CA2243692A1 - Increasing the molecular weight of polycondensates - Google Patents

Increasing the molecular weight of polycondensates Download PDF

Info

Publication number
CA2243692A1
CA2243692A1 CA002243692A CA2243692A CA2243692A1 CA 2243692 A1 CA2243692 A1 CA 2243692A1 CA 002243692 A CA002243692 A CA 002243692A CA 2243692 A CA2243692 A CA 2243692A CA 2243692 A1 CA2243692 A1 CA 2243692A1
Authority
CA
Canada
Prior art keywords
hydrogen
polycondensate
process according
bis
c4alkyl
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.)
Abandoned
Application number
CA002243692A
Other languages
French (fr)
Inventor
Rudolf Pfaendner
Kurt Hoffmann
Heinz Herbst
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
Individual
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 Individual filed Critical Individual
Publication of CA2243692A1 publication Critical patent/CA2243692A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014Nitrogen containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276Polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/914Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42Chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48Polymers modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065Preparatory processes
    • C08G73/0655Preparatory processes from polycyanurates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00General processes for preparing compounds provided for in this subclass

Abstract

By heating at above the melting point and/or glass transition point of the polycondensate and adding an aromatic dicyanate; or adding a mixture comprising an aromatic dicyanate and a polyfunctional compound selected from the class of sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary aromatic amines; or adding a mixture comprising (i) an aromatic dicyanate; (ii) at least one polyfunctional compound selected from the class of sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary amines, and (iii) a difunctional epoxide, it is possible to bring about an increase in the molecular weight and/or viscosity of virgin polycondensate and polycondensate recyclates.

Description

Increasinq the molecular weiqht of ~oiycondensates e The invention relates to a process for increasing the molecular weight and/or viscosity of polycondensates and to the polycondensates obtainable by the process.

Polycondensates, such as polyamides, polyesters and polycarbonates, are important engineering plastics with a wide variety of potential uses, for example in the form of films, bottles, fibres and injection mouldings. It is common to these polymers that they are prepared by polycondensation reactions.

Damage to such polycondensates through processing and use leads, owing to chain ctea-vage, to polymer fragments containing functional end groups.

The mechanical and physical properties of polymers are crucially dependent on the molecu-lar weight of the polymer. High-grade recycling of used polyesters, polyamides and polycar-bonates from production wastes, for example from fibre production and injection moulding, is only possible to a restricted extent without aftertreatment, owing to the reduced molecular weight. For certain applications there is also a demand for high molecular mass virgin poly-cGndensates, the synthesis of which is difficult.

Increasing the molecular weight of polycondensates such as polyamides or polyesters, for example, is known in principle. One possiL ilily, for example, is post-condensation in the so-lid state ("solid state polycondensation") as is described in "Ullmann's Encyclopedia of Indu-strial Chemistr~l~ Vol. A 21, 5th Edition", page 188 lpolyamides] and page 236 ~polyesters]
(1992) and is also practised industrially. An alternative method is the build-up of molecular weight by means of reactive additives, such as epoxi~es, tetracarboxylic dianhydrides, di-isocyanates, bi~ioxazolines or dicarboxylic bis;.~,ides, which is referred to in general as chain extension and is disclosed, for example, in EP-A-0 074 337.

-r EP-A-0 604 367 discloses a process for increasing the molecular weight of polyamides which comprises heating a polyamide, with the addition of a pol~unctional epoxy resin and of a sterically hindered hydroxyphenyl-alkyl-phosphonic ester or monoester, at above the melting point or glass transition point of the polyamide.

W O 97/30105 PCT~EP97/00492 US 5,496,920 likewise discloses a process for increasing the molecular weight of poly-amides, which comprises heating a polyamide, with the addition of a bismaleimide and of a sterically hindered hydroxyphenyl-alkyl-phosphonic ester or monoester, at above the mel-ting point andlor glass transition point of the polyamide.

The use of reactive additives, for example epoxides, for building up the molecular weight of polycondensates has the disadvantage that relatively long reaction times are quite often necessary. Under such conditions, it is not possible to rule out follow-on reactions, such as discoloration, increased oxidation or uncontrolled crosslinking of the polycondensate, for example. Moreover, commercially available epoxides are often liquid products, especially if a high content of functional groups is necessary, whose addition to the polycondensate employed causes difficulties.

The object of the present invention, therefore, was to provide a system for building up the molecular weight of polycondensates which is highly effective in a relatively short reaction timc and which lacks the disadvantages set out above.

WO-A-90/00574 discloses the preparation of polyiminocarbonates starting from bisphenols and dicyanates.

JP-A-04 20~ 316 discloses a resin composition comprising two polyesters with different glass transition temperatures and a polycyanate. This resin composition is suitable, in con-tact with sheet steel, for reducing the vibration of the sheet steel ("damping sheet steel") In a relatively large temperature range, and can also be used as a bonding coat between two steel sheets. In that publication there is no indication that polycyanates are suitable for in-ducing an increase in the molecular weight of the polyester in the melt.

It has now surprisingly been found that aromatic dicyanates are suitable for increasing the molecular weight and/or viscosity of virgin polycondensate or polycondensate recyclate (i.e.
recycled polycondensate) or of a mixture thereof.

The present invention therefore provides a process for increasing the molecular weight and/or viscosity of polycondensates, which comprises heating a polycondensate, with the W O 97/3010'i PCTAEP97/00492 addition of at least one aromatic dicyanate, at above the melting point or glass transition point of the polycondensate.

The invention also provides a process for increasing the molecular weight and/or viscosity of polycondensates which comprises heating a polycondensate, with the addition of at least one aromatic ~icyanate and at least one polyfunctional compound selected from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphos-phonites or secondary aromatic amines, at above the melting point or glass transition point of the polycon~ensate.

The present invention also provides a process for increasing the molecular weight and/or viscosity of polycondensates which comprises heating a polycondensate, with the addition (i) of at least one aromatic dicyanate; (ii) of at least one polyfunctional compound selected from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and mono-esters, diphosphonites or secondary aromatic amines; and (iii) of a difunctional epoxide, at above the melting point or glass transition point of the polycondensate.

The increase in molecular weight brings about improvement in the properties of the polycon-densates, which becomes evident, ~or example, in the injection-moulding sector, in the ex-trusion sector and, in particular, in connection with recyclates. With the aid of the novel pro-cess it is possible, in particular, to achieve an increase in molecular weight in polycondensate recyclates from production wastes, as are obtained, for example, during the manufacture of fibres, or from the collection of used industrial components, for example from automotive and electrical applications. This allows recyclates to be passed on for high-grade re-use, for example as high-performance fibres, injection mouldings, extrusion applications or foams.
Such recyclates also originate, for exarnple, from industrial or domestic collections of re-cyclable materials, from production waste, for example from fibre production and trimmings, or from obligalory takeback schemes, for example collections of PET drinks bottles.

A preferred p~lycondensate is a polycondensate recyclate.

The novel process is of particular interest if the polycondensate is a polyamide, a polyester, a polycarbonate or a copolymer of these polymers.

W O97/~OlOS PCTAEP97/00492 In addition to polyester, polyamide or polycarbonate, the present invention also embraces the corresponding copolymers and blends, for example PBT/PS, PBT/ASA,P~3T/ABS, PBT/PC,PET/ABS,PET/PC,PBT/PET/PC,PBT/PET,PA/PP,P~PE and P~ABS.How-ever, in this context it must be borne in mind that the novel process, like all methods which permit substitution reactions, for example transesterification or transamidation, between the blend components, may result in the blend being influenced, i.e. may lead to the formation of copolymeric structures.

0~ particular interest is a process wherein the polycondensate is a PBTIPC blend or a blend comprising predominantly PBT/PC or a corresponding recyclate or a blend of a recyclate and a virgin polymer component.

The term polyamides, i.e. both virgin polyamides and polyamide recyclates, refers to alipha-tic and aromatic polyamides or copolyamides derived from diamines and dicarboxylic acids andlor from aminocarboxylic acids or their corresponding lactams. Examples of suitable po-lyamides are PA 6, P A 11, P A 1 2, P A 46, P A 6.6, P A 6.8, P A 6.10 or P A 6.12, P A 10.12, P A 12.12 and also amorphous polyamides of the types Trogamid PA 6-:}-T and Grilamid TR
55. Polyamides of the type mentioned are generally known and are obtainable commercial-IY-As polyamides use is preferably made of crystalline or partly crystalline polyamides, and es-pecially PA 6 or PA 6.6 or mixtures thereof, and also of recyclates based on them, or copo-lymers thereof.

The polyester, i.e. both virgin polyester and polyester recyclate, can comprise homopoly-esters or copolyesters which are composed of aliphatic, cycloaliphatic or aromatic dicar-boxylic acids and diols or hydroxycarboxylic acids.

The aliphatic dicarboxylic acids can contain 2 to 40 carbon atoms, the cycloaliphatic dicar-boxylic acids 6 to 10 carbon atoms, the aromatic dicarboxylic acids 8 to 14 carbon atoms, the aliphatic hydroxycarboxylic acids 2 to 12 carbon atoms, and the aromatic and cycloali-phatic hydroxycarboxylic acids 7 to 14 carbon atoms.

W O 971~0105 PCT~EP97/00492 The aliphatic diols can contain 2 to 12 carbon atoms, the cycloaliphatic diols 5 to 8 carbon atoms, and the aromatic diols 6 to 16 carbon atoms.
.

The diols referred to as aromatic are those in which two hydroxyl groups are attached to one or to different aromatic hydrocarbon r~' c~Ls It is additionally possible for the polyesters to be branched with small amounts, for example, from 0.1 to 3 mol%, based on the dicarboxylic acids present, of more than difunctional mo-nomers (e.g. pentaerythritol, trimellitic acid, 1 ,3,5-tri(hydroxyphenyl)benzene, 2,4-dihydroxy-benzoic acid or 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane).

