DE1011392B - Process for the partial saponification of shaped structures from high-melting polymers with ester groups in the chain - Google Patents

Description

It is known that fibers made from high-melting linear polymers with ester groups in the chain, in particular those made of polyethylene terephthalate, more by treatment with aqueous solutions of alkalis in the heat or to saponify less extensively. This takes place without any noticeable swelling and, if it has shrunk Material is used, even without a change in length, a gradual and uniform dissolution of the fiber substance from the surface, so that the process amounts in practice to a refinement of the fiber. Remarkably, the specific strength is largely retained in this reaction, at least as long as the loss of substance does not exceed about 10%. At the same time there is an improvement in the grip and Due to the etching of the originally very smooth surface, a generally very desirable damping of the Sheen, which gives the polyester threads a greater resemblance to silk. From the partial saponification of the The process differs essentially from cellulose ester fibers in that there is no layer and no transition zone arises with pronounced swellability in aqueous alkali. Because of the lack of swelling the saponification reaction proceeds relatively very slowly, so that the process is not straightforward can be carried out continuously on the running thread or on the rolling piece. The same goes for that Use in printing or padding processes. If you do not accept unusually long treatment times If you want to take, you have to use relatively drastic working conditions, which are often not permissible with fiber blends use.

It has now been found that the heterogeneous saponification of shaped structures, such as threads, fibers and flat structures, of hydrophobic, high-melting points High polymers with ester groups in the chain despite the lack of swelling and despite the low affinity of the Polyester, especially the aromatic polyester, can increase very significantly to aqueous agents, if they with aqueous solutions of alkaline cleavage agents, especially the alkali metal hydroxides, in the presence of Strong organic base cations of the quaternary base type or their equivalents as long as in treated with heat until the desired weight loss has occurred. Accelerator in the sense of In addition to the quaternary ammonium hydroxides and salts thereof, which are stable in aqueous solution, the invention organic sulfonium and phosphonium hydroxides as well as the quaternary bases in the basicity equal or near coming guanidines and biguanides. Instead of the free bases, their soluble salts can be used with any anions can be used.

The following compounds, for example, are listed in detail:

N-methyl-N - dodecyl -N-dioxyäthyl-ammoniumhy process for partial saponification

of shaped structures

high melting point polymers

with ester groups in the chain

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M.

Dr. Paul Schlack, Leitershofen via Augsburg,

and Dr. Josef Nüsslein, Frankfurt / M.,

have been named as inventors

hydroxide, N-trimethyl-N- [4-isopropylbenzyl] -ammonium hydroxide, N-trimethyl-N-phenacyl-ammonium hydroxide, N-trimethyl-N- [xenyl (= residue of diphenyl) -l-methyl] ammonium hydroxide, N-trimethyl-N-p-phenoxybenzylammonium hydroxide, N-dimethyl-N-octadecyl-N-oxyethylammonium hydroxide, the mixture of N-dimethyl-N-palmkernfettalkyl-N-benzyl-ammoniurnhydroxyde.das Mixture of the palm kernel fatty acid amides of the general formula

RCO-NH- (CH ₂ ) _x - N ^

R '"

OH

where RCO - the palm kernel fatty acid residue, R 'and R "are alkyl residues or together an alkylene residue, R'" is a /? - oxyethyl residue and χ is a number greater than 1. Also: dodecylguanidine, Ν-dodecyl-N'N '' - ethylene guanidine, pentadecyl biguanide, pentadecyldimethylsulfonium hydroxide.

Of the alkylguanidines, primarily the N, N ', N "-trialkylguanidines, which are distinguished by their particularly high basicity, come in question, then the monoalkyl and the N, N-dialkylguanidines. Aromatic on nitrogen substituted guanidines or biguanides are relatively weak bases and are therefore essential for the process not suitable. The alkali hydroxides, especially sodium hydroxide, are the main saponifying agents and potassium hydroxide in question. Strongly alkaline reacting salts, such as sodium sulfide, are less effective.

709 586 * 386

3 4

sam. The concentration of the alkaline solutions to be used is generally only light to medium colorations

can be obtained depending on the saponification agent, method of operation and type, but can still be used in delicate

and the amount of accelerator added can achieve very beautiful color effects in wide nuances. The effective

Boundaries fluctuate. Salt-like saponifying agents can be used as accelerators according to the invention

expediently used in higher concentration. With 5 coming substances depends on the constitution and

the practically preferred caustic soda can be used at molecular size. When using diluted alkalis

Using the very effective thin ethyl palm kernel fat, products that have a residual

alkylbenzylammonium hydroxide as accelerator itself having at least 8 to 10 carbon atoms, preferably

with 1% sodium hydroxide solution at the boiling point or in the form of an unbranched paraffin chain or in the form

work with good success. Upwards there is basically ^{l0 of} an at least 2-ring aromatic radical

no limit set. About irregularities and ways. But with increasing concentration

To avoid fiber damage, it is advisable to also use bases or salts with a lower molecular weight

To carefully control the process and to make the established ones more and more effective, e.g. B. Compounds such as trimethyl

Conditions to be adhered to within narrow limits. It must be hexylammonium chloride, trimethylbenzylammonium

Care must also be taken that the material to be treated is ^l 5 chloride, while higher-molecular substances are

Solubility in strong alkalis can be as uniform as possible with the saponification agent,

stays in touch. Particular caution is at the place, nitrogen bases with one or more oxyalkyl-

when in the presence of swelling agents, such as. B. groups, ζ. B. Alkyltrioxyäthylammoniumhydroxyde

Phenyhnethylcarbinol or benzyl alcohol, worked or substituted by polyglycol ether residues on the nitrogen

will. ²⁰ tuated bases, can despite relatively higher

The method according to the invention can not only be soluble in strong alkalis not only with molecular weights

aqueous liquors are carried out in which that and thus be effective. In alkaline printing pastes

The goods to be treated are moved or by which the goods themselves cause very low molecular weight substances, such as

is passed through continuously, but also by trimethylbutylammonium acetate, even monoethyl

Padding or printing the saponifying agent in 25 guanidine and guanidine itself, e.g. B. as guanidine rhodanide,

The presence of thickeners such as methyl cellulose still accelerates saponification noticeably.

Oxyethyl cellulose or polyvinyl alcohol, optionally compared to the known treatment with alkalis

in the presence of swelling agents, here z. B. Di- results from the method of the invention alone

Ethylene glycol, diphenyl-1-polyglycol ether, N-methyl- not only a very considerable acceleration, the one

N-oxyäthyl-N- [xenyhnethyl] -amine, N-Methylbutyrolac- 3 ° can exceed the power of ten, but also a

camouflage. It can also be carried out in such a way that significant fiber protection. So you have it in your hand

one the strong bases or their salts, in particular either very quickly at high temperature, for. B. 80

those with solubility in esters increasing acids, like up to 120 °, or with still tolerable reaction

p-Methoxybenzoic acid or salicylic acid, only after a period of time at a relatively low temperature, e.g. B. 40

Essence of the actual saponification agent through 35 to 70 °, to work and thus the process can too

Expand padding, printing or spraying of dispersions onto fiber blends and mixed fabrics

or solutions, if appropriate also in organic ones, which the alkaline saponification in its previous form

Solvents such as' methanol, isopropyl alcohol or not readily applicable. This applies in particular

Butylglycol, which is applied to the goods, again especially preferred for blends with cellulose fibers.

in the presence of thickeners and combinations with cotton, a merchandise can be

if necessary swelling agents, and then the nitrogen ization take place. So can fibers made from linear

connections by steaming, preferably under pressure, polyesters and cellulose ester fibers at the same time in yarns,

or by dry heating to high temperature woven or knitted fabrics according to the process of the invention

fixed. Subsequently or later the soil will be changed. In this case is special

soaping agent as a liquor or pad solution for the +5 pre-treatment of the polyester fibers with the

brought kung. Special saponification effects can be of quick interest. Are also very suitable

Finally, through partial reservation, mixtures of polyester fibers and polyamide threads are achieved,

are, especially basic, soluble as salts where at high temperature, z. B. Cooking temperature,

Synthetic resins are suitable as reservation agents, e.g. B. expediently avoids alkali concentrations in which

film-forming polyamides with basic groups. 50 for polyamide fibers there is an optimum cleavage. at

Particularly valuable optical effects are achieved, ■ fibers made of polycaprolactam z. B. this is the case

if the treated fibers already pigments or sodium hydroxide solution at about 10 to _16/0 by weight solutions °,

contain pigment-like substances. To increase the Instead of structures made of terephthalic acid polyesters

The saponification agent can also have a fine effect - other synthetic fibers with ester can also

dispersed groups in the chain due to the presence of cationic active agents by the process of the invention

positively charged pigments may be added, e.g. B. zinc treated, so z. B. Polycon fibers

sulfide. The possibility of threads or fibers with and densat the 4- [cu-oxybutoxy] -benzoic acid, fibers from

without pretreatment with the saponification accelerators polyester amides, ζ. B. from sebacic acid and amino

in a mixture, in particular in a pattern according to the arrangement of ethanol or of sebacic acid, hexamethylenediamine

to process, enables the production of another 60 and hexamethylene glycol, fibers made of polyurethane,

fashionably valuable effects, also in terms of dyeing - especially those with very low water absorption,

sees that the partially saponified threads are not only z. B. the polyurethane from hexamethylene diisocyanate

by refining the titer and changing optical we- and hexamethylene glycol and finally fibers from the

kung, but also through easier dye absorption polyester of oxypivalic acid.

distinguish. So when using it you can say 65

fiber-affine accelerator or accelerator which can be fixed on the fiber Example 1
the basic character for coloring with selected

acidic dyes, in particular monosulfonic acids, such as a yarn produced by the worsted yarn process

e.g. AlizarindirektblauA, use, if necessary from polyethylene terephthalate fiber of the single titer,

using so-called carriers. If 7 ° 3.00 den was added to sodium hydroxide solution of various concentrations

tration with and without the addition of N-dimethyl-N-palm kernel fatty alkyl-N-benzyl ammonium chloride treated as an accelerator under the conditions given in the table. The weight losses and the very strong effect of the accelerator can be seen from the list.

Conc Be Treat Temperature
Γ el til F Weight tration faster lung loss gin NaOH / l g / l duration 60 ° ° / o 4g 2 hours. 60 ° 0.23 4g - 5 hours 100 ° 0.41 4g 5 hours 60 ° 1.61 4g 1 2 hours. 60 ° 2.26 4 g 1 5 hours 100 ° 5.60 4g 1 5 hours 60 ° 27.00 10 g 2 hours. 60 ° 0.28 10 g 5 hours 100 ° 0.53 10 g 5 hours 60 ° 3.30 10 g 1 2 hours. 60 ° 3.78 10 g 1 5 hours 100 ° 9.5 10 g 1 5 hours 100 ° 56.00 25 g 1 H. 100 ° 6.3 25 g - 2 hours. 100 ° 12.95 25 g 20 hours 60 ° 77.50 25 g 1 2 hours. 100 ° 11.1 25 g 1 3 min. 100 ° 6.9 25 g 1 1 H. 60 ° 71.2 50 g 2 hours. 60 ° 2.3 100 g .— 2 hours. 60 ° 5.9 200 g 2 hours. 60 ° 13.4 350 g - 2 hours. 60 ° 40.1 50 g 1 2 hours. 60 ° 18.5 100 g 1 2 hours. 60 ° 26.3 200 g 1 2 hours. 60 ° 65.4 350 g 1 2 hours. 81.7

The last group shows that as the concentration of alkali hydroxide increases, the action of the quaternary base gradually diminishes. Nevertheless, the acceleration at 350 g Na OH / l is still 100 ° / ₀ .

Example 2

A gabardine fabric made from a polyethylene terephthalate yarn, The single fiber titer of 3.0 denier was treated with 2.5% sodium hydroxide solution for 1 hour at 90 °. That The fabric was now softer to the touch than the starting material and had lost 4.4% in weight. as the same tissue in the same sodium hydroxide solution with the addition of 1 g / l of the quaternary mentioned in Example 1 Ammonium salt was saponified at 60 ° instead of 90 °, there was a weight loss of 5.9%. That, The fabric was now much softer and more appealing to the touch than that at a higher temperature without additives treated.

Example 3

Polyethylene terephthalate fiber with a single titer of 3.0 was compared with 2.5% sodium hydroxide solution with the addition of 2.8 millimoles / 1 of various organic Bases or salts of such bases partially saponified. The following values were obtained:

Saponification accelerator Time Tempe
rature Weight
loss
7 » Dodecylguanidine
Dodecylguanidine
N-trimethyl-N- [xenyl-
1 -methylj-ammonium-
chloride 10 min.
20 min.
1 H.
1 H. 100 °
100 °
100 °
100 ° 10.9
19.6
15.9
6.3 without addition

Example 4

The same yarn as in Example 3 was made with 2.5% sodium hydroxide solution in the presence of varying amounts N-dimethyl-N-palm kernel fatty alkyl-N-benzyl ammonium chloride Treated for 2 hours at 60 °. The following values were found:

accelerator
g / i Weight loss
Vo 2.0
1.0
0.5 11.1
10.9
9.8

It can be seen from these figures that in the case of the Liquor ratio 1:40 the increase in the amount of accelerator to the 4-fold only insignificant Increase in the degree of saponification has the consequence and that you can practically also with even smaller amounts than 0.5 g / l can work.

Example 5

A crimped tow of continuous ethylene poly terephthalate filaments (single denier 3.0 denier) was under Pressing in a circulation apparatus at 100 ° with a treated aqueous liquor containing 250 g of soda per liter

4 ^NC liquor and contains 0.63 g dodecylguanidine. The liquor was allowed to circulate for 15 minutes, the fiber mass being uniformly saponified to an extent of 15%. The yarns produced from this cable after cutting into stacks and spinning the fibers using the worsted yarn process show, after processing on socks, when worn, less tendency to twist than similar yarns made from unsaponified material.

Example 6

A tightly beaten, non-heatset Gabardinegewebe of a worsted yarn of polyethylene terephthalate, 3.0 denier individual fiber, is padded with a set to p _H 4 aqueous solution containing per liter 50 g cellulose glycolate (Tylose HB 1000 of the trade) and 50 g N-dimethyl -N-palm kernel fatty alkyl-N-benzyl-ammonium chloride contains. The fabric, dried at low temperature, is then steamed at 130 ° for 30 minutes to fix the applied aid and finally rinsed at 60 °. After saponification in 2.5% sodium hydroxide solution at 69 ° for 1 hour, the weight decrease was 15.8%, while in the same bath a piece of fabric that had not been pre-impregnated was saponified to only 5.6%. The fabric, which was hard before the treatment and tending to crease, was now soft and practically crease-free. Despite the weight loss, it showed no tendency to pilling and was clearly superior to the starting material, which was already relatively cheap in this respect because of its density.

1 Oil

Example 7

A spinning tow made of polyethylene terephthalate, single fiber titer 3.0 denier with a total titer of 40,000 denier, combined on the spinning machine, is impregnated with an aqueous, 36 ° warm solution containing 10 g of N-dimethyl-N-palm kernel fatty alkyl-N-benzylammonium chloride, 10 gN per liter -Trimethyl-N- [xenyl-1-methyl] ammonium chloride contains. The pinched cable is stretched 1: 4 in saturated steam at 100 °, then mechanically crimped by upsetting and finally steamed in a closed vessel at 140 ° for 20 minutes. The cable is passed tubular U-then through two series-connected containers with memory means for the cable and simultaneously with a 3 ° / _o aqueous sodium hydroxide solution heated to 95 ° treated. The residence time is such that the weight loss is 5%. After saponification, the tow, washed in countercurrent, is passed through a dryer and then cut into stacks. ao

Example 8

A fabric made of polyethylene terephthalate silk is printed with a paste containing 100 g of sodium hydroxide per kilo, 8 g of oxyethyl cellulose and 1 g of dodecyltrioxyethylammonium glycolate and 1.5 g of trimethyl [xenylmethyl] ammonium glycolate contains. Steaming under pressure at 140 ° produces a matt effect. The etched area is colored with alizarin direct blue A and other water-soluble acetate silk dyes in medium Sound on.

Example 9

A wire of 0.22 mm thickness, oriented 1: 4, and obtained by melt spinning from the polyurethane obtained from 1,4-butanediol-1,4-bischloroformate and hexamethylenediamine, obtained according to patent specification 912 863, is _{treated for 2} hours at 85 ° in an aqueous liquor which one liter contains 300 g of sodium hydroxide and 1 g of N-dimethyl-N-palm kernel fatty alkyl-N-benzyl ammonium chloride. After this time, the wire, which continues to show good tensile strength, has experienced a weight loss of 9.8% due to partial saponification. The surface is slightly roughened; in addition, the material shows a significantly increased

Absorption capacity for certain acidic dyes, such as pure alizarin blue FFB. Do you work in the same way? without the addition of the salt of the capillary-active quaternary base, almost no weight loss can be observed. If the saponification agent is allowed to act at 100 °, the weight decrease is already slowing 2 minutes 8%.

If the method is applied to threads made of polycaprolactam, then occurs under the specified conditions no saponification even in the presence of the accelerator

Claims (4)

Patent claims: 1. Process for the partial saponification of shaped structures, such as threads, fibers and flat structures, made of hydrophobic, high-melting high polymers with ester groups in the chain, in particular from polyalkylene terephthalates, characterized in that they are mixed with aqueous alkaline Cleavage agents, especially alkali hydroxides, in the presence of ions of strong organic bases from the nature of the quaternary nitrogen bases or their equivalents, optionally in the presence of thickeners treated in the heat until the desired weight loss has occurred. 2. The method according to claim 1, characterized in that organic bases are used, which have a hydrocarbon radical with at least 8 carbon atoms, preferably in the form of a unbranched paraffin chain. 3. The method according to claim 1 and 2, characterized in that strong organic bases are used that contain aromatic nuclei. 4. The method according to claim 1 to 3, characterized in that strong organic bases or Salts of those from solution or dispersion are applied to the structures, optionally in Presence of thickeners, whereupon the bases by a heating process, preferably in Fixed in the presence of steam and finally after-treated with aqueous alkalis in the heat will. Cited publications:
British Patent Specification No. 455 622,652 948,609 945, © 709 586/386 6.57