DE2202476A1 - Process for making a polyester and catalyst for the process - Google Patents

Description

HOMSEN

PATENT ADVERTISER TS OFFICE IEDTKE - DÜHLING TEL. (Οβ 11) 530211 TELEX: 5-24303 lopat

530212

PATENTA N WALTE Munich: Frankfurt / M .:

Dipl.-Chem. Dr. D. Thomsen Dipl.-Ing. W. Welnkauff

Dipl.-Ing. H. Tiedtke (Fuchshohl 71)

Oipl.-Chem. G. Buehling
Dipl.-Ing. R. Kinne
Dipl.-Chem. Dr. U. Eggers

8000 Munich 2

Kaiser-Ludwig-Platz 6 January 19, 1972

Imperial Chemical Industries Limited London (Great Britain)

Process for the production of a polyester and catalyst for

the procedure

The invention relates to the production of high po? ynaerer "polyesters divalent feroiaatischeii of dicarboxylic acids ^1V ti alcohols.

Po lyes': 3r of aromatic-m dicarboxylic acids and dihydric alcohols are known

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Oral agreements. In particular, through Τ · Ι · (οη. Require a sharp statement Potttcheck (Munich) Account 11 * 874 Dresdner Benk (Munich) Account 5563 709

Usable thermoplastics which can be processed from films » Fibers and molded parts with a favorable combination of physical and chemical properties« Examples of such polyesters include those made from terephthalic acid or 1,2-di (p ~ carbo: x _< 7phenoxy) Ethane and ethylene glycol or 1,4-butanediol or I ^ -dihydroxymethylcyclohexane have been made, mention o Many processes for making these polyesters have been proposed. In general, however, they go through the formation of the bite-star of the aromatic diacid with the dihydric alcohol and the polycondensation of this intermediate product from high-polymer polyester with elimination of the dihydric alcohol by heating the melt with reduced dimness Making dicarboxylic acid with a dihydric alcohol (commonly known as transesterification). It is also possible to form the bisester by direct esterification of the dicarboxylic acid with the dihydric alcohol.

Thus the very desirable characteristic properties of the high polymer polyester of Dihydric alcohols and aromatic dicarboxylic acids are not changed, weakened or lost

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be _t is usually preferred that the l> olykonderisierbare material consists essentially of only one or more Biseßtern aromatic dicarboxylic acids with dihydric alcohols is ". However, the presence of a small amount of another polycondensable material can be taken in. Purchase _t when z ^ B "that aims to improve Anfärbesrkeit, Sun ZCB _o Up" and about 5 mol of the dihydric alcohol part of the bz * fi four diester by at least Another polyhydroxyl compound and / or up to about 5% 1% of the aieomatic dicarboxylic acid can be replaced by at least one further dicarboxylic acid. BJs to about 5 Mo 1% of the polycondensable mixture may also consist of other mono- or substances polyfunktioneIlen _t z, Bο monohydric alcohols and / or their esters with. the dicarboxylic acids * amines and / or diamines and or their amides with the dicarboxylic acids, amino alcohols and / or their condensation products with the dicarboxylic acids, and / or amino acids, hydroxyl acids, lactams and / or lactones and / or their condensation products with the dicarboxylic acids and / or with the dihydric alcohols, but it is generally preferred that at least 85 mol%, preferably at least 95 mol% of the polycondensable mixture

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from one or more bisesters of the aromatic Dicarboxylic acids with sweiwertigep. Alcohol drinks ",

Usually these procedures, in particular the polycondensation, catalyzed using various types of metal compounds »

It has now been found * that it is beneficial * when the metal becomes bound to an inert substrate. As advantages are the change in catalytic For example, see properties of the metal and the improved quality of the product. So they usually result very active catalysts based on titanium but often yellowish products «, when using titanium compounds in accordance with the invention A less colored product is obtained. Another advantage of the invention Catalysts consists in the fact that they are insoluble in the reactants of the polycondensation are and can be operated as a solid catalyst layer with a large particle size, the γόη flows through the reactants and products.

The catalysts for the process according to the invention are considered to be marked by

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Structures of the formula Ϊ

Vm

where Z is the surface of a substrate

inorganic material means, M a metal atom with the valence η However

no titanium atom represents »X is a single bond or a divalent bond

Represents a group, in particular -O-, m represents an integer from 1 to n-1

and
L represents other ligands that the remaining

Validity requirements of the KetalXatems M

fulfill.

The inorganic material used as the substrate is essentially inert apart from an asur bond. katalytisehen genus necessary surface active! tat _o Examples of suitable materials can be silica j ionerde, magnesia, Aluminiums.il ikat ", boron phosphate, zirconia, mixtures mention this and related substances"

M is preferably a metal dex * groups IXA bis VIII or groups HB to VB. In the sense of the

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In the present invention, germanium is regarded as a metal ο magnesite, calcium, germanium, tin, Antimony, zinc, cadmium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, iron, cobalt, Nickel, cerium and lanthanum have all proven to be effective The same supported catalysts have proven their worth for this process. Metals that are otherwise colored polymers if they are not bound to a carrier, they often lead to colorless polymers, if they are formed as supported catalysts and these supported catalysts from the polymer melt to be filtered »

The preferred ligands L are hydroxyl, oxyhydrocarbyl, Hydrocarbyl ligands, hydroxyl-substituted derivatives of the Qxyhydrocarbyl- »and Hydrocarbyl ligands, as well as halide ligandsο Of these, halide groups are unfavorable if that Process should take place in a metal autoclave, since corrosion problems can occur " When using glass apparatus, however, halide ligands are readily permitted »inevitable set the hydrocarbyl ligands during the polycondensation in oxyhydrocarbyl ligands or their derivatives substituted with hydroxyl groups, you can use alcohols to achieve this Conversion before the start of the polycondensation

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implemented verderic halide ligands can on exchanged in the same way. Preferred alcohols for this purpose are lower alkane mono- or diols, like ZoBo methanol, ethanol and ethylene glycol

The catalysts for the process according to the invention can be produced via various reactions, with typical starting materials being the have the following structures:

Z-OH Z OR Z Y Z-- -H

II III IV V

where Z is again the surface of the carrier material

represents
R is a hydrocarbyl group, especially one

Represents an alkyl group, and Y represented a halogen atom

These starting materials have a large number of reactive groups only bound to the surface. “Such substances can be identified with ζ « Β. react with a transition metal hydrocarbyl complex, although most of the carrier material is chemically inert and only serves as a carrier. The carrier material is regularly activated by heating it to 200 to 700 ° C before use ο

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In a first reaction for the preparation of suitable catalysts for the process according to the invention the starting material II comes into contact with a hydrolyzable compound of the metal in question M brought. If the metal compound is inconsistent in the presence of water, it normally can with the hydroxyl groups on the surface of the carrier material react. Metal compounds with halide, oxyhydrocarbyl or organometallic ligands are generally suitable, the latter one or more metal-carbon bonds of the iT- or f-type or an intermediate type ο

Examples of suitable metal halides include titanium, zirconium or hafnium tetrachloride or tetrabromide, vanadium tetrachloride or oxychloride, Tin (II) or tin (IV) chloride or bromide, antimony trichloride and germanium tetrachloride or - mention bromide »

As examples of suitable metal oxyhydrocarbyl compounds you can use germanium, titanium, zirconium or hafnium alcoholates, e.g. the isopropylates and glycolates, to mention α

Examples of suitable organometallic compounds include tetra (W-allyl) titanium and zirconium

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ti;

or -hafnium, 5etra (W * -methallyl) titanium or - »zircon, Tetra (benzyl) zirconium or titanium * iTetra «1- (methylene ~ 1-naphthyl) zirconium or titanium, tetra (trimethylsilylmethylene) aircon, Di (cyclopentadienyl) manganese, di (alkyl) zinc and trialkyls of aluminum.

Metal compounds with mixed ligands of 0 _o a _& kind may also be used, for example, tri (TT'-allyl) -zirkon or-titanium chloride, bromide or iodide and the corresponding ΤΓ-MethaHyl- or Benzylverb indungenο

It is not absolutely necessary to be at the production of the catalyst is based on the already existing carrier material, since this is also the case can be formed after the introduction of the metal. For example, a trialkoxysilane that has the fourth bond connected to the metal atom can be hydrolyzed to form a silica-like Material with a high metal content is created.

A reaction is performed with one or more hydroxyl groups of the Seisi coordinated so ürägermaterials to form one or more bonds X. In all of the above compounds, X represents the radical ~ O ~. The quantities of the carrier material and the metal compound are to _t

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that most of the hydroxyl groups are converted, where, each heball atom with the (support material over 1 to n-1 bonds of type -0- are connected. The number of hydroxyl groups on the surface the carrier material can be determined by treating the material with methyl magnesium bromide and the volume of methane released is measured. If the metal compound is colored, then it is It is also possible to add a solution of this compound to a suspension of the carrier material until you can see that the color of the metal compound always remains in the solution. This indicates that no more metal compounds react with the carrier material ο

When using an organometallic compound, the solution method is a good control of the reaction bevorzugtα zweckmäsig used to low temperatures (below 0 ⁰ C), in order to avoid premature decomposition of the organometallic compound. The carrier material is also expediently freed from adsorbed water, for example by heating, so that only the superficial hydroxyl groups remain. When using organometallic compounds, the solvent and the suspension medium should be anhydrous.

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Some metal compounds can (with the hydroxyl group of the carrier material) are implemented in the vapor phase. This possibility can be used for the purpose " massively realize that the steam together with an inert gas, much like nitrogen, over the heated substrate is passed. This method is suitable for some transition metal halides, EoB. Titanium halides, as well as for Germaniuntetrachlor id <>

Another useful method is that a slurry of the metal compound in Ethylene glycol brought into contact with the heated carrier material, ZoBo silica or alumina willo

In an analogous manner, catalysts can be prepared from starting materials of structures III and IV, which can themselves be obtained from starting materials of the formula II by reaction with other alcohols (including diols) or with halogen Contact with e.g. Germanium tetrahalide can be produced with the formation of a single bond to the germanium atom _c

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2202A76

Before the catalytic compositions prepared in the manner described are measured as a catalyst in Inventive ~ used method _T can be further reacted with alcohols or water to convert all the ligands L in Qxyhydrocarbyl- or Hydroxylligande "Such a measure is favorable especially in the presence of halogen atoms that would otherwise cause metal autoclaves to corrode. The catalysts prepared in this way have the structure Z - Om - M - (Oβ) n - m (VI) in which Z, m and η have the meanings given and R is a hydrogen atom or a lower alkyl group or its hydroxyl-substituted derivative having 1 to θ carbon atoms >

Examples of suitable alcohols include methanol Mention ethanol or isopropanol.

Instead of or in addition to treatment with the above monovalent alcohols can dihydric alcohols, * be used thylenglykol _t Ä particular.

According to the invention, these catalysts can be used for the production of polymers from polycondensable Mixtures are used that

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mainly or entirely from bisesters of aromatic dicarboxylic acids with divalent ones Alcohols exist »

The invention can be applied with particular advantage to the production of polyesters in which the dicarboxylic acid consists of at least 80 Mo 1% terephthalic acid. Other aromatic But acids can also be used »As examples of other aromatic dicarboxylic acids one can use isophthalic acid and binuclear dicarboxylic acids, ZoB. those of the formula VII

HOOC COOH

- A ^ V * V VII

Mention, in which A is a single bond or an alivalent atom or a group free of Zerewitinoff water hydrogen atoms, aSoB- -0-, CR ¹ R, ~ S- _t -SO-, -CO-, -SO ₂ -, ~ N (Hydrocarb: / l) - and ~ O (CH _{2) n} O- _t, wherein R and R each represents a hydrogen atom or οine monovalent hydrocarbon group or üus & mmen a divalent Hydrocarb.fl ^ uppe _t such "B, wherein -. (CH ₂ ), .- and η represents a positive integer / on at least 2 »Possibly 1- * όηϊί ο ein oder- iiuh ^ ore Uta- an Isii Köhlern.tr> :. Yfit; anieλ

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dee core or _o the cores of these, a · "or izweikernige" acids bonded hydrogen atoms are replaced by other monovalent atoms or groups which are inert in the reaction mixture, eg "halogen atoms, nitro groups, hydrocarbyl Zob _o alkyl groups, and Hydrocarbylosygruppen, z.Bo alkoxy _groups? to be replaced =

Examples of dihydric alcohols that can be used are α, ω-polymethylene glycols, in particular with the structure HO (CH ₂ J _x OH, where χ means 2 to 10, branched aliphatic diols, sB 3t3 »5 ~ trimethylhexane ~ diol- Mention (1 _t S) and neopentyl glycol, and alicyclic diols, for example “B _o 1,4-M (hydroit3rmethyl) cyclohexane and 2.2 _t 4,4-tetramethylcyclobutanediol (1, 3)" , 4) and especially ethylene glycol.