In the case o~ polyesters consisting of at least 2 monomers, these can be distributed ran-domly, or the polymers can be block copolymers.

Suitable dicarboxyl;c acids are linear and branched saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.

Suitable aliphatic dicarboxylic acids are those with 2 to 40 carbon atoms, examples being oxalic, malonic, dimethylmalonic, succinic, pimelic, adipic, trimethyladipic, sebacic and aze-laic acids and dimer acids (dimerization products of unsaturated aliphatic carboxylic acids such as oleic acid), and alkylated malonic and succinic acids, such as octadecylsuccinic acid.

Suitable cycloaliphatic dicarboxylic acids are 1,3-cyclobutanedicarboxylic acid, 1,3-cyclo-pentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-di(carbo-xylmethyl)cyclohexane and 4,4'-dicyclohexyldicarboxylic acid.

Particularly suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, o-phthalic acicl, and 1,3-, 1,4-, 216- or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicar-boxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 1,1 ,3-trimethyl-5-carboxyl-3-(p-carboxyphenyl)indane, 4,4'-diphenyl ether dicarboxylic acid, bis-(p-carboxyphenyl)methane or bis-(p-carboxyphenyl)ethane.

W O97/30105 PCT~EP97/00492 Preference is given to the aromatic dicarboxylic acids, especially terephthalic acid, isophtha-lic acid and 2,6-naphthalenedicarboxylic acid.

Other suitable dicarboxylic acids are those containing -CO-NH- groups; they are described in DE-A-2 414 34~. Also suitable are dicarboxylic acids containing N-heterocyclic rings, for example those which are derived from carboxyalkylated, carboxyphenylated or carboxy-benzylated monoamine-s-triazinedicarboxylic acids (cf. DE-A-2 121 184 and 2 533 675), from mono- or bishydantoins, frorn unsubstituted or halogenated benzimidazoles, or from parabanic acid. The carboxyalkyl groups in these compounds can contain 3 to 2~ carbon atoms.

Suitable aliphatic diols are the linear and branched aiiphatic glycols, especially those having 2 to 12, in partlcular 2 to 6, carbon atoms in the molecule, for example ethylene glycol, 1,2-and 1,3-propylene glycol, 1,2-,1,3-, 2,3- or 1,4-butanediol, pentylglycol, neopentylglycol, 1,6-hexanediol and 1,12-dodecanediol. An example of a suitable cycloaliphatic diol is 1,4-dihydroxycyclohexane. Examples of further suitable aliphatic diols are 1,4-bis(hydroxy-methyl)cyclohexane, aromatic-aliphatic diols, such as p-xylylene glycol or 2,~-dichloro-p-xylylene glycol, 2,2-bis(,~-hydroxyethoxyphenyl)propane, and also polyoxyalkylene glycols, such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol.
The alkylenediols are preferably linear and, in particular, contain 2 to 4 carbon atoms.

Preferred diols are the alkylenediols, 1,4-dihydroxycyclohexane, and 1,4-bis(hydroxy-methyl)cyclohexane. Particular preference is given to ethylene glycol,1,4-butanediols and 1,2- and 1,3-propylene glycol.

Further suitable aliphatic diols are the ,B-hydroxyalkylated, especially ~-hydroxyethylated, bisphenols, such as 2,2-bis[4'-(~-hydroxyethoxy)phenyl~propane. Further bisphenols are mentioned later.

A further gfoup of suitable aliphatic diols are the heterocyclic diols described in DE-A 1 812 003, 2 342 432, 2 342 372 and 2 453 326. Examples are N,N'-bis(~-hydroxy-ethyl)-5,5-dimethylhydantoin, N,N'-bis~-hydroxypropyl)-5,5-dimethylhydantoin, methylene W O 97/3010!; PCTrEP97/00492 bis[N-(~B-hydroxyethyl)-5-methyl-5-ethylhydantoin], methylene bis[N-(~-hydroxyethyl)-5,5-dimethyl-hydantoin], N,N'-bis(,B-hydroxyethyl)benzimidazolone, N,N'-bis(~-hydroxyethyl)-(tetrachloro)-be~ zolone, or N,N'-bis(~B-hydroxyethyl)~tetrabromo)benzimidazolone.

Suitable aromatic diols are monocyclic diphenols and especially bicyclic diphenols carrying a hydroxyl gr~up on each aromatic ring. The term aromatic is preferably taken to mean hydrocarbon-aromatic radicals, for example phenylene or naphthylene. Besides, for example, hydroquinone, resorcinol and 1,5-, 2,6- and 2,7-dihydroxynaphthalene, particular mention should be made of the bisphenols which can be described by the followingformulae:

Fl' R' R~ R' ?~¦~ ~ Ho3 R" R" R" R"

~A~A~
R" R"

R' R' ~OH

R" R"

~A~}A~A~
R" R"

WO97130105 PCT~EP97/00492 - - R' R' OH

R" R"

The hydroxyl groups can be in the m-position, but in particular in the p-position; R' and R" in these formulae can be alkyl of 1 to 6 carbon atoms, halogen such as chlorine or bromine, and especially hydrogen atoms. A can be a direct bond, or oxygen, sulfur, -SO-, -SO2-, ~ C=o, -P(O)(C1-C20alkyl)-, substituted or unsubstituted alkylidene, cycloalkylidene or alkylene.

Examples of unsubstituted or substituted alkylidene are ethylidene, 1,1- or 2,2-propylidene, 2,2-butylidene, 1,1-isobutylidene, pentylidene, hexylidene, heptylidene, octylidene, dichloro-ethylidene and trichloroethylidene.

Examples of substituted or unsubstituted alkylene are methylene, ethylene, phenylmethy-lene, diphenylmethylene and methylphenylmethylene. Examples of cycloalkylidene are cyc-lopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.

Examples of bisphenols are bis(p-hydroxyphenyl) ether or thioether, bis(p-hydroxyphenyl) sulfone, bis(p-hydroxyphenyl)methane, bis(4-hydroxyphenyl)-2,2'-biphenyl, phenylhydro-quinone, 1,2-bis(p-hydroxyphenyl)ethane, 1-phenylbis(p-hydroxyphenyl)methane, diphenyl-bis(p-hydroxyphenyl)methane, diphenylbis(p-hydroxyphenyl)ethane, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, bis(3,5-dimethyl-4-hydroxyphenyl)-m-diisopropylbenzene, 2,2-bis(3',5'-dimethyl-4'-hydroxyphenyl)-propane, 1,1- or 2,2-bis(p-hydroxyphenyl)butane, 2,2-bis(p-hydroxyphenyl)hexafluoropro-pane, 1,1-dichloro- or 1,1,1-trichloro-2,2-bis(p-hydroxyphenyl)ethane, 1,1-bis(p-hydroxyphe-nyl)cyclopentane and, especially, 2,2-bis(p-hydroxyphenyl)propane (bisphenol A) and 1,1-bis(p-hydroxyphenyl)cyclohexane (bisphenol C).

W O 9713010~; PCT~EP97/00492 g Examples of suitable polyesters of hydroxycarboxylic acids are polycaprolactone, polypiva-lolactone or the polyesters of 4-hydroxycyclohexanecarboxylic acid or 4-hydroxybenzoic acid.

Also suitable are polymers which contains predominantly ester linkages, but which can also contain other linkages, such as, for example polyesteramides or polyesterimides.
Polyesters with aromatic dicarboxylic acids have acquired the greatest importance, espe-cially the polyalkylene terephthalates. Preference is therefore given to novel moulding com-positions in wl-ich the polyester is built up from at least 30 mol%, preferably at least 40 mol%, of aromatic dicarboxylic acids, and at least 30 mol%, preferably at least 40 mol%, of alkylenediols having preferably 2 to 12 carbon atoms, based on the polyester.

In particular in this case the alkylenediol is linear and contains 2 to 6 carbon atoms, for example ethylene or tri-, tetra- or hexamethylene glycol, and the aromatic dicarboxylic acid is terephthalic and/or isophthalic acid.

The novel process is likewise of particular interest if the polycondensate is a polyester.

Particularly suitable polyesters are PET, PBT or PEN (polyethylene naphthylate) and cor-responding copolymers, especial preference being given to PET and its copolymers. The process also acquires particular importance in connection with PET recyclates, which are obtained, for example, from bottle collections, for example from collections by the drinks industry. These materials consist, preferably, of terephthalic acid, 2,6-naphthalene-dicarbo-xylic acid and/or isophll,alic acid in co",bi"ation with ethylene glycol and/or 1,4-bis(hydroxy-methyl)cyclohexane.

The term polycarbonate (PC) refers both to virgin polycarbonate and to polycarbonate re-cyclate. PC is obtained, for example, from bisphenol A and phosgene or a phosgene ana-logue, such as trichloromethyl chlorofor",ate, triphosgene or diphenylcarbonate, by conden-sation, in the latter case generally with addition of a suitable transesterification catalyst, for example a bor~hydride, an amine, such as 2-methylimidazole, or a quaternary ammonium salt; besides bisphenol A, other bisphenol components can additionally be used, and mo-nomers which are halogenated in the benzene ring can also be employed. Particularly sui-CA oi243692 1998-07-20 W O 97/~0105 PCTrEP97/00492 table bisphenot components which may be mentioned are 2,2-bis~4'-hydroxyphenyl)propane (bisphenol A), 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)methane, bis(4-hy-droxyphenyl)methane, bis(4-hydroxy-5-propylphenyl)-methane, 1,1-bis(4'-hydroxyphenyl)-ethane, bis(4-hydroxyphenyl)cyclohexylmethane, 2,2-bis(4'-hydroxyphenyl)-1-phenylpro-pane, 2,2-bis(3',5'-dimethyl-4'-hydroxyphenyl)propane, 2,2-bis(3',5'-dibromo-4'-hydroxyphe-nyl)propane, 2,2-bis(3',5'-dichloro-4'-hydroxyphenyl)-propane, 1,1-bis(4'-hydroxyphenyl)-cyclododecane, 1,1-bis(3',5'-dimethyl-4'-hydroxyphenyl)-cyclododecane, 1,1-bis(4'-hydroxy-phenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4'-hydroxy-phenyl)-3,3,5,5-tetramethylcyclo-hexane, 1,1-bis(4'-hydroxyphenyl)-3,3,5-trimethylcyclo-pentane and the other bisphenols indicated further above. Furthermore, the polycarbonates may also be branched as a result of sppropriate amounts of monomers having a functionality of more than two (examples as given further above for the polyesters).

