US3575944A

US3575944A - Process of improving the basic dye acceptance of acrylonitrile-polymer containing fibers by using an alkaryl polyethoxy phosphate ester

Info

Publication number: US3575944A
Application number: US604550A
Authority: US
Inventors: Ernest F Stroh
Original assignee: Monsanto Co
Current assignee: Monsanto Co
Priority date: 1966-12-27
Filing date: 1966-12-27
Publication date: 1971-04-20
Anticipated expiration: 1988-04-20

Abstract

A PROCESS OF IMPROVING THE BASIC DYE ACCEPTANCE OF ACRYLONITRILE-POLYMER CONTAINING FIBERS BY MIXING, PRIOR TO EXTRUSION INTO SAID ACRYLONITRILE POLYMER, FROM ABOUT 0.5 TO ABOUT 10%, BASED ON THE WEIGHT OF THE POLYMER, OF AN ALKARYL POLYETHOXY PHOSPHATE ESTER.

Description

United States PROCESS OF IMPROVING THE BASIC DYE AC- CEPTANCE OF ACRYLONlTRILE-POLYMER CONTAINING FIBERS BY USING AN ALKARYL POLYETHOXY PHOSPHATE ESTER Ernest F. Stroh, Decatur, Ala., assignor to Monsanto Company, St. Louis, M0. N Drawing. Filed Dec. 27, 1966, Ser. No. 604,550 Int. Cl. (108E 45/00 US. Cl. 260-855 2 Claims ABSTRACT OF THE DISCLOSURE A process of improving the basic dye acceptance of acrylonitrile-polymer containing fibers by mixing, prior to extrusion into said acrylonitrile polymer, from about 0.5 to about based on the weight of the polymer, of an alkaryl polyethoxy phosphate ester.

This invention is concerned with a process of improving the basic dyeability acceptance uptake of acrylonitrile polymer containing fibers. More particularly, the invention relates to a process of improving the basic dyeability acceptance of acrylonitrile polymer containing fibers by incorporating in the acrylonitrile polymer an alkaryl polyethoxy phosphate ester.

Basic dyestuffs are desirable in coloring acrylonitrile containing fibers because of the brightness of shade imparted by these dyes, this brightness being unmatched by other types of dyes. These fibers however have a low affinity for basic dyes. This is especially true with filaments of yarn wherein the stretching of the yarn packs the chain molecules and, as a result, the acrylonitrile units are more inaccessible to the dye molecules. To overcome this low affinity for basic dyes, dyeing of acrylonitrile fibers is being carried out at high temperatures over a prolonged period of contact time. However, the fact still remains that acrylonitrile containing fibers are difiicult to dye with basic dyestuffs and good penetration of the dye is extremely slow, i.e. the basic dyeability uptake of these fibers is poor. Also, acidic agents, e.g. phosphoric acids and lower organic acids such as vinyl carboxylates have been incorporated in acrylic fibers to improve their affinity for basic dyes, however such acidic agents impart a corrosive characteristic to the fiber which is undesirable in the processing thereof.

It is an object of this invention to provide a process of improving the basic dyeability of acrylonitrile polymer containing fibers.

Another object of this invention is to provide a process of improving the basic dyeability of acrylonitrile polymer containing fibers without adversely affecting the processing of the fibers.

Other objects of the invention will become apparent as the invention is fully developed in the specification.

These and other objects of this invention are accomplished by providing a process of improving the basic dye acceptance of an acrylonitrile-polymer containing article comprising introducing into said acrylonitrile polymer from about 0.5% to about 10% of an alkaryl polyethoxy phosphate ester, the percents based on weight of the acrylonitrile polymer. The phosphate ester is introduced into the acrylonitrile-polymer by mixing it with the polymer before the polymer is formed into an article e.g. where the article is a fiber the phosphate ester is introduced prior to extrusion of the acrylonitrile polymer.

The invention is applicable to acrylonitrile-polymer containing articles, especially fibers. The term fiber is meant to include any filamentary article formed from an acrylonitrile polymer. The term acrylonitrile polymer is 3,575,944 Patented Apr. 20, 1971 defined as one containing at least about by weight of polymerized or copolymerized acrylonitrile. For example, the acrylonitrile polymer can be a copolymer of from about to about 98% of acrylonitrile and from about 2 to about 20% of another copolymerizable monoolefinic monomer. Suitable copolymerizable mono-olefinic monomers include acrylic, alpha-chloroacrylic and methacrylic acids; the acrylates such as methylmethacrylate, ethylmethacrylate, butylmethacrylate, methoxymethyl methacrylate, beta chloroethyl methacrylate, and the corresponding esters of acrylic and alpha-chloroacrylic acids; vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, l-chloro-1-bromoethylene; methacrylonitrile; acrylamide, methacrylamide, alpha-chloroacrylamide, and monoalkyl substitution products thereof; methylvinyl ketone; vinyl carboxyla-tes such as vinyl acetate, vinyl chloroacetate, vinyl propionate and and vinyl stearate; N vinyl imides such as N-vinylphthalimide and N-vinyl succinimide; methylene malonic esters; vinyl sulfonic acids; ethylene alpha, beta-dicarboxylic acids and their anhydrides and derivatives thereof such as diethylcitraconate, diethylmesaconate; styrene; vinyl naphthalene; vinyl-substituted tertiary heterocyclic amines such as vinyl pyridines and alkyl-substituted vinyl pyridines, for example 2 vinylpyridine, 4 vinylpyridine, 2 methyl- 5-vinylpyridine; 1 vinylimidazole and alkyl-substituted l-vinylimidazole such as 2-, 4-, and S-methyl-l-vinylimidazole, vinyl pyrrolidone, vinyl piperidone and other similar mono-olefinic copolymerizable monomeric materials.

The acrylonitrile polymer can also be a ternary interpolymer. For example it can be a polymer obtained by the interpolymerization of acrylonitrile and two or more of any of the monomers enumerated above. More specifically, the ternary polymer can contain from about 80 to about 98% of acrylonitrile, from about 1 to about 10% of a vinylpyridine or a l-vinylimidazole, and from about 1 to about 18% of another copolymerizable monoolefinic materials such as methacrylonitrile, vinyl acetate, methylmethacrylate, vinyl chloride, vinylidene chloride, and the like.

The acrylonitrile polymer can also be a blend of polyacrylonitrile or a copolymer of from about 80 to about 99% of acrylonitrile and from about 1 to about 20% of at least one other mono-olefinic copolymerizable monomeric material with from about 2 to about 50% of the weight of the blend of a copolymer of from about 30 to about 98% of a vinyl substituted tertiary heterocyclic amine and from about 10 to about 70% of at least one other mono-olefinic copolymerizable monomer. Preferably, When the polymeric material comprises a blend, it will be a blend of from about 80 to about 99% of a copolymer of from about 80 to about 98% of acrylonitrile and from about 2 to about 20% of another mono-olefinic monomer such as vinyl acetate with from about 1 to about 20% of a copolymer of from about 30 to about of a vinyl-substituted tertiary heterocyclic amine such as vinyl pyridine, l-vinylimidazole, and vinyl lactam, and from about 10 to about 70% of acrylontrile to give a polymer having an overall vinyl-substituted tertiary heterocyclic amine content of from about 2 to about 10%, the percents based on weight of the polymer blend.

The alkaryl polyethoxy phosphate esters useful in the invention are defined by the formula:

wherein R may be hydrogen or identical with R and R is an alkaryl polyethoxy grouping, preferably R is an alkyl phenyl poly (oxyethylene) glycol residue corresponding to the formula:

wherein n is an integer from about 2 to about 30, R is an alkyl group containing from about 5 to about 15 carbon atoms, and R is hydrogen or an alkyl grouping containing from about 5 to about 15 carbon atoms and is in a position ortho to the repeating oxyethylene group.

These phosphate esters can be obtained by reacting P With a condensation product of at least 1 mole of ethylene oxide with 1 mole of an alkyl aryl compound containing a reactive hydrogen atom. For example, the esters can be obtained as a reaction product obtained from reacting, under substantially anhydrous conditions and at a temperature below about 230 F., about one mole of P 0 with 24.5 moles of a compound selected from the group: pentylphenylpoly (oxyethylene) glycol, di (neopentyl) phenylpoly (oxyethylene) glycol, hexylphenylpoly (oxyethylene) glycol, Z-ethylhexylphenylpoly (oxyethylene) glycol, di (Z-ethylhexyl) phenylpoly (oxyethylene) glycol, and dodecylphenylpoly (oxyethylene) glycol. A catalytical amount of phosphorus or hypophosphorus acid may be added to the reaction mass to inhibit color formation. Methods for phosphonating the alkyl aryl oxyethylene compounds are described in US. Pats. Nos. 3,004,056 and 3,004,057. A commercially available alkaryl polyethoxy phosphate ester is Phosphonol N, a trade name of Beacon Chemical Industries, Inc., 33 Richdale, Cambride 40, Mass.

In the practice of this invention the alkyl aryl polyethoxy phosphate esters are introduced into the acrylonitrile polymer by mixing the esters with the spin dope containing the acrylonitrile polymer. The phosphate esters are mixed uniformly throughout the spin dope before the polymer is formed into an article, e.g. the phosphate ester is mixed with the acrylonitrile polymer dissolved in a solvent and the resulting solution extruded and processed into a fiber.

The amount of the polyethoxy phosphate esters incorporated in the acrylonitrile polymers should be within the range of from about 0.5% to about the percents based on weight of the polymer. Amounts within the range of from about 1% to about 8% are preferred. Higher amounts, i.e. in excess of 10% are useful, however such higher amounts are costly for the degree of improvement derived therefrom.

The following examples are submitted to illustrate specific Working embodiments of the invention. The samples within the examples are tested for basic dye accepta-nce, herein abbreviated as BDA, by measuring the amount of dye absorbed in each sample after it has been immersed for 2 hours in an aqueous dyebath at 206 F., the dyebath containing 20% of C. I. Name Basic Blue 22 (Sevron Blue 26, a trade name of E. I. du Pont de Nemours and Co. Inc., Wilmington, Del.), 5% of ammonium acetate and 1% of acetic acid. The fiber BDA is reported as percent dye on weight of fiber, and is determined by measuring the optical density of the exhausted dyebath on a Bausch & Lomb Model 505 Spectrophotometer and calculating the amount of dye remaining in the bath, then calculating the BDA as follows:

Percent- BDA Wt. of dyestutf) wt. of dyestuff added to bath remaining in bath wt. of fiber dyed X 100 4 EXAMPLE