite antioxidant selected from sterically hindered aryl phosphite antioxidants, and mixtures of two or more thereof; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, polypropylene glycol, and a mixture of two or more thereof, or a reaction product of at least one of these epoxy compounds.

[0088] (A) at least one copolyetherester; (B) a phenolic antioxidant selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof; (C) a thioester antioxidant selected from dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], and mixtures thereof; (D) a phosphite antioxidant selected from bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and mixtures thereof; (E) a copolyetherester resin composition comprising an epoxy compound selected from epoxy compounds prepared by the reaction of epichlorohydrin with a diol, such as diphenylolpropane, polypropylene glycol, and a mixture of two or more thereof, or a reaction product of at least one of these epoxy compounds.

[0089] (A) at least one copolyetherester; (B) a phenolic antioxidant selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof; (C) a thioester antioxidant selected from dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], and mixtures thereof; (D) a phosphite antioxidant selected from sterically hindered aryl phosphite antioxidants, and mixtures of two or more thereof; (E) a copolyetherester resin composition comprising poly(bisphenol A-co-epichlorohydrin) glycidyl endcapped, poly(bisphenol F-co-epichlorohydrin) glycidyl endcapped, 2,2-bis(4-hydroxyphenyl)propane-epichlorohydrin copolymer, and an epoxy compound selected from epoxy compounds prepared by reaction of epichlorohydrin with a diol, such as polypropylene glycol, and mixtures of two or more thereof, or a reaction product of at least one of these epoxy compounds.

[0090] (A) at least one copolyetherester; (B) a phenolic antioxidant selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) the phosphite antioxidant bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; (E) a copolyetherester resin composition comprising an epoxy compound, poly(bisphenol A-co-epichlorohydrin), a glycidyl endcap, or a reaction product of this epoxy compound.

[0091] In these particularly preferred compositions, as well as all of the copolyetherester resin compositions described herein, the amounts of components (A), (B), (C), (D), (E), and other components, if present, are complementary, i.e., the sum of the weight percentages of the components of the copolyetherester resin composition equals 100 wt.%.

[0092] manufacturing The copolyetherester resin compositions of the present invention are melt mixed blends in which all of the polymeric components are well dispersed in one another and all of the non-polymeric ingredients are well dispersed in and bound by the polymer matrix such that the blend forms a cohesive whole. Any melt mixing method may be used to combine the polymeric components and non-polymeric ingredients of the present invention.

[0093] The polymeric components and non-polymeric ingredients of the copolyetherester compositions of the present invention can be added to a melt mixer, such as, for example, a single or twin screw extruder; a blender; a single or twin screw kneader; or a Banbury mixer, either simultaneously by single step addition or stepwise, and then melt mixed. When the polymeric components and non-polymeric ingredients are added stepwise, a portion of the polymeric components and / or non-polymeric ingredients are added first and melt mixed, and the remaining polymeric components and non-polymeric ingredients are then added and further melt mixed until a well mixed composition is obtained.

[0094] Those skilled in the art can select compounding conditions that can promote or retard the reactivity of the epoxy compounds. For example, reactivity can be accelerated at higher compounding temperatures, in the presence of optional catalysts, or during longer residence times in the melt mixing stage. In some preferred processes, compounding is carried out at temperatures above 200°C, and some epoxy groups are expected to react with the copolyetherester carboxylic acid ends during compounding. In other preferred processes, some epoxy groups remain unreacted after compounding is complete. In these preferred processes, the amount of optional catalyst may be reduced or the catalyst may be omitted. In still other preferred processes, all or a portion of the epoxy groups remaining in the composition after compounding may react with the copolyetherester acid ends formed by thermo-oxidative chain scission when the composition is exposed to dry heat at 150°C.