The novel process is also of particular interest if the polycondensate is a polycarbonate.

The polycondensate copolymers or blends which can be used in the novel process are pre-pared in a conventional manner from the startin~ polymers. The polyester component is preferably PBT and the PC component is preferably a PC based on bisphenol A. The poly-ester:PC ratio is preferably from 95:5 to 5:95, particular preference being given to a ratio in which one component makes up at least 75%.

The invention acquires particular importance in connection with polycondensate recyclates as obtained from production waste, collections of recyclable material, or as a result of obli-gatory takeback schemes, for example in the automotive industry, in the electrical sector, compact discs or twin-wall sheets. The polycondensate recyclates have suffered thermal and/or hydrolytic damage in a variety of ways. Moreover, these recyclates may also include minor amounts of admixed plastics having a different structure, for example polyolefins, po-lyurethanes, ABS or PVC. Furthermore, these recyclates can also include customary impu-rities, for example residues of dyes, adhesives, contact media or paints, traces of metal, traces of water, traces of service fluids, or inorganic salts.

Aromatic dicyanates in the context of this invention are known, for example, from US-3 491 060 and are, preferably, compounds of the formula I

W O 97/3010~ PCTAEP97/00492 R2~,X ~ R,;

in which X is a direct bond, oxygen, sulfur, -SO-, -SO2-, --~ ~ , Rg--I--Rlo I 9~ 1-- , C2-C~8alkylene, C2-C18alkenylene or ~N--R" , R~o Rto R1, R2, R3 and R4 independently of one another are hydrogen, Cl-C2salkyl~ Cs-cl2cycloalk unsubstituted or C1-C4alkyl-substituted phenyl; C,-C~phenylalkyl, hydroxyl, C,-Cz5alkoxy or -O-CN, with the proviso that at least one of the radicals R1, R2, R3 and R4 is -O-CN, Rs, R6, R, and F28 independently of one another are hydrogen, Cl-C2salkyl~ C5-C~2cycloalkyl, or unsubstituted or C1-C4alkyl-substituted phenyl; C,-Cgphenylalkyl, hydroxyl, C1-C25alkoxy -O-CN, with the proviso that at least one of the radicals R5, R6, R7 and R8 is -O-CN, Rg and R1o independently of one another are hydrogen, C1-C12alkyl, trifluoromethyl or phenyl, or Rg and Rlo, together with the carbon atom to which they are attached, form a Cs-c8cycloalkylidene ring which is unsubstituted or is substituted by 1 to 3 C1-C4alkyls; and R11 is hydrogen or C1-C12alkyl.

C2-C~8alkylene is a branched or unbranched radical such as, for example, ethylene, propy-lene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octa-methylene, decamethylene, dodecamethylene or octadecamethylene. Preference is given to C2-C12alkylene, especially C2-C8alkylene, for example C2-C4alkylene.

C2-C18alkenylene is a branched or unbranched radical having one or more C-C double bonds, such as, for example, vinylene, methylvinylene, octenylethylene or dodecenylethy-lene. Preference is given to C2-C1zalkenylene, especially C2-C8alkenylene, for example C2-C4~1kenylene.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical such as, 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-methylhexyl, n-heptyl, iso-heptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trim~thylhexyl, 1,~,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,t,3,3,5,5-hexamethylhexyl, tridecyi, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa-decyl, eicosyl or docosyl. One of the preferred definitions of R1, R2, R4, R5, R6, R7 and R8 is, for example, C,-C18alkyl, especially C,-C,2alkyl, e.g. C1-C8alkyl. A preferred definition of Rg and R10 is, for example, C1-C8alkyl, especially C1-C4alkyl, e.g. methyl. A particularly pre-ferred definition of R" is, for example, C1-C8alkyl, especially C,-C4alkyl, e.g. methyl, ethyl, n-propyl or n-butyl.

C5-C12cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl. A preferred definition of R" R2, R3, R4, R5, R6, R7 and R8 is, for example, C5-C8cycloalkyl, especially Cs-c7cycloalkyl~ e.g. cyclohexyl.

C1-C~alkyl-substituted phenyl, which preferably contains 1 to 3, especially 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 or 2-ethylphenyl, 2,6-diethylphenyl.

C7-Cgphenylalkyl is, for example, benzyl, a-methylbenzyl or a,a-dimethylbenzyl. Benzyl is preferred.

Alkoxy having up to 25 carbon atoms is a branched or unbranched radical such as, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. A
preferred definition of R" R2, R3, R4, R5, R6, R7 and R8 is, for example, C,-Cl8alkoxy, espe-cTally C1-C12alkoxy, e.g. C1-C8alkoxy. Methoxy is particularly prelerl~d.

W O 97/3010~; PCT~EP97/00492 A C,-C4alkyl-substituted C5-C8cycloalkylidene ring, which preferably contains 1 to 3, espe-cially 1 or 2 branched or unbranched alkyl groups, is, for example, cyclopentylidene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptyl-idene or cyclooctylidene. Preference is given to cyclohexylidene and 4-tert-butylcyclohexy-lidene.

Particular preference is given to the compounds of the formula I in which X is a direct bond, oxygen, ~_~ , R9--C--R9 ~ R9 Ic~Cl , C2-Ct2alkylene or C2-C~2alkenylene, R~o R~o R~ 2, R3 and R4 independently of one another are hydrogen, Cl-C~8alkyl, C5-C8cycloalkyl, phenyl, benzyl, C,-C,8alkoxy or -O-CN, with the proviso that at least one of the radicals R"
R2, R3 or R4 is -O-CN, R5, R6, R, and R8 independently of one another are hydrogen, C,-C,8alkyl, C5-C8cycloalkyl, phenyl, benzyl, C1-C,8aikoxy or -O-CN, with the proviso that at least one of the radicals R5, R6, R, or R8 is -O-CN, and R9 and R10 independently of one another are hydrogen, C~-C8alkyl, trifluoromethyl or phenyl, or R9 and R~o, 1ogether with the carbon atom to which they are attached, form a C5-C6cycloalkylidene ring.

Examples of particularly preferred aromatic dicyanates of the formula I are the compounds of the formula la, Ib, Ic, Id, le or If NC--o~ I H~o--CN (la) CA 02243692 l998-07-20 NC - O ~ CH~ ~ O - CN (I~) NC--0~ I F~O--CN (IC3 CH
NC--0~ 1 ~0--CN (Id) H

H3C~ ,CH3 H3C~ ,CH3 ,~C'~3~C'~ (le) NC CN

NC--0~o--CN

The compound of the formula la is also referred to as BPC (!~isehenol A dicyanate). The compounds of the formulae la to If are obtainable commercially under the following names:
AroCy~B-10 (Rhone-Poulenc, compound of the formula la); AroCy~ M-10 (Rhone-Poulenc, compound of the formula Ib); AroCy~ F-10 (Rhone-Poulenc, compound of the formula Ic);
AroCy~ L-10 (Rhone-Poulenc, compound of the formula Id); RTX~ 366 (Rhone-Poulenc, compound of the formula le); and XU~ 71787 (Dow Chemical Co., compound of the formula If).

WO 97/30105 PCT/Er97/00492 Of particular interest are the aromatic dicyanates of the formula I in which Rl and R5 are hydrogen, R2, R4, R6 and R8 are hydrogen or methyl, and R3 and R7 are -O-CN.

Of specific interest are the compounds of the formula I in which X is a direct bond, --~ , R9--C--R~o or R1 is hydrogen, R2 is hydrogen or C1-C4alkyl, R3 is -O-CN, R4 is hydrogen or C,-C4alkyl, Rs is hydrogen, R6 is hydrogen or C,-C4alkyl, R7 is -O-CN, R8 is hydrogen or C,-C4alkyl, and R9 and R1o independently of one another are hydrogen, methyl or trifluoromethyl.
Very particular preference is given to the compounds of the formula I in which X is P~9~ ,O

R, and R2 are hydrogen, R3 is -O-CN, R4, R5 and R6 are hydrogen, R, is -O-CN, R8 is hydrogen, and R,~ and Rlo independently of one another are hydrogen or methyl.

Parti~ularly preferred aromatic dicyanates are those of the formula la and Id.

W O97130105 PCT~EP97/00492 Based on 100 parts of polycondensate, preferably from 0.01 to 5 parts, particularly prefe-rably from 0.02 to 2 parts and, in particular, from 0.0~ to 1 part of the aromatic dicyanate are employed.

