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Publication numberUS3284428 A
Publication typeGrant
Publication dateNov 8, 1966
Filing dateMay 21, 1963
Priority dateMay 21, 1963
Publication numberUS 3284428 A, US 3284428A, US-A-3284428, US3284428 A, US3284428A
InventorsAlbin F Turbak, Noshay Allen, Karoly Gabriel
Original AssigneeExxon Research Engineering Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Dyeable polyolefins
US 3284428 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,284,428 DYEABLE POLYOLEFINS Alhin F. Turbak, New Providence, Allen Noshay, East Brunswick, and Gabriel Karoly, Elizabeth, N.J., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed May 21, 1963, Ser. No. 282,117 6 Claims. (Cl. 260-933) 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 diflicult 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 diamines. 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-diamine compounds is that when the polymer which has been blended with these compounds 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-diamine 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 preesnt in amount sof between about 0.1 to 1.0' weight percent of the polymer. They often are used together. See for example Industrial and Engineering Chemistry, volume 1, No. 4, p. 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 [i mercaptopro-pionic acid, and zinc dibutyl dithiocarbamate. Some examples of phenolic stabilizing agents are: N-lauroyl p-amino phenol; 4,4-methylene bis(2,6- ditertiary phenol); 4,4 benzi'lidene bis(2,6 ditertiary phenol); 2-hydroxy, 4-methoxy benzophenone; Z-hydroxy, 4-octoxy benzophenone; dipinenediphenol; 4,4-isobutylidene bisphenol; and 3-methyl, 6-t-butyl phenol. 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 l-butene and poly l-heptene. Polymers or copolymers of 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-1-pentene and 3,284,428 Patented Nov. 8, 1966 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 ditferent alphaolefins such as ethylene-propylene copolymers, ethylenel-hexene copolymers and alpha-olefin-aromatic olefin copolymers containing from 1 to 15% by weight of an aromatic olefin, such as for example copolymers of styrene and 4-methyl-l-pentene. Also, blends of one or more of the previously mentioned polymers can be employed. The polymers and copolymers employed in the invention have 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 or'ganometallic activators. Examples of these catalysts are TiCl +AlEt and TiCl -|-AlEt 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-diamine derivatives of this invention are prepared by reacting the diamine compounds with a soluble nickel salt in a ratio of 1 mole of nickel salt to 2 to 3 moles of diamine compound to produce a nickel salt derivative of the diamine compound. The nickel salt may be any soluble salt such as the halides, nitrate, or acetate. Nickel chloride is preferred.

The diamine compounds useful in this invention are terminal, vicinal diamines containing a terminal primary amine function. These compounds are described by the following formula:

p where R R and R can be hydrogen, or any alkyl or aryl group, preferably a C C group. Examples of compounds that are operative include ethylene diamine, 1,2- propylene diamine, 2-methyl-l,2-propylene diamine, 1,2- hexene diamine, N-(Z-hydroxydodecyl) 1,2 ethylene diamine or N-hexyl ethylene diamine. Preferred is 1,2-propylene diamine.

Diamine compounds which do not fit the description above are inoperative. Thus if the diamine groups are not vicinal, or if there is no unsubstituted terminal primary amine group, they are not useful in the instant invention since they yield discolored or undyeable fibers. Examples of inoperative compounds are the nickel salts of 1,3-propylene diamine; N-dodecyl-l,3-propylene diamine; 2,3-butylene diamine; methyl hydrazine; hydrazine and phenyl hydrazine.

The dyes which are preferably applied to the fibers of this invention include selected mordant and metallizable dyes such as those produced by the National Aniline Division of the Allied Chemical Co. Many of these are known as National Polypropylene dyes and specific examples are National Aniline Green B, National Polypropylene Red 2B, National Polypropylene Yellow R and National Polypropylene Blue B.

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 10 weight percent of dye based on the Weight of the goods to be dyed. The temperature of compound 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 and can range from 25 to 120 C. 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 TiCl 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 spun into fibers by methods known in the art. When these fibers were contacted with the National Polypropylene dyes, essentially no dye pickup and retention were observed.

Example 2 A sample of bis (ethylene diamine) nickel (II) chloride was prepared according to the procedure described in volume VI of Inorganic Synthesis, p. 198 (McGraw-Hill; 1960). 0.5 weight percent of this material was blended with polypropylene resin which contained phenolic and sulfur-containing stabilizers. Specifically, in this and the following examples, about 0.5 weight percent of each of Z-hydroxy, 4-octoxy benzopheno-ne, and dilaurylthiodipropionate were in the polypropylene, although these amounts can vary between 0.1 and 1.0 weight percent.

This blend of resin and diamine was melt spun at about 540 F. to produce fibers. These fibers were white having a tenacity of 4.8 gms./ denier, and when contacted with National Aniline Polypropylene dyes, gave medium depths of shade which were fast to washing, dry cleaning (as determined in warm perchloroethylene) and light (as determined in a Fade-O-Meter).

It is to be understood that any dyed fibers referred to in the subsequent examples were similarly fast to washing, dry cleaning and light. Additionally these fibers had satisfactory physical properties.

Example 3 Example 2 was repeated using his (1,2-propylene diamine) nickel (II) chloride prepared by the same procedure. Again white fibers were obtained both with and without added stabilizers showing that this additive was also unaffected by the presence of sulfur and phenolcontaining additives. Deep green shades were obtained when these fibers were dyed in dyebaths containing an orange dispersion of National Aniline Green Polypropylene dye (which turns green on complexing with the nickel).

Example 4 Tris (2-methyl-propylene-1,2-diamine) nickel (II) chloride dihydrate was prepared by adding 13.7 g. (0.155 mole) of 2-methyl-propylene-1,2-diamine to 11.9 g. (0.05 mole) of NiCl -6H O dissolved in 70 cc. of H 0. The purple solution was filtered, evaporated to 30 cc. on a steam bath, cooled to C. in an ice bath and filtered. The solid was slurried with 30 cc. of 95% ethanol, filtered and dried to give 14.3 g. of a lavender product.

Found: Ni= 13.3%; N;=18.94% Calculated for (CH z C-- CH1] Nick-21110 =13.5% Ni; 19.5% N,

On milling 0.5 weight percent of this product at 330 F. with polypropylene resin a light blue homogeneous blend both in the presence and absence of sulfur or phenolic stabilizers was obtained. White fibers were obtained from these blends. These fibers exhibited good dyeability with National Aniline Polypropylene dyes.

Example 5 Bis (Z-rnethyl-1,2-propylene-diamine) nickel (II) chloride was prepared from the tris derivative of Example 4 by disproportionation with nickel chloride, according to the procedure of Example 2. The product separated as a light blue powder.

Found: 19.0% Ni; 17.8% N2 Calculated for (CH )zCHCHg:| Ni Clg=10.0% Ni; 18.3% N:

This product gave white fibers when spun (at 540 F.) at 0.5% conc. level in polypropylene containing the stabilizing additives. These fibers dyed to deep shades with National Aniline Polypropylene dyes.

Example 6 Bis (2,3-butylene-diamine) nickel (II) dichloride was prepared from the tris derivative by dis-proportionation with NiCl -oH O according to the procedure of Example 2. This product was a bright yellow solid as compared to the bluish powders obtained when at least one amine group occupied a terminal position. This product when blended at 0.5% with polypropylene and milled at 330 F. gave a yellow blend which spun into discolored grey fibers.

Example 7 N-(Z-hydroxydodecyl) ethylene diamine was prepared by refluxing 46 g. of 1,2-dodecene oxide in 60 g. of ethylene diamine overnight. The product was separated from excess ethylene diamine by extracting several times with hot petroleum ether. Evaporation of the petroleum ether gave 52.7 g. of white solid product. 22 g. of this product was dissolved in cc. of CH OH and added to 11.9 g. of NiCl -6H O in 50 cc. of CH OH to give a blue solution. Addition of this solution to 500 cc. of acetone caused precipitation of a lavender colored solid nickel derivative. When 1 weight percent of this additive was blended with polypropylene stabilized with phenolic and sulfur-containing additives, it gave essentially white fibers containing 0.1% nickel which displayed good dyeability with National Aniline Polypropylene dyes.

Example 8 Example 7 was repeated using a C epoxide in place of the dodecene oxide. Again good white fibers were obtained which dyed well.

Example 9 Bis (1,3-propylene diamine) nickel (II) chloride was prepared by adding 7.4 g. of 1,3-propylene diamine (0.1 mole) dissolved in 25 ml. of CH OH to 11.9 g. of NiCl -6H O (0.05 mole) in 50 cc. of CH OH. To the resulting blue clear liquor was added 300 cc. of anhydrous ether in a slow stream. The lavender product which formed was filtered and dried.

Found: 20.92% Ni; 20.19% N Theoretical for [NH (CH NH NiCl =20.9% Ni; 20.14% N It should be noted that the product decomposed in the presence of acetone. This is contrasted to the stability of the 1,2-propylene diamine nickel derivative which was prepared using acetone, thus showing a different metal chelate strength for the 1,3 vs. the 1,2 derivative.

When 0.5 weight percent of this additive was blended with polypropylene containing stabilizers it gave undesirable yellow green fibers although they dyed to medium shades with National Aniline polypropylene dyes. Thus when the diamine functions are not vicinal, the nickel derivatives give undesirable behavior during spinning.

Example 10 The nickel derivative of N-dodecyl-l,3-propylene diamine was prepared by reaction of the diamine with NiCl -6H O in a 2/1 molar ratio in MeOH. The product was a deep green solid and yields undesirable highly colored fibers when blended with polypropylene.

Example 11 Example was repeated using N-octadecyl-l,3-propylone diamine. Similar results were obtained showing that N-substituted 1,3-propylene diamine nickel derivatives are not useful.

Example 12 A nickel derivative of hexamethylene diamine was prepared by reacting hexamethylene diamine with in a 2/1 molar ratio in CH OH. The product was a green solid and when it was blended with polypropylene resin containing phenolic and sulfur-containing stabilizers, a deep yellow green pad was produced which yielded highly colored fibers. Thus when the amine groups are separated by six carbon atoms the resulting nickel derivative will not blend with stabilized polypropylene to yield a composition from which white fibers can be produced.

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 salt derivative of a vicinal diamine having the following formula:

wherein R R and R can be hydrogen or a C C alkyl or aryl group.

2. The composition of claim 1 wherein the polymer is =polypropylene.

3. The composition of claim 2 wherein the diamine is 1,2-propylene diamine.

4. The composition of claim 1 wherein the diamine is 1,2-propylene diamine.

5. A substantially white fiber produced from the composition of claim 1.

6. The composition of claim 4, wherein the nickel salt derivative of the vicinal diamine is bis (ethylene diamine) nickel (II) chloride.

References Cited by the Examiner UNITED STATES PATENTS 2,984,634 5/1961 Caldwell et a1 260-93.7

JOSEPH L. SCHOFER, Primary Examiner.

L. EDELMAN, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2984634 *Jan 30, 1957May 16, 1961Eastman Kodak CoCrystalline polymerized monoolefinic hydrocarbons containing metal salt of carboxylic acid
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6312631Mar 16, 1998Nov 6, 2001Henkel Kommanditgesellschaft Auf AktienUse of amphiphiles for permanent improvement of colorant compatibility of polyolefin-based shaped bodies, fibers and films
WO1998042767A1 *Mar 16, 1998Oct 1, 1998Norbert BialasUse of amphiphiles for permanent improvement of colorant compatibility of polyolefin-based shaped bodies, fibers and films
U.S. Classification524/204, 524/583, 8/DIG.900, 8/928, 524/252
International ClassificationC08K5/17
Cooperative ClassificationY10S8/928, C08K5/17, Y10S8/09
European ClassificationC08K5/17