[0095] Purpose The copolyetherester resin compositions of the present invention may be shaped into articles using methods known to those skilled in the art, such as injection molding, blow molding, injection blow molding, extrusion molding, thermoforming, melt casting, vacuum molding, rotational molding, calendar molding, slush molding, filament extrusion, and fiber spinning. These molding processes are typically operated at temperatures about 20-30°C above the melting point of the copolyetherester composition. Such articles may include films, fibers and filaments; wire and cable coatings; solar cable coatings; fiber optic coatings; tubing and pipes; fabrics or textiles made from fibers and filaments, such as those used in clothing or carpets; films and membranes, such as roofing and breathable membranes in buildings / structures; automotive parts, such as body panels, airbag doors, dashboards, engine covers, rocker panels, constant velocity joint boots, air ducts, or air filter covers; parts for home appliances, such as washers, dryers, refrigerators, and heating ventilation air conditioning units; connectors in electrical / electronic applications; parts for electronic devices, such as computers; parts for office, indoor, and outdoor furniture; and footwear components.

[0096] The copolyetherester compositions of the present invention exhibit excellent thermal stability, in a preferred embodiment, the compositions of the present invention exhibit a time to 50% retention of break strain after heat aging at 150° C. for at least 720 hours, more preferably at least 750 hours, and especially more preferably at least 780 hours, when the break strain is measured according to ISO 527-2 at 23° C.

[0097] Alternatively, in a preferred embodiment, the compositions of the present invention exhibit a relative retention of break strain of greater than 60% after exposure to air at 150° C. for 600 hours, when the break strain is measured according to ISO 527-2 at 23° C.

[0098] Alternatively, in a preferred embodiment, the compositions of the present invention exhibit a relative retention of break strain of greater than 40% after 800 hours exposure to air at 150° C., when the break strain is measured according to ISO 527-2 at 23° C.

[0099] Alternatively, in a preferred embodiment, the compositions of the present invention exhibit a relative retention of break strain of greater than 30% after exposure to air at 150° C. for 1,000 hours, when the break strain is measured according to ISO 527-2 at 23° C.

[0100] The relative retention of break strain is the ratio of the break strain after x hours of exposure at high temperature (e.g. 150°C) to the break strain before heat exposure. The ratio is expressed as %. All measurements of break strain retention before and after heat aging are performed according to ISO 527-2. The break strain measurements are performed at 23°C and at a speed of 200 mm / min. The extensometer distance is 20 mm and the distance between the tensile clamps is 40 mm. The test specimens injection moulded according to ISO 527-2 / 5a are kept in the test laboratory under ambient conditions for at least one day (approximately 12-36 hours) before any measurements.

[0101] This thermal stability makes the compositions of the present invention particularly suitable for use in fluid duct and joint protection, especially those exposed to high temperatures, including automotive fluid ducts such as air ducts, constant velocity joint (CVJ) boots, and rack and pinion boots.

[0102] The following examples are provided to further illustrate the present invention. These examples, which represent preferred modes presently contemplated for carrying out the invention, are intended to illustrate, but not to limit, the present invention. EXAMPLES

[0103] The base resin was a copolyetherester having a Shore D hardness of 55D as measured with a type D durometer according to ISO 7619-1. The base resin was stabilized with a phenolic antioxidant as set forth in Table 1 below to obtain a total phenolic antioxidant content of 0.3 wt% based on the total weight of the "base resin formulation" consisting of the copolyetherester and the phenolic antioxidant as set forth below. The copolyetherester has approximately 40 wt% hard segments composed of polybutylene terephthalate and approximately 40 wt% soft segments composed of polyether terephthalate. The percentage of hard segments is approximately 60 wt%. The polyether blocks are derived from polytetramethylene glycol and have a molecular weight of approximately 1000 g / mol. The copolyetherester has a tensile modulus of approximately 180 MPa at 23°C, measured according to ISO standard 527-2 at a speed of 1 mm / min.

[0104] [Table 1]

[0105] The compositions of the invention and the comparative compositions were compounded in a Werner & Pfleiderer extruder with a diameter of 30 mm. The extruder is a twin-screw compounder with a length / diameter ratio of 29 / 1. The barrel temperature was set at 220°C. The throughput was about 13 kg per hour and the torque varied between 83 and 88%, based on the maximum torque allowed by the extruder. The various additives used are shown in Table 2 below:

[0106] [Table 2]

[0107] The base resin was compounded with the raw materials in the amounts shown in Table 1. Tensile bars according to the dimensions specified in ISO 527-2 / 5a were injection molded at a melt temperature of 235° C. and a mold temperature of about 45° C. The bars were exposed to an air flow at 150° C. in an oven. The bars were removed from the oven at predetermined intervals, cooled to 23° C., stored at room temperature in the laboratory for at least one day, and then stretched to measure the tensile properties and the breaking strain was measured according to ISO 527-2 at 23° C. at a speed of 200 mm / min.

