DE1595270A1 - Process for the production of copolyesters - Google Patents

Description

Patent attorneys

Dr. W. Schalk, Dipl.-Ing. P. Wirth
Dipl.-Ing. G Donnenberg

Dr. V. Schn.KJ Kowarzik Alpine Chemische Aktien-Dr. P. Wemhold, Dr. D. Gudel Society
6 Frankfurt / M., Gr. Eschenheimer Str. 39 _{,: u} £ _s tein / lirol / ust reach

Process for the production of copolyesters

It is known that polyester, the fiber or film-forming property ' own shafts by polycondensation of.

(a) aromatic dicarboxylic acids in which the carboxyl groups . are separated from one another by at least 2 carbon atoms, ■ their low molecular weight esters, especially alkyl esters with.

1 -: ^ C atoms, or other polyoster-forming derivatives or • Mixtures of these compounds with

(b) Diols of the general formula

KO - (CY ₂ ) _n - OH (I)

or to produce mixtures of these, woijßi. η is an integer

• from 2 to 10 and Y is hydrogen or low molecular weight alkyl, ' in particular with 1 to 4 carbon atoms.

It has now been found that new fiber- and film-forming copolyesters with particularly valuable properties are obtained if the aromatic dicarboxylic acids mentioned above under (a) or their polyester-forming derivatives or mixtures thereof with (b) diols of the formula (I) or mixtures from such diols with the addition of (c) small amounts of olefinically unsaturated

• th dicarboxylic acids, whose polyester-forming derivatives or

mix out. polycondensed them.

■ " ■ 90988A / 1701

LKJ documents -, -. N. , "Ι" .i 2 Ur. I sentence 3 d «· Change« «··, v.4. 9.1967)

Preferred aromatic dicarboxylic acids (a) are terephthalic acid, Isophthalic acid or naphthalene-2,6-dicarboxylic acid and mixtures thereof are possible and as low molecular weight esters of these acids are preferably the dimethyl esters, of the diols (b) Ethylene glycol is particularly preferred. Among olefinically unsaturated Dicarboxylic acids (c) are dicarboxylic acids with at least one olefinic -C = C double bond, e.g. maleic acid, Fumaric acid, citraconic acid, mesaconic acid, itaconic acid, Cyclohexene (2) dicarboxylic acid (1,4) or 4-carboxy cinnamic acid.

It is often very beneficial to add one or more Dihydroxy compounds (d) of the formula

(II)

and or »or one or more diols of the formula

H (0CH ₂ CH ₂ ) _a 0 - <^ A \ _ R - / 7X-O (CH ₂ CH ₂ O) ₁ JH (III)

to use. In the formulas (II) and (III), R is the direct one Bond or a group of the formula

-C-, -CH ₂ CH ₂ -, -0-, -S-, -SO ₂ -, -CO- or -NX-, X · "·

X is hydrogen or a low molecular weight, optionally sub-

9098 8 ^ / 1701

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structured alkyl with

preferably up to ^ carbon atoms, a an integer from 0 to 10, b an integer from 1 to 10 and A and B rings optionally containing further substituents. A particularly suitable compound of the formula (II) is 2,2-BiS- ( ¹ J -'-hydroxyphenyl) propane and of the formula (III) the 2,2-bis- £ 4 '- (2 "-hydroxy. ethoxy) -pheny IJ -propane. · ■

The diols (b) are generally used in excess, based on the aromatic dicarboxylic acids (a), for example, as is customary in the production of polyethylene terephthalate, 2.2 to 6 mol of diol per 1 kol of dicarboxylic acid. The olefinically unsaturated dicarboxylic acids or their polyester-forming derivatives (c) are used in terms of up to 3 mol, in particular 0.1-1 mol, based on aromatic dicarboxylic acids. The dihydroxy compounds (d) and the diols (e) are used with particular advantage in Kengen up to 40 Mo 1 $ and for the production of fiber ^! and film-forming condensates, preferably from 2 to 15 ViOl ¹ Ji, based on the amount of aromatic dicarboxylic acids used. For the production of injection molding and extrusion plastics, a higher content, for example from 10 to ho ^ MoI advantageous.

The new copolyesters are used in the manufacture of aromatic polyesters obtained in the usual manner, for example by adding terephthalic acid or a mixture of terephthalic acid and isophthalic acid or their low molecular weight DIalkyl esters, ethylene glycol in excess and up to 1 M

9 0 9884/1701 bad ORIGINAL

an olefinically unsaturated dicarboxylic acid or its low molecular weight dialkyl esters, based on aromatic ones

* Dicarboxylic acids, polycondensed with exclusion of oxygen and in the presence of esterification catalysts and optionally stabilizers. The reaction proceeds in 2 steps, and that is condensed in the first stage, preferably at atmospheric or superatmospheric pressure and temperatures up to 27Q ⁰ C and in the second stage under reduced pressure and at temperatures of 250 to 300 ⁰ C and insbesonere 270-280 ⁰ C. By using these reaction temperatures during the reaction times customary for the production of linear polyesters containing terephthalic acid, it is ensured that the olefinically unsaturated dicarboxylic acids react with crosslinking or branching. The esterification catalysts used can be, for example, oxides of the metals manganese, cobalt, zinc, lead or cadmium or the salts of these metals of boric acid, phosphorous acid, phosphoric acid or low molecular weight aliphatic carboxylic acid, preferably with 1 to 6 carbon atoms, e.g. manganese tetraborate, cobalt acetate, Zinc oxide or blel oxide. Organisehe and inorganic phosphorus veinings ^ «they e.g. Trfpheny / liihosphli * 3ΊΊ-

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The copolyesters obtained in this way are characterized by high • Melting points, good crystallizability, light color and good mechanical properties. As a special Characteristic they show one from the concentration of the olefinically unsaturated dicarboxylic acid dependent branching. and / or cross-linking of the polymer chains. This will be the performance properties and in particular the mechanical properties of the products, e.g. strength, elongation and elasticity Behavior ,, improved. The copolyesters can be processed in the usual way, e.g. by directing the melt or after blending with a copolyester of others Composition processed into threads, wires, films, granules or other shaped bodies. Pigments can be added here e.g. carbon black or inorganic or organic pigment dyes, furthermore optical brighteners, matting agents, like titanium dioxide or silicon dioxide, or plasticizers. These Additions can also be made before or during the polycondensation? reaction can be inflicted. "

In the following examples, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius. The "intrinsic viscosity" was determined in a solution by. 1- _; g polyester in 100 ml of a mixture

Phcenpl and Tetraehlorät-han owned. - - * "

BADORlGiNAL 909884/1701

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Example 1

A mixture of 500 parts of dimethyl terephthalate, 390 parts of ethylene glycol and 2 parts of dimethyl maleate is in the presence of 0.35 parts of zinc oxide and 0.17 Parts of triphenylphosphine are heated with stirring under oxygen-free nitrogen. Distill within 2 1/2 hours Methanol and ethylene glycol at temperatures up to 246 ° above. Stirring is then continued at 0.2 to 0.5 mm Hg pressure and at temperatures between .274 and 276 °. Receives after 2 1/2 hours one one. Copolyester that has an intrinsic viscosity of 0.62 and melts at 257 to 260 °. The product can be spun very well into practically white fibers that can be cold-drawn and have excellent mechanical and elastic properties.

Example 2 . . -.

A mixture of 500 parts of dimethyl terephthalate, 390 parts of ethylene glycol and 1.9 parts of dimethyl pumarsate is in the presence of 0.35 parts of manganese tetraborate and 0.17. Share triphenylphosphine under pure nitrogen and heated with stirring. Methanol "and ethylene glycol distill over within 1 3/4 hours at temperatures up to 2βΟ °. Then in vacuo under a pressure of 0.2 mm Hg. and at temperatures between 27 °" and 276 * ^? ^ . eitergerührV Nacif * 4 1/2% tüiiöen ^ ^{"^} ernält iüri ¹ a copolyester having an intrinsic viscosity VOEN ^" ^ 0.65 uM a melting point of 259-260 °, AEE £ excellently

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to cold-stretchable fibers with very good textile properties lets spin.

Example 3

A Geraisch of 500 parts of terephthalic acid dimethyl ester, 30 parts of ethylene glycol, 18.3 parts of 2,2-bis (4 '-hydroxyphenyl) propane and 1 part of maleic acid dimethyl ester in the presence of 0.35 parts of zinc oxide and Q, 17 parts of triphenylphosphine under pure Nitrogen and heated with stirring. Within 2 hours, distill over at temperatures up to 251 · methanol and ethylene glycol. Stirring is then continued in vacuo at 0.2 to 0.5 ram Hg and at temperatures between 274 and 276. After 4 hours, a copolyester is obtained which has an intrinsic viscosity of 0.54 and melts at 251 to 253 ×. The product can be spun very well into cold-stretchable fibers.

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If the mixture used in Example 3 is replaced by a from 487 parts of terephthalic acid methyl ester, 13 parts

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Example 5 '*

By transesterification and polycondensation of a mixture of 500 parts · dimethyl terephthalate, 390 parts of ethylene glycol ^k, 50.5 parts of 2,2-bis [4 ^f - (2 "-hydroxy-ethoxy) -phenyl] propane and 2 parts of dimethyl itaconate in In the presence of 0.35 part of zinc oxide and 0.17 part of triphenylphosphine, in the procedure given in the preceding examples, after 4 hours a copolyester is obtained which has an intrinsic viscosity of 0.63 and melts at 241 ° -243 °. The product is slightly yellow in color. Pipes made from this can be stretched very well and are excellent. Properties. .

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Xan heated a mixture of 500 parts of dimethyl terephthalate, 390 parts of ethylene glycol and 2 parts of dimethyl citraconate in the presence of 0.35 parts of zinc oxide and 0.17 parts of triphenylphosphine and in the absence of oxygen for 2 1/2 hours with stirring at temperatures up to 245 °. In the process, methanol and ethylene glycol distill off. Stirring is then continued at 275 ° in vacuo (ultimate vacuum 0.2 torr). After 3 hours, a practically white copolyester is obtained which melts at 250-252 ° and has an intrinsic viscosity of 0.52. The fibers made from it can be excellently ^: drawn; and '. have very good textile properties.

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Claims (1)

Claims _; 1. Process for the production of copolyesters, - thereby marked, draws that one 'or more aromatic dicarboxylic acids, .'in which the carboxyl groups through, at least 3 Carbon atoms are separated from each other ', or their polyester-forming Derivatives (a) together with up to 3 mol $, based on aromatic dicarboxylic acids (a), of one or more olefinically unsaturated dicarboxylic acids (c) with diols of the formula HO - where η is an integer from 2 to 10 and Y is hydrogen or mean low molecular weight alkyl (b), polycondensed, 2. The method according to claim 1, characterized in that one as olefinically unsaturated dicarboxylic acids (c). Maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexene (2) dicarboxylic acid- (l, 4) or 4-carboxy-cinnamic acid is used. 3. The method according to claims 1 and 2, characterized in that that one'die olefinically unsaturated dicarboxylic acids or their polyester-forming derivatives (c) in amounts of 0.1 to 1 based on aromatic dicarboxylic acids ^ used. BATH ORIGINAL Documents .n.>. ^ .i.?. 2N 909884 / 17Ö1 4. The method according to claim 1, characterized in that · one additionally a dihydroxy compound (d) of the formula H0- <A V- R- < 3 V-OH (II) and / or a diol (e) of the formula H (OCH ₂ CH ₂ ) _a 0- / T \ - R - <^ T \ -0 (CH ₂ CH ₂ O) _b H (III) . uses, wherein R is the direct bond or a group of Formula '. · -C-, -CH ₀ CH ₀ -, -Q-, -S-, -SO ₀ - , -CO- or -NX-, j ccc χ ■ X is hydrogen or a low molecular weight, optionally substituted alkyl, preferably with up to 4 carbon atoms, a is an integer from 0 to 10, b is an integer from 1 to 10 and A and B may contain further substituents Rings mean. 5. The method according to claim 4, characterized in that one the aromatic dihydroxy compounds (d) and / or the Diole (s) in amounts up to 40 mol #, based on aromatic Dicarboxylic acids (a). 9 0 9 88 4/17 0 1 * ^BAD original 6, method according to claims 1 "to 5> characterized in that one with the addition of esterification catalysts and optionally polycondensed by inorganic and / or organic phosphorus compounds with a stabilizing effect. 7. Saturated fiber and film forming copolyesters, such as them by polycondensation of one or more aromatic dicarboxylic acids (a), their carboxyl groups by at least 3 carbon atoms are separated from each other, or their .Polyester-forming functional derivatives with a diol (b) of the general formula = HO- (CY ₂ ) ^ OH (I) where η is an integer from 2 to 10 and Y is hydrogen or denote additional molecular alkyl, and with up to 3 ΙΊο1- $, based on aromatic dicarboxylic acids (a), one or more olefinically unsaturated dicarboxylic acids (c) or their Polyester-forming derivatives · can be obtained. The patent attorney ■ ... 'BAD ORIGINAL 9 09 884/17 01