It is an advantage of the present invention that the catalyst mass is essentially insoluble in the monomers and, in the polymer Isto So, the catalyst can be filtered off from the polymer melt before further treatment. Tons of purpose, it is also when the catalyst particles or granules of the order of 0.5 bie ^ O mm diameter pressed and used in this form for ease der.r.ön distance ..? At such! 'One-piece catalyst kaüi as fixed

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Catalyst layer are used, with the polyaerbiltienaen substances through this layer one or more times in a discontinuous or continuous processes «For this purpose, clay is particularly well suited because it can be processed into abrasion-resistant particles.

_{The amount of} catalyst used Ϋ calculated as percent by weight of metal based on the total weight of the dimethyl ester of terephthalic acid that is treated in the process, or the corresponding ester when using other acids, can be in the range before. 0.0001 to 10%, preferably O _1005-2%, lawn ".

If the catalysts are used in these concentrations, rapid conversions can be achieved *, In addition, many catalysts were used observed according to the invention that the clarity of the Polymeiisatschitelze is better than that of the high molecular weight polyester made after many processes using conventional catalyst systems based on e.g. metal acetates and metal oxides without stabilizing means are obtained ^ Man can also use large amounts of catalyst

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A particular advantage of the present invention is that titanium compounds are used can »You can also use simple titanium compounds, but the discoloration of the products too large. However, the supported catalysts according to the invention result in a substantial improvement the color achieved with the same high catalyst activity

For the production of the bis-glycol ester or ,, of the oligomer and for the subsequent polycondensation, the usual reaction conditions can be used are used »Other additives, ZcB, substances for matting, stabilizing, pigmenting and / or other types of modification of the high molecular weight polyester obtained, can before, during or are added after the implementation in question "

In the following the invention is explained in more detail by means of examples, all parts being by weight are related o

Example 1

a) Preparation of the catalyst Y-alumina with a particle size of 17 to 25 millimicrons (20 parts) was 2 hours under

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Nitrogen heated to 500 ^° C. It was then cooled to room temperature under nitrogen, kept under vacuum for 5 minutes and then brought back to atmospheric pressure under nitrogen «

The alumina support was then suspended in toluene (100 parts) and treated with a solution of Tetra (benzyl) zircon (3 parts) mixed in a mixture of toluene (30 parts) and decalin (120 parts) »

After settling of the solid, the liquid was ebgessogen with a syringe _t whereupon the brownish crude zirconium-supported catalyst was dried under vacuum vrurde "

The dry material was then treated with oxygen-free ethylene glycol (200 parts) with stirring.

Polycondensation

1,500 parts of a bis (ethylene glycol) e3te: ps of terephthalic acid prepared by direct esterification (Direct esterification monomer) were placed in a glass-lined autoclave. Of the Autoclave was then heated to melt the contents Fhenyl (methyl) phosphinic column (2 quotes) hi;> was added and the mixture wmvle with the

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Slurry of the catalyst in glycol, shown in the manner described, was added. The polycondensation was then carried out at 80 ^° C. and 0.1 to 0.3 Torr for 3 hours.

Example 2

a) Preparation of the catalyst

Silica (MANOSIL having a particle size of 12 to 50 millimicrons) (27 parts) was placed in an oven at 400 to 500 ⁰ C for 3 to 5 hours lasig in a nitrogen stream calcinierto on the active carrier material was added titanium tetrachloride as a vapor in a nitrogen stream at 300 ⁰ C for 2 _{t for} 5 hours and then nitrogen alone for 48 hours while cooling to room temperature »

The supported catalyst was treated under nitrogen with 100 ml of absolute ethanol to hydrolyze the halogen atoms located on the surface, whereupon the alkylated supported catalyst obtained in this way was ^{dried at 100 °} C. under vacuum _{or the like}

One part (22 parts) of the catalyst was heated with ethylene glycol (100 parts) for 3 hours under reflux and stirring and then filtered off, washed with ethanol and dried at 100 ° C. under vacuum = the catalyst contained 1

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b) polycondensation

A stainless steel autoclave was prepared for polycondensation

Direct solidification monomer (600 parts) and then 1 _r 668 parts of the catalyst according to 2a were introduced into the autoclave. The amount of titanium was 0 _T 005% by weight of metallic titanium as based on the Dime thy1terephthalat bereohnet _β

