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EP1882009A1 - Verfahren zur verbesserung der wärme- und lichtstabilität von polyestern - Google Patents

Verfahren zur verbesserung der wärme- und lichtstabilität von polyestern

Info

Publication number
EP1882009A1
EP1882009A1 EP06755115A EP06755115A EP1882009A1 EP 1882009 A1 EP1882009 A1 EP 1882009A1 EP 06755115 A EP06755115 A EP 06755115A EP 06755115 A EP06755115 A EP 06755115A EP 1882009 A1 EP1882009 A1 EP 1882009A1
Authority
EP
European Patent Office
Prior art keywords
tert
bis
butyl
process according
chain extender
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06755115A
Other languages
English (en)
French (fr)
Inventor
Natacha Berthelon
Daniel Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP06755115A priority Critical patent/EP1882009A1/de
Publication of EP1882009A1 publication Critical patent/EP1882009A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to process for improving the thermal and light stability of polyesters, especially polyester fibers, which comprises adding to the polyesters a chain extender.
  • U.S. 6,469,078 discloses a process for increasing the molecular weight and/or for the modification of polycondensates during processing in the melt, which comprised adding to the polycondensate a blend comprising a) at least one polyfunctional anhydride (polyanhydride); b) at least one polyfunctional compound, the functional groups of which can react with the anhydride groups of component a); and c) at least one phosphonate.
  • WO-A-2004/101666 discloses masterbatches useful for modifying thermoplastic polymers, in particular to masterbatches comprising dispersed polyol branching agent and/or chain coupling agents, such as for example dianhydrides.
  • the instant invention pertains therefore to a a process for improving the thermal and light stability of polyesters which comprises adding to the polyesters a chain extender.
  • polyesters which are polyester fibers.
  • the polyester is particularly preferably polyethylene terephthalate (PET), polybutylene te- rephthalate (PBT), polyethylene naphthalate, polytrimethylene terephthalate (PTT) or copo- lyesters. Especially preferred are polyethylene terephthalate or polyethylene naphthalate.
  • the polyesters may be homopolyesters or copolyesters which are composed of aliphatic, cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acids.
  • the polyesters can be prepared by direct esterification (PTA process) and also by trans- esterification (DMT process). Any of the known catalyst systems may be used for the preparation.
  • Preferred diacids are selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms, and mixtures thereof.
  • diacids are terephthalic acid, isophthalic acid, o-phthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4 1 - dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and mixtures thereof.
  • terephthalic acid and 2,6-naphthalene dicarboxylic acid are especially preferred.
  • Preferred diols are compounds of the formula A
  • R is an aliphatic, cycloaliphatic or aromatic moiety of 2 to 18 carbon atoms.
  • such diols are for example ethylene glycol, diethylene glycol, triethylene glycol, propane-1 ,3-diol, propane -1 ,2-diol, butane-1 ,4-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, 1 ,4- cyclohexanedimethanol, 3-methylpentane-2,4-diol, 2-methylpentane-1 ,4-diol, 2,2-diethylpro- pane-1 ,3-diol, 1 ,4-di-(hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)-propane, 2,4- dihydroxy-1 ,1 ,3,3-tetramethylcyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)propane, 2,2-bis- (4-hydroxypropoxyphenyl)ethane and mixture
  • the diol is ethylene glycol or 1 ,4-cyclohexanedimethanol.
  • various diesters may be used.
  • diesters that correspond in respect of their acid moiety to the aforementioned diacids may be used.
  • Suitable diesters therefore also include the aliphatic and the aromatic kind.
  • Very suitable diesters are for example the d-C 4 alkyl esters of terephthalic acid, iso- phthalic acid, o-phthalic acid or naphthalene dicarboxylic acid.
  • esterification and transesterification processes are carried out in the presence of a catalyst.
  • Catalysts of interest for the esterification process are for example antimony or germanium compounds, e.g. antimony(lll)oxide (Sb 2 O 3 ) or germanium dioxide (GeO 2 ).
