DE2225282A1 - New compositions based on polyesters with good affinity for colors and processes for their preparation - Google Patents

Description

Dr. F Zumstein sen. - Dr. E-Aesmann
Dr-R-Koenineberger - PW. Phys. R. Holzbauer

in. F. Γ -.! π ·: · Ιο · α μη.

Patent attorneys

8 monks Ί. Bräuhcuwlraße 4/1 »

RH 3753

RHONE-POULENC-TEXTILE, Paris, France

New compositions based on polyesters with good affinity for colors and processes for their preparation

The present invention relates to new compositions based on polyesters which have a good parbaffinity for have acidic dyes. The invention also relates to a method of making these compositions.

The aromatic dicarboxylic acids, especially terephthalic acid, and polyesters derived from aliphatic, cyclanic or cycloaliphatic diols are of great commercial interest for numerous fields of application due to their increased Strength, flexibility, wrinkle resistance, etc.

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However, the filaments and fibers obtained from these polyesters are due to the lack of reactive sites on the macromolecular ones Chains difficult to dye.

A particularly interesting one because of its increased lightfastness as well as its low manufacturing price The class of dyes is that of the acidic dyes. Unfortunately, unlike polyester, they have polyamides, for example, have no affinity for these types of dyes.

In U.S. Patent 2,891,929 it was suggested to use amine groups in the polyester by replacing part of the dicarboxylic acid with an amino acid during the condensation of the dicarboxylic acid to introduce with the diol. The polymers thus obtained, however, have a marked tendency while yellowing from the heat treatments to which they are subjected in the course of their preparation or processing.

It has also been suggested in the reagents during transesterification the starting materials or the polycondensation leading to the formation of the polyester is a mixture of an alkaline earth metal and a quaternary ammonium halide. The polyesters obtained in this way have good transparency and good heat resistance, but they have no special Color affinity.

There have now been new compositions based on polyesters, those of at least one aromatic dicarboxylic acid and aliphatic, cyclanic or cycloaliphatic diols with 2 to 10 carbon atoms originate, with these compositions 0.1 to 10 ^, based on the sum of the repeating Groupings of the polymer (s) contain on groupings derived from a product of the formula

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■ Ν® (R) ₄ . 1 / η Χ ^ηΘ _(Ι)

are derived in the

the radicals R, which can be the same in pairs, mean aliphatic, cyclanic, cycloaliphatic or aromatic radicals, which for all of the radicals R at least carry a group which is capable of forming ester bonds, two of these radicals also together forming a saturated one or unsaturated ring which may contain other nitrogen atoms, which may be quaternized,

X ⁿ ® means a stable anion with the valency η of an organic acid or inorganic oxygen acid and

η represents an integer greater than or equal to 1.

The invention also relates to a method for producing such compositions by polycondensation of at least one aromatic dicarboxylic acid and alinatic, cycianic or cycloaliphatic ^! Diols with 2 to 10 carbon atoms in the presence of 0.1 to 10 mol $, based on the moles of acidic reaction component, on a product of the formula I. If desired, you can add a small amount to the reaction mixture Amount of an aliphatic dicarboxylic acid and / or a polyethylene glycol admit to modify somewhat the property of the product obtained.

The product I can during the transesterification between the product, which leads to the formation of the aromatic dicarboxylic acid, and are added to the diol or diols used. It can also be added during the condensation of a dicarboxylic acid with this or these diols. One can also if desired this product "condense with a dicarboxylic acid, which can be aliphatic or aromatic, to form a

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2225

Polymer to form at any point during the transesterification or the condensation of the above-mentioned products or simply with the polyester, its color affinity one wants to improve, can be mixed.

Any desired dicarboxylic acid can be used to make this polymer having a number of carbon atoms that can be up to 12 or even more, use.

Quaternary ammonium sulfates, sulfonates, phosphonates or nitrates, for example, which have at least one group capable of forming ester bonds on one or more radicals bonded to a nitrogen atom can be mentioned as products of the formula I. For example, dimethyl di (3-hydroxyethyl) ammonium p-toluene sulfonate, methyl ethyl di - (3-hydroxyethyl) ammonium p-toluene sulfonate, N, N'-dimethyl-N, N ¹ -di - (ß-hydroxyäthylj-piperazinium-di-p-toluenesulphonate, trimethyl 1-2-hydroxy-5-carbomethoxybenzylammonium-ptoluenesulphonate, benzylmethyl-di- (ß-hydroxyethyl) -ammonium-ptoluenesulphonate, dibenzyl ~ di- (ß-hydroxy) -ammonium-ptoluenesulfonate, benzyl-tri- (ΰ-hydroxyethyl) -ammonium-p-toluenesulfonate, methylbenzyl-di-Qx-carboxypropyl) -ammonium-p-toluenesulfonate, dirnethyl-di - (^ - carboxypropyl) -ammonium-p- Use toluenesulfonate, dibenzyl-di- (c'-carboxypropyD-ammonium-p-toluenesulfonate, and the like.

