DE1545013A1 - Process for the production of modified polyesters - Google Patents

Description

DR. E. WIEGAND

MDNCHEN

DIPL-ING. W. NIEMANN

HAMBURG PATENTANWXLTE

MONKS 15

NUSSBAUMSTRASSE 10
TELEPHONE: 555476

26, SoV ₃ 1963

W. 11602/63 9 / Hir

Teijin Limited, Usaka (Japan)

Process for the production of modified xolyesters,

The invention relates to a method for producing modified or modified polyesters. In particular, the invention relates to a process for modifying synthetic rolyesters, such as rolyethylene terephthalate, to give the fibers and mimes made from it · improved dye absorption »

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.fibers and '. textiles, -the also synthetic lolyesters, such as .tolyäthylenterephthalat, are made, have mostly been dyed with disperse dyes, since they have no affinity for ionic dyes. However, disperse dyes are known to be expensive, In addition, when dyeing mixed yarn, which is composed of »olle and χ · οIyester fibers, Often the problem with disperse dyes is due to the difference in dye affinity between the two types of fiber dirty or stained.

Accordingly, there is a strong need for modified ones .. olyesters, the affinity for ionic dyes and in particular have cheap acid dyes and the together with full at the same shade and depth can be dyed in the same dye bath.

In the endeavor towards synthetic production such iolyester, the affinity for acid dyes will have in British Patent 734 416 a Proposed copolymerization of polyesters with aromatic or aliphatic tertiary amines. The one in this However, mixed polyesters obtained in this way with aromatic / mines still have an insufficient affinity for acid dyes. Furthermore, it is difficult to introduce a sufficient tightness of aliphatic amines into polyester, even in the case of melt polymerization under very mild conditions, as the amines tend to decompose.

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In the course of an extensive development work, a production method for modified ones was invented according to the invention polyester, 'which has a very high affinity for [acid dyes have strength and elongation properties retained to a degree sufficient for clothing and induction purposes.

The invention provides a method for producing modified x ^; OIyesters with a very high affinity for acid dyes, in which in the molten state linear x-olyesters, e.g. polyalkylene terephthalate, are mixed with a small amount of an amino group-containing i-olyamide that has a stable chemical structure and is evenly miscible with the polymer without significant decomposition , and further subjecting the mixture to heating under reduced pressure, if desired.

According to the invention, the term "polyamides containing amino groups which, when mixed with linear polyesters such as polyalkylene terephthalate, have stable chemical structures" is intended to include: the basic / imino group of one or each of the carboxyl groups is separated by at least three carbon atoms as the dicarboxylic acid component; (2) the mixed polyamides, which consist of diamine mixtures in which at least 60 $ consist of m-xylylenediamine, as the

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Uiamine component and one or more "aliphatic" tertiary aminod! carboxylic acids, of which up to 60 # by one or more aliphatic or aromatic dicarboxylic acids, such as adipic acid, pimelic acid, azelaic acid, Sebacic acid., Terephthalic acid and isophthalic acid can be obtained as the dicarboxylic acid component.

Examples of the aliphatic tertiary aminodiacid are given below;

N-methyl-2,5-bis (2-carboxyethyl) pyrrolidine U -iithyl-2,5-bis (2-carboxyethyl) pyrrolidine ^ -n-tropyl ^ jS-bisi 2-carboxyethyl) pyrrolidine xJ-n-butyl- 2,5-bis (2-carboxyethyl) pyrrolidine N-ji-J3enzyl-2,5-bis (carboxyethyl) pyrrolidine / methyl-2- (2-carboxyethyl) -5- (4-carboxybutyl) pyrrolide in ii-ethyl -2- (2-carboxyethyl) -5- (4-carboxy butyl) pyrrolidine jw-n-propyl ^ - (2-carboxyethyl) -5- (4-carboxybutyl) pyrrolidine Nn-i3utyl-2- (2-carboxyethyl) -5- (4-carboxybutyl) pyrrolidine il-benzyl-2- (2-carboxyethyl) -5- (4-carboxybutyl) pyrrolidine N-methyl-2,6-bis (2-carboxyethyl) hexahydropyridine (-pyli-

dine)

U-ethyl-2,6-bis (2-carboxyethyl) hexahydropyridine H-n-Propyl-2,6-bis (2-carboxyethyl) hexahydropyridine H-n-Butyl-2,6-bis (2-carboxyethyl) hexahydropyridine N-benzyl-2,6-bis (carboxyethyl) hexahydropyridine

Methyl bis (3-carboxyps! Pyl) amine

ethyl bis (3-carboxypropyl) amine

n-propyl bis (3-carboxypropyl) amine

n-butyl bis (3-carboxypropyl) amine

Benzyl bis (3-carboxypropyl) amine

5-l) imethylamino-hexahydroisophthalic acid S-diethylamino-hexahydroiaophthalic acid 5- (1-pyrrolidine) -hexahydroieophthalic acid 5 - (! - piperidine) -hexahydroisophthalic acid

