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WO1996029357A1 - Use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position or tautomers thereof for controlling the crystallization of linear polyesters and/or polyester polyols and method for the preparation thereof - Google Patents

Use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position or tautomers thereof for controlling the crystallization of linear polyesters and/or polyester polyols and method for the preparation thereof Download PDF

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Publication number
WO1996029357A1
WO1996029357A1 PCT/NL1996/000115 NL9600115W WO9629357A1 WO 1996029357 A1 WO1996029357 A1 WO 1996029357A1 NL 9600115 W NL9600115 W NL 9600115W WO 9629357 A1 WO9629357 A1 WO 9629357A1
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WO
WIPO (PCT)
Prior art keywords
substituted
acid
polyester polyols
polyester
linear polyesters
Prior art date
Application number
PCT/NL1996/000115
Other languages
French (fr)
Inventor
Benjamin Mets
Franciscus Cornelis Maria Rieken
Original Assignee
Desmepol B.V.
Mets Holding B.V.
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Filing date
Publication date
Application filed by Desmepol B.V., Mets Holding B.V. filed Critical Desmepol B.V.
Priority to AU48914/96A priority Critical patent/AU4891496A/en
Publication of WO1996029357A1 publication Critical patent/WO1996029357A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to the control of the crystal ⁇ lization of linear polyesters and/or polyester polyols.
  • linear polyesters are to be understood as polymers which have been obtained by polycondensation of organic dicar- boxylic acids and glycols.
  • polyesters are polyethylene terephthalate (PET), polyethylene isophthalate (PEI) and polybutylene terephthalate (PBT) .
  • the organic dicarboxylic acids employed are, for example, phthalic acid, isophthalic acid, terephthalic acid or naph- thalenedicarboxylic acids or mixtures thereof.
  • the glycols employed are, for example, ethylene glycol, diethylene glycol, propylene glycol or 1,4- butanediol or mixtures thereof.
  • polyester polyols are sometimes referred to as polyester polyols or, in brief, poly ⁇ ols.
  • polyester polyols which are prepared by polycondensation of dicarboxylic acids with an excess, based on the dicarboxylic acid, of diols are employed, for example, for the preparation of polyurethanes.
  • polyester polyols which are prepared by polycondensation of dicarboxylic acids with an excess, based on the dicarboxylic acid, of diols are employed, for example, for the preparation of polyurethanes.
  • polyester polyols which are prepared by polycondensation of dicarboxylic acids with an excess, based on the dicarboxylic acid, of diols are employed, for example, for the preparation of polyurethanes.
  • polyester polyols which are prepared by polycondensation of dicarboxylic acids with an excess, based on the dicarboxylic acid, of diols are employed, for example,
  • a known method for controlling the crystallization of linear polyesters such as PET comprises the copolymerization of a dicarboxylic acid with a glycol and a third component (Kirk-Othmer, "Encyclopedia of Chemical Technology", Volume 18 (1981), p. 551).
  • a dicarboxylic acid with a glycol and a third component
  • terephthalic acid with ethylene glycol and a small amount of l,4-bis(hydroxymethyl)cyclohexane (1,4-cyclohexanedimethanol)
  • a polyester is pre ⁇ pared from l,4-bis(hydroxymethyl)cyclohexane and a mixture which mainly consists of terephthalic acid and a small amount of isophthalic acid, the amorphous poly(l,4-cyclohexyldimethylene terephthalate-co-isophthalate) is obtained, which has a lower melting point than poly(l,4-cyclohexyldimethylene terephthalate) .
  • Polyesters are processed, by means of injection-moulding, into various articles.
  • bottles made of PET are obtained by injection- moulding followed by stretching ("stretch blow moulding").
  • stretching particularly in the case of biaxial stretching
  • the PET becomes semicrystalline.
  • This technique has the drawback, however, that more processing steps are required.
  • a preform of the polyester is produced and said preform is then heated, in a heating appa ⁇ ratus, to a temperature which is between the glass transition temperature and the melting temperature of the polyester.
  • the preform softens and can be processed by means of biaxial stretching to produce, for example, a bottle.
  • only a small number of different shapes of bottles can be produced.
  • Bottles made from polyester have therefore also been obtained, for some time now, by injection-moulding followed by blowing ("extrusion blow moulding").
  • amorphous polyesters which crystallize slowly or not at all is advis ⁇ able (European Plastic News, January 199 ⁇ P- 24). It is known, however, that the preparation of such polyesters which have the desired crystal ⁇ lization behaviour requires large amounts, even up to 30 molX, of a co- reactant such as l,4-bis(hydroxymethyl)cyclohexane.
  • the present application provides a solution for this problem, in that only a small amount of a coreactant is necessary for the pre- paration of a polyester which is sufficiently amorphous and which can be used for, for example, injection-moulding followed by blowing. It has been found that the use of only small amounts of l,3-5 ⁇ triazines which are substituted in the 2-, 4- and 6-position, or tautomeric forms thereof as a coreactant provides polyesters which are sufficiently amorphous. The present application therefore relates to the use of 1,3.5 ⁇ triazines which are substituted in the 2-, 4- and 6-position, or tautomers thereof for controlling the crystallization of linear polyesters and/or polyester polyols.
  • the substituents of the l,3.5 ⁇ triazines which are substituted in the 2-, 4- and 6-position may react, for example, with a carboxyl group, water being eliminated and a chemical bond being formed between the carbon atom of the carboxyl group and an atom of the substituent.
  • substituents are known in organic chemistry and are, for example, hydroxyl, thiol and amino groups.
  • the substituents of the 1,3,5-triazines which are substituted in the 2-, 4- and 6-position may also be, for example, masked or pro ⁇ tected hydroxyl, thiol or amino groups known per se, for example ester, thioester or amide groups.
  • substituted 1,3,5-triazines may be employed which have two or three substituents. If 1,3,5-triazines are employed in which only two carbon atoms are substituted, the 1,3.5-tria- zines can be substituted in the 2- and 4-, 2- and 6- or 4- and 6-po ⁇ sition. If the substituted 1,3,5-triazines have three substituents, at least two of these can react with a carboxyl group in the ways described hereinabove. Examples of such 1,3,5-triazines are 2,4-diamino-l,3.5 _ tria- zine and 2,4-diamino-6-phenyl-l,3,5-triazine.
