Synonyms: IRGANOX ;IRGANOX WL;Einecs ; ANTIOXIDANT ;ylester,calciumsalt();ANTIOXIDANT (IRGANOX );calciuM. Irganox® Recommended use of the chemical and restriction on use. Recommended use*: stabilizer. Unsuitable for use: This material is. Used as an antioxidant for polypropylene fibers. Offers good processing stability. Provides very high extraction resistance and extreme low volatility.

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The present invention relates to a process for increasing the molecular weight of polyesters and to the polyesters obtainable by said process. Polyesters as exemplified by polyethylene terephthalate PET and polybutylene terephthalate PBTas well as polyester copolymers and polyester blends with e.

Partially crystalline polyesters are used for injection moulding compounds and have superior strength and rigidity, high dimensional stability and good wear properties. Amorphous polyesters have high transparency, superior toughness and very good resistance to stress-cracking, and can be processed to hollow objects.

A further utility of PET is fibre production. The mechanical and physical properties depend essentially on the molecular weight of the polymer. Owing to reduced molecular weight, it is only possible to achieve a limited high-quality recycling of used polyesters and production waste without carrying out an aftertreatment. It is generally known to enhance the material properties of used polyesters, i.

Fakirov, Kunststoffe 74and R. Koine, Kunststoffe 82 However, this method is troublesome and, moreover, is highly sensitive to the impurities that may be present in waste material. It is therefore the object of this invention to provide a process that makes it possible to increase the molecular weight of polyesters, especially PET, in a relatively short time.

Surprisingly, it has been found possible to increase the molecular weight of polyesters substantially by fusing the polyester and blending it with a mixture of at least one tetracarboxylic dianhydride and a sterically hindered hydroxyphenylalkylphosphonic acid ester or half-ester.

This molecular weight increase effects an enhancement of the properties of the polyesters, preferably of those used for injection moulding and of recyclates, especially PET bottle scrap material.

In addition, mixtures of these polyesters are also suitable. Their composition will depend essentially on the desired properties for a specific end use.


The aliphatic dicarboxylic acids may contain from to 2 to 40 carbon atoms, the cycloaliphatic dicarboxylic acids from 6 to 10 carbon atoms, the aromatic dicarboxylic acids from 8 to 14 carbon atoms, the aliphatic hydrocarboxylic acids from irtanox to 12 carbon atoms and the aromatic and cycloaliphatic hydroxycarboxylic acids from 7 to 14 carbon atoms. The aliphatic diols may contain from 2 to 12 carbon atoms, the irgxnox diols from 5 to 8 carbon atoms and the aromatic diols from irgaox to 16 carbon atoms.

Aromatic diols will be understood as meaning those in which two hydroxyl groups are bonded to one or to different aromatic hydrocarbon radicals. The polyesters may also be branched with minor amounts, typically 0. If the polyesters are based on at least two monomers, said monomers can be randomly distributed, or they may be irganix polymers. Suitable dicarboxylic acids are linear and branched saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.

Suitable aliphatic dicarboxylic acids are those containing 2 to 40 carbon atoms, typically suberonic acid, oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, octadecylsuccinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, azelaic acid and dimer acids dimerisation products of unsaturated aliphatic carboxylic acids such irganoz oleic acidalkylated malonic and succinic acids such as octadecylsuccinic acid.

Suitable aromatic dicarboxylic acids are: The aromatic dicarboxylic acids are preferred, including in particular terephthalic acid and isophthalic acid. Dicarboxylic acids that contain N-heterocyclic rings are also suitable, for example those that are derived from carboxyalkylated, carboxyphenyla- ted or carboxybenzylated monoamine-s-triazinedicarboxylic acids q.

DE-OS 2 and 2mono- or bishydantoins, benzimidazolenes or halogenated benzimidazo- lenes or parabanic acid. The carboxyalkyl groups in these compounds may contain from 3 to 20 carbon atoms.

Suitable aliphatic diols are the linear and branched aliphatic glycols, preferably those containing 2 to 12, most preferably 2 to 6, carbon atoms in the molecule, typically including: The alkylene diols 1245 preferably linear and preferably contain 2 to 4 carbon atoms.


Preferred diols are the alkylene diols, 1,4-dihydroxycyclohexane and l,4-bis hydroxy- methyl cyclohexane. Ethylene glycol and 1,4-butanediol are especially preferred. Further bis- phenols are mentioned hereinafter. A further group of suitable aliphatic diols comprises the heterocyclic diols disclosed iryanox. Suitable aromatic diols are mononuclear diphenols and, preferably, dinuclear diphenols which carry a hydroxyl group at each aromatic nucleus.

Aromatic will iryanox understood as meaning preferably aromatic hydrocarbon radicals such as phenylene or naphthylene. In addition to e.

EP0748346A1 – Increasing the molecular weight of polyesters – Google Patents

The hydroxyl groups may be in m-position, but are preferably in p-position. R’ and R” in this formula may be alkyl of 1 to 6 carbon atoms, halogen such as chloro or bromo and, preferably, hydrogen atoms. Unsubstituted or substituted alkylidene is exemplified by: Illustrative examples of unsubstituted or substituted alkylene are methylene, ethylene, phenylmethylene, diphenylmethylene, methylphenylmethylene. Illustrative examples of cycloalkylidene are cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.

