DE1545078C - Process for the production of dyeable, linear polyesters - Google Patents

Description

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 the metal sulfonate of a fluorene compound 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 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 only a low affinity for dyes in conventional dyeing processes. Attempts have been made to improve the dyeability of polyesters, particularly in film and fiber form. So you can z. B. use small amounts of certain amino alcohols in the condensation, thereby improving the colorability of z. B. polyethylene terephthalate is achieved. However, 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 to air oxidation and light. Furthermore, the use of toxic compounds, such as. B. of chlorobenzenes or chlorophenols have been described for the dyeing process. In addition one can vat or acetate dyes at superatmospheric pressure and temperatures above 100 ⁰ C auffärben, fiber swelling agent or dye carrier use or pigments which are mixed directly with the Polyäthylenterephthalatschmelze before spinning to apply.

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

(I)

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 fluorene compounds used to prepare the modified linear polyesters of the present invention are the monosulfo- and disulfo-9,9- (carboxyalkyl) fluorene, their monohydric metal sulfonate salts, their acyloxy metal sulfonate salts, and the esters thereof. The compounds encompassed by the formula I 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 polyesters used monosulfo-9,9 - di - (carboxyalkyl) - fluorene - and disulfo - 9,9 - di (carboxyalkyl) - fluorene compounds can be represented by the following formula, which is a subclass of Formula I:

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 stands for lithium, sodium, potassium, rubidium or cesium, R stands for a hydrogen atom or a monovalent alkyl group with 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

(II A)

ROOCH, "C.

2ΐΛ - η

C "H ₂ " C00R

20th

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

(Π B)

ROOCH

C "H," C00R

ROOCH

COOR

30th

As starting materials for the production of monosulfo - 9,9 - di - (carboxyalkyl) - fiuoren- 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 HB are made by known sulfonation processes. So z. B. that through the following general formula

45

9,9-Di- (carboxyalkyl) -fiuoren shown with conc. Sulfuric acid are sulfonated. At temperatures up to about 65 ° C., 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 13O ⁰ 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 z. B. can be used:

Lithium-9,9-di- (2'-carboxyethyl) -fluoren-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-9- (2'-carboxyethyl) -9- (5'-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 ^ - ^ '- carboxyethyl ^ - ^' - carboxy-

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

octyl) fluorene-2,7-disulfonate; Disodium-9,9-di- (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'-carbomethoxyethyl) -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'-carbopropionoxyethyl) -

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 ^^ '- carbooctanoxyäthyl ^^' - 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'-carbohexanoxyäthyi) -9- (3 '-carbohexanoxypropyl) -fluoren-2,7-di-

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

sulfonate;
pinodium-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:

fluorine compounds by the formula

SO ₃ M'Z (III)

ROOCH

C "H," COOR

35

40

ROOCH, "C" C _n H _7n COOR

in which X "stands for a hydrogen atom or a - SO ₃ M'Z radical, M 'for BeryBhim, 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, such as 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) -fluorenverbindungen used according to the invention are characterized by the following formula:

SO ₃ M'Z (III A)

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) -fluorenes are prepared by reacting a divalent metal salt of a monocarboxylic acid of the general formula M '(00CR ") ₂ with the free sulfonic acid compounds falling under the subclasses of formula II.

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 in order to achieve complete conversion ensure 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 are used. The reaction can at any suitable temperature and is preferably carried out at temperatures from about 50 to about 150 ° C., especially 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.

and the di- (acyloxymetallsulfo) -9,9-di- (carboxyalkyl) AIs Mono - (acyloxymetallsulfo) - 9.9 - di - (carboxyalkyl) - used in the process according to the invention

fluorenes and di- (acyloxymetallsulfo) -9,9-di- (carboxyalkyl) -fluorenes are z. B. suitable:

2-hexanoyloxybarium sulfo-9,9-di- (3'-caiboxy-

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

ethyl fluorine;
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'-carboxy-

ethyl) 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-

oxyethyl) -9- (5'-carboxypentyl) fluorene; 2,7-di- (octanoyloxycalcium sulfo) -9- (2'-carb-

oxyethyl) -9- (3 '-carboxypropyl) -fluorene; 2,7-di- (nonanoyloxybarium sulfo) -9,9-di-

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

(2'-carboxyethyl) 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-

ethyl) -9- (3 '-carboethoxypropyl) fluorene; 2-nonanoyloxystannosulfo-9- (2'-carboethoxyethyl) -9- (3'-carbopentanoxypropyl) fluorene; 2-butanoylbarium sulfo-9- (2'-carbomethoxy-

ethyl) -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-Acetoxycalciumsulfo-9- (2'-carbopentanoxyethyl) -9- (8 '-carbopentanoxyoctyl ^ fluorene; 2-acetoxycalcium sulfo-9- (2'-carbomethoxy-

ethyl) -9- (10'-carbomethoxydecyl) fluorene; 2,7-di- (benzoyloxycalcium sulfo) -9,9-di- (2'-carboethoxyethyl) fluorene;
2,7-di- (butanoyloxy zinc sulfo) -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- (octanoyloxymagnesiumsulfo) -9- (2'-carboethoxyethyl) -9- (4'-carboethoxybutyl) -fl uoren; 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- (butanoyloxycalcium sulfo) -9- (2'-carbo-

decanoxyethyl) -9- (5'-carbodecanoxypentyl) -

fluorene; ■

- 25 2,7-di- (decanoyloxybarium sulfo) -9- (2'-carbo-

methoxyethyl) -9- (5'-carbomethoxypentyl) -

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

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

ethoxy ethyl) -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'-carbopropoxynonyl) fluorene; 2,7-di- (propionyloxystannosulfo) -9- (2'-carbo-

methoxyethyl ^ -ClO'-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 ) _n 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,
ρ, ρ'-dicarboxydiphenylethane, ρ, ρ'-dicarboxydiphenylhexane, p, p '-dicarboxydiphenyl sulfide, ρ, ρ'-dicarboxydiphenylsulfone, ρ, ρ'-dicarboxydiphenylhexane, ρ, ρ'-dicarboxydiphenylether, ρ, ρ'-dicarboxydiphenyl ether, ρ, ρ'-dicarboxydiphenyl ether, ρ, ρ, etc.

209 546/523

9 10

Mixtures of two or more that are modified from those according to the invention can also be used

Dicarboxylic acids can be used. Polyester-made fibers compared to unmodified

There will be no disadvantages in their molar ratio of glycol to fused polyester fibers

Have dicarboxylic acid compounds of at least about physical properties and a

1.3: 1 used. However, it can also have an excess of 5 better dyeability,

of glycol to dicarboxylic acids, which between about the reaction mixture can be in the usual way

2 to 10 moles of glycol per mole of Dicarbonsäureverbin- also other additives, such as. B. color inhibitors, pig-

can be used. A suitable cement, matting agent, titanium dioxide, barium carbon

ratio is between about 1.3 to 7 mol, in particular natural or viscosity stabilizers, are added,

about 1.5 to about 5 moles, glycol per mole of the dicarbon- io The reduced viscosity I _{R of} the invention

Acid compounds. produced polyester is given by the equation

The one used in the method of the invention

Amount of sulfonated fluorene compound can be between, «ι

see about 0.1 to 10 mole percent, especially of I _R = ■ -

0.15 to about 4 mol percent, based on the aro-15 °
matic dicarboxylic acid or its dialkyl ester,