  • 1,3,5-triazines which are substituted in the 2-, 4- and 6-position by a substituent which can react with a carboxyl group in the ways described hereinabove.
  • l,3.5"triazines are cyanuric acid, thiocyanuric acid, melamine and 2,4,6-tris(hydro ⁇ ymethyl)- 1,3.5-triazine.
  • the 1,3,5-triazines which are substituted in the 2-, 4- and 6- position can occur in various tautomeric structures.
  • the use of these tautomeric structures is likewise deemed to form part of the invention.
  • the 1,3,5-triazine employed which is substituted in the 2-, 4- and 6-position is, in particular, a cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted. If cyanuric acid, thiocyanuric acid or melamine are employed, it can be employed as such, but it can also be prepared, during the pre ⁇ paration of the polyesters (in situ) , from the chemical compounds suitable for this purpose.
  • Cyanuric acid may be formed, for example, from urea or biuret, and thiocyanuric acid may be formed, for example, from thiourea.
  • the invention therefore also relates to the use of 1,3,5-tria ⁇ zines which are substituted in the 2-, 4- and 6-position, or tautomers thereof, for controlling the crystallization of linear polyesters and/or polyester polyols, the 1,3,5-triazine or, respectively, the cyanuric acid, thiocyanuric acid or a tautomeric form thereof, any of which may be substituted, being prepared in situ during the preparation of the linear polyesters and/or polyester polyols.
  • 1,3,5-triazines which are sub ⁇ stituted in the 2-, 4- and 6-position, or tautomers thereof can be employed, the number of moles of the 1,3,5-triazine employed being lower than the number of moles of monomer from which the polyester is prepared.
  • the monomer from which the polyester is prepared is prepared by esterification of a dicarboxylic acid, for example terephthalic acid, and an equimolar amount of a glycol, for example ethylene glycol.
  • the monomer can be prepared by transesterification of a diester of the dicarboxylic acid, for example dimethyl terephthalate, with the glycol, for example ethylene glycol, an excess being employed, for example a molar ratio of the acid to the glycol of 1:1.7.
  • the monomer therefore mainly comprises a monoglycol ester of the dicarboxylic acid, but it may also comprise oligomers, for example dimers and trimers of said monoglycol ester.
  • 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, or, respectively, the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted, the molar ratio of the 1,3,5-triazine or the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted, to the monomer from which the polyester is prepared, being from 0.0001 to 1, preferably from 0.01 to 0.5-
  • the invention provides a method for the preparation of linear polyesters and/or polyester polyols from polyols and aromatic dicar ⁇ boxylic acids, wherein 1,3,5-triazines are employed at the same time which are substituted in the 2-, 4- and 6-position, or tautomers thereof.
  • 1,3,5-triazines are employed at the same time which are substituted in the 2-, 4- and 6-position, or tautomers thereof.
  • use is made at the same time, for the preparation of linear polyesters and/or polyester polyols from polyols and aromatic dicarboxylic acids, of a 1,3,5-triazine which is substituted in the 2-, 4- and 6-position.
  • the 1,3,5-triazine used is a cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted.
  • cyanuric acid, thiocyanuric acid or melamine is employed.
  • the glycols which can be employed comprise polyglycols, for example ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, l,4-bis(hydroxymethyl)cyclohexane and 1,7-heptanediol, but also polyester polyols, for example PET which has terminal hydroxyl groups, or polyether polyols or mixtures thereof.
  • polyester polyols, ethylene glycols, diethylene glycols, propylene glycols or 1,4- bis(hydroxymethyl)cyclohexane or mixtures thereof are employed.
  • the dicarboxylic acids which may be employed comprise aromatic dicarboxylic acids, for example benzenedicarboxylic acids or naphthalene- dicarboxylic acids.
  • aromatic dicarboxylic acids for example benzenedicarboxylic acids or naphthalene- dicarboxylic acids.
  • benzenedicarboxylic acids for example phthalic acid, isophthalic acid and terephthalic acid or naphthalenedi- carboxylic acids, for example 1,2- 1,4-, 1,5", 1,6-, 1,7", 1,8-, 2,3-, 2,6-, 2,7- or 2,8-naphthalenedicarboxylic acid are employed. It is also possible to employ mixtures of one or more aromatic dicarboxylic acids.
  • polyesters it is therefore possible to employ one or more benzenedicarboxylic acids or naphthalenedicarboxylic acids.
  • dicarboxylic acids which are able to react with a hydroxyl group, for example di ⁇ esters, dithioesters, diamides and diacyl chlorides.
  • the invention also provides a method for the preparation of linear polyesters and/or polyester polyols, 1,3,5-triazines which are substituted in the 2-, 4- and 6-position being prepared in situ from the chemical compounds suitable for this purpose.
  • preference is given to the use of cyanuric acid, thiocyanuric acid or melamine, any of which may be substituted, the cyanuric acid which may be substituted being prepared from a urea which may be substituted or a biuret which may be substituted and a thiocyanuric acid which may be sub ⁇ stituted being prepared from a thiourea which may be substituted.
  • 1,3,5-triazines which are substituted in the 2-, 4- and 6-position for example cyanuric acid, thiocyanuric acid or melamine
  • a catalyst is employed which in water has a pH of from 5 to 1.
  • the catalyst which is employed for the preparation of the cyanuric acid may be identical with that employed for the preparation of the polyester.
  • One example is orthophosphoric acid.
  • cyanuric acid or thio- cyanuric acid or tautomers thereof, any of which may be substituted are prepared in situ in the presence of a catalyst which in water has a pH of from 5 to 7.
  • the preparation in situ of 1,3,5-triazines which are sub ⁇ stituted in the 2-, 4- and 6-position, for example cyanuric acid or thio- cyanuric acid, is carried out in a solvent whose boiling point is higher than the temperature at which the 1,3,5-triazine sublimes.
  • the solvent may, for example, be a glycol which has a high boiling point and which is also used for the preparation of the polyester. According to the present invention, preference is given to the use of glycols such as ethylene glycol, diethylene glycol, propylene glycol and 1,4-butanediol, and in particular ethylene glycol.