Illustrative examples Of bisphenols are: Suitable polyesters of hydroxycarboxylic acids typically include polycaprolactone, polypivalolactone or the polyesters of 4-hydroxycyclohexanecarboxylic acid or 4-hydroxybenzoic acid, 5-hydroxynaphthalene-l-carboxylic acid, 6-hydroxynaphtha- lenecarboxylic acid. Polyesters with aromatic dicarboxylic acids have achieved the greatest importance, in particular the polyalkylene terephthalates. The most preferred polyester is the amorphous PET used for the manufacture of blow-moulded bottles.

A further preferred form comprises the polyester recyclates originating from domestic and industrial waste or from useful material collections, from production waste or from obligatory retumables. As regards the chemical composition of the polyester recyclates, the particulars given above apply likewise. Polyester recyclates consist primarily of PET hollow objects, especially PET bottle materials of different provenance and having a varying degree of damage.

The PET bottle materials originating from different manufacturers comprise polyethylene terephthalate and also copolymers of different structure and composition, but with a preponderant content of PET structures. The recyclates may also contain minor amounts of other polymers, including polyolefins or PVC. These recyclates may furthermore contain standard impurities such as dye residues, paint residues, metal traces, fuel residues or inorganic salts.

Tetracarboxylic dianhydrides useful within the scope of this invention are those of formula. In case of R being an alkanetetrayl radical, the tetracarboxylic dianhydride may be such as butane- 1 ,2,3,4-tetracarboxylic dianhydride. Sterically hindered hydroxyphenylalkylphosphonic acid esters and half-esters are disclosed, inter alia, in US-Aand may be illustrated by the following formula:. R- is isopropyl, tert-butyl, cyclohexyl or cyclohexyl which is substituted by 1 to 3.

R 3 is G r C 2 oalkyl or substituted or unsubstituted phenyl or naphthyl. Substituents defined as alkyl containing up to 20 carbon atoms may suitably be methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl, stearyl, as well as corresponding branched isomers.

C 2 -C 4 Alkyl is preferred. Suitable substituents of the phenyl or naphthyl radicals are typically groups. Ca is particularly preferred.

Preferred compounds of formula II are those that contain at least one tert-butyl group as Rj or R 2. Compounds in which R! Very particularly preferred sterically hindered hydroxyphenylalkylphosphonic acid esters and half-esters are. The process can be carried out in any heatable apparatus fitted with a stirrer. It is preferred to carry out the process in closed apparatus excluding atmospheric oxygen, conveniently in an inert gas atmosphere N 2.

The process may, however, also be carried out in an extruder and also in the presence of air. For the addition, the tetracarboxylic dianhydride and the phenol can independently of each other be in the irhanox of a powder, liquid, granulate or in compacted form, or also in some cases on a substrate such as silica irgqnox or together with a polymer powder or wax such as a polyethylene wax. A mixture with polyethylene wax is a preferred form of addition, especially when using the metal salts of the phenol.

The temperature will depend on the polyester used. In the case of amorphous polyesters, the process is carried out in the range from c. The amount of tetracarboxylic anhydride and sterically hindered hydroxyphenylalkylphosphonic irganlx ester or half -ester will depend on the initial molecular weight of the polymer and on the desired final molecular weight.


Thus, when using a severely damaged polyester, i. But if 14225 a low increase in molecular weight is desired, then it is preferred to use a tetracarboxylic anhydride and a phenol in low concentration. Those skilled in the art will be familiar with these co-stabilisers, which will be chosen in accordance irvanox the specific requirement made of the final product.

In particular, light stabilisers or also antioxidants can be added “Plastics Additives Handbook”, Ed. Particularly suitable co- stabilisers include:.

Alkylthiomethylphenols, for example 2,4-dioctylthiomethyltert-butylphenol, 2,4-dioctylthiomethylmethylphenol, 2,4-dioctylthiomethylethylphenol, 2,6-di-do- decylthiomethylnonylphenol. Hydroquinones and alkylated hvdroquinones, for lrganox 2,6-di-tert-butyl methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di- phenyloctadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butylhydroxy- anisole, 3,5-di-tert-butylhydroxyanisole, 3,5-di-tert-butylhydroxyphenyl stearate, bis- 3,5-di-tert-butylhydroxyphenyl adipate.

antioxidant 1425 (irganox 1425) factory – antioxidant 1425 (irganox 1425) manufacturing

Hvdroxylated thiodiphenyl ethers, for example 2,2′-thiobis 6-tert-butylmethyl- phenol2,2′-thiobis 4-octylphenol4,4′-thiobis 6-tert-butylmethylphenol4,4′-thio- bis 6-tert-butylmethylphenol4,4′-thiobis- 3,6-di-sec-amylphenol4,4′-bis- 2,6-dim- ethylhydroxyphenyl disulfide.