[0108] The change in break strain with time of thermal exposure provides a good indication of the degradation of the polymer due to thermo-oxidation. From the data, the value of the time required to retain 50% of the break strain was determined for each composition. This data is shown in Table 3.

[0109] [Table 3]

[0110] The data in Table 3 show that the combination of thioester, phosphite, epoxy, and phenolic antioxidants provides the best thermal stability for the copolyetherester elastomer, retaining 50% of the break strain after 800 hours exposure to 150° C. air flow.

[0111] Further phosphites and phosphonites were used in compositions according to the invention, E2 to E5, and the results are listed in Table 4.

[0112] The data in Table 4 show that a combination of thioester, phosphite, epoxy, and phenolic antioxidants provides the best thermal stability for the copolyetherester elastomers.

[0113] The relative retention of break strain is the ratio of the break strain after x hours of exposure at high temperature (e.g. 150°C) to the break strain before heat exposure. The ratio is expressed as a percentage. All measurements of break strain retention before and after heat aging are done according to ISO 527-2 at 23°C under a speed of 200 mm / min.

[0114] While certain preferred embodiments of the present invention have been described and specifically exemplified above, it is not intended that the invention be limited to such embodiments. Various modifications may be made without departing from the scope and spirit of the invention as set forth in the following claims.

[0115] [Table 4]

[0116] The claims of the parent application as filed are as follows: [1] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) at least one epoxy compound, or a reaction product of said at least one epoxy compound. [2] The copolyetherester resin composition according to [1], wherein the at least one copolyetherester is selected from copolyetheresters prepared from monomers comprising: (1) poly(tetramethylene oxide) glycol or poly(trimethylene oxide) glycol, poly(propylene oxide) glycol, and mixtures of two or more thereof; (2) a dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures thereof; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol, and mixtures thereof; or the at least one copolyetherester is selected from copolyetheresters prepared from monomers comprising: (1) poly(tetramethylene oxide) glycol; (2) terephthalic acid; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol, and mixtures thereof. [3] The at least one phenolic antioxidant is selected from the group consisting of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6(1H,3H,5H)-trione (AO-20), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (AO-30), 4,4'-butylidene-bis(6-tert-butyl-m-cresol) (AO-40), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (AO-50), benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl- (AO-80). , 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (AO-330), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (EVERNOX-10), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (EVERNOX-76), octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate (EVERNOX-1135), 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (EVERNOX MD-1024), 3,3'-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N'-hexamethylenedipropionamide (EVERNOX-1098), N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], and mixtures of two or more thereof; preferably, the at least one phenolic antioxidant is selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof. [4] The copolyetherester resin composition according to any one of [1] to [3], wherein the at least one phenolic antioxidant is a 1:1 mixture of N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide]. [5] The copolyetherester resin composition according to any one of [1] to [4], wherein the at least one thioester antioxidant is selected from dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], 3,3'-thiodipropionic acid dioctadecyl ester, 4,4'-thiobis(2-tert-butyl-5-methylphenol) bis(3-(dodecylthio)propionate), neopentanetetrayl 3-(dodecylthio)propionate, di(tridecyl)thiodipropionate, and mixtures of two or more thereof; preferably, the at least one thioester antioxidant is selected from dilauryl thiodipropionate, thiodiethylene bis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], and mixtures thereof. [6] The copolyetherester resin composition according to any one of [1] to [5], wherein the at least one thioester antioxidant is dilauryl thiodipropionate. [7] The copolyetherester resin composition according to any one of [1] to [6], wherein the at least one phosphite and / or phosphonite antioxidant is selected from diphosphites, sterically hindered aryl phosphites, hindered amine stabilizer phosphites, pentaerythritol diphosphites, and mixtures of two or more thereof. [8] The at least one phosphite and / or phosphonite antioxidant is selected from the group consisting of tris(2,4-di-fe / f-butylphenyl)phosphite, 1,3,7,9-tetratert-butyl-11-(2-ethylhexoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocin, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(nonylphenyl)phosphite, isodecyldiphenylphosphite, 4,4'-isopropylidenediphenol C 12~15 and mixtures of two or more thereof; preferably, the at least one phosphite and / or phosphonite antioxidant is selected from alcohol phosphite, triisodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, diisodecyl phenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite (ADK STAB PEP-36), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (Ultranox 626), 2,2'2"-nitrilo[triethyl-tris[3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl]]phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'diyl bisphosphonite. [7] The copolyether ester resin composition according to any one of [1] to [7], wherein the aryl group is selected from bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, and a mixture of two or more thereof. [9] The copolyetherester resin composition according to any one of [1] to [8], wherein the at least one epoxy compound is selected from those having two or more epoxy groups per molecule, and mixtures of two or more thereof.