  • antimony or germanium compounds e.g. antimony(lll)oxide (Sb 2 O 3 ) or germanium dioxide (GeO 2 ).
  • titanium catalysts as disclosed for example in D E-A- 19 513 056 or titanium based catalysts in combination with cobalt and phosphorous based compounds as disclosed for example in DE-A-19 518 943.
  • Catalysts of interest for the transesterification process are for example titanium compounds, e.g. titanium(IV)butoxide.
  • the catalysts are preferably used in the preparation of polyesters in an amount of 0.005 to 0.035 % by weight of the total amount of reactants.
  • Polyesters may be produced in a conventional batch process, wherein the product of the transesterification or esterification is formed in one vessel and then transferred to a second vessel for polymerization.
  • the second vessel is agitated and the polymerization reaction is continued until the power used by the agitator reaches a level indicating that the polyester melt has achieved the desired intrinsic viscosity and therefore, the desired molecular weight.
  • the esterification or transesterification is typically conducted at an elevated temperature between for example 200 to 35O 0 C to produce a polyester having an intrinsic viscosity of 0.3 to 0.8 dl/g, commonly about 0.6 to 0.75 dl/g (determined by ASTM D-4603-86 at 3O 0 C in a mixture of 60 % by weight of phenol and 40 % by weight of tetrachloroethane).
  • these steps may also be carried out in a continuous process.
  • the continuous process disclosed in WO-A-97/44376 is conducted by combining the diol with the diacid or diester at a temperature of about 240 to 29O 0 C and at a pressure of from about 30 to 600 kPa for about 1 to 5 hours to yield low molecular weight oligomers and water.
  • a continuous feed of reactants is used employing a molar ratio of diol to diacid or diester of from about 1.0 to 1.6. The water or alcohol so produced is removed as the reaction proceeds.
  • the oligomers are agitated at a temperature of about 240 to 305 0 C for about 1 to 4 hours in the presence of a polymerization catalyst to form the polyester melt.
  • the polycondensation reaction begins in a first vessel operated at a pressure range of from about 0 to 10 kPa.
  • Diol produced in the polycondensation is removed from the polyester melt using an applied vacuum.
  • the polyester melt is typically agitated to allow the diol to escape from the polyester melt.
  • the molecular weight and thus the intrinsic viscosity of the polyester melt increases.
  • the temperature of each vessel is generally increased and the pressure decreased to allow greater polymerization in each successive vessel.
  • the final vessel is generally operated at a pressure of from about 0 to 5.5 kPa.
  • Each of the polymerization vessels communicates with a flash vessel. The retention time in the polymerization vessels and the feed ratio of the reactants into the continuous process are determined in part based on the target molecular weight of the polyester.
  • the polymerization catalyst employed in the continuous process is generally added prior to, at the start of, or during the polymerization stage.
  • chain extender employed may already be added prior to, at the start of, or during the polymerization stage.
  • the resulting polyester which is still in the form of a melt, is generally filtered and the typically extruded and pelletized before being worked up into specific polyester articles or injection molded in a preform or coating into an item such as a bottle.
  • Such steps are also typically labeled as “polyester processing” but refer of course to later working of the finished polyester rather than to the chemical processing steps used to form the polyester in the first place.
  • polyester melt may be extruded into polyester sheets, filaments, pellets, chips or similar particles (so-called primary extrusion step).
  • the polyester melt is extruded shortly or immediately after exiting the polycondensation stage, whereupon it is quenched, for example in a water trough or alternative cooling unit.
  • the formation of pellets or chips is particularly convenient for storage, transport and handling purposes.
  • the pellets of chips may be subjected to solid state polymerization (SSP), for example, to raise the intrinsic viscosity to 0.7 to 1.2 dl/g, preferably to about 0.83 dl/g.
  • SSP solid state polymerization
  • the pellets or chips are re-melted and re-extruded or injection molded.
  • the extrusion and injection molding conditions are conventional.