O- N- and S-benzyl compounds, for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxy- dibenzyl ether, octadecylhydroxy-3,5-dimethylbenzylmercaptoacetate, tris 3,5-di-tert- butylhydroxybenzyl amine, bis 4-tert-butylhydroxy-2,6-dimethylbenzyl dithio- terephthalate, bis 3,5-di-tert-butylhydroxybenzyl sulfide, isooctyl-3,5di-tert-butyl hydroxybenzylmercaptoacetate. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis 3,5-di-tert-butyl hydroxybenzyl malonate, bis[octadecyl 3-tert-butylhydroxymethylbenzyl ]malo- nate, bis[dodecylmercaptoethyl-2,2-bis- 3,5-di-tert-butylhydroxybenzyl ]malonate, bis- [4- 11 ,3,3-tetramethylbutyl phenyl]-2,2-bis 3,5-di-tert-butylhydroxybenzyl malonate.

Aromatic hydroxybenzyl compounds, for example l,3,5-tris 3,5-di-tert-butylhy- droxybenzyl -2,4,6-trimethylbenzene, l,4-bis 3,5-di-tert-butylhydroxybenzyl -2,3,5,6- tetramethylbenzene, 2,4,6-tris 3,5-di-tert-butylhydroxybenzyl phenol.

Triazine compounds, for example 2,4-bis octylmercapto 3,5-di-tert-butyl hydroxyanilino -l,3,5-triazine, 2-octylmercapto-4,6-bis 3,5-di-tert-butylhydroxy- anilino – 1 ,3,5-triazine, 2-octylmercapto-4,6-bis 3,5-di-tert-butylhydroxyphenoxy – 1 ,3,5-triazine, 2,4,6-tris 3,5-di-tert-butylhydroxyphenoxy -l ,2,3-triazine, 1 ,3,5-tris- 3,5-di-tert-butylhydroxybenzyl isocyanurate, l,3,5-tris 4-tert-butylhydroxy-2,6-di- methylbenzyl isocyanurate, 2,4,6-tris 3,5-di-tert-butylhydroxyphenylethyl -l,3,5-tri- azine, l,3,5-tris 3,5-di-tert-butylhydroxyphenylpropionyl -hexahydro-l,3,5-triazine, l,3,5-tris 3,5-dicyclohexylhydroxybenzyl isocyanurate.

Benzylphosphonates, for example dimethyl-2,5-di-tert-butylhydroxybenzylphos- phonate, diethyl-3,5-di-tert-butylhydroxybenzylphosphonate, dioctadecyl-3,5-di-tert- butylhydroxybenzylphosphonate, dioctadecyltert-butylhydroxymethylbenzyl- phosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butylhydroxybenzyl- phosphonic acid. Acylaminophenols- for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- 3,5-di-tert-butylhydroxyphenyl carbamate.

Esters of 3,5-di-tert-butylhvdroxyphenyl acetic acid with mono- or polyhydric alcohols, e. N,N’-bis 3,5-di- tert-butylhydroxyphenylpropionyl hexamethylenediamine, N,N’-bis 3,5-di-tert-butyl- 4-hydroxyphenylpropionyl trimethylenediamine, N,N’-bis 3,5-di-tert-butylhydroxy- phenylpropionyl hydrazine.

Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl- phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis 4- tert-butylbenzoyl resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl- 4-hydroxybenzoate, hexadecyl 3,5-di-tert-butylhydroxybenzoate, octadecyl 3,5-di-tert- butylhydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butylhydroxy- benzoate.

Nickel compounds, for example nickel complexes of 2,2′-thio-bis-[4- l,l,3,3-tetra- methylbutyl phenol], such as the 1: Oxamides, for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioc- tyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′- ethyloxanilide, N,N’-bis 3-dimethylaminopropyl oxamide, 2-ethoxytert-butyl-2′-ethox- anilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disub- stituted oxanilides.

Metal deactivators, for example N,N’-diphenyloxamide, N-salicylal-N’-salicyloyl hydrazine, N,N’-bis salicyloyl hydrazine, N,N’-bis 3,5-di-tert-butylhydroxyphenyl- propionyl hydrazine3-salicyloylamino-l,2,4-triazole, bis benzylidene oxalyl di- hydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N’-di- acetyladipoyl dihydrazide, N,N’-bis salicyloyl oxalyl dihydrazide, N,N’-bis salicyloyl – thiopropionyl dihydrazide. Basic co-stabilisers, for example, irgahox, poly vinylpyrrolidone, dicyandiamide, tri- allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyure- thanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium rici- noleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

Nucleating agents, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid or sodium or aluminum benzoates. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

Other additives, irganoz example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents and blowing agents, for mixtures of recyclates in particular co-compatibilisers, typically copolymers, preferably block copolymers, of iranox with butadiene and optionally acrylonitrile.

The co-compatibilisers may be copolymers of ethylene and propylene and a third optional monomer component, e. Chlorinated polyethylene or ethylenevinyl acetate copolymers 142 also suitable co-compatibilisers, although it irgnaox depends on the particular composition of the recyclate. Other suitable co-compatibilisers contain in particular polar groups, for example maleic anhydride-styrene copolymers or graft polymers containing acrylic acid groups.