CA2164805A1 - Process for the preparation of polyesters and copolyesters - Google Patents
Process for the preparation of polyesters and copolyestersInfo
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- CA2164805A1 CA2164805A1 CA002164805A CA2164805A CA2164805A1 CA 2164805 A1 CA2164805 A1 CA 2164805A1 CA 002164805 A CA002164805 A CA 002164805A CA 2164805 A CA2164805 A CA 2164805A CA 2164805 A1 CA2164805 A1 CA 2164805A1
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- Prior art keywords
- titanium dioxide
- polycondensation
- mol
- preparation
- dioxide
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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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
For the preparation of polyesters and copolyesters, titanium dioxide precipitates and/or titanium dioxide/silicon dioxide coprecipitates having a composition of TiO2:SiO2 > 90:10 mol/mol and/or titanium dioxide/zirconium dioxide coprecipitates having a composition of TiO2:ZrO2 > 95:5 mol/mol, which have been obtained by hydrolytic precipitation of the corresponding metal alcoholates formed from mono- or polyhydric alcohols, are proposed as polycondensation catalysts.
They offer increased safety for the ecosystem and have a higher catalytic activity than Sb2O3, so that the preferred amount used is only 10 to 100 ppm, based on the esters or oligoesters to be subjected to poly-condensation.
They offer increased safety for the ecosystem and have a higher catalytic activity than Sb2O3, so that the preferred amount used is only 10 to 100 ppm, based on the esters or oligoesters to be subjected to poly-condensation.
Description
Process for the preparation of polyesters and copolyesters Akzo Nobel nv, Arnhem Description:
Polyesters and copolyesters are in general prepared by a two-stage process, regardless of their structure, which can extend from aliphatic to completely aromatic via numerous possible variations. In the first stage, in particular, dicarboxylic acid esters are transesterified or dicarboxylic acids are esterified with excess dialcohols to prepare the esters to be subjected to polycondensation or a polyester precondensate which comprises a mixture of oligoesters and can have an average relative molecular weight, depen~ing on the molar ratio of the starting compounds, of as a rule between 100 and 2000. Limited amounts of starting components of higher functionality, such as glycerol, pentaerythritol and trimellitic acid, can also be employed for any desired branching modification. Equivalent procedures for the first stage are the reaction of dicarboxylic acid chlorides with diols, the addition of ethylene oxide onto dicarboxylic acids, the esterification of an anhydride with a dialcohol, the reaction of anhydrides with epoxides and the reaction of dicarboxylic acids or dicarboxylic acid esters with the diacetate of a diol.
The second reaction stage is the actual polycondensation, in which the desired high molecular weight of the polyesters or copolyesters must be achieved, alcohol and/or water being split off. As well as applying vacuum, passing through an inert gas and increasing the reaction temperature, the polycondensation is accelerated, in particular, by specific polycondensation catalysts.
A legion of polycondensation catalysts for accele-ration of the polycondensation reaction has already been proposed for the preparation of film- and fibre-forming polyesters. Since the overwhelming majority of compounds mentioned in numerous patents have an inadequate catalytic activity or other disadvantages, almost exclusively sb23 has become accepted as the polycondensation catalyst in the art. Unfortunately, this catalyst has recently met objections in terms of environmental policy, so that its replacement generally seems desirable.
Attempts are continuously being made to provide substitute catalysts for Sb2O3. In particular, alkoxy titanates, specifically tetrabutyl titanate, have already been proposed, these compounds being used either only for the transesterification (JA Patent 74 11 474), for the transesterification and polycondensation (JA-A 77 86 496) or only for the polycondensation (JA-A 80 23 136), since they are catalytically active for both stages. Since the use of titanium compounds causes discolorations in the polycondensed polyesters, according to JA-A 78 106 792, it is necessary to pretreat titanium compounds with various organic substances, for example amines, or to combine them with other polycondensation catalysts, in particular with Sb2O3 (JA-A 78 109 597).
It is known from DE P 947 517 to employ metal oxides, such as zinc oxide, boron trioxide, lead oxide and titanium oxide, as polycondensation catalysts for the preparation of polyethylene terephthalate. However, the polycondensation time with these metal oxides is disproportionately long and, from the examples therein, lasts 7-14 hours. For this reason, in BE P 619 210, Sb2O3 is used as a further polycondensation catalyst when Tio2 is used for preparation of the polyesters therein (cf.
Example 1), as a result of which the speed of the polycondensation increases immensely. These circumstances of course resulted in the expediency of using only Sb2O3 or titanium tetrabutylate as the polycondensation catalyst (cf. the other examples of BE P 619 210).
Polyesters and copolyesters are in general prepared by a two-stage process, regardless of their structure, which can extend from aliphatic to completely aromatic via numerous possible variations. In the first stage, in particular, dicarboxylic acid esters are transesterified or dicarboxylic acids are esterified with excess dialcohols to prepare the esters to be subjected to polycondensation or a polyester precondensate which comprises a mixture of oligoesters and can have an average relative molecular weight, depen~ing on the molar ratio of the starting compounds, of as a rule between 100 and 2000. Limited amounts of starting components of higher functionality, such as glycerol, pentaerythritol and trimellitic acid, can also be employed for any desired branching modification. Equivalent procedures for the first stage are the reaction of dicarboxylic acid chlorides with diols, the addition of ethylene oxide onto dicarboxylic acids, the esterification of an anhydride with a dialcohol, the reaction of anhydrides with epoxides and the reaction of dicarboxylic acids or dicarboxylic acid esters with the diacetate of a diol.
The second reaction stage is the actual polycondensation, in which the desired high molecular weight of the polyesters or copolyesters must be achieved, alcohol and/or water being split off. As well as applying vacuum, passing through an inert gas and increasing the reaction temperature, the polycondensation is accelerated, in particular, by specific polycondensation catalysts.
A legion of polycondensation catalysts for accele-ration of the polycondensation reaction has already been proposed for the preparation of film- and fibre-forming polyesters. Since the overwhelming majority of compounds mentioned in numerous patents have an inadequate catalytic activity or other disadvantages, almost exclusively sb23 has become accepted as the polycondensation catalyst in the art. Unfortunately, this catalyst has recently met objections in terms of environmental policy, so that its replacement generally seems desirable.
Attempts are continuously being made to provide substitute catalysts for Sb2O3. In particular, alkoxy titanates, specifically tetrabutyl titanate, have already been proposed, these compounds being used either only for the transesterification (JA Patent 74 11 474), for the transesterification and polycondensation (JA-A 77 86 496) or only for the polycondensation (JA-A 80 23 136), since they are catalytically active for both stages. Since the use of titanium compounds causes discolorations in the polycondensed polyesters, according to JA-A 78 106 792, it is necessary to pretreat titanium compounds with various organic substances, for example amines, or to combine them with other polycondensation catalysts, in particular with Sb2O3 (JA-A 78 109 597).
It is known from DE P 947 517 to employ metal oxides, such as zinc oxide, boron trioxide, lead oxide and titanium oxide, as polycondensation catalysts for the preparation of polyethylene terephthalate. However, the polycondensation time with these metal oxides is disproportionately long and, from the examples therein, lasts 7-14 hours. For this reason, in BE P 619 210, Sb2O3 is used as a further polycondensation catalyst when Tio2 is used for preparation of the polyesters therein (cf.
Example 1), as a result of which the speed of the polycondensation increases immensely. These circumstances of course resulted in the expediency of using only Sb2O3 or titanium tetrabutylate as the polycondensation catalyst (cf. the other examples of BE P 619 210).
The object of the present invention is to provide, for the general synthesis of polyesters and copolyesters, new polycondensation catalysts as a replacement for Sb2O3 which offer increased safety for the ecosystem and are distinguished in particular by a higher catalytic activity than that of Sb2O3, Tio2 and titanium tetra-butylate each in the same concentration.
The invention relates to a process for the preparation of polyesters and copolyesters by polyconden-sation of polyester-forming starting components, esters or oligoesters being prepared in a first reaction stage and subjected to polycondensation in a second reaction stage in the presence of titanium catalysts, which is characterized in that, in the polycondensation stage, a titanium dioxide precipitate and/or a titanium dioxide/
silicon dioxide coprecipitate having a composition of TiO2:SiO2 of > 90:10 mol/mol and/or a titanium dioxide/
zirconium dioxide coprecipitate having a composition of TiO2 : ZrO2 of > 95:5 mol/mol, which have been obtained by hydrolytic precipitation of the corresponding metal alcoholates formed from mono- or polyhydric alcohols, is employed as the polycondensation catalyst for polyconden-sation of the esters or oligoesters.
On the basis of the fact that TiO2 is a poor polycondensation catalyst for the synthesis of polyesters (cf. Comparison Examples la and lb), it is surprising that the titanium dioxide precipitates, titanium dioxide/silicon dioxide coprecipitates and titanium dioxide/zirconium dioxide coprecipitates employed according to Claim 1 are highly active polycondensation catalysts at all, in particular for the preparation of thread-forming high molecular weight polyesters and copolyesters, and moreover even in the very small amounts preferably used.
For the use according to the invention as a polycondensation catalyst, it is preferable for the titanium doxide [sic] precipitates, titanium dioxide/
silicon dioxide coprecipitates and titanium dioxide/
The invention relates to a process for the preparation of polyesters and copolyesters by polyconden-sation of polyester-forming starting components, esters or oligoesters being prepared in a first reaction stage and subjected to polycondensation in a second reaction stage in the presence of titanium catalysts, which is characterized in that, in the polycondensation stage, a titanium dioxide precipitate and/or a titanium dioxide/
silicon dioxide coprecipitate having a composition of TiO2:SiO2 of > 90:10 mol/mol and/or a titanium dioxide/
zirconium dioxide coprecipitate having a composition of TiO2 : ZrO2 of > 95:5 mol/mol, which have been obtained by hydrolytic precipitation of the corresponding metal alcoholates formed from mono- or polyhydric alcohols, is employed as the polycondensation catalyst for polyconden-sation of the esters or oligoesters.
On the basis of the fact that TiO2 is a poor polycondensation catalyst for the synthesis of polyesters (cf. Comparison Examples la and lb), it is surprising that the titanium dioxide precipitates, titanium dioxide/silicon dioxide coprecipitates and titanium dioxide/zirconium dioxide coprecipitates employed according to Claim 1 are highly active polycondensation catalysts at all, in particular for the preparation of thread-forming high molecular weight polyesters and copolyesters, and moreover even in the very small amounts preferably used.
For the use according to the invention as a polycondensation catalyst, it is preferable for the titanium doxide [sic] precipitates, titanium dioxide/
silicon dioxide coprecipitates and titanium dioxide/
zirconium dioxide coprecipitates to have been obt-ained by hydrolytic precipitation of the corresponding metal alcoholates formed from monohydric alcohols having 1-6 C
atoms. A titanium dioxide precipitate or a titanium dioxide/silicon dioxide coprecipitate from the required composition range, like a corresponding titanium dioxide/
zirconium dioxide coprecipitate, can be employed as the polycondensation catalyst by itself or as a mixture with the other particular type of precipitate or, in the case of the coprecipitates mentioned, as a mixture with its own type having a different composition within the required composition ranges.