  • reaction mixture instead of the reaction mixture being heated to a temperature at which the glycol boils, it can also be heated to a temperature which is lower than the boiling point of the glycol, under the condition that the reaction is carried out under elevated pressure.
  • the invention therefore relates to a method wherein a molar ratio of the 1,3,5-triazine or the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted, to the monomer from which the polyester is prepared, employed is from 0.0001 to 1, preferably from 0.01 to 0.5.
  • the invention also provides linear polyesters and/or polyester polyols which can be obtained by employing the above-described methods, and which comprise glycols, aromatic dicarboxylic acids and 1,3,5-tria ⁇ zines which are substituted in the 2-, 4- and 6-position, or tautomeric forms thereof.
  • polyesters and polyester polyols can be prepared from the pure chemical compounds or from polyester waste. Such processes and preparation methods are described, for example, in DE-A-2,014,818, FR-A-2,386,572 and US-A-3.767,6 ⁇ l.
  • the 1,3,5-triazine which is substituted in the 2-, 4- and 6-po- sition can be added at any time during the polycondensation. This means that the 1,3,5-triazine can be added at the beginning of the preparation of the monomer, but also at the beginning of the polycondensation of the monomer.
  • the linear polyesters and/or polyester polyols according to the invention preferably comprise glycols, aromatic dicarboxylic acids and 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, or tautomers thereof.
  • the linear polyesters and/or polyester polyols prefer ⁇ ably comprise glycols, aromatic dicarboxylic acids and cyanuric acid, thiocyanuric acid, melamine, any of which may be substituted or tautomers thereof.
  • the linear polyesters and/or polyester polyols according to the invention comprise, as the glycol components, one or more ethylene glycols, diethylene glycols, polyethylene glycols, propylene glycols, polypropylene glycols, 1,4-butanediols, 1,5-pentanediols, 1,6-hexane- diols, l,4-bis(hydroxymethyl)cyclohexanes, 1,7-heptanediols or polyester polyols.
  • the linear polyesters and/or polyester polyols ac ⁇ cording to the invention comprise polyester polyols, ethylene glycols, diethylene glycols, propylene glycols or 1,4-bis(hydroxymethyl)cyclo- hexane.
  • the linear polyesters and/or polyester polyols according to the invention comprise, as the dicarboxylic acid components, one or more benzenedicarboxylic acids or naphthalenedicarboxylic acids, the benzene ⁇ dicarboxylic acids preferably being phthalic acids, isophthalic acids or terephthalic acids, and naphthalenedicarboxylic acids preferably being 1,2-, 1.4-, 1,5-, 1,6-, 1,7-. 1,8-, 2,3-. 2,6-. 2,7- or 2,8-naphthalene- dicarboxylic acids.
  • the linear polyesters and/or polyester polyols may therefore comprise one or more polyester polyols, ethylene glycols, diethylene glycols, propylene glycols, l,4-bis(hydroxymethyl)cyclohexane, benzenedi- carboxylic acids or naphthalenedicarboxylic acids.
  • the polyesters according to the invention can be very well postcondensed in the solid state.
  • Postcondensation means that the polyesters according to the in ⁇ vention are heated under reduced pressure to below the melting point of the polyester for a certain time, glycols being eliminated, as a result of which the polyesters reach a higher molecular weight and a higher viscosity.
  • the polyesters are heated, according to the in ⁇ vention, for from 15 to 30 hours until the desired viscosity is attained.
  • Said postcondensation makes it possible to prepare polyesters which have a high molecular weight and a high viscosity which in turn is beneficial to the strength of the polyesters and which moreover further delays crystallization.
  • the intrinsic viscosity of the polyester polyols according to the invention increases, the more 1,3,5-triazine which is substituted in the 2-, 4- and 6-position is employed.
  • the polyester polyols according to the invention are clear, do not crystallize or crystallize slowly and have increased functionality.
  • the incorporation of 1,3,5-tria ⁇ zines in the polyester polyols according to the invention confers flame- retardant characteristics upon polyurethanes which are made from such polyester polyols.
  • the polyesters according to the invention are highly suitable for the fabrication of products and articles which have relatively thick walls, for example bottles for repeated use, thick plates, bubble packs, shrink film and weldable film.
  • polyesters or polyester waste it is also possible to reprocess polyesters or polyester waste to give polyesters or polyester polyols whose crystallization is retarded by the use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, or tautomers thereof.
  • Such reprocessing is sometimes referred to as glycolysis.
  • polyester waste is heated, for example, with a glycol to a temperature at which the glycol boils.
  • depolymerization of the polyester takes place, and the monomer is obtained from which the original polyester had been prepared.
  • Methods for such a glycolysis are described, for example, in EP-A-0,104,736 and US 4,048,104.
  • the 1,3,5-triazine for example cyanuric acid, or a chemical compound from which the 1,3,5-triazine can be prepared, for example urea
  • the 1,3,5-triazine for example cyanuric acid, or a chemical compound from which the 1,3,5-triazine can be prepared, for example urea, is added and a polyester according to the invention is thus obtained.
  • Example I This example describes a general procedure for the preparation of a polyester from an organic dicarboxylic acid, a glycol and a 1,3,5- triazine which is substituted in the 2-, 4- and 6-position.
  • a first step the preparation takes place, in a stainless- steel reactor provided with a condenser, a water separator, a stirrer, a heating device and a pressure controller, of a monomer from terephthalic acid and ethylene glycol.
  • the mixture which contains terephthalic acid and ethylene glycol in a molar ratio of 1:1.7, is heated to a temperature at which reflux occurs (approximately 200 - 300°C) .
  • a suitable catalyst for example orthophosphoric acid
  • Example II This example describes a general procedure for the preparation of a polyester from an organic diester, a glycol and a 1,3.5-triazine which is substituted in the 2-, 4- and 6-position.
  • Example III The procedure described in Example I is carried out, except that instead of terephthalic acid dimethyl terephthalate is employed. The first step is complete when no more methanol separates.
  • This example describes a general procedure for the preparation of a polyester from an organic diester, a glycol and a 1,3.5-triazine which is substituted in the 2-, 4- and 6-position.
  • the procedure described in Example I is carried out, except that a mixture containing terephthalic acid, ethylene glycol and cyanuric acid in a molar ratio of 1:1.7:0.3 is heated to a temperature at which reflux occurs (approximately 200 - 300°C).
