DE1494686A1 - Process for the production of lightfast and colorable textile fibers and molded parts - Google Patents

Description

U9A686

DR.-ING. TH. MEYER DR. FUES DIPL.-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLDPSCH

COLOGNE 1, DEICHMANNHAUS

Cologne, July 21, 1969 Kl / En

Montecatini Edison S.p.A.,

1-2 Largo Guido Donegani, Milan (Italy)

Process_for_ the_production_ of non-genuine_and_colourable Textile fibers and molded parts (IV)

The invention relates to the production of textile fibers, pollen, ribbons, molded parts and the like based on crystalline polyolefins and disperse dyes of the normal type and the phenolic type are particularly easy to dye and have high lightfastness.

According to the invention, lightfast and dyeable textile fibers and molded parts are produced by spinning or extruding mixtures of crystalline polyolefins with metal derivatives of polybasic aliphatic carboxylic acids, for example the dimers, trimers or polymers of unsaturated aliphatic acids with 18 carbon atoms or mixtures thereof .

The preferred crystalline polyolefin is polypropylene used, which consists essentially of isotactic macromolecules and duroh stereospecific polymerization of Propylene is produced. They are also suitable for the purposes

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of the invention polyolefins which are prepared by polymerizing olefins of the general formula RCH = CH ₂ , in which R is an alkyl or aryl radical or a hydrogen atom, for example polyethylene, polybutene-1, poly-4-methylpentene-1, polystyrene and the like. like

It has already been suggested that polypropylene fibers can be colored to improve by adding various substances to the polymer prior to spinning that improve its colorability of changing pasers.

Processes for improving the affinity of polyolefin fibers for basic dyes and disperse dyes are also known by adding long-chain fatty acids or metal salts of saturated or unsaturated fatty acids. In particular, British patent specification 904.79Ö

15 'Described products based on crystalline α-olefin polymers, in particular polypropylene, which contain 2 to 10% _t, preferably 3 to 7 % dimers or trimers of linoleic acid and can be dyed with basic dyes and disperse dyes.

French patent I.3I5.298 describes products which can be colored with basic dyes and disperse dyes and which are made from polyolefins and 0.5 to 20% by weight of metal salts of saturated or unsaturated fatty acids (stearates, laurates, oleates, linoleates of aluminum, chromium , Nickel, cobalt, cadmium etc.) and possibly up to 15 % aluminum oxide or colloidal silica.

The invention relates to a process for the production of fibers and molded parts based on α-01efin polymers which by disperse dyes of the normal and phenolic types and are particularly easy to dye by reactive dyes and

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have a particularly high lightfastness. The scope of the invention also includes those produced by this process Products, i.e. molded parts such as piping, pollen, ribbons, etc., which are colored in uni tones.

According to the invention it has surprisingly been found that Molded parts, especially textile fibers, and films, with a particular affinity for normal or phenolic disperse dyes and high lightfastness are obtained when mixtures of crystalline α-olefin polymers with 0.1 to 10 wt .- # des Product of the reaction of dimers, trimers or polymers of unsaturated aliphatic acids with 18 carbon atoms or their mixtures with a salt of a metal of group IB, IIIB, VIA, VIIA and VIII of the Periodic Table are spun or extruded.

Linoleic acid is preferably used for this, but other acids such as oleic acid, isoleic acid, elaine acid, ct-linolenic acid, Rapic acid, stearolic acid and heptadecenoic acid are used with the double bonds in different positions will.

The products which are obtained by dimerization, trimerization and polymerization of unsaturated aliphatic acids having 18 carbon atoms, in particular linoleic acid, are available commercially under the names "Empol" or "Emery" (Emery Industries Inc., Cincinnati, Ohio) . These commercial products are usually mixtures of acid dimers (dibasic acid with 36 carbon atoms), acid trimers (tribasic acid with 5 ² ^ carbon atoms) and possibly small amounts of monobasic acid with 18 carbon atoms.