  • the polyester may be extruded at a temperature in the range of 240 to 315 0 C
  • a process for improving the thermal and light stability of polyesters which comprises adding to the polyesters a chain extender which is selected from the group consisting of anhydrides, epoxides, oxazolines, oxazolones, oxazines, isocyanates, acyllactams, male- imides, alcohols and hindered phenolic aromatic phosphates or mixtures thereof.
  • a chain extender which is selected from the group consisting of anhydrides, epoxides, oxazolines, oxazolones, oxazines, isocyanates, acyllactams, male- imides, alcohols and hindered phenolic aromatic phosphates or mixtures thereof.
  • R is a radical of the formulae (Ba) - (BK)
  • Q is -CH 2 -, -CH(CH 3 )-, -C(CH 3 J 2 -, -C(CF 3 J 2 -, -S-, -O-, -SO 2 -, -NHCO-, -CO- or >P(O)(CrC 20 alkyl) and wherein the aromatic rings in the formulae (Ba)-(Be) are unsubstitut- ed or substituted by one or several C r C 6 alkyl groups, C r C 6 alkoxy groups or halogen atoms.
  • the tetracarboxylic dianhydride may be, for example, butane-1 ,2,3,4-tetracarboxylic dianhydride.
  • Preferred tetracarboxylic dianhydrides are those containing aromatic rings.
  • tetracarboxylic dianhydrides of different structure.
  • Individual particularly preferred tetracarboxylic dianhydrides are: pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, 1 ,1 ,2,2-ethanetetracarboxylic dianhydride, 1 ,2,3,4-cyclopentanetetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3 cyclohexane-1 ,2-dicarboxylic dianhydride, bis(3,4-dicarbonacidphenyl) ether dianhydride, bis(3,4-dicarboxylic acid phenyl)thioether dianhydride, bisphenol A bisether dianhydride, 2,2-bis(3,4-dicarboxylic phenyl
  • the epoxides contain, for example, two epoxy radicals, for example those of formula C
  • radicals are directly bound to carbon, oxygen, nitrogen or sulfur atoms, wherein, if
  • Diglycidyl ester and di( ⁇ -methylglycidyl)ester obtainable by reacting a compound containing two carboxyl groups in the molecule with epichlorohydrin or glycerol dichlorohydrin or ⁇ -methylepichlorohydrin. The reaction is usefully carried out in the presence of bases.
  • Compounds containing two carboxyl groups in the molecule may be aliphatic dicarboxylic acids.
  • these dicarboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linolic acid.
  • cycloaliphatic dicarboxylic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4- methylhexahydrophthalic acid.
  • Aromatic dicarboxylic acids may also be used, such as phthalic acid or isophthalic acid.
  • Diglycidyl ether or di( ⁇ -methylglycidyl)ether obtainable by reacting a compound containing two free alcoholic hydroxyl groups and/or phenolic hydroxyl groups with a suitably substituted epichlorohydrin under alkaline conditions or in the presence of an acid catalyst with subsequent treatment with alkali.
  • Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene)glycols, propane-1 ,2-diol, or poly(oxypropy- lene)glycols, propane-1 ,3-diol, butane-1 ,4-diol, poly(oxytetramethylene)glycols, pentane- 1 ,5-diol, hexane-1 ,6-diol, sorbitol, and from polyepichlorohydrins.
  • acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly(oxyethylene)glycols, propane-1 ,2-diol, or poly(oxypropy- lene)glycols, propane-1 ,3-diol, butane-1 ,4-diol, poly(oxytetramethylene)glycols, pentane-
  • cycloaliphatic alcohols such as 1 ,3- or 1 ,4-dihy- droxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1 ,1-bis(hydroxymethyl)-cyclohex-3-ene, or they have aromatic nuclei such as N,N-bis(2- hydroxyethyl)aniline or p,p 1 -bis(2-hydroxyethylamino)diphenylmethane.