vary. definitely; where AN is the difference between the

In the process according to the invention, the flow time of the solution and the flow time of the solution are calculated amounts of aryldicarboxylic acid compound, N ₀ is the flow time of the solvent, and dung, glycol, sulfonated fluorene modification-20 C is the concentration of the polymer in grams and catalyst in a reaction vessel one- per 100 ecm solution. The values given here lead and in an inert atmosphere to a reduced viscosity at a poly temperature of about 150 to about 270.degree. C., preferred merisate concentration of 0.2 g per 100 ecm of solution, between about 170 to about 250.degree , heated. Then, using a 3: 2 mixture of phenol, any excess of glycol 25 and tetrachloroethane as solvent is measured, removed by heating the polyester can under reduced pressure to about 280 ° C. between an inert atmosphere Vary 0.2 to about 3, with values of about or at atmospheric pressure a flow of a 0.35 to about 1 being preferred,
inert gas passes through the melt. Then the fibers .wurden the polycondensation takes place at about 225 to 325 ° C, 30 dyed, in particular from an aqueous solution, preferably between about 260 to about 290 ° C at the boiling point of the dyebath. The cationic and reduced pressures of about 0.1 to about or basic and disperse dyes are 20 mm Hg, preferably between about 0.1 to about easily absorbed and provide deep tones. The 5 mm, also in an inert atmosphere. The amount of color on the fiber or the depth of the coloration. The total reaction at atmo- 35 is roughly proportional to the K / S value; This is a spherical print, taking a measure of the light reflection from the colored sample. Flow of an inert gas through the molten material. The greater the KjS value, the deeper the dye mixture is passed and the speed of the exercise. A K / S value of 20 is about twice as low as the gas flow with advancing polycondensation than a KjS value of 10. The determination of the increase. The total reaction time can be between 40 KjS value is in "Color in Business, Science and about 1 to 12 hours, what is used by Industry", 1952, pp. 314 to 342, described.
The polyester produced according to the invention contour, the pressure, the starting monomers or the viscosity desired from the melt to form fibers and yarns for the polyester depends on the catalyst and its concentration. to be spun. Before spinning from the r _A

To shorten the reaction time and thus the melt, the modified polyesters were dried over night at 90 ° C and a pressure of 2 mm Hg, preferably in contact with a monomers and then reacted from the melt in a suitable catalyst to reduce possible discoloration. Any piston spinning machine at 280 to 285 ° C with a known poly esterification catalyst can be used. B. antimony oxide, zinc acetate, manganese 50 0.38 mm diameter extruded. The speed at the nozzle opening was 90 cm / min., And magnesium methoxide, sodium methoxide, barium - the yarn was fed at a speed of about oxide, cadmium formate, black lead, dibutyltin oxide, 45 m / Min., Ie a draw ratio of 50: 1, tetraisopropyl titanate or calcium titanium silicate. removed. The yarn was then stretched by an electrical The catalyst concentration can hot drawn from about 0.001 55 trically heated mandrel at 90 ° C., and up to about 1 percent by weight, based on the total amount of 200 to 500%, and then about an amount introduced by electrolyte on dicarboxylic acid-linked heated rod at 150 ⁰ C continuously with fertilize, be varied. The preferred amount is 10% relaxation annealed. The yarns were then woven into fabrics between about 0.005 to about 0.5 weight percent. The spinning method used, in particular between 0.01 to about 0.2 weight 60, is common and known for polyester.
percent. The substances were manufactured in

It was not to be expected that the sulfonated absence of carriers or dyeing auxiliaries

Fluorene modifier has a sufficient chemical color. The dye baths used had flotation

cal and thermal resistance would have a ratio of 40: 1 and contained as an emulsifier

in order to remove the 65 1% of the sodium sulfate derivative of 7-ethyl-2-methyl-

Polycondensation conditions as well as those for verundecanol-4. The color concentration was 3%,

spin the polyester necessary high tempera- tures on the weight of the fabric, and the dye

doors to endure. It was also surprising that genes were carried out at boiling temperature.