  • Example IV This example describes a general procedure for the preparation of a polyester from a different polyester, a glycol and a 1,3.5-triazine which is substituted in the 2-, 4- and 6-position.
  • Example V In the reactor of Example I, a mixture of PET, ethylene glycol and cyanuric acid in a molar ratio of 1:1:0.4 is heated to a temperature at which reflux occurs. In a second step, a sufficient amount of ethylene glycol is distilled off under reduced pressure, until the polyester has the desired intrinsic viscosity. Subsequently, the product is removed from the reactor and is granulated.
  • Example V In the reactor of Example I, a mixture of PET, ethylene glycol and cyanuric acid in a molar ratio of 1:1:0.4 is heated to a temperature at which reflux occurs. In a second step, a sufficient amount of ethylene glycol is distilled off under reduced pressure, until the polyester has the desired intrinsic viscosity. Subsequently, the product is removed from the reactor and is granulated.
  • Example V Example V
  • This example describes a general procedure for the preparation of a polyester polyol from a polyester, a diethylene glycol and a 1,3,5- triazine which is substituted in the 2-, 4- and 6-position.
  • Example VI The procedure described in Example IV is carried out, except that instead of ethylene glycol diethylene glycol is employed.
  • the pro ⁇ duct obtained can be used for the preparation of polyurethane foam.
  • This example describes a general procedure for the preparation of a polyester, according to which the 1,3.5-triazine which is sub- stituted in the 2-, 4- and 6-position is prepared in situ.
  • Example VII In the reactor of Example I, a mixture of ethylene glycol and urea in a molar ratio of 1:0.47 is heated to a temperature at which reflux occurs (approximately 225 - 250°C). Ammonia and carbon dioxide escape in the process. The reaction is complete when no more ammonia separates. Subsequently, terephthalic acid is added in an amount of 1 mol per 1.7 mol ethylene glycol. After the polycondensation, the product is removed from the reactor and is subsequently granulated.
  • Example VII Example VII
  • Polyesters are prepared from terephthalic acid, ethylene glycol and cyanuric acid and from 1,4-naphthalenedicarboxylic acid, ethylene glycol and cyanuric acid according to the procedure of Example I.
  • a sample is taken at certain times, which is rapidly cooled to room temperature. Whether or not crystallization of these samples takes place is then established visually (crystalline polyesters are opaque, amorphous polyesters are transparent).
  • the polyesters were gra- nulated. An experiment was then carried out in order to establish whether the polyesters crystallize under conditions prevailing during postcon ⁇ densation.
  • the polyesters were heated, for at most 1 hour, to a tempe ⁇ rature of l6 ⁇ * C, and whether crystallization of the polyester did or did not occur was established visually.
  • Example VII An experiment as described in Example VII was carried out with polyester polyols of PET, diethylene glycol and cyanuric acid, which were prepared according to the procedure described in Example V. Whether crystallization of the polyester polyol did or did not take place was established after 1 week. The results are reproduced in the following Table 2, "++" to "—” indicating a gradation from complete crystalliza- tion to no crystallization.

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Abstract

The invention relates to the use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position or tautomers thereof for controlling the crystallization of linear polyesters and/or polyester polyols. The 1,3,5-triazine may be, respectively, a cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted, and is prepared in situ during the preparation of the linear polyesters and/or polyester polyols.

Description

Use of 1. . -triazines which are substituted in the 2-. - and 6-position
ΩΣ. tSUtQWers thereof for controlling the crystallization of linear polyesters and/or polyester polvols and method for the preparation there- £_£..
The present invention relates to the control of the crystal¬ lization of linear polyesters and/or polyester polyols.
In this description, linear polyesters are to be understood as polymers which have been obtained by polycondensation of organic dicar- boxylic acids and glycols. Examples of such polyesters are polyethylene terephthalate (PET), polyethylene isophthalate (PEI) and polybutylene terephthalate (PBT) . The organic dicarboxylic acids employed are, for example, phthalic acid, isophthalic acid, terephthalic acid or naph- thalenedicarboxylic acids or mixtures thereof. The glycols employed are, for example, ethylene glycol, diethylene glycol, propylene glycol or 1,4- butanediol or mixtures thereof.
If these polyesters have terminal hydroxyl groups, these poly¬ mers are sometimes referred to as polyester polyols or, in brief, poly¬ ols. These polyester polyols which are prepared by polycondensation of dicarboxylic acids with an excess, based on the dicarboxylic acid, of diols are employed, for example, for the preparation of polyurethanes. In the present description use is made of the general term "polyesters" to indicate the group of polymers comprising linear polyesters and/or polyester polyols. A known method for controlling the crystallization of linear polyesters such as PET comprises the copolymerization of a dicarboxylic acid with a glycol and a third component (Kirk-Othmer, "Encyclopedia of Chemical Technology", Volume 18 (1981), p. 551). Thus it is possible, by copolymerization of terephthalic acid with ethylene glycol and a small amount of l,4-bis(hydroxymethyl)cyclohexane (1,4-cyclohexanedimethanol) , to obtain an amorphous and clear polyester which has a lower melting point than crystallizing PET of a normal grade. If a polyester is pre¬ pared from l,4-bis(hydroxymethyl)cyclohexane and a mixture which mainly consists of terephthalic acid and a small amount of isophthalic acid, the amorphous poly(l,4-cyclohexyldimethylene terephthalate-co-isophthalate) is obtained, which has a lower melting point than poly(l,4-cyclohexyldimethylene terephthalate) .
Polyesters are processed, by means of injection-moulding, into various articles. Thus bottles made of PET are obtained by injection- moulding followed by stretching ("stretch blow moulding"). As a result of said stretching, particularly in the case of biaxial stretching, the PET becomes semicrystalline. This technique has the drawback, however, that more processing steps are required. In a first step, a preform of the polyester is produced and said preform is then heated, in a heating appa¬ ratus, to a temperature which is between the glass transition temperature and the melting temperature of the polyester. As a result, the preform softens and can be processed by means of biaxial stretching to produce, for example, a bottle. Moreover, only a small number of different shapes of bottles can be produced. Bottles made from polyester have therefore also been obtained, for some time now, by injection-moulding followed by blowing ("extrusion blow moulding"). For this purpose, however, the use of amorphous polyesters which crystallize slowly or not at all is advis¬ able (European Plastic News, January 199 ι P- 24). It is known, however, that the preparation of such polyesters which have the desired crystal¬ lization behaviour requires large amounts, even up to 30 molX, of a co- reactant such as l,4-bis(hydroxymethyl)cyclohexane.
