DE1569446B2 - IMPROVING THE COLORABILITY AND PROCESSABILITY OF SHAPED BODIES MADE OF POLYMERIC PLASTICS - Google Patents

Description

i 569 446

The processing, in particular the dyeing and printing of moldings made of polymeric plastics is sometimes associated with considerable difficulties. For example, polypropylene fibers difficult to dye, finish and process, even if they have special finishes, plasticizers and waterproofing agents have been treated, and also with polyester fibers, dyeing is and printing associated with great difficulty, so that polypropylene fibers in spinning as Mixture with epoxidized compounds or as post-chlorinated material and polyester fibers be used as a mixture with sulfonic acid compounds.

From the German Auslegeschrift 1006 383 is a Process known according to which threads made of polyesters based on terephthalic acid to improve the dyeing properties with sulfur trioxide or halides of oxo acids of sulfur in the presence of inert ones Solvents are treated.

In the Austrian patent 209 304 is a method for treating fibers made of polymers of oi-olefins. Be here too sulfonated or chlorosulfonated the olefin polymers in solution.

Austrian Patent 210135 describes a process for treating films made from highly crystalline polymers of α-olefins, the purpose of which is to make these films adhesive by introducing polar groups. In this process too, the sulfonation, which improves the adhesiveness of the polyolefin film, is carried out in the presence of a solvent. ■ ^:

From the Belgian patent 556 902 processes are known for the vulcanization of polyolefins to improve. Here, copolymers of aliphatic olefins are catalytically chlorosulfonated. However, these aforementioned methods of improving the processability of these fibers deteriorate the fiber strength and the flexibility and elongation in general, and something even more important falls are very expensive and tedious, which is especially true for the chlorination of the polypropylene fiber. aside from that larger amounts of solvent are required, which further increases the cost of the process.

The present invention is a. Process for improving the dyeability and processability of moldings made of polymeric plastics, in particular polypropylene and polyester fibers, by treating them with SO ₃ , optionally in the presence of a sulfonation catalyst, which is characterized in that the moldings are reacted with SO ₃ in the gas phase , the gas phase containing 5 to 10% SO ₃ and the reaction taking place for 2 to 60 seconds.

ίο This treatment can be carried out before or together with an irradiation-catalyzed graft polymerization. For the reaction with gaseous sulfur trioxide this can be used in its tx -, - β- or y-modification, whereby polypropylene or fiber-forming polyesters as well as fibers, yarns or textiles made therefrom can easily be substituted with sulfonic acid esters. If fibers are to be treated, this synthetic fiber can then be in any form, for example as a yarn, as a single fiber, as a card sliver, i.e. before spinning. However, the method according to the invention is of course not limited to fibers, but can be used in general for plastic molded bodies. The material is easily substituted in any form by the sulfonic acid group.

The sulfonation can be supported by a catalyst, for example by an interface activator for the terminal sulfonation, such as pyridine, picoline or morpholine. In this reaction it is sufficient if SO _{3 is taken up} in the appropriate range of 0.1 to 2.0%. If too much sulfur is incorporated, the synthetic fiber, especially polypropylene or polyester fiber, becomes brittle.
The fiber improved in this way can be easily dyed by basic dyes, cationic dyes, disperse dyes, fatty dyes, azo dyes, naphthol dyes, sulfur dyes and vat dyes and is very resistant to solvents, detergents and detergents. The material treated in this way can also be treated with synthetic resin finishes, plasticizers and water-repellent agents. If the light fastness and the dye affinity are to be increased, the sulfonic acid salt of any metal, such as potassium, sodium, aluminum, nickel, barium, calcium, magnesium, molybdenum, zinc or antimony can be formed.

■ ■ -. - "Dry"
air - -N ₂ + -
dry Tabel! SO ₃ SO ₃ ['/ "] reaction time temperature e? V-VJnL ■ '.' ._ ■ .. ■. - ■ '*.'. ' : '' ■■ - ■ air '--- SO ₃ ■ ■ ■ '■' ■ -. ■ - - (Concentration) attempt Dl D] ': D] - · -. ■■ ,,, . "". ' [Sec ·] [ ⁰ C] No. 0.7 3.9 " ■ ^; 4.6 - [G] 0.25 5.4 ί - - ■ '■ 10 50 1.4 7.8 9.2 1 0.5 5.4 20th 50 1 2.1 11.7 13.8 2 0.5 3.6 30th 50 2 0.7 3.9 4.6 2 0.5 10.4 10 50 3 1.4 7.8 9.2 2 0.5 10.4 20th 50 4th 2.1 11.7 13.8 2 0.5 3.6 30th 50 5 1.5 3.9 5.4 2 0.5 9.2 10 50 6th 3.0 7.8 10.8 2 0.8 7.4 20th 50 7th 4.5 11.7 16.2 3 0.5 3! 30th 50 8th 5.9 11.7 17.6 2 1.1 6.3 30th 50 9 4th 10

*) The sulfur trioxide content is determined by a neutralization process using sodium hydroxide. . ,, ' ^:

example

In a reaction vessel described below, four different types of fibers are made Polyoxymethylene, polycarbonate, polyester and polypropylene treated with sulfur trioxide.

The following reaction vessel was used: A bomb containing liquid sulfur trioxide is heated from the bottom so that the liquid sulfur trioxide evaporates to gaseous sulfur trioxide. Dry air and gaseous nitrogen, which serve to dilute the gaseous sulfur trioxide, are each passed through flow meters into the top of the bomb. The upper part of the bomb is connected to a gas suction pump via a reaction chamber. · '·' ■ ■ ^'·:; ; ^{:; V} - ^l ■■■ "- <■■ '* ■■' ■■■ ^:. " - ' ■ .'-'-' ■ "■ - ·": - ■ -

The reaction time for sulfonation in the reaction chamber is determined by the suction time of the gas suction pump regulated. The reaction chamber is heated by steam, which is passed through the side walls of the reaction chamber, so that the reaction temperature is reached is variable. The above "fibers are loosely dispersed in a stainless steel container, and then the container is placed in the reaction chamber. The experimental conditions, to increase the dyeability of the fibers by sulfonation ' are given in Table 1.

After each of polyoxymethylene, polycarbonate, polyester and polypropylene fibers were treated in accordance with Experiment Nos. 1 to 10, the fibers were dyed at a temperature of 100 ° C. for 1 hour using the six dispersed dyes shown in Table 2. . - ■■ : ·.: ·. ·

The molded bodies that were not treated in the manner described above were: only colored with a very light color, while the molded bodies that had received the above treatment showed deep real color, which is special applies to the materials which were treated for a period of 10 to 20 seconds and with 10.4% sulfur dioxide. These had - exceptional; good ■ properties *. The results are given in Table 2 ... 'I '---'. ".ν; - · '.:, · -;. ::'" ./ \ ;;; ·: ;;: -Wy- ^ w.

Table 2 Ent authenticity Wa Weight stood between ² ) relationship coloring 4th of dye T iViit ^ Colorants to be colored JLrflWill J 4th material depth 3 (Weight colour 4th percent) depth 3 2 colour 4th Color index depth 3 Yellow 64 4th colour 4th depth 3 2 colour 4th CL depth 2 Yellow 42 4th colour 4th <> depth 3 2 colour 4th CL depth 3 Red 4 4th colour 4th depth 3 2 colour 4th CI. depth 3 Red 60 4th colour 4th depth 3 2 colour 4th CI. depth 3 Blue 71 4th colour depth 3 2 colour CL Blue 55 4th

^x ) Determined by exposure to sunlight for 40 hours in a device suitable for this purpose, the evaluation being carried out on a scale from 1 to 8, the value 8 standing for the best lightfastness.

² ) Determined by: washing the samples and comparing the washed samples with a standard gray wedge and evaluating the wash fastness on a scale from 1 to 5, the number 5 standing for the best wash fastness.

If polypropylene or polyester fibers are modified in this way with the simultaneous application of an irradiation or pre-irradiation process with ionizing radiation, an SO ₃ group is grafted onto each individual monomer unit. In the case of sulfate formation, this becomes very complete and effective when irradiation is used.

The plastics, for example polypropylene, polyester or polyacrylic fibers, which have been _{treated in this way using SO 3} , can be grafted with any desired monomers using the same irradiation or pre-irradiation method as is known for materials not treated according to the invention. is. In this way, the surface finish. unit and other properties of the material treated according to the invention can be further modified as desired.

Therefore, if the surface texture is to be changed even further by grafting, then that is the one according to the invention Treatment and grafting expediently can be carried out in one operation. .

It is a great advantage of the process _{according to the invention that the shaped bodies can be treated with SO 3} without losing their fiber strength, flexibility and elongation. By using gaseous SO ₃ , the concentration of SO ₃ and the reaction temperature can be precisely regulated.

Claims (3)

Patent claims: 1. A process for improving the colorability and processability of molded articles made of polymeric plastics by treating them with SO ₃ , optionally in the presence of a SuI-fonierungskatalysators, characterized in that the molded articles with SO ₃ by simply combining them in the gas phase at normal or Reacts elevated temperature, the gas phase containing 5 to 10% SO ₃ and the reaction takes place for 2 to 60 seconds. 2. The method according to claim 1, characterized in that the molded body made of polymers Polypropylene and polyester fibers are used for plastics. 3. The method according to claim 1 or 2, characterized in that the treatment is carried out before or together with a radiation-catalyzed _{Pf 1 opfpolymerization.}