Among the basic and disperse dyes that The fibers produced from the polyesters produced in accordance with the invention are easily colored by the on p. 432 and 433 of the "American Dyestuff Reporter", Vol. 43, 1954, called "Genacryl" dyes, such as 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; Methylenes 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 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 180 ⁰ C heated. The methanol formed during the reaction was distilled off. The temperature was then held at 235 ° C. for 1 hour in order to remove the excess glycol. The reaction mixture was then heated 7.25 hours at 28O ⁰ C, with a heavy stream of nitrogen was passed through the melt for carrying 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. With Genacryl Pink G dyed yarn had a K / S value of 0; with Celliton Fast Red GGA Ex. Cone, was the K / S value 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. The temperature was increased to 230 ° C. to remove the excess glycol. The reaction mixture was then ^{heated to 270 °} C. and the polycondensation was carried out for 5.5 hours at this temperature and atmospheric pressure, a rapid stream of nitrogen being 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.

B e i s ρ i e 1 1

A mixture of 100 g of dimethyl terephthalate,

1.3984 g of sodium 9 \ 9 - di - (2 '- carbomethoxyethyl) - fluorene-2-sulfonate (0.631 mole percent), 100 g of ethylene glycol, 0.02 g of antimony oxide, 0.03 g of zinc acetate and 0.02 g manganese acetate was placed in a reaction vessel and heated 4.75 hours at 18O ⁰ C. The methanol formed during the reaction was distilled off. ¹ Then 1 hour at 23O ⁰ C and then to carry out the polycondensation 4.5 hours at 280 ⁰ C was heated to distill off 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 4 ¹ Z 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 possessed a reduced viscosity of 0.55 and a F. of 249 to 25 Γ C. It showed excellent fiber forming Properties. Fabrics made from the fibers were stained with Genacryl Pink G and possessed a K / S value of 4.4; when stained with Celliton Fast Red GGA Ex. Cone, the K / S value was 19.9.

A polyester was prepared in a similar manner by using 9,9-di- (2'-carbomethoxyethyl) instead of sodium - fluorene - 2 - sulfonate 2 - propionoxy-

magnesium sulfo - 9.9 - di - (2 '- carbomethoxyethyl) fluorene has been used.

Example 3

A series of polycondensations was carried out by adding 1.22 mole percent (batch A and B) and 1 mol percent (batch C and D) sodium 9.9 - di - (2 '- carbomethoxyethyl) - fluorene - 2 - sulfonate, based on the total amount of esters introduced, were used as modifying agents. The charges 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, ° 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 - (2 '- 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 F'j 4V was heated for ₂ hours at 270 ° C. A stream of nitrogen was passed through the melt throughout the 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 KJS value was 19.0.

A film-forming polyester was prepared in a similar manner by replacing sodium 9,9-di- (T- carbomethoxyethyl) fluorene-2-sulfonate with 2-acetoxyzinc sulfo-9,9-di- (2 '- carbomethoxyethyl) fluorene .

Example 5

Two polycondensations were carried out using 1.5 mole percent sodium - 9.9 - di- (2 ' - carbomethoxyethyl) - fluorene - 2 - sulfonate, based on the total amount of the ester charge, as Modifying agent carried out. The feeds and reaction conditions are as follows specified:

545 078

approach A. 120 B. 170 Dimethyl terephthalate, g Sodium 9,9-di- (2'-carbo- 4.1450 5.8696 methoxyethyl) fluorene 120 175 2-sulfonate, g 0.0248 0.0352 Ethylene glycol, g 0.0372 0.0528 Antimony oxide, g 0.0248 0.0352 Zinc acetate, g Manganese acetate, g 4th 4.5 Ester exchange: 180 180 Time, hours Temperature, ⁰ C Removal of the over 1.25 1 liquid glycol: 235 180 to 270 Time, hours Temperature, ⁰ C 4.75 5 Polycondensation: 285 270 Time, hours 0.70 0.65 Temperature, ⁰ C 250 to 252 254 to 256 Reduced viscosity .. Melting point, ⁰ C

Example 7

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:

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 of zinc acetate and 0.0354 g of manganese acetate were placed in a reaction vessel and heated to 180 ° C. for 4.5 hours, the methanol formed during the reaction being distilled off. To remove excess ethylene glycol, the reaction mixture was then heated for 1 hour 180-270 ° C and for carrying out polycondensation for 5 hours at 27O 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 X / 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