[10] The copolyetherester resin composition according to any one of [1] to [9], wherein the at least one epoxy compound is selected from poly(bisphenol A-co-epichlorohydrin) glycidyl endcapped, poly(bisphenol F-co-epichlorohydrin) glycidyl endcapped, tetraglycidyl ether of tetraphenol ethane, polypropylene glycol diglycidyl ether copolymer of ethylene / n-butyl acrylate / glycidyl methacrylate, copolymer of ethylene / n-methyl acrylate / glycidyl methacrylate, resorcinol diglycidyl ether, and mixtures of two or more thereof; preferably, the at least one epoxy compound is poly(bisphenol A-co-epichlorohydrin) glycidyl endcapped.

[11] The copolyetherester resin composition according to any one of [1] to

[10] , further comprising at least one arylamine antioxidant, wherein the arylamine antioxidant is preferably 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

[12] The copolyetherester resin composition according to any one of [1] to

[11] , wherein the copolyetherester is present in an amount of 50 to 98 wt %; or the at least one phenolic antioxidant is present in an amount of 0.1 to 0.6 wt %; or the at least one thioester antioxidant is present in an amount of 0.1 to 2.0 wt %; or the at least one phosphite and / or phosphonite antioxidant is present in an amount of 0.05 to 2.0 wt %; or the at least one epoxy compound is present in an amount such that epoxide groups are present in the composition at 0.01 to 2.0 wt %; or the arylamine antioxidant is present in an amount of 0.4 to 1.6 wt %, based on the total weight of the copolyetherester resin composition.

[13] (A) at least one copolyetherester; (B) a phenolic antioxidant which is a 1:1 mixture of N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide]; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) a phosphite antioxidant selected from bis(2,4-di-fe / f-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and mixtures thereof; (E) an epoxy compound selected from poly(bisphenol A-co-epichlorohydrin) glycidyl endcapped, poly(bisphenol F-co-epichlorohydrin) glycidyl endcapped, tetraglycidyl ether of tetraphenol ethane, polypropylene glycol diglycidyl ether, and a mixture of two or more thereof; or a reaction product of the epoxy compound.

[14] (A) at least one copolyetherester; (B) a phenolic antioxidant selected from N,N'-propane-1,3-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], N,N'-hexane-1,6-diylbis[3-(3,5-di-butyl-4-hydroxyphenyl)propionamide], and mixtures thereof; (C) dilauryl thiodipropionate, a thioester antioxidant; (D) the phosphite antioxidant bis(2,4-di-fe / f-butylphenyl)pentaerythritol diphosphite; (E) a copolyetherester resin composition comprising an epoxy compound, poly(bisphenol A-co-epichlorohydrin), a glycidyl endcap, or a reaction product of the epoxy compound.

[15] The copolyetherester resin composition according to any one of [1] to

[14] , wherein the time until 50% of the breaking strain is retained, as measured according to ISO 527-2 using a test piece conforming to ISO 527-2 / 5a, is at least 720 hours.

[16] A part produced from the copolyetherester resin composition according to any one of [1] to

[15] .

[17] The part according to

[16] , which is a fluid duct.

[18] The part according to

[16] , which is an automotive fluid duct or an automotive gas duct.

Claims

[Claim 1] (A) at least one copolyetherester; (B) at least one phenolic antioxidant; (C) at least one thioester antioxidant; (D) at least one phosphite and / or phosphonite antioxidant; (E) at least one epoxy compound, or a reaction product of said at least one epoxy compound.

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