Polyfunctional compounds from the class of the stericaily hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters have been disclosed, for example, in US-A-4 778 840 and are, for example, compounds of the formula ll R2l >~\ 11 HO ~ H2)n 1--OR24 (~) OR~

in which R21 is isopropyl, tert-butyl, cyclohexyl or cyclohexyl which is sl Ihstitl ~ted by 1 to 3 C,-C4alkyl groups, R22 is hydrogen, C,-C4alkyl, cyclohexyl or cyclohexyl which is substituted by 1 to 3 C,-C4-alkyl groups, R23 is Cl-C20alkyl, or unsubstituted or C,-C4alkyl-substituted phenyl or naphthyl, R24 is hydrogen, C,-C20alkyl, unsubstituted or C1-C4alkyl-substituted phenyl or naphthyl; or j Mr+
.s _ ~

Mr+ is an r-valent metal cation, nis1,2,3,4,50r6,and ris 1, 20r3.

Where substituents are alkyl having up to 20 carbon atoms, the r~levant radicals are those such as methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl, stearyl and corresponding branched isomers. A preferred definition of R23 and R24 is C,-C~2alkyl, especially C1-C~alkyl, e.g. C2-C4alkyl.

W O 97/30105 PCT~EP97~00492 C1-C4alkyl-substituted phenyl or naphthyl, which preferably contains 1 to 3, especially 1 or 2 alkyl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphe-nyl, 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.

C1-C4alkyl-substituted cyclohexyl, which preferably contains 1 to 3, especially 1 or 2 branched or unlbranched alkyl group radicals, is, for example, cyclopentyl, methylcyclopen-tyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclo-hexyl or tert-butylcyclohexyl.

A mono-, di- or trivalent metal cation is preferably an alkali metal, alkaline earth metal, heavy metal or aluminium cation, for example Na+, K~, Mg~+, Ca~, Batt, Zn++ or Al+++. Ca++
is especially preferred.

r,~f~rled compounds of the formula ll are those having at least one tert-butyl group as ra-dical R2, or R2~. Very particular preference is given to compounds in which R21 and R22 are both tert-butyl.

n is preferably 1 or 2, especially 1.

Very particularly preferred sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters are the compounds of the formulae lla and llb.

(CH3)3C o (CH3~3C O
HO~--CH2--I--OCH2CHS HO~CH2--I--o~3 ca2+
(CH3)3C ocH2cH3 _ (CH3)3C OCH2CH3 (lla) (llb) " .

The compound of the formula lla is obtainable commercially under the name Irganox~1222 (Ciba-Geigy) and that of the formula llb under the name Irganox~142~ (Ciba-Geigy).

W O 97/30105 PCT~EP97100492 Based on 100 parts of polycondensate, preferabiy from 0.01 to 5 parts, particularly prefe-rably from 0.02 to 2 parts and, in particuiar, from 0.05 to 1 part of a sterically hindered hy-droxyphenyl-alkyl-phosphonic ester or rnonoester are empioyed.

Polyfunctional compounds from the class of the diphosphonites are known, for example, from GB-A-2 247 241 and are, for example, compounds of the formula lll R~<R3, R3~<R37 R3~o P Y P O~R38 (111) R34 R35 - 2 ~ R40 R3s _ 2 in which R31, R32, R33, R34, R3s, R36, R37, R38, R3g and R40 independently of one another are hydrog~n or Ct-C8alkyl, Y is 1,4-phenylene, 1,3-phenylene, ~z~}z~ or G~
~z~ , and Z is a direct bond, phenylene, oxygen, sulfur, -SO-, -SO2- or ~C=o Alkyl having up to 8 carbon atorns is a branched or unbranched radical such as, 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-methylhexyl, n-heptyl, iso-heptyl, 1 ,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, tert-octyl or 2-ethyl-hexyl. One of the preferred definitions of R3l, R~, R33, R34, R35, R36, R3,, R38, R39 and R40 is, for example, C1-C6alkyl, especially C~-C4alkyl, e.g. methyl or tert-butyl.

CA 02243692 l998-07-20 W 097/~OlO'i PCT~EP97/00492 Preference is given to the compounds of formula lll in which at least two of the radicals R3~, R32,R331 R34and R35 and at least two of the radicals R~, R37,R38, R39 and R40 are hydrogen.

Also of intere~it are the compounds of formula 111, in which R32, R34, R35, R37, R39 and R40 are hydrogen.

Particular preference is given to the compounds of the formula 111 in which Y is ~z~ and Z is a direct bond.

Very particular preference is given to tet-akis(2,4-di-tert-butylphenyl) 4,4'-biphenylene-di-phosphonite (Irgafos0PEPQ, Ciba-Geigy) of the formula Illa C(CH3)3 C~CH3)3 (CH3)3C--- ~ 0 - P ~ p _ o ~ C(CH3)3 Based on 100 par~s of polycondensate, preferably from 0.01 to 5 parts, particularly prefe-rably from 0.02 to 2 parts and, in particular, from 0.05 to 1 part of a diphosphonite are em-ployed.

Compounds from the class of the secondary aromatic amines are known, for example, from R. Gachter and H. Muller, Hanser Verlag, aPlastics Additives Handbook, 3rd Ed.", page 44 to 45 (1990) ~md are, for example, compounds of the formula IV

W O ~713~105 PCTnEP97100492 - R4l I R45 R42~,~N ~R46 R4~ ~ R47 R~" R.,8 in which R4l is hydrogen or C,-C25alkyl, R42 is hydrogen, Cl-C2salkyl or benzyl, R43 is hydrogen, Cl-C25alkyl, C5-C12cycloalkyl, benzyl, a-methylbenzyl or a,a-dimethylbenzyl;

or R42 and R43 together form a divalent group R

R~ is hydrogen, C1-C25alkyl or benzyl, R45iS hydrogen or Cl-C2salkyl, R46 is hydrogen, Cl-C25alkyl or benzyl, R4, is hydrogen, C1-C25alkyl, C5-Cl2cycloalkyl, benzyl, a-methylbenzyl, a,a-dimethylbenzyl or ~H
--N~ ; or R46 and R47 together form a divalent group R
Rso R ,8 is hydrogen, Cl~C25alkyl or benzyl, R49iS hydrogen or Cl-C25alkyl, and Rso is Cs-Cl2cycloalkyl~ ~¦3R49 or ~}R49 Alkyl having up to 25 carbon atoms is a branched or unbranched radical such as, 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-methylhexyl, n-heptyl, iso-heptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa-W O97/30105 PCT~EP97/00492 decyl, eicosyl or docosyl. One of the preferred definitions of R4" R42, R44, R45, R46 and R48 is, for example, C1-C18alkyl, especially C,-C,2alkyl, e.g. C,-C8alkyl. A preferred definition of R43 and P~47is, for example, C~-C~8alkyl, especially C,-C12alkyl, e.g. C4-C~2alkyl. A particularly preferred definition of R43 and R4~is C4-C~Oalkyl, especially C4-C8alkyl, e.g. tert-butyl or tert-octyl.

C5-C,2cycloalk~l~1 is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl. A preferred definition of R43, R47 and Rsois~ for example, C5-C8cycloalkyl, especially C5-C7cycloalkyl, e.g. cyclohexyl.

Particular preference is given to the compounds of the formula IV in which R4, and R42 independently of one another are hydrogen or C~-C~8alkyl, R43is hydrogen, C,-C18alkyl~c5-C8cycloalkyl~ benzyl, a-methylbenzyl or a,a-dimethylbenzyl;

or R42 and R43 logether form a divalent group R4 ~

R44,R45 and R46 independently of one another are hydrogen or C1-C18alkyl, R4~is hydrogen, C,-C,8alkyl,C5-C8cycloalkyl, benzyl, a-methylbenzyl, a,a-dimethylbenzyl or ,H ,~
--N\ ; or R46 and R47 together form a divalent group R4 R~
R48 and R49 independently of one another are hydrogen or C1-C,8alkyl, and R~is C5-C8cycloalkyl, ~ R49 or ~ R49 .

Of particular interest are the secondary aromatic amines of the formula IV, in which R41,R44, R4s,R46 and R48 are hydrogen.

Of specific interest are the compounds of the formula IV, in which R41 and R42 are hydrogen, W O 97/30105 PCTtEP97tOO492 R43 is hydrogen, C4-Cl2alkyl, cyclohexyl, benzyl, a-methylbenzyl or a,oc-dimethylbenzyl; or R42 and R43 together form a divalent group R

R44, R45 and R46 are hydrogen, R47 is hydrogen, C4-Cl2alkyl, cyclohexyl, benzyl, a-methylbenzyl, a,a-dimethylbenzyl or --N~

R48 and R49 is hydrogen, and R~o is cyclohexyl, phenyl or ,B-naphthyl.

Very particular preference is given to the secondary aromatic amines of forrnulae IVa, IVb, IVc, IVd, IVe and IVf.

IH Hl [~ ~ ~3 ~ ~1~ '~ (IVb) N N
H H

~C~ ~C~0 ~ ~3R~ (IVd~
HsC CH3 H3C CH3 R' = n-butyl or n-octyl W O 97/3010'i PCT~EP97/00492 H

(CH3)3C~ \cJ3~N ~'C / C(CH3~3 ~NJ3 H

An especially preferred secondary aromatic amine is the compound of the formula IVe [4,4'-di-tert-octyidiphenylamine, Irganox~ 5057 (Ciba-Geigy)].

The compounds of the formula IV are known and some are commercially available or ca be prepared as described in R. Gachter and 11. Muller, Hanser Verlag, "Plastics Additives Handbook, 3rd Ed.," page 44 to 45 (1990) in analogy to the literature references cited therein.

Based on 100 parts of polycondensate, preferably from O.Q1 to 5 parts, particularly prefe-rably from 0.02 to 2 parts and, in particular, from O.û5 to 1 part of a secondary aromatic amine are e"l,rloyed.

