DE1185812B - Process for improving the color affinity of objects made from crystalline polyolefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C08f

German KL: 39 b -22/06

Number: 1185 812

File number: J 20206IV c / 39 b

Filing date: July 7, 1961

Opening day: January 21, 1965

Crystalline polyolefins are those that have a high degree of molecular symmetry. These Polymers, in particular isotactic and syndiotactic polypropylene, are known to be used as starting materials used for valuable shaped objects such as threads, fibers and films. The hydrocarbon polymers however, have a hydrophobic character and do not contain any groups which are chemically reactive towards dyes. The coloring of articles which consist of crystalline polyolefins is therefore an essential one The problem is that the use of dyes by the usual dyeing processes is ineffective is.

The invention now relates to a method for improving the ink receptivity of Objects made of crystalline polyolefins by adding amino compounds, which thereby is characterized in that the polyolefin, an optionally polymeric amine before or after the Verfor- ao mung has been added, is treated with a quaternizing agent commonly used per se.

Quaternizing agent is understood to mean a reactive compound which is preferably in liquid form and which converts the amine into a quaternary ammonium salt, for example (R ₄ N) ⁺ X ", where R is an organic radical and X is the salt-forming anion. The liquid quaternizing agent is preferably used as such, but it can also be used as a solution in an inert solvent. If the amine is added to the polyolefin before shaping, it is advantageous if its boiling point is high in order to avoid losses due to evaporation, for example during the melt extrusion, It is also advantageous to use tertiary amines which have long hydrocarbon chains, namely those with more than 6 carbon atoms, and which are very compatible with the polyolefin. Polymeric amines are also suitable, such as, for example, poly - (dialkylaminoalkylene acrylate) or poly (dialkylaminoalkylene methacrylate).

As the amines and quaternizing agents penetrate into the polyolefins, the ionic quaternizing salts formed are incorporated into the structure and form affinity centers for many classes of dyes and especially for the important class of acidic wool dyes. Acid wool dyes can be applied to articles made from stereoregular polyolefins which have been subjected to the treatment of the present invention by conventional dyeing techniques to improve color affinity
of articles made of crystalline polyolefins

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr

and Dipl.-Ing. S. Staeger, patent attorneys,

Munich 5, Müllerstr. 31

Named as inventor:

John Mather,

William Alexander O'Neill,

James Walter Stimpson,

Harrogate, Yorkshire (UK)

Claimed priority:
Great Britain of July 20, 1960 (25 261),
dated May 15, 1961

including the use of carriers. The washfastness of the dyeings has proven to be very good Proven to be satisfactory.

It has been found that, in general, an amount between 1 and 10 percent by weight of the quaternary ammonium salt is sufficient to impart good color affinity to the articles.
The inventive method can be used in a satisfactory manner, for. B. apply to filaments and fibers of crystalline polymers and copolymers of propylene, and it is possible to continuously introduce and quaternize the amine at any stage during the course of spinning and drawing and further processing, if desired. It has been found, however, that after the fibers and filaments have been drawn, movement of the amine either into or out of the polyolefin is restricted and, accordingly, it is desirable to introduce the amine before the drawing treatment, ie before the polymer has acquired a high molecular orientation .

409 769/443

Example 2

10

Stereoregular polypropylene can be used in the form of staple fibers for the im the following listed items for which dyeability is of particular importance: carpets, Blankets, woolen clothing such as suits, coats and dresses, fur fabrics, velvet, decorative fabrics, such as velvet fabrics for seating furniture covers as well as rep for curtains, knitted objects such as Jersey articles and undergarments, non-woven textiles such as linings and interlinings.

In the form of coarse monofilament yarn, the polypropylene is special with improved dyeability valuable for carpets and other floor coverings.

Improved dyeability can also be useful with heavy yarn made by blending Staple fibers made of stereocrystalline polypropylene with other staple fibers, for example cotton or viscose.

In cases where good lightfastness is necessary, it is advantageous to use the mass in a known manner Way, a stabilizing agent, for example a known U.V. absorber or an antioxidant admit.

The invention is explained in more detail in the following examples, in which the parts and percentages are refer to weight.

example 1

9 parts of isotactic polypropylene powder were intimately mixed with 1 part of tri-n-octylamine. These Mixture was melt spun at 260 ° C. The resulting fiber turned into a for 30 minutes Immersed in dimethyl sulfate bath at 20 ° C. She was then first treated with concentrated ammonia solution and finally washed with water. The fiber thus treated had a strong affinity for it acidic dyes, for example Carbolan Blue B (Color Index Acid Blue 138) and Azo Geranine2G (C. 1.18050).

40

Isotactic polypropylene fiber was made in cetyldimethylamine immersed at 80 ° C and stretched before treating with dimethyl sulfate at 20 ° C for 30 minutes was treated. This fiber showed a similar appearance after washing with ammonia solution and water Affinity for acidic dyes, like the product prepared according to Example 1.

Example 3

5% poly-diethylaminoethylene methacrylate was added to isotactic polypropylene powder, and the mass was melt spun at 240 ° C. The fibers were soaked in a 80 ° C for 5 minutes Dimethyl sulfate solution immersed and then washed with ammonia and water before stretching. That The product had a good affinity for dispersed and acidic dyes, such as Dispersol Echt Scarlet G (CI. 11110) and Carbolan Yellow 3 G (CI. Acid Yellow 72).

Example 4

Isotactic polypropylene fibers were immersed in trinonylamine at room temperature and then stretched at 120 ° C with a stretch ratio of 5: 1. The drawn yarn, which is about 1% amine was immersed in dimethyl sulfate for 20 minutes, then washed with ammonia and water. The treated fibers had a very strong affinity for acidic dyes such as for example Azogeranin 2 G (C.I. 18050), Coomassie Real Black BS (CI. 26370), Coomassie Green 3 G (CI. 65005) and Coomassie Navy Blue 2RN (CI. 26360).

Example 5

A sample of linear polyethylene film was treated according to the procedure of Example 2 and showed a substantial improvement in color affinity.

Similar results were obtained under the operating conditions of Examples 1 to 4 when Methyl iodide, formic acid-formaldehyde and tetramethylene dibromide as quaternizing agents Instead of dimethyl sulfate were used.

Also, similar results were obtained under the working conditions of Examples 1 to 4 when an ethylene-propylene copolymer (20/80 mole) was used.

By comparative tests it was found that untreated fibers of polypropylene were only one low affinity for dispersed dyes and no affinity at all for acidic dyes possessed, while fibers containing non-quaternizing amine had considerable color affinity, however, the colorations were less intense and these had poor wash fastness exhibited, especially in undrawn yarn.

Claims (3)

Patent claims: 1. Process for improving the color affinity of articles made from crystalline polyolefins by adding amine compounds, characterized in that the polyolefin, to which an optionally polymeric amine has been added before or after the shaping is treated with a common quaternizing agent. 2. The method according to claim 1, characterized in that an amine-containing polyamide threads treated with the quaternizing agent before or after stretching. 3. The method according to claim 1 and 2, characterized in that the amine is a tertiary amine, which has at least one linear hydrocarbon chain with more than 6 carbon atoms or a poly (dialkylaminoalkylene acrylate) or a poly (dialkylammoalkylene methacrylate) is used will. Considered publications:
Belgian patent specification No. 558 380.