The closed autoclave was cooled to 0 _t 1 to 0.3 Torr and 1.5 hours at 280 ⁰ C heated "After cooling, the colorless product had an intrinsic viscosity of 0.77»

c) To compare this supported catalyst with a catalyst not supported by a support material the procedure according to Example 2b using titanium tetraisopropoxide (0.143 parts «0.005% by weight Ti based on dimethyl terephthalate) repeated. The product obtained had a deep orange color »

d) For comparison, 1.668 parts of activated silica (HANOSIL) were used as the polycondensation catalyst used ο After 1.5 hours in a container off

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stainless steel, however, there was no polymer "

Example 3

a) Preparation of the catalyst

Silica (AEBOSIL having a particle size from 15 to 20 millimicrons) (30 parts) was heated for 2.5 hours in a dry drying Stickstoffstro »to 300 ⁰ C.

The remaining, at the surface hydroxyl groups have been characterized methylated _t that of a stream of nitrogen entrained methanol vapor for 1.5 hours passed over the silica at 39O ° C »excess methanol was purged 1 hour by a stream of dry nitrogen.

The oven was then brought to 750 ° C and the silica was left at that temperature for 70 hours

—2
held under a vacuum of 10 torr, on the

The surface of the silica remained jSi «= H groups and some £ Si-OH groups _{or the like}

The silica prepared in this way vir ^ .e to: 0? ° 0 heated and carried away by nitrogen Germanium tetra chloride vapor treated for 2 hours Excess Germanium chloride was removed

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purged with nitrogen *

Pas residual chlorine was (χ 2 200 parts) _s wherein Aikoholyse caused by the silica with absolute A'thanol located on the germanium .Sthylatgruppen instead chlorine atoms "

After filtering, the silica was dried. It contained 0.58% Ge ₀

b) polycondensation

The polycondensation of 600 parts Direktveresterungsmonomer (NaOH catalyst) was carried out at 280 ⁰ C without stabilizing agent, wherein as the catalyst, 11.5 parts of the germanium-containing supported catalyst (Doho 0 * 067 parts Ge) can be used. After 1.5 hours, a polymer with an intrinsic viscosity of 0.64 and a pale leather-yellow color (because of catalyst granules that could be filtered off from the melt) was obtained »

Example 4

a) Manufacture of the catalytic converter

SortierS ^ese ^ ^ RDE (30 parts) was u with a particle size 295-500 abortion adsorbed water for 2 hours at 300 ⁰ C in a

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Nitrogen stream heated »The remaining hydroxyl groups on the surface were made by the fact that methanol vapor entrained by a nitrogen stream was passed over the silica at 50O ⁰ C for 1.5 hours. The methylated clay was then ^{kept at 700 °} C. for 72 hours, with Sl — H groups and some Si — OH groups remaining on the surface

The prepared silica was heated to 300 ⁰ C and treated 1.5 hours Geraianiumtetrachloriddampf using nitrogen as a carrier gas. The excess GeCl. was flushed out with nitrogen. The remaining chlorine was removed by refluxing the silica with ethyl glycol for 2 hours, with glycolate groups formed on the germanium instead of chlorine.

After filtering, the silica was dried. It contained 2.05% Ge ₀

Polycondensation

The polycondensation of the direct esterification monomer (600 parts) was ^{carried out at 280 °} C. without stabilizing agents, with 3.27 parts of the carrier containing 2.05% germanium as the catalyst.

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catalyst (doh. 0.067 parts Ge) were used o After 1.5 hours, a polymer with a Grens viscosity of 0.7 and a good color was obtained. However, the polymer contained black catalyst particles. These could be ^{filtered off from the molten polyester at 280 °} C. using a glass sinter with porosity 1. This gave a polymer with a good color, which had been completely freed from germanium and had a limiting viscosity of 0.68 "

Example 5

a) Preparation of the catalyst

MANOSIL (particle size 15 ms 20 millimicrons) (20 parts) was prepared by heating at 300 ⁰ C for 1.5 hours in a stream of nitrogen dried by heating at 700 ° C for a further 1 _r 5 hours, the powder was rapidly quenched in germanium tetrachloride "After pumping of the excess GeCl at room temperature, the solid was refluxed for 2 hours with ethylene glycol (250 parts). The solid was dried after filtering off the excess ethylene glycol. It contained 15-5% germanium *

b ensation) Polykond

The polycondensation xiurde from 600

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Parts Birektveresterungsmonomer without stabilizing agents using O _t 125 parts of the above catalyst carried out _o The reaction was conducted at 280 ⁰ C for 1 '5 hours in a steel autoclave. Polyethylene terephthalate was obtained with an intrinsic viscosity of O ,, 75 and a very good color »

Example 6

a) Preparation of the catalyst

26 parts of MANOSIL (particle size 15 to 20 myx) were heated ^{to 300 0} G under vacuum for 2 hours.

