DE1277510B - Modified polyester fibers or threads - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

DOIf

German class: 29 b -3/60

P 12 77 510.9-43 (P 19677)

November 18, 1957

September 12, 1968

Main patent application P16544IVc / 29b relates to Fibers or threads made from polyesters with chain links that have sulfonate groups in the form of a Have, exist or contain metal salt.

If the residue of the polyester containing the metal sulfonate group, through more than two ester bonds is bound to the polymer molecule, it has a crosslinking effect: a hardenable, modified one is created Polyester. However, the preferred fibers or threads consist of such modified polyesters, in which the radical containing the metal sulfonate group is attached to the polymer molecule by one or two Ester bonds is bound.

The modified thread-forming polyesters can be colored directly with basic dyes. As detailed in the description of the main patent, polyethylene glycol terephthalates are used modified, for example, by adding one or more metal sulfonate groups to its molecule of arylene residues incorporated.

The present invention now relates to fibers or threads according to the patent application P 16544IVc / 29b, which are characterized that the chain links of the fiber or thread-forming polyester alkylene radicals which carry sulfonate groups with sulfonic acid salt groups. Such fibers or threads can be dyed directly with basic dyes will.

A preferred type of modified polyester consists of a polyethylene glycol terephthalate, which is low Quantities of a unit contain the following structure:

Λ. jL · I

SO ₃ M

Here M is a metal atom,
- Z -

SO ₃ M

a metal salt of an alkylene radical bearing a sulfonate group such that —X— is separated from the —SO ₃ M-ReSt by at least 3 carbon atoms, —X — is the same

- O —C -

'Il ο

- O - (CH ₂ ) "[ _{O (CH 2} ) J _m - O

Fibers or threads of modified polyesters

Addition to registration: P16544IV c / 29 b—
Interpretation document 1128 594

Applicant:

E. I. du Pont de Nemours and Company,

Wilmington, Del. (V. St. A.)

Representative:

Dr.-Ing. W. Abitz and Dr. D. Morf,

Patent attorneys,

8000 Munich 27, Pienzenauer Str. 28

Named as inventor:
John Malcolm Griffing, Gluten, NC;
William Roscoe Remington, Wilmington, Del.
(V. St. A.)

Claimed priority:
V. St. ν. America November 19, 1956
(622811)

or

-C- [O (CH ₂ ) J ₁₁₁ -O O

is, - Y - is - X - or hydrogen, η and m are integers and η is greater than 1.

The fibers or threads according to the invention consist of modified polyesters which are produced in this way be that you have a small amount of one or more compounds that at least one ester-forming functional group and at least one sulfonate group bonded to an alkylene radical in Contain the form of a metal salt in the polycondensation of the reaction mass before the Synthesis of the polyester to be modified is complete. The polyester can be manufactured by adding a dicarboxylic acid or an ester thereof and an aliphatic glycol or a Ester of the same or an ester of an aromatic

809 600/543

3 4

Bringing diols into reaction with one another or by example

An oxyacid or an oxyester of the self-condensing On a conventional spinning device, threads are made sation submits. By transesterification and by modified from one for better colorability Polycondensation reactions result in linear con-polyethylene glycol terephthalate produced. The herdensation polyester of a thread-forming type. The 5 position of the thread-forming polyester happens as the sulfonate group-containing compound can be one of the following:

Metal salt of a sulfomonocarboxylic acid ester or ¹ 0.8 parts of sodium 3-oxypropane-1-sulfonate will be a sulfodicarboxylic acid ester, or it can be in 49 parts of dimethyl terephthalate, 34.5 parts of the ethyl form of a monohydric or dihydric alcohol lenglycol, 0.023 parts of manganese acetate. 2,5 hydrate and are present, which has a carboxylic acid ester group and at least 10 0.015 parts of antimony trioxide added, the least one containing a sulfonic acid group, or the ratio of sulfonate salt to dimethyl in the form of a preformed polyester, the terephthalate is about 2 mol percent. Methanol from a sulfonate group-containing compound is removed from the reaction mixture when the bond and a base component of the thread temperature is produced from 165 to forming polyester in the course of 3 hours, for example with a 15 220 ⁰ C is increased. The mixture is then polycondensed with dicarboxylic acid or its ester or with a 275 ° C. and 1 mm Hg for 3 hours, aliphatic glycol or its ester or with a. This gives a polycondensate of an oxy acid or an oxy ester. With the present intrinsic viscosity of 0.32 (measured in a Mi invention, a modified polishing compound composed of 58.8 parts by weight of phenol and 41.2 parts by weight of ethylene glycol terephthalate is particularly suitable. 20 parts by weight of trichlorophenols

The modified polyesters from which the inven- The excellent colorability of this polyester

appropriate fibers or threads are built up, results from the following experiment:
"can be made by making a film molded from this polyester

Before the end of the polycondensation reaction mixture was used at 125 ° C. for 529 hours with an aqueous solution small amounts of one or more compounds of 3% (based on the weight of the film) of one of the composition 1,3,3-trimethyl-2- (p- (N-methyl-N-beta-cyanoethyl-

t> 2; R 'amino) -styryl) -pseudoindolium salt, a basic

ι dye of the quaternary ammonium salt type,

or »M as described in U.S. Patent 2,164,793

^ 30 is treated. The film will be in medium

incorporated, in which M is a metal atom, tinted red, while one of a Ver

same sample of unmodified polyethylene-gly-

- Colterephthalate pressed film only a weak one

j tint absorbed by dye.

