US3294864A - Polyolefins blended with amineepoxide condensate - Google Patents

Description

United States Patent 3,294,864 POLYOLEFINS BLENDED WITH AMINE- EPOXIDE CONDENSATE Gabriel Karoly, Elizabeth, Allen Noshay, Fords, Fritz B. Marktschelfel, Berkeley Heights, and Alhin F. Turbak, New Providence, N.J., assignors to Essa Research and Engineering Company, a corporation of Delaware No Drawing. Filed Oct. 5, 1962, Ser. No. 228,754 4 Claims. (Cl. 260836) This invention relates to a process for treating alpha olefin polymers to render them dyeable.

Poly alpha olefin polymers have found increasing interest as textile materials because of their desirable properties of strength and low cost. One of the more diflicult problems encountered, however, has been concerned with the relative ease of dyeing and relative quality of dyed filaments in view 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 addition of certain condensation products of a polyepoxide and an amine compound to the polymer prior to spinning in amounts that produce considerable improvements in dye characteristics, permits satisfactory spinning without extensive loss in fiber tensile properties while providing a readily dyeable textile filament with unusually improved fastness properties. One to twenty weight percent of condensate may be blended with 99 to 80 weight percent of polymer, although it is preferred to use 3 to 12 weight percent of condensate with 97 to 88% of polymer.

The preparation of textile filaments by melt spinning of poly alpha olefins places rather stringent requirements upon materials that may be blended with these polymers. High spinning temperatures and prolonged heating of polymers at those temperatures require that blended materials have satisfactory heat stability. It has been found that blending of such heat stable products of the condensate of polyepoxy compounds and amine compounds is easily accomplished when these products are linear and when the nitrogen in these condensed compounds is present in the tertiary amineform. When the products are crosslinked totally or in substantial pa-rt,--they do not blend satisfactorily with the textile filament polymer for good spinning. In addition, when a substantial number of secondary amine groups are present in the condensation prodnot blending agent, severe degradation of the blend is observed during melt spinning. Thus primary amines are not suitable in this invention since when they are reacted with a polyepoxy compound, a product is produced which contains secondary amine groups.

When poly alpha olefin filaments containing the condensation products of this invention are subjected to typical dyeing procedures, it is found that the dye uptake is improved and more importantly, the resistance of the dyed product to fading in light, in washing, and in dry cleaning is greatly improved.

The products of this invention may be made by preparing a solution of an epoxide compound in a convenient solvent such as ethyl alcohol, propyl alcohol, butyl alcohol, methyl ethyl ketone, methyl butyl ketones, cyclohexanone, cyclopentanone, benzene, toluene or xylene and then slowly mixing with a compatible solution of the amine compound at a temperature between 2060 C. The solution may then be heated, for example, to reflux for 1-10 hours, after which time the solvent may be removed by distiilation, leaving in the case of resinous products as an example, a syrupy product. This can then be further heated at about 120140 C. until the condensation is substantially completed. The viscous product is then poured from the reactor or flask and solidifies on 3,294,864 Patented Dec. 27, 1966 ice cooling to ambient temperatures. To determine the requirement of linearity (substantially not crosslinked), the solidified product is tested for alcohol solubility. A positive test indicates linearity and compatibility with polyolefin product. The condensate product may then be broken up and blended with the poly alpha olefin by the well known methods of milling, Banbury mixing, powder blending and solution blending. The blends may then be subjected to well known melt spinning techniques to produce readily dyeable monoand multifilament yarn. These blends may also be wet or dry spun as well. Prior to dyeing, these yarns may be drawn, twisted, plied and knitted or woven into various textile products. In addition, the blended material may instead be extruded in the form of films and foils.

The polymers treated by the process of the invention are alpha monoolefin homopolymers and copolymers. The alpha olefin homopoly-mer 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 and poly 1- butene. Polymers or copolymers of branched chain alpha olefins where the branching occurs no closer than the 3rd carbon atom can also be employed, such as poly 4-methyll-pentene, poly 4,4-dimethyl-l-pentene and poly B-methyll-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 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 organo metallic 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 polyepoxides suitable for use in this invention include those organic compounds which contain two or more epoxide groups (oxirane rings) and 4 or more carbon atoms.

Thus, one class of these materials which may be used are diepoxide compounds such as vinylcyclohexene dioxide, butadiene diepoxide and Epon 828, the diglycidyl ether of Bisphenol A.

Also suitable are polye-poxidized homopolymers or copolymers of butadiene. These are prepared by first p0.- lymerizing butadiene alone or in conjunction with materials copolymerizable therewith such as styrene. Various methods of polymerization, such as sodium polymerization, emulsion polymerization, and the like, are known in the art and any of these methods may be used. These polymers are then treated with an oxidizing material. These include air, oxygen, and H 0 alone or in the presence of peracetic or performic acid. It is further desirable to treat the polymers with hydrogen to reduce some of their unsaturation. This may be done either before or after the epoxidation step. A preferred polybutadiene oxidized with H is sold as Oxiron, Other polyepoxy compounds may also be used such as Epon 1031 which has the following structure:

The amino compounds suitable for use in this invention are C -C preferably C C alkyl, aryl, or aralkyl compounds having at least one secondary amine group attached thereto. Secondary monoarnines, or secondary polyamines are useful in this invention.

Examples of secondary monoairnines are diethylamine, diphenylamiue and piperidine. Preferred is piperidine. Piperazine is an example of a preferred polyamine.

The reaction product of the polyepoxide and amino compound is a condensate which will range in consistency between liquid and solid. This condensate is blended with a poly alpha olefin and extruded or spun into sheets, films, foils or preferably fibers. These are then treated with one or more dyes in aqueous media according to standard techniques known in the art.

In general the aqueous dye baths employed contain from 0.1 to 10 weight percent dye based on the weight of fiber. The temperature of dyeing and the time ofimmersion depends on the proportion of polymer and condensate in the blend, the particular polymer and condensate employed, the type and concentration of dye employed, and the intensity of color desired, These parameters can easily be determined by routine experimentation for any particular modified polymer-dye combination. 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.

The classes of dyes suitable for use in this invention include not only dispersed dyes but also acid dyes such as Anthraquinone Blue SKY, and premetallized dyes such as Neolau Yellow GR, After the fiber or fabric made from the polymer blend has been immersed in the dye bath for a suitable period of time, it is removed, scoured, Washed with water, and dried.

The invention will be better understood from the fol lowing examples.

Example I A vinylcyclohexene dioxide-piperazine condensate was prepared specifically as follows: 135 g. of vinylcyclohexene dioxide was dissolved in 100 ml. of absolute ethyl alcohol and added over a period of 90 minutes at 80 C. to a stirred solution of 86 g. piperazine in 150 ml. of absolute alcohol. After 4 hours of refluxing, the alcohol was stripped off and the molten condensate poured into a dish. The condensate contained 10.12 weight percent nitrogen.

Example 2 A vinylcyclohexene dioxide-hex'amethylene diamine condensate was prepared specifically as follows: 350 g. (2.5 moles) of vinylcyclohexene dioxide was dissolved in 250 ml. of absolute ethyl alcohol, and added over 90 minutes, between 70-80 C., under vigorous stirring to 116 g. (1 mole) of hexamethylene diamine dissolved in 100 ml. absolute alcohol. The mixture was refluxed at 82 C. for 8 hours, then the alcohol was stripped off and the molten condensate poured into a dish. The condensate contained about nitrogen and was fully soluble in alcohol thereby indicating its non-crosslinked nature.

Example 3 Condensates as prepared in Examples 1 and 2 were blended with polypropylene prepared by standard methods at low pressure. The polymer had an inherent viscosity of 2.1. These blends were then melt spun into fibers and treated with dyes as shown in Table I following:

Prernetallized Dye Dispersed Dye Moderate-High.

Moderate-High. Fair-Moderate High.

Fastness:

U.V. Light No break after 20- No or slight break 30 hours in the after hours in Fadeometer. the Fadeometer. Washing High e High. Dry Cleaning High 8 (1) Piperazine-vinylcyelohexene dioxide condensate as prepared in Example 1.

(2) Hexamethylene diamine-vinylcyclohexene dioxide condensate as prepared in Example 2.

Anthraquinone Blue SKY.

b Sevron Red L.

G Neolan Yellow GR.

d Latyl Yellow iRL.

* Acid and prernetallized dyes.

The results recorded in Table I supra serve to espe cially point up the significance of the invention. In Compound (1) the piperazine-vinylcyclohexene dioxide condensate is linear and the nitrogens are substantially all tertiary. The spinning stability is high as shown by the high tenacity of 4.39 g./denier and the modest elongation of 26.8%. In Compound 2, the nitrogens of the linear condensate are largely secondary and the resultant tenacity is low (0.88 g./den.) and the elongation is high (113%) which is typical of a. degraded unstable polymer blend. The dye absorption and the fastness improvements are good for both but the latter fiber is not commercially satisfactory.

Example 4 To a flask containing 34 g. of piperidine in 200 cc. of tetrahydrofuran at reflux was added 20 g. of Epon 1031, dissolved in cc. of tetrahydrofuran. The addition was dropwise over a 1 hour period with vigorous stirring. The reaction was then stirred for an additional 3 hours. After standing overnight the tetrahydrofurau was stripped oif under vacuum and the viscous residue was dissolved in 200 cc. of benzene. The product was precipitated with 600 cc. of heptane which was added to the stirred benzene solution. The excess liquor was then poured off and the precipitate was hardened in 400 cc. more heptane. The solid obtained on evaporation of solvent was crushed and the powder further dried to give .a light yellow powder having 5.2% nitrogen.

This product was blended at 6% by weight in a polypropylene powder and spun into fibers. It should be noted that a polypropylene blend with Epon 1031 without amine treatment did not spin satisfactorily under the same conditions.

The fibers obtained from the blend had good tenacity and good dyeability with acid and dispersed dyes, and exhibited good light fastness for 1215 hours in Fadeometer exposure. Typical acid dyes used are Du Pont Blue SKY and Du Pont Rubine R.

Example 5 To a one liter flask was added 8.5 g. of pi-peridine (0.1 mole) dissolved in 300 cc. of tetrahydrofuran. The liquor was heated to reflux and 17.7 g. of Oxiron 2000 (0.1 mole equivalent of oxirane), which is an epoxidized polybutadiene, was dissolved in 100 cc. of tetrahydrofuran and dropped in over a one hour period. The mixture was stirred and heated for another hour. During the addition the mixture changed from colorless to a pink color.

The mixture was added to isopropanol and some tacky solid separated. The upper liquor was evaporated and finally flashed free of solvent at 7080 C. and 0.2 mm. pressure leaving a reddish polymeric residue. When blended with polypropylene at 5 to concentration the fibers obtained had increasedaffinity for acid dyes and satisfactory tensile properties.

Example 6 The preparation described in Example 2 was repeated with the exception that the heating was extended an additional 16 hours to a total of 24 hours. The recovered resin was now substantially crosslinked. It was insoluble in alcohol and could not be satisfactorily blended with polypropylene.

From the above examples it can be seen that the blended polymer as prepared by this invention is spinnable and can be dyed to produce a stable, fade resistant product with satisfactory tenacity and elongation.

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 spinnable composition of matter comprising a blend of 80-99 weight percent of a C C poly alpha monolefin with 1 weight percent of a linear condensate consisting essentially .of the reaction product of vinylcyclohexene dioxide and a secondary polyamine compound.

2. The composition of claim 1 wherein the poly alpha monolefin is polypropylene.

3. The composition of claim 2 wherein the amine is piperazine, and wherein 123 weight percent of the condensate is used.

4. A method for improving the dyeability of a spinnable C C poly alpha monolefin which comprises blending -99 weight percent of the poly alpha monolefin with 20-1 weight percent of a linear condensate consisting essentially of the reaction of vinylcyclohexene dioxide and a secondary polya-mine compound.

References Cited by the Examiner UNITED STATES PATENTS 2,917,469 12/ 1959 Phillips et al 2602 2,921,037 1/ 1960 Andres et al 2602 2,948,688 8/1960 Bender et a1 260-2 3,013,998 12/1961 Battaglioli 260836 3,051,664 8/1962 Turner 2602 3,098,697 7/ 1963 Cappuccio et al. 260836 XR 3,215,487 11/1965 Cappnccio et al. 855

MURRAY TILLMAN, Primary Examiner.

WILLIAM H. SHORT, Examiner.

I. W. SANNER, G. F. LESMES, Assistant Examiners.

Claims (1)

1. A SPINNABLE COMPOSITION OF MATTER COMPRISING A BLEND OF 80-99 WEIGHT PERCENT OF A C2-C12 POLY ALPHA MONOLEFIN WITH 20-1 WEIGHT PERCENT OF A LINEAR CONDENSATE CONSISTING ESSENTIALLY OF THE REACTION PRODUCT OF VINYLCYCLOHEXENE DIOXIDE AND A SECONDARY POLYAMINE COM:POUND.