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generally includes the manufacture of rolyesters, in particular .Polyalkylene terephthalate, the. working level of Reaction of terephthalic acid or its functional derivatives with an alkylene glycol or its functional Derivatives to initially be an intermediate of comparatively low molecular weight, and the stage of further! reaction thereof under reduced pressure or in an inert atmosphere for the production a polymer with a high molecular weight, the Has fiber or film-forming properties. These reactions can be carried out either continuously or in batches. By replacing one of the prices of i'erephthalic acid by other dicarboxylic acids or hydroxy acids and one I'eilea of alkylene glycol by another divalent It is also possible for alcohols, random or block polyalkylene terephthalate in the same way as above.

The polyamides used in the invention are said to have the jig juice, alternately in a molten state uniform in the homo- and hiseh-polyalkylene terephthalates (hereinafter referred to as base polyesters) to be soluble and not substantially decompose under the severe conditions of melting and mixing to show with melted base polyesters. The amino-containing polyamides given above meet those listed both demands in good measure,

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It has been found that other ala the olyamides listed in the invention, z,] \ x-olyamides, which are obtained from an aliphatic tertiary amino dicarboxylic acid and methylenedianine or decaiuethylenediamine, do not mix homogeneously with polyesters, although they are among them withstand the conditions of intermingling with molten base polyesters. Anuereroeit3 suffer almost all rolyamides from other than those specified in the invention iuninodicarboxylic acids, such as <X- and ß-amino dicarboxylic acids, z. B. Methyliminodiedsigsäure and / 3. β'-n-Butyliminodicarboxylic acid, and various uianines decompose under the conditions of mixing with molten basic polyesters.

The thermal stability and miscibility of the amino-containing iolyainides with the basic polyesters are therefore only given if their carboxylic acid component consists mainly of one or more aliphatic tertiary amine carboxylic acids and their diamine component is mainly formed by m-xylylenediamine. In such aiiiino-containing polyamides, no more than 60-5 of the dicarboxylic acid component can be replaced by other dibasic acids, for example adipic, ximelin, .izelain, sebaoin, without any detrimental effect on the miscibility of the polyamides with the round polyesters and their thermal stability -, i'erephthal- and Ieophthaisäuren, provided that not less than 6Q γο of the dialaine component consists of m-xylylenediamine.

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l) The amino-containing polyamides can be different Polymerization processes are easily obtained as high molecular weight polymers and, accordingly, can be carried out by easy mixing of the same with base polyesters high Molecular weight in the molten state modified polyesters are produced which have the appropriate strength and Have elongation properties for use as textiles and industrial materials.

The amino-containing irolyami.de can polyesters the basic at a freely selectable stage after the completion of the polymerization reaction of the base polyester to one Added point before pinning or piling operations and mixed with these, preferably this happens either immediately after the polymerization reaction or just before spinning. Since the polyamide containing amino groups has an amino group or groups at its ends, has a carboxyl group or carboxyl groups or derivatives thereof, the case may arise that the Amino-containing polyamide and the base polyester mixed together State together form a block copolymerized modified polyester,

However, it is unsure whether the amino-containing polyamide after addition to the base polyester reacts with the latter with incorporation or whether a larger part of the polyamide does not react with the base polyester and only present in mixed form with the polyester.

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In any case, with the mere messing of the base polyester with the amino-containing polyamide in the molten state, the lowering of the softening point of the resulting ! Polymerizate, compared with that of the base polyester, is very low and therefore a modified Polyester of excellent thermal resistance obtained will. In the modified polyester obtained in this way, there is presumably a very small proportion of the amino-containing Contain polyamides in blookmischpolymerisiert with it. If the one with the amino-containing polyamide in melted State of mixed base polyester is further heated under reduced pressure, the resultant has modified polyester has a slightly lower softening point than the base polyester, but shows increased physical properties Strength properties compared to the product, which is melted by the mere mixing of the two components State is preserved. It can be assumed that the block polymerisation is due to the additional heating stage the base polyester is further promoted with the amino-containing rolyamide.

Since the modified polyester according to the invention contains the amide group which is one of the am the strongest hydrophilic functional groups is its dye rate with acid dyes very much increased and it can therefore be dyed simultaneously with wool in one and the same dye bath. Another tr

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The advantage of the presence of the amide group is that it enables the modified polyester according to the invention to be used when dyeing with various jacid dyes to be dyed to the exact same shade as wool. In contrast, amine-modified Polyalkylene terephthalate, since it contains no amide groups, with numerous acid dyes are not always included dyed the same shade as wool. On this side, a process for permanent / ischpolymeriaieren was previously used of aliphatic aminoglycols or iiminodicarboxylic acids proposed with polyalkylene terephthalate, but such modified .tolyeaters, the aminoglycols or aminodicarboxylic acids contain, under any coloring conditions with solar red (Solar Red) always colored orange-red, while Wool and the modified polyester according to the invention can both be dyed sharply with the same dye. Furthermore, the modified polyesters according to the invention cannot be effectively dyed only with acid dyes but also with a variety of techniaohen anionic dyes, e.g., chelate dyes such as Cibaran brilliant blue uL and neolan rose BA, and chromium dyes different types, namely to the clarification effect as with V / olle, i.e. to the same color and the same color depth ©.