  • cycloaliphatic alcohols such as 1 ,3- or 1 ,4-dihy- droxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1 ,1-bis(hydroxymethyl)-cyclohex-3-ene, or they have aromatic nuclei such as N,N-bis(2- hydroxy
  • the epoxides can also be derived from mononuclear phenols, for example from resorcinol, pyrocatechol or hydroquinone; or they are based on polynuclear phenols such as on 4,4'- dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2- bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4 1 -dihydroxydiphenylsulfone, 9,9'-bis(4- hydroxyphenyl)fluorene, or on condensates, obtained under acid conditions, of phenols with formaldehyde such as phenol novolaks. 3.
  • mononuclear phenols for example from resorcinol, pyrocatechol or hydroquinone
  • polynuclear phenols such as on 4,4'- dihydroxybiphenyl, bis(4-hydroxyphenyl
  • Di(N-glycidyl) compounds are obtainable, for example, by dehydrochlorination of the reaction products of epichlorhydrin with amines containing two aminohydrogen atoms.
  • amines are, for example, aniline, toluidine, n-butylamine, bis(4- aminophenyl)methane, m-xylylenediamine or bis(4-methylaminophenyl)methane.
  • the di(N-glycidyl) compounds also include N.N'-diglycidyl derivatives of cycloalkylene ureas, such as ethylene urea or 1 ,3-propylene urea, and N,N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin.
  • N.N'-diglycidyl derivatives of cycloalkylene ureas such as ethylene urea or 1 ,3-propylene urea
  • N,N'-diglycidyl derivatives of hydantoins such as of 5,5-dimethylhydantoin.
  • Di(S-glycidyl) compounds such as di-S-glycidyl derivatives, which are derived from di- thiols, such as ethane-1 ,2-dithiol or bis(4-mercaptomethylphenyl) ether.
  • the difunctional epoxides mentioned above can contain minor amounts of mono- or trifunctional components.
  • Diglycidyl compounds having aromatic structures are mainly used.
  • epoxides are, for example, a) liquid diglycidyl ethers of bisphenol A such as Araldit ® GY 240, Araldit ® GY 250, Araldit ® GY 260, Araldit ® GY 266, Araldit @ GY 2600, Araldit @ MY 790; b) solid diglycidyl ethers of bisphenol A such as Araldit ® GT 6071, Araldit ® GT 7071, Araldit ® GT 7072, Araldit ® GT 6063, Araldit ® GT 7203, Araldit ® GT 6064, Araldit ® GT 7304, Araldit ® GT 7004, Araldit ® GT 60
  • Araldit MY 0510 I) tetraglycidyl-4-4'-methylenebenzamine or N, N, N 1 , N 1 - tetraglycidyldiaminophenylmethane such as Araldit MY 720, Araldit MY 721.
  • difunctional epoxides are diglycidyl ethers based on bisphenols, for example based on 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)- sulfone (bisphenol S), mixtures of bis(ortho/para-hydroxyphenyl)methane (bisphenol F) or Araldit ® MT 0163.
  • Solid epoxides of the diglycidyl ether of bisphenol A type are very particularly preferred, e.g.: Araldit ® GT 6071, GT 7071, GT 7072, GT 6097 and GT 6099 or liquid epoxides of the bisphenol F type such as Araldit ® GY 281 or PY 306.
  • R 8 , R 9 , R 10 and Rn are each independently of one another hydrogen, halogen, CrC 2 oalkyl, C 4 -Ci 5 cycloalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; d-C 2 oalkoxy or C 2 -C 2 ocarboxyalkyl,
  • Ri 2 is a trivalent linear, branched or cyclic aliphatic radical containing 1 to 18 carbon atoms
  • Ci -C 4 al kyl-su bstituted benzenetriyl Ci -C 4 al kyl-su bstituted benzenetriyl
  • Ri 2 is a divalent linear, branched or cyclic aliphatic radical containing 1 to 18 carbon atoms
  • R , or R 12 is also an unsubstituted or
  • Halogen is, for example, fluoro, chloro, bromo or iodo. Chloro is particularly preferred.