Difunctional epoxides in the context of this invention can have an aliphatic, aromatic, cyclo-aliphatic, araliphatic or heterocyclic structure; they include epoxide groups as side groups, or these groups form part of an alicyclic or heterocyclic ring system. The epoxide groups are preferably attached as glycidyl groups to the remainder of the molecule by way of ether or ester linkages, or the compounds are N-glycidyl derivatives of heterocyclic amines, amides or imides. Epoxides of these types are generally known and commercially available.

The epoxides contain two epoxide radicals, for example those of the formula V

W O 97/3010S PCT~EP97/00492 C~--(CH2)m C--CH (V), R6l R62 R6s which are attached directly to carbon, oxygen, nitrogen or sulfur atoms and in which R6, and R~33 are both hydrogen, R62 is hydrogen or methyl and m is o; or in which P~61 and R63 to-gether are -CH2CH2- or -CH2CI 12CH2-, R62 is then hydrogen and m is O or 1.

Examples of epoxides are:

1. Diglycidyl and di(B-methylglycidyl) esters obtainable by reacting a compound with two carboxyl groups in the molecule and epichlorohydrin and/or glycerol dichlorohydrin and/or B-methylepichlorohydrin. The reaction is expediently carried out in the presence of bases.

As compounds of two carboxyl groups in the molecule, aliphatic dicarboxylic acids can be used. Examples of these dicarboxylic acids are glutaric acid, adipic acid, pirnelic acid, su-beric acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid.
It is however also possible to employ cycloaliphatic dicarboxylic acids such as, for example, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-me-thylhexahydrophthalic acid.

Furthermore, aromatic dicarboxylic acids, for example phthalic acid or isophthalic acid, can be used.

2. Diglycidyl or di(l3-methylglycidyl) ethers obtainabie by reacting a compound with two free alcoholic hydroxyl groups and/or phenolic hydroxyl groups and a suitab!y substituted epi-chlorohydrin under alkaline conditions, or in the presence of an acidic catalyst with subse-quent alkali treatment.

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-W O 97/30105 PCT~EP97/00492 lene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-d;ol, sorbitol, and from polyepichlorohydrins.

However, they are also derived, for example, from cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis(4-hydro~ycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)-propane or t,1-bis(hydroxymethyl)cyclohex-3-ene, or they possess aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)diphenylmethane.

The epoxides can also be derived from mononuclear phenols, such as, for example, from resorcinol, pyrocatechol or hydroquinone; or they are based on polynuclear phenols such as, for example!, on 4,4'-dihydroxybiphenyl, bis(4-hydroxphenyl)methane, 2,2-bis(4-hydroxy-phenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenylsul-fone, 9,9'-bis(4-hydroxyphenyl)fluorene, or on condensation products of phenols with form-aldehyde that a.re obtained under acldic con~lilions, such as phenol novolaks.
3. Di-(N-glycidyl) compounds are obtainable, for example, by dehydrochlorination of the reaction products of epichlorohydrin with amines containing two amino hydrogen atoms.
~xamples of these amines are aniline, toluidine, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediarnine or bis(4-methylaminophenyl)methane.

Also included a.mong the di(N-glycidyl) compounds, however, are N,N'-diglycidyl derivatives of cycloalkylen~eureas, such as ethyleneurea or 1,3-propyleneurea, and N,N'-diglycidyl deri-vatives of hydantoins such as of 5,~-dimethylhydantoin.
4. Di(S-glycidyl) compounds, such as di-S-glycidyl derivatives derived from dithiols, such as, for example, ethane-1,2-dithiol or bis(4-mereaptol"ethylphenyl) ether.

. Epoxides with a radical of the formula V in which R6,and R63 together are -CH2CH2- and m is O are, for example, bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether or 1,2-bis(2,3-epoxycyclopentoxy)ethane; an example of epoxides with a radical of the for-mula V in which R6l and R63 together are -CH2CH2- and m is 1 is (3',4'-epoxy-6'-methylcyclo-hexyl)methyl 3,4-epoxy-6-methylcyclohexanecarboxylate.

' CA 02243692 l998-07-20 W O 97/301QS PCT~EP97/00492 Owing, for example, to their preparation process, the abovementioned difunctional epoxides may include small amounts of mono- or trifunctionai fractions.

Predominantly, use is made of diglycidyl compounds having aromatic structures.

If desired, it is also possible to employ a mixture of epoxides of different structures.

On the other hand, tri- and polyfunctional epoxides can be added supplementarily in order, if desired, to obtain branching. Examples of such epoxides are:

a) liquid bisphenol A diglycidyl ethers, such as Araldit~GY 240, Araldit~GY 250, Araldit~GY
260, AralditlGY 266, Araldit~GY 2600 or AralditlMY 790;

b) solid ~isphenol A diglycidyl ethers, such as AralditlGT 6071, Araldit~GT 7071, Araldit~GT
7072, Araldit~GT 6063, Araldit~GT 7203, Araldit~GT 6064, Araldit~GT 7304, Araldit~GT
7004, Araldit~GT 6084, Araldit~GT 1999, Araldit~GT 7077, Araldit~GT 6097, Araldit~GT
7097, Araldit~GT 7008, Araldit~GT 6099, Araldit~GT 6608, Araldit~G~ 6609 or Araldit0GT
6610;

c) liquid bisphenol F diglycidyl ethers, such as AralditLGY 281, Araldit-GY 282, Araldit~PY
302, or Araldit~PY 306;

d) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy Resin~0163;

e) solid and liquid polyglycidyl ethers of phenol-formaldehyde novolak such as EPN 1138, EPN 1139, GY 1180, PY 307;

f) solid and liquid polyglycidyl ethers of o-cresol-formaldehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1298;

g) liquid glycidyl ethers of alcohols, such as Shell~Glycidylether 162, Araldit~DY Q390 or Araldit''DY 0391;

CA 02243692 l998-07-20 W O97/3010_; PCT~EP97/00492 h) liquid glycidyl esters of carboxylic acids, such as Shell~Cardura E terephthalic ester, tri-mellitic ester, ~,raldit~PY 284 or mixtures of aromatic glycidyl esters, for example Araldit~PT
9tO;

i) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit~PT 810;

J) liquid cycloaliphatic epoxy resins such as Araldit~CY 179.

k) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as Araldit~MY 0510;

I) tetraglycidyl-4-4'-methylenebenzamine or N,N,N',N'-tetraglycidyldiaminophenylmethane, such as AralditDMY 720, Araldi~MY 721.

Particularly preferred difunctional epoxides are diglycidyl ethers based on bisphenols such as, for example, on 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)-sulfone (bisphenol S) or mixtures of bis(ortho/para-hydroxyphenyl)methane (bisphenol F).

Very particular preference is given to epoxides of the bisphenol A diglycidyl ether type, for example: Aralclit~GT 6071, GT 7071, GT 7072, ~T 6097 and GT 6099 or epoxides of the bisphenol F type, such as Araldit~GY 281 or PY 306. Of very special interest is an epoxide of the bisphenol A diglycidyl ether type, such as Araldit~GT 6071, for example.

Based on 100 parts of polycondensate, preferably from 0.01 to 5 parts, particularly prefe-rably from 0.02 to 2 parts and, in particular from 0.05 to 1 part of a difunctional epoxide are employed.

The process can be carried out in any vessels which can be heated and are fitted with a stirring device. These may, for example, be closed apparatus from which atmospheric oxy-gen is excluded, working for example under an inert gas atmosphere such as nitrogen, or else with vacuum degassing. The process is preferably conducted in an extruder.
5 PCT~EP97/00492 The polycondensate that is to be heated and the novel additives are usually charged to the apparatus at the beginning of heating; however, subsequent metered addition of the novel additives to the polycondensate is also possible, it being possible for the mixture of the additives or else the individual components to be added in any desired sequence. Heating at above the melting point or glass transition point is generally carried out until the novel additives are homogeneously distributed. Homogeneous distribution can take place, for example, by means of stirring or kneading in an extruder. The temperature here depends on the polycondensate used. In the case of crystalline polycondensates, it is praferred to operate in the range between melting point and a temperature about 50~C above the mel-ting point. In the case of amorphous polycondensates, the process is expediently carried out, for instance, in the region of 50~C and 150~C above the respective glass transition temperature.

For their addition, the novel additives can independently of one another be present in the form of a liquid, powder or granules, or in compacted form, or else on a substrate material, such as silica gel, together with a polymer powder or wax, for example a polyethylene wax, or as a concentrate, for example in a masterbatch.

The amount of additives depends on the initial molecular weight of the polycondensate and on the desired final molecular weight.

The novel process has the advantage that the increase in molecular weight and/or viscosity takes place within short reaction times, and the additives can be added in solid form. The novel process also has the advantage that the polycondensate undergoes no addilional dis-coloration. The combination of (i) aromatic dicyanates with (ii) polyfunctional compounds selected from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphites and secondary aromatic amines leads synerDistic~lly to the build-up of the molecular weight of virgin polycondensate or polycondensate recyclate, with elenlion of the linear chain structure.

In addition to the additives described above, stabilkers can be added to the polyconden-sate. These stabilizers are generally known to the skilled worker and are chosen depending on the specific requirements regarding the end product. In particular it is possible to add light stabilizers or else antioxidants (R. Gachter, H. Muller, Hanser Verlag, "Plastics Addi-W O 97/301Q~; PCT~@P97/00492 tives Handbook, 3rd Ed.," especially pages 82 to 85 and 255 to 258 (1990)). Among these, those whlch may be mentioned as particularly suitable are:

1. Antioxldants 1.1. Esters of ,B-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. vvith methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy-iene glycol, trlethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy-droxyethyl)oxamide, 3-thiaundecanol, 3-thiapenPdec~nol, trimethylhexanediol, trimethylol-propane, 4-hyclroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.2. Esters of ,~-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-hydric alcohol~" e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene gly col, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-t~ioxati_y~'Q[~ octane.