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The amount of the amino-containing polyamide blended into the base polyester in the present invention should be such that the aliphatic tertiary aminod! carboxylic acid in the polyamide 0.5 to 20 mol- ″, preferably 2 to 15 mol->, to the dicarboxylic acid component in the Base polyester is. An admixture of amino-containing polyamide in an amount that is a lesser mole percentage the aliphatic tertiary aminodicarboxylic acid as 0.5 M0I-9S leads does not bring the satisfactory improvement the dyeability. On the other hand, if the amount of the polyamide added increases the molar percentage to over 20 mol-? 5 increased, the physical properties of the modified polyester, e.g. thermal resistance and Melt viscosity, undesirably affected, while no substantial improvement in dyeability is achieved. Accordingly, addition within the above range is preferred.

The modified polyesters made in accordance with the present invention are particularly useful as materials for Production of moldings or molded parts, in particular by extrusion, injection molding, slip casting etc., and they can be used to make yarn, fabric, film, bristles, other machine parts, pipes, reinforcements, accessories, Isolated rush etc. to be processed.

The modified according to the invention Polyesters are particularly valuable when they are

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spun into fibers. Conventional additives for fiber-forming polyesters, e.g., titanium oxide, may be added or a substance may be incorporated therein be dissolved with the modified polyethylene terephthalate is miscible, e.g. an organic acid ester.

The fibers obtained from the modified polyesters according to the invention can be used as textiles in woven or knitted in the usual manner, as well as used as a non-woven product such as felt physical properties of these products are largely the same as those of the products made from the basic polyesters, e.g. as obtained from terephthalic acid and glycole will. Furthermore, the products with acid dyes, e.g. Alizarin light blue-AA, Roccelin-NS and Bolarset-Orange, as well as with anionic dyes, e.g. metal and chelate dyes, like Gibaran-Brillantblau-GL, Neolanrosa-BA etc., stained too deep colors. With a suitable regulation of the added amount of the amino-containing polyamide can mixed spun yarns composed of the modified polyester and wool in one and the same dye bath be colored evenly. The fibers and films obtained from the modified polyesters according to the invention have also a high affinity for disperse dyes, which adds to the usefulness of such fibers and films further increases.

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The invention is illustrated below with the aid of exemplary embodiments further explained.

In the examples, the proportions are based on the weight and the GrößeC ^} means the grundmolar6 ViskositätjBzahl the o-Ohlorphenollösung of the polyester at 55 ⁰ O.

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Working method 1

The following procedure explains the production of a homopolyamide of N-n-eutylpyrrolidine-2,5-dipropionic acid / m-xylylenediamine (100/100 MoI- ''.).

A mixture of 32.7 parts of tf-n-butylpyrrolidine-2,5-bis (ethyl propionate), 14.3% of m-xylylenediamine and 20% of dried toluene was kept at reflux for 2 hours; then a toluene / ethanol mixture below 240 ⁰ O was distilled off from the reaction mixture; the residue obtained was stirred for 2 hours at 240 ⁰ C in an inert gas flow under atmospheric pressure and then stirred for 8 hours at 270 ⁰ O at a pressure below 0.5 mm Hg. Eb a light yellow solid homopolyamide was obtained.

Its melting point was ^{83-87 0} O and the intrinsic viscosity L ^ J was 0.21.

Working method 2

This method of operation explains the procedure for Production of the homopolyamide used according to the invention from N-ethyl-2- (2-carboxyethyl) -5- (4-carboxybutyl) pyrrolidine / m-xylylenediamine (100/100 mol -? *).

A mixture of 32.7 parts of jn-ethyl-2- (2-ethoxy ~ carbonylethyl) -5- (4-ethoxycarbonylbutyl) pyrrolidine, 14.3 parts of m-xylylenediamine and 20 parts of dried toluene was refluxed for 2 hours. Then the toluene-ethanol mixture was from the reaction mixture below

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240 ⁰ U distilled off; the resulting residue was stirred for 2 hours at 24 ° 0 in a stream of inert gas> aiter atmospheric pressure and then heated for 8 hours at 270 G and a pressure of less than 0.5 mm Hg with lead. An amorphous, light yellow, solid comopolyamide was obtained which had an intrinsic viscosity Lrβ of 0.22.