  • Alkyl containing up to 20 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1 -methyl hexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-tri- methylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,
  • C 4 -Ci 5 Cycloalkyl in particular C 5 -Ci 2 cycloalkyl, is e.g. cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl.
  • C 5 -C 8 Cycloalkyl is preferred, in particular cyclohexyl.
  • Alkyl-substituted phenyl which preferably contains 1 to 3, more preferably 1 or 2, alkyl groups is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl- 6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
  • Alkoxy containing up to 20 carbon atoms is a branched or unbranched radical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy.
  • a preferred meaning of R 8 , R 9 , Ri O and Rn is alkoxy containing 1 to 12, preferably 1 to 8, e.g. 1 to 4, carbon atoms.
  • Carboxyalkyl containing 2 up to 20 carbon atoms is a branched or unbranched radical, for example carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxypentyl, carboxy- hexyl, carboxyheptyl, carboxyoctyl, carboxynonyl, carboxydecyl, carboxyundecyl, carboxydodecyl, 2-carboxy-1 -propyl, 2-carboxy-1 -butyl or 2-carboxy-1-pentyl.
  • a preferred meaning of R 8 , Rg, Rio and Rn is C 2 -Ci 2 carboxyalkyl, in particular C 2 -C 8 carboxyalkyl, e.g. C 2 -C 4 carboxyalkyl.
  • radical may be interrupted by oxygen, sulfur or ⁇ ,_ R , means that the three bonding
  • sites may be at the same atom or at different atoms. Examples thereof are methanetriyl, 1 ,1 ,1-ethanetriyl, 1 ,1 ,1-propanetriyl, 1 ,1 ,1-butanetriyl, 1,1 ,1-pentanetriyl, 1 ,1 ,1-hexanetriyl, 1 ,1 ,1-heptanetriyl, 1 ,1 ,1-octanetriyl, 1,1 ,1-nonanetriyl, 1,1 ,1-decanetriyl, 1,1 ,1-undecanetriyl, 1 ,1 ,1 -dodecanetriyl, 1 ,2,3-propanetriyl, 1 ,2,3-butanetriyl, 1 ,2,3-pentanetriyl, 1 ,2,3- hexanetriyl, 1 ,1 ,3
  • radical may be interrupted by oxygen, sulfur or ⁇ ._ R , means that the two bonding sites
  • ⁇ may be at the same atom or at different atoms. Examples thereof are methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, unde- cylene or dodecylene.
  • Unsubstituted or d-C 4 alkyl-substituted benzenetriyl which preferably contains 1 to 3, more preferably 1 or 2, alkyl groups is, for example, 1 ,2,4-benzenetriyl, 1 ,3,5-benzenetriyl, 3- methyl-1 ,2,4-benzoltriyl or 2-methyl-1 ,3,5-benzenetriyl. 1 ,2,4-Benzenetriyl and 1 ,3,5-benzenetriyl are particularly preferred.
  • R 8 , R 9 , R 10 and Rn are each independently of one another hydrogen or CrC 4 alkyl
  • Ri 2 is 1,2,4-benzenetriyl or 1 ,3,5-benzenetriyl.
  • Preferred difunctional compounds from the class of the bisoxazolines in the sense of this invention are described by T. Loontjens et al., Makromol. Chem., Macromol. Symp. 75, 211- 216 (1993) and are, for example, compounds of formulae
  • Ru is a direct bond or unsubstituted or d-C 4 alkyl-substituted phenylene
  • Ri 5 and Ri 6 independently of one another, are hydrogen or C r C 4 alkyl.
  • Preferred diisocyanates are tetramethylenediisocyanate, hexamethylenediisocyanate, dode- camethylenediisocyanate, eicosan-1 ,20-diisocyanate, 4-butylhexamethylenediisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylenediisocyanate, OCN(CH 2 ) 2 ⁇ (CH 2 ) 2 NCO, toluene-2,4- diisocyanate, p-phenylenediisocyanate, xylylenediisocyanate, 3-isocyanatomethyl-3,5,5-tri- methylcyclohexylisocyanate, naphthalenediisocyanate, sulfonyldiisocyanate, 3,3'-, 4,4'- and 3,4'-diisocyanates of diphenylmethane, 2,2-diphenylpropane and diphenyl ether
  • diisocyanates listed above are commercially available or can be prepared from commercially available amines.
  • diisocyanate generators such as polymeric urethanes, uretdion dimers and higher oligomers, cyanurate polymers, urethanes and polymeric urethanes of cyanurate polymers and thermally dissociable adducts of Schiff s bases.
  • s is a number from 1 to 16, in particular from 5 to 10, and
  • R 26 is an aromatic radical, for example one of the formulae:
  • Trifunctional compounds form the acyllactam class in the sense of this inventino are known and are, for example, compounds of the formula Ga
  • z is a number from 1 to 16, in particular from 3 to 9.
  • R 28 is an aliphatic, aromatic, cycloaliphatic or heterocyclic radical
  • R 29 and R 30 independently of one another, are hydrogen, d-C 4 alkyl, CrC 6 alkoxy, phenyl or phenoxy.
  • the aliphatic, aromatic, cycloaliphatic or heterocyclic radicals have a maximum of 40 carbon atoms, can be unsubstituted or substituted, and can also be interrupted by -O-, -S-, -(CH 2 ) I-6 , -C(O)-, -P(O)(CrCi 8 alkyl)- or -(O)S(O)- (sulfone).
  • Examples of possible substi- tuents are CrCi 8 alkyl, CrCi 8 alkoxy, hydroxyl, phenyl and phenoxy.
  • An aromatic radical R 28 is, for example, a radical having 6-40 carbon atoms, such as pheny- lene, biphenylene or naphthylene or represents phenylene or biphenylene radicals linked by one of the groups such as -O-, -S-, -(CH 2 )i -6 , -C(O)-, -P(O)(C r Ci 8 alkyl)- or -(O)S(O)-.
  • a cycloaliphatic radical R 28 is, for example, a radical having 5-10 carbon atoms, such as cyclopentylene, cyclohexylene or cyclooctylene.
  • a heterocyclic radical R 28 is, for example, an N-containing 5- or 6-membered ring, such as pyridylene, pyridazylene or pyrazolylene.
  • R 28 is preferably an aromatic radical of one of the formulae: formulae:
  • R 29 and R 30 are preferably hydrogen or d-C 4 alkyl; R 29 is particularly preferably hydrogen and R 30 is particularly preferably hydrogen or methyl; and R 29 and R 30 are very particularly preferably hydrogen.
  • Bismaleimides are obtained by reacting diamines with maleic anhydride, and some are commercially available. Further suitable bismaleimides are described in WO-A-93/24488.
  • Polyfu notional compounds from the alcohol class as chain extenders in the sense of this invention are known and are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, bistrimethylolethane, trismethylol propane, sorbitol, maltitol, isomaltitol, lactitol, lycasine, mannitol, lactose, leucrose, tris(hydroxyethyl)isocyanurate, palatinitol, tetramethylolcyclohexanol, tetramethylolcycopentanol, tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol or 1- O- ⁇ -D-glycopyranosyl-D-mannitol dihydrate. Particular preference is given to pentaerythritol, dipenta
  • Preferred hindered phenolic aromatic phosphates are compounds of the formula I
  • R 6 is isopropyl, tert-butyl, cyclohexyl or cyclohexyl which is substituted by 1-3 CrC 4 alkyl groups,
  • R 7 is hydrogen, CrC 4 alkyl, cyclohexyl or cyclohexyl which is substituted by 1-3 Ci-C 4 alkyl groups,
  • R 8 is CrC 2 oalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl or naphthyl,
  • R 9 is hydrogen, CrC 2 oalkyl, unsubstituted or C r C 4 alkyl-substituted phenyl or naphthyl; or is
  • M r+ is an r-valent metal cation
  • p is 1, 2, 3, 4, 5 or 6, and r is 1 , 2 or 3.