The new compositions obtained have a good color affinity for acidic, simple and metal-containing dyes. These color affinity is particularly valuable when the polymers are to be used for the production of filaments and fibers.

OWGlNA INSPECTED 209850/1216

222 5

It is generally preferred to use compositions containing 1 to 3 % of groupings derived from the product of Formula I, based on the total number of repeating groupings of the composition, for technical as well as practical and economic reasons.

The dyed products obtained in this way have particularly good lightfastness combined with excellent washfastness, Fastness to cleaning and sublimation resistance, as the dye is then chemically bonded to the fiber.

In addition, it is then possible to dye fabrics made of mixtures of polyester and full-fiber in a single bath offers certain economic advantage.

T's is also possible to produce products made from yarns with basic Dyes can be dyed, such as polyesters modified by groups -SCUNa, and yarns according to the invention, which can be dyed with acidic dyes. By coloring the raw products thus obtained with basic and acidic dyes can be used to create different effects in color contrast, with each type of yarn compared to the dyes for the other species is completely protected.

The process according to the invention is of particular value when it is a question of diols having 4 carbon atoms and more derived polyesters, but you already get valuable results with polyesters made from Diols with 2 carbon atoms originate. It is particularly surprising to find that products that contain an anion and a q'iaternary ammonium cation contain polymers derived therefrom be able to give a color affinity for acidic dyes.

2 0 9 8 5 0/1216 ° ^WGINAL

22? ^ "3 2

The following examples, in which without any information to the contrary the parts and percentages parts and percentages by weight serve to further explain the invention.

In these examples, the dyes are indicated by their CI-E designations from the Color Index, edition 1956 and its additions, and the viscosity number IV is derived from the viscosity in solution, measured at 25 ^° C. with a solution of 1 % (weight / volume) Polymer in orthochlorophenol, by the formula

tv - specific viscosity -innn ^iV "concentration ^{x ιυυυ}

in which the concentration is expressed in g / l.

example 1

Dimethyl di (ß-hydroxyethyl) ammonium p-toluenesulfonate is produced (A) from methyl diethanolamine, which is added slowly and with stirring Methyl p-toluenesulfonate is added, forth. The product A is washed and dried under slightly reduced pressure.

Is reacted slowly with stirring to the product A of sebacoyl chloride in amounts stöchlornetrischen au, heated to bring the temperature to 15O ⁰ C, the pressure at 1 Torr is lowered, and then holds this pressure and this temperature for 3 hours upright. A pale yellow rubber-like polymer B is obtained in this way.

ORIGINAL INSPECTED 209850 / 121S

21 5282

Place in a stainless steel reaction vessel at the same time the following components:

Dimethyl terephthalate 3880 parts

Ethylene Glycol 3 100 parts

Mangana acetate 1.9 parts

Antimony (3) oxide 1.6 parts

The methanol formed by the reaction is heated and then the excess glycol is distilled off.

When the temperature reaches 225 ⁰ C., are employed 0.63 parts of phosphorous acid and at 230 ⁰ C ^ 9 parts of a glycolic 20 ^ strength Titanoxydsuspension. When the mass has reached a temperature of 24o ° C, is lowered progressively the pressure to 0.5 Torr within 4o minutes while the temperature is brought to 287 ⁰ C.

After 45 minutes of polycondensation, the vacuum is released with nitrogen on, adds 190 parts of the polymer B and brings it back with stirring for 15 minutes under vacuum.

A slightly yellowish polymer is obtained, which is then poured and granulated. It has a viscosity number of 58 and a softening point of ⁰

After drying for 3 hours at 160 ° C., the granules are melted and extruded through a spinneret which has 23 orifices 0.34 mm in diameter. The received Filaments wound up at 75 m / min are then passed over a drawing pin and a plate under the following conditions stretched:

INSPECTED 209850/1216

Extension pin temperature 75 ° C

Temperature of the plate 10O ⁰ C

Degree of stretching 4.8

Drawing speed 100 m / min

The yarn obtained has a linear density of 74 dtex / 23 individual threads, a dry strength of 2.3 g / tex and a dry elongation of 17 % .