Arb eitsweise 3

This procedure explains the preparation of an ilomopolyamide used in the process according to the invention, that from ßenzyl-bis (3-carboxypropyl) amine / m-xylylenediamine (100/100 Mol-yS) is prepared.

A mixture of 30.9 parts of benzyl bis (3-methoxycarbonylpropyl) amine, 14.3 parts of m-xylylenediamine and 20 parts of dry toluene was heated under reflux for 2 hours. A toluene-methanol mixture was below 240 ⁰ C distilled off from the Keaktionsmisehung and the resulting residue was first stirred for 2 hours at 24O ⁰ O in an inert gas flow under atmospheric pressure and then for 8 hours at 270 ⁰ C under a pressure of less than 0, Heated to 5 mm Hg. An amorphous, light yellow solid homopolyamide with an intrinsic molecular viscosity of 0.22 was obtained.

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Working method 4

This way of working explains the production of a mixed polyamide of N-n-butylpyrrolidine-2,5-dipropionic acid used according to the invention: adipic acid / ni-xylylenediamine (50150/100 mol- '·'.).

A mixture of 65.4 parts of li-n-butylpyrrolidine-2,5-bis (ethyl propionate), 40.4 parts of diethipate, 55.7 parts of m-xylylenediamine and 60 parts of dried. Toluene was heated for 2 hours under reflux and the toluene-ethanol mixture formed was below 240 ⁰ G distilled off from the Keaktionsmisohung. The residue thus obtained was stirred for 2 hours in an inert gas stream at 240 ^u C under atmospheric pressure and then at 27O ⁰ C for 8 hours at a pressure below 0.5 mm Hg. tie Obtained as a light yellow solid Miechpolyamid, including melting point was in the range 119-122 ° C and the intrinsic viscosity was 0.30 Lv ^ J.

Working method 5

This, working method explains the division of a mixed polyamides of 5-diethylaminohexahydroisophthalic acid used according to the invention: sebaoic acid / m-xylylenediamine (50: 50/100 mole: »),

A mixture of 27.1 parts of dimethyl 5-diethylamino-hexahydroisophthalate, 23.0 parts of dimethyl sebacate, 28.6 parts of m-xylylenediamine and 40 parts of dried

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Toluene was heated under Mickluss for 8 hours; a toluene-methanol mixture below 24 ° C. was distilled off from the reaction mixture which resulted. The -. Lagging behind was heated hours under Kühren initially 2 at 240 G in a stream of inert gas at atmospheric pressure and then for 8 hours at 270 ⁰ C under a l> jerk mm Hg of less ALB 0.5. Us an amorphous light yellow solid mixed polyamide with an intrinsic molar viscosity C ^ of 0.28 was obtained.

Working method 6

This procedure illustrates the production of a mixed polyamide used in accordance with the invention N-n-Butylpyrrolidine-2,5-dipropionic acid / m-xylylenediamine: hexamethylenediamine (100 / 8E: 2O mol-: ').

A mixture of 32.7 parts of diethyl Nn-butylpyrrolidine-2,5-dipropionate, 11.4 parts of m-xylylenediamine, 2.4 parts of ilexamethynindiamine and 20 parts of dried toluene was heated under reflux for 2 hours; then a toluene ^ thanolgemisoh below 24O ⁰ C was distilled off the Reaktionsmisohung. The resulting residue was purified hours under Kühren initially 2 at 240 ⁰ C in an inert gas flow under atmospheric pressure and then for 8 hours at 27O ⁰ C under Einei; Heated pressure less than 0.5 mm Hg. It was a light yellow solid mixed polyamide with

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one, -: ehnielzpunkt of 71 - 70 ° G and one basal molar Viscosity number Πΐχΐ of 0.23 obtained.

Working method 7

This procedure illustrates the preparation of an isohpolyamide used in the process according to the invention from H-ethylhexahydropyridine- ^ ö-dipropionic acid: adipic acid / m-xylylenediamine: hexamethylenediamine (80: 20/80: 20 mol-i).

A mixture of 22.8 parts of dimethyl-N-ethylhexahydxpyridine-2,6-dipropionate, 3.5 parts of methyl adipate, 11.4 parts of m-xylylene inine, 2.4 parts of hexamethylenediamine and 20% of dried i'oluene was heated under reflux for 2 hours; then toluene was distilled off from the Methanolgeniisch Iieaktionsmischung below 240 ⁰ G. i ^ he resulting residue was first run 2 ütunden at 24O ⁰ G in an inert gas stream and then for 8 hours at 27O ⁰ G under a pressure of less than 0.5 mm Hg heated. An amorphous, light yellow solid polyamide with an intrinsic viscosity D ^ of 0.23 was obtained.