  • Ci-C 2O alkyl substituents are radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, stear ⁇ l or corresponding branched isomers; C 2 -C 4 alkyl radicals are preferred.
  • CrC 4 alkyl-substituted phenyl or naphthyl, which preferably contains 1 to 3, in particular 1 or 2, alkyl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethyl- phenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2- methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl, 1 ,6-dimethylnaphthyl or 4-tert-butylnaphthyl.
  • Ci-C 4 alkyl-substituted cyclohexyl which preferably contains 1 to 3, in particular 1 or 2, branched or unbranched alkyl radicals, is, for example, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl or tert-butylcyclohexyl.
  • a monovalent, divalent or trivalent metal cation is preferably an alkali metal cation, alkaline earth metal cation, heavy-metal cation or aluminium cation, for example, Na + , K + , Mg ++ , Ca ++ , Ba ++ , Zn ++ or Al +++ . Particular preference is given to Ca ++ .
  • Preferred compounds of the formula I are those which contain at least one tert-butyl group as R 6 and R 7 . Very particular preference is given to compounds in which R 6 and R 7 are simultaneously tert-butyl.
  • p is preferably 1 or 2, very particularly preferably 1.
  • Very particularly preferred compounds of the formula I are the compounds of the formual Ia and Ib
  • polyesters which comprises adding to the polyesters a chain extender selected from the group consisting of anhydrides, alcohols and hindered phenolic aromatic phosphates or mixtures thereof.
  • the chain extender is preferably added to the polyester to be stabilized against thermal and light-induced degradation in an amount of from 0.01 to 10 %, in particular from 0.01 to 5 %, for example from 0.01 to 2 %, based on the weight of the polyester.
  • novel process for improving the thermal and light stability of polyesters which comprises adding to the polysters a chain extender may comprise further costabilizers (additives) such as, for example, the following:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 l -methylund
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di- dodecylthiomethyl-4-nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquino
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers for example 2,2 1 -thiobis(6-tert-butyl-4-methylphenol), 2,2 1 -thiobis(4-octylphenol), 4,4 1 -thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl- 2-methylphenol), 4,4 1 -thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4- hydroxyphenyl)disulfide.
  • 2,2 1 -thiobis(6-tert-butyl-4-methylphenol 2,2 1 -thiobis(4-octylphenol), 4,4 1 -thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl- 2-methylphenol), 4,4 1 -thiobis(3,6-di-sec-amylphenol), 4,
  • Alkylidenebisphenols for example 2,2 1 -methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2 1 -methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2 1 -methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2 1 -methylenebis(4 J 6-di-tert-butylphenol), 2,2 1 -ethylidenebis(4,6-di-tert-butyl- phenol), 2,2 1 -ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2 1 -methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2 1 -methylenebis[6-methylenebis
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-hydroxy-5
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 J 4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2 J 3 J 5 J 6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilinoJ-I .S. ⁇ -triazine, 2-octylmercapto-4 J 6-bis(3 J 5-di-tert-butyl-4-hydroxyanilino)-1 ,3 J 5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 J 3 J 5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N 1 -bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phos,
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-i-phospha ⁇ .Z-triox
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • Aminic antioxidants for example N.N'-di-isopropyl-p-phenylenediamine, N.N'-di-sec- butyl-p-phenylenediamine, N,N l -bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1- ethyl-3-methylpentyl)-p-phenylenediamine, N,N l -bis(1-methylheptyl)-p-phenylenediamine, N.N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2- naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3- dimethylbutyl)-N'-
  • 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5 1 -methylphenyl)-benzo- triazole, 2-(3 1 ,5 1 -di-tert-butyl-2 1 -hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2 1 -hydroxyphe- nyl)benzotriazole, 2-(2 l -hydroxy-5 l -(1,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl ⁇ '-hydroxyphenylJ-S-chloro-benzotriazole, 2-(3 1 -tert-butyl-2'-hydroxy-5 1 -methylphe- nyl)-5-chloro-benzotriazole, 2-(3 1 -sec-butyl-5 1 -tert-butyl-2'-
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2 1 ,4 1 -trihydroxy and 2 1 -hydroxy-4,4 1 -dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4- hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, neopentyl tetra( ⁇ -cyano- ⁇ , ⁇ -di- phenylacrylate.
  • Nickel compounds for example nickel complexes of 2,2 l -thio-bis[4-(1,1 ,3,3-tetrannethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexy
  • Sterically hindered amines for example bis(2,2 J 6 J 6-tetramethyl-4-piperidyl)sebacate J bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 , 2,2,6, 6-pentamethyl-4- piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6- pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N 1 -bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4- tert-oct
  • N- ⁇ .e-tetrannethyl ⁇ -piperidyO-n-dodecylsuccininnide N-(1, 2,2,6,6- pentamethyl-4-piperidyl)-n-dodecylsuccinimide
  • 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8- diaza-4-oxo-spiro[4,5]decane a reaction product of 7,7 J 9 J 9-tetramethyl-2-cycloundecyl-1- oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1 ,1-bis(1 , 2,2,6, 6-pentamethyl-4- piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N 1 -bis-formyl-N,N 1 -bis(2,2,6,6
  • Oxamides for example 4,4 1 -dioctyloxyoxanilide, 2,2 1 -diethoxyoxanilide, 2,2'-dioctyloxy- S.S'-di-tert-butoxanilide, 2,2 1 -didodecyloxy-5,5 1 -di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani- lide, N,N 1 -bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2 1 -ethyl-5,4 1 -di-tert-butoxanilide, mixtures of o- and p-methoxy- disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides
  • Metal deactivators for example N.N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N 1 -bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N.N-ditetradecylhydroxylamine, N 1 N- dihexadecylhydroxylamine, N.N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. 6.
  • Nitrones for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N- octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl- alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-
  • Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ - dodecyl
  • Polvamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or pol year boxy lie acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or pol year boxy lie acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copoly
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • the costabilizers are added, for example, in concentrations of 0.01 to 10%, relative to the total weight of the polyester to be stabilized.
  • aldehyde scavengers are for example polyvinyl alcohols, (meth)acrylamides homo- or copolymers, hydroxylamines, nitrones, amine oxides, poly[glyceryl(meth)acrylates], aminic antioxidants, benzofuran-2-ones, phosphites, phosphonites or phosphonates or mixtures thereof.
  • Aldehydes of special interest are formaldehyde, acetaldehyde or propionaldehyde.
  • a preferred subject of the present invention is also the use of a chain extenders as outlined above for improving the thermal and light stability of polyesters.
  • Polyesters with such improved properties are especially useful for the preparation of articles such as for example fibers, films, pipes, profiles, bottles, tank or containers.
  • a preferred embodiment of the present invention relates therefore also to an article containing a polyester with improved thermal and light stability which comprises a chain extender.
  • Example 1 Stabilization of polyester fibers.
  • a PET powder [RT 21 (Kosa)] is dried in a vacuum oven for eight hours at 120°C.
  • Appropriate amounts of the chain extenders are added to the dried PET powder.
  • the formulations are mixed in a turbo mixer and extruded in a twin-screw extruder (Berstorff ZE25 33D).
  • the polymer string is then granulated.
  • the obtained granulates are dried for one hour at 190 0 C followed by one hour at 100°C in a vacuum drying oven.
  • the granules are then processed through a fiber extruder Spinboy Il to produce yarns of 40 filaments of 4.5 Denier each.
  • the fibers are then further tested in a Weather-O-Meter (WOM) [light stability] according to ISO 4892-2.
  • the yarns were separately tested for their heat stability in an air-circulating oven at 120°C (heat stability). The results are summarized in Table 1.

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