The preparation of the titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxidetzirnonium [sic] dioxide coprecipitates used according to the invention is known in principle (cf., for example, B.E. Yoldes, J. Non-Cryst. Solids, 38 and 39, 81 (1980); E.A. Barringer, H.K. Bowen, J.Am.Ceram. Soc., 65 C 199 (1982); E.A. Barringer, Ph. D.
Thesis, MIT (1982); B. Fegley jr., E.A. Barringer, H.K. Bowen, J.Am.Ceram. Soc., 67, C 113 (1984)). The starting substances are metal alkoxides of the formula M(OR)m, wherein M is Ti, Si and Zr, according to the desired oxide or mixed oxide, and m is the integer 4, which are subjected to hydrolysis. The oxide network is formed by polymerization reactions during this process.
Suitable alcohols for the preparation of the metal alkoxides by methods known per se are, for example, monohydric alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butanol, propyl alcohol, isobutyl alcohol, n-amyl alcohol, 3-methyl-1-butanol, n-hexanol, 2-hexanol, 2-heptanol, n-octanol and n-decanol, which can be used individually or as a mixture. However, it is also possible to use polyhydric alcohols, if appropriate as a mixture with monohydric alcohols, such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, glycerol, trimethylolpropane and pentaerythritol.
The organometallic compounds, in the case of preparation of a titanium dioxide precipitate, for example, titanium tetraisopropylate, are subjected to a hydrolysis which can be effected in various ways. Thus, for example, the titanium tetraalkoxide, dissolved in absolute alcohols, for example ethanol, can be hydrolysed by means of addition of water or an aqueous alcohol within a period of about 20 minutes to 2 hours at 0 to 50C. However, the hydrolysis can also be effected by adding water or an aqueous alcohol solution dropwise to the undissolved pure titanium tetraalkoxide under the conditions mentioned above. The water required for the hydrolysis, however, can also be contained in a gas phase as moisture, for example by passing damp nitrogen into the titanium tetraalkoxide at 0 to 50C for 3 to 30 hours. The as it were "in situ formation of a dispersion of TiO2 precipitate in glycol suitable for use in the reactor can also be advantageous. In this case, the undissolved pure titanium tetraalkoxides can be precipitated as TiO2 precipitate under the above conditions by addition of glycol which contains the amount of water needed for the hydrolysis. If the glycol contains smaller amounts of water, the hydrolysis can additionally be carried out by passing, for example, damp nitrogen into the reaction vessel.
The preparation of the TiO2/SiO2 and TiO2/ZrO2 coprecipitates is carried out in an analogous manner, except that in each case two tetraalkoxides of titanium and silicon or of titanium and zirconium, of which the alkoxides otherwise can be identical or different, are in each case used for their precipitation. Advantageous forms of the preparation, at room temperature, of the precipitates and coprecipitates used according to the invention are described in the experimental part A in Examples 1 to 6. Under the hydrolytic conditions therein, gel formation, which is to be avoided, is excluded, and, - 6 - 21 64805 AGw24ag during this precipitation of the TiO2 and the Ti/Si and Ti/Zr mixed oxides takes place.
The amounts added of the precipitates and coprecipitates according to the invention which are used as the polycondensation catalyst can be varied within wide limits and include a total amount of about 5 to 500 ppm, based on the esters or oligoesters to be subjected to polycondensation. Their upper limit can therefore in principle be of the same order of magnitude as in the case where Sb2O3 is used, which is as a rule employed as a polycondensation catalyst in an amount of about 300 to 400 ppm.
If attention must be paid to achieving good colour values for certain fields of use of the polyesters and copolyesters prepared, however, it is preferable to use the titanium dioxide precipitate and/or the titanium dioxide/silicon dioxide coprecipitate and/or the titanium dioxide/zirconium dioxide coprecipitate in a total amount of only 10 to 100 ppm, based on the esters or oligoesters to be subjected to polycondensation. The increased catalytic activity of the precipitates and coprecipitates used according to the invention allows the use of added amounts which are considerably lower than in the case where Sb2O3 is used, the same polycondensation time and a completely acceptable b* value of 3.0 to 8.0 then being achieved with the polyesters thus prepared. This b* value range corresponds in particular to the values which are likewise obtained in the preparation of polyethylene terephthalate using 400 ppm of Sb2O3 as the polycondensa-tion catalyst. The titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxide/
zirconium dioxide coprecipitates used according to the invention are preferably added in the form of a 5 to 20%
strength suspension in glycol to the esters or oligo-esters synthesized in the first reaction stage, for example the bisglycol ester of the dicarboxylic acid(s) to be subjected to polycondensation and/or the preconden-sate of one or more such bisglycol esters, before their polycondensation. However, it is in principle also possible for the precipitates and coprecipitates even to be added at any point in time during the first reaction stage, and in the case of transesterification, if appro-priate together with one or more transesterification catalysts. In the case of transesterification in the first reaction stage, it may sometimes be advantageous to block the transesterification catalysts after the tran-sesterification by addition of phosphorus compounds in a manner known per se. Suitable phosphorus compounds are, for example, carbethoxymethyldiethyl phosphonate, ditpolyoxyethylene)hydroxymethyl phosphonate, tetra-isopropyl methylenediphosphonate and H3P04, an added P
concentration of 30-50 ppm in general being adequate.
Under customary reaction conditions, the precipitates and coprecipitates used according to the invention are in principle suitable as polycondensation catalysts for the preparation of the most diverse polyesters and copolyesters for which Sb203 has been employed to date as the polycondensation catalyst, if appropriate also in combination with one or more other polycondensation catalysts. The most diverse fields of use also correspond to the various types of polyesters and copolyesters.
If alkyd resins and saturated polyester resins (hydroxy-polyesters) having a relative molecular weight of < 10,000 are prepared with the precipitates and coprecipitates used according to the invention, these can be used as binders in varnishes and paints. In modern usage, alkyd resins here are understood as meaning oil-or fatty acid-modified polyesters of polycarboxylic acids and polyalcohols and reaction products thereof with, for example, vinyl compounds, epoxy resins, silicones, diisocyanates and organometallic compounds ("modified"
alkyd resins). Polycarboxylic acids which are employed for alkyd resins are essentially phthalic acid, isophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimerized fatty acids, hexahydrophthalic- acid, hexahydroterephthalic acid, maleic acid, fumaric acid and, for the purpose of flameproofing, halogen-cont~;n;ng dicarboxylic acids, such as tetrachlorophthalic anhydride. Polyols which are used are in general glycerol, pentaerythritol, dipentaerythritol, trimethylolpropane, trimethylolethane, sorbitol and difunctional polyols, such as ethylene glycol, propylene 1,2-glycol, butane-1,3- and -1,4-diol, diethylene glycol, dipropylene glycol and neopentylglycol. The third compon-ent for the preparation of alkyd resins are long-chain fatty acids, either synthetic fatty acids, such as pelargonic acid, abietic acid and synthetic fatty acid mixtures (C7-Cg), or naturally occurring fatty acids, which are used almost exclusively in the form of their fats and oils, for example linseed oil, castor oil, coconut oil, soya oil and cottonseed oil. In contrast, no longer-chain fatty acids are employed in the polyconden-sation for the preparation of saturated polyester resins, which are defined in DIN 55 945, while otherwise the saturated polycarboxylic acids and polyalcohols used are essentially the same as those employed for the prepara-tion of alkyd resins.
If (co)polyesters are synthesized as precursors for polyurethanes having a relative molecular weight of < 10,000 using the precipitates and coprecipitates in question, this leads, depending on their further processing on the basis of known procedures, not only to polyurethane varnishes, but also to a diversity of different types of plastics having variable useful use properties (thermosets, thermoplastics, casting elastomers, rigid and flexible foams, compression moulding compositions, rigid and flexible coatings, adhesives). The low molecular weight polyesters and copolyesters as precursors for polyurethanes are in general prepared from saturated aliphatic or aromatic dicarboxylic acids and difunctional or di- and trifunctional alcohols and are linear or slightly to severely branched. With the coprecipitates used according to the invention, it is possible to prepare the entire wide range of hydroxy-polyesters known for this, having hydroxyl numbers of 28-300 mg of KOH/g and acid numbers of usually less than 1 mg of KOH/g. The highly branched polyesters among them, which are chiefly obtained on the basis of aromatic or hydroaromatic dicarboxylic acids, are used mainly as binders for polyurethane varnishes.
The precipitates and coprecipitates used according to the invention are particularly suitable, under customary reaction conditions, as polycondensation catalysts for the preparation of the known high-melting fibre- and film-forming polyesters, such as polyethylene terephthalate, polybutylene terephthalate, poly(ethylene 2,6-naphthalenedicarboxylate), poly(butylene 2,6-naphthalenedicarboxylate), poly(1,4-dimethylenecyclo-hexane terephthalate) and copolyesters thereof based on high homopolyester contents of at least 80 mol per cent, which belong to the class of thermoplastic polyesters.
Such polyesters and copolyesters in principle have a molecular weight of > 10,000. The polyalkylene terephthalates preferably subjected to polycondensation with the coprecipitates, in particular polyethylene terephthalate and polybutylene terephthalate, can, as copolyesters, comprise up to 20 mol per cent of units which are derived from at least one other polyester-forming component. Furthermore, it is of course of no significance for the use of the polycondensation catalysts according to the invention whether the bisglycol esters of the dicarboxylic acid(s) to be subjected to polycondensation and/or the precondensates of one or more such bisglycol esters have been prepared by a transesterification process or by a direct esterification process.
The polycondensation catalysts according to the invention are thus suitable both for the preparation of a fibre-forming polyethylene terephthalate having an intrinsic viscosity [~] of 0.65-0.75, which as a rule is lo - 21 6 4 8 0 5 AGW2409 further processed to staple fibres for textile purposes, and for the preparation of fibre-forming polyethylene terephthalates having an intrinsic viscosity [~] of 0.75-0.80 and 0.95-1.05, from which filament yarns are prepared for industrial purposes. The increased molecular weights can be achieved by continuous polycondensation with direct spinning or, preferably, by post-condensation in the solid phase. For post-condensation in the solid phase, it is advantageous to block any transesterifica-tion catalysts present by phosphorus compounds in a manner known per se. Phosphorus compounds which are suitable for this are, for example, di(polyoxyethylene)-hydroxymethyl phosphonate, tetraisopropyl methylene-diphosphonate and H3PO4, an added P concentration of 30-50 ppm being sufficient.
The fibre- and film-forming thermoplastic polyesters prepared with the polycondensation catalysts according to the invention, in particular polyethylene terephthalate and polybutylene terephthalate, can of course also be processed, for example, to all types of shaped articles and profiles by means of injection moulding and extrusion. For example, if a polyethylene terephthalate prepared with the polycondensation cata-lysts according to the invention is processed to PET
bottles, these have a high transparency and a lower acetaldehyde content.
The other polyester-forming components for fibre-and film-forming copolyesters can be an aliphatic diol, such as ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol and poly(tetra-hydrofuran)diol, an aromatic diol, such as pyrocatechol, resorcinol and hydroquinone, an alicyclic diol, such as 1,4-cyclohexanedimethanol and cyclohexanediol, an aliphatic dicarboxylic acid, such as adipic acid, sebacic acid and decanedicarboxylic acid, an aromatic dicarb-oxylic acid, such as isophthalic acid, 5-sodium-sulpho-isophthalic acid, sodium-sulphoterephthalic acid and 2,6-naphthalenedicarboxylic acid, and an alicyclic dicarboxy-lic acid, such as hexahydroterephthalic acid and 1,3-cyclohexanedicarboxylic acid. The analogous polyester-forming components for copolyester formation are also possible for the thread-forming homopolyesters, some of which have already been mentioned above, which do not belong to the class of polyalkylene terephthalates.
The film- and fibre-forming polyesters can of course also comprise, as customary modifying agents, known branching agents, such as pentaerythritol, tri-mellitic acid, pyromellitic acid and trimesic acid or esters thereof, in the small amounts customary for this purpose of, for example, 1 to 15 micro-equivalents per g of polymer, these guaranteeing high-speed spinning at 3000 to 4000 m/min or more, and also draw-texturing at a rate of at least 1000 m/minute. These branching agents are advantageously added as a solution in ethylene glycol to the bisglycol ester of the dicarboxylic acid(s) to be subjected to polycondensation.
The term copolyester also includes the extensive class of polyether-esters. As is known, the thermoplastic polyether-esters are block copolymers which are syn-thesized from mutually incompatible rigid crystalline and flexible amorphous segments. The rigid and short-chain segments generally chiefly comprise an aromatic poly-ester, for example ethylene terephthalate units or butylene terephthalate units, while the flexible and long-chain segments comprise, in particular, the reaction product of an aliphatic polyether, for example poly(butylene glycol) or poly(ethylene glycol) with an aliphatic, cycloaliphatic or aromatic dicarboxylic acid.
Both the long-chain and the short-chain ester units are often copolyesters which result from the limited co-use of one or more other dicarboxylic acid and glycol compon-ents. Thermoplastic polyether-esters, for the preparation of which the titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxide/zirconium dioxide coprecipitates employed according to the invention as polycondensation catalysts are also suitable, are described, for example, in US-A 3,023,192, GB-B 682 866, DE-C 23 52 584, EP-A-0 051 220 and EP-A-0 109 123.
The titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxide/zirconium dioxide coprecipitates used according to the invention are also suitable for the preparation of completely aromatic or liquid-crystalline polyesters if this is carried out on the basis of customary polycondensation catalysts, such as Sb2O3 and titanium alkoxides. Thus, for example, completely aromatic polyesters of 10-90 mol per cent of a hydroxy-naphthalene-carboxylic acid, 5-45 mol per cent of at least one other aromatic dicarboxylic acid, for example terephthalic acid, and 5-45 mol per cent of at least one aromatic diol, for example hydroquinone, are known from US-A 4,421,908.
According to EP-A-0 472 366, completely aromatic polyesters are prepared from (A) isophthalic acid, (B) hydroquinone and (C) from 4,4-dihydroxybiphenyl and/or p-hydroxybenzoic acid and/or 2-hydroxy-6-naphtha-lenecarboxylic acid and (D) a phenol. And EP-A-0 496 404 describes completely aromatic polyesters which are obtained by reaction of at least one dialkyl ester of an aromatic dicarboxylic acid, for example DMT, with at least one aromatic polycarbonate, for example poly(4,4'-isopropylidene-diphenylene carbonate) and/or an aromatic dialkyl dicarbonate. In these processes, mentioned by way of example, for the preparation of completely aromatic polyesters, the polycondensation catalysts used therein, such as Sb2O3, titanium alkoxides and zirconium alkoxides, can be replaced in an advantageous manner by the specific precipitates and coprecipitates according to the invention, quite irrespective of whether they are added as early as in the first reaction stage or in the subsequent actual polycondensation stage.
The invention is illustrated in more detail with the aid of the following examples. The relative solution viscosity stated therein was measured at 25C -as a 1%
strength solution in m-cresol. The number of carboxyl groups has been stated as carboxyl group equivalents/106 g or mmol/kg of the polymer. This parameter was determined by titration of the polymer in o-cresol with potassium hydroxide.
The L* a* b* colour system was taken as the basis for evaluation of the colour of the polyesters. This is one of the colour systems for standardization of colour measurement and was recommended in 1976 by the CIE
(Commission Internationale de l'Eclairage) because of its relatively high accuracy in describing perceptible colours and colour differences. In this system, L* is the lightness factor and a* and b* are colour measurement numbers. In the present case, the b* value, which indi-cates the yellow/blue balance, is important. A positive b* value means yellow discoloration and a negative b*
value blue discoloration. Polyesters prepared con-ventionally with antimony trioxide have a b* value of between 3 and 8. Higher values are also accepted for products for which colour is not critical.
Preparation of the TiO2 precipitates and TiO2/SiO2 and TiO2/ZrO2 coprecipitates Example 1 Catalytically active titanium dioxide precipitate No. 1 10.80 g of titanium(IV) tetraisopropylate (38 mmol) are dissolved in 263 ml of absolute ethanol (solution A). 27.02 g of distilled water (1.5 mol) are mixed with 263 g of absolute ethanol (solution B).
Solution A is initially introduced into the reaction vessel and solution B is added dropwise at 22C in the course of 30 minutes. A white precipitate separates out.
The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 2 Catalytically active titanium dioxide precipitate No. 2 27.02 g of distilled water (1.5 mol), if appropriate mixed with 263 g of absolute ethanol, are added dropwise to 10.80 g of titanium(IV) tetraisopropylate (38 mmol) in the course of 30 minutes.
A white precipitate separates out. The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol.
The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 3 Catalytically active titanium dioxide precipitate No. 3 80 Nl/hour of nitrogen, saturated with water via a wash bottle, are passed into 10.80 g of titanium(IV) tetraisopropylate (38 mmol) for 24 hours. A white precipitate separates out. The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 4 Catalytically active titanium dioxide precipitate No. 4 150 ml of glycol (water content about 0.02 % by weight) are added to 10.80 g of titanium(IV) tetra-isopropylate (38 mmol). In addition, 80 l/hour (s.t.p.) of nitrogen, saturated with water via a wash bottle, are passed in for a period of 60 minutes. A white precipitate separates out. The titanium dioxide precipitate dispersion formed is employed without further processing.
Example 5 Catalytically active titanium dioxide precipitate No. 5 34.04 g of titanium(IV) tetrabutylate (0.1 mol) are heated to about 120C together with 62.07 g of glycol (1.0 mol). 32.4 g of dibutylamine (0.25 mol) are added dropwise at this temperature as a transesterification catalyst. The butanol formed is distilled off overnight, while stirring. The residue of the titanium alcoholate formed from glycol is precipitated by means of water contA;n;ng hydrochloric acid (pH=3), a white precipitate separating out. The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 6 Catalytically active titanium dioxide precipitate No. 6 34.04 g of titanium(IV) tetrabutylate (0.1 mol) are heated to about 120C together with 92.09 g of glycerol (1.0 mol). 32.4 g of dibutylamine (0.25 mol) are added dropwise at this temperature as a transesterification catalyst. The butanol formed is distilled off overnight, while stirring. The residue of the titanium alcoholate formed from glycerol is precipitated by means of water contA;n;ng hydrochloric acid (pH=3), a brownish precipitate separating out. The mixture is centrifuged three times for 20 minutes and the residue is mixed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 7 Catalytically active titanium dioxide/silicon dioxide coprecipitate (TiO2:SiO2 = 95:5 mol/mol) 11.37 g of titanium(IV) tetraisopropylate (40 mmol) and 0.44 g of tetraethoxysilane (2.1 mmol) are dissolved with 100 ml of absolute ethanol (solution A).
10.27 g of distilled H2O (0.57 mol) are mixed with 100 ml of absolute ethanol (solution B). Solution A is initially introduced into the reaction vessel, and solution B is added dropwise at 22C in the course of 30 minutes. A
white precipitate separates out. After the mixture has been stirred for 1 hour, it is centrifuged and the residue is washed 3 times with distilled H2O~ The resulting Tio2/Sio2 coprecipitate is dried at 70C in vacuo.
Ex~mple 8 Catalytically active titanium dioxide/zirconium dioxide coprecipitate (TiO2:ZrO2 = 97:3 mol/mol) 25.58 g of titanium(IV) tetraisopropylate (90.0 mmol) and 0.92 g of zirconium(IV) tetrapropylate (2.8 mmol) are dissolved in 263 g of absolute ethanol (solution A). 27.02 g of distilled H2O (1.5 mol) are mixed with 263 g of absolute ethanol (solution B).
Solution A is initially introduced into the reaction vessel, and solution B is added dropwise at 22C in the course of 30 minutes. A white precipitate separates out.
After the mixture has been stirred for 1 hour, it is centrifuged. The residue is washed once with distilled H2O and then washed with ethanol and centrifuged for in each case 20 minutes. The resulting TiO2/ZrO2 coprecipitate is dried at 60-70C in vacuo for 24 hours.
Polycondensation Examples Example 9 Polyethylene terephthalate was prepared in a two-stage process. In the first stage, the transesterifica-tion, the reaction of ethylene glycol and dimethyl terephthalate (= DMT) in a molar ratio of 2.5:1 was carried out in the presence of 100 ppm of ZnAc2.2 H2O (Ac = acetate) and 150 ppm of MnAc2~4 H2O, based on the DMT, at temperatures in the range from 165 to 265C, the continuous increase in temperature from 165C to 265C
being carried out not too quickly in order to avoid sublimation of the DMT. The methanol liberated during the transesterification is [sic] distilled off over a-column.
When the reaction temperature had reached 240C, 50 ppm of phosphorus, based on the DMT employed, were added as ethyl phosphonoacetate in order to block the trans-esterification catalysts.
As soon as the reaction temperature of 250C was reached, 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 1 were added in the form of a 5% strength by weight suspension in glycol.
The polycondensation reaction was carried out at 290C
under a vacuum of 1.3 mbar. After a reaction time of 96 minutes, a polymer having a relative solution viscosity of 1.665 was obtained. The b* value was 9.0 and the COOH
end group content was 18.3 equivalents/106 g of polymer.
Example lO
Polyethylene terephthalate was prepared in a two-stage process. In the first stage, the transesterifica-tion, the reaction of ethylene glycol and dimethyl terephthalate was carried out in the presence of 55 ppm of MnAc2.4 H2O or 75 ppm of MnAc2.2 H2O, based on the DMT, in a manner otherwise the same as in Example 7 [sic]. However, the transesterification catalysts were blocked with an equivalent amount of phosphorous acid, which was added in the form of a 70% strength by weight solution in glycol.
At 250C, 100 ppm, based on the bis-(2-hydroxy-ethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 3 were added in the form of a 5% strength by weight suspension in glycol.
The polycondensation reaction was carried out at 283C
under a vacuum of 0.8 mbar, [sic] After a reaction time of 88 minutes, a polymer having a relative solution viscosity of 1.654 was obtained. The b* value was 7.5 and the COOH end group content was 19.3 equivalents/106 g of polymer.
Example 11 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 4 were added in the form of a 5% strength by weight suspension in glycol.
The polycondensation reaction was carried out at 276C
under a vacuum of 0.5 mbar. After a reaction time of 82 minutes, a polymer having a relative solution viscosity of 1.614 was obtained. The b* value was 7.5 and the COOH
end group content was 20.1 equivalents/106 g of polymer.
Example 12 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 2 were added in the form of a 5% strength by weight suspension. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 98 minutes, a polymer having a relative solution viscosity of 1.653 was obtained. The b* value was 6.5 and the COOH
end group content was 14.8 equivalents/106 g of polymer.
Example 13 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 5 were added in the form of a 5% strength by weight suspension. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 101 minutes, a polymer having a relative solution viscosity of 1.635 was obtained. The b* value was 8.2 and the COOH
end group content was 17.6 equivalents/106 g of polymer.
Example 14 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 6 were added in the form of a 5% strength by weight suspension. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 92 minutes, a polymer having a relative solution viscosity of 1.634 was obtained. The b* value was 10.4 and the COOH
end group content was 17.7 equivalents/106 g of polymer.
Example 15 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide/zirconium dioxide coprecipitate having the composition TiO2:ZrO2 =
97:3 mol/mol prepared according to Example 8 were added in the form of a 5% strength by weight suspension in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 80 minutes, a polymer having a relative solution viscosity of 1.634 was obtained. The b* value was 7.3 and the COOH end group content was 16.9 equivalents/106 g of polymer.
Example 16 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide/silicon dioxide coprecipitate having the composition of TiO2:SiO2 = 95:5 mol/mol prepared according to Example 7 were added in the form of a 5% strength by weight suspension in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 bar. After a reaction time of 97 minutes, a polymer having a relative solution viscosity of 1.646 was obtained. The b* value was 9.2 and the COOH end group content was 17.5 equivalentstl06 g of polymer.
Example 17 Polyethylene terephthalate was prepared in a two-stage process, a direct esterification of terephthalic acid with ethylene glycol to give bis-(2-hydroxyethyl) terephthalate being carried out in the first stage. In the second reaction stage, the polycondensation was carried out using a) 400 ppm of Sb2O3, b) 100 ppm of Tio2/SiO2 (95:5 mol/mol) and c) TiO2/ZrO2 (97:3 mol/mol) as polycondensation catalysts.
a) Sb2O3 as the polycondensation catalyst 1707 g (10.3 mol) of terephthalic acid are heated up in the esterification autoclave together with 1020 g of glycol (16.4 mol) and 1 ppm of defoamer M 10 (from Dow Corning) until an increased pressure of 7 bar has been established by the water split off (235C batch temperature). The time this pressure is reached is evaluated as the starting time of the reaction. The increased pressure is maintained for 60 minutes, during which the internal temperature is increased to about 250C. The water vapour thereby discharged is condensed in the condenser and collected in a measuring cylinder. After a total of 60 minutes, the internal pressure is reduced step-wise to normal pressure in the course of a further 60 minutes (temperature between 250 and 260C). The product is then drained into the polycondensation autoclave. Immediately after draining, 50 ppm of phosphorus are added as ethyl phosphonoacetate (EPA) at 240C. 400 ppm of Sb2O3, based on the bis-(2-hydroxyethyl) terephthalate present, are then added in the form of a 1.1% strength solution in glycol at an internal temperature of 250C (after about 5 minutes). A vacuum programme which reduces the internal pressure to about 1 torr in the course of 25 minutes is then started, with further -heating.
The internal temperature is regulated by the peak procedure (peak temperature: 298C). The reaction end point is determined by measuring the power consumption of the stirrer. After 95 minutes, a product having a solution viscosity of 1.681 is obtained. The carboxyl end group content was 20.1 mmol/kg.
- b) TiO2/SiO2 (95:5 mol/mol) as the polycondensation catalyst Example 17 a) was repeated, with the modification that at 250C 100 ppm of TiO2/SiO2 (95:5 mol/mol), based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 5% strength dispersion in glycol.
After 94 minutes, a product having a solution vis-cosity of 1.669 is obtained. The carboxyl end group content was 12.2 mmol/kg, and is thus significantly better than in experiment 17 a).
c) TiO2/ZrO2 (97:3 mol/mol) as the polycondensation catalyst Example 17 a) was repeated, with the modification that at 250C 50 ppm of TiO2/ZrO2 (97:3 mol/mol), based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 5% strength dispersion in glycol.
After 84 minutes, a product having a solution vis-cosity of 1.682 is obtained. The carboxyl end group content was 13.4 mmol/kg, and is thus likewise more favourable than in experiment 17 a).
Example 18 Post-condensation in the solid phase a) Polycondensation catalyst Sb2O3 About 2 g of polyethylene terephthalate having a relative solution viscosity (SV) of 1.681 and a carboxyl end group concentration of 20.1 mmol/kg, prepared using 400 ppm of Sb2O3 as the polycondensa-tion catalyst in accordance with Example 17 a), are introduced into a glass tube immersed in a metal bath. Under a continuous stream of nitrogen, the polymer is first kept at 140C for one hour (pre-crystallization) and then kept at 231C for a further 4 hours. After the post-condensation, the SV
was 1.880 and the carboxyl end group content was 11.0 mmol/kg.
b) Polycondensation catalyst TiO2 precipitate About 2 g of polyethylene terephthalate having a relative solution viscosity (SV) of 1.654 and a carboxyl end group content of 19.3 mmol/kg, prepared using 100 ppm of TiO2 precipitate as the polycondensation catalyst in accordance with Example 9, are introduced into a glass tube immersed in a metal bath. Under a continuous nitrogen atom [sic], the polymer is first kept at 140C for one hour (pre-crystallization) and then kept at 231C for a ~urther 4 hours. After the post-condensation, the SV
was 1.982 and the carboxyl end group content was 10.6 mmol/kg.
Example 19 Preparation of a malonate resin a) Catalyst: dibutyl-tin oxide A 2000 ml five-necked flask which was equipped with a metal stirrer, dropping funnel, nitrogen inlet tube, thermocouple for the internal temperature, a 300 mm long Vigreux silver-jacketed column and a distillation column head was used as the apparatus for this example. The reaction batch comprised the following components:
312.45 g (3 mol) of pentane-1,5-diol as component A, 560.60 g (3.5 mol) of diethyl malonate as component B, 0.87 g (= 0.1% by weight, based on A -+ B) of dibutyl-tin oxide as component C, 43.5 g (15% by weight, based on A + B) of m-xylene as component D, 130.5 g (15% by weight, based on A + B) of xylene as component E.
The dibutyl-tin oxide customary for this reaction was used as the catalyst. Components A, B, C and D
were weighed into a flask and the flask was flushed with nitrogen. The mixture was then heated slowly and the first drops of ethanol were distilled off at an internal temperature of 115C. At a falling rate of distillation, the internal temperature was increased to 200C. Component E was then addition-ally added dropwise as an entraining agent for the distillation and removal of the ethanol/m-xylene distillate continued. When the conversion had reached 99.5%, the polycondensation was interrupted.
This conversion was achieved after 16 hours.
The total amount of distillate at this point in time was 378.03 g. The amount of ethanol distilled off was 274.92 g ttheoretical total amount = 276.42 g).
The Gardner colour number was 13.
b) Catalyst: TiO2 precipitate The experiment under a) was repeated with the cata-lyst according to the invention. The reaction batch comprised the following components:
312.45 g (3 mol) of pentane-1,5-diol as component A, 560.60 g (3.5 mol) of diethyl malonate as component B, 0.87 g (0.1% by weight, based on A + B) of TiO2 precipitate as component C as in Example 3, 43.5 g (5% by weight, based on A + B) of m-xylene as component D, 87.0 g (10% by weight, based on A + B) of m-xylene as component E.
Components A, B, C and D were weighed into the flask and the flask was flushed with nitrogen. The mixture was then heated slowly and the first drops of ethanol were distilled off as a mixture with m-xylene at an internal temperature of 142C. At a falling rate of distillation, the internal tempera-ture was increased to 200C. Component E was then additionally added dropwise as an entraining agent for the distillation and removal of the ethanol/
m-xylene distillate continued. When the conversion reached 99.8%, the polycondensation was dis-continued. This conversion was reached after only 6 hours.
The total amount of distillate at this point in time was 342.28 g. The amount of ethanol distilled off was 276.04 g (theoretical total amount of ethanol =
276.42 g). The Gardner colour number was 10.
Comparison Examples Comparison Examples la and lb a) An attempt was made to prepare a polyethylene tere-phthalate analogously to Example 7, in which commer-cially available titanium dioxides were to function as polycondensation catalysts. For this purpose, after the transesterification carried out in accord-ance with Example 7 and after blocking of the trans-esterification catalysts when the reaction tempera-ture reached 250C, 500 ppm of Hombitec KO 3 TiO2 (a titanium dioxide from Sachtleben), based on the bis-(2-hydroxyethyl) terephthalate present, were added to the reaction batch as the polycondensation cata-lyst in the form of a 10% strength by weight suspension in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar.
After a reaction time of 180 minutes, the experiment was discontinued, since no adequate melt viscosity and therefore no ade~uate relative viscosity either had been established because the molecular weight of the polycondensation product was too low.
b) A second attempt carried out under the same reaction conditions, in which 500 ppm of Tilcom HPT 3 TiO2 (titanium dioxide from Tioxide), based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 10% strength by weight suspension in glycol, pro-ceeded with the same negative result.
Comparison Example 2 Example 8 was repeated with the modification that at 250C, 340 ppm of Sb2O3, based on the bis-(2-hydroxy-ethyl) terephthalate present, were added. The polyconden-sation reaction was thus carried out at 283C under a vacuum of 0.8 mbar. After a reaction time of 180 minutes, a polymer having a relative solution viscosity of 1.590 was obtained. The b* value was 4.8 and the COOH end group content was 22.5 equivalents/106 g of polymer.
This comparison example shows in particular that the catalytic activity of the catalysts used according to the invention is considerably higher than that of Sb2O3, and with the former it is therefore possible to achieve the same polycondensation times as when Sb2O3 is used by considerably reducing the amount of catalyst employed, and - if the colour values of the thread-forming polyesters are important for certain uses - also to achieve practically the same b* values (Examples 7, 8, and 9).
Comparison Example 3 Example 7 was repeated with the modification that at 250C, 213 ppm of titanium tetrabutylate, based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 5%
strength by weight solution in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 3.5 mbar. After a reaction time of 134 minutes, a polymer having a relative solution viscosity of 1.633 was obtained. The b* value was 15.5 and the COOH
end group content was 20.2 equivalents/106 g of polymer.
This comparison example shows in particular that, although titanium tetrabutylate has a higher catalytic activity than Sb2O3 at a significantly poorer b* value, it has to be employed in a higher concentration than the catalysts used according to the invention to achieve comparably short polycondensation times.
atoms. A titanium dioxide precipitate or a titanium dioxide/silicon dioxide coprecipitate from the required composition range, like a corresponding titanium dioxide/
zirconium dioxide coprecipitate, can be employed as the polycondensation catalyst by itself or as a mixture with the other particular type of precipitate or, in the case of the coprecipitates mentioned, as a mixture with its own type having a different composition within the required composition ranges.
The preparation of the titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxidetzirnonium [sic] dioxide coprecipitates used according to the invention is known in principle (cf., for example, B.E. Yoldes, J. Non-Cryst. Solids, 38 and 39, 81 (1980); E.A. Barringer, H.K. Bowen, J.Am.Ceram. Soc., 65 C 199 (1982); E.A. Barringer, Ph. D.
Thesis, MIT (1982); B. Fegley jr., E.A. Barringer, H.K. Bowen, J.Am.Ceram. Soc., 67, C 113 (1984)). The starting substances are metal alkoxides of the formula M(OR)m, wherein M is Ti, Si and Zr, according to the desired oxide or mixed oxide, and m is the integer 4, which are subjected to hydrolysis. The oxide network is formed by polymerization reactions during this process.
Suitable alcohols for the preparation of the metal alkoxides by methods known per se are, for example, monohydric alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butanol, propyl alcohol, isobutyl alcohol, n-amyl alcohol, 3-methyl-1-butanol, n-hexanol, 2-hexanol, 2-heptanol, n-octanol and n-decanol, which can be used individually or as a mixture. However, it is also possible to use polyhydric alcohols, if appropriate as a mixture with monohydric alcohols, such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, glycerol, trimethylolpropane and pentaerythritol.
The organometallic compounds, in the case of preparation of a titanium dioxide precipitate, for example, titanium tetraisopropylate, are subjected to a hydrolysis which can be effected in various ways. Thus, for example, the titanium tetraalkoxide, dissolved in absolute alcohols, for example ethanol, can be hydrolysed by means of addition of water or an aqueous alcohol within a period of about 20 minutes to 2 hours at 0 to 50C. However, the hydrolysis can also be effected by adding water or an aqueous alcohol solution dropwise to the undissolved pure titanium tetraalkoxide under the conditions mentioned above. The water required for the hydrolysis, however, can also be contained in a gas phase as moisture, for example by passing damp nitrogen into the titanium tetraalkoxide at 0 to 50C for 3 to 30 hours. The as it were "in situ formation of a dispersion of TiO2 precipitate in glycol suitable for use in the reactor can also be advantageous. In this case, the undissolved pure titanium tetraalkoxides can be precipitated as TiO2 precipitate under the above conditions by addition of glycol which contains the amount of water needed for the hydrolysis. If the glycol contains smaller amounts of water, the hydrolysis can additionally be carried out by passing, for example, damp nitrogen into the reaction vessel.
The preparation of the TiO2/SiO2 and TiO2/ZrO2 coprecipitates is carried out in an analogous manner, except that in each case two tetraalkoxides of titanium and silicon or of titanium and zirconium, of which the alkoxides otherwise can be identical or different, are in each case used for their precipitation. Advantageous forms of the preparation, at room temperature, of the precipitates and coprecipitates used according to the invention are described in the experimental part A in Examples 1 to 6. Under the hydrolytic conditions therein, gel formation, which is to be avoided, is excluded, and, - 6 - 21 64805 AGw24ag during this precipitation of the TiO2 and the Ti/Si and Ti/Zr mixed oxides takes place.
The amounts added of the precipitates and coprecipitates according to the invention which are used as the polycondensation catalyst can be varied within wide limits and include a total amount of about 5 to 500 ppm, based on the esters or oligoesters to be subjected to polycondensation. Their upper limit can therefore in principle be of the same order of magnitude as in the case where Sb2O3 is used, which is as a rule employed as a polycondensation catalyst in an amount of about 300 to 400 ppm.
If attention must be paid to achieving good colour values for certain fields of use of the polyesters and copolyesters prepared, however, it is preferable to use the titanium dioxide precipitate and/or the titanium dioxide/silicon dioxide coprecipitate and/or the titanium dioxide/zirconium dioxide coprecipitate in a total amount of only 10 to 100 ppm, based on the esters or oligoesters to be subjected to polycondensation. The increased catalytic activity of the precipitates and coprecipitates used according to the invention allows the use of added amounts which are considerably lower than in the case where Sb2O3 is used, the same polycondensation time and a completely acceptable b* value of 3.0 to 8.0 then being achieved with the polyesters thus prepared. This b* value range corresponds in particular to the values which are likewise obtained in the preparation of polyethylene terephthalate using 400 ppm of Sb2O3 as the polycondensa-tion catalyst. The titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxide/
zirconium dioxide coprecipitates used according to the invention are preferably added in the form of a 5 to 20%
strength suspension in glycol to the esters or oligo-esters synthesized in the first reaction stage, for example the bisglycol ester of the dicarboxylic acid(s) to be subjected to polycondensation and/or the preconden-sate of one or more such bisglycol esters, before their polycondensation. However, it is in principle also possible for the precipitates and coprecipitates even to be added at any point in time during the first reaction stage, and in the case of transesterification, if appro-priate together with one or more transesterification catalysts. In the case of transesterification in the first reaction stage, it may sometimes be advantageous to block the transesterification catalysts after the tran-sesterification by addition of phosphorus compounds in a manner known per se. Suitable phosphorus compounds are, for example, carbethoxymethyldiethyl phosphonate, ditpolyoxyethylene)hydroxymethyl phosphonate, tetra-isopropyl methylenediphosphonate and H3P04, an added P
concentration of 30-50 ppm in general being adequate.
Under customary reaction conditions, the precipitates and coprecipitates used according to the invention are in principle suitable as polycondensation catalysts for the preparation of the most diverse polyesters and copolyesters for which Sb203 has been employed to date as the polycondensation catalyst, if appropriate also in combination with one or more other polycondensation catalysts. The most diverse fields of use also correspond to the various types of polyesters and copolyesters.
If alkyd resins and saturated polyester resins (hydroxy-polyesters) having a relative molecular weight of < 10,000 are prepared with the precipitates and coprecipitates used according to the invention, these can be used as binders in varnishes and paints. In modern usage, alkyd resins here are understood as meaning oil-or fatty acid-modified polyesters of polycarboxylic acids and polyalcohols and reaction products thereof with, for example, vinyl compounds, epoxy resins, silicones, diisocyanates and organometallic compounds ("modified"
alkyd resins). Polycarboxylic acids which are employed for alkyd resins are essentially phthalic acid, isophthalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimerized fatty acids, hexahydrophthalic- acid, hexahydroterephthalic acid, maleic acid, fumaric acid and, for the purpose of flameproofing, halogen-cont~;n;ng dicarboxylic acids, such as tetrachlorophthalic anhydride. Polyols which are used are in general glycerol, pentaerythritol, dipentaerythritol, trimethylolpropane, trimethylolethane, sorbitol and difunctional polyols, such as ethylene glycol, propylene 1,2-glycol, butane-1,3- and -1,4-diol, diethylene glycol, dipropylene glycol and neopentylglycol. The third compon-ent for the preparation of alkyd resins are long-chain fatty acids, either synthetic fatty acids, such as pelargonic acid, abietic acid and synthetic fatty acid mixtures (C7-Cg), or naturally occurring fatty acids, which are used almost exclusively in the form of their fats and oils, for example linseed oil, castor oil, coconut oil, soya oil and cottonseed oil. In contrast, no longer-chain fatty acids are employed in the polyconden-sation for the preparation of saturated polyester resins, which are defined in DIN 55 945, while otherwise the saturated polycarboxylic acids and polyalcohols used are essentially the same as those employed for the prepara-tion of alkyd resins.
If (co)polyesters are synthesized as precursors for polyurethanes having a relative molecular weight of < 10,000 using the precipitates and coprecipitates in question, this leads, depending on their further processing on the basis of known procedures, not only to polyurethane varnishes, but also to a diversity of different types of plastics having variable useful use properties (thermosets, thermoplastics, casting elastomers, rigid and flexible foams, compression moulding compositions, rigid and flexible coatings, adhesives). The low molecular weight polyesters and copolyesters as precursors for polyurethanes are in general prepared from saturated aliphatic or aromatic dicarboxylic acids and difunctional or di- and trifunctional alcohols and are linear or slightly to severely branched. With the coprecipitates used according to the invention, it is possible to prepare the entire wide range of hydroxy-polyesters known for this, having hydroxyl numbers of 28-300 mg of KOH/g and acid numbers of usually less than 1 mg of KOH/g. The highly branched polyesters among them, which are chiefly obtained on the basis of aromatic or hydroaromatic dicarboxylic acids, are used mainly as binders for polyurethane varnishes.
The precipitates and coprecipitates used according to the invention are particularly suitable, under customary reaction conditions, as polycondensation catalysts for the preparation of the known high-melting fibre- and film-forming polyesters, such as polyethylene terephthalate, polybutylene terephthalate, poly(ethylene 2,6-naphthalenedicarboxylate), poly(butylene 2,6-naphthalenedicarboxylate), poly(1,4-dimethylenecyclo-hexane terephthalate) and copolyesters thereof based on high homopolyester contents of at least 80 mol per cent, which belong to the class of thermoplastic polyesters.
Such polyesters and copolyesters in principle have a molecular weight of > 10,000. The polyalkylene terephthalates preferably subjected to polycondensation with the coprecipitates, in particular polyethylene terephthalate and polybutylene terephthalate, can, as copolyesters, comprise up to 20 mol per cent of units which are derived from at least one other polyester-forming component. Furthermore, it is of course of no significance for the use of the polycondensation catalysts according to the invention whether the bisglycol esters of the dicarboxylic acid(s) to be subjected to polycondensation and/or the precondensates of one or more such bisglycol esters have been prepared by a transesterification process or by a direct esterification process.
The polycondensation catalysts according to the invention are thus suitable both for the preparation of a fibre-forming polyethylene terephthalate having an intrinsic viscosity [~] of 0.65-0.75, which as a rule is lo - 21 6 4 8 0 5 AGW2409 further processed to staple fibres for textile purposes, and for the preparation of fibre-forming polyethylene terephthalates having an intrinsic viscosity [~] of 0.75-0.80 and 0.95-1.05, from which filament yarns are prepared for industrial purposes. The increased molecular weights can be achieved by continuous polycondensation with direct spinning or, preferably, by post-condensation in the solid phase. For post-condensation in the solid phase, it is advantageous to block any transesterifica-tion catalysts present by phosphorus compounds in a manner known per se. Phosphorus compounds which are suitable for this are, for example, di(polyoxyethylene)-hydroxymethyl phosphonate, tetraisopropyl methylene-diphosphonate and H3PO4, an added P concentration of 30-50 ppm being sufficient.
The fibre- and film-forming thermoplastic polyesters prepared with the polycondensation catalysts according to the invention, in particular polyethylene terephthalate and polybutylene terephthalate, can of course also be processed, for example, to all types of shaped articles and profiles by means of injection moulding and extrusion. For example, if a polyethylene terephthalate prepared with the polycondensation cata-lysts according to the invention is processed to PET
bottles, these have a high transparency and a lower acetaldehyde content.
The other polyester-forming components for fibre-and film-forming copolyesters can be an aliphatic diol, such as ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol and poly(tetra-hydrofuran)diol, an aromatic diol, such as pyrocatechol, resorcinol and hydroquinone, an alicyclic diol, such as 1,4-cyclohexanedimethanol and cyclohexanediol, an aliphatic dicarboxylic acid, such as adipic acid, sebacic acid and decanedicarboxylic acid, an aromatic dicarb-oxylic acid, such as isophthalic acid, 5-sodium-sulpho-isophthalic acid, sodium-sulphoterephthalic acid and 2,6-naphthalenedicarboxylic acid, and an alicyclic dicarboxy-lic acid, such as hexahydroterephthalic acid and 1,3-cyclohexanedicarboxylic acid. The analogous polyester-forming components for copolyester formation are also possible for the thread-forming homopolyesters, some of which have already been mentioned above, which do not belong to the class of polyalkylene terephthalates.
The film- and fibre-forming polyesters can of course also comprise, as customary modifying agents, known branching agents, such as pentaerythritol, tri-mellitic acid, pyromellitic acid and trimesic acid or esters thereof, in the small amounts customary for this purpose of, for example, 1 to 15 micro-equivalents per g of polymer, these guaranteeing high-speed spinning at 3000 to 4000 m/min or more, and also draw-texturing at a rate of at least 1000 m/minute. These branching agents are advantageously added as a solution in ethylene glycol to the bisglycol ester of the dicarboxylic acid(s) to be subjected to polycondensation.
The term copolyester also includes the extensive class of polyether-esters. As is known, the thermoplastic polyether-esters are block copolymers which are syn-thesized from mutually incompatible rigid crystalline and flexible amorphous segments. The rigid and short-chain segments generally chiefly comprise an aromatic poly-ester, for example ethylene terephthalate units or butylene terephthalate units, while the flexible and long-chain segments comprise, in particular, the reaction product of an aliphatic polyether, for example poly(butylene glycol) or poly(ethylene glycol) with an aliphatic, cycloaliphatic or aromatic dicarboxylic acid.
Both the long-chain and the short-chain ester units are often copolyesters which result from the limited co-use of one or more other dicarboxylic acid and glycol compon-ents. Thermoplastic polyether-esters, for the preparation of which the titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxide/zirconium dioxide coprecipitates employed according to the invention as polycondensation catalysts are also suitable, are described, for example, in US-A 3,023,192, GB-B 682 866, DE-C 23 52 584, EP-A-0 051 220 and EP-A-0 109 123.
The titanium dioxide precipitates and titanium dioxide/silicon dioxide and titanium dioxide/zirconium dioxide coprecipitates used according to the invention are also suitable for the preparation of completely aromatic or liquid-crystalline polyesters if this is carried out on the basis of customary polycondensation catalysts, such as Sb2O3 and titanium alkoxides. Thus, for example, completely aromatic polyesters of 10-90 mol per cent of a hydroxy-naphthalene-carboxylic acid, 5-45 mol per cent of at least one other aromatic dicarboxylic acid, for example terephthalic acid, and 5-45 mol per cent of at least one aromatic diol, for example hydroquinone, are known from US-A 4,421,908.
According to EP-A-0 472 366, completely aromatic polyesters are prepared from (A) isophthalic acid, (B) hydroquinone and (C) from 4,4-dihydroxybiphenyl and/or p-hydroxybenzoic acid and/or 2-hydroxy-6-naphtha-lenecarboxylic acid and (D) a phenol. And EP-A-0 496 404 describes completely aromatic polyesters which are obtained by reaction of at least one dialkyl ester of an aromatic dicarboxylic acid, for example DMT, with at least one aromatic polycarbonate, for example poly(4,4'-isopropylidene-diphenylene carbonate) and/or an aromatic dialkyl dicarbonate. In these processes, mentioned by way of example, for the preparation of completely aromatic polyesters, the polycondensation catalysts used therein, such as Sb2O3, titanium alkoxides and zirconium alkoxides, can be replaced in an advantageous manner by the specific precipitates and coprecipitates according to the invention, quite irrespective of whether they are added as early as in the first reaction stage or in the subsequent actual polycondensation stage.
The invention is illustrated in more detail with the aid of the following examples. The relative solution viscosity stated therein was measured at 25C -as a 1%
strength solution in m-cresol. The number of carboxyl groups has been stated as carboxyl group equivalents/106 g or mmol/kg of the polymer. This parameter was determined by titration of the polymer in o-cresol with potassium hydroxide.
The L* a* b* colour system was taken as the basis for evaluation of the colour of the polyesters. This is one of the colour systems for standardization of colour measurement and was recommended in 1976 by the CIE
(Commission Internationale de l'Eclairage) because of its relatively high accuracy in describing perceptible colours and colour differences. In this system, L* is the lightness factor and a* and b* are colour measurement numbers. In the present case, the b* value, which indi-cates the yellow/blue balance, is important. A positive b* value means yellow discoloration and a negative b*
value blue discoloration. Polyesters prepared con-ventionally with antimony trioxide have a b* value of between 3 and 8. Higher values are also accepted for products for which colour is not critical.
Preparation of the TiO2 precipitates and TiO2/SiO2 and TiO2/ZrO2 coprecipitates Example 1 Catalytically active titanium dioxide precipitate No. 1 10.80 g of titanium(IV) tetraisopropylate (38 mmol) are dissolved in 263 ml of absolute ethanol (solution A). 27.02 g of distilled water (1.5 mol) are mixed with 263 g of absolute ethanol (solution B).
Solution A is initially introduced into the reaction vessel and solution B is added dropwise at 22C in the course of 30 minutes. A white precipitate separates out.
The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 2 Catalytically active titanium dioxide precipitate No. 2 27.02 g of distilled water (1.5 mol), if appropriate mixed with 263 g of absolute ethanol, are added dropwise to 10.80 g of titanium(IV) tetraisopropylate (38 mmol) in the course of 30 minutes.
A white precipitate separates out. The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol.
The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 3 Catalytically active titanium dioxide precipitate No. 3 80 Nl/hour of nitrogen, saturated with water via a wash bottle, are passed into 10.80 g of titanium(IV) tetraisopropylate (38 mmol) for 24 hours. A white precipitate separates out. The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 4 Catalytically active titanium dioxide precipitate No. 4 150 ml of glycol (water content about 0.02 % by weight) are added to 10.80 g of titanium(IV) tetra-isopropylate (38 mmol). In addition, 80 l/hour (s.t.p.) of nitrogen, saturated with water via a wash bottle, are passed in for a period of 60 minutes. A white precipitate separates out. The titanium dioxide precipitate dispersion formed is employed without further processing.
Example 5 Catalytically active titanium dioxide precipitate No. 5 34.04 g of titanium(IV) tetrabutylate (0.1 mol) are heated to about 120C together with 62.07 g of glycol (1.0 mol). 32.4 g of dibutylamine (0.25 mol) are added dropwise at this temperature as a transesterification catalyst. The butanol formed is distilled off overnight, while stirring. The residue of the titanium alcoholate formed from glycol is precipitated by means of water contA;n;ng hydrochloric acid (pH=3), a white precipitate separating out. The mixture is centrifuged three times for 20 minutes and the residue is rinsed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 6 Catalytically active titanium dioxide precipitate No. 6 34.04 g of titanium(IV) tetrabutylate (0.1 mol) are heated to about 120C together with 92.09 g of glycerol (1.0 mol). 32.4 g of dibutylamine (0.25 mol) are added dropwise at this temperature as a transesterification catalyst. The butanol formed is distilled off overnight, while stirring. The residue of the titanium alcoholate formed from glycerol is precipitated by means of water contA;n;ng hydrochloric acid (pH=3), a brownish precipitate separating out. The mixture is centrifuged three times for 20 minutes and the residue is mixed once with distilled water and once with ethanol. The resulting titanium dioxide precipitate is dried at 65C in vacuo.
Example 7 Catalytically active titanium dioxide/silicon dioxide coprecipitate (TiO2:SiO2 = 95:5 mol/mol) 11.37 g of titanium(IV) tetraisopropylate (40 mmol) and 0.44 g of tetraethoxysilane (2.1 mmol) are dissolved with 100 ml of absolute ethanol (solution A).
10.27 g of distilled H2O (0.57 mol) are mixed with 100 ml of absolute ethanol (solution B). Solution A is initially introduced into the reaction vessel, and solution B is added dropwise at 22C in the course of 30 minutes. A
white precipitate separates out. After the mixture has been stirred for 1 hour, it is centrifuged and the residue is washed 3 times with distilled H2O~ The resulting Tio2/Sio2 coprecipitate is dried at 70C in vacuo.
Ex~mple 8 Catalytically active titanium dioxide/zirconium dioxide coprecipitate (TiO2:ZrO2 = 97:3 mol/mol) 25.58 g of titanium(IV) tetraisopropylate (90.0 mmol) and 0.92 g of zirconium(IV) tetrapropylate (2.8 mmol) are dissolved in 263 g of absolute ethanol (solution A). 27.02 g of distilled H2O (1.5 mol) are mixed with 263 g of absolute ethanol (solution B).
Solution A is initially introduced into the reaction vessel, and solution B is added dropwise at 22C in the course of 30 minutes. A white precipitate separates out.
After the mixture has been stirred for 1 hour, it is centrifuged. The residue is washed once with distilled H2O and then washed with ethanol and centrifuged for in each case 20 minutes. The resulting TiO2/ZrO2 coprecipitate is dried at 60-70C in vacuo for 24 hours.
Polycondensation Examples Example 9 Polyethylene terephthalate was prepared in a two-stage process. In the first stage, the transesterifica-tion, the reaction of ethylene glycol and dimethyl terephthalate (= DMT) in a molar ratio of 2.5:1 was carried out in the presence of 100 ppm of ZnAc2.2 H2O (Ac = acetate) and 150 ppm of MnAc2~4 H2O, based on the DMT, at temperatures in the range from 165 to 265C, the continuous increase in temperature from 165C to 265C
being carried out not too quickly in order to avoid sublimation of the DMT. The methanol liberated during the transesterification is [sic] distilled off over a-column.
When the reaction temperature had reached 240C, 50 ppm of phosphorus, based on the DMT employed, were added as ethyl phosphonoacetate in order to block the trans-esterification catalysts.
As soon as the reaction temperature of 250C was reached, 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 1 were added in the form of a 5% strength by weight suspension in glycol.
The polycondensation reaction was carried out at 290C
under a vacuum of 1.3 mbar. After a reaction time of 96 minutes, a polymer having a relative solution viscosity of 1.665 was obtained. The b* value was 9.0 and the COOH
end group content was 18.3 equivalents/106 g of polymer.
Example lO
Polyethylene terephthalate was prepared in a two-stage process. In the first stage, the transesterifica-tion, the reaction of ethylene glycol and dimethyl terephthalate was carried out in the presence of 55 ppm of MnAc2.4 H2O or 75 ppm of MnAc2.2 H2O, based on the DMT, in a manner otherwise the same as in Example 7 [sic]. However, the transesterification catalysts were blocked with an equivalent amount of phosphorous acid, which was added in the form of a 70% strength by weight solution in glycol.
At 250C, 100 ppm, based on the bis-(2-hydroxy-ethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 3 were added in the form of a 5% strength by weight suspension in glycol.