The present application provides a solution for this problem, in that only a small amount of a coreactant is necessary for the pre- paration of a polyester which is sufficiently amorphous and which can be used for, for example, injection-moulding followed by blowing. It has been found that the use of only small amounts of l,3-5~triazines which are substituted in the 2-, 4- and 6-position, or tautomeric forms thereof as a coreactant provides polyesters which are sufficiently amorphous. The present application therefore relates to the use of 1,3.5~triazines which are substituted in the 2-, 4- and 6-position, or tautomers thereof for controlling the crystallization of linear polyesters and/or polyester polyols.
The substituents of the l,3.5~triazines which are substituted in the 2-, 4- and 6-position may react, for example, with a carboxyl group, water being eliminated and a chemical bond being formed between the carbon atom of the carboxyl group and an atom of the substituent. Such substituents are known in organic chemistry and are, for example, hydroxyl, thiol and amino groups. The substituents of the 1,3,5-triazines which are substituted in the 2-, 4- and 6-position may also be, for example, masked or pro¬ tected hydroxyl, thiol or amino groups known per se, for example ester, thioester or amide groups. If the substituents are ester groups, reaction with carboxyl groups takes place via a so-called transesterification. Examples of cyanuric acid and derivatives thereof are described in Kirk- Othmer, Encyclopedia of Chemical Technology, third edition, Volume 7. p. 397 - 410.
According to the invention, substituted 1,3,5-triazines may be employed which have two or three substituents. If 1,3,5-triazines are employed in which only two carbon atoms are substituted, the 1,3.5-tria- zines can be substituted in the 2- and 4-, 2- and 6- or 4- and 6-po¬ sition. If the substituted 1,3,5-triazines have three substituents, at least two of these can react with a carboxyl group in the ways described hereinabove. Examples of such 1,3,5-triazines are 2,4-diamino-l,3.5_tria- zine and 2,4-diamino-6-phenyl-l,3,5-triazine.
According to the present invention, preference is given to the use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position by a substituent which can react with a carboxyl group in the ways described hereinabove. Examples of such l,3.5"triazines are cyanuric acid, thiocyanuric acid, melamine and 2,4,6-tris(hydroχymethyl)- 1,3.5-triazine.
The 1,3,5-triazines which are substituted in the 2-, 4- and 6- position can occur in various tautomeric structures. The use of these tautomeric structures is likewise deemed to form part of the invention. According to the present invention, the 1,3,5-triazine employed which is substituted in the 2-, 4- and 6-position is, in particular, a cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted. If cyanuric acid, thiocyanuric acid or melamine are employed, it can be employed as such, but it can also be prepared, during the pre¬ paration of the polyesters (in situ) , from the chemical compounds suitable for this purpose. Cyanuric acid may be formed, for example, from urea or biuret, and thiocyanuric acid may be formed, for example, from thiourea. The invention therefore also relates to the use of 1,3,5-tria¬ zines which are substituted in the 2-, 4- and 6-position, or tautomers thereof, for controlling the crystallization of linear polyesters and/or polyester polyols, the 1,3,5-triazine or, respectively, the cyanuric acid, thiocyanuric acid or a tautomeric form thereof, any of which may be substituted, being prepared in situ during the preparation of the linear polyesters and/or polyester polyols.
According to the invention, 1,3,5-triazines which are sub¬ stituted in the 2-, 4- and 6-position, or tautomers thereof can be employed, the number of moles of the 1,3,5-triazine employed being lower than the number of moles of monomer from which the polyester is prepared. The monomer from which the polyester is prepared, is prepared by esterification of a dicarboxylic acid, for example terephthalic acid, and an equimolar amount of a glycol, for example ethylene glycol. Alter- natively, the monomer can be prepared by transesterification of a diester of the dicarboxylic acid, for example dimethyl terephthalate, with the glycol, for example ethylene glycol, an excess being employed, for example a molar ratio of the acid to the glycol of 1:1.7. The monomer therefore mainly comprises a monoglycol ester of the dicarboxylic acid, but it may also comprise oligomers, for example dimers and trimers of said monoglycol ester. Preference is given to the use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, or, respectively, the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted, the molar ratio of the 1,3,5-triazine or the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted, to the monomer from which the polyester is prepared, being from 0.0001 to 1, preferably from 0.01 to 0.5-
The invention provides a method for the preparation of linear polyesters and/or polyester polyols from polyols and aromatic dicar¬ boxylic acids, wherein 1,3,5-triazines are employed at the same time which are substituted in the 2-, 4- and 6-position, or tautomers thereof. In a preferred embodiment of the invention use is made at the same time, for the preparation of linear polyesters and/or polyester polyols from polyols and aromatic dicarboxylic acids, of a 1,3,5-triazine which is substituted in the 2-, 4- and 6-position. More preferably, the 1,3,5-triazine used is a cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted. In particular, cyanuric acid, thiocyanuric acid or melamine is employed. For the purpose of preparing the polyesters according to the invention, the glycols which can be employed comprise polyglycols, for example ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, l,4-bis(hydroxymethyl)cyclohexane and 1,7-heptanediol, but also polyester polyols, for example PET which has terminal hydroxyl groups, or polyether polyols or mixtures thereof. Preferably, polyester polyols, ethylene glycols, diethylene glycols, propylene glycols or 1,4- bis(hydroxymethyl)cyclohexane or mixtures thereof are employed.
For the purpose of preparing the polyesters according to the invention the dicarboxylic acids which may be employed comprise aromatic dicarboxylic acids, for example benzenedicarboxylic acids or naphthalene- dicarboxylic acids. Preferably, benzenedicarboxylic acids, for example phthalic acid, isophthalic acid and terephthalic acid or naphthalenedi- carboxylic acids, for example 1,2- 1,4-, 1,5", 1,6-, 1,7", 1,8-, 2,3-, 2,6-, 2,7- or 2,8-naphthalenedicarboxylic acid are employed. It is also possible to employ mixtures of one or more aromatic dicarboxylic acids. It is therefore possible to employ one or more benzenedicarboxylic acids or naphthalenedicarboxylic acids. For the purpose of preparing the polyesters according to the invention it is likewise possible to employ derivatives of dicarboxylic acids which are able to react with a hydroxyl group, for example di¬ esters, dithioesters, diamides and diacyl chlorides.
