SU374343A1 - (USSR) and FEB.Hemifaserverk Schwarz "Wilhelm Peak" - Google Patents

Description

METHOD OF OBTAINING

one

This invention relates to the field of producing stabilized α-polyesters.

A known method for the preparation of stabilized polyethers based on diols and terephthalic acid or its ether-forming derivatives by introducing in the process of their synthesis an inhibitor-stabilizer system, for example, Mg hypophosphites, Cd diphenylphosphine .a, Mn (CH3COO) 2, ZnO.

However, the known inhibitor-stabilizer systems are not effective enough. By using them, the content of diethylene glycol in the final product cannot be reduced and, consequently, its quality can be improved.

According to the invention, in the preparation of polyesters, in particular polyethylene glycol terephthalate, in the presence of known catalysts, an inhibitor-stabilizer system of the general formula is used

TK

-R

N: -in

/ R

R r

N

K, "

1 where R is an alkyl and / or aryl residue, as well as a substituted alkyl and / or aryl residue, which is a strong inhibitor and stabilizer.

B .Ka4ecTBie system and stabilizer inhibitor is best to use compounds of the above General Formula with a higher B1 high killing temperature in order to maximize the use of system efficiency.

In such compounds, alkyl and / or aryl, as well as substituted alkyl and / or aryl moieties are ethyl, propyl, iso-propyl, and butyl, and also phenyl or substituted phenyl.

The most suitable compounds of the Mia sistema inhibitor stabilizer are hexa ethyl, hexa-iso-propyl or hexa-L- (p-hydroxyethyl) triamide D phosphoric or phosphorous acid.

These compounds of the inhibitor stabilizer system. The given general formula may be noted separately and in, mixtures up to 1 wt. %, mostly from 10 to weight. %, Relative to acid-containing components or their proizvods. STABILIZED POLYESTERS

In addition, stabilizer inhibitor compounds are carried out predominantly before or in the esterification trocass or in the poly1CON | Sensation process (by continuous or batch method.

The polyester can be obtained by a continuous or periodic method in the presence of an inhibitor stabilizer system as follows. To (Mixtures of terephthalic acid and ethylene glycol are added wt.% Of the amount of terephthalic acid of the indicated compound of the system and inhibitor stabilizer and the esterification reaction is carried out. (Increased temperature with a pressure of the ether: the addition of an appropriate β-esterification catalyst).

According to the chosen reaction conditions at a temperature above 220 ° C and a constant displacement: the aniE occurs a continuous distillation of water formed during the esterification reaction. Upon reaching the degree of esterification | B, more than 90% of the reaction mixture is preliminarily condensed with the addition of a catalyst for nolycondensation and distilling the ethylene glycol, polycondensed and subjected to further processing.

Instead of terephthalic acid, mixtures of terephthalic acid with sebacic and / or isophthalic and / or diphenyl dicarboxylic CI | Slots can also be used. In addition to this, alkyl esters of terephthalic acid MAY be used. As diol, ethylene glycol is preferably used either alone or in a mixture with 1,4-butane / diol and / or 1,4-bis (hydroxymethyl) cyclohecoean. It is also possible to introduce small amounts of a, n: alr-imer, unsaturated aliphatic dicarboxylic acids, or 2,5-digi-Droxyterephthalic acid for crosslinking.

The proposed inhibitor – stabilizer system has several advantages compared with known inhibitors and stabilizers. When using compounds of the triamnd type of phosphoric or phosphorous acid, neutral reactive substances with a high inhibitory and stabilizing effect were obtained, which, due to the high boiling point, are very active and contribute to the improvement of the quality of polyesters, allow to obtain end products with low content diethylene glycol, so that the hairs obtained from them have a high melting point and are melting and extremely lightfast. In addition, the additives of the compounds proposed are not applicable to the increased corrosion of the material of the reaction apparatus, which makes it possible to obtain final products with a high degree of whiteness. According to the amount of additives used, it is possible to modify the properties of the polyester within certain limits, changing the crystalline and dielectric properties. A significant advantage of the proposed inhibitors is, moreover, that they combine the functions of inhibitor and stabilizer in one system and are therefore well applicable also to the direct esterification reaction of dicarboxylic acids with polyhydric alcohols, which usually result in a large amount of di-ether.