84.8 parts of a toluene solution of titanium tetrachloride (with 1.523 parts of titanium tetrachloride) were in a round bottom glass flask which had been flushed well with nitrogen. The solution was then with 50 parts anhydrous *, oxygen-free Toluene diluted ο

The activated silica was poured into the titanium tetrachloride solution under nitrogen. That Mixture was stirred and then flushed with nitrogen overnight. Then 100 parts oxygen-free ethanol mixed with the supported catalyst, whereupon the mixture was stirred for 3 hours was »The catalyst was then filtered off and

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washed with toluene, dried and then refluxed with distilled water for 1 hour ο The mixture was left to stand overnight, then filtered the product, washed it with distilled water, and dried it under vacuum C for 4 hours.

The catalyst contained 1.93% titanium «

b) polycondensation

Direct esterification monomer (600 parts) was polycondensed with 1.2 ^ 5 parts of the above catalyst (corresponding to 0.0050% Ti based on dimethyl terephthalate) in a stainless steel autoclave. A fiber-forming polyester with an intrinsic viscosity of 0.72 was obtained 1.5 hours at 280 ^° C. and 0 _s 1 to 0.3 Torr.

Example 7

a) Manufacture of the catalyst

10 parts of alumina as 1/8 "tablets were heated for 1.5 hours to 500 ⁰ C in a nitrogen stream Dampffiormiges titanium tetrachloride was passed 2 hours by the tablets at 300 ⁰ C, after which the

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Tablets were perfused over Nacbt with nitrogen while maintaining the temperature at 23 ⁰ C would fall down Then, the tablets were erhitst 2 hours with 200 parts säuerstoffreiem ethanol under reflux and nitrogen, decanted whereupon the liquid and the process was repeated. Finally, the tablets were erhitst 2 hours 200 parts of distilled water under reflux, filtered, washed with distilled water and dried at 140 ⁰ C under vacuum. The catalyst contained 0.87% titanium.

b) polycondensation

1 part of the tablets was 2.5 hours with 50 Share ethylene glycol under reflux and stick fabric heated, whereupon the glycol was poured off and the "wet" tablets were used as a polycondensation catalyst. In apparatus from Glass obtained a good quality polyester, and the tablets could easily be made from polyester could be filtered out.

Examples 8 to 28

a) Preparation of the catalyst

This procedure is described in three parts:

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1o activation of the carrier material; 2r implementation with the metal genus; 3 ο Post-treatment of the Eataly sator-s η

1 Activation of the carrier material

1.a) Silica (VN3 MANOSIL variety with a TeilchengrSsse 15-20 mu) for 2 hours at 0.1 torr to 200 ⁰ G was heated under nitrogen and cooled under nitrogen anschlieesend η The activated material was then stored under nitrogen

1ob) silica (^ particle size 295 to 500 u) was ^{heated to 4CX) 0} C under nitrogen at 1 atmosphere for 3 hours o The product was cooled under nitrogen or used in situ in the following stage of the process «

1oc) Powdered alumina was heated for 2 hours under nitrogen to 500 ⁰ C, and then cooled under nitrogen

1 "d) Powdered zirconium oxide was ^{treated as with aluminum oxide but at 300 0} C"

1, e) clay tablets (3.2 mm type 000-3P, manufactured by Ketjens in Amsterdam)

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according to 1oc) prepared _o

1.f) Powdered magnesium oxide was ^{treated like aluminum oxide but at 30O 0} C »

2. Implementation with metal compounds , 2 _o a) D ^ ampfphase implementation

Volatile metal compounds, such as titanium tetrachloride, can be reacted with the hydroxyl-containing carrier material as follows. The volatile, liquid metal halide is flowed through by nitrogen, the entrained vapor being passed over the carrier material for 2 to 3 hours, since it was heated to the temperature given in the table. After cooling under nitrogen, the product is treated with solvent in the whiteness described below _{or the like}

2.b) reaction in he d Flü lar phase The activated carrier was covered with water and oxygen-free solvent and then treated by one of the following two methods:

I) When using a metal alkenyl or aryl, ζ «Β _ο titanium tetrabenzyl, the

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Carrier material is cooled to -30 ° C and daim treated with the organometallic compound "A solution of the organometallic complex was Depending on the number of -OH functional groups added to the support material until an excess was present _o Then, the mixture was stirred for 15 Hinuten, whereupon the above liquid has been withdrawn *

Xl) When using a metal halide, this was oxygen-free in the relevant Solvent, ZoB "toluene, dissolved and then heated with the support material under reflux and nitrogen for 2 to 3 hours

2.c) immersion process

The support material was activated in the manner indicated and heated to 300 to 700 ⁰ C. At this temperature it was then quickly entered into a solution of the metal halides or alkoxides under nitrogen, this solution room temperature had "The excess metal compound was removed by washing or vacuum filtration removed «

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- ⁵⁰ "

5, post-treatment of the catalyst After the reaction with the metal compound was the supported catalyst was washed with an inert solvent in order to remove any unreacted metal compound then with a hydroxyl-containing solvent treated under nitrogen at reflux temperature for 2 to 3 hours o In some examples, used several solvents one after the other

The symbols used have the following meanings:

VT water

A * G ethylene glycol

JC ethanol

The catalyst was then ^{dried at 200 °} C. and stored under nitrogen.

B) polycondensation (PK)

The polycondensation of the bis (ethylene glycol) ester the terephthalic acid (300 parts) was in one with QIa? lined autoclave lit stirrer, Heating and ventilation openings carried out ο The ester produced by direct esterification of terephthalic acid was introduced into the autoclave and heated. The polycondensation was

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carried out at 285 ° C and 0.5 Torr for 1 to 2 hours «In some experiments, 0 _s 5% by weight of titanium dioxide was added as a matting agent»

The polymer obtained was collected and filtered free of the catalyst »The limiting viscosity (G-V) was in each case in 1% strength by weight solution in redistilled o-chlorophenol determined at 25 ° C

The results are shown in the table below remove c

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Bepl. Support material Hetallverbin- specialist treatment- wt% catalyst- P-K- G-V

and activation and ommitation of metal in abundance of time

"Method set" Catalyst Catalyst (parts) (min)

8 1.a _{TiCl 4} 2.a X XO 1.44 2.8

at 300 ⁰ C

9 1.b _{TiCl 4} 2.a X XO X 0.34 3.8 ^ at 40O ⁰ C

co 10 1.b Oe (OCHgCHgOH) ₄ XO 0.67 10.0

2 2.c at 700 ⁰ O

Ϊ 11 1.b TiCl * 2.b.II X XO V 1.93 1.25 · ■ * *

- »12 1.e Ti (p-methyl-Xo X 0.66 1.0

5 beniTl) 4 »

* " 2, bI

13 Lc OeCl ₄ 2. c XO 5 * 84 1.15

at 400 ^° C

14 1, c SnCl ₄ 2.b.II V 7.16 1.06

15 Lc SbCl, 2.boII W 11.99 2.00

16 1.d Oe (OCHgCHgOH) ₄ XG 0.06 3.00, 2. c at 300 ⁰ C

$ 17 1-f ^{Τ1 (31} 4 2.b.II XG 2.27 1.4

80 0.65 I. 90 0.60 I. 90 0.63 90 0.71 O 90 0.77 90 0.65 90 0.71 90 0.61 90 0.57 90 0.62

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209835/1164

Claims (2)

- 3 * claims fyi Process for the production of a polyester, according to which a polycondensable material, which consists of at least 85% by weight of a bisester of an aromatic dicarboxylic acid with a dihydric alcohol, is heated under conditions suitable for a polycondensation, characterized by the use of a catalyst of structure 1 wherein Z represents the surface of an inorganic carrier material other than titanium dioxide; M is a metal with valence η; X represents a single bond or a divalent group; m represents an integer from 1 to n-1 and L more ligands that the remaining value needs of the metal "saturate" 2. Catalyst for polycondensation according to claim 1, characterized by the structure 209835/1164 - 55 - where Z is the surface of an inorganic carrier material ^ in addition to titanium dioxide; II is a metal of valence η; R represents a hydrogen atom or a lower alkyl group en or the / hydroxyl-substituted derivative with up to 8 carbon atoms and m represented a whole number from 1 to n-1 209835/1 184