Working method 8

This procedure explains the preparation of a micpolyamide used in the process according to the invention from Nn-13utylijyrrolidine-2,5-dipropionic acid: Iaophthalic acid / m-xylylenediamine: decamethylenediamine (50 1 50/70: 30

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Mon 1-4).

^ a mixture of 16.4 parts of II-n-nutylpyrrolidine-2, 5-bis (propionic acid diethyleate), 11.1 parts of diethyl isophthalate, 1% of m-xylylene diacin, 5.4 parts
Decamethylenediamine and 20% dried toluene were heated under reflux for 2 hours; After toluene-j \ thanolgemisch was distilled off below 240 C by the Beaktionsmischung, the resulting residue with stirring, first 2 Jtunden at 24O ⁰ G in a. · Stream of inert gas at atmospheric pressure and then at 270 ⁰ C 8 ütunden was

heated under a pressure of less than 0.5 ηω Hg. It
an amorphous, pale yellow solid polyamide with an intrinsic viscosity Lt ^] of 0.24 was obtained.

Working method 9

! This procedure explains a procedure for
Production of a mixed polyamide from if-n-butylpyrrolidine-
-2,5-dipropionic acid / m-jiylylenediamine: hexamethylenediamine
(100/50: 50 KoI- ,;).

i-jine solution of 65 »4 parts of Wn-butylpyrrolidine-2,5-bis (propionic acid diethyl ester), 13.9 parts of m-xylylenediamine, 12.1 parts of hexamethylenediamine and 30 parts of dried loluene are heated under reflux for 2 hours;
after distilling off the toluene / ethanol mixture from
the reaction mixture at a temperature below 240 ⁰ C, the residue was at 240 G in a stream of inert gas

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atmospheric pressure for 2 hours and then stirred below 0.5 mm Hg at 270 ⁰ C'8 hours at a pressure. A crystalline, light yellow, solid idsch polyamide was obtained.

Hein Hehnelzpunkt was in the range between 111 ° and 116 ⁰ C and the grujid molar viscosity number C ^ J was 0.36.

A. rb e it swe1se 10

This procedure explains the process for the production of an IvIi sch polyamide used in accordance with the invention from n-butyl-bis (3-carboxypropyl) amine / m-xylylene-amine Decamethylenediamine (100 / '5o: 50 Ποί- ^.).

A mixture of 27.5 times n-Butyl-bis- (3-methoxycarbonylpropyl) amine, 7.5 parts of m-xylylenediamine, 9.4 parts Decamethylenediamine and 2ü parts of dried toluene were heated under reflux for 2 hours. Then the toluene-methanol mixture was used distilled off from the reaction mixture and the resulting residue was initially under Tiihren 2 hours at 240 C in a stream of inert gas under atmospheric conditions Pressure and then heated for 8 hours at 270 ° C under a pressure of less than 0.5 mm Hg. It became a amorphous light yellow solid polyamide with a basic molar Obtained viscosity number t. · ^ Of 0.30.

Example 1

A fuss from 97! 'Hurry dimethyl terephthalate, 69 parts of ethylene glycol and 0.02 parts of titanium tetraethoxide

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was 3 hours at 16O - 22O ⁰ C was heated and the methanol formed was distilled off. The reaction mixture was kept at 275 ° C. and polymerized first for one hour under a pressure of 760-10 mm Hg and then for 1.5 hours under a pressure of 10-0.5 mm Hg. 18.5 parts of the liomopolyamtfids obtained according to procedure 1 were added to the resulting ι ο Iy nie ri s at, while the former was kept at 275 ° g, and the mixture was stirred for 40 minutes; it gave an SiOH durchsicljtiges (transparent) light yellow polymer having a i.rweichungspunkt of 25913 ⁰ C and a giundmolaren Viskositutszahl C ¹ ^} of 0.53.

Hach drying in hot air at HO ⁰ G for 5 hours, the polymer at 275 ⁰ C with a dpinngeschwindigKeit of 700 m / min was spun. Immediately after the start of the spinning process, the polymer had an intrinsic viscosity L ^ 1 of 0.52 and at the end of the spin treatment the intrinsic viscosity was C ^ 0.50. After 4f3-iacher extension at 70 ⁰ C, the fiber has a titer of 3.2 denier, a strength of 4.5 g / de and an elongation at break of 38 ·> had ί.

0.1 i'eile of the fiber produced in this way were containing, colored 0.5 parts Alizarinlichtblau-AA, 3 parts hisesaig, 15 parts of Glauber's salt and 82 parts of \ 7asser at 100 ⁰ C for one hour in a bath; then the material was in a 0.2% synthetic wetting agent

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solution (detergent solution) 20 minute "purged at 7O ⁰ O and then with / ater at the · same lemperatur washed. The fiber was dyed to a deep · ülau.

■ Example 2

jine solution from 97! 'rush dimethyl terephthalate, 69 parts ... ethylene glycol and 0.02 parts titanium tetraethoxide was heated for 5 hours at 160 - 220 0 and the formed Methanol was distilled off. The reaction mixture was held at 275 ° 0 and under a pressure of 760-10 mm Hg an uterus and then under a pressure of 10-0.5 mm Hg polymerized over 1.5 hours. The Iolyiaerisat obtained was kept at 285 ° and there were 31 leile according to Procedure 4 added polyamides obtained. the Mixture became 40 l / dn at a pressure below 0.5 mm Hg stirred and gave a translucent light yellow! polymer with a point of deviation of 257.9 ° 0 and one intrinsic viscosity Ct ^ jI of 0.60.

The iolymerisat was dissolved in hot jjuft 6 hours at 140 ⁰ C dried at 275 ⁰ G with a Hpinngeschwindigkeit of 600 m / min and then spun at 4.5 times at 00 ⁰ C stretched. The resulting fiber had a linear density of 2.8 denier, a tenacity of 4.1 g / de and an elongation at break of 46 ^.

0.1 part by weight of this fiber and 0.1 part by weight, full were put together in a bath containing 0.5 part

; - 9 0 9 8 2 6/1 2 3 Λ bad ofhginal

Chibaran-Brillantblau-GL, 3 parts Liieesaig, 15 parts G-laubersala and 82 parts', / aaser contained, one hour at 1ÜÜ ν colored and then in the same '.,' Eise as in Example 1 flushed. The two rasem became similar to a deep one Colored blue.

■ Example 3

A mixture of 97 parts of dimethyl terephthalate, 8.7 parts of idinethyl adipate, 77 parts. thylenglycol and 0.022 part of titanium tetraethoxide was 3 utunden at 150 - 23O ⁰ C was heated to remove methanol formed daa: then the Lea ^ was tionarnischung at 275 ° 0 under a pressure of 760 to 10 mm Hg for one hour and then under a pressure polymerized from 10-0.5 uim Lg over 1.5 hours.

The polymer obtained was kept at 260 G, while 18.5 i'eile of that obtained according to procedure 1 Uomopolyamide was added and stirred under a pressure of 10 µm Hg for 40 minutes. JJs became thermoscopic light yellow polymer with a softening point left to right of 239> 4 ° 0 and an intrinsic molar viscosity of £ .7 ^ of 0.55 received.

Awake drying in hot air at 140 ° C. for 6 hours, the polymerizate was spun at 260 ° with an internal speed of 100 m / min and stretched at 80 ° to 4.5 times, all of the resulting pairs had a titer of 2.9 denier, a strength of 4 »2 g, de and a hot

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elongation of 4-8 ^ i. u'enn 0.1 (weight parts of the Paser with C'ibaran-Brillantblau-GL were colored as in Example 2, resulted in a deep blue coloration.

Example 4

! A llisohung of 97 parts of dimethyl terephthalate, 9.7 parts Diinethylisophthalat, 77 parts Jvthylenglyool and 0.022 part of titanium tetraethoxide was 3.5 hours at 160-230 ⁰ O heated au remove the methanol formed;

The reaction mixture was then polymerized at 275 C under a pressure of 760-10 mn Hg for one hour and then under a pressure of 10-0.5 mm Hg for 1.5 hours. In this / else a polymer having a softening point of 240.3 ⁰ C and an intrinsic Via ositätszahl was obtained from 0.88.

After drying in hot air at 160 ⁰ C for 2 hours, the polymer was mixed with 18.5 parts of the obtained according to working example 1 Homopol ^ amide and mixed for 40 minutes at 26O ⁰ G under Pühren. Then the mixture was spun at the same temperature at a spinning speed of 700 m / min. Immediately after the start of the spinning process, the polymer had an intrinsic viscosity t-vp of C.53 and at the end of the process the intrinsic viscosity was L ^ 0.51.

When stretched 3.9 times at 70 ° G, the fiber had a titer of 3.1 denier, a tenacity of 2.6 g / de and an elongation at break of 41 #.

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0.1 'files of this fiber were made with Oibaran Brilliant Blue GrL colored to a deep blue when uie in the same “Were treated as in Example 2.

Example 5

Line mixture of 97 'filing of dimethyl terephthalate, 69 parts of y / thylenglyool and 0.02 part of titanium tetraethoxide was 3 hours at 160 - 22O ⁰ C and the heated !! ethanol formed was distilled off. The reaction mixture was then polymerized first for one hour under a pressure of 760-10 mm Hg and then for 1.5 hours under a pressure of 10-0.5 mm Hg, while always maintaining the temperature of 275 °. The resulting base polyester was kept at 275 ° C, 18.5 'files of the homopolyamide obtained in accordance with the procedure were added and the mixture was stirred for 40 minutes under a pressure of less than 0.5 mm Hg, resulting in a transparent pale yellow polymer obtained with a softening point of 258.1 ⁰ C and an intrinsic viscosity L ^ J of 0.57.