The invention also provides a method for the preparation of linear polyesters and/or polyester polyols, 1,3,5-triazines which are substituted in the 2-, 4- and 6-position being prepared in situ from the chemical compounds suitable for this purpose. In a preferred embodiment preference is given to the use of cyanuric acid, thiocyanuric acid or melamine, any of which may be substituted, the cyanuric acid which may be substituted being prepared from a urea which may be substituted or a biuret which may be substituted and a thiocyanuric acid which may be sub¬ stituted being prepared from a thiourea which may be substituted.
If 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, for example cyanuric acid, thiocyanuric acid or melamine, are prepared in situ, this is done in the presence of an acidic catalyst. In general a catalyst is employed which in water has a pH of from 5 to 1. The catalyst which is employed for the preparation of the cyanuric acid may be identical with that employed for the preparation of the polyester. One example is orthophosphoric acid. Preferably, cyanuric acid or thio- cyanuric acid or tautomers thereof, any of which may be substituted, are prepared in situ in the presence of a catalyst which in water has a pH of from 5 to 7.
The preparation in situ of 1,3,5-triazines which are sub¬ stituted in the 2-, 4- and 6-position, for example cyanuric acid or thio- cyanuric acid, is carried out in a solvent whose boiling point is higher than the temperature at which the 1,3,5-triazine sublimes. The solvent may, for example, be a glycol which has a high boiling point and which is also used for the preparation of the polyester. According to the present invention, preference is given to the use of glycols such as ethylene glycol, diethylene glycol, propylene glycol and 1,4-butanediol, and in particular ethylene glycol. Instead of the reaction mixture being heated to a temperature at which the glycol boils, it can also be heated to a temperature which is lower than the boiling point of the glycol, under the condition that the reaction is carried out under elevated pressure. The cyanuric acid or thiocyanuric acid or tautomers thereof, any of which may be substituted, is therefore prepared at a temperature of from 200° to 300"C, preferably from 225° to 275°C.
According to the invention it is preferable to employ a small amount of the 1,3,5-triazine which is substituted in the 2-, 4- and 6-po¬ sition. The invention therefore relates to a method wherein a molar ratio of the 1,3,5-triazine or the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted, to the monomer from which the polyester is prepared, employed is from 0.0001 to 1, preferably from 0.01 to 0.5.
The invention also provides linear polyesters and/or polyester polyols which can be obtained by employing the above-described methods, and which comprise glycols, aromatic dicarboxylic acids and 1,3,5-tria¬ zines which are substituted in the 2-, 4- and 6-position, or tautomeric forms thereof. Examples of such polymers are: polyesters prepared from ethylene glycol, terephthalic acid and cyanuric acid polyesters prepared from ethylene glycol, dimethyl terephthalic acid and urea - polyesters prepared from PET, ethylene glycol and cyanuric acid polyesters prepared from ethylene glycol, diethylene glycol, terephthalic acid and melamine polyesters prepared from ethylene glycol, dimethyl terephtha¬ late, isophthalic acid and biuret - polyesters prepared from ethylene glycol, l,4-bis(hydroxy- methyl)cyclohexane, terephthalic acid and urea polyester polyols prepared from PET, diethylene glycol and urea polyester polyols prepared from PET, diethylene glycol, isophthalic acid and thiocyanuric acid - polyesters prepared from 1,4-naphthalenedicarboxylic acid, ethylene glycol and melamine.
To prepare such polyesters and polyester polyols, existing polymerization or polycondensation processes can be employed, such as batch processes, semicontinuous and continuous processes. Such polyesters can be prepared from the pure chemical compounds or from polyester waste. Such processes and preparation methods are described, for example, in DE-A-2,014,818, FR-A-2,386,572 and US-A-3.767,6θl.
The 1,3,5-triazine which is substituted in the 2-, 4- and 6-po- sition can be added at any time during the polycondensation. This means that the 1,3,5-triazine can be added at the beginning of the preparation of the monomer, but also at the beginning of the polycondensation of the monomer.
The linear polyesters and/or polyester polyols according to the invention preferably comprise glycols, aromatic dicarboxylic acids and 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, or tautomers thereof. The linear polyesters and/or polyester polyols prefer¬ ably comprise glycols, aromatic dicarboxylic acids and cyanuric acid, thiocyanuric acid, melamine, any of which may be substituted or tautomers thereof.
The linear polyesters and/or polyester polyols according to the invention comprise, as the glycol components, one or more ethylene glycols, diethylene glycols, polyethylene glycols, propylene glycols, polypropylene glycols, 1,4-butanediols, 1,5-pentanediols, 1,6-hexane- diols, l,4-bis(hydroxymethyl)cyclohexanes, 1,7-heptanediols or polyester polyols. Preferably, the linear polyesters and/or polyester polyols ac¬ cording to the invention comprise polyester polyols, ethylene glycols, diethylene glycols, propylene glycols or 1,4-bis(hydroxymethyl)cyclo- hexane. The linear polyesters and/or polyester polyols according to the invention comprise, as the dicarboxylic acid components, one or more benzenedicarboxylic acids or naphthalenedicarboxylic acids, the benzene¬ dicarboxylic acids preferably being phthalic acids, isophthalic acids or terephthalic acids, and naphthalenedicarboxylic acids preferably being 1,2-, 1.4-, 1,5-, 1,6-, 1,7-. 1,8-, 2,3-. 2,6-. 2,7- or 2,8-naphthalene- dicarboxylic acids.
The linear polyesters and/or polyester polyols may therefore comprise one or more polyester polyols, ethylene glycols, diethylene glycols, propylene glycols, l,4-bis(hydroxymethyl)cyclohexane, benzenedi- carboxylic acids or naphthalenedicarboxylic acids.
Because the invention makes it possible for the crystallization of polyesters to be controlled in such a way that crystallization thereof takes place very slowly but does ultimately take place, the polyesters according to the invention can be very well postcondensed in the solid state. Postcondensation means that the polyesters according to the in¬ vention are heated under reduced pressure to below the melting point of the polyester for a certain time, glycols being eliminated, as a result of which the polyesters reach a higher molecular weight and a higher viscosity. Preferably, the polyesters are heated, according to the in¬ vention, for from 15 to 30 hours until the desired viscosity is attained.
Said postcondensation makes it possible to prepare polyesters which have a high molecular weight and a high viscosity which in turn is beneficial to the strength of the polyesters and which moreover further delays crystallization.
The intrinsic viscosity of the polyester polyols according to the invention increases, the more 1,3,5-triazine which is substituted in the 2-, 4- and 6-position is employed. The polyester polyols according to the invention are clear, do not crystallize or crystallize slowly and have increased functionality. Moreover, the incorporation of 1,3,5-tria¬ zines in the polyester polyols according to the invention confers flame- retardant characteristics upon polyurethanes which are made from such polyester polyols.
Owing to the controllable crystallization, in particular owing to a retarded crystallization, the polyesters according to the invention are highly suitable for the fabrication of products and articles which have relatively thick walls, for example bottles for repeated use, thick plates, bubble packs, shrink film and weldable film.
According to the invention it is also possible to reprocess polyesters or polyester waste to give polyesters or polyester polyols whose crystallization is retarded by the use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, or tautomers thereof. Such reprocessing is sometimes referred to as glycolysis.
In such a glycolysis, polyester waste is heated, for example, with a glycol to a temperature at which the glycol boils. In the process, depolymerization of the polyester takes place, and the monomer is obtained from which the original polyester had been prepared. Methods for such a glycolysis are described, for example, in EP-A-0,104,736 and US 4,048,104. Then the 1,3,5-triazine, for example cyanuric acid, or a chemical compound from which the 1,3,5-triazine can be prepared, for example urea, is added and a polyester according to the invention is thus obtained. It goes without saying that it is also possible, in a first step, for the 1,3,5-triazine to be prepared from the chemical compound suitable for this purpose, whereupon the polyester waste is added.
The invention will be illustrated with reference to the fol¬ lowing examples. Example I This example describes a general procedure for the preparation of a polyester from an organic dicarboxylic acid, a glycol and a 1,3,5- triazine which is substituted in the 2-, 4- and 6-position.
In a first step the preparation takes place, in a stainless- steel reactor provided with a condenser, a water separator, a stirrer, a heating device and a pressure controller, of a monomer from terephthalic acid and ethylene glycol. The mixture, which contains terephthalic acid and ethylene glycol in a molar ratio of 1:1.7, is heated to a temperature at which reflux occurs (approximately 200 - 300°C) . Optionally, an amount of 0.03 mol, based on the terephthalic acid, of a suitable catalyst, for example orthophosphoric acid, is added. The reaction is complete when no more water separates.
In a second step, 0.25 mol of cyanuric acid per mole of monomer obtained in the first step is added, and the excess of ethylene glycol is distilled off under reduced pressure until the polyester has the desired intrinsic viscosity. Owing to the reduction in pressure, distilling off can be carried out at a lower temperature, because the boiling point of ethylene glycol is then lower. Then the polyester obtained is removed from the reactor and is granulated. Example II This example describes a general procedure for the preparation of a polyester from an organic diester, a glycol and a 1,3.5-triazine which is substituted in the 2-, 4- and 6-position.
The procedure described in Example I is carried out, except that instead of terephthalic acid dimethyl terephthalate is employed. The first step is complete when no more methanol separates. Example III
This example describes a general procedure for the preparation of a polyester from an organic diester, a glycol and a 1,3.5-triazine which is substituted in the 2-, 4- and 6-position. The procedure described in Example I is carried out, except that a mixture containing terephthalic acid, ethylene glycol and cyanuric acid in a molar ratio of 1:1.7:0.3 is heated to a temperature at which reflux occurs (approximately 200 - 300°C). Example IV This example describes a general procedure for the preparation of a polyester from a different polyester, a glycol and a 1,3.5-triazine which is substituted in the 2-, 4- and 6-position.
In the reactor of Example I, a mixture of PET, ethylene glycol and cyanuric acid in a molar ratio of 1:1:0.4 is heated to a temperature at which reflux occurs. In a second step, a sufficient amount of ethylene glycol is distilled off under reduced pressure, until the polyester has the desired intrinsic viscosity. Subsequently, the product is removed from the reactor and is granulated. Example V
This example describes a general procedure for the preparation of a polyester polyol from a polyester, a diethylene glycol and a 1,3,5- triazine which is substituted in the 2-, 4- and 6-position.
The procedure described in Example IV is carried out, except that instead of ethylene glycol diethylene glycol is employed. The pro¬ duct obtained can be used for the preparation of polyurethane foam. Example VI
This example describes a general procedure for the preparation of a polyester, according to which the 1,3.5-triazine which is sub- stituted in the 2-, 4- and 6-position is prepared in situ.
In the reactor of Example I, a mixture of ethylene glycol and urea in a molar ratio of 1:0.47 is heated to a temperature at which reflux occurs (approximately 225 - 250°C). Ammonia and carbon dioxide escape in the process. The reaction is complete when no more ammonia separates. Subsequently, terephthalic acid is added in an amount of 1 mol per 1.7 mol ethylene glycol. After the polycondensation, the product is removed from the reactor and is subsequently granulated. Example VII
In order to determine the effect of the amount of cyanuric acid employed on the rate of crystallization, the following experiments were carried out.
Polyesters are prepared from terephthalic acid, ethylene glycol and cyanuric acid and from 1,4-naphthalenedicarboxylic acid, ethylene glycol and cyanuric acid according to the procedure of Example I. During the second step, a sample is taken at certain times, which is rapidly cooled to room temperature. Whether or not crystallization of these samples takes place is then established visually (crystalline polyesters are opaque, amorphous polyesters are transparent).
After the second step was complete, the polyesters were gra- nulated. An experiment was then carried out in order to establish whether the polyesters crystallize under conditions prevailing during postcon¬ densation.
The polyesters were heated, for at most 1 hour, to a tempe¬ rature of l6θ*C, and whether crystallization of the polyester did or did not occur was established visually.
