US3299030A - Dyeable polyolefins - Google Patents

Description

United States Patent 3,299,030 DYEABLE POLYOLEFINS Albin F. Turbak, Danville, Ill., and Allen Noshay, East Brunswick, and Gabriel Karoly, Elizabeth, N.J., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Aug. 22, 1963, Ser. No. 303,916

7 Claims. (Cl. 260--93.7)

This invention relates to a process for treating alphaolefin polymers to render them dyeable, and the composition produced thereby.

Poly alpha-olefin polymers have found increasing interest as textile fibers and 'materials because of their desirable properties of strength and low cost. One of the more difficult problems encountered, however, has been the poor dye acceptance of such fibers because of the inertness of a hydrocarbon polymer. Although a poly alpha-olefin material, such as polypropylene, can be dyed, its fastness to typical textile environments has been inadequate.

It has now been found that the receptivity of alphaolefin polymers to dyeing may be improved by blending the polymer with 0.1 to 20.0 weight percent, preferably 0.2 to 5.0 weight percent, of a nickel derivative of a specific class of amino acids. The polymer may then be spun into fibers and contacted with dyes. By means of this treatment, not only is the dye uptake of the polymer improved, but more importantly, the resistance of the dyed product to light, washing, and dry cleaning is improved.

An additional and very important advantage of these nickel-amino acid substances is that when the polymer which has been blended with these materials is spun into filaments at high temperature and pressure, the resulting fiber is white.

The fiber does not discolor at such extreme conditions of temperature and pressure because these particular nickel-amino acid substances do not react with the phenolcontaining or sulfur-containing stabilizers which are often conventionally dispersed in the hot polymer mix. These stabilizers are generally present in amounts of between about 0.1 to 1.0 weight percent of the polymer. They often are used together. See for example Industrial & Engineering Chemistry, volume 1, No. 4, pp. 236 et seq. Some examples of these stabilizing agents which contain sulfur are: di-tert-octyl trisulfide, di-tert-octyl tetrasulfide, dilaurylthiodipropionate, the esters of polysulfides derived from fl-mercaptopropionic acid, and zinc dibutyl dithiocarbamate. Some examples of phenolic stabilizing agents are: N-lauroyl p-amino phenol; 4,4'-methylene bis(2,6- ditertiary butyl phenol); 4,4-benzylidene bis(2,6-ditertiary butyl phenol); 2-hydroxy, 4-methoxy benzophenone; 2-hydroxy, 4-octoxy benzophenone; dipinenediphenol; 4,4'-isobutylidene bisphenol; 3-methyl, 6-t-butyl phenol and 4-methyl, 2,6-di-t butylphenol. The advantage of producing a white fiber is obvious to those skilled in the art. Discoloration in a fiber not only limits its use to dyed fabrics but also interferes with the proper dyeing of the textile produced therefrom, since muddy, dull, and impure hues are produced.

While this invention is principally directed to the dyeing of fibers or filaments, it may also be used to dye poly alpha-olefin films, foils, and other formed products.

The polymers treated by the process of the invention are alpha-olefin homopolymers and copolymers. The alpha-olefin homopolymer can be prepared by any known process, such as the so-called Ziegler process, see for example Belgian Patent 533,362 and Belgian Patent 538,782. Examples of homopolymers within the scope of the invention include polyethylene, polypropylene, poly 1- butene and poly l-heptene. Polymers or copolymers of 3,299,030 Patented Jan. 17, 1967 branched chain alpha-olefins where the branching occurs no closer than the third carbon atom can also be employed such as poly 4,4-dimethyl-1-pentene, poly 4- methyl-l-pentene and poly 3-methyl-1-butene. In general, the homopolymers are prepared from alpha-olefins having from 2 to 12 carbon atoms. The copolymers employed in the process of the invention include copolymers of two different alpha-olefins such as ethylene-propylene copolymers, ethylene-l-hexene copolymers and alphaolfin-aromatic olefin copolymers containing from 1 to 15% by weight of an aromatic olefin, such as for example copolymers of styrene and 4-methyl-1-pentene. Also, blends of one or more of the previously mentioned polymers can be employed. The polymers and copolymers employed in the invention have viscosity average molecular weights ranging from 100,000 to 1,000,000. The preferred polymers and copolymers of the invention are those prepared by the use of alkyl metal catalysts. Most preferred is polypropylene. Catalysts which are useful in this process are mixtures of reducible heavy transition metal compounds and reducing metal containing substances, or mixtures of partially reduced heavy transition metal compounds and organometallic activators. Examples of these catalysts are The catalysts used for preparing the preferred polymers employed in the instant process are those catalysts given on page 6, line 20 to page 10, line 21 of copending application Serial No. 831,210, filed August 3, 1959, now abandoned.

The nickel-amino acid derivatives of this invention can be prepared by reacting the amino acid with a nickel salt, preferably nickel chloride, in methanol, diluting with an equal volume of water, and precipitating the desired product from solution by adjusting the .pH to about 7 with caustic. Elemental analysis indicates that a complex thereby forms having the following general structure: [amino acidhNi'ZH- O. About 1 mole of nickel halide can be reacted with 1 to 3 moles of amino acid, although it is preferred to use 1 mole of nickel halide to 2 moles of amino acid.

The amino acids of this invention are organic car-boxylic acids having a primary or secondary amino group in a position alpha to the carboxyl group. They may be represented by the formula where R and R are substituted and unsubstituted alkyl,

scription have been found to be unsuitable for the pres-.

ent invention. Thus, for example, a blend of the polymer with the nickel complex or derivative of ,B-alanine could not be spun into fibers; a blend with the nickel derivative of picolinic acid could be spun into fibers but would not accept dyes; and a blend with nickel N-lauryl-B-imino dipropionate formed unsatisfactory green colored fibers.

The dyes which are useful in this invention are chelatable dyes. These include the National Polypropylene series of dyes produced by the National Aniline Company. Examples of these are Violet 3BR, Green B, Brilliant Blue B and Brilliant Orange R. Also useful are ortho hydroxy azo dyes generally. These dyes include monoazo dyes, conjugated diand multi-azo dyes as well as azo pyrazolone, o,o-dihydroxy azo, and o-hydroxy-o-carboxy azo type dyes. Examples of these are Orasol Yellow 3G (Solvent Yellow 17), Sudan Orange RRA (Solvent Orange 7), Sudan Red 4BA (Oil Red 24), and Oil Red (Solvent Red 27).

The polymer blend which has been melt spun or extruded into fibers or molded objects is contacted with the aqueous dye bath. In general the dye baths employed contain from 0.1 to weight percent of dye based on the weight of the goods to be dyed. The temperature of dyeing and the time of immersion depend on the proportion of nickel compound in the blend, the particular nickel derivative employed, the concentration of dye employed, and the intensity of color desired. These parameters can easily be determined by routine experimentation. The temperature of dyeing is not critical although the dye bath is usually maintained at the boiling point.

This invention will be more fully understood by reference to the following examples.

EXAMPLE 1 A polypropylene polymer was formed by passing propylene gas into a dispersion containing Al(Et) and TiC1 in an aromatic diluent at a temperature of 80 C.

Hydrogen was used to control the molecular weight. A crystalline polypropylene resulted having an intrinsic viscosity of 1.5 (in tetralin at 120 C.) and a melt index of 20. This polymer was blended with 0.5 weight percent of each of 2-hydroxy, 4-octoxy benzophenone and dilaurylthiodipropionate and then spun into fibers by methods known in the art. When these fibers were contacted with the dyes suitable for this invention such as the National Polypropylene dyes and Orasol Yellow 36, essentially no dye pickup and retention were observed.

EXAMPLE 2 A nickel derivative of D,L-alanine (racemic mixture of a-alanine) was prepared specifically as follows: 0.5 mole of D,L-alanine and 0.25 mole of NiCl -6H O were stirred in a mixture of 750 ml. methanol and 375 m1. H O. Stirring was continued for minutes, while heating gently on a steam bath. The reaction product was soluble. The pH of the solution was adjusted to 7 with 50% aqueous NaOH. The resulting light blue precipitate was filtered and dried in a vacuum oven at 55 C. The yield was 48.8 gms. Analysis found: C, 26.56; H, 5.91; N, 10.73; Ni, 22.31. Calculated for C, 26.6; H, 5.9; N, 10.3; Ni, 21.5.

0.5 weight percent of this derivative was blended with the stabilized polypropylene powder of Example 1 by mixing in a Waring Blendor and extruding and pelletizing in a Brabender extruder at 500 F.

This blend was spun at 580 F. in a continuous spinning unit into 165/34 multifilaments which were then drawn at a 3.8/1 ratio. The fibers obtained had 3.0 g.p.d. tenacity and 62% elongation, and they were optically white.

The resulting fibers were contacted with National Aniline Polypropylene Green B, Violet 3BR, and Brilliant Orange R, as follows: The dyeings were carried out in water at 95 C. for 1 hour in dye baths containing 1 weight percent dyestulf and 0.5 weight percent nonionic (Igepal) surfactant. The fibers dyed We l with all three dyestuffs.

4 The dyed fibers were examined according to the AATCC test procedures, and found to have a rating of 5 for wash, dry cleaning and light fastness.

EXAMPLE 3 The nickel derivative of D,L-tyrosine was prepared under the same conditions as used in Example 2 for D,L- alanine. Stabilized polypropylene of Example 1 was blended with 0.5 weight percent of the nickel derivative of tyrosine in a Waring Blendor, extruded into pellets and spun into /34 multifilaments. The white fiber obtained had 3.65 g.p.d. tenacity and 38% elongation. It was dyed with the National Polypropylene dyes listed in Example 2. These dyeings also displayed good dyeability and fastness properties.

EXAMPLE 4 The nickel derivative of D,L-leucine was prepared under the same conditions as used in Example 2 for D,L- alanine. Stabilized polypropylene of Example 1 was blended with 1.0 weight percent of the nickel derivatives of leucine in a Waring Blendor, extruded into pellets and spun into 165/34 multifilaments. The white fiber obtained had 3.67 g.p.d. tenacity and 38% elongation. It was dyed with the National Polypropylene dyes listed in Example 2. These dyeings also displayed good dyeability and fastness properties.

EXAMPLE 5 Example 2 was repeated with the exception that ,8- alanine was used instead of D,L-alanine (an alpha amino acid). Satisfactory fibers could not be spun from the blend with stabilized polypropylene owing to the formation of gas during spinning which caused bubbles in the fiber and led to excessive breakage even when the take-up speed was kept low.

This invention has been described in connection with certain specific embodiments thereof; however, it should be understood that these are by way of example rather than by way of limitation, and it is not intended that the invention be restricted thereby.

What is claimed is:

1. A dyeable composition of matter comprising a polymer of a hydrocarbon alpha olefin blended with a nickel derivative of an alpha amino acid of the formula:

0 R-oH-ii-OH NITR where R and R are selected from the class of substituted and unsubstituted alkyl, aryl and aralkyl residues, and hydrogen.

2. The composition of claim 1 wherein R is a C -C residue and R is hydrogen or a phenyl group.

3. The composition of claim 2 wherein the polymer is polypropylene.

4. The composition of claim 3 wherein the alpha amino acid is tyrosine.

5. The composition of claim 3 wherein the alpha amino acid is leucine.

6. The composition of claim 2 wherein the alpha amino acid is a-alanine.

7. The composition of claim 1 wherein the alpha amino acid is 2-phenyl glycine.

No references cited.

JOSEPH L. SCHOFER, Primary Examiner. L. EDELMAN, Assistant Examiner,

Claims (1)

1. A DYEABLE COMPOSITION OF MATTER COMPRISING A POLYMER OF A HYDROCARBON ALPHA OLEFIN BLENDED WITH A NICKEL DERIVATIVE OF AN ALPHA AMINO ACID OF THE FORMULA: