DE1545078B2 - Process for the production of dyeable, linear polyesters - Google Patents

Description

ROOCH _2n C _n C _n H _2n COOR

used in which X is a hydrogen atom or an SO ₃ M, SO ₃ H or SO ₃ M'Z group, Y is an SO ₃ M, SO ₃ H or SO ₃ M'Z group, R is a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms and η an integer from 1 to 10, where M is a lithium, sodium, potassium, rubidium or cesium atom and M 'is a beryllium, magnesium, calcium, zinc -, strontium, barium or tin atom and Z represents an acyloxy radical.

2. The method according to claim 1, characterized in that the metal sulfonate I in an amount of 0.15 to 4 mol percent based on the aromatic dicarboxylic acid or its Dialkyl ester, is used.

The invention relates to a process for the production of dyeable, linear polyesters by polycondensing an aromatic dicarboxylic acid or a dialkyl ester thereof with a aliphatic glycol of 2 to 10 carbons and 0.1 to 10 mole percent based on the aromatic Dicarboxylic acid or its dialkyl ester, a metal sulfonate of an aromatic compound, the two Contains carboxyl or ester groups.

Linear polyesters made from aromatic dicarboxylic acids and glycols are known to have conventional Staining process only has a low affinity for dyes. Attempts have been made to the To improve the dyeability of polyesters, especially in filament and fiber form. So you can z. B. use small amounts of certain amino alcohols in the condensation, which is an improvement the dyeability of z. B. polyethylene terephthalate is achieved. However, the The heat resistance of the modified polyethylene terephthalate is greatly reduced. Another possibility is the chemical incorporation of long-chain polyalkylene oxides with molecular weights in the order of magnitude from 1000 to 6000. However, this modification made the polyethylene terephthalate very sensitive against air oxidation and light. Furthermore, the use of toxic compounds, such as. B. from Chlorobenzenes or chlorophenols for the dyeing process have been described. Besides, you can Vat or acetate dyes at above atmospheric pressure and temperatures above 100 ° C color, use fiber swelling agents or dye carriers or pigments that directly interact with the polyethylene terephthalate melt mixed before spinning.

In British patent specification 826 248 a process for the production of polyesters is described, in which one dicarboxylic acid or its ester-forming derivative with a diol and 0.5 to 10 mole percent a compound condensed, the at least one ester-forming group, at least one metal sulfonate group and preferably contains an aromatic nucleus. However, these products show usual staining methods do not give very satisfactory results.

There was therefore a need for polyesters that could be dyed better, their physical properties however, were not deteriorated.

The inventive method is now characterized in that the metal sulfonate one Fluorene compound of the general formula

ROOCH

C "H," COOR

used in which X is a hydrogen atom or an SO ₃ M, SO ₃ H or SO ₃ M'Z group, Y is an SO ₃ M, SO ₃ H or SO ₃ M'Z group, R is a hydrogen atom or an alkyl radical with 1 to 10 carbon atoms and η an integer from 1 to 10, where M is a lithium, sodium, potassium, rubidium or cesium atom, M 'is a beryllium, magnesium, calcium, zinc , Strontium, barium or tin atom and Z represents an acyloxy radical.

The sulfonated ones used to make the modified linear polyesters of the present invention Fluorene compounds are the monosulfo- and disulfo-9,9- (carboxyalkyl) -fluorenes, their monovalent metal sulfonate salts, their acyloxy metal sulfonate salts and the esters thereof. That of the formula I all the more Compounds included are (II) the monosulfo-9,9-di- (carboxyalkyl) -fluorenes, the disulfo-9,9-di- (carboxyalkyl) -fluorenes including their monovalent metal salts and esters and (III) the mono- (acyloxymetallsulfo) -9,9- di- (carboxyalkyl) -fluorenes, the di- (acyloxymetallsulfo) -9,9- (carboxyalkyl) -fluorenes and their esters.

The modified for the preparation of the invention linear polyester used monosulfo-9,9-di- (carboxyalkyl) -fluorene- and disulfo-9,9-di- (carboxyalkyty-fluorene compounds can be represented by the following formula, which is a subclass of Formula I:

X '- \ x X Λ JY' (Π)

ROOCH _2n C _n C _n H _2n COOR

545

in which X 'stands for a hydrogen atom or a -SO ₃ H-ReSt or a -SO ₃ M-ReSt, Y' stands for an SO ₃ H-ReSt or an SO ₃ M-ReSt, M for lithium, sodium, potassium , rubidium or cesium, R represents a hydrogen atom or a monovalent ^j alkyl group having 1 to about 10 carbon atoms, ζ. B. a methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylbutyl, heptyl. Octyl, decyl, etc., and η is an integer with a value from 1 to about 10, preferably 2 to about 6, is.

The monosulfo-9,9-di- (carboxyalkyl) -fluorenes suitable as modifying agents according to the invention are characterized by the following formula:

15th

-Y '

ROOCH _2n C _n C _n H _2n COOR

(II A)

20th

and the disulfo-9,9-di (carboxyalkyl) fluorene are characterized by the following formula:

(II B)

ROOCH _2n C _n C _n H _2n COOR

ROOCH

COOR

30th

As starting materials for the production of the monosulfo - 9,9 - di - (carboxyalkyl) - fluorene and Disulfo-9,9-di- (carboxyalkyl) -fluoren derivatives used 9,9-di- (carboxyalkyl) -fluorenes belong to a class of known compounds. The sulfonated fluorene compounds falling under the formulas IIA and IIB are made by known sulfonation processes. So z. B. that through the following general formula

45

9,9-di (carboxyalkyl) fluorene shown with conc. Sulfuric acid are sulfonated. At temperatures up to about 65 ^° C., the monosulfonation prevails, and yields of 80% or more of the monosulfonic acid derivatives are achieved. At temperatures above 65 and preferably from about 90 to 130 ^° C., the disulfonation is the main reaction. In both cases, however, small amounts of other sulfenic acid derivatives are also obtained; a change in temperature causes a change in the ratio of monosulfo and disulfo compounds formed.

As metal sulfonates of a fluorene compound in the process according to the invention, as monosulfo 9,9-di- (carboxyalkyl) -fluorenes and as disulfo-9,9-di- (carboxyalkyl) -fluorenes ζ. Β. be used:

Lithium-9,9-di- (2'-carboxyethyl) fluorene-2-

sulfonate;
Lithium-9,9-di- (3'-carboxypropyl) -fluoren-2-

sulfonate;

65 lithium-9,9-di- (4'-carboxybutyl) -fluorene-2-

sulfonate;
Lithium-9- (2'-carboxyethyl) -9- (7'-carboxy-

heptyl) fluorene-2-sulfonate;
Sodium 9,9-di- (3'-carboxypropyl) -fluoren-2-

sulfonate;
Sodium 9- (2'-carboxyethyl) -9- (5'-carboxy-

pentyl) fluorene-2-sulfonate;
Potassium-9,9-di- (2'-carboxyethyl) -fluoren-2-

sulfonate;
Potassium 9- (2'-carboxyethyl) -9- (3'-carboxy-

propyl) fluorene-2-sulfonate; Potassium 9- (2'-carboxyethyl) -9- (6'-carboxyhexyl) -

fluorene-2-sulfonate;
Rubidium-9,9-di- (2'-carboxyethyl) -fluoren-2-

sulfonate;
Rubudium ^ - ^ '- carboxyethyl ^ - ^' - carboxy-

pentyl) fluorene-2-sulfonate; Cesium-9,9-di- (2'-carboxyethyl) -fluoren-2-

sulfonate;
Dilithium-9,9-di- (2'-carboxyethyl) -fluoren-2,7-

disulfonate;
Dilithium-9- (2'-carboxyethyl) -9- (3'-carboxy-

propyl) fluorene-2,7-disulfonate; Dilithium-9- (2'-carboxyethyl) -9- (4'-carboxy-

butyl) fluorene-2,7-disulfonate; Dilithium-9- (2'-carboxyethyl) -9- (8'-carboxy-

octyl) fluorene-2,7-disulfonate; Disodium-9,9-dj- (2'-carboxyethyl) -fluoren-2,7-

disulfonate;
Disodium 9- (2'-carboxyethyl) -9- (4'-carboxy-

butyl) fluorene-2,7-disulfonate; Dipotassium-9,9-di- (2'-carboxyethyl) -fluoren-2,7-

disulfonate;
Dipotassium-9- (2'-carboxyethyl) -9- (5'-carboxy-

pentyl) fluorene-2,7-disulfonate; :

Dirubidium-9,9-di- (3'-carboxypropyl) -fluorene-

2,7-disulfonate;
Dicesium-9- (2'-carboxyethyl) -9- (3'-carboxy-

propyl) fluorene-2,7-disulfonate; Lithium-9- (2 '-carbomethoxy ethyl) -9- (5' -carbo-

methoxypentyl) fluorene-2-sulfonate; Sodium 9,9-di- (2'-carbomethoxyethyl) -

fluorene-2-sulfonate;
Potassium 9,9-di- (3'-carbomethoxypropyl) -fluorene-

2-sulfonate;
Cesium-9,9-di- (2'-carbomethoxyethyl) -fluoren-

2-sulfonate;
Sodium 9,9-di- (3'-carboethoxypropyl) -fluoren-

2-sulfonate;
Potassium-9- (2 '-carboethoxyethyl) -9- (7' -carbo-

ethoxyheptyl) fluorene-2-sulfonate; Potassium 9,9-di- (2'-carboisopropionoxyethyl) -

fluorene-2-sulfonate;
Lithium-9,9-di- (2'-carbopropionoxyethyi) -

fluorene-2-sulfonate;
Sodium 9- (2 '-carbobutanoxyethyl) -9- (3' -carbo-

butanoxypropyl) fluorene-2-sulfonate; Lithium-9,9-di- (2'-carbopentanoxyethyl) -

fluorene-2-sulfonate;
Sodium 9- (2'-carbopentanoxyethyl) -9- (4'-carbo-

pentanoxybutyl) fluorene-2-sulfonate; Sodium 9,9-di- (3'-carboheptanoxypropyl) -

fluorene-2-sulfonate;
Sodium 9- (2'-carbooctanoxyethyl) -9- (4'-carbo-

octanoxybutyl) fluorene-2-sulfonate; Potassium 9,9-di- (2'-carbononanoxyethyl) fluorene-2-sulfonate;

Potassium-9,9-di- (2'-carbodecanoxyethyl) -fluoren-

2-sulfonate;
Disodium-9,9-di- (2 '~ carbomethoxyethyl) -

fluorene-2,7-disulfonate;
Disodium 9- (2'-carbomethoxyethyl) -9- (3 '-carbo-

methoxypropyl) fluorene-2,7-disulfonate; Dirubidium-9,9-di- (2'-carboethoxyethyl) -fluorene-

2,7-disulfonate;
Dicesium-9- (2'-carbopropionoxyethyl) -9- (3'-carbopropionoxypropyl) -fluoren-2,7-

disulfonate;
Disodium 9- (2'-carboethoxyethyl) -9- (5'-carbo-

ethoxypentyl) fluorene-2,7-disulfonate; Disodium 9,9-di (2'-carbobutanoxyethyl) fluorene-2,7-disulfonate;

Dilithium-9- (2'-carbohexanoxyethyl) -9- (3 '-carbohexanoxypropyl) -fluoren-2,7-di-

sulfonate;
Dilithium-9- (2'-carbooctanoxyethyl) -9- (3 '-carbooctanoxypropyl) -fluoren-2,7-di-

sulfonate;
Disodium-9,9-di- (2'-carbononanoxyethyl) -

fluorene-2,7-disulfonate;
Dipotassium 9,9-di- (2'-carbodecanoxyethyl) -fluoren-2,7-disulfonate etc.

The mono- (acyloxymetallsulfo) which can be used for the production of the modified linear polyesters according to the invention - 9,9 - (carboxyalkyl) fluorene and di (acyloxymetallsulfo) -9,9-di (carboxyalkyl) fluorene compounds are represented by the following formula, which is a subclass of Formula I:

fluorene compounds by the formula

SO ₃ M'Z

ROOCH _2n C _n C _n H _2n COOR

(III)

35

40

SO ₃ M'Z (III A) ROOCH _2n C _n C _n H _2n COOR

and the di- (acyIoxymetallsuIfo) -9,9-di- (carboxyalkyl) -

in which X "stands for a hydrogen atom or a - SO ₃ M'Z radical, M 'for BeryHkim, magnesium, calcium, zinc, strontium, barium or tin, Z for an acyloxy radical, - OOCR"; R "stands for a monovalent hydrocarbon radical, such as an alkyl radical with 1 to about 10 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylbutyl, heptyl , Octyl, 2-ethylhexyl, decyl radical, or an aryl radical, such as a phenyl, naphthyl radical, or an aralkyl radical, such as a benzyl, phenethyl radical, or an alkaryl radical, e.g. a tolyl, xylyl radical, R stands for a hydrogen atom or an alkyl radical having 1 to about 10 carbon atoms and η is an integer with a value of 1 to 10, preferably 2 to 6.

The mono- (acyloxymetallsulfo) - 9.9 - di - (carboxyalkyl) - fluorene compounds used according to the invention are characterized by the following formula:

ZMO ₃ S ΛΛΛ / "SO ₃ M'Z (III B)
ROOCH _2n C _n C _n H _2n COOR

The Acyloxymetallsulfo - 9,9 - di - (carboxyalkyl) -fluorene are prepared by reacting a divalent metal salt of a monocarboxylic acid of the general formula M '(OOCR') 2 it produced ^m the covered sub-classes of formula II free sulfonic acid.

The acyloxy metal sulfo - 9,9 - di - (carboxyalkyl) fluorene compounds of Formula III can be obtained by heating a mixture on the fluorene sulfonic acid of Formula II and the divalent metal salt a monocarboxylic acid. The reaction is preferably carried out using a large excess of the divalent metal acylate in the presence of a solvent.

Suitable solvents are e.g. B. acetic acid, propionic acid, methanol, ethanol, benzene, toluene, hexane, Heptane, cyclohexane, etc.

The divalent metal acylate is used in excess to ensure complete conversion and to prevent the formation of the metal disulfonate salt. However, from about 0.5 or less to about 10 equivalents or more of the divalent metal acylate per equivalent of the sulfonic acid radicals present in the fluorene sulfonic acid can be used. The reaction can be carried out at any suitable temperature and is preferably conducted at temperatures of about 50 to about 150 ⁰ C, in particular at the reflux temperature of the solvent used.

In a typical reaction, a hot solution of magnesium in acetic acid becomes a hot solution from 9,9 - di - (carboxymethyl) - fluorene - 2 - sulfonic acid added and so 2-acetoxymagnesiumsulfo-9,9-di- (carboxymethyl) - made of fluorene. By using 9,9-di (carboxymethyl) fluorene-2,7-disulfonic acid 2,7-di- (acetoxymagnesiumsulfo) -9,9-di- (carboxymethyl) -fluorene is produced.

Usable divalent metal acylates are e.g. B .:

Beryllium acetate,

Beryllium propionate,

Beryllium butyrate,

Beryllium octanoate,

Beryllium benzoate,

Beryllium toluate,

Calcium butyrate,

Calcium formate,

Calcium isobutyrate,

Calcium toluate,

Zinc acetate,

Zinc benzoate,

Zinc caproate,

Zinc nonanoate,

Zinc formate,

Strontium acetate,

Strontium pentoate,

Magnesium acetate,

Magnesium benzoate,

Magnesium laurate,

Magnesium salicylate,

Calcium acetate,

Calcium benzoate,

Strontium formate,

Strontium benzoate,

Strontium toluate,

Barium acetate,

Barium benzoate,

Barium butyrate,

Barium decanoate,

Stannous acetate,

Stannopropionate,

Stannobenzoate,

Stannous 2-ethylhexanoate

etc.

As mono - (acyloxymetallsulfo) - 9,9 - di - (carboxyalkyl) - used in the process according to the invention

fluorenes and di- (acyloxymetallsulfo) -9,9-di- (carboxyalky]) fluorenes are ζ. Β. suitable:

2-hexanoyloxybarium sulfo-9i9-di- (3 '-carboxy-

propyl) fluorene;
2-propionoxycalcium sulfo-9,9-di- (2'-carboxy-

ethyl) fluorene;
2-propionoxyzinksulfo-9,9-di (2'-carboxyethyl) fluorene;

2-propionoxystannosulfo-9,9-di- (2'-carboxy-

ethyl) fluorene;
2-pentanoyloxyberyllium sulfo-9- (2'-carboxy-

ethyl) -9- (4'-carboxybutyl) fluorene; 2-butanoyloxybarium sulfo-9- (2'-carboxyethyl) -

9- (8'-carboxyoctyl) fluorene; 2-octanoyloxycalcium sulfo-9,9-di- (carboxy-

methyl) fluorene;
2-benzoyloxybarium sulfo-9,9-di (2'-carboxyethyl) fluorene;

2,7-di- (acetoxybarium sulfo) -9,9-di- (2'-carboxy-

ethyl) fluorene;
2,7-di- (acetoxystrontium sulfo) -9- (2'-carboxy-

ethyl) -9- (4'-carboxybutyl) fluorene; 2,7-di- (butanoyloxycalcium sulfo) -9,9-di- (2'-carb-

oxyethyl) fluorene;
2,7-di- (butanoyloxyzinc sulfo) -9- (2'-carboxy-

ethyl) -9- (4'-carboxyheptyl) fluorene; 2,7-di- (pentanoyloxystannosulfo) -9- (2'-carb-

oxyethyl) -9-9- (3-carboxypropyl) fluorene;

2,7-di- (hexanoyloxyberyllium sulfo) -9,9-di-

(2'-carboxyethyl) fluorene; 2,7-di- (hexanoyloxymagnesium sulfo) -9,9-di-

(4'-carboxybutyl) fluorene; 2,7-di- (heptanoyloxybarium sulfo) -9,9-di-

(2'-carboxyethyl) fluorene; 2,7-di- (heptanoyloxystannosulfo) -9- (2'-carb-

oxy ethyl) -9- (5 '-carboxy pentyl) fluorene; 2,7-di (octanoyloxycalcium sulfo) -9- (2'-carboxyethyl) -9- (3 '-carboxy propyl) fluorene;

2,7-di- (nonanoyloxybarium sulfo) -9,9-di-

(2'-carboxy ethyl) fluorene; 2,7-di- (decanoyloxybarium sulfo) -9,9-di-

(2'-carboxy ethyl) fluorene; 2,7-di- (benzoyloxybarium sulfo) -9,9-di- (2'-carb-

oxyethyl) fluorene;
2,7-di- (toluyloxybarium sulfo) -9,9-di- (2'-carb-

oxyethyl) fluorene;
2-pentanoyloxystannosulfo-9,9-di- (2'-carbo-

propoxyethyl) fluorene;
2-butanoyloxycalcium sulfo-9,9-di- (2'-carbo-

hexanoxyethyl) fluorene;
2-acetoxyzinksulfo-9,9-di- (2'-carbononanoxy-

ethyl) fluorene;
2-heptanoyloxybarium sulfo-9- (2'-carboethoxy-

ethy l) -9- (3 '-carboethoxypropyl) fluorene; 2-nonanoyloxystannosulfo-9- (2'-carboethoxyethyl) -9- (3 '-carbopentanoxy propyl) fluorene; 2-butanoylbarium sulfo-9- (2'-carbomethoxyethyl) -9- (4'-carbomethoxybutyl) fluorene;

2-octanoylstannosulfo-9- (2'-carbopentanoxyethyl) -9- (4'-carbopentanoxybutyl) fluorene; 2-butanoyl calcium sulfo-9- (2'-carbopropoxy-

ethyl) -9- (6'-carbopropoxyhexyl) fluorene; 2-acetoxyzinksulfo-9- (2'-carbomethoxyethyl) -9- (7'-carbomethoxypentyl) fluorene; 2-acetoxycalcium sulfo-9- (2'-carbopentanoxyethyl) -9- (8'-carbopentanoxy octyl) fluorene; 2-acetoxycalcium sulfo-9- (2'-carbomethoxy-

ethyl) -9- (10'-carbomethoxydecyl) fluorene; 2,7-di- (benzoyloxycalcium sulfo) -9,9-di- (2'-carbo-

ethoxyethyl) fluorene;
2,7-di- (butanoyloxyzinksulfo) -9,9-di- (2'-carbo-

propoxyethyl) fluorene;
2,7-di- (hexanoyloxystannosulfo) -9,9-di-

(2'-carbooctanoxyethyl) fluorene; 2,7-di- (pentanoyloxymagnesiumsulfo) -9,9-di-

(2'-carbopentanoxyethyl) fluorene; 2,7-Di- (acetoxyberylliumsulfo) -9- (2'-carbononanoxyethyl) -9- (3'-carbononanoxypropyl) -

fluorene;
2,7-di- (octanoyloxymagnesium sulfo) -9- (2'-carbo-

ethoxy ethy l) -9- (4 '-carboethoxybutyl) fluorene; 2,7-Di- (pentanoyloxymagnesium-sulfo) -9- (2'-carbobutanoxyethyl) -9- (4'-carbobutanoxy-

butyl) fluorene;
2,7-di- (pentanoyloxystrontium sulfo) -9- (2'-carboheptanoxyethyl) -9- (5'-carbo-

heptanoxypentyl) fluorene;
2,7-Di- (butanoyloxycalciumsulfo) -9- (2'-carbodecanoxyethyl) -9- (5 '-carbodecanoxypentyl) -

fluorene; ·

2,7-Di- (decanoyloxybariumsulfo) -9- (2'-carbomethoxyethyl) -9- (5 '-carbomethoxypentyl) -

fluorene;
2,7-di- (heptanoyloxyzinksulfo) -9- (2'-carbopropoxyethyJ) -9- (6'-carbopropoxyhexyl) -

fluorene;
2,7-di- (octanoyloxycalcium sulfo) -9- (2'-carbo-

ethoxyethyl) -9- (7'-carboethoxyheptyl) fluorene; 2,7-di- (butanoyloxystannosulfo) -9- (2'-carboheptanoxyethyl) -9- (8'-carboheptanoxyoctyl) -

fluorene;
2,7-di- (acetoxybarium sulfo) -9- (2'-carbopropoxy-

ethyl) -9- (9 '-carbopropoxynoBylI-fluorene; 2,7-di- (propionyloxystannosulfo) -9- (2'-carbomethoxyethyl) -9- (10'-carbomethoxydecyl) - fluorene etc.

Suitable aliphatic diols with 2 to 10 carbon atoms for the production of the polyesters are the aliphatic diols of the general formula HO (CH ₂ ) "OH

in which η is an integer from 2 to 10, such as. B. ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol or decamethylene glycol.

The dicarboxylic acid compounds used to make the polyesters are the aromatic ones Dicarboxylic acids or their dialkyl esters. The most preferred dicarboxylic acid is terephthalic acid and the dialkyl esters thereof, such as e.g. B. dimethyl terephthalate and similar esters in which the alkyl groups preferably contain 1 to about 5 carbon atoms. Other suitable aromatic Dicarboxylic acids and their esters are, for. B .:

p, p '-diphenylcarboxylic acid,
p, p'-Dicarboxydiphenylethane, p, p '-Dicarboxydiphenylhexane, p, p'-Dicarboxydiphenylsulfid, p.p'-Dicarboxydiphenylsulfon, p, p'-Dicarboxydiphenyläther, ρ, ρ'-Dicutanindyparhenoxyb, etc.

209 546/523

Mixtures of two or more dicarboxylic acids can also be used.

There will be a molar ratio of glycol to dicarboxylic acid compounds of at least about 1.3: 1 used. However, there can also be an excess of glycol to dicarboxylic acids, between about 2 to 10 moles of glycol per mole of dicarboxylic acid compound can be used. A suitable relationship is between about 1.3 to 7 moles, in particular about 1.5 to about 5 moles, of glycol per mole of the dicarboxylic acid compounds.

The amount of sulfonated fluorene compound used in the process of the invention can be between about 0.1 to 10 mol percent, in particular from 0.15 to about 4 mol percent, based on the aromatic Dicarboxylic acid or its dialkyl ester, vary.

In the present process the quantities calculated on Aryldicarbonsäureverbindung, glycol, sulfonated fluorine modifying agent and catalyst are introduced into a reaction vessel and preferably heated in an inert atmosphere to a temperature of about 150 to about 27O ⁰ C between about 170 to about 250 ⁰ C. Any excess glycol present is then removed by heating to about 280 ° C. under reduced pressure in an inert atmosphere or by passing a stream of an inert gas through the melt at atmospheric pressure. Thereafter, the polycondensation is carried out at about 225 to 325 ° C, preferably from C and reduced pressures from about 0.1 to about 20 mm Hg, preferably between about 260 mm to about ⁰ 29o between about 0.1 to about 5, and likewise in an inert atmosphere. Optionally, the entire reaction can be carried out at atmospheric pressure with a stream of inert gas being passed through the molten mixture and the rate of gas flow increasing as the polycondensation proceeds. The total reaction time can be between about 1 to 12 hours, depending on the catalyst used and its concentration, the temperature, the pressure, the starting monomers or the viscosity desired for the polyester.

To shorten the reaction time and thus to reduce possible discoloration the monomers are preferably reacted in contact with a suitable catalyst. It can be any known poly esterification catalyst can be used, such as B. antimony oxide, zinc acetate, manganese acetate, cobalt (II) acetate, zinc succinate, zinc borate, Magnesium methoxide, sodium methoxide, barium oxide, cadmium formate, black lead, dibutyltin oxide, Tetraisopropyl titanate or calcium titanium silicate. The catalyst concentration can be from about 0.001 up to about 1 percent by weight, based on the total amount of dicarboxylic acid compounds introduced, can be varied. The preferred amount is between about 0.005 to about 0.5 percent by weight, in particular between 0.01 to about 0.2 percent by weight.

The sulfonated fluorene modifying agent was not expected to be sufficiently chemically and thermal resistance in the presence of other reactants would have the Polycondensation conditions and the high temperatures necessary for spinning the polyester to endure. It was also surprising that the modified from the inventive Polyester-made fibers compared to unmodified polyester fibers have no disadvantages in their have physical properties and have improved dyeability.

The reaction mixture can also contain other additives, such as. B. color inhibitors, pigments, matting agents, titanium dioxide, barium carbonate or viscosity stabilizers, are added. The reduced viscosity I _{R of} the polyesters prepared according to the invention is given by the equation

- AIL. JL
^R NC

certainly; where AN is the difference between the flow time of the solution and the flow time of the solvent, N ₀ is the flow time of the solvent, and C is the concentration of the polymer in grams per 100 ecm of solution. The values given here for the reduced viscosity were measured at a polymer concentration of 0.2 g per 100 ecm of solution using a 3: 2 mixture of phenol and tetrachloroethane as solvent. The reduced viscosity of the polyesters can vary between about 0.2 to about 3, with values of about 0.35 to about 1 being preferred.

The fibers were dyed by known methods, in particular from an aqueous solution at the boiling point of the dyebath. The cationic or basic and disperse dyes are easily absorbed and provide deep tints. The amount of color on the fiber or the depth of a color is roughly proportional to the K / S value; this is a measure of the light reflection from the colored sample. The larger the K / S value, the deeper the color. A K / S value of 20 is about twice as low as a K / S value of 10. The determination of the K / S value is in "Color in Business, Science and Industry", 1952, p. 314 bis 342.

The polyesters produced according to the invention can be spun from the melt into fibers and yarns. Before being spun from the melt, the modified polyesters were dried overnight at 90 ° C. and a pressure of 2 mm Hg and then from the melt in a piston spinning machine at 280 to 285 ° C. using a spinneret with 30 holes of 0.38 each mm diameter extruded. The speed at the nozzle orifice was 90 cm / min. And the yarn was taken off at a speed of about 45 m / min., Ie a draw ratio of 50: 1. Then the yarn was drawn hot to an electrically heated mandrel at 9O ⁰ C, namely 200 to 500%, and then continuously over an electrically heated rod at 15O ⁰ C annealed at 10% relaxation. The yarns were then woven into fabrics. The spinning process used is common and known for polyester.

The fabrics were prepared according to standard methods in the absence of vehicles or dyeing auxiliaries . colored. The dye baths used had a liquor ratio of 40: 1 and contained as an emulsifier 1% of the sodium sulfate derivative of 7-ethyl-2-methylundecanol-4. The color concentration was 3% by weight based on the weight of the fabric, and the dyeings were carried out at boiling temperature.

The basic and disperse dyes which slightly dye the fibers produced from the polyesters produced according to the invention include the "Genacryl" dyes mentioned on pages 432 and 433 of the "American Dyestuff Reporter", Vol. 43, 1954, WJe ₁ z. B. Genacryl Red 6 B (a basic dye of the quaternary ammonium type), Genacryl Pink G (Basic Red; Color Index No. 48 015), Genacryl Blue 6G; Celliton Fast Red GGA Ex. Cone. (Disperse Red 17; Color Index No. 11 210); Celliton Fast Blue AF Ex. Cone. (Color Index No. 61 115); Fuchsine SBP (a triphenylmethane type basic dye); Fuchsine Cone. Basic Violet 14 (Color Index No. 12 510); Methyl violet 2B; Brilliant blue 6G; Methylene Blue SP; Victoria Green WB (Color Index 657); Victoria Green (Basic Green 4; Color Index No. 42,000); Rhodamine B (Color Index 749); Brilliant Green B (color index 662); Sevron Brillant Red 4G; Maxiion Red BL; Basacryl Blue GL.

Four samples of linear polyesters were used for comparison. These were:

Sample A

A commercially available sample of polyester fiber, ie a polyethylene terephthalate polyester. Fabrics made from this polyester were dyed as described above and the K / S values of the dyed fabrics were determined. Genacryl Pink G did not stain the fabric and the K / S value was 0; Celliton Fast Red GGA Ex. Cone, produced a red coloration with a K / S value of 14.2; Fuchsine Cone. Basic Violet 14 and Victoria Green were both very weakly substantive with K / S values of 0.2; and Celliton Fast Blue AF Ex. Cone, provided a light blue tint with a K / S value of 4.0.

Sample B

A mixture of 136 g of dimethyl terephthalate, 1.37 g of dimethyl isophthalate, 120 g of ethylene glycol and 0.1099 g of calcium flakes, 0.0687 g of zinc borate and 0.0137 g of antimony oxide as a catalyst was placed in a reaction vessel and subjected to a nitrogen atmosphere for 2.5 hours 18O ⁰ C heated. The methanol formed during the reaction was distilled off. The temperature was then ^{kept at 235 °} C. for 1 hour in order to remove the excess glycol. The reaction mixture was then heated to 280 ° C. for 7.25 hours, a vigorous stream of nitrogen being passed through the melt to carry out the polycondensation. The ethylene glycol formed during the polycondensation was distilled off. The polyester produced was white and had a reduced viscosity of 0.67. A fabric dyed with Genacryl Pink G had a K / S value of 0; with Celliton Fast Red GGA Ex. Cone, the K / S value was 15.

Sample C

This was a commercially available sample of polyester fibers made from ethylene glycol and a mixture of 90% dimethyl terephthalate and 10% dimethyl isophthalate. Yarn dyed with Genacryl Pink G had a K / S value of 0; with Celliton Fast Red GGA Ex. Cone, the K / S value was 16.3.

Sample D

A mixture of 120 g of dimethyl terephthalate, 6.4896 g of 9.9 - di - (2 '- carbomethoxyethyl) - fluorene (3 mol percent), 120 g of ethylene glycol, 0.0126 g of antimony oxide, 0.0507 g of zinc acetate and 0.0378 g Manganese acetate was placed in a reaction vessel and ^{heated to 180 °} C. for 4.75 hours under a nitrogen atmosphere. The methanol formed during the reaction was distilled off. To remove the excess glycol, the temperature was raised to 230 ⁰ C. Then, the reaction mixture was heated to 27O ⁰ C and the polycondensation is carried out for 5.5 hours at this temperature and atmospheric pressure, a rapid stream of nitrogen was passed through the melt. The ethylene glycol formed during the polycondensation was distilled off. The polyester was white and had a reduced viscosity of 0.70. A fabric dyed with Genacryl Pink G had a K / S value of 0.1, indicating that it had poor substantivity for the dye.

The following examples serve to illustrate the invention. Unless otherwise stated, all parts are Parts by weight.

For example

A mixture of 100 g of dimethyl terephthalate,

1.3984 g of sodium 9 \ 9 - di - (2 '- carbomethoxyethyl) fluorene-2-sulfonate (0.631 mol percent), 100 g of ethylene glycol, 0.02 g of antimony oxide, 0.03 g of zinc acetate and 0.02 g of manganese acetate was placed in a reaction vessel and heated to 180 ° C. for 4.75 hours. The methanol formed during the reaction was' distilled off. Then 1 hour at 23O ⁰ C and then heated for 4.5 hours 280 ° C to carry out polycondensation for distillation of the excess glycol. The ethylene glycol formed during this final period of heating was removed by passing a vigorous stream of nitrogen through the reaction mixture. A white polyester with a reduced viscosity of 0.47 and a temperature of 258 to 260 ° C. was thus obtained.

The polyester had excellent fiber and film-forming properties. The fibers were woven into fabrics and dyed with Genacryl Pink G; the K / S value was 2.4.
In a similar manner, a fiber-forming polyester was prepared by adding sodium 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonate with 2-acetoxybarium sulfo-9,9-di (2'-carbomethoxyethylene) fluorene was replaced.

Example 2

A mixture of 100 g of dimethyl terephthalate, 2.1084 g of sodium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene-2-sulfonate (0.97 mol percent), 100 g of ethylene glycol, 0.02 g of antimony oxide, 0, 03 g of zinc acetate and 0.02 g of manganese acetate were placed in a reaction vessel and ^{heated to 180 °} C. for 5 hours, the methanol formed during the reaction being distilled off. The reaction mixture was heated for 1 hour to 235 ° C and then to carry out the polycondensation A ¹ I for ₂ hours at 28O ⁰ C to remove excess ethylene glycol. The ethylene glycol formed during the polycondensation was distilled off, which by passing through

leading a rapid nitrogen flow through the melt was facilitated. The polyester had a reduced viscosity of 0.55 and a F. of 249 to 251 ° C. It showed excellent fiber-forming properties. Fabrics made from the fibers were dyed with Genacryl Pink G and had an iC / 5 value of 4.4; when stained with Celliton Fast Red GGA Ex. Cone, the K / S value was 19.9.

In a similar way, a polyester was prepared by using instead of sodium -9,9- di- (T- carbomethoxyethyl) - fluorene - 2 - sulfonate 2 - propionoxy-

magnesium sulfo - 9,9 - di - (T - carbomethoxyethyl) fluorene was used.

Example 3

A number of polycondensations were carried out using 1.22 mol percent (batch A and B) and 1 mol percent (batch C and D) sodium 9.9 - di - (T - carbomethoxyethyl) - fluorene - 2 - sulfonate, based on the total amount of esters introduced, were used as modifying agents. The feeds and reaction conditions were as follows:

approach

Dimethyl terephthalate, g

Sodium 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonate, G

Ethylene glycol, g

Antimony oxide, g,

Zinc acetate, g

Manganese acetate, g

Ester exchange:

Time, hours ...

Temperature, ⁰ C

Removal of the excess glycol:

Time, hours ... .'....

Temperature, ⁰ C,

Polycondensation:

Temperature, ⁰ C,

Reduced viscosity

Melting point, ⁰ C

100

2.8184 100 0.02 0.03 0.02

5.5 180

230

3 280

0.56 247 to 56.1

1.5825
60

0.0115
0.0173
0.0115

6.5 '
180

0.75

235

4.5
270

0.59
246 to 248

120

2.7456
120
0.0245
0.0368
0.0245

4th
180

1.25
235

4.75
280

0.76
249 to 251

120

2.7456
120
0.0245
0.0368
0.0245

4.5
180

0.75
180 to 270

4.5
270

0.63
257 to 259

The polyesters were spun into fibers and woven. The fabrics produced were made with Genacryl Pink G (I) and Celliton Fast Red GGA Ex. Cone. (II) colored and the K / S values determined:

K / S values approach
B. C. A. 8.1
20.8 7.4
20.8 Dye I. 10.9
20.8 Dye II .....

Example 4

A mixture of 170 g of dimethyl terephthalate, 5.4560 g of sodium 9.9 - di - (T - carbomethoxyethyl) fluorene-2-sulfonate (1.4 mol percent), 175 g of ethylene glycol, 0.0351 g of antimony oxide, 0.0526 g of zinc acetate and manganese acetate 0.0351 g was placed in a reaction vessel and heated 3.75 hours at 180-195 ⁰ C, with the methanol formed during the reaction was distilled off. Then the reaction mixture to remove excess ethylene glycol 1.25 hours at 180 to 27O ⁰ C and then to carry out the polycondensation was heated 4V for ₂ hours at 270 ° C. A stream of nitrogen was passed through the melt during the entire reaction. Thus, a white polyester having a reduced viscosity of 0.55, a F. from 258 to 26O ⁰ C, and excellent fiber and film-forming properties was obtained. The fabrics made from these fibers were dyed with Genacryl Pink G and had a K / S value of 6.3; when stained with Celliton Fast Red GGA Ex. Cone, the K / S value was 19.0.

In a similar manner, a film-forming polyester was prepared by adding sodium 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonate was replaced by 2-acetoxyzinksulfo-9,9-di- (2'-carbomethoxyethyl) -fluoren.

Example 5

Two polycondensations were carried out using 1.5 mol percent sodium 9.9 di (T- carbomethoxyethyl) fluorene 2 sulfonate, based on the total amount of ester charge, as a modifier. The feeds and reaction conditions are given below:

Dimethyl terephthalate, g
Sodium 9,9-di- (2'-carbomethoxyethyl) fluorene
2-sulfonate, g

Ethylene glycol, g

Antimony oxide, g

Zinc acetate, g

Manganese acetate, g

Ester exchange:

Time, hours

Temperature, ⁰ C

Removal of the excess glycol:

Time, hours

Temperature, ⁰ C ...
Polycondensation:

Time, hours

Temperature, ⁰ C ...
Reduced viscosity
Melting point, ° C ...

approach

120

4.1450 120
0.0248 0.0372 0.0248

4th
180

1.25

235

4.75 285

0.70 250 to 252

170

5.8696 175 0.0352 0.0528 0.0352

4.5 180

1 180 to 270

5 270

0.65 254 to 256

The polyesters were spun into fibers and woven. The fabrics were made with Genacryl Pink G (I) and Celliton Fast Red GGA Ex. Cone. (II) colored; the K / S values were as follows:

B. e i s ρ i e 1 A. At ₅ pcs B. Dye I. 20.8
25.3
6th 11.8
25.3 Dye II ...

A mixture of 170 g of dimethyl terephthalate, 6.2480 g of sodium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene-2-sulfonate (1.6 mol percent), 1.75 g of ethylene glycol, 0.0351 g of antimony oxide, 0.0527 g of zinc acetate, and 0.0351 g of manganese acetate was heated in a reaction vessel and 3.5 hours from 180 to 195 ⁰ C, with the methanol formed during the reaction was distilled off. Then the reaction mixture to remove excess ethylene glycol was heated for 1 hour at 195 to 27O ⁰ C. The polycondensation took place for 3.66 hours at 270 ^° C. and atmospheric pressure, a rapid stream of nitrogen being passed through the melt. A white polyester with a reduced viscosity of 0.61 and a temperature of 259 to 261 ° C. was thus obtained. The resin showed good fiber-forming properties and could be drawn easily when cold. The fabrics made from the fibers were dyed with Genacryl Pink G and had a K / S value of 9.7; when staining with Celliton Fast Red GGA Ex. Cone, the K / S value was 19.

Similarly, a polyester was prepared by adding sodium - 9,9 - di - (2 '- carbomethoxyethyl) fluorene - 2 - sulfonate by 2 - acetoxy calcium sulfo-9,9-di- (2'-carbomethoxyethyl) fluorene was replaced.

Example 7

A mixture of 170 g of dimethyl terephthalate, 6.8640 g of sodium 9.9 - di - (T - carbomethoxyethyl) fluorene-2-sulfonate (1.75 mole percent), 175 g of ethylene glycol, 0.0354 g of antimony oxide, 0.0530 g Zinkacefat and 0.0354 g of manganese acetate was placed in a reaction vessel and heated for 4.5 hours 180 ⁰ C, with the methanol formed during the reaction was distilled off. To remove excess ethylene glycol, the reaction mixture was then heated for 1 hour 180-270 ⁰ C and to carry out the polycondensation for 5 hours at 270 ⁰ C (at atmospheric pressure), a heavy stream of nitrogen was passed through the melt. A white polyester with a reduced viscosity of 0.62 and a temperature of 253 to 255 ° C. was thus obtained.

The polyester was spun into fibers and fabrics were woven from them. The fabrics have been dyed; the K / S values were as follows:

Genacryl Pink G 21.7

Celliton Fast Red GGA Ex. Cone 20.8

Fuchsine Cone. Basic Violet 14 ...... 19.0

Victorie Green 21.7

Celliton Fast Blue AF, Ex. Cone 16.9

In a similar manner, a fiber-forming polyester was obtained by using instead of sodium 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonate 2-Butanoyloxystannosulfo - 9,9 - di - (2 '- carbomethoxyethyl) fluorene was used.

Example 8

A mixture of 70 g of dimethyl terephthalate, 4 g of sodium 9,9-di- (2'-carbomethoxyethyl) -fluoren-2 - sulfonate (2.4 mol percent), 80 g ethylene glycol, 0.0148 g antimony oxide, 0.0222 g zinc acetate and 0.0148 g of manganese acetate was placed in a reaction vessel

given and heated to 180 to 190 ° C for 4.5 hours, the methanol formed during the reaction being distilled off. To remove excess ethylene glycol, the reaction mixture was 0.75 hour and then 235 ° C at atmospheric pressure for 5 hours at 260-285 ⁰ C., whereby a heavy stream of nitrogen was bubbled through the melt; so the polycondensation took place. A white polyester with a reduced viscosity of 0.54 and an F. of 248 to 250 ^° C. was obtained.

In a similar way a polyester was made,

by using instead of sodium 9,9-di- (T- carbomethoxyethyl) fluorene-2-sulfonate 2-acetoxyberyllium sulfo-9,9-di- (2 '-carbomethoxyethyl) -fluorene.

B e i s ρ i e 1 9

It was a polycondensation using 2.5 mol percent sodium 9,9-di- (2'-carbomethoxyethyl) - fluorene - 2 - sulfonate, based on the total amount of ester feed, as a modifier carried out. The materials and reaction conditions introduced were as follows:

Dimethyl terephthalate, g 120

Sodium 9,9-di- (2'-carbometh-

oxyethyl) fluorene-2-sulfonate, g 6.9520
Ethylene glycol, g 120

209 546,523

I 545 078

17 18

Antimony Oxide, g 0.0254 Example 12

Zinc acetate, g 0.0381

Manganese acetate, g 0.0254 A mixture of 120 g dimethyl terephthalate,

Ester exchange: 2.531g disodium-9,9-di- (2'-carbomethoxyethyl) -

Time, hours 5.5 5 fluorene - 2.7 - disulfonate (0.75 mole percent), 120 g

Temperature, ⁰ C 180 ethylene glycol, 0.0245 g antimony oxide, 0.0367 g of zinc acetate removal of the excess and 0.0245 g of manganese acetate was dissolved in a glycol: given reaction vessel and 4.75 hours 180 ⁰ C.

Time, hrs 0.75 heated, with that formed during the reaction

Temperature, ⁰ C 180 to 270 io methanol was distilled off. The reaction mixture

Polycondensation: was to remove excess ethylene Time, hr 5 glycol 0.75 hour 28O ⁰ C and then for performing temperature ⁰ C 270 of the polycondensation guide 7 hours at atmos-

Reduced viscosity 0.63 spherical pressure heated to 290 to 295 ° C. While

Melting point, ° C 244 to 246 15 of the entire reaction was in the reaction vessel

maintain a nitrogen atmosphere. So became

The fibers made from this polyester are a polyester with a reduced viscosity of

were woven into fabrics and dyed. Preserved when stained at 0.66 and at a temperature of 257 to 259 ° C. Of the

with Genacryl Pink G the K / S value was 21.7; polyester was extruded into fibers that were cold

Staining with Celliton Fast Red GGA Ex. Cone, 20 could be stretched 5 to 6 times,

the K / S value 24. In a similar manner, a fiber-forming polyester was prepared by using the disodium-9,9-di- (2'-carbo-

For example, 10 methoxyethyl) fluorene-2,7-disulfonate by 2,7-di-

(acetoxybariumsulfo) - 9.9 - di- (2 '- carbomethoxyethyl) -

A mixture of 120 g of dimethyl terephthalate, 25 fluorene was replaced.
8.404 g of sodium - 9.9 - di - (2 '- carbomethoxyethyl) - _R · ·, ,,
fluorene - 2 - sulfonate (3 mol percent), 120 g ethylene- ß e 1 s ρ 1 e 1 1 j
glycol, 0.0257 g of antimony oxide, 0.0385 g of zinc acetate, a mixture of 120 g of dimethyl terephthalate and 0.0257 g of manganese acetate was placed in a reaction vessel 3.386 g of disodium 9.9 di (2'-carbomethoxyethyl) given and heated to 180 ° C for 5 hours, 30 fluorene-2,7-disulfonate (1 mol percent), 120 g of ethylene, the methanol glycol formed during the reaction, 0.0247 g of antimony oxide, 0.037 g of zinc acetate being distilled off. The reaction mixture was and 0.0247 g of manganese acetate was heated 5.75 hours on to remove excess ethylene glycol 180 to 200 ⁰ C, wherein the during the reac-formed 0.75 hours at 180 to 270 ° C and then to transit tion Methanol was distilled off. The polycondensation reaction at atmospheric pressure was heated to 270 ° C. for 5 hours to remove excess pressure. During the ethylene glycol schüssigem 1.25 hours at 280 ⁰ C throughout the reaction, nitrogen was passed through the atmospheric pressure and then at 4.5 hours melt. For example, a white polyester with a reduced viscosity of 0.54 from one to 300 ^° C. was heated to carry out the polycondensation to 280. Maintained F. from 244 to 246 ° C throughout the reaction. The polyester could be easily spun into fibers by the reaction mixture, which leads to woven fabrics. Thus, a white polyester was reduced with a. When stained with Genacryl Pink G, the adorned viscosity of 0.70 and an F. of 258 resulted in a K / S value of 21.7; obtained from staining with Celliton Fast to 260 ⁰ C. The polyester had excellent Red GGA Ex. Cone, it was 23.5. good fiber-forming properties.

In a similar way a fiber-forming poly- 45 In a similar way a polyester was made,

ester prepared by the sodium 9,9-di- (2'-carbo- by the disodium - 9,9 - di - (T - carbomethoxy-

methoxyethyl) fluorene-2-sulfonate by 2-acetoxyethyl) fluorene-2,7-disulfonate by 2,7-di- (acetoxy-

strontium sulfo-9,9-di- (2'-carbomethoxyethyl) fluorene magnesium sulfate) - 9,9 - di - (T - carbomethoxyethyl) -

was replaced. fluorene was replaced.

Example 11 ^$ ° example ^

A mixture of 120 g of dimethyl terephthalate,

A mixture of 30 g of dimethyl terephthalate, 4.228 g of disodium-9,9-di- (T- carbomethoxyethyl) -

3.577 g sodium - 9.9 - di - (T - carbomethoxyethyl) - fluorene - 2.7 - disulfonate (1.25 mole percent), 120 g

fluorene - 2 - sulfonate (5 mol percent), 30 g ethylene 55 ethylene glycol, 0.0248 g antimony oxide, 0.0273 g zinc

glycol, 0.0101g antimony oxide and 0.0151g zinc acetate and 0.0248 g manganese acetate was 4.75 hours

acetate was placed in a reaction ^{vessel and heated to 18O 0} C, the during the reaction

Heated 2.75 hours at 180 ⁰ C., which was distilled off during tion formed methanol. The Rea-

methanol formed in the reaction was distilled off. tion mixture was used to remove excess

Then the reaction mixture to remove schüssigem 60 ethylene glycol 0.66 hours at 280 ⁰ C was

of excess ethylene glycol for 1.75 hours and then to carry out the polycondensation

270 ° C and then to carry out the poly at atmospheric pressure for 5.7 hours to 290

condensation heated for 3 hours at a pressure of 3 mm to 295 ^{° C.} Throughout the reaction

Hg heated ^{to 270 °} C. in a nitrogen atmosphere. nitrogen was passed through the reaction mixture

The polyester obtained had a reduced viscosity. So was a polyester with a reduced

tat of 0.33 and a F. 232-237 ⁰ C. The viscosity of 0.64 and a F. 258-260 ° C

Resin had excellent fiber and film-forming properties and excellent fiber-forming properties

Properties. ■ received.

545 078

In a similar manner, a polyester was prepared by replacing the disodium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene-2,7-disulfonate with 2,7-di- (propionoxycalcium sulfo) - 9.9 - di - ( 2 '- carbomethoxyethyl) fluorene was replaced.

Example 15

A mixture of 120 g of dimethyl terephthalate, 5.095 g of disodium 9,9-di- (2'-carbomethoxyethyl) fluorene-2,7-disulfonate (1.5 mol percent), 120 g of ethylene glycol, 0.025 g of antimony oxide, 0.0375 g Zinc acetate and 0.025 g of manganese acetate were heated to 180 ° C. for 5.25 hours, the methanol formed during the reaction being distilled off. The reaction mixture was heated to remove excess ethylene glycol 0.5 hour 28O ⁰ C and then by carrying out the polycondensation at atmospheric pressure 6.25 hours at 290-295 ° C. Nitrogen was bubbled through the reaction mixture throughout the reaction. A polyester with a reduced viscosity of 0.60 and a temperature of 253 to 255 ° C. was thus obtained.

In a similar manner, a fiber-forming polyester was prepared by adding the disodium 9,9 di- (2'-carbomethoxyethyl) fluorene-2,7-disulfonate by 2,7 - di - (acetoxyzinksulfo) - 9,9 - di - (2 '- carbomethoxyethyl) fluorene was replaced.

Example 16

A mixture of 194 g of dimethyl terephthalate, 4.831 g of dilithium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene-2,7-disulfonate (1 mol percent), 180 g of ethylene glycol, 0.02 g of antimony oxide and 0.09 g Zinc acetate was placed in a reaction vessel and heated at 183 to 186 ° C. for 8 hours, the methanol formed during the reaction being distilled off. The reaction mixture was heated to 265 to 270 ° C. for 2.25 hours to remove excess ethylene glycol. The polycondensation was carried out by 4,75stündiges heating to 272-274 ⁰ C at atmospheric pressure to give a fast stream of nitrogen was passed through the melt. A white, crystalline, fiber-forming polyester with a reduced viscosity of 0.64 and a F. of 257 to 26 ° C. was obtained.

A fiber-forming polyester was produced in a similar manner by replacing the dilithium-9.9 - di - (2 '- carbomethoxyethyl) - fluorene - 2,7 - disulfonate 2,7-di (acetoxyberyllium sulfo) -9,9-di (2'-carbomethoxyethyl) fluorene was used.

Example 17

A mixture of 194 g of dimethyl terephthalate, 4.4583 g of lithium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene - 2 - sulfonate (1 mol percent), 180 g of ethylene glycol, 0.02 g of antimony oxide and 0.09 g of zinc acetate was placed in a reaction vessel and heated at 185 to 189 ° C. for 4.25 hours, the methanol formed during the reaction being distilled off. The reaction mixture was heated from 220 to 267 ° C. in the course of 2.75 hours to remove excess ethylene glycol. The polycondensation was carried out by 4,2stündiges heating to 265-275 ⁰ C at atmospheric pressure to give a vigorous stream of nitrogen was passed through the melt. A white, crystalline, fiber-forming polyester with a reduced viscosity of 0.55 and a melting point of 251 to 254 ° C. was thus obtained. The fibers spun from this resin from the melt were woven and given a luminous shade with a K / S value of 6.7 with Genacryl Pink G and an intense shade with a K / S with Celliton Fast Red GGA Ex. Cone - Colored value of 21.7.

Example 18

A mixture of 150 g of dimethyl terephthalate, 6.2746 g of potassium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene-2-sulfonate (1.75 mol percent), 150 g of ethylene glycol, 0.0156 g of antimony oxide and 0, 0703 g of zinc acetate was placed in a reaction vessel and ^{heated to 180 to 195 °} C. for 3 hours, the methanol formed during the reaction being distilled off. The reaction mixture was heated from 195 to 235 ° C. in the course of 0.25 hours to remove excess ethylene glycol. The polycondensation was carried out by heating at 265 ° C. for 4.25 hours at atmospheric pressure, with a vigorous stream of nitrogen being passed through the melt. A white, crystalline polyester with excellent fiber-forming properties was obtained, which could be cold drawn by 400%. It had a melting point of 256 to 258 ° C and a reduced viscosity of 0.52. The fibers obtained from this resin by spinning from the melt became a medium-intensive tint with Genacryl Pink G with a K / S value of 13.3 and with Celliton Fast Red GGA Ex. Cone, a deep red tint with a K / S value of 20.75 stained.