A skein of 20 g of this yarn is placed in a bath of the following Composition immersed:

CI acid red 174 0.4 g

Diammonium phosphate 1 g

Condensate of stearyl and oleyl

amines with ethylene oxide 0.5 g

Water 1000 ml

Acetic acid for pH J5 -

Trichlorobenzene 10 g

After boiling in this bath for 45 minutes, the yarn is washed, rinsed and pressed off at 60 ° C. in an aqueous solution containing 1.5% of an alkyl sulfate. It is strongly colored red. This color does not disappear after 20 minutes of extraction in water and methylene chloride.

For comparison it should be noted that: 3 a yarn made under the same conditions, but without the addition of polymer B during the Polyethylene glycol terephthalate produced from polycondensation only takes on a very light pink color, which occurs when washed 6o ° C under the same conditions as specified above, disappears.

ORIGINAL INSPECTED 209850/1216

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Example 2

Place in a stainless steel reaction vessel at the same time the following components:

Dimethyl terephthalate ^ 88o parts

Butanediol-CM) 2250 parts

stoichiometric polytriethanol- '
amine titanate 0.9 parts

The mixture is heated and distilled off all of the methanol formed and then sets 88 parts of a 20 percent Titanoxydsuspension in butanediol, while the temperature is 245 ⁰ C. The pressure is lowered to 1 Torr within
4o minutes while the mass is brought to 255 ⁰ C.

After 45 minutes of polycondensation, 122 parts of the product A described in Example 1 are added and the polycondensation is started 15 minutes away.

The polymer is poured, cooled and granulated. It is completely white and has a viscosity number of 96, a melt viscosity at 260 ° C of 14OO P and a softening temperature of 221.3 ° C.

After drying for 2 hours at 140 ° C., the granules are melted and extruded by means of an extruder through a spinneret with j53 openings of 0.50 mm diameter (winding speed: 1300 m / min).

ORIGINAL INSPECTED

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2 22.5? * 2 - ίο -

The threads are drawn through a drawing pin and a plate under the following conditions:

Temperature of the stretching pin 85 ⁰ C

Temperature of the plate 165 ⁰ C

Degree of stretching 2.2

Drawing speed 650 m / min

The yarn obtained has a linear density of 167 dtex / 33 individual threads, a dry strength of 42.1 g / tex and a dry elongation of 16 % .

A skein of 20 g of this yarn is placed in a bath of the following Composition brought:

CI acid blue 40 with ethylene oxide Q.s. 0 Λ g ml Diammonium pha t Q.s 1 G PH Condensate of stearyl and Oley! Amines 0 , 5 g water 1000 acetic acid for

- 4th

After boiling for 5 minutes in this bath, the yarns are washed, rinsed and pressed at 60 ° C. in an aqueous solution containing 1.5% of an alkyl sulfate. The strand is colored blue. The color does not disappear after 20 minutes of extraction with water and methylene chloride.

A comparison sample made from polytetramethylene glycol terephthalate produced in an identical manner, but without product A, assumes a light blue coloration which ^{disappears completely when washed at 60 °} C. under the same conditions as above.

ORIGINAL SNSPECTED

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Example 3

Man is methyl-ethyl-di- (beta-hydroxyethyl) ammonium p-toluenesulfonate (C) by slowly adding Kthyldiäthanolamin to methyl p-toluenesulfonate in an equimolar amount and heating for 2 hours at 150 ⁰ C forth.

1595 parts of adipoyl chloride are slowly added to 2780 parts of product C in a reaction vessel under a pressure of 20 torr. The temperature rises rapidly to 8o ° C, and the mixture is heated for 3 hours under 1.5 Torr at 15O ⁰ C

A pale yellow, very viscous polymer D is obtained.

This polymer is mixed in an amount of 4% with PoIyäthylenglykolterephthalat with a Schrnelzviskosität at 285 ⁰ C of 2800 P, and extruding the mixture through a spinneret, the openings 252 with 0.23 mm diameter, by means of a twin-screw extruder.

The filaments thus obtained are to a degree of 4.1 in an aqueous bath of 67 ⁰ C, 3% by weight of an oiling agent to mineral oil-based, drawn at a speed of 100 m / min. They then have a titer of 3.3 dtex, a dry strength of 25.2 g / tex and a dry elongation of 34.1 %.

20 g of loose fibers obtained in this way are placed in a bath consisting of the following components:

ORIGINAL INSPECTED

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S. ο, S. ml S. 1 G pH 5 0, G Q. , 4 Q. , 5 1000 for

- 12 -

CI acid green 88
Diamronium Phosphate

Condensate of stearyl and oleyl amines with ethylene oxide

water

acetic acid

Trichlorobenzene 10 g

After boiling for 30 minutes, the bath will be exhausted. After washing at 60 ° C. in an aqueous solution containing 1.5 % of an alkyl sulfate, rinsing and pressing, the loose fibers are colored green. The color can withstand extraction with water and with methylene chloride.