Particularly suitable for the purposes of the invention are the metal derivatives of the product "Empol 1014", which consists of 95 % dimeric

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Linoleic acid, 4 % of the trimeric acid and 1 % of the monobasic acid. The metal derivatives of the product "Empol 1024" (76 # dimer, 24 % trimer, 1 % monobasic acid) and the product "Emery 3162-D" (90 % trimeric acid and 10 % dimer acid) are just as suitable. The compounds that are used to change the colorability of the polymers used according to the invention are prepared by the dimers, trimers or polymers of unsaturated aliphatic fatty acids having 18 carbon atoms, in particular linoleic acid, with the metal salts, preferably in the presence of organic and inorganic solvents at temperatures between room temperature (about 25 ° C) and the boiling point of the solvent are reacted. Aluminum, chromium, cobalt, nickel, copper and manganese are particularly suitable

15 derivatives of this acid.

As mentioned above, the amounts of the invention be of the metal derivatives of the polybasic aliphatic carboxylic acids of 0.1 to 10 wt -.% Of the crystalline a-olefin polymers. In the case of mixtures to be used for the production of fibers by the melt spinning process, the amount of these metal derivatives is preferably 0.5 to 2 wt .- #.

The metal compounds are generally added to the polyolefins by simply mixing the metal compound with the polyolefins while stirring. However, it can also be added in other ways, e.g. by mixing the polyolefins with a solution of the metal compound in a suitable solvent and subsequent evaporation of the solvent or by adding the metal compound to the olefin on completion the polymerization. It is also possible to apply the metal compound to the article manufactured from the polyolefins to be applied, e.g. by immersing the objects in a

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solution or dispersion of the metal compound and subsequent evaporation of the solvent. In the case of yarns, the application can be carried out before or after stretching for a period of a few seconds to a few hours at temperatures from room temperature to 10 ° C
olefins are made.

temperature up to 10 ° C below the softening point of the poly

The mixtures are granulated and then in a melt spinner preferably of the type which is the subject of applicant's Italian patent 614.043, preferably through spinnerets of the type which is the subject of applicant's Italian patent 000.248, the ratio of Length to diameter at the holes is greater than 1, spun. Granulation and spinning are done with exclusion of oxygen, preferably in an inert gas atmosphere (e.g. nitrogen). The mixtures are preferably in the presence spun or extruded with a small amount of a "solid dispersant"

During mixing, in addition to that used according to the invention Metal compound opacifying agents and organic or inorganic pigments and compounds that make up the polymer against the effects of light. Stabilize heat and aging, to which polymers are added.

After spinning, the parsers are at draw ratios of between 1 are: 2 and 1:10 at temperatures between 80 and 15O ⁰ C in the stretching devices which heated with hot air, steam or a similar medium or are provided with a heating plate, stretched. The fibers can then be stabilized against a subsequent change in shape by a treatment which is carried out at temperatures between 80 and 160 ° C. with unhindered shrinkage according to the method of Italian patents 566,914 and

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588,318 of the applicant is made.

The mixtures according to the invention can be spun monofilament or multifilament and for the production of endless yarns or staple yarns or used by bulky yarns. They are not only suitable for making yarn, but also of foils, tapes, molded parts and the like.

The fibers and moldings produced according to the invention have a remarkably good dyeability with disperse dyes of normal and phenolic type and better fastness, especially to light.

In comparison with similar methods known heretofore, the method according to the invention enables the achievement to be more remarkable economic advantages due to the low cost of the modifying agents used and of their Production of the required starting products. The lightfastness, washfastness, resistance to trichlorethylene and the rubbing fastness of the dyeings obtained are very good.

The measurement methods mentioned in the examples are described below.

2o l. Measurement of the volatility of the metal derivatives

The measurements were made in air and under nitrogen. For the measurements in air, the weight losses were determined in a muffle furnace at 200 ^° C. and at 300 ^° C. on samples of 3 to 5 g in a porcelain dish using a method which is that of RG Charles (I. Inorg. Nucl. Chem. , 9, 145 (1959)) is analogous to the method described. In the measurements under nitrogen, the weight losses at 250 ⁰ C, and "c determined in the embodiment shown in Fig. 1 apparatus were the

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consists of a pyrox glass tube. The Pyrex tube was immersed in a bath of molten salt after 0.5 to 1 g of the sample was placed in a glass dish on the bottom of the tube. Before placing in the salt bath, the tube is placed under vacuum and then purged with nitrogen. This is repeated several times. The interior of the tube is kept under nitrogen throughout the experiment. Before treatment, the samples were ^{dried at 250 and 500 °} C. under air or nitrogen at 120 ^° C. to constant weight.

2. Determination of the compatibility from measurements of the Krlstalllsatlonsgeschwindigkelt

With the help of a new method, which is based on the measurement of the crystallization rate and which is described in an article by Parrini and G. Corrieri "Compatibility of polymeric and non-polymeric substances with crystalline polymers", which is in print, the degree of compatibility of the added Metal compounds determined with polypropylene. This method enables the compatibility of the added metal compounds with polypropylene to be determined on the basis of the fact that the compatible substances lengthen the crystallization time while it is shortened by incompatible substances. The additive is intimately mixed with polypropylene either mechanically or by dissolving the additive in a suitable solvent which is inert to polypropylene. The mixture is dried and then pressed in a carving press to form a sheet 1 mm thick, which is then cut into pieces and made according to the method of P. Parrini and G. Corrieri ¹¹ Makromol. Chem. "62, 83 (1963) in Dilatometers filled with mercury. The dilatometric measurements allow the determination of the specific volume of the sample to be examined as a function of time at constant temperatures. From the curves of the specific volume as

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By puncturing the time, one arrives at the semicrystallization times, which are an indication of the rate of crystallization of the polymer. The presence of compatible substances extends the semi-crystallization time while it in the presence of incompatible substances compared to the additive-free polymer under the same conditions is either shortened or remains unchanged. When carrying out the compatibility measurements with increasing It is possible to create a curve of the semi-crystallization time as a function of the percentage amounts of the additive Concentration to draw an accurate tolerability curve results.

The examples refer to the compatibility curves of the investigated Systems referenced. It can be seen from the curves that the addition can be regarded as compatible, when the crystallization time becomes longer with an increase in the concentration of the additive. If on the other hand the increase the concentration of the additive does not cause a prolongation of the crystallization time, the upper limit is the Compatibility of the additive with polypropylene (beyond which the additive is no longer compatible) than achieved · In the figures, curve 1 always relates to the additive-free polypropylene, while the other curves refer to the metal derivatives.

25 3. Melt index

The melt index was measured according to ASTM Test Method 1238-57 at a temperature of 250 ⁰ C with a load of 2l6o g on a plate which had a thickness of 1 mm and consisted of polypropylene plus additive in an amount such that the final mixture Contained 0.1 % metal. The panels are either immediately after molding or after determination

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Subjected for 15 minutes at 300 ^° C. in a carving press. The melt index of the original plate is compared to the melt index of the plate held at 300 ° C for 15 minutes. Without the addition of metal, the plate, which consists of polypropylene alone and is kept at 300 ° C. for 15 minutes, has a melt index of 15 to 16 (for a polymer from the same batch).

4. Dyeing methods and dyes

The fibers are 20 to 30 minutes at 60 ⁰ C with a solution of the product of the trade name "Diapon T" (manufactured by the Applicant, Natriummethylolcyltaurinsulfcnat) (2 g / l) and sodium carbonate (1 g / l) rinsed. They are then rinsed well with running water.

^b ) Chelating_Dyes_ ^ 01efin ₌ _and_Nagrolene classes}

The dyes are made by kneading with the same amount by weight of a 10 # solution of the product of the trade name "Dispergal 0" (manufactured by the applicant, condensation product of ethylene oxide and ricinoleic acid). Then the volume is made up with warm water.

The dyeings are carried out at a ratio of fiber to liquor of 1:30. The water is heated to 40 ° C, whereupon 6 % of the product "Dispergal 0" and 2 % (based on the weight of the fiber) of a 56% acetic acid solution are added, whereby the pH is adjusted to 3.5-4 . The fibers are immersed in the dyebath, the dye is added after 15 to 20 minutes, the liquor is heated to the boil over 45 minutes and then allowed to boil for 60 to 90 minutes. The dyed fibers are washed with a 2 lgen solution of the product “Dispergal 0” for 20 minutes at 95 ° C. and then

30 rinsed with running water.

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The following dyes were used:

(manufactured by Verona-Bayer)

Yellow I5863 Bordeaux 14096 Orange 13904 Bordeaux I3906 Orange 13955 blue 14110 Orange 2352 dark blue 13954

(Manufacturer Allied Chemical)

Naprolene Brilliant Yellow GM Naprolene brilliant orange RM Naprolene scarlet fever RBM

Naprolene brilliant violet 3 RM Naprolene brilliant blue BM Naprolene dark blue 2 BM Naprolene-Grürt BM

c) Chelating dyes (Mayfon class, manufacturer

The Mayfön dyes are sold as ready-to-use pastes. The dyeings are carried out with a ratio of fiber to liquor of 1:30. Heating the water to 40 ⁰ C ₄ mixture is acidified with 2% acetic acid (56 £ solution), and outputs the

2o fibers in the bath. The dye is added and the temperature was raised within 45 minutes to 50 to 6O ⁰ C. The liquor is held at this temperature for 30 minutes. 1.5 to 3 % formic acid (80% solution) are then added, followed by dyeing for a further 60 minutes. The colored fibers

25 are washed for 20 minutes at 95 ° C. with a 2 # solution of the product “Dispergal 0” and rinsed with running water. The following dyes were used in the experiments:

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- li -

Mayfon golden yellow 386 Mayfon golden yellow 123 Mayfön orange 8 Mayfon red 13

5 d) disperse dyes

The dyeings are carried out with a ratio of fiber to liquor of 1:30. The water is heated to 40 ° C. the fibers and sets the dispersion of the dye in water to. The liquor is heated to the boil and kept at this temperature for 60 minutes. The dyed fibers are 20 minutes washed at 40 ° C with a solution containing 1 cnr contains a surface-active agent (Aionico SCl, manufacturer Montecatini), and then rinsed with running water. The following dyes were used in these experiments

15 det:

Yellow ER Scarlet GR Pink B 2o Blue FB

Normal dispersion dyes

Setacyl-Yellow 3 G (C.I.Dispersgelb 20) (Geigy) Cibacet-Scarlet BR (C.I. Disperse Red 18) (Ciba) Setacyl-Brilliant Blue BG (C.I. Disperse Blue 3) (Geigy) Duranol-Brilliantgelb 6G (CI. 58.900) (I.C.I.) Dispersol-Uniorange G (CI. II.005) (I.CI.) Artisil director orange 2R (CI. II.005) (Sandoz)

e) Basic dyes

The dyeings with basic cationic dyes were made

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made with a ratio of fiber to liquor of 1:30. The liquor was acidified with 2% (based on the fiber weight) of a 56 # acetic acid solution, whereupon 1 % of the product "Dispergal 0" was added and the fibers were inserted. The dye was added and the liquor was heated to boiling, whereupon the dyeing was continued for 60 minutes at this temperature. The dyed fibers were washed with a solution containing 1 cm ^ of the product "Aionico SCl" per liter at 40 ° C. for 20 minutes. The following dyes were used in these experiments:

Neorling green JlOb (Ciba)
Malachite Green Crystals (ACNA) Astrazon Blue G (Bayer)
Sevron Brilliant Red 4G (du Pont) 15 Astrazon Red 6B (Bayer)

5. Assessment of the authenticity of the dyeings

The fastness properties of the dyeings were determined by the following methods (Manuale Unitex, III Ed., 1959, Milan):

Washfastness A standard Unitex-9

2o wash fastness B "Unitex-10

Washfastness when used

of trichlorethylene "Unitex-14

Perspiration fastness "Unitex-13

Rubbing fastness "Unitex-15

25 6. Determination of the stability of polypropylene fibers against thermal-oxidative degradation

The resistance of the fibers to thermal-oxidative degradation is referred to as the ratio (referred to as VR) between the time it takes to reach the embrittlement point of the test Fiber is required and the time it takes to reach the embrittlement point of a standard fiber,

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printed out «when both pasers are placed in a ventilated oven kept at the desired temperature. A heating cabinet with air circulation and adjustable heat is used for this.

Description of the test and evaluation of the results

a) 19 pasers with a length of 30 cm and a total titre of 200 den are produced. One end of these strands is attached to a hook and the other end to a weight of 0.6 g. A cotton thread is used for this in order to avoid any direct contact between the fiber to be tested and the metal of the hook and the weight.

b) 19 fibers of the sample to be tested and 19 standard fibers are hung ^{in the heating cabinet kept at HO 0 C.} The Pasern of the various samples must be placed in the oven in a statistically unordered manner in order to cancel out the influence of the differences between the various parts of the oven. For this reason, more than 1 paser per sample is placed in the oven. The simultaneous presence of the test sample and the standard sample is a guarantee that the oven will not behave completely evenly over time.

0) The time it takes for the weight to fall off at one end the pasern is attached is determined. Since the drop in weight is caused by embrittlement of the fibers, the in this way determined the average time required for the test sample to reach the embrittlement point.

d) The ratio of the average time to reach the embrittlement point of the test sample to the corresponding time for the standard fiber is the value VR.

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e) The standard sample consists of a continuous polypropylene yarn with a titer of 10 den / pads. This yarn contains a stabilizing mixture consisting of a thioester and a phenolic compound and is made opaque with TiOp. This standard sample reaches the embrittlement point at 110 C within about 200 hours.

In the spinning tests described in the following examples polypropylene was used with the following properties:

Io intrinsic viscosity (determined in tetrahydronaphthalene at 135 C) (corresponding to a melt index of 12) 1.56

Ash content $ 0.015

Residue after extraction with heptane

The comparative dyeings were carried out with polypropylene fibers , each containing 3 % of the additives of application P 14 94 6Θ6.2 (nickel compound from linoleic acid trimers and dirner mixes), British patent 904.798 (linoleic acid trimers and dimer mixtures), French U.S. Patent 1,315,298 ( aluminum stearate) and U.S. Patent 2,948,634 (nickel sulfate). These fibers were dyed with 3% each of an acid dye (Alizarin Sky Blue R), a disperse dye (Cibacet Blue OP) and two chelate dyes (Aizen Blue POL and Aizen Red BL).

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example 1

100 g of the product of the trade name "Empol 1014" (95 # dimeric, trimeric 4% and 1% monobasic linoleic acid) in 600 cnr acetone are mixed with vigorous stirring with 44 g of nickel acetate tetrahydrate in 600 cm- ⁵ methanol. A precipitate is formed immediately, which is filtered off, washed with acetone and with methanol, and then dried. The product obtained is a powder of the probable formula (CjoHpqOpNi), which softens at 220 to 25O ° C and is practically insoluble in the following solvents: water, methanol, ethanol, xylene, trichlorethylene, dimethylformamide, chloroform, ether, benzene, heptane . The analysis shows a Ni content of 9.8 % (calculated for C ₁₈ H ₂₉ O ₂ Ni = 9.5).

The measurement of volatility has the following results:

15 weight loss

in air under nitrogen at 250 at 300 at 250 at 300

after 1 hour 8.35 11 2.4 6 after 2 hours 10.9 17.2 3.2 7.6

The determination of the compatibility with polypropylene shows that the nickel derivative is compatible up to 2 # (FIG. 2). A mixture of the nickel derivative with polypropylene (Ni content 0.1 %) shows the following changes in the melt index:

25 melt index of the plate immediately after

pressing 6.25

Melt index of the plate after 15 minutes at 300 ° C. (without the addition of the metal derivative = 15-16) 9.25

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The nickel derivative thus slows down the degradation under the processing conditions.

75 g of the nickel derivative are mixed with 4.760 kg of polypropylene, 30 g of didocecoyl thiodiglycolate, 15 g of calcium stearate, 7.5 g of a phenolic compound and 10 g of TiOp all in one at room temperature Henschel mixer mixed. The mixture obtained is in an extruder under an oxygen-free atmosphere at 230.degree granulated. The granulate is spun in a melt spinning device under the following conditions:

Io spinning conditions

Screw temperature 230 ⁰ C Head temperature 230 ⁰ C Spinning temperature 230 ⁰ C Spinneret type 60 / 0.8 χ 16 mm 15th Maximum pressure 75 kg / cm Take-off speed 500 m / minute Stretching conditions temperature 130 ⁰ C medium Steam 2o Stretch ratio 1: 4.5

After stretching, the paser has the following properties:

Strength 5.05 g / elongation 29 %

The fibers obtained can be easily dyed with the dyes of the olefin and naprolene classes. You are too easily dyed with disperse dyes, especially Polysetile dyes. The fastness properties of the dyeings are given in the following table.

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To wash 5 B. E c h t 5 hey i t 5 5 Rub 4th 5 5 Sweat V5 5 5 5 Naprolene
Brilliant yellow OM 4/5 5 5 4/5 5 5 5 5 5 Naprolene glasses
Iiantorange RM V5 5 4th 4/5 5 5 Trichloro
ethylene 5 5 5 Olefin orange
13955 5 5 5 5 5 4th 4th 5 V5 5 Olefin orange
2532 5 5 5 4/5 5 5 4/5 5 5 5 N-aprolene-
Brilliant blue BM 5 5 5 4/5 5 5 5 5 5 4/5 Olefin dark
blue 13954 4/5 5 4/5 5 'V5 5 Naprolene
Dark blue 2BM 5 5 4th 4/5 V5

After 450 hours of actual exposure to the sun, the fiber still has 75 % of its original strength. Without the addition of the modifying agent, the fiber becomes brittle after 150 hours of exposure to the sun.

Example 2

500 cnr acetone are placed in a 3 l Pyrex glass beaker. 100 g of the product with the trade name "Erapol 1014" (95 % Dinieres, 4 % trimers and 1 % monobasic linoleic acid) are dissolved in acetone. A solution of 45 g of cobalt acetate in 500 g of methanol is added to the solution while stirring. A precipitate forms immediately, which is filtered off on a drainage tube, washed with acetone and methanol and dried.

The cobalt derivative obtained in these catfish, which is the true

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Apparent formula ( ^c 18 ^H 2Q ° 2 ^Co ^ n ^nat * ^{is a} powder ^{with a} light hazelnut color which softens at 195 to 205 ° C. The analysis shows a cobalt content of 12.3 % (calculated for ^C 18 ^H 29 ° 2 ^{Co =} 9 »53 %) ' The product is insoluble in the following solvents: chloroform, trichlorethylene, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, xylene, water, methanol, ethanol and acetone.

1.2 g of the cobalt derivative are combined with 98.8 g of polypropylene Room temperature mixed in a ball mill. The mixture will in a laboratory spinning device (heated cylinder, Piston and spinneret) spun using a spinneret with 4 bores 0.8 mm in diameter and 16 mm in length. The fibers obtained have good dyeability and excellent fastness when colored with the dyes of the olefin and Naprolene classes. They can also be dyed with disperse dyes, especially Polisetile dyes.

Example 3

5.7 g of the product of the trade name "Einpol 1014" are diluted with 20 carbons of ethanol and 0.8 g of NaOH in 50 cnr of H ₂ O neutralized. This solution is in 6.48 g of aluminum sulfate (Al ₂ (SO ₄ ), 18 H ₂ O), which is dissolved in 100 cm ^{5 of} water, stirred in. A white precipitate forms, which is filtered off, washed first with water and then with acetone and finally dried. The product becomes a powdery one contain white solid that contains 4.1 % aluminum and softens at around 200 ° C. The analysis shows an aluminum content of 4.1% (calculated for C ₁₈ H ₂₉ Og) ₂ AlOH * 4.47 %).

2 g of this aluminum derivative are at room temperature in a ball mill with 96.75 g of polypropylene, 0.6 g of didodecoyl thiodiglycolate, 0.3 g of calcium stearate, 0.15 β of a phenol

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bond and 0.2 g TiO ₂ mixed. The mixture obtained is spun using the spinning device described in Example 2 (nozzle with 4 bores 0.8 mm in diameter and 16 mm in length). The fibers obtained have good dyeability and excellent fastness when colored with the dyes of the olefin and Naprolene classes. They can also be dyed with disperse dyes, especially Polisetile dyes.

Example 4

26.3 g of the commercially available product "Empol 1024" are added 30 cnr ethanol and diluted with 3.65 g NaOH, which is in 50 cmrP Water is dissolved, neutralized. This solution is added to an aqueous manganese acetate solution over 5 minutes with stirring (35 * 4 g manganese acetate in 300 cnr water).

The whole is stirred for 1 hour; a precipitate forms which is filtered, washed with water and dried. ,

The metal derivative is a white-pink powder that forms between 70 and 13O ° C softened. The analysis shows a manganese content of

8.01 % (calculated for C ₁₈ H ₂₉ O ₂ Mn = 8.95 %). The product is in water, methanol, ethanol, acetone, chloroform and xylene

insoluble.

1.2 g of the manganese derivative are mixed with 97 * 55 g of polypropylene, 0.6 g of didodecoyl thiodiglycolate, 0.3 g of calcium stearate, 0.15 g of a phenolic compound and 0.2 g of TiO ₂ at room temperature.

25 door mixed in a ball mill.

The mixture obtained in this way is spun in a laboratory spinning device (heated cylinder, piston and spinneret), with the spinneret 4 holes with a diameter of 0.8 mm and

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has a length of 16 mm. The obtained Pasern can color well and have olefin and naprolen class dyes excellent authenticity. You can be with disperse dyes, especially Polisetile dyes, to dye.

Example 5

200 cc of water and 3.4 g of copper (I) acetate monohydrate are used put in a 1 l Pyrex glass beaker and stir with a solution of 100 cnr water, 10.3 g "Empol 1024" and 1.7 g of NaOH are added. A precipitate forms immediately, which is filtered off, washed with water and dried. The copper derivative is a blue solid that softens at around 200 ° C.

A mixture is made from 1 g of the copper derivative and 99 g of polypropylene manufactured. The mixture is spun in the laboratory spinner described in Example 3. the Fibers obtained can be with the dyes of the olefin and Naprolene classes and with disperse dyes, in particular Polisetile dyes, dye.

2o example 6

200 cnr water and 4.2 g chromium acetate monohydrate are placed in a 1 l Pyrex glass beaker and a solution of 100 cm × ⁵ water, 10.3 g "Empol 1024" and 1.7 g NaOH are added while stirring. After a while, a $ & £ precipitate forms, which is filtered off, washed with water and dried. The chromium derivative is a blue-green solid that begins to soften at around 160 C.

A mixture is made from 1 g of the chromium derivative and 99 g of polypro-

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pylen produced. The mixture is spun on a laboratory spinner of the type described in Example 3. The fibers obtained can be mixed with the dyes of the olefin and naprolene classes and with disperse dyes, especially Polisetile dyes.

Examples 7-11

These examples are provided to illustrate that not all organic metal compounds can be used for the purposes of the invention. Gemisehe are described, which consist of polypropylene and metal derivatives, which are described in the technical literature and are commercially available. The metal derivatives are used in such an amount that 0.1 % metal is present in the end product.

The following table shows the metal compounds used and the properties of those made from polypropylene and Me tal oil connection existing products listed. From the values given it can be seen that those in the examples 7 to 9 additives used are not suitable for the purposes of the invention, since they cause a considerable breakdown of the Polypropylene cause and result in fibers of a grayish color, which are not suitable for textile use.

The additives used in Examples 10 and 11 are unsuitable because the resulting polypropylene fibers are not can be colored with chelating dyes (olefin and naprolene classes).

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example

Netall derivative

Contract weight loss enamel enamel color of the dyeable

propylene friendliness after 1 hour with poly under nitrogen at

250 ⁰ C 50O ⁰ C index to index to fibers
fresh plate
pressed after 13
the minutes
Plate b. 300 ⁰ C

ability with chelating dyes (olefin and naprolene)

Nickel thiobis 2 %

octylphenolpheno- (fig 3) lat (1)

Complex of butyl 2 %

amine and nickel (Fig. 4) thiobia octylphenolate (2)

Nickel thiobis 1 %

ootylphenolat (1) fig. 5)

Niokel-N, N'-dibu- 0.5Ji

tyldithiocarbamate (Fig. 6)

Zinc-Ν, Ν ¹ -dibutyldithiooarbaraat

4.90

21Ji 4.40

3 *

(1) Italian patent 609.246

(2) Japanese Patent 1216/63

not definable
(too high)

84.4

not definable

16.7

23

grey black

black green

grey black

greenish black

White

Yes

Yes

Yes

no

no

(υ ro

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Example 12

100 g of a dimer of oleic acid in 600 ml of acetone were mixed with 44 g of nickel acetate tetrahydrate and 600 ml of methanol while stirring. A white precipitate immediately precipitated out and was filtered, washed with methanol and acetone and dried. The dry powder had a nickel content of 9.5 %.

1.2 g of this powder were mixed with 98.8 g of polypropylene (fy_7 = 1.56, ash content 0.015 % residue after the heptane extraction 96.2 %) and this mixture was mixed in a spinning device through a spinneret with openings of 0.8 mm diameter and 16 min length. The fibers obtained showed good absorbency and fastness after staining with plasto-soluble chelating dyes.

009811/1329

Claims (6)

Claims 1) Process for the production of lightfast textile fibers and molded parts that can be dyed with disperse dyes, characterized in that mixtures of crystalline Polyolefins and 0.1 to 10 weight percent of the reaction products of salts of metals in groups IB, HIB, VIA, VIIA and VIII of the Periodic Table with dimers, trimers or polymers of unsaturated aliphatic acids with 18 carbon atoms or mixtures thereof spun or extruded. 2) The method according to claim 1, characterized in that linic acid is used as the unsaturated aliphatic acid. 3) Method according to claims 1 and 2, characterized in that that one uses polyolefins obtained by polymerizing olefins of the general formula 15 R-CH = CH ₂ , in which R is hydrogen, alkyl or aryl, were obtained. 4) Process according to claims 1 to 3 * characterized in that that the metal salts are those of copper, aluminum, Chromium, Manganese, Cobalt or Nickel used with that the dimers, trimers or polymers of the unsaturated aliphatic carboxylic acids are reacted in the presence of a solvent at temperatures between room temperature and the boiling point of the solvent. 5) Process according to Claims 1 to 4, characterized in that one additionally opacifying agents, organic or 009811/1329 No documents (Art. 7 % 1 Para. 2 No. I Clause 3 of the amendment from 4.9.1967) U9A686 inorganic pigments, stabilizers and / or solid dispersants are used. 6) Textile fibers and molded parts based on crystalline polyolefins, characterized by a content of 0.1 up to 10% by weight of reaction products of salts of the metals of Oruppen IB, IHB, VIA, VIIA and VIII of the Periodic Table with dirneres, trimers or polymers of unsaturated aliphatic acids with 18 carbon atoms or mixtures thereof. 009811/1329