Example 19

A mixture of 150 g of dimethyl terephthalate, 7.1947 g of potassium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene - 2 - sulfonate (2 mol percent), 150 g of ethylene glycol, 0.0157 g of antimony oxide and 0.0707 g Zinc acetate was placed in a reaction vessel and heated at 180 to 195 ° C. for 6 hours, the methanol formed during the reaction being distilled off. The mixture was heated to 235 ° C. in the course of 15 minutes to remove excess ethylene glycol. The polycondensation was carried out by 4,5stündiges heating at 265 to 27O ⁰ C at atmospheric pressure while nitrogen was passed through the melt. A white polyester with excellent fiber-forming properties which could be cold-drawn was obtained. The resin melted at 257-259 ° C and had a reduced viscosity of 0.56. The fibers obtained from this resin by spinning from the melt became an intense tint with Genacryl Pink G with a / C / S value of 21.74 and with Celliton Fast Red GGA Ex. Cone, a very deep red tint with a K. / S value of 19.85 stained.

Example 20

A mixture of 194 g of dimethyl terephthalate, 9.8 g of methyl 4- [2-sodium sulfo-9- (2'-carbomethoxy) -fluoren-9-yl] -hexanoate (2 mole percent), 180 g of ethylene glycol, 0.02 g of antimony oxide and 0.09 g of zinc acetate were placed in a reaction vessel and allowed for 5.25 hours heated to 180 to 187 ° C, during which the methanol formed during the reaction was distilled off. the Reaction mixture was used to remove excess

Schüssigem ethylene glycol heated to 231 to 238 ⁰ C for 3 hours. The polycondensation was carried out by heating for 4.5 hours at 265 to 279 ° C. at atmospheric pressure, a vigorous stream of nitrogen being passed through the melt. Thus, a fiber-forming polyester having a reduced viscosity of 0.6 was obtained.

Example 21

A mixture of 19.4 g of dimethyl terephthalate, 0.91 g of the bis (2-methylpentyl) ester of potassium 9,9-di (2'-carboxyethyl) fluorene-2-sulfonate (1.5 mol percent) , 20 g of ethylene glycol, 0.002 g of antimony oxide and 0.009 g of zinc acetate were placed in a reaction vessel and heated to 188 to 199 ° C. for 4 hours, the methanol and 2-methylpentanol formed during the reaction being distilled off. Then, the reaction mixture was heated 2.5 hours to about 23O ⁰ C to distill excess ethylene glycol. The polycondensation took place for about 4 hours at a temperature between 260 to 269 ° C. and atmospheric pressure, a vigorous stream of nitrogen being passed through the melt. A crystalline, fiber-forming polyester was obtained in this way, which was cold-stretchable and had a reduced viscosity of 0.45 and a melting point of 255 to 256 ° C.

Example 22

A mixture of 175 g of dimethyl terephthalate, 5.47 g of dimethyl isophthalate (3 mole percent), 4.28 g of lithium - 9.9 - di - (2 '- carbomethoxyethyl) - fluorene-2-sulfonate (1 mole percent), 180 g of ethylene glycol, 0.018 g of antimony oxide and 0.081 g of zinc acetate were placed in a reaction vessel and heated to 185 to 186 ° C. for 5 hours, the methanol formed during the reaction being distilled off. The reaction mixture was then heated to 265 ° C. for 3.5 hours to remove excess ethylene glycol. The polycondensation was carried out for 4 hours at 265 to 267 ° C. and atmospheric pressure, with a vigorous stream of nitrogen being passed through the melt. A white crystalline polyester with a reduced viscosity of 0.58 and a temperature of 243 to 245 ° C. was obtained. The fibers obtained from this polyester by spinning from the melt were Genacryl Pink G to a medium-intense color with a K / S value of 10.1 and Celliton Fast Red GGA Ex. Cone, an intense color with a K / S value of 20.8 stained.

22nd
Example 23

A mixture of 155 g of dimethyl terephthalate,

4.74 g of disodium - 9 - (2 '- carbomethoxyethyl) -9 - (5' - carbomethoxypentyl) - fluorene - 2.7 - disulfonate (1 mol percent), 150 g of ethylene glycol, 0.016 g of antimony oxide and 0.072 g of zinc acetate were placed in a reaction vessel and heated to 176 to 187 ° C. for 4.25 hours, the methanol formed during the reaction being distilled off. Then the reaction mixture to remove excess ethylene glycol 1.5 hours to 235-275 ⁰ C was heated. The polycondensation took place for 5.25 hours at 275 ° C. and atmospheric pressure, with a vigorous stream of nitrogen being passed through the melt. A fiber-forming crystalline polyester with a reduced viscosity of 0.58 and a temperature of 267 ° C. was thus obtained.

Example 24

A mixture of 15 g of dimethyl terephthalate, 0.7191 g of potassium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene - 2 - sulfonate (2 mole percent), 35 g of 1,4-cyclohexanedimethanol (50 g of a 70% methanol solution), 0.0016 g of antimony oxide and 0.0071 g of zinc acetate was placed in a reaction vessel and

Heated 3.75 hours at 195-206 ⁰ C, with the methanol formed during the reaction was distilled off. The reaction mixture was then ^{heated to 245 to 250 °} C. for 2.25 hours in order to remove excess glycol. A rapid stream of nitrogen made it easier to distill off the glycol. The polycondensation took place for 6.5 hours at 295 to 300 ^° C. and atmospheric pressure, a rapid stream of nitrogen being passed through the melt. A solid polyester was obtained.

The sulfonated polyesters used according to the invention for the production of the dyeable, linear polyesters Fluorenes can also be used with known benzenesulfonate chain terminators, such as. B. methyl 3-sodium sulfobenzoate and methyl - 4 - sodium sulfobenzoate, can be used to make polyester yarns that have unexpectedly good dyeing properties, as can be seen from the following comparative tests:

A. To produce polyesters, a series of polycondensations was carried out in the presence of a sulfonated chain terminator and in the absence of the sulfonated fluorene modifier for Comparative purposes with the polyesters of control samples A to D were carried out. The charges and results were as follows:

approach

Dimethyl terephthalate, g

Methyl 3-sodium sulfobenzoate, g
Methyl 4-sodium sulfobenzoate, g

Ethylene glycol, g.

Antimony oxide, g.

Zinc acetate, g

Manganese acetate, g .;

Ester exchange:

Time, hours

Temperature, ⁰ C

150
2.3562

150
0.0457 0.0685

4.5 180

174
3.3320

180
0.0355
0.0532
0.0355

4.5
180

150

4.2060
150
0.0308
0.0463
0.0308

4.5.
180

194

4.0222
200
0.0396
0.0592
0.0396

4.75
180

Continued 24

approach
B: C

Removal of excess glycol:

Time, hours

Temperature, ⁰ C

Polycondensation:

Time, hours

Temperature, ⁰ C

Reduced viscosity

Melting point, ⁰ C

if / S values, with

Genacryl Pink G

Celliton Fast Red GGA Ex. Cone ....

1 180 to

280 0.56

257 to 1
to 270

270

0.57
to 253

7.3

1 to

1 280

0.61 to

2.9 12.9

1 180 to

1 280

0.71 249 to

3.3

B. A series of polycondensations was carried out for comparison with the polyesters from A. both a chain terminator and 9,9-di- (2'-carbomethoxyethyl) -fluoren-2-sulfonic acid were used as modifiers. The experiments are listed below:

approach

Dimethyl terephthalate, g

Sodium dimethyl-9,9-di- (2'-carbomethoxy-

ethyl) fluorene-2-sulfonate, g

Methyl 3-sodium sulfobenzoate, g

Methyl 4-sodium sulfobenzoate, g

Ethylene glycol, g

Antimony oxide, g

Zinc acetate, g

Manganese acetate, g

Ester exchange:

Time, hours

• Temperature, ⁰ C

Removal of the excess glycol:

Time, hours

Temperature, ⁰ C

Polycondensation:

Time, hours

Temperature, ⁰ C

Reduced viscosity

Melting point, ⁰ C

K / S values with

Genacryl Pink G

Celliton Fast Red GGA Ex. Cone

194

3.5464

4.5696 200 0.0404 0.0606 0.0404

6.5 180

1 180 to

6.5 270

0.54 246 to

12.1 22.0 181.3
4.1536

3.8080
184
0.0378
0.0568
0.0378

3.75
180

to 270

6.25
275

0.58
to 260

11.2
20.7

172.3

3.9468 3.3320

180 0.0359 0.0539 0.0359

4.25 180

1 to

6 270

0.50 to

19.8

25.3

176.8

4.0480 2.8560

180 0.0367 0.0551 0.0367

4.5 180

1 180 to

270 0.53 250 to

22.8 20.8

Unexpected technical advantages of the method according to the invention over the known method result from the following comparison test:

Polyethylene terephthalate samples each containing 2 mole percent dimethyl (5-sodium sulfo) isophthalate (SIP) and sodium 9,9-di (2'-carbomethoxyethyl) fluorene-2-sulfonate (SFD) were 90 minutes Stained with Celliton Fast Red GGA or Genacryl Pink G at boiling point. The dyes were used in an amount of 3%, based on the weight of the fibers, with a liquor ratio of 40: 1. Then the color depth (K / S) was measured. The following values were obtained:

Celliton Fast Red GGA Genacryl Pink G SIP 20.8
25.3 19.0
19.9 SFD

This example shows the superiority of the modifying agents used according to the invention

209 546 · '523

over the modifying agents known from British patent specification 826,248.