^SQ * ^{M 35} example 2

A metal salt of a sulfonate group-bearing thread is made on a conventional spinning apparatus

Alkylene radical such that R _{modified from the - SO 3} M - from one for better colorability

Group is separated by at least 3 carbon atoms, made polyethylene glycol terephthalate.

R equals 40 The production of the thread-forming polyester takes place as follows:

- C-lower alkyl 86 parts of diethyl malonate become a solution Il of sodium ethoxide was added, which was obtained from 8.24 parts of sodium and 169 parts of absolute ethanol.

Q OH 45 g ^este lst ^lst - This solution is set while stirring

I! 43.66 parts of propane sultone, whereupon the temperature

O noticeably increases. The solution is then under

Heated to reflux conditions for 30 hours. The fixed one

- ~ ^c ~ O-lower alkyl mass, which separates out on cooling, Na-

Ii 50 trium 4,4-dicarbethoxy-1-butanesulfonate, has after

O recrystallization from ethanol has a melting point

- (CH ₂ ) "0H ^{of 160} ° ^c

1.5 parts of this product are 49 parts

- 0 (CH ₂ J _n OH Ien dimethyl terephthalate, 34.5 parts of ethylene glycol,

- O - (CH ₂₎ TO (CH)] - OH hydrate ^S-5 ^ 0 ^ ₅₀₂₃ parts of manganese acetate and 0.015 part of antimony trioxide was added, the volume .wobei ° ^"he ratio of the sulfonate salt to dimethyl terephthalate.

- Q - [OfCH ₂ ) "] _m - OH '- is ^about 2 mole percent. After removing the

Methanol from the reaction mixture and poly

n and m integers, η greater than 1 and R 'equal to R 60 condensation according to that given in Example 1

or hydrogen. Way you get a polycondensate from a

The sulfonate group can be in the form of an alkali intrinsic viscosity of 0.32 (measured in a mi

or alkaline earth salt or a lead or lanthanum mixture of 58.8 parts by weight of phenol and 41.2 parts

salt are present. The trichlorophenol containing the sulfonate group by weight.

Compound is preferably used in an amount of 65. The excellent colorability of this polyester

0.5 to 10, preferably 2 to 5 mol percent, based on the following experiment:

on the amount of film in the filament-forming polymer. A film pressed from this polyester is

contained terephthalates used. 1 hour at 125 ° C with an aqueous solution of

3% (based on the film weight) of the basic dye used in Example 1 became. The film is colored red with a medium shade.

In the manufacture of polyethylene glycol terephthalates, which are modified with sulfonic acid salt, the reaction mixture can other Giycole, such as 1,4-bis (oxy-epoxy) benzene, or other esters, such as Isophthalates, succinates, adipates and p-p'-bi-benzoates in amounts of up to about 10 mole percent or more can be added to make complex copolyesters. Other polymeric substances, especially those which contain ester or hydroxyl end groups can be used in amounts of up to about 10 percent by weight are mixed with those for the production of the fibers or threads according to the invention in the melt.

Other substances can also be present in the reaction mixture, such as catalysts, pigments, matting agents and color inhibitors as described in the parent specification.

If the modified polyesters described above are dyed with basic dyes, these latter are preferably from aqueous solutions at temperatures between 100 and 125 ° C applied. The aqueous solution can be acidic and there can also be other additives for dye liquors, such as sodium sulfate, sodium acetate or quaternary Ammonium salts, be present. The modified polyester fibers or filaments according to the invention become uniform by the basic dyes applied from hot aqueous solutions penetrated. This penetration gives the dyed structures fastness properties and abrasion resistance.

Claims (2)

35 claims; 1. Fibers or threads made of polyesters with chain links containing sulfonate groups, exist, according to patent application P16544 FVc / 29b, characterized in that the chain links carrying sulfonate groups are alkylene radicals with sulfonic acid salt groups. 2. fibers or threads according to claim 1, characterized in that the polymer molecule of the modified polyester consists of a polyethylene glycol terephthalate, which small amounts a unit of structure —X — Z — Y— SO ₃ M
contains, in which M is a metal atom, SO ₃ M is a metal salt of an alkylene radical bearing a sulfonate group such that —X— is separated from the SO ₃ M ReSt by at least 3 carbon atoms, —X— is the same - ο — c— - O - (CH ₂ UO (CH ₂ ) _B ] _m - O- or -C
O [O (CH ₂ ) ^ - O- is, —Y— is —X— or hydrogen, η and m are integers, and η is greater than 1. Considered publications:
German Auslegeschrift No. 1 006 383;
U.S. Patent Nos. 2,698,856, 2,744,087, 777,830. β Federal Dracking Company Beate.