Dye I.,
Dye II

approach

20.8

25.3

11.8

25.3

Example 6

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 were placed in a reaction vessel and heated to 180 to 195 ° C. for 3.5 hours, the methanol formed during the reaction being distilled off. Then the reaction mixture to remove excess ethylene glycol was heated for 1 hour at 195 to 27O ⁰ C. The polycondensation was 3.66 hours at 27O ⁰ C and atmospheric pressure to give a fast stream of nitrogen was 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.

A polyester was prepared in a similar manner by replacing sodium 9,9 di (2 '- carbomethoxyethyl) fluorene - 2 - sulfonate with 2 - acetoxycalciumsulfo-9,9-di (2'-carbomethoxyethyl) fluorene . A mixture of 70 g of dimethyl terephthalate, 4 g of sodium 9,9-di- (T- carbomethoxyethyl) fluorene-2-sulfonate (2.4 mol percent), 80 g of ethylene glycol, 0.0148 g of antimony oxide, 0.0222 g of 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 ⁰ 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. There was obtained a white polyester having a reduced viscosity of 0.54 and a F. of 248 to 25O ⁰ C.

In a similar way a polyester was made,

by instead of sodium 9,9-di- (T- carbomethoxyäthyl) - fluorene - 2 - sulfonate 2 - Acetoxyberylliumsulfo - 9,9 - di - (T - carbomethoxyäthyl) - fluorene was used.

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 accomplished. 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 Examples

Zinc acetate, g 0.0381

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

Ester exchange: 2.531 g 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, hour 5 glycol 0.75 hours to 280 ⁰ C and then to the through temperature, ⁰ C 270 conduct the polycondensation 7 hours at atmo-

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

Melting point, ⁰ 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. 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. A fiber-forming polyester was prepared in a similar manner 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) - B e i s D i e 1 13

fluorene - 2 - sulfonate (3 mole percent), 120 g ethylene-P

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) and heated for 5 hours at 180 ⁰ C, 30 fluoren-2,7-disulfonate (1 mole), 120 g Äthylenwobei the methanol formed during the reaction glycol, 0.0247 g antimony oxide, 0.037 g of zinc acetate was distilled off. The reaction mixture was and 0.0247 g of manganese acetate was heated 5.75 hours at 180 to remove excess ethylene glycol to 200 ° C, wherein the during the reac-formed 0.75 hours at 180 to 27O ⁰ C and then to transit tion Methanol was distilled off. The conduct of the polycondensation at an atmospheric reaction mixture was ^{heated to 270 °} C. for 5 hours to remove excess pressure. During the total reaction, ethylene glycol 1.25 hours at 280 ° C., nitrogen was passed through the melt and then at atmospheric pressure for 4.5 hours. 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 26O 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 - (2 '- 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 ⁵ ° B eis ρ ie 1 14

A mixture of 120 g of dimethyl terephthalate,

A mixture of 30 g of dimethyl terephthalate, 4.228 g of disodium - 9.9 - di - (2 '- 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, 0.0101 g antimony oxide and 0.0151 g 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

27O ⁰ C and then to carry out the poly at atmospheric pressure 5.7 hours at 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

did of 0.33 and a m.p. of 232 to 237 ° C. The viscosity of 0.64 and a F. of 258 to 260 ⁰ C

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

Properties. · receive.

In a similar way, a polyester was prepared by the disodium - 9,9 - di - (T - carbomethoxyethyl) fluorene-2,7-disulfonate with 2,7-di- (propion-

* 'oxycalciumsulfo) - 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 was heated 5.25 hours at 18O ⁰ C, with the methanol formed during the reaction was distilled off. The reaction mixture was heated to remove excess ethylene glycol 0.5 hours at 280 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.

