US2921042A

US2921042A - Acrylonitrile polymer compositions containing modified bentonite and fibers formed therefrom

Info

Publication number: US2921042A
Application number: US421683A
Authority: US
Inventors: John R Caldwell
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1954-04-07
Filing date: 1954-04-07
Publication date: 1960-01-12
Anticipated expiration: 1977-01-12

Description

United States Patent ACRYLONITRILE POLYMER COMPOSITIONS CON- TAINING MODIFIED BENTONITE AND FIBERS FORMED THEREFROM John R. Caldwell, Kingsport, Tenn., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Application April 7, 1954 Serial No. 421,683

16 Claims. (Cl. 26030.4)

This invention relates to the manufacture of synthetic filaments and fibers from novel spinning solutions contaiuing acrylonitrile polymers, in which a major portion of the polymer is acrylonitrile, and a dye assisting component comprising bentonite which has been modified by treatment with an amine salt to produce a hydrophobic and organophilic condition in place of the normal hydrophilic condition.

The presence of the modified bentonite in the filaments and fibers permit dyeing to heavy shades by known methods with various cellulose acetate dyes, acid wool dyes, vat dyes, and direct cotton dyes. I

The ironing temperature or hot bar sticking temperature of the fiber is raised substantially by the presence 7 j 'An object, therefore, of the present invention is to U provide acrylonitrile polymer fibers having greatly enhanced dye affinity for cellulose acetate dyes, acid wool dyes, vat dyes and direct cotton dyes.

Anotherobject of the invention is to provide a new method for preparing intimate mixtures of acrylonitrile polymers with a modified bentonite which has a hydrophobic and organophilic surface thereon. Another object is to provide spinning solutions that contain dissolved acrylonitrile polymersand highly dispersed particles of bentonite which have been treated with an amine salt to produce an organophilic-surface thereon. ;Still another object is to furnish acrylontrile polymer fibers having an improved ironing or hot bar sticking te p ra re V Other objects will appear hereinafter. I

"-In accordance with the present inventionthese and other obj ects are attained by treating bentonite particles with 'an amine salt under .conditions that produce an organophilic surface on the bentonite particles. The treated bentonite is then dispersed in' a solution of the selected acrylonitrile polymer. In these dispersions, .the bentonite particles are so' small that they readily pass through filters and spinnerettes. Fibers spun, from the compositions by standard spinning procedures can be dyed to heavy shades by various methods of dyeing with cellulose acetate dyes, acid wool dyes, vat dyes and cer tain direct cotton dyes. The ironing temperature or hot bar sticking temperature of the fiber is also raised 20-30 C. by the presence ofthebentonite.

Bentonite is a colloidal clay mineral that solvates in water and becomes highly dispersed. The natural product will not disperse in organic solvents because the surface of the particles is highly organophobic.

Bentonite has, heretofore, been employed in connection with the spinning of filaments and fibers from spinhing solutions in a different manner than contemplated Patented Jan. 12,- 1960 ice deposits a superficial layer of bentonite on the surface of the filament. This layer is readily lost during processing and has no effect on the ultimate properties of the fiber.

In contrast to that prior fiber surface treatment, the process of the present invention gives a product in which the bentonite which has organophilic properties is uniformly dispersed throughout the entire cross-section of the fiber.

In general, the organophilic bentonite is prepared by mixing a water dispersion of bentonite with a water solu. tion of an amine salt. The amine preferably contains at least 10 to 18 carbon atoms. An adsorbed layer of amine is formed on the particle surface and the particles become both hydrophobic and lose their ability to solvate with water, as well as organophilic and hence acquire, however, the property of solvating with many types of organic liquids.

Suitable primary aliphatic amine salts for treating the bentonite particles are the hydrochlorides and acetate salts of decylamine, dodecylamine, hexadecyl and octadecylamine.

I have found that bentonite treated as described above disperses readily in solvents such as dimethylformamide, dimethyl acetamide, gamma-butyrolacetone, ethylene carbonate, and succinodinitrile to give an ultimate particle size of one micron or less. The treated bentonite can be added to solutions of acrylonitrile polymers in the types of solvents listed above. These solutions can be filtered, and then spun by the wet or dry spinning methods without appreciable loss of bentonite.

Various well known Wet and dry spinning methods can be employed with my novel spinning solutions. The wet or dry spinning methods described in Emmett V. Martin US. application Serial No. 159,089, filed April 29, 1950, for Improvement in Spinning Acrylonitrile, now Patent 2,697,023 of December 14, 1954, also may be employed to spin the spinning compositions of the present invention. The resulting fibers have a high tensile strength and improved elastic properties. 7 V

I have found that bentonite treated with amines containing from 12 to 18 carbon atoms is especially suitable for the process of the invention. The treated bentonite is mixed with solutions of acrylonitrile polymers by stirring. In some cases the dispersion rate is facilitated by heating. From 5% to 30% and preferably 8% to 15% of the treated bentonite is employed based on the weight of the acrylonitrile polymer.

It has also been found that dispersion of the treated bentonite in the organic solvent is aided by the presence of a glycol such as ethylene glycol or diethylene glycol. For example, the wet precipitate of treated bentonite may be mixed with the glycol and the water evaporated to leave a coating of glycolon the bentonite particles.

Polyacrylonitrile or acrylonitrile interpolymers .may be used in the process. The interpolymers should con tain at least acrylonitrile, and. preferably 87% to acrylonitrile. The following monomers are useful in the preparation of interpolymers: vinyl acetate, methyl acetate, methyl methacrylate, isopropenyl acetate, vinyl chloride, methallyl alcohol, N-allyl acetamide, and methacrylonitrile. A particular useful class of interpolymers is derived from acrylamides as represented by: acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-isopropyl acrylamide and N,N-di

polymer.

. 3 The present invention will be further illustrated in the following examples.

Example 1 A dodecyl amine complex of bentonite was prepared as follows: 100 grams of bentonite was dispersed in 1500 cc. of water. The dispersion was allowed to stand for 3 hours, then decanted from the residue of grit and sand. A solution of 25 g. dodecyl amine hydrochloride in a mixture of 200 cc. of water and 200 cc. alcohol was added to the bentonite dispersion with good agitation. The bentonite settled out as a fiocculant precipitate which was washed by decantation. After filtering, the precipi tate was dried at 50-60" C. The particles of bentonite were coated with dodecyl amine. These treated particles readily dispersed when agitated and heated with solvents in which acrylonitrile polymers are soluble such as: dimethylformamide, or with gamma-butyrolactone, or with dimethyl acetamide, or with ethylene carbonate.

A spinning solution was prepared by dispersing 1.0 gram of this treated bentonite in 40 cc. of dimethylformamide, then adding 8 g. of polyacrylonitrile. The solution was extruded through a multihole spinnerette into a coagulating bath consisting of 75 water-25 dimethylformamide. The filaments were washed, dried, and drafted 600% at 130160 C. The yarn had a strength of 2.0 grams per denier and an elongation of 16%. Different portions of this yarn were separately dyed with the cellulose acetate dyes, acid wool dyes, vat dyes, and direct cotton dyes. The acid wool dyes showed excellent .fastness to laundering. These fibers had a hot bar sticking temperature of 250 -260 C.

Example 2 A spinning solution was formed and spun into filaments dyed and otherwise processed as in Example 1 except that 2.0 grams of the treated bentonite was added to the solution. Results comparable to those shown in Example 1 were obtained. 1

Example 3 Example 4 Bentonite is treatedwith octadecyl amine hydrochloride as described above in Example 1. Nine grams of polyacrylonitrile and 1.4 grams of the treated bentonite are stirred into 50 cc. dimethylformamide with heating. Fibers are spun by extrusion into an aqueous precipitating bath. The fibers dye well with cellulose acetate dyes, acid Wool dyes and vat dyes. They stick to the hot bar at 265-275 C.

Example 5 One part of bentonite that has been treated by the method of Example 1 with oleyl amine hydrochloride is mixed with 19 parts of a polymer having-the composition 90% acrylonitrile% isopropenyl acetate. Fibers spun from dimethyl acetamide solvent show excellent atfinity for the above-mentioned cellulose acetate dyes, acid wool dyes and vat dyes. The fibers stick to the hot bar at 240-250 C.

Example 6 20 parts of bentonite that had been treated with octadecyl amine acetate is mixed with 80 parts of a polymer having the composition 95% acrylonitrile-5% N-methyl methacrylamide in butyrolactone solvent. Fibers spun by the dry spinning process from the mixture dye heavily with the aforementioned acid wool dyes, cellulose acetate dyes, and vat dyes.

Example 7 Eight parts of bentonite that has been treated with octadecyl amine hydrochloride by the process of Example 1 is mixed with 92 parts of an interpolymer having the composition acrylonitrile-10% N-isopropyl acrylamide. Ethylene carbonate is used as solvent. Fibers spun by the dry spinning method from this mixture dye well with the aforesaid vat dyes, cellulose acetate dyes, acid wool dyes and direct cotton dyes.

Example 8 One part of bentonite that has been treated with oleyl amine hydrochloride by the method of Example 1 is mixed with 19 parts of a polymer having the composition 90% acrylonitrile-10% vinyl acetate. Fibers dry spun from dimethyl acetamide solvent show excellent aflinity for the aforesaid cellulose acetate dyes, acid wool dyes, and vat dyes. The fibers stick to the hot bar at 240-250 C.

The following dyes are among those which can be employed to color the fibers of the present invention.

Cellulose acetate dyes:

Eastman Blue BGF Eastman Blue BNN Eastman Fast Violet SRLF Eastman Fast Yellow GLF Eastone Scarlet BG Eastone Orange 3R Color index Acid wool dyes: number Brilliant Milling Blue BA 37 Brilliant Milling Red RA 487 Brilliant Milling Green B 667 Brilliant Milling Yellow 66 138 Fast Light Yellow R 636 Scarlet 4RA Xylene Milling Black B 304 Vat dyes:

Ponsol Jade Green 1101 Ponsol Navy Blue RA 1100 Ponsol Red BND 1162 Ponsol Violet RRD 1104 Ponsol Yellow 3R 452 Sulfanthrene Brown GR 121 Mordant dyes:

Omega Chrome Brown 2R 98 Omega Chrome Dark Violet D 169 Omega Chrome Orange G 274 Omega Chrome Red B 652 Omega Chrome Yellow 3G 52 Omega Chrome Black P g 204 These cellulose acetate dyes, wool dyes, vat dyes, and mordant dyes may be applied to the fibers by the method shown in Diserens, Louis, Chem. & Tech. of Dyeing and Printing, New York, The Reinhold Corporation, vol. I (1948), vol. II (1951), translated from the second German edition.

I claim: 1

. 1. A synthetic spinning solution comprising an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers of acrylonitrile with not more than 20% of mono-ethylenically unsaturated monomers in an organic solvent therefor containing a dispersion of finely-divided bentonite having a surface coating thereon of a primary aliphatic amine having from 10 to 18 carbon atoms in the alkyl radical.

2. A synthetic spinning solution comprising an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers of acrylonitrile with not more than 20% of mono-ethylenically unsaturated monomers'in an organic solvent therefor containing a dispersion of finely-divided bentonite having a surface coating thereon of dodecyl amine.

3. A synthetic spinning solution comprising an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers of acrylonitrile with not more than 20% of mono-ethylenically unsaturated monomers in an organic solvent therefor containing a dispersion of finely-divided bentonite having a surface coating thereon of octadecyl amine.

4. A synthetic spinning solution comprising an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers of acrylonitrile with not more than 20% of mono-ethylenically unsaturated monomers in an organic solvent therefor containing a dispersion of finely-divided bentonite having a surface coating thereon of oleyl amine.

5. Synthetic fibers composed of an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers of acrylonitrile with not more than 20% of mono-ethylenically unsaturated monomers and containing finely-divided bentonite particles with a coating thereon consisting of a primary aliphatic amine having from -18 carbon atoms in the alkyl radical.

6. Synthetic fibers composed of an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers of acrylonitrile with not more than 20% of mono-ethylenically unsaturated monomers and containing finely-divided bentonite particles with a coating thereon consisting of dodecyl amine.

7. Synthetic fibers composed of an acrylonitrile polymer selected from the group consisting of p'olyacro nitrile and copolymers of acrylonitrile with not more than 20% of mono-ethylenically unsaturated monomers and containing finely-divided bentonite particles with a coating thereon consisting of octadecyl amine.

8. Synthetic fibers composed of an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers of acrylonitrile with not more than 20% of-mono-ethylenically unsaturated monomers and containing finely-divided bentonite particles with a coating thereon consisting of oleyl amine.

9. Synthetic fibers composed of polyacrylonitrile containing finely divided bentonite particles which are coated with an organophilic coating consisting of octadecyl amine.

10. A synthetic fiber spinning solution comprising polyacrylonitrile dissolved in dimethylformamide and containing a dispersion of finely divided bentonite having a surface coating thereon of dodecyl amine.

11. A synthetic fiber spinning solution comprising polyacrylonitrile dissolved in gamma-butyrolactone and containing a dispersion of finely divided bentonite having a surface coating thereon of octadecyl amine.

12. A synthetic fiber spinning solution comprising polyacrylonitrile dissolved in dimethylformamide and containing a dispersion of finely divided bentonite having a surface coating thereon of octadecyl amine.

13. A synthetic fiber spinning solution comprising acrylonitrile and 10% isopropenyl acetate dissolved in dimethyl acetamide and containing a dispersion of finely divided bentonite having a surface coating thereon of oleyl amine.

14. A synthetic fiber spinning solution comprising acrylonitrile-5% N-methyl methacrylamide dissolved in butyrolactone and containing a dispersion of finely divided bentonite having a surface coating thereon of octadecyl amine.

15. A synthetic fiber spinning solution comprising 90% acrylonitrile-10% N-isopropyl acrylamide dissolved in ethylene carbonate and containing a dispersion of finely divided bentonite having a surface coating thereon of octadecyl amine.

16. A synthetic fiber spinning solution comprising 90% acrylonitrile-10% vinyl acetate dissolved in dimethyl acetamide and containing a dispersion of finely divided bentonite having a surface coating thereon of oleyl amine.

References Cited in the file of this patent UNITED STATES PATENTS 2,531,396 Carter Nov. 28, 1950 2,707,692 Hecht May 3, 1955 2,739,067 Ratcliff Mar. 20, 1956 2,769,792 Ham Nov. 6, 1956 2,808,385 Caldwell Oct. 1, 1957 FOREIGN PATENTS 675,627 Great Britain July 16, 1952 OTHER REFERENCES Journal of Physical & Colloid Chemistry, volume 53 (1949), article by J. W. Jordan, pages 294-305.

Claims

1. A SYNTHETIC SPINNING SOLUTION COMPRISING AN ACRYLONITRILE POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYACRYLONTRILE AND COPOLYMERS OF ACRYLONTRILE WITH NOT MORE THAN 20% OF MONO-ETHYLENICALLY UNSATURATED MONOMERS IN AN ORGANIC SOLVENT THEREFOR CONTAINING A DISPERSION OF FINELY-DIVIDED BENTONTINE HAVING A SURFACE COATING THEREON OF A PRIMARY ALIPHATIC AMINE HAVING FROM 10 TO 18 CARBON ATOMS IN THE ALKYL RADICAL.