1.3. Esters of ~-~3.5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. \~,lith methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glyc,ol, 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[2.2.2loctane.

1.4. Esters of 3.5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric aico-hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycoll, 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-trioxabicyclot2.2.2loctane.

W O97/30105 PCT~EP97/00492 1.5. Amides of ,~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl~-hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyi]propionyloxy)ethyl]oxamide (Naugard~XL-1 supplied by Uniroyal).

1.6. Tocopherols. for example a-tocopherol"B-tocopherol, ~-tocopherol, ~-tocopherol and mixtures thereof (vitamin E).

Among these, preferred antioxidants are those of the type Irganox21098 (N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine) or Irganox~245 (ester of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with triethylene glycol), plere,~bly in combination with aromatic phosphites or phosphonites (see item 3).

2~ UV absorbers and li~ht stabilisers 2~1. 2-l2'-Hydroxyohenyl)benzotriazoles. for example 2-(2'-hydroxy-5'-methylphenyl)-benzo-triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)ben~o(,ia~ole, 2-(5'-tert-butyl-2'-hydroxyphe-nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyi)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-methylphe-nyl)-~-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-t2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotri-azole, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hy-droxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl~-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hy-droxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methyiphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-ben~ollia~ole-2-ylphenol]; the transeste-i~ication productof 2-~3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazoie with polyethy-W O97130105 PCTAEP97/0049~

iene glycol 300; [R--CH2CH2 Coo-CH2CHz~ where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1, 3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)-phenyl]benzotriazole.

2.2. 2-HydroxybenzophenonQs. for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of s~lbstituted and unsubstituted benzoic acids. as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben-zoyl) resorcinol, benzoyl resorcinot, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo-ate, hexadecyl 3,~-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxy-ben~oate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2 4. Acrylates. for example ethyl a-cyano-,B,~-diphenylacrylate, isooctyl o~-cyano-,~,~-diphe-nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-~-methyl-p-methoxy-cinna-mate, butyl a-cyano-~-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycin-namate and N-l,~-carbomethoxy-~-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds. for example nickel complexes of 2,2'-thio-bis-~4-(1,1,3,3-tetrame-thylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldilh.ocarbamate, 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-nyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
.

2.6. Sterically hindered amines. for example bis(2,2,6,6-tetramethyl-4-piperidyl)seb~c~te, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)seba-cate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)seb~c~te. bis(1,2,2,6,6-pentamethyl-4-pi-peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxy-ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic conden-W O 97/30105 PCTrEP~7/00492 sates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylami-no-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl~nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethanediyl)-bjs-(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-Z,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-tri~7~spiro[4.5]decan-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetrame-thylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis-(2,2,6,6-tetramethyl-4-piperi-dyl)hexamethylenediamine and 4-morpholino-2,~i-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl )-1,3,5-triazine and 1,2-bis~3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pen-tamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylarnino)ethane, 8-acetyl-3-dode-cyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro~4.5ldecane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetrame-thyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-( i ,2,2,6,6-pentamethyl-4-piperidyl)pyrroli-dine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1 ,2-bis(3-ami-nopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-te-tramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-do-decylsuccinimid, N-(t,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin, 1,t-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of maleic acid anhydride-o~-olefin-copolymer with 2,2,6,6-tetramethyi-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides. for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani-lide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disub-stituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

W O 97/301Q'; rCT~EP97/00492 2.8. 2-(2-Hydn~xypheny~)-1.3.5-triazines. for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-pro-pyloxyphenyl) -6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphe-nyl)-l ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-tri-azine, 2-~2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-tri-azine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[4-~dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-di-methylphenyl)-1,3,5-triazine, 2-12-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl3-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphe-nyl)-6-phenyl-1,3,5-triazine, 2-{2-hydlroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phe-nyl}-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine.

3. Phosphites and phosphonites. for example triphenyl phosphite, diphenyl alkyl phosphitas, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos-phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecy!
pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol di-phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)penltaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-bu-tylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benzld,g]-1,3 2-dioxaphosphocin, 6-fluoro-2,4,8,1 0-tetra-tert-butyl-1 2-methyl-dibenzld,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo~triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-.~,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-di-yl)phosphite.

Especially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos~168, Ciba-Geigy), tris(nonylphenyl) phos-phite, (CH3)3C ~ C(CH3)3 (CH3)3C ~C(CH3)3 (A) H3C--~C (CH9)3 (cH3)3c--~p--o--CH2CH2 N (B) (CH3)3C _ 3 3 (cH3)3c ~C (CH3)3 p- o CH2CH(C4H9)cH2c~3 (CH3)3c--~
C(CH3)3 (CH3)3C ~ o Xo~ ~C(CH3)3 (D
C(CH3)3 (CH3)3C

c(CH3)3 (cH3)3c H3C~ 'oXo'~CH3 (E) C(CH3)3 (CH3)3C

W 097/3P105 . PCT~EP97/00492 (F) H,7C1, ~~ P~ X al ~--P OCHZCHa (G

Very particular preference is given to tris(2,4-di-tert-butylphenyl) phosphite [Irgafos~168, Ciba-Geigy], bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (Irgafos~38, Ciba-Geigy, formula (G)~ and 2,2',2"-nitrilo[triethyl tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite [Irgalos~12, Ciba-Geigy, formula (B)~.

4. Polvamide stabilisers. for example, copper salts in combination with iodides and/or phos-phorus compounds and salts of divalent manganese.

5. Fillers and reinforcina agents. for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car-bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fi-bers.
6. Other additives. for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agenlts, optical brighteners, flameproofi"g agents, anli~ Llic agents and blowing agents.

The additional additives and/or stabilizers are added to the polycondensate in concentra-tions, for example, of from O.O1 to 10 %, based on the overall weight of the polycondensate.

Among such additions, preference is given to light stabilizers from c~ ses 2.1, 2.6 and 2.7, for example light stabilizers of the type Chimassorb$944, Chimassorb~119, Tinuvin0234, Tinuvin0312, Tirluvin0622 or Tinuvin770. Preference is also given to aromatic phosphites or phosphonites.

W O 97/30105 PCT~EP97/00492 Where the polycondensate is a recyclate, it can also be employed mixed with virgin material or together with virgin material, for example in a coextrusion process.

The invention additionally provides for the use of an aromatic dicyanate for increasing the molecular weight and/or viscosity of virgin polycondensate or polycondensate recyclate.

The invention also provides for the use of a mixture comprising an aromatic dicyanate and, in addition, at least one polyfunctional compound selected from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and se-condary aromatic amines for increasing the molecular weight and/or viscosity of virgin poly-condensate or polycondensate recyclate.

The present invention also provldes for the use of a mixture comprising (i) an aromatic di-cyanate, (ii) at least one polyfunctional compound selected from the class of sterically hin-dered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secon-dary aromatic amines, and (iii) a difunctional epoxide for increasing the molecular weight and/or viscosity of virgin polycondensate or polycondensate recyclate.

The preferences regarding the use correspond to those for the process.

The inv~ntion provides, furthermore, a composition comprising (a) a virgin polycondensate or polycondensate recyclate or a mixture thereof, and (b) an aromatic dicyanate.
The invention additionally provides a composition comprising (a) a virgin polycondensate or polycondensate recyclate or a mixture thereof, (b) an aromatic dicyanate, and (c) at least one polyfunctional compound selected from the class of the sterically hindered hydroxyphe-nyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary aromatic amines.

The present invention additionally provides a composition comprising (a) a virgin polycon-densate or polycondensate recyclate or a mixture thereof, (b) an aromatic dicyanate, (c) at least one polyfunctional compound seiected from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary aromatic amines, and (d) a difunctional epoxide.

CA 02243692 l998-07-20 W O 97/3010~ PCT~EP97/00492 _ The preferences regarding the compositions correspond to those for the process.

The invention further provides, in addition, polycondensates obtainabte by the novel pro-cess.

The examples which follow illustrate the invention in more detail without limiting it thereto.
As in the rest of ~he description, parts and percentages are ~y weight unless stated other-wise.

Example 1: Increasing the molecular weight and/or viscosity of polyamide 6.

In a Plasticorder from Brabender with a W 50 mixing chamber, a polyamide 6 (~ure-than~B30 S from Bayer) is processed under nitrogen at a temperature of 235~C and at 40 revolutions/minu~e with the additives indicated in Table 1. The torque of the polyamide is determined after 6 and 15 minutes. The larger the number, the higher the molecular weight.
After 1~ minutes the melt index (MFR) is measured (at 235~C under 2.16 kg in accordance with ISO 1133). A large increase in the melt index denotes severe chain degradation, and thus a reduction in molecular weight. The results are compiled in Table 1.