The results of the experiments are reproduced in Table 1, "+" being intended to indicate that the polyester crystallized, "+/-" that the polyester crystallized only slightly, and "-" that the polyester did not crystallize. It was found that the experiments involving polyesters of terephthalic acid and naphthalenedicarboxylic acid gave the same results.
Table 1
Molar ratio 1.00 h 1.30 h 2.00 h 2.30 h 160° cyanuric acid: monomer
0.00 + + + + +
0.14 + + + - +
0.28 + + - - */-
0.54 + - - - -
It is found that, as more cyanuric acid is employed, an amorphous polyester is obtained even at a shorter reaction time. It is also found that, if cyanuric acid is employed, polyesters can be obtained which are amorphous at 160°. It is also possible, however, with a low level of cyanuric acid, to obtain a polyester which crystallizes slowly. Ultimately, this polyester does crystallize, so that it can be postcon- densed very well in the solid state. Example VIII
An experiment as described in Example VII was carried out with polyester polyols of PET, diethylene glycol and cyanuric acid, which were prepared according to the procedure described in Example V. Whether crystallization of the polyester polyol did or did not take place was established after 1 week. The results are reproduced in the following Table 2, "++" to "—" indicating a gradation from complete crystalliza- tion to no crystallization.
Table 2
Molar ratio 1 week cyanuric acid: monomer
0.00 ++
0.14 +
0.28 ♦/-
0.54 -
1.00 —
It is found that, if cyanuric acid is employed, amorphous, transparent polyester polyols can be prepared.

Claims

CLAI S 1. Use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position, or tautomers thereof for controlling the crystallization of linear polyesters and/or polyester polyols.
2. Use according to Claim 1, wherein the 1,3.5-triazine specified in Claim 1 respectively is a cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted.
3. Use according to Claim 1 or 2, wherein, for controlling the crystallization, the 1,3,5-triazine specified in Claim 1 or the cyanuric acid, thiocyanuric acid or a tautomeric form thereof, any of which may be substituted, is prepared in situ during the preparation of the linear polyesters and/or polyester polyols.
4. Use according to Claims 1 - 3. wherein the molar ratio of the 1.3.5-triazine specified in Claim 1 or the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be sub¬ stituted, to the monomer from which the polyester is prepared, is from 0.0001 to 1, preferably from 0.01 to 0.5.
5- Method for the preparation of linear polyesters and/or polyester polyols from polyols and aromatic dicarboxylic acids, wherein the 1,3,5-triazine specified in Claim 1 is employed at the same time.
6. Method according to Claim 5, wherein the l,3.5-triazine specified in Claim 1 and employed at the same time is a cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be substituted.
7- Method according to Claim 5 or 6, wherein the polyols employed comprise one or more polyester polyols, ethylene glycols, diethylene glycols, propylene glycols or l,4-bis(hydroxymethyl)cyclohexane.
8. Method according to Claims 5 - 7, wherein the aromatic dicar¬ boxylic acids employed comprise one or more benzenedicarboxylic acids or naphthalenedicarboxylic acids.
9- Method according to Claims 5 " 8, wherein during the prepara¬ tion of linear polyesters and/or polyester polyols the cyanuric acid which may be substituted is prepared from a urea which may be substituted or a biuret which may be substituted and a thiocyanuric acid with may be substituted is prepared from a thiourea which may be substituted.
10. Method according to Claims 5 " 9. wherein cyanuric acid or thiocyanuric acid or tautomers thereof, any of which may be substituted, are prepared in situ in the presence of a catalyst which in water has a pH of from 5 to 7.
11. Method according to Claims 5 - 10, wherein cyanuric acid or thiocyanuric acid or tautomers thereof, any of which may be substituted, are prepared in situ at a temperature of from 200* to 300*C, preferably from 225* to 275*C.
12. Method according to Claims 5 - H, wherein a molar ratio of the 1.3.5-triazine specified in Claim 1 or the cyanuric acid, thiocyanuric acid, melamine or a tautomeric form thereof, any of which may be sub¬ stituted, to the monomer from which the polyester is prepared, is employed from 0.0001 to 1, preferably from 0.01 to 0.5«
13. Linear polyesters and/or polyester polyols obtainable according to the method of Claims 5 - 12.
14. Linear polyesters and/or polyester polyols which comprise polyols, aromatic dicarboxylic acids and 1,3,5-triazines which are sub¬ stituted in the 2-, 4- and 6-position, or tautomers thereof.
15. Linear polyesters and/or polyester polyols according to Claim 14, which comprise polyols, aromatic dicarboxylic acids and cyanuric acid, thiocyanuric acid, melamine, any of which may be substituted, or tautomers thereof.
16. Linear polyesters and/or polyester polyols according to Claim 14 or 15, which comprise one or more polyester polyols, ethylene glycols, diethylene glycols, propylene glycols or l,4-bis(hydroxymethyl)- cyclohexane.
17- Linear polyesters and/or polyester polyols according to Claims 14 - 16, which comprise one or more benzenedicarboxylic acids or naphtha- lenedicarboxylic acids. l8. Linear polyesters and/or polyester polyols according to Claims 14 - 17, which comprise one or more polyester polyols, ethylene glycols, diethylene glycols, propylene glycols, l,4-bis(hydroxymethyl)cyclohexane, benzenedicarboxylic acids or naphthalenedicarboxylic acids.
PCT/NL1996/000115 1995-03-20 1996-03-18 Use of 1,3,5-triazines which are substituted in the 2-, 4- and 6-position or tautomers thereof for controlling the crystallization of linear polyesters and/or polyester polyols and method for the preparation thereof WO1996029357A1 (en)

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WO2017079206A1 (en) * 2015-11-03 2017-05-11 Invista North America S.Ar.L. Modified polyester
RU2721424C2 (en) * 2015-05-28 2020-05-19 Коим Асиа Пасифик Пте. Лтд. Fire-retardant and autocatalytic polyesters for polyurethanes
EP4180475A1 (en) 2021-11-10 2023-05-17 Norchem Limited Process for producing a triazine ring containing compound, addition product, triazine ring containing polyol, use of the addition product, use of the triazine ring containing polyol and pu/pir foam obtained by using the triazine ring containing polyol
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