B e i s ρ i e 1 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 to 183 to 186 °} C. for 8 hours, the methanol formed during the reaction being distilled off. The reaction mixture was heated to remove excess ethylene glycol by 2.25 hours at 265 to 27O ⁰ C. The polycondensation was carried out by heating to 272 to 274 ° C. for 4.75 hours at atmospheric pressure, a rapid stream of nitrogen being passed through the melt. A white, crystalline, fiber-forming polyester with a reduced viscosity of 0.64 and a melting point of 257 to 261 ° 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 has been used.

B e i s ρ i e 1 17

A mixture of 194 g of dimethyl terephthalate, 4.4583 g of lithium - 9.9 - di - (T - 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 made placed in a reaction vessel and ^{heated to 185 to 189 °} C. for 4.25 hours, the methanol formed during the reaction being distilled off. The reaction mixture was heated to remove excess ethylene glycol course of 2.75 hours from 220 to 267 ⁰ C. 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 PoIykondensation 4,25stündiges was carried out by heating to 265 ⁰ C at atmospheric pressure to give a vigorous stream of nitrogen was 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 - (T - carbomethoxyethyl) fluorene - 2 - sulfonate (2 mol percent), 150 g of ethylene glycol, 0.0157 g of antimony oxide and 0.0707 g of zinc acetate was placed in a reaction vessel and heated to 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 heating for 4.5 hours at 265 to 270 ° C. at atmospheric pressure, with nitrogen being 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 were given an intense tint with Genacryl Pink G with an iC / S value of 21.74 and with Celliton Fast Red GGA Ex. Cone, a very deep red tint with a K / Stained S value of 19.85.

Example 20

A mixture of 194 g of dimethyl terephthalate, 9.8 g of methyl 4- [2-sodium sulfo-9- (2'-carbomethoxy) -nuoren-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, the methanol formed during the reaction being distilled off. the Reaction mixture was used to remove excess

Schüssigem ethylene glycol heated to 231 to 238 ° C for 3 hours. The polycondensation took place through Heat at 265-279 ° C for 4.5 hours at atmospheric pressure with a vigorous stream of nitrogen was passed through the melt. Thus, a fiber-forming polyester with a reduced Viscosity of 0.6 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 230 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 disodium - 9 - (2 '- carbomethoxyethyl) -, 9 - (5 '- carbomethoxypentyl) - fluorene - 2.7 - disulfonal ·; (1 mole percent), 150 g of ethylene glycol, 0.016 g of antimony oxide and 0.072 g of zinc acetate was placed in a reaction vessel given and heated to 176-187 ° C for 4.25 hours, during the reaction formed methanol was distilled off. Then the reaction mixture was used to remove excess Ethylene glycol heated to 235 to 275 ° C for 1.5 hours. The polycondensation took place 5.25 hours at 275 ° C and atmospheric pressure, with a vigorous stream of nitrogen through the melt was directed. There was thus obtained a fiber-forming crystalline polyester having a reduced viscosity of 0.58 and a m.p. of 267 ° C.

Example 24

A mixture of 15 g of dimethyl terephthalate, 0.7191 g of potassium - 9.9 - di - (2 '- carbomethoxyethyl) fluorene-2-sulfonate (2 mol 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 were placed in a reaction vessel and

Heated for 3.75 hours to 195 to 206 ° C., the methanol formed during the reaction being 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

23 1 545 07
continuation 1 8th Ans
B. 1 24 D. 1 YES 180 to 280 180 to 270 atz
C. 180 to 280 Removal of excess glycol:
Time, hours 1 1 1 1 Temperature, ⁰ C 280
0.56
257 to 259 270
0.57
251 to 253
7.3 180 to 280 280 Polycondensation:
Time, hours 1 0.71
249 to 251 Temperature, ⁰ C 280
0.61
254 to 256
2.9
12.9 3.3 Reduced viscosity Melting point, ⁰ C K / S values with
Genacryl Pink G Cellitoh Fast Red GGA Ex. Cone