WO97/~OlOS PCT~EP97/00492 Table 1:
Torque [Nm] after Exampte Additives Melt 6 min. 15 min. index 1 as) -- 3.4 3.4 43.7 1b9) 0.50 % Araldit~GT 6071a)4.7 4.9 23.8 1c 0.25 % BPCb) 5.4 5.0 22.5 ld 0.50 % BPCb) 6.1 5.3 17.5 1e 0.75 % BPCb) 7.2 7.1 14.3 1f 1.00 % BPCb) 8.3 7.7 12.2 19 0.50 % BPCb) 7.8 7.8 12.0 0.50 % Irganox61222C) 1h 1.00 % BPCb) 10.4 10.5 7.8 1.00 % Irganox~1425d) 1i 1.00 % BPCb) 9.2 8.0 11.1 0.50 % Irgafos~ PEPQ~) 1k 0.50 % BPCb) 6.6 6.8 12.1 0.50 % Irganox~5057~) 11 1.00 % BPCb) 11.0 10.0 7.7 0.50 % Irganox65057"
0.50 % BPCb) lm 0.50 % Irganox~1222C) 9.4 10.1 7.5 0.50 % Araldit0GT 6071~) a) Araldit~GT 6071 (Ciba-Geigy) ls bisphenol A diglycidyl ether with an epoxide number of 2.15-2.22 eq/kg and a softening range of 70-75~C.

b) BPC is bisphenol A dicyanate and is a compound of the formula la W O 97/30105 PCT~EP97/00492 NC - O ~ I H~O - CN (la) c) Irganox~t222 (Ciba-Geigy) is a compound of the formula lla (CH3)3C O
HO~CH2--I--OCH2CH3 (lla) (CH3)3C OCH2CH3 d) Irganox2'1425 (Ciba-Geigy) is a compound of the formula llb (CH3)3c O
HO~CH2--I--~ ca2 (llb) _ (CH3)3C OCH2CH3 e) Irgafos~PEPQ (Ciba-Geigy) is a compound of the formula Illa C(CH3)3 C,~CH3)3 (CH3)3C~O--P~P--o~C(CH3)3 f) Irganox~505 7 (Ciba-Geigy) is 4,4'-di-tert-octyldiphenylamine and is a compound of the formula IVe (CH ) C~C\ J~N~C C(CH3)3 ~IVe) g) Comparison examples E~xample 2: Increase in molecular weight and/or viscosity of polyamide 6.6.

In a TW 200 twin-screw extruder from Haake, a polyamide 6.6 (Durethan0A 30 S from Bayer) is processed at a temperature of 290~C and 40 revolutions/minute with the additives indicated in Table 2. After 15 minutes the melt index (MFR) is measured (at 275~C under 2.16 kg in accordance with ISO 1133). A large increase in the melt index denotes severe chain degradation and thus a reduction in molecular weight, and a large decrease in the melt index denotes an increase in moleG~ r weight. The results are compiled in Table 2.

Table 2:
Example AdditivesMelt Index [g/10 min]
2ad) 63.0 2b 0.50 % AroCy~B-10a) 36.0 2c 0.50 % AroCy~L-10b) 22.0 0.50 % AroCy~B-10a) 2d 30.0 0.25 % Irganox~1425C) W O 97/3010'i . PCTAEP97/00492 a~ AroCy0B-1 O (Rhone-Poulenc) is a compound of formula la NC--O~CH, O--CN (la) b) AroCy~L-10 (Rhone-Poulenc) is a compound of formula Id NC--o~ I H~o--CN (Id) c) Irganox~1425 (Ciba-Geigy) is a compound of formula llb tCH3)3C O
HO~CH2--I--o~3 ca2~ (~Ib) _ (CH3)3C OCH2CH3 d) Comparison example.

Claims (31)

WHAT IS CLAIMED IS:
1. A process for increasing the molecular weight and/or viscosity of polycondensates, which comprises heating a polycondensate, with addition of at least one aromaticdicyanate, at above the melting point or glass transition point of the polycondensate.
2. A process according to claim 1, wherein at least one polyfunctional compound selected from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary aromatic amines is additionally employed.
3. A process according to claim 2, wherein at least one difunctional epoxide is additionally employed.
4. A process according to claim 1, wherein the polycondensate is a polycondensate recyclate.
5. A process according to claim 1, wherein the aromatic dicyanate is a compound of the formula I

in which X is a direct bond, oxygen, sulfur, -SO-, -SO2-, , , , C2-C18alkylene, C2-C18alkenylene or , R1, R2, R3 and R4 independently of one another are hydrogen, C1-C25alkyl, C5-C12cycloalkyl, unsubstituted or C1-C4alkyl-substituted phenyl; C7-C9phenylalkyl, hydroxyl, C1-C25alkoxy or -O-CN, with the proviso that at least one of the radicals R1, R2, R3 and R4 is -O-CN, R5, R6, R7 and R8 independently of one another are hydrogen, C1-C25alkyl, C5-C12cycloalkyl, unsubstituted or C1-C4alkyl-substitutad phenyl; C7-C9phenylalkyl, hydroxyl, C1-C25alkoxy or -O-CN, with the proviso that at least one of the radicals R5, R6, R7 and R8 is -O-CN, R9 and R10 independently of one another are hydrogen, C1-C12alkyl, trifluoromethyl or phenyl, or R9 and R10, together with the carbon atom to which they are attached, form a C5-C8cycloalkylidene ring which is unsubstituted or is substituted by 1 to 3 C1-C4alkyls; and R11 is hydrogen or C1-C12alkyl.
6. A process according to claim 5, wherein X is a direct bond, oxygen, , , , C2-C12alkylene or C2-C12alkenylene, R1, R2, R3 and R4 independently of one another are hydrogen, C1-C18alkyl, C5-C8cycloalkyl, phenyl, benzyl, C1-C18alkoxy or -O-CN, with the proviso that at least one of the radicals R1, R2, R3 or R4 is -O-CN, R5, R6, R7 and R8 independently of one another are hydrogen, C1-C18alkyl, C5-C8cycloalkyl, phenyl, benzyl, C1-C18alkoxy or -O-CN, with the proviso that at least one of the radicals R5, R6, R7 or R8 is -O-CN, and R9 and R10 independently of one another are hydrogen, C1-C8alkyl, trifluoromethyl or phenyl, or R9 and R10, together with the carbon atom to which they are attached, form a C5-C6cycloalkylidene ring.
7. A process according to claim 5, wherein R1 and R5 are hydrogen, R2, R4, R6 and R8 are hydrogen or methyl, and R3 and R7 are -O-CN.
8. A process according to claim 5, wherein X is a direct bond, , or , R1 is hydrogen, R2 is hydrogen or C1-C4alkyl, R3 is -O-CN, R4 is hydrogen or C1-C4alkyl, R5 is hydrogen, R6 is hydrogen or C1-C4alkyl, R7 is -O-CN, R8 is hydrogen or C1-C4alkyl, and R9 and R10 independently of one another are hydrogen, methyl or trifluoromethyl.
9. A process according to claim 5, wherein X is , R1 and R2 are hydrogen, R3 is -O-CN, R4, R5 and R6 are hydrogen, R7 is -O-CN, R8 is hydrogen, and R9 and R10 independently of one another are hydrogen or methyl.
10. A process according to claim 2, wherein the polyfunctional compound from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters is a compound of the formula II
in which R21 is isopropyl, tert-butyl, cyclohexyl or cyclohexyl which is substituted by 1 to 3 C1-C4alkyl groups, R22 is hydrogen, C1-C4alkyl, cyclohexyl or cyclohexyl which is substituted by 1 to 3 C1-C4alkyl groups, R23 is C1-C20alkyl, or unsubstituted or C1-C4alkyl-substituted phenyl or naphthyl, R24 is hydrogen, C1-C20alkyl, unsubstituted or C1-C4alkyl-substituted phenyl or naphthyl; or is Mr+ is an r-valent metal cation, n is 1, 2, 3, 4, 5 or 6, and r is 1, 2 or 3.
11. A process according to claim 2, wherein the polyfunctional compound from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters is a compound of the formula IIa or IIb
12. A process according to claim 2, wherein the polyfunctional compound from the class of the diphosphonites is a compound of the formula III

in which R31, R32, R33, R34, R35, R36, R37, R38, R39 and R40 independently of one another are hydrogen or C1-C8alkyl, Y is 1,4-phenylene, 1,3-phenylene, or , and Z is a direct bond, phenylene, oxygen, sulfur, -SO-, -SO2- or .
13. A process according to claim 2, wherein the polyfunctional compound from the class of the diphosphonites is a compound of the formula IIIa
14. A process according to claim 2, wherein the polyfunctional compound from the class of the secondary aromatic amines is a compound of the formula IV

in which R41 is hydrogen or C1-C25alkyl, R42 is hydrogen, C1-C25alkyl or benzyl, R43 is hydrogen, C1-C25alkyl, C5-C12cycloalkyl, benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl;

or R42 and R43 together form a divalent group , R44 is hydrogen, C1-C25alkyl or benzyl, R45 is hydrogen or C1-C25alkyl, R46 is hydrogen, C1-C25alkyl or benzyl, R47 is hydrogen, C1-C25alkyl, C5-C12cycloalkyl, benzyl, .alpha.-methylbenzyl, .alpha.,.alpha.-dimethylbenzyl or ; or R46 and R47 together form a divalent group , R48 is hydrogen, C1-C25alkyl or benzyl, R49 is hydrogen or C1-C25alkyl, and R50 is C5-C12cycloalkyl, or .
15. A process according to claim 2, wherein the polyfunctional compound from the class of the secondary aromatic amines is a compound of the formula IVe
16. A process according to claim 3, wherein the difunctional epoxide is a compound which contains epoxide radicals of the formula V