After frocknung in hot air at 140 ⁰ C for 6 hours, the i-olymerisat was at a spinning speed of 600 m / min spun at 275 ⁰ C and stretched at 80 ⁰ C to 4.5 times. The resulting fiber had a linear density of 2.8 denier, a tenacity of 3.8 g / de and an elongation at break of $ 45. The fiber was stained a deep blue when in the same - / ice as in

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Example 1 was dyed and rinsed.

Example 6

To a base polyester, which was obtained from a mixture of 97 parts of dimethyl terephthalate, 69 parts of ethylene glycol and 0.02 part of titanium tetraethoxide in the same way as in Example 1, 19.0 parts of that according to procedure 2 were obtained The homopolyainide obtained was exposed while the former was kept at 275 ⁰ O. The mixture was stirred for 40 minutes at a pressure below 0.5 mm Hg and a transparent yellow polymer resulted with a softening point of 258.6 G and a basal molar Viscosity number Dv ^ J of 0.55.

After drying in hot air at HO ⁰ O for 6 hours, the polymer was ^{spun at 275 0} O with a spinning speed of 600 m / min and stretched 4.5 times ^{at 80 0 O.} The resulting easer had a 'i'iter of 2.7 denier, a tenacity of 3.9 g / de and an elongation at break of 4-2 ψ. This paser was stained to a deep blue with alizarine light blue-AA when treated in the same manner as in Example 1.

B EISP iel 7

To a ΰ-round polyesxer, which consists of a r.isdung of 97% of dimethyl terephthalate, 69 parts of ethylene glycol and 0.02 part of titanium tetraethoxide in the same V / eise as

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BATH

- 2 B -

obtained in Example 1, 33 parts of the obtained according to working example 5 i-iachpolyamids were added, while the former was maintained at 275 ⁰ O "Ide mixture was stirred at a iruck below 0.5 nra Hg iiinuten 40 to give a transparent yellow xolymeriaat with a deflection point of 257 0 and an intrinsic molar viscosity number O ^ J of 0.54.

iiach hours drying in hot air at 140 ⁰ C for 6 was the polymer at 275 ⁰ U with Einei opinngeschwindigkeit of 600 m / min and spun at 80 ⁰ C, the un 4,5-faohe stretched. The resulting fiber had a linear density of 2.8 denier, a tensile strength of 3.5 g / de and an elongation at break of 45 ". This fiber was stained with alizarine light blue-AA to a deep blue when in the same as in Example 1 was treated.

Example 8

To a base polyester, which had been obtained in the same 7eise as in Example 1 from a λίϊβοίηπ ^ of 97 parts of dimethyl terephthalate, 69 parts of ethylene glycol and 0.2 parts of titanium tetraethoxide, 19 parts of deB were obtained according to procedure 4. iischpolyamids added, while the former was maintained at 275 ⁰ C. The ^T 'ischung was stirred for 40 minutes at a pressure below 0.5 mn Hg, yielding a clear yellow irolynerisat having a softening point of 259 »C 1 and an intrinsic Vis

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^BAD o _nQ

viscosity number \ jy \\ of 0.56.

after drying for 6 hours in a hot air of 14O ⁰ C was iolymerisat at 275 ⁰ C with a lipinngeschwindigkeit of öüO m / min and spun at OEO ° G to 4.5 times stretched. The resulting fiber had a linear density of 2.9 denier, a tenacity of 3.8 g / de and an elongation at break of $ 41. This fiber was dyed deep blue when it was dyed and washed with alizarin light blue-AA as in Example 1 »

Example 9

To a base polyester, which had been obtained in Example 1 from a mixture of 97 parts of dimethyl terephthalate, 69 parts ^ thylenglycol and 0.02 part of titanium tetraethoxide, 21 parts of LIischpoIyamide obtained in operation have been added, while the former was maintained at 275 ⁰ O. The mixture was stirred for 40 minutes at a pressure below 0.5 mm Hg and gave a transparent yellow polymer with a softening point of 257-4 ° and an intrinsic viscosity of

After drying in hot air at 140 ° 0 for 6 hours was rolymerisat at 275 ° 0 with a spinning speed of 600 m / min and spun at 8O ⁰ C to 4.5 times stretched. The resulting fiber had a titer of

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2.6 denier, a tenacity of 5.7 g / de and an elongation at break of 46> 9.

This raser was stained deep blue when stained and washed with alizarin light blue-AA as in Example 1 became.

Example 10

To a base polyester, which had been prepared as in Example 1 from a mixture of 97 parts of dimethyl terephthalate, 69 parts and 0.02 part of titanium tetraethoxide thylenglycol ..., 54 were obtained according to the Leile operation 6 lischpolyamids added, while the former at 275 ⁰ C was held. The mixture was stirred for 40 minutes at a pressure below 0.5 mm Hg, yielding a clear yellow lolymerisat having a softening point of 259.8 ⁰ C and an intrinsic viscosity [V ^ J of 0.59 "

After drying for 6 hours in a hot air of 14O ⁰ C was iolymerisat stretched 4.5 times at 275 ⁰ C with a spinning speed of 6CO iu / min and spun at 80 ⁰ C. The calibrating fiber had an i'iter of 2.9 denier, a tenacity of 5.9 g / de and an elongation at break of 58%.

This pair was colored deep blue whoever they like in example 1 stained with alizarin light blue AA and rinsed became.

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Comparative example 1

A mixture of 97 parts of dimethyl terephthalate, 69 parts and 0.02 parts Ithylenglycol was litantetraäthoxyd 3 hours at 16ü - heated 2 John ⁰ C, remove the formed Kethano1 to. The reaction mixture was then polymerized at 275 ° C. for one hour under a pressure of 760-10 mm Hg and then for 1.5 hours under a pressure of 10-0.5 mm Hg.

! The polymer obtained was kept at 275 °, 18.1 parts of that obtained according to procedure 9 were obtained Mixed polyamides were added and it was oü i'minutes under stirred to a pressure of about 0.5 mm Hg, an opaque result resulted light yellow peat fabric.

An opaque polymer produced from the semi-transparent l ^"v ILM was observed with an optical Microscope of 200-fold magnification. A dispersion of round polyamide particles was found in the polyethylene terephthalate background. Furthermore, the I ¹ Hm was stretched 2.3 times at SO ⁰ O, dyed in the same way as in Example 2 with Cibaran Brilliant Blue GL and rinsed and examined again under the microscope. It was observed that the ethylene terephthalate background remained completely uncolored and only the dispersed polyamide particles which had been stretched into an oval shape as a result of the stretching treatment had been colored blue.

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Vergleio hsbei s piel 2
iiiiie mixture of 97 'files dimethyl terephthalate,

! 69 hone Athylenglycol and 0.02 'rush i'itantetraäthoxyd was bü 3.5 hours at 1 - 210 ⁰ G brought to the reaction and methanol formed dab was NBDE; 8tilliert. Then, the Jxeaktionsmischung was polymerized for one hour under a pressure of 10 mm 76ü-Itg and further 1, 5 otunden mm under a pressure of 10 to 0.5 iig, while the temperature was maintained at 275 ⁰ C.

The resulting polymerizate was melted and while the melted mass was still the temperature of 275 ° G retained 19 parts of the mixed polyamide obtained according to procedure 7 were added. The .mixture was

Stirred for 70 minutes under a pressure of 0.5 mm Hg to give an opaque pale yellow solid jrolymerizate.

.cJin made from the lolyuerisat film was semi-transparent; when viewed with an optical kicroskop of 2ou magnification it was observed that were dispersed in the ± olyfc-tliylenterephchalatuntergrund round of Jeilchen! "ischpolyamids' eiterhin of Jr C was 2.5 times stretched at 8O ^{0 1} Hm in which the same as in Example 2, stained with iJibaran-Jriliantblau-uL and washed and checked again under the microscope. It was observed that the polyethylene terephthalate base remained completely uncolored and only the dispersed ...

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that became oval in shape as a result of the otreok treatment were colored blue.

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Claims (5)

Pat entanaprUohe (Vj) Process for the production of modified polyester, characterized in that one in molten State a linear polyester, whose dioarboxylic acid component mainly consists of terephthalic acid and its Glyool component mainly from an alkylene glycol is composed, mixed with at least one polyamide, the diamine component of which is mainly composed m-xylylenediamine and its diacid component for Mainly consists of at least one aliphatic tertiary amino dioarboxylic acid in which the basic amino group Each of the carboxyl groups is separated by at least three carbon atoms. 2) Method naoh Anspruoh 1, characterized in that nan the linear polyester with the at least a polyamide mixed in a molten state »and the The mixture is then heated under reduced pressure. 3) Method according to Anspruoh 1 or 2, characterized in that at least 60 mol # of the diamine component of the polyamide consist of m-xylylenediamine. 909826/1234 4) Method according to one of the Anaprüohe 1-3, characterized! that at least 40 mol $ the
The dioarboxylic acid component of the polyamide consists of one or more aliphatic tertiary amino dioarboxylic acids in which the basic amino group is separated from each of the carboxyl groups by at least three carbon atoms. 5) Method naoh one of claims 1-4, characterized in that the polyamide and the linear Polyester mixed in the molten state in such a proportion »that the amount of aliphatic tertiary aminodloarboxylic acid in the polyamide 0.5-20 to the dioarboxylic acid © component of the polyester bath
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