B. For comparison with the polyesters of A.

carried out a series of polycondensations,

) '■) where both a chain terminator and 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonic acid were used as modifying agents. The trials 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, ° 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

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
180 to 270

270

0.50
251 to 253

19.8

25.3

176.8

4.0480 2.8560

180 0.0367 0.0551 0.0367

4.5 180

1 180 to 270

270 0.53 250 to 252

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

i 545 078

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

As indicated by the K / S values, the presence of a chain terminator alone causes some improvement in dyeability. However, this improvement is not as great as when the polyester is made using a sulfonated fluorene modifier. Furthermore, when a combination of sulfonated chain terminator and sulfonated fluorene modifier is used, a lower total amount of modifier is required than when either of the sulfonated compounds is used alone. It has also been found that a combination of 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 gave just as deep a shade as is achieved with 2 to 3 mole percent sodium 9,9-di- (2'-carbomethoxyethyl) fluorene-2-sulfonate 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) -fluoren-2,7-disulfonic acid and 400 ecm of methanol was refluxed for 5 hours and then cooled. 9,9-Di (2'-carbomethoxyethyl) fluorene-2,7-disulfonic acid was obtained from a small portion of the reaction mixture. The remainder of the reaction mixture was reacted with methanolic sodium hydroxide to a pH of 7.5; a precipitate formed. The precipitate was filtered off, the filtrate was concentrated on the steam bath and, after cooling, crystals formed again which were filtered off. The two crystalline fractions were combined, recrystallized from methanol and so the stable up to 340 ⁰ C, pure disodium - 9,9 - di - (2 '- carbomethoxyäthyl) - fluorene 2,7-disulfonate in the form of crystals. The disulfonate was identified by infrared and elemental analysis:

C ₂₁ H 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 prepared by reaction with the appropriate hydroxide using the procedures described above.

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 receive.

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 to 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 receive.

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. Ck

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 for 4 hours at 0 to 10 ° C, then heated within 2 hours to 25 ° C and then heated for 1 hour at 40 ⁰ C.

After cooling the solution to 30 ⁰ C 150 cc of methanol were added dropwise and the solution heated to reflux 4V2 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 and thus a viscous residue obtained. The residue was recrystallized twice from acetonitrile, Ge rl dried and then the melt at 95 to 100 ⁰ C ^v · sodium 9- (2'-carbomethoxyäthyl) -9- (5'-carbomethoxypentyl) fluorene-2-sulfonate in Preserved 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, most of the methanol being distilled off and the new methanol once was replaced. The solution was reacted with methanolic lithium hydroxide to a pH of 7.0, the clear solution was evaporated on a steam bath and a clear, viscous residue was obtained. After dissolving 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) -fluoren-2,7-disulfonate was filtered off. The crystals were dried at 1 mm Hg at 100 ^° C. and did not melt at 400 ^{° C.}

6. In a glass reaction flask equipped with an air cooler, thermometer and stopper, 26 g of 9- (2 '- carboxyethyl) - 9 - (5' - carboxypentyl) - fluorene, 100 g of sulfuric acid and 0.2 g of mercury-2-sulfate were placed given, the reaction mixture at 100 ⁰ 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 was noticed. 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 no solid crystallized out after cooling. The methanol was on the steam bath evaporated and so obtained a viscous residue,

which slowly crystallized when standing. After dissolving 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'-carbomethoxyä thy 1) - 9 - (5 '- carbomethoxypentyl) - fluorine - 2,7 - disulfonate from. After cooling, the white Filtered off crystals and dried.

By heating a mixture of barium acetate and 9 - (2 '- carbomethoxyethyl) - 9 - (5' - carbomethoxypentyl) - fiuoren - 2,7 - disulfonic acid in methanol at reflux temperature was the 2,7-di- (acetoxybarium sulfo) - 9 - (2 '- carbomethoxyethyl) - 9 - (5' - carbomethoxypentyl) fluorene receive.

Claims (2)

Patent 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