which are attached directly to carbon, oxygen, nitrogen or sulfur atoms and in which R61 and R63 are both hydrogen, R62 is hydrogen or methyl and m is 0; or in which R61 and R63 together are -CH2CH2- or -CH2CH2CH2-, R62 is then hydrogen and m is 0 or 1.
17. A process according to claim 3, wherein the difunctional epoxide is an epoxide of the bisphenol A diglycidyl ether or bisphenol F diglycidyl ether type.
18. A process according to claim 1, wherein from 0.01 to 5 parts of the aromatic dicyanate are employed per 100 parts of polycondensate.
19. A process according to claim 2, wherein from 0.01 to 5 parts of the polyfunctional compound are employed per 100 parts of polycondensate.
20. A process according to claim 3, wherein from 0.01 to 5 parts of the difunctional epoxide are employed per 100 parts of polycondensate.
21. A process according to claim 1, wherein the polycondensate is a polyamide, apolyester, a polycarbonate or a copolymer of these polymers.
22. A process according to claim 21, wherein the polyamide is a polyamide 6 or polyamide 6.6 or a corresponding recyclate or copolymer thereof.
23. A process according to claim 21, wherein the polyester is a PET or PBT or a corresponding recyclate or copolymer thereof.
24. A process according to claim 1, wherein the polycondensate is a PBT/PC blend or a blend comprising predominantly PBT/PC or a corresponding recyclate or a blend of a recyclate and a virgin polymer component.
25. The use of an aromatic dicyanate for increasing the molecular weight and/or viscosity of virgin polycondensate or polycondensate recyclate.
26. The use of a mixture comprising an aromatic dicyanate and, in addition, at least one polyfunctional compound selected from the class of sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary aromatic amines for increasing the molecular weight and/or viscosity of virgin polycondensate or polycondensate recyclate.
27. The use of a mixture comprising (i) an aromatic dicyanate, (ii) at least one polyfunctional compound selected from the class of sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary aromatic amines, and (iii) a di-functional epoxide for increasing the molecular weight and/or viscosity of virgin polycondensate or polycondensate recyclate.
28. A composition comprising a) a virgin polycondensate or polycondensate recyclate or a mixture thereof, and b) an aromatic dicyanate.
29. A composition according to claim 28 additionally comprising (c) at least one polyfunctional compound selected from the class of the sterically hindered hydroxyphenyl-alkyl-phosphonic esters and monoesters, diphosphonites and secondary aromatic amines.
30. A composition according to claim 29 additionally comprising (d) a difunctional epoxide.
31. A polycondensate obtainable by a process according to claim 1, 2 or 3.
CA002243692A 1996-02-15 1997-02-04 Increasing the molecular weight of polycondensates Abandoned CA2243692A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH393/96 1996-02-15
CH39396 1996-02-15

Publications (1)

Publication Number Publication Date
CA2243692A1 true CA2243692A1 (en) 1997-08-21

Family

ID=4185999

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002243692A Abandoned CA2243692A1 (en) 1996-02-15 1997-02-04 Increasing the molecular weight of polycondensates

Country Status (9)

Country Link
US (1) US6706824B1 (en)
EP (1) EP0880553B1 (en)
JP (1) JP4200390B2 (en)
AU (1) AU1721597A (en)
CA (1) CA2243692A1 (en)
DE (1) DE69702498T2 (en)
ES (1) ES2148930T3 (en)
TW (1) TW482781B (en)
WO (1) WO1997030105A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999028367A1 (en) * 1997-12-01 1999-06-10 Ministero Dell'universita' E Della Ricerca Scientifica E Tecnologica A method for increasing the molecular weight of polyester resins
DE59900888D1 (en) * 1998-01-26 2002-04-04 Ciba Sc Holding Ag Increase in molecular weight and stabilization of polycondensates with diepoxides of sterically hindered amines
MY119540A (en) 1998-04-24 2005-06-30 Ciba Spacialty Chemicals Holding Inc Increasing the molecular weight of polyesters
US6242638B1 (en) 1999-03-12 2001-06-05 Vantico Inc. Cyanate esters having flame resistant properties
DE50011006D1 (en) * 1999-05-21 2005-09-29 Ciba Sc Holding Ag Molecular weight buildup and modification of polycondensates
WO2005030834A1 (en) * 2003-09-25 2005-04-07 Ciba Specialty Chemicals Holding Inc. Molecular weight increase and modification of polycondensates
US20060100330A1 (en) * 2004-11-10 2006-05-11 Natarajan Kavilipalayam M Composition for use in forming an article
US7375167B2 (en) * 2005-05-09 2008-05-20 Basf Se Hydrolysis-resistance composition
CN101184593B (en) * 2005-05-26 2012-02-08 卡拉工业公司 Method and apparatus for making crystalline polymeric pellets and granules
US9032641B2 (en) 2005-05-26 2015-05-19 Gala Industries, Inc. Method and apparatus for making crystalline polymeric pellets and granules
TWI440658B (en) * 2005-08-31 2014-06-11 Gala Inc Method and apparatus for underwater pelletizing polymer biomaterial composites with reduced moisture content
JP2012046734A (en) * 2010-07-30 2012-03-08 Fujifilm Corp Method for producing polyester sheet, polyester film and method for producing the polyester film
KR102082304B1 (en) * 2013-05-02 2020-02-27 에스케이케미칼 주식회사 Copolymer polyester resin and molded product using same
JP6466425B2 (en) * 2013-06-17 2019-02-06 エスケー ケミカルズ カンパニー リミテッド Heat-shrinkable film-forming composition containing polyethylene terephthalate resin and copolymerized polyester resin, and heat-shrinkable film
JP6369156B2 (en) * 2013-08-09 2018-08-08 三菱ケミカル株式会社 Lithographic polymer manufacturing method, resist composition manufacturing method, and pattern-formed substrate manufacturing method

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5689880A (en) * 1979-12-21 1981-07-21 Mitsubishi Gas Chem Co Inc Coating method
JPS5690823A (en) * 1979-12-24 1981-07-23 Mitsubishi Gas Chem Co Inc Curable resin composition
JPS5690824A (en) * 1979-12-24 1981-07-23 Mitsubishi Gas Chem Co Inc Curable resin composition
US4414366A (en) * 1980-12-05 1983-11-08 Allied Corporation Low color compositions comprising a cross-linked polycyanurate polymer and a thermoplastic polymer
US4334045A (en) * 1980-12-05 1982-06-08 Allied Corporation Low color compositions comprising a cross-linked polycyanurate polymer and a thermoplastic polymer
US4645805A (en) * 1984-03-14 1987-02-24 Mitsubishi Gas Chemical Company, Inc. Adhesive composition and adhesive film or sheet on which the composition is coated
DE3413547A1 (en) * 1984-04-11 1985-10-24 Bayer Ag, 5090 Leverkusen HEAT-CURABLE CYANATE RESIN AND ITS USE FOR THE PRODUCTION OF COMPOSITES
DE3633777C2 (en) * 1985-10-03 1996-08-22 Mitsubishi Gas Chemical Co Hot melt adhesive composition
JPS646019A (en) * 1987-06-29 1989-01-10 Toray Industries Curable polymer composition
US4902752A (en) * 1987-10-05 1990-02-20 Hi-Tek Polymers, Inc. Polycyanate esters of polyhydric phenols blended with thermoplastic polymers
US4885346A (en) * 1987-12-17 1989-12-05 Ciba-Geigy Corporation Mixture containing dicyanate or polycyanate compound, substituted bicyclo[2.]hept-5-ene-2,3-dicarboximide and thermoplastic
DE3802979A1 (en) * 1988-02-02 1989-08-10 Basf Ag HEAT-RESISTABLE RESIN MIXTURE
US5089555A (en) * 1989-03-10 1992-02-18 Somar Corporation Thermosetting powder composition
US5403896A (en) * 1989-12-26 1995-04-04 Alliedsignal Inc. Blow molding compositions of polyamide and cyanate components
US5143785A (en) * 1990-08-20 1992-09-01 Minnesota Mining And Manufacturing Company Cyanate ester adhesives for electronic applications
US5250635A (en) * 1991-02-28 1993-10-05 Miles Inc. Polycarbonate composition with reduced drip rate on burning
JP3231814B2 (en) * 1991-07-12 2001-11-26 ミネソタ マイニング アンド マニュファクチャリング カンパニー Anisotropic conductive film
EP0643741A1 (en) * 1992-06-03 1995-03-22 AlliedSignal Inc. Process for producing polyester or polyamide compositions comprising lactamyl phosphites as chain extending agents
DE59305338D1 (en) * 1992-12-22 1997-03-13 Ciba Geigy Ag Molecular weight increase of polyamides
US5496920A (en) * 1993-06-07 1996-03-05 Ciba-Geigy Corporation Increasing the molecular weight of polyamides
ATE324405T1 (en) * 1994-06-22 2006-05-15 Ciba Sc Holding Ag INCREASE THE MOLECULAR WEIGHT OF POLYCONDENSATE
US5705548A (en) * 1995-12-25 1998-01-06 Sumitomo Chemical Company, Limited Polyester powder coating composition

Also Published As

Publication number Publication date
ES2148930T3 (en) 2000-10-16
TW482781B (en) 2002-04-11
WO1997030105A1 (en) 1997-08-21
JP4200390B2 (en) 2008-12-24
EP0880553A1 (en) 1998-12-02
JP2000504761A (en) 2000-04-18
EP0880553B1 (en) 2000-07-12
DE69702498D1 (en) 2000-08-17
US6706824B1 (en) 2004-03-16
AU1721597A (en) 1997-09-02
DE69702498T2 (en) 2000-11-30

Similar Documents

Publication Publication Date Title
US5807932A (en) Increasing the molecular weight of polycondensates
MXPA97002646A (en) Increase the molecular weight of policondensa
US5744554A (en) Polyester/polycarbonate blends having enhanced properties
CA2243692A1 (en) Increasing the molecular weight of polycondensates
EP0770104B1 (en) Increase in molecular weight of polycondensates
US5693681A (en) Increasing the molecular weight of polyesters
US5859073A (en) Polyester/polycarbonate blends having enhanced properties
US6028129A (en) Increasing the molecular weight of polycondensates and stabilizing them, using diepoxides of sterically hindered amines
CA2158859C (en) Increasing the molecular weight of polyesters and premix useful for this process
US5747606A (en) Increasing the molecular weight of polyesters and premix useful for this process
US6025463A (en) Increasing the molecular weight of polyamides
CA2181713C (en) Increasing the molecular weight of polyesters

Legal Events

Date Code Title Description
EEER Examination request
FZDE Dead