As indicated by the / C / S values, effected the presence of a chain terminator alone provides some improvement in dyeability. These However, improvement is not as great as when the polyester is made using a sulfonated one Fluorene modifier is produced. Will also be a combination of sulfonated chain terminators and sulfonated fluorene modifier is used, a lower total amount is used of modifying agents is necessary than when using either of the sulfonated compounds alone will. It has also been found that a combination of from about 1.2 to about 1.6 mole percent methyl 3-sodium sulfobenzoate and about 0.5 mole percent sodium - 9.9 - di - (2 '- carbomethoxyethyl) - fluorene - 2 - sulfonate just as deep a tint as it provided with 2 to 3 mol percent sodium 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonate is achieved alone without the benzenesulfonate chain terminator.

The manufacture of some of the sulfonated fluorene modifiers, which are used as starting compounds in the process according to the invention, takes place according to the following process:

1. A mixture of 46 g of 9,9-di- (2'-carboxyethyl) fluorene-2,7-disulfonic acid and 400 ecm of methanol were refluxed for 5 hours and then cooled. A small portion of the reaction mixture gave 9,9-di (2'-carbomethoxyethyl) fluorene-2,7-disulfonic acid won. The remainder of the reaction mixture was made with methanolic sodium hydroxide reacted to a pH of 7.5; a precipitate formed. The precipitation was filtered off, the filtrate concentrated on the steam bath, and formed after cooling again crystals which were filtered off. The two crystal fractions were combined, from methanol recrystallized and so the up to 340 ° C stable, pure disodium - 9.9 - di - (2 '- carbomethoxyethyl) - fluorene-2,7-disulfonate obtained in the form of crystals. The disulfonate was determined by infrared and elemental analysis identified:

C ₂ iH ₂₀ O ₁₀ SNa ₂ :

Calculated ... C 46.49, H 3.78, S 11.82;
found .... C 45.95, H 3.82, S 11.83.

Similarly, 9,9-di (2'-carbopentanoxyethyl) fluorene-2,7-disulfonic acid was found by esterification of 9,9 - di - (2 '- carboxyethyl) - fluorene - 2,7 - disulfonic acid made with pentanol. This ester became the dipotassium, dilithium and dicesium salt by reaction with the appropriate hydroxide using the procedures described above manufactured.

By heating a mixture of tin acetate and 9,9 - di - (2 '- carbomethoxyethyl) - fluorene - 2,7 - disulfonic acid in methanol at reflux temperature was 2.7 - di - (acetoxytin sulfo) - 9.9 - di - (2 '- carbomethoxyethyl) fluorene obtain.

2. A warm solution of 448 g of 9,9-di (2'-carbomethoxyethyl) fluorene-2-sulfonic acid in 1 l of warm methanol was reacted with a methanolic potassium hydroxide solution to a pH of 7.1. After cooling, the potassium 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonate crystallized and was filtered off. After two recrystallizations from methanol, the white crystals melt at 203 bis 204 ° C.

By heating a mixture of strontium 'acetate and 9,9-di (2'-carbomethoxyethyl) fluorene-2-sulfonic acid in methanol at reflux temperature, 2-acetoxystrontium sulfo-9,9-di- (2'-carbomethoxyethyl) fluorene was added obtain.

3. In a glass flask equipped with a reflux condenser and thermometer, 49 g of potassium 9,9-di (2'-carbomethoxyethyl) fluorene-2-sulfonate, 150 ecm of 2-methylpentanol and 1 drop of tetraisopropyl titanate were added, the solution for 7 hours Heated to reflux and the excess 2-methylpentanol was distilled off under reduced pressure on a steam bath, whereupon a sticky, semi-solid residue remained in the flask. The residue was dissolved in acetone at 200 ecm and the solution was filtered hot to remove traces of insoluble materials. After evaporation of the solvent on a steam bath, the bis (2-methylpentyl) ester of potassium 9,9-di (2'-carboxyethyl) fluorene-2-sulfonate obtained was dried at 115 ° C. and 2 mm Hg pressure and so obtained a white solid, fi

4. 14 g conc. Sulfuric acid (98%) was slowly added to 27 g of acetic anhydride at -10 ^{to 0 ° C. with stirring.} A solution of 50 g of 9- (2'-carbomethoxyethyl) - 9 - (5 '- carbomethoxypentyl) - fluorene in 75 ecm of ethylene dichloride was then added dropwise to the cold solution. The temperature of the solution was kept at 0 to 10 ° C. for 4 hours, then warmed to 25 ° C. over the course of 2 hours and then heated to 40 ° C. over 1 hour.

After the solution had cooled to 30.degree. C., 150 ecm of methanol were added dropwise and the solution _{was refluxed for 4V for 2 hours.} The methyl acetate and ethylene dichloride-methanol azeotrope formed were distilled off and replaced by fresh methanol during the distillation. Then the

■ 40 methanol solution reacted with methanolic sodium hydroxide to a pH value of 7.1, the solvent evaporated on the steam bath to obtain a viscous residue. The residue was recrystallized twice from acetonitrile, dried and so that melting at 95 to 100 ° C Sodium 9 - (2 '- carbomethoxyethyl) - 9 - (5' - carbomethoxypentyl) fluorene-2-sulfonate obtained in the form of crystals.

5. A mixture of 96 g of 9,9-di (2-carbomethoxyethyl) fluorene-2,7-disulfonic acid was refluxed in 500 ecm of methanol for 8 hours, the Most of the methanol was distilled off and the new methanol was replaced once. The solution was reacted with methanolic lithium hydroxide to a pH of 7.0, the clear solution evaporated on a steam bath to give a clear, viscous residue. After solving the Residue in 150 ecm of methanol, the solution was poured into 1 liter of ether and the precipitated solid Dilithium 9,9-di (2'-carbomethoxyethyl) fluorene-2,7-disulfonate was filtered off. The crystals were at Dried 1 mm Hg at 100 ° C and did not melt at 400 ° C.

6. To a glass reaction flask fitted with an air condenser, thermometer, and stopper, add 26 grams 9 - (2 '- carboxyethyl) - 9 - (5' - carboxypentyl) - fluorene, 100 g of sulfuric acid and 0.2 g of mercury-2-sulfate are added, the reaction mixture at 100 ° C. for 8 hours

I 545

heated, cooled to room temperature and then poured onto 60 g of ice. After standing for several days no solid crystallized and the solution was neutralized with methanolic sodium hydroxide, ■; whereupon sodium sulfate precipitated. After filtering off the solid sodium sulfate, the solution was on the The steam bath was evaporated, the residue was dissolved in 200 ecm of methanol and refluxed for 6 hours heated, methanol being distilled off and replaced by fresh methanol. About half the methanol solution was reacted with methanolic sodium hydroxide to a pH of 7.0, but after cooling, no solid crystallized out. The methanol was on the steam bath evaporated to give a viscous residue which slowly crystallized on standing. After loosening the residue in 150 ecm warm methanol, treatment of the solution with animal charcoal and filtration the solution was added dropwise to 300 ecm boiling dioxane; the methanol was distilled off, and so the white crystalline disodium 9- (2'-carbomethoxyethyl) -9- (5'-carbomethoxypentyl) -fluorene-2,7-di- sulfonate. After cooling, the white crystals were filtered off and dried.

By heating a mixture of barium acetate and 9- (2'-carbomethoxyethyl) -9- (5'-carbomethoxypentyl) - fluorene - 2,7 - disulfonic acid in methanol at reflux temperature was the 2,7-di- (acetoxybariumsulfo) -9- (2'-carbomethoxyethyl) -9- (5'-carbo- methoxypentyl) fluorene obtained.

Claims (3)

i 545 078 claims: 1. Process for the production of dyeable, linear polyesters by polycondensation 1. an aromatic dicarboxylic acid or a dialkyl ester thereof with 2. an aliphatic glycol of 2 to 10 carbons and 3. 0.1 to 10 mol percent, based on the aromatic dicarboxylic acid or its dialkyl ester, a metal sulfonate of an aromatic compound that has two carboxyl or ester groups contains, in the presence of catalysts, characterized in that that the metal sulfonate of a fluorene compound of the general formula