A comparison sample prepared in the same way as above, but without the addition of polymer D and immersed in the same dye bath only takes on a faint yellow-greenish color, which disappears when washed at 60 ° C.

Example 4

At the same time, 200 parts of N, N ¹ -bis (β-hydroxyethyl) piperazine and 420 parts of methyl p-toluenesulfonate are introduced into a reaction vessel. The mixture is brought to 140 ° C. for 2 hours. The product obtained is recrystallized from methanol and dried under vacuum. So we get N, N ^! -Dimethyl-N, N ¹ -di (β-hydroxyethyl) -piperazinium-di-p-toluenesulfonate (E).

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Immediately place in a stainless steel reaction vessel the following ingredients in good time while stirring:

Dimethyl terephthalate 388 parts Butanediol- (1.4) 225 parts

polytriethanolamine titanate, 0.09 parts

The transesterification of the alcohols begins at about 155 ^° C. After 2 1/2 hours, all of the methanol formed has been distilled off and the temperature of the mass has been reached

One then reduces the pressure progressively down to 1 Torr within 4o minutes, while the mass is brought to 225 ⁰ C. After 45 minutes of polycondensation lifts the vacuum with nitrogen and sets 11 parts of the product to E. The polycondensation is then continued for 10 minutes.

A white polymer P is obtained, which is poured into water and then into grains with dimensions between 0.2 and 0.5 mm crushed. 2 g. Of this powder are placed in a bath, which consists of the following components:

CI acid red 228 Q.s 0 * , 04 G Diammonium phosphate Q.s 0 • ,1 G Condensate of stearyl and Oleylamines with ethylene oxide 0 , 05 G water 100 ml acetic acid for pH 5

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2225? 82 - 14 -

After boiling for 30 minutes at atmospheric pressure, the bath is practically exhausted and the powder has taken on a violet-red color, which after washing at 60 ^° C. in an aqueous solution containing 1.5 % of an alkyl sulfate and during extraction with Water or with Methy.lenchlorid remains.

For comparison it should be mentioned that under identical conditions, however, polytetramethylene glycol terephthalate produced and colored without the addition of product E is only one takes on a dirty rose color which disappears almost completely on washing and completely on extraction.

Example 5

A stirred or shaking vessel equipped with an inlet for gaseous hydrogen chloride is brought into motion the following components at the same time:

Methyl p-hydroxybenzoate 456 g

Trihydroxymethylene 112.5 g

Zinc chloride 75 g

Chloroform I800 g

The whole thing is dissolved at about 40 to 45 ^° C. Hydrogen chloride is then passed in for 15 hours at this temperature.

After washing, 1-hydroxy-2-chloromethyl-4-carbomethoxybenzene is obtained, that one in benzene with the introduction of dimethylamine Brings to the boil for 8 hours. After precipitation and filtration, the i-hydroxy ^ -N-dirnethylarninomethyl ^ - carbomethoxybenzene from methanol.

ORIGINAL INSPECTED . .. 209850/1216

22 ^ 5282

Bring 52 * 25 parts under nitrogen and with agitation of this product and 46.5 parts of methyl p-toluenesulfonate.

After gentle heating, the temperature rises spontaneously to about 80 ^° C. and the movement is stopped after 20 minutes. Leave to stand overnight. After purification, 75 parts of trimethyl (2-hydroxy-5-carbomethoxybenzyl) ammonium ρ-toluenesulfonate (F) are obtained.

The polycondensation is then repeated under the conditions of Example 4, the product E being replaced by the product F replaced. The polymer obtained after comminution is in the form of a very light yellow powder. 2 g of this powder are placed in a bath of the following composition:

CI acid blue 4θ 0.04 g

Diammonium phosphate 0.1 g

Condensate of stearyl and
Oleylamines with ethylene oxide 0.05 g

Water Q.s. 100 ml

Acetic acid Q.s. for pH 3 - 4

After boiling for ^ 0 minutes, the powder has turned blue, which persists after washing and extraction.

Example 6

Place in a stainless steel reaction vessel at the same time while moving the following components:

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Dimethyl terephthalate 2028 parts, dimethyl isophthalate 676 parts, 1,4-dihydroxymethylcyclohexane 2534 parts Butyl orthotitanate 6.8 parts

The temperature is increased rapidly to 260 ° C. and then decreased 1 1/2 hours the pressure within 20 minutes to 1 Torr.

After 15/4 hours, 150 parts of that described in Example 1 are used Product B after releasing the vacuum with nitrogen.

The polycondensation is continued for 10 minutes. Then the polymer is cast and granulated. There is then a softening point of 237 ⁰ C and a melt viscosity at 26o ° C of 1550 P in the form of very pale yellow transparent Stücke.mit.

The dry polymer is melted at 265 ⁰ C and having through a spinneret, the 23'öffnungen with 0.34 mm diameter at a speed of 75 m / min extruded.

The filaments obtained are drawn on a plate of 100 ⁰ C to a level of 4 at a speed of 33 m / min.

A yarn is obtained which has a titer of 98 dtex / 23 individual threads! has a strength of 13> 3 g / tex and a dry elongation of 29.8 % .

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A skein of 20g of this yarn is placed in a bath of the following composition:

CI acid red 266

Diammonium phosphate

Condensate of stearyl and oley amines with ethylene oxide

water

Orthophenylphenol acetic acid

After boiling in this bath for 45 minutes and washing at 60 ° C in an aqueous solution containing 1.5% of one Alkyl sulfate, the strand obtained is colored red and its color remains after extraction with water and water for 20 minutes with methylene chloride.

For comparison purposes, it should be noted that a yarn obtained from a copolyester prepared in the same way but without incorporating product B only takes on a very light pink coloration which ^{disappears completely after washing at 60 °} C. in the same detergent solution as above .

S. 0.4 G - 4th 1 G S. 0.5 G Q. 1000 ml 10 G Q. for PH 3

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Claims (1)

2275282 Claims 1. Compositions based on polyesters derived from at least one aromatic dicarboxylic acid and optionally an aliphatic dicarboxylic acid and aliphatic, cyclanic or cycloaliphatic diols having 2 to 10 carbon atoms, these compositions being 0.1 to 10 fo, based on the sum of the repeating groupings of the polymer or polymers, on groupings derived from a product of the formula N ® (R) ₄ . l / n X ^ne (I) originate in the the radicals R, which can be identical in pairs, are aliphatic, cyclanic, cycloaliphatic or aromatic radicals, which carry at least one group for all of the radicals R which is capable of forming ester bonds, where two of these radicals can also together form a saturated or unsaturated ring, the other optionally may contain quaternized nitrogen atoms, X ⁿ ® means a stable anion with the valency η of an organic acid or an inorganic oxygen acid and η is an integer ^ 1. 2. Composition according to claim 1, characterized in that they contain 1 to 1%, based on the repeating groupings of the polymer or of the polymers, of groupings which originate from the product of the formula I. 209850/1216 22z;:? P2 - ■ 19 - y. Compositions according to claim 1, consisting of a copolyester derived from at least one aromatic dicarboxylic acid and optionally an aliphatic dicarboxylic acid and at least one aliphatic or cycloaliphatic diol, with a content of 0.1 to 10 %, based on the repeating groupings of the polymer, on groupings derived from a product of the formula I. 4. Compositions according to claim 1, consisting of a mixture of a polyester, which consists of at least one aromatic Dicarboxylic acid and optionally an aliphatic dicarboxylic acid and at least one aliphatic or cycloaliphatic Diol originates, and a polyester from at least one aliphatic or aromatic dicarboxylic acid and a product of the formula I, optionally with an aliphatic or cycloaliphatic diol, the number of which is derived from this product originating groupings 0.1 to 10 Jo of the total number of repeating groupings of the polymers. 5. Process for the preparation of the compositions according to one of claims 1 to J5, characterized in that at least one aromatic dicarboxylic acid and optionally an aliphatic dicarboxylic acid and at least one aliphatic, cyclanic or cycloaliphatic diol with 2 to 10 carbon atoms in the presence of 0.1 to 10 mol $, based on the moles of the acidic reagent _{s of} a product of the formula I polycondensed. 6. Process for the preparation of the compositions, according to a of claims 1, 2 or 4, characterized in that a polyester which consists of at least one aromatic dicarboxylic acid and optionally an aliphatic dicarboxylic acid and at least one aliphatic or cycloaliphatic Diol originates, and a polyester from at least one aliphatic 209850/1216 see or aromatic dicarboxylic acid and a product of the
Formula I, optionally with an aliphatic or cycloaliphatic diol, is mixed in amounts such that the number of groupings originating from this product makes up 0.1 to 10% of the total number of repeating groupings in the mixture. 7. Threads, films and other fabrics with good affinity for acidic dyes derived from compositions according to one of claims 1 to 4. 209850/1216