DE1806884C3 - Process for the production of modified polyester - Google Patents

Description

The invention relates to a process for the production of modified polyesters by reacting terephthalic acid, dimethyl terephthalate or [ßis- (ß hydroxyäthyD-terephthalat] with dihydric alcohols in the presence of catalysts known for the production of polyesters, the reaction being mixed before completion the implementation of a small amount of alkali metal sulfonates of aromatic compounds containing a hydroxyl group / usctzl.

It is known that the film and fiber-forming Polyester that has a small fraction of an organic group with a sulfonate substituent in the form of an alkali salt, have an affinity for basic dyes (e.g. USA patents 3 018 272, 3 057 827 and 3 301819). The processes previously described for making the modified polyesters of this type have been based on the use a compound which has at least one ester-forming functional group together with at least contains a sulfonate group in the form of a metal salt as a modifying component, e.g. B. Potassium p-hydroxyethoxybenzenesulfonate and sodium 3,5-dicarbomeihoxybenzenesulfonate. These procedures passed in the addition of the modifying component either to the starting materials or to the Reaction mixture during the exchange or polycondensation reaction. In these ways of working however, according to the prior art, the disadvantage often occurred. that the manufacture of the modifying Component was relatively complicated from the compounds readily available on the market; it was expensive to purify the modifying component to such a high degree of purity that polyester can be removed from Fiber quality were produced. The resulting modified polyesters were not satisfactory Resistance to the action of acids or alkali; or those stained with the help of basic dyes Pieces had poor color fastness to sunlight. Thus, there was a strong need for Elimination of these disadvantages.

The object of the invention is accordingly to produce the modified polyesters with the aid of a technically and economically efficient uncomplicated process that is particularly easy to dye with basic dyes own.

This object is achieved by the method according to the invention.

The invention relates to a process for producing modified polyesters by reaction of terephthalic acid, dimethyl terephthalate or [bis (/ i-hydroxyäihyl) -terephthalate] with dihydric alcohols ία presence of for the production of polyesters known catalysts, with the reaction seemiseh before the end of the reaction

ίο a small amount of alkali metal sulfates more aromatic "Compounds that contain a hydroxyl group, adds, which is characterized by. that one alkali in uUlsalze \ on m-phenolsulfonic acid or 2-Chlorphei: 4-sulfonic saturate or a lithium salt of

ρ-phenol sulphate ... n acidic; in an amount of 0.5 to 8 mul percent. based on that in the reaction mixture existing acid component, used.

By using the mentioned phenol sulfones is e-> not only possible to use modified polyester

ao better transparency than that of the known th polyester, but that the modified polyesters obtained in this way also have a very pronounced one Have an affinity for basic dyes. I became more renewed by the fact that the resulting polycondens sat subjected to hydrolysis by means of an alkali, determined by analysis of the hydrolyte product, dall the phenol sulfone used essentially quantitatively into the polyester molecule by means of the ether bond was introduced. For example, if that with

Sodium m-phenolsulfonate modified polyethylene terephthalate was hydrolyzed with an alkali, was sodium m - (/ i-hydroxyethoxy) benzene sulfonate in an amount corresponding to 98 mole percent of the sodium m-phenolsulfonate added to the reaction system, won.

It was now surprising that the phenol sulfonates of the type indicated above are essentially quantitative in the polyester molecule by means of the etherbiiKiuiig be bound under the usual polyester synthesizing conditions. It wasn't expected because it is known that under the usual conditions of the synthesis of polyesters im Case of most phenol sulfonates, which are very similar to the phenol sulfonates given above are, a desulfonation occurs This has the consequence, that a chemical bond cannot take place in the polyester molecule and thus an extremely discolored one Polycondensate is formed or, even if there is a bond in the polyester molecule, the proportion of such Bonds is small and, moreover, because side reactions (e.g. desulfonation) in a considerable Extent arise, the resulting polycondensate has no water-like white color and its Affinity for basic dyes is also unsatisfactory. For example, sodium resorcinol-4-sulfonate desulfonates under the. Conditions of polyester polymerization, and that synthesized in its presence Polyester is not only extremely discolored but also has a low melting point and is not crystalline and therefore of no practical value. On the other hand, in the case of sodium 2-naphthenol-6-sulfonate or sodium resorcinol- ^ o-disulfonate is noteworthy Obtain cloudy polyesters, and the improvement in their affinity for basic dyes is not very big. If again sodium p-phenolsulfonate is used, the resulting polyester is cloudy, has a low melting point, and has a considerable degree of affinity for basic coloring

3 4

Mofle. however, in terms of its practicality, it is fiber-quality polyesters. UaV, the

v.endharkeii imhelnedigend. In this lulle was starting materials au high purity ge ·

d.irch analysis by cleaning the disfiguring poly- The obtained according to the invention

,. • -.!, - ι- a hydrolysis iinterv.arl. icst provided. that modified polyesters are also oxydaiioiis-

^s "'■' .. ^dc> used Nairiiim-p-phenohulfonats 5 resistant. Furthermore, the chemical component

c:; h · Ath.erbiiiuuiiu in the polycondensate formed using one according to the invention

hold and that part of the rest during the poly-sodium-m-phennKiiifonai modili / ierler Pohäihylen-

k.üdeiisalionsreaktion had been desullomeri and terephthalate fiber. for example their reduction

ii. !,. ■ - had released phenol. the tensile strength wedge under the conditions in which they

I) ie according to the invention prepared modilizierten m in boiling 5 ⁽ "" aqueous sulfuric acid 2 hours

IvUesians are thermoplastic and have been used for a long time to manufacture. 3! ^V "· a value that \ ol! out-

\,: in synthetic fiber or polyethylene film suitable ". is sufficient to ensure practical use.

M, - are obtained by converting -, on Terepluhal- hold. On the other hand, the reduction in traction

v: ire. '.dimethyl terephthalate or bis- (p'-li> dro.xyäi! iyli strength under identical conditions in 1 all oh

icicphthaku with dihydric alcohols and assign 15 with sodium 3.5-di-icarbo \ y methoxy) -benzenesulfonate

,:; .- Ahphaiische alcohol final group on. modified polyethylene terephthalate only 5 ~ "".

In accordance with the definition, the above-referenced examples are used to explain the invention

ii.:e selected modifying component to the explained. Unless otherwise stated. are parts

H.jküonsverbindungen we ending the synthesis of the?. | and percentages are based on weight.
ii,. 'diii / icrenden polyester-, added, and an- 20

The synthesis of the polyester is then terminated. ti e 1 -. ρ ι e I 1
Ii, e modifying component can be added to either (a) A 500 ml three-neck flask. which is designed with a distillation material or latioiis column to the reaction mixture, was tercphthalate with 153 g of dimethyl, r or 'during the polycondensation, 11: 0 g of ethylene glycol, 3.3 g of nairium; j - ¹ ICIi will. The moilizing component can contain 25 m-phenolsulfonate. 0.02 g of l'aknim acetate. 0.0Sg lead-i ^! these or, if necessary, are charged using oxy.J and 0.06 g of antimony trioxide, whereupon the appropriate medium is added. The eye mixture is heated for 4 hours at 200 ° C. while stirring with iii-mmen, in which the phenol is heated with the aid of a motorized stirrer. v.he hydroxyl i ^n. Distill off / udestill the methanol that has formed over a small amount of grain. Anponenie the etherhindum'with the alcoholic case was after (bringing about the reaction, -y. The reaction proceeds for 4 hours at 2X0 C under emperalurene after the synthesis of the reduced pressure of 0.5 mm Hg has been carried out, whereby polyester has reached a considerable extent, and a colorless transparent polycondensate is obtained there too the solubility The basic molar viscosity of this polycondensate under the conditions of polyester synthesis, measured in o-chlorophenol at 25 ° C., is sufficiently large, the modifying cone can be 0.466 (dl g), while the softening point, measured component during the latter stages of the procedure with a penetrometer.2W) C. When for

J.jr Synthesis üCS Polycler ·. Granted V. earth. So ChrirakiCri .-> iefUilg this Poiykonueilsiits i "iCi 2οί C

The time of addition should mainly be melt-spun according to purpose-4P and then drawn 3rd fold

considerations of annoyance are decided. became a thread with a tensile strength of

The proportion in which the above-mentioned 3.4 g-'den and an elongation \ on 21 "' _{o are} obtained.

Polyester modifying component is used, 0.1 g of the resulting oriented thread was used

is preferably 1.0 to 5.0 mole percent based on 90 minutes at 110 C using a

on the acid present in the reaction mixture 45 flea temperature dyeing with 20 ml of a

component. aqueous 0.005 ^0; Igen solution of the basic color

With regard to the device, catalysts, additive Aizen Cathiion Violet 3 BLH stained. Fs

rates and polymerization conditions. which was determined by measuring the dye concentration in

Invention are applicable, such purposeful the remaining liquid using a

moderately to be used, the 5 ° Spectrophotomcters found that the thread

Production of known synthetic polyester absorbed dye SS% was, furthermore, was when

be turned. 20 ml of an aqueous 0.04% solution of the basic

The method according to the Frfindimg has a dye Nichilon Black MHF was used

Number of unexpected technical advantages in comparison and the dyeing of the thread for 90 minutes hot

using the state-of-the-art method, which was carried out therein 55 130 C, the thread to a

exist. an ester-forming modifying composite colored black shade.

Subsequently, 20 g of the according to this was added. According to the invention, for. B. Sodium game obtained sulfonate-containing polyester in zerni-phenolsulfonate directly to the polyester polymer in smaller form in a 300 ml flask with a round salion system, without the need to bring ⁶ ° soil, then 200 ml of water is added , add this first to its ester-forming derivative, in which 9 g of sodium hydroxide have been dissolved, e.g. B. sodium m - (/? - hydroxyethoxy) benzene sulfonate, and then about 10 hours of boiling under reflux. It is readily apparent that one heats the long one. After finding that the water simplification of the process had become a technical advantage, the water became clear. In addition, the purification of sodium ^ß 5 is completely distilled off, whereupon about 100 ml of methanol m-phenolsulfonate can be carried out much more easily than this was added. Then it was filtered. After sodium m - (/? - hydroxyethoxy) benzo [sulphide] evaporate the methanol from the methanol filtrate. It is an indispensable requirement for Ilrlan- hydrochloric acid was added and the pH adjusted to 2

iiclii. iN'after distilling the water and methanol ·; a small amount of acetone was added from this liquid acidified with hydrochloric acid, followed by the inorganic salts such as common salt which precipitated were separated by filtration. The filtrate was heated under reduced pressure to remove the ethylene glycol to be distilled off, whereupon a large amount of acetone was added and crystals were separated. When these crystals are made using a methanol-benzene mixture were extracted, whereupon the meihanol-benzene mixture was evaporated, and then the crystals were dried under conditions of 110 to 120 "C and 10 mm Hg for 5 hours, colorless crystals were obtained. By measuring the IR and NMR spectrum it was found that this is in accordance with the standard sodium m - (/} - hydioxyethoxy) benzene sulfonate stood. Furthermore, the values of the elemental analysis were:

C 39.67, H 3.92%;

calculated values:
C 40.00, H 1.78%.

Comparative experiment

For comparison, when a polyester was synthesized as in (a) except that 3.3 g Sodium p-phenolsulphonate instead of 3.3 g of sodium m-phenolsulphonate was used, a milky white polycondensate with a basal molar Viscosity of 0.561 (dl / g) and a softening point of 250 ° C were obtained. When a thread is spun and pulled under the same conditions as in (a), a thread was pulled with a tensile wedge of 3.4 g / den and an elongation of 43% obtained when dyeing under identical conditions as described above, using Aizen Cathilon Violet 3 BLH, a dye absorption of 46% showed, however, when staining under identical conditions as described above, black tint cannot be obtained using Nichilon Black MHF. If further these polymers of hydrolysis, as described above, using ν η sodium hydroxide Was subjected to 0.236 g of sodium p - (/ J-hydroxyethoxy) benzene sulfonate and 0.034 g of unreacted sodium p phenolsulfonate recovered. Another The experiment showed that a proportion, corresponding to 37% of the originally added sodium p-phenolsulfonate «, decomposed to phenol and sodium bisulfate.

Example 2

100 g of bis (/? - hydroxyethyl) terephthalate, 6 g of diethylene glycol, 1.5 g of sodium m-phenol sulfate, 0.02 g of calcium acetate, 0.05 g of lead oxide and 0.06 g of antimony trioxide were placed in a polymerization vessel given and reacted for 4 hours under the conditions of 28Q ^C C and 10 to 0.5 mm Hg, a colorless, transparent polycondensate being obtained. The intrinsic viscosity of this polycondensate was 0.534 (dl / g), and its softening point was 248 ⁰ C. This polycondensate was spun and drawn under identical Bedirgungen as in Example 1, and it has a yarn having a tensile strength of 4.3 g / den and an elongation of 22%. When this thread was dyed under the identical conditions as in Example 1 using Aizen Cathilon Violet 3 BLH, the dye absorption was 96%.

Example 3

A polycondensate was synthesized as in Example 1 from 153 g of dimethyl terephthalate, 120 g of ethylene glycol, 3.3 g of sodium m-phenol sulfate, 0.02 g of calcium acetate and 0.06 g of antimony trioxide. The polycondensate obtained was colorless and transparent, and its intrinsic viscosity was 0.48 (dl / g), and the softening point was 259 ¹ C. This polycondensate was spun into a thread as in Example 1 and drawn in a similar manner, with one oriented Thread with a tensile strength of 3.5 g / den and an elongation of 28% was obtained. When 0.1 g of this oriented thread was dyed for 90 minutes at 120 ° C. in 20 ml of an aqueous 0.005% solution of Aizen Calhilon Violet 3 BLH, the dye absorption was 96%. Further, this thread became a deep black shade using 20 ml of a 0.03% aqueous solution

ao Nichilon Black MHF stained under the conditions of 130 C and 90 minutes.

Example 4

If a polyester as in Example 1 using

Preparation of 153 g of dimethyl terephthalate, 120 g of ethylene glycol, 3.7 g of sodium 2-chlorophenol-4-sulfonate, 0.10 g Calcium acetate and 0.06 g of antimony trioxide was synthesized, a polycondensate with a slightly milky white shade, an intrinsic viscosity of 0.57 (dl / g) and a softening point of 260C, which one when it is woven and drawn was, an oriented thread with a tensile strength of 4.2g / 'den and an elongation of 22% revealed. When 0.1 g of this thread is heated for 90 minutes at 120 ° C using a device of the type a pressurized high temperature stainer with 20 ml of an aqueous 0.005% Solution of Aizen Cathilon Violet 3 BLH, the dye absorption was 92%.

For example! 5

A polycondensate was prepared as in Example 1 using 153 g of dimethyl terephthalate, 120 g

Ethylene glycol, 8.4 g diethylene glycol, 5.5 g sodium 2-chlorophenol-4-sulfonate, 0.1 g calcium acetate, 0.08 g lead acetate and 0.06 g antimony trioxide were synthesized, whereupon the polycondensate was synthesized in a manner similar to that above written, spun and drawn. The resulting oriented filament had an intrinsic viscosity of 0, ^4, 8 (dl / g), a softening point of 246 ° C, a tensile strength of 3.3 g / d and an elongation of 26%. It was dyed under the same conditions as in Example 1 using Aizen Calhilon Violet 3 BLH, with the result that the dye absorption was 96%. Further, when it was stained with Nichilon Black MHF, it was observed that it stained to a deep black hue.

Example 6

153 g of dimethyl terephthalate, 120 g of ethylene glycol, 3.16 g of sodium m-phenol sulfonate, 0.15 g of calcium acetate and 0.06 g of antimony trioxide were used, and the polycondensation and operations of the Spinning and drawing were carried out as in Example 1, an oriented 12-thread yarn being obtained whose monofilament count was 2.04 den

and which had an intrinsic molar viscosity of 0.518, a softening point of 260 ⁰ C, a tensile strength of 3.77 g / den and an elongation of 26%. 2 g of this oriented yarn were 60 minutes at 98 ° C with 160 ml of an aqueous 2 % sodium hydroxide solution treated. If the weight loss was measured after treatment, they bexrug 4.2 ° / _0> and the decrease of tensile strength was 5.6%.

Comparative experiment

One for comparison purposes under similar conditions but using 4.77 g of sodium 3,5-di- (carbomethoxy) -benzoisulfonate in place of 3.16 g of the aforementioned sodium m-phenol sulfonate (2 mole percent in both cases) was synthesized Polycondensate had an intrinsic viscosity of 0.532 and a softening point of 256 ° C. That obtained from this polycondensate by spinning and pulling the freshly spun threads 12-thread yarn had a tensile strength of 3.82g / den, an elongation of 27%, and its monofilament fineness was 2.06. If this yarn is loaded in a similar manner with an aqueous 2% sodium hydroxide solution

was the weight loss
and the decrease in tensile strength 10.3%.

Example 7

140 g of terephthalic acid, 200 g ethylene glycol and 0.05 g of sodium hydroxide were reacted at 200 ⁰ C 8 Stunder long in the same manner as in Example 1 wherein water and part of the Äthylenglycols were distilled off. Then the reaction mixture was ir

ίο transfer a polycondensation vessel. After adding of 3.3 g of sodium m-phenol sulfonate and 0.06 g of antimony trioxide, finally obtaining a reduced pressure of 0.5 mmHg, the reaction carried out at 280 ° C for 3.5 hours.

The polycondensate obtained had a softening point of 256 ° C. and an intrinsic viscosity of 0.45 (dl / g). This polycondensate was au! spun and drawn in the same manner as in Example 1 and then dyed under the same conditions. The adsorption of the basic dye "Aizen Cathilon Violet 3 BLH" to the polycondensal was 87% · Furthermore, the polycondensate was when used colored by »Nichilon Black MHF« to a deep black shade.

309637/2 «

Claims (1)

Claim: Process for the production of modified polyesters by reacting terephthalic acid. Dimethyl terephthalate or bis (/} - hydroxyethyl) lerephthalate with dihydric alcohols in the presence of known for the production of polyesters Catalysts, the reaction mixture being given a small amount before the end of the reaction Alkali metal sulfonaic of aromatic compounds containing a hydroxyl group, thereby adding characterized in that one Alkalimciallsalzc \ on m-phenol sulfonic acid or 2-chlorophenol-4-sulfonic acid or a lithium salt of p-phenolsulfonic acid in an amount from 0.5 to X mole percent, based on the acid component present in the reaction mixture, used.