When using the proposed system, an inhibitor-stabilizer at the beginning of the reaction and esterification, the content of the resulting; diethylene glycol is reduced to such an extent that, after the esterification reaction, products with a lower content of carboxyl end groups are obtained. Finally, the proposed compounds are readily available. Thus, phosphoric acid hexaethyl triamide is used as a solvent in industry, so that in economic OT; IO is more; and iTO is also an advantage.

EXAMPLE 1 0.16 g of calcium acetate was dissolved in 124 g of ethylene glycol, 0.16 g of phosphoric acid hexaethyl-MIDA, and 166 g of terephthalic acid were added with vigorous stirring. So obtained; By way of suspension, the conversion is carried out in a cylindrical glass tube with polished nozzles for a mixer, a column, a thermo meter, and a nitrogen supply, which is in the oil bath n-p-mix and low flow of nitrogen brings the oil temperature The bath is up to 225 ° C. The reaction water is collected in the column from ethylene glycol, condensed in a condenser and collected in a graduated collection. The bath temperature rises when the reaction ends. At the end of the esterification reaction, ethylene glycol is distilled off under pre-condensation and precondensed with polycondensation with the addition of 0.008 g of antimony trioxide, 30 g of forcondensate for 3 hours at 280 ° C and a vacuum of 1 Torr. The polymer obtained has a melting point of 259 ° C, a diethylene glycol content of 0.8%, and is processed in v-films or films, with good mechanical properties.

Example 2. 0.16 g of calcium acetate, 0.32 g of phosphoric acid hexaisopropyltriamide are dissolved in 93 g of ethylene glycol and, with vigorous stirring, boil 166 g of terephthalic acid. The suspension obtained by this method is converted into a-V-0.5-L volume. After washing with nitrogen, the temperature of the reaction mixture is adjusted to 250 ° C with stirring, and the pressure rises to 3.5 atm, and the reaction water is distilled through the column. At the end of the conversion, after addition of 0.060 g of antimony trioxide, the forcondensation under normal pressure is carried out and then polycondensed at 280 ° C under vacuum of 1 Torr. The melting point of the polyester obtained was 259 ° C, the diethylene glycol content was 1%. The resulting polymer is characterized by good color and heat resistance.

Example 3. In 93 g of ethylene glycol pacTiBr, 0.16 g of calcium acetate, 0.16 g of phosphoric hexaphenyl triamide I1 are added, with intensive stirring, 166 g of terephthalic acid are added. The suspension obtained in a similar way is slowly added to the already etherification of aEEN-reavdionic mixture of terephthalic acid and ethylene glycol at 230 ° C, which is in a cylindrical glass with ground grinding for the agitator, column, thermometer and nitrogen supply, and during placement and weak nitrogen nitrogen An oil bath temperature of 235 ° C and a pressure of 3.5 atm are brought to the reaction. The reaction water separates out through the top of the column, condenses in the condenser and collects in a graduated collection. After the co-version, FORCONDENSATION and 30 g of the sod poly condo poly: KO; den; removed at 280 ° C in 1 gorr after addition of 0.008 g of antimony trioxide. The resulting polymer contains 0.85% diethylene glycol and is suitable for making fibers and flax metal.

Example 4. 0.16 g of calcium acetate, 0.32 g of phosphoric hexamethyltriamide are dissolved in 93 g of ethylene glycol, and 166 g of terephthalic acid are added with vigorous stirring. The resulting suspension is transferred to a 0.5 l autoclave. After washing with nitrogen, the temperature of the reaction mixture was brought to 250 ° C with stirring, and the pressure increased to 3.25 atm. The water formed during the esterification reaction is distilled through the column. At the end of the conversion, 0.060 g of antimony trioxide is added. Fork condensation is carried out at normal pressure and then polycondensed at 280 ° C under vacuum of 1 horr. The melting point of the polyester obtained was 259 ° C, the diethylene glycol content was 0.95%. The polymer has a good color and thermostability nose.

PRED ME of the invention

A creeping method, stabilizing polyesters based on diols and terephthalic acid or its ether derivatives by introducing an inhibitor-stabilizer system during their synthesis, characterized in that, in order to improve the quality of polyether, compounds of the general formula are used as an inhibitor-stabilizer system.

0

where R is an alkyl and / or aryl or substituted alkyl and / or aryl residue.