The polycondensation reaction was carried out at 283C
under a vacuum of 0.8 mbar, [sic] After a reaction time of 88 minutes, a polymer having a relative solution viscosity of 1.654 was obtained. The b* value was 7.5 and the COOH end group content was 19.3 equivalents/106 g of polymer.
Example 11 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 4 were added in the form of a 5% strength by weight suspension in glycol.
The polycondensation reaction was carried out at 276C
under a vacuum of 0.5 mbar. After a reaction time of 82 minutes, a polymer having a relative solution viscosity of 1.614 was obtained. The b* value was 7.5 and the COOH
end group content was 20.1 equivalents/106 g of polymer.
Example 12 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 2 were added in the form of a 5% strength by weight suspension. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 98 minutes, a polymer having a relative solution viscosity of 1.653 was obtained. The b* value was 6.5 and the COOH
end group content was 14.8 equivalents/106 g of polymer.
Example 13 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 5 were added in the form of a 5% strength by weight suspension. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 101 minutes, a polymer having a relative solution viscosity of 1.635 was obtained. The b* value was 8.2 and the COOH
end group content was 17.6 equivalents/106 g of polymer.
Example 14 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide precipitate prepared according to Example 6 were added in the form of a 5% strength by weight suspension. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 92 minutes, a polymer having a relative solution viscosity of 1.634 was obtained. The b* value was 10.4 and the COOH
end group content was 17.7 equivalents/106 g of polymer.
Example 15 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide/zirconium dioxide coprecipitate having the composition TiO2:ZrO2 =
97:3 mol/mol prepared according to Example 8 were added in the form of a 5% strength by weight suspension in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar. After a reaction time of 80 minutes, a polymer having a relative solution viscosity of 1.634 was obtained. The b* value was 7.3 and the COOH end group content was 16.9 equivalents/106 g of polymer.
Example 16 Example 9 was repeated, with the modification that at 250C 100 ppm, based on the bis-(2-hydroxyethyl) terephthalate present, of the titanium dioxide/silicon dioxide coprecipitate having the composition of TiO2:SiO2 = 95:5 mol/mol prepared according to Example 7 were added in the form of a 5% strength by weight suspension in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 bar. After a reaction time of 97 minutes, a polymer having a relative solution viscosity of 1.646 was obtained. The b* value was 9.2 and the COOH end group content was 17.5 equivalentstl06 g of polymer.
Example 17 Polyethylene terephthalate was prepared in a two-stage process, a direct esterification of terephthalic acid with ethylene glycol to give bis-(2-hydroxyethyl) terephthalate being carried out in the first stage. In the second reaction stage, the polycondensation was carried out using a) 400 ppm of Sb2O3, b) 100 ppm of Tio2/SiO2 (95:5 mol/mol) and c) TiO2/ZrO2 (97:3 mol/mol) as polycondensation catalysts.
a) Sb2O3 as the polycondensation catalyst 1707 g (10.3 mol) of terephthalic acid are heated up in the esterification autoclave together with 1020 g of glycol (16.4 mol) and 1 ppm of defoamer M 10 (from Dow Corning) until an increased pressure of 7 bar has been established by the water split off (235C batch temperature). The time this pressure is reached is evaluated as the starting time of the reaction. The increased pressure is maintained for 60 minutes, during which the internal temperature is increased to about 250C. The water vapour thereby discharged is condensed in the condenser and collected in a measuring cylinder. After a total of 60 minutes, the internal pressure is reduced step-wise to normal pressure in the course of a further 60 minutes (temperature between 250 and 260C). The product is then drained into the polycondensation autoclave. Immediately after draining, 50 ppm of phosphorus are added as ethyl phosphonoacetate (EPA) at 240C. 400 ppm of Sb2O3, based on the bis-(2-hydroxyethyl) terephthalate present, are then added in the form of a 1.1% strength solution in glycol at an internal temperature of 250C (after about 5 minutes). A vacuum programme which reduces the internal pressure to about 1 torr in the course of 25 minutes is then started, with further -heating.
The internal temperature is regulated by the peak procedure (peak temperature: 298C). The reaction end point is determined by measuring the power consumption of the stirrer. After 95 minutes, a product having a solution viscosity of 1.681 is obtained. The carboxyl end group content was 20.1 mmol/kg.
- b) TiO2/SiO2 (95:5 mol/mol) as the polycondensation catalyst Example 17 a) was repeated, with the modification that at 250C 100 ppm of TiO2/SiO2 (95:5 mol/mol), based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 5% strength dispersion in glycol.
After 94 minutes, a product having a solution vis-cosity of 1.669 is obtained. The carboxyl end group content was 12.2 mmol/kg, and is thus significantly better than in experiment 17 a).
c) TiO2/ZrO2 (97:3 mol/mol) as the polycondensation catalyst Example 17 a) was repeated, with the modification that at 250C 50 ppm of TiO2/ZrO2 (97:3 mol/mol), based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 5% strength dispersion in glycol.
After 84 minutes, a product having a solution vis-cosity of 1.682 is obtained. The carboxyl end group content was 13.4 mmol/kg, and is thus likewise more favourable than in experiment 17 a).
Example 18 Post-condensation in the solid phase a) Polycondensation catalyst Sb2O3 About 2 g of polyethylene terephthalate having a relative solution viscosity (SV) of 1.681 and a carboxyl end group concentration of 20.1 mmol/kg, prepared using 400 ppm of Sb2O3 as the polycondensa-tion catalyst in accordance with Example 17 a), are introduced into a glass tube immersed in a metal bath. Under a continuous stream of nitrogen, the polymer is first kept at 140C for one hour (pre-crystallization) and then kept at 231C for a further 4 hours. After the post-condensation, the SV
was 1.880 and the carboxyl end group content was 11.0 mmol/kg.
b) Polycondensation catalyst TiO2 precipitate About 2 g of polyethylene terephthalate having a relative solution viscosity (SV) of 1.654 and a carboxyl end group content of 19.3 mmol/kg, prepared using 100 ppm of TiO2 precipitate as the polycondensation catalyst in accordance with Example 9, are introduced into a glass tube immersed in a metal bath. Under a continuous nitrogen atom [sic], the polymer is first kept at 140C for one hour (pre-crystallization) and then kept at 231C for a ~urther 4 hours. After the post-condensation, the SV
was 1.982 and the carboxyl end group content was 10.6 mmol/kg.
Example 19 Preparation of a malonate resin a) Catalyst: dibutyl-tin oxide A 2000 ml five-necked flask which was equipped with a metal stirrer, dropping funnel, nitrogen inlet tube, thermocouple for the internal temperature, a 300 mm long Vigreux silver-jacketed column and a distillation column head was used as the apparatus for this example. The reaction batch comprised the following components:
312.45 g (3 mol) of pentane-1,5-diol as component A, 560.60 g (3.5 mol) of diethyl malonate as component B, 0.87 g (= 0.1% by weight, based on A -+ B) of dibutyl-tin oxide as component C, 43.5 g (15% by weight, based on A + B) of m-xylene as component D, 130.5 g (15% by weight, based on A + B) of xylene as component E.
The dibutyl-tin oxide customary for this reaction was used as the catalyst. Components A, B, C and D
were weighed into a flask and the flask was flushed with nitrogen. The mixture was then heated slowly and the first drops of ethanol were distilled off at an internal temperature of 115C. At a falling rate of distillation, the internal temperature was increased to 200C. Component E was then addition-ally added dropwise as an entraining agent for the distillation and removal of the ethanol/m-xylene distillate continued. When the conversion had reached 99.5%, the polycondensation was interrupted.
This conversion was achieved after 16 hours.
The total amount of distillate at this point in time was 378.03 g. The amount of ethanol distilled off was 274.92 g ttheoretical total amount = 276.42 g).
The Gardner colour number was 13.
b) Catalyst: TiO2 precipitate The experiment under a) was repeated with the cata-lyst according to the invention. The reaction batch comprised the following components:
312.45 g (3 mol) of pentane-1,5-diol as component A, 560.60 g (3.5 mol) of diethyl malonate as component B, 0.87 g (0.1% by weight, based on A + B) of TiO2 precipitate as component C as in Example 3, 43.5 g (5% by weight, based on A + B) of m-xylene as component D, 87.0 g (10% by weight, based on A + B) of m-xylene as component E.
Components A, B, C and D were weighed into the flask and the flask was flushed with nitrogen. The mixture was then heated slowly and the first drops of ethanol were distilled off as a mixture with m-xylene at an internal temperature of 142C. At a falling rate of distillation, the internal tempera-ture was increased to 200C. Component E was then additionally added dropwise as an entraining agent for the distillation and removal of the ethanol/
m-xylene distillate continued. When the conversion reached 99.8%, the polycondensation was dis-continued. This conversion was reached after only 6 hours.
The total amount of distillate at this point in time was 342.28 g. The amount of ethanol distilled off was 276.04 g (theoretical total amount of ethanol =
276.42 g). The Gardner colour number was 10.
Comparison Examples Comparison Examples la and lb a) An attempt was made to prepare a polyethylene tere-phthalate analogously to Example 7, in which commer-cially available titanium dioxides were to function as polycondensation catalysts. For this purpose, after the transesterification carried out in accord-ance with Example 7 and after blocking of the trans-esterification catalysts when the reaction tempera-ture reached 250C, 500 ppm of Hombitec KO 3 TiO2 (a titanium dioxide from Sachtleben), based on the bis-(2-hydroxyethyl) terephthalate present, were added to the reaction batch as the polycondensation cata-lyst in the form of a 10% strength by weight suspension in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 1.3 mbar.
After a reaction time of 180 minutes, the experiment was discontinued, since no adequate melt viscosity and therefore no ade~uate relative viscosity either had been established because the molecular weight of the polycondensation product was too low.
b) A second attempt carried out under the same reaction conditions, in which 500 ppm of Tilcom HPT 3 TiO2 (titanium dioxide from Tioxide), based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 10% strength by weight suspension in glycol, pro-ceeded with the same negative result.
Comparison Example 2 Example 8 was repeated with the modification that at 250C, 340 ppm of Sb2O3, based on the bis-(2-hydroxy-ethyl) terephthalate present, were added. The polyconden-sation reaction was thus carried out at 283C under a vacuum of 0.8 mbar. After a reaction time of 180 minutes, a polymer having a relative solution viscosity of 1.590 was obtained. The b* value was 4.8 and the COOH end group content was 22.5 equivalents/106 g of polymer.
This comparison example shows in particular that the catalytic activity of the catalysts used according to the invention is considerably higher than that of Sb2O3, and with the former it is therefore possible to achieve the same polycondensation times as when Sb2O3 is used by considerably reducing the amount of catalyst employed, and - if the colour values of the thread-forming polyesters are important for certain uses - also to achieve practically the same b* values (Examples 7, 8, and 9).
Comparison Example 3 Example 7 was repeated with the modification that at 250C, 213 ppm of titanium tetrabutylate, based on the bis-(2-hydroxyethyl) terephthalate present, were added as the polycondensation catalyst in the form of a 5%
strength by weight solution in glycol. The polycondensation reaction was carried out at 290C under a vacuum of 3.5 mbar. After a reaction time of 134 minutes, a polymer having a relative solution viscosity of 1.633 was obtained. The b* value was 15.5 and the COOH
end group content was 20.2 equivalents/106 g of polymer.
This comparison example shows in particular that, although titanium tetrabutylate has a higher catalytic activity than Sb2O3 at a significantly poorer b* value, it has to be employed in a higher concentration than the catalysts used according to the invention to achieve comparably short polycondensation times.
Claims (14)
1. Process for the preparation of polyesters and copolyesters by polycondensation of polyester-forming starting components, esters or oligoesters being prepared in a first reaction stage and subjected to polycondensa-tion in a second reaction stage in the presence of titanium catalysts, characterized in that, in the poly-condensation stage, a titanium dioxide precipitate and/or a titanium dioxide/silicon dioxide coprecipitate having a composition of TiO2:SiO2 of > 90:10 mol/mol and/or a titanium dioxide/zirconium dioxide coprecipitate having a composition of TiO2 : ZrO2 of > 95:5 mol/mol, which have been obtained by hydrolytic precipitation of the corresponding metal alcoholates formed from mono- or polyhydric alcohols, is employed as the polycondensation catalyst for polycondensation of the esters or oligoesters.
2. Process according to Claim 1, characterized in that titanium dioxide precipitates, titanium dioxide/
silicon dioxide coprecipitates and titanium dioxide/
zirconium dioxide coprecipitates which have been obtained by hydrolytic precipitation of the corresponding metal alcoholates formed from monohydric alcohols having 1-6 C
atoms are employed.
silicon dioxide coprecipitates and titanium dioxide/
zirconium dioxide coprecipitates which have been obtained by hydrolytic precipitation of the corresponding metal alcoholates formed from monohydric alcohols having 1-6 C
atoms are employed.
3. Process according to one or more of Claims 1 to 2, characterized in that the titanium dioxide precipitate and/or the titanium dioxide/silicon dioxide coprecipitate and/or the titanium dioxide/zirconium dioxide coprecipi-tate is employed in a total amount of 5 - 500 ppm, based on the esters or oligoesters to be subjected to polycondensation.
4. Process according to Claim 3, characterized in that the titanium dioxide precipitate and/or the titanium dioxide/silicon dioxide coprecipitate and/or the titanium dioxide/zirconium dioxide coprecipitate is employed in a total amount of 10 to 100 ppm, based on the esters or oligoesters to be subjected to polycondensation.
5. Process according to one or more of Claims 1 to 4, characterized in that the titanium dioxide precipitate and/or the titanium dioxide/silicon dioxide coprecipitate and/or the titanium dioxide/zirconium dioxide coprecipitate is added in the form of a 5 to 20% strength by weight suspension in glycol to the esters or oligoesters to be subjected to polycondensation before their polycondensation.
6. Process according to one or more of Claims 1 to 5, characterized in that any transesterification catalysts present from the first reaction stage are blocked by additional addition of one or more phosphorus compounds.
7. Process according to Claim 6, characterized in that carbethoxy-methyl-diethyl phosphonate, di(polyoxy-ethylene)hydroxy-methyl phosphonate, tetraisopropyl methylene-diphosphonate and/or H3PO4 are employed as the blocking agent.
8. Use of the polycondensation catalysts according to Claims 1 to 5 for the preparation of alkyd resins having a relative molecular weight of < 10,000.
9. Use of the polycondensation catalysts according to Claims 1 to 5 for the preparation of saturated polyester resins having a relative molecular weight of < 10,000.
10. Use of the polycondensation catalysts according to Claims 1 to 5 for the preparation of polyesters and copolyesters as precursors for polyurethanes having a relative molecular weight of < 10,000.
11. Use of the polycondensation catalysts according to Claims 1 to 5 for the preparation of thermoplastic polyesters and copolyesters having a relative molecular weight of > 10,000.
12. Use of the polycondensation catalysts according to Claim 11 for the preparation of polyethylene tereph-thalate, polybutylene terephthalate, poly(ethylene 2,6-naphthalene-dicarboxylate), poly(butylene 2,6-naphtha-lene-dicarboxylate), poly(1,4-dimethylenecyclohexane terephthalate) and copolyesters thereof based on high homopolyester contents of at least 80 mol per cent.
13. Use of the polycondensation catalysts according to Claim 11 for the preparation of polyether-esters.
14. Use of the polycondensation catalysts according to Claims 1 to 5 for the preparation of completely aromatic or liquid-crystalline polyesters.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4443648A DE4443648C2 (en) | 1994-12-08 | 1994-12-08 | Process for the production of polyesters and copolyesters |
| DEP4443648.3 | 1994-12-08 |
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| CA2164805A1 true CA2164805A1 (en) | 1996-06-09 |
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|---|---|
| EP (1) | EP0716112B1 (en) |
| JP (1) | JP3442555B2 (en) |
| KR (1) | KR100372965B1 (en) |
| CN (1) | CN1069661C (en) |
| AR (1) | AR000293A1 (en) |
| AT (1) | ATE207094T1 (en) |
| BR (1) | BR9505694A (en) |
| CA (1) | CA2164805A1 (en) |
| CO (1) | CO4440535A1 (en) |
| DE (2) | DE4443648C2 (en) |
| ES (1) | ES2165404T3 (en) |
| TW (1) | TW388765B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA982924B (en) * | 1997-04-17 | 1998-10-09 | Akzo Nobel Nv | Filament-forming chain branced polyester and copolyesters |
| CA2293676A1 (en) * | 1997-06-10 | 1998-12-17 | Akzo Nobel Nv | Method for producing polyesters and copolyesters |
| WO2000024827A1 (en) * | 1998-10-26 | 2000-05-04 | Toray Industries, Inc. | Polyester composition, method for producing the same and polyester film |
| US6346070B1 (en) | 1998-12-25 | 2002-02-12 | Mitsui Chemicals Inc | Catalyst for polyester production, process for producing polyester using the catalyst, polyester obtained by the process, and uses of the polyester |
| EP1679332A4 (en) * | 2003-09-16 | 2010-03-24 | Mitsubishi Chem Corp | Process for producing aliphatic polyester and aliphatic polyester |
| JP4609386B2 (en) * | 2006-06-28 | 2011-01-12 | 堺化学工業株式会社 | Polycondensation catalyst for producing polyester and method for producing polyester using the same |
| PT3310835T (en) * | 2015-06-18 | 2022-09-20 | Basf Se | Method for producing a rigid polyurethane foam |
| CN110663685B (en) * | 2019-10-23 | 2021-10-12 | 扬州大学 | Mesoporous silica supported PPTE nano pesticide preparation |
| CN112280028B (en) * | 2020-10-26 | 2022-04-22 | 中国科学院青岛生物能源与过程研究所 | Method for preparing high molecular weight poly (butylene glycol) carbonate by catalyzing inorganic salt and Ti/Si composite material |
| CN113999379B (en) * | 2021-12-31 | 2022-03-15 | 江苏新视界先进功能纤维创新中心有限公司 | Titanium composite catalyst for polyester synthesis and preparation and application thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE579782A (en) * | 1958-06-20 | |||
| CH455290A (en) * | 1966-01-12 | 1968-06-28 | Inventa Ag | Process for the production of clear linear polyester with a high degree of whiteness |
| JPS4841949B1 (en) * | 1970-03-23 | 1973-12-10 | ||
| DE2214775C3 (en) * | 1972-03-25 | 1975-08-21 | Basf Ag, 6700 Ludwigshafen | Process for the production of polybutylene terephthalate |
| JPS5236189A (en) * | 1975-09-17 | 1977-03-19 | Teijin Ltd | Process for producing polysters |
| DE2811982A1 (en) * | 1978-03-18 | 1979-09-27 | Huels Chemische Werke Ag | METHOD FOR PRODUCING HIGH MOLECULAR POLY (ETHYLENE TEREPHTHALATE) |
| US4421908A (en) * | 1982-03-08 | 1983-12-20 | Celanese Corporation | Preparation of polyesters by direct condensation of hydroxynaphthoic acids, aromatic diacids and aromatic diols |
| FR2570077B1 (en) * | 1984-09-11 | 1987-05-29 | Rhone Poulenc Films | PROCESS FOR THE PREPARATION OF POLYESTER |
| DE3905911A1 (en) * | 1989-02-25 | 1990-08-30 | Basf Ag | NEW SS-METHOXYACRYLATES, THEIR PREPARATION AND USE |
| JPH086029B2 (en) * | 1989-10-11 | 1996-01-24 | 日本ポリウレタン工業株式会社 | Interior skin material |
| US5120822A (en) * | 1990-08-21 | 1992-06-09 | E. I. Du Pont De Nemours And Company | Polyester process comprising the addition of a tetraalkyl zirconate catalyst |
| JPH04301233A (en) * | 1991-03-29 | 1992-10-23 | Sony Corp | Optical pickup |
| DE4400300A1 (en) * | 1994-01-07 | 1995-07-13 | Akzo Nobel Nv | Process for the production of film- and fiber-forming polyesters and copolyesters |
-
1994
- 1994-12-08 DE DE4443648A patent/DE4443648C2/en not_active Expired - Fee Related
-
1995
- 1995-11-23 CO CO95055576A patent/CO4440535A1/en unknown
- 1995-11-28 TW TW084112665A patent/TW388765B/en not_active IP Right Cessation
- 1995-11-30 CN CN95119980A patent/CN1069661C/en not_active Expired - Fee Related
- 1995-12-01 ES ES95118905T patent/ES2165404T3/en not_active Expired - Lifetime
- 1995-12-01 AT AT95118905T patent/ATE207094T1/en not_active IP Right Cessation
- 1995-12-01 DE DE59509716T patent/DE59509716D1/en not_active Expired - Fee Related
- 1995-12-01 EP EP95118905A patent/EP0716112B1/en not_active Expired - Lifetime
- 1995-12-06 AR AR33452595A patent/AR000293A1/en not_active Application Discontinuation
- 1995-12-06 JP JP31798795A patent/JP3442555B2/en not_active Expired - Fee Related
- 1995-12-07 BR BR9505694A patent/BR9505694A/en not_active IP Right Cessation
- 1995-12-08 CA CA002164805A patent/CA2164805A1/en not_active Abandoned
- 1995-12-08 KR KR1019950047625A patent/KR100372965B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0716112A2 (en) | 1996-06-12 |
| AR000293A1 (en) | 1997-10-22 |
| DE4443648C2 (en) | 1999-01-21 |
| DE4443648A1 (en) | 1996-06-13 |
| KR960022680A (en) | 1996-07-18 |
| KR100372965B1 (en) | 2003-05-01 |
| CN1069661C (en) | 2001-08-15 |
| CN1124257A (en) | 1996-06-12 |
| JPH08208822A (en) | 1996-08-13 |
| JP3442555B2 (en) | 2003-09-02 |
| ATE207094T1 (en) | 2001-11-15 |
| BR9505694A (en) | 1997-11-11 |
| EP0716112A3 (en) | 1996-10-09 |
| EP0716112B1 (en) | 2001-10-17 |
| DE59509716D1 (en) | 2001-11-22 |
| ES2165404T3 (en) | 2002-03-16 |
| TW388765B (en) | 2000-05-01 |
| CO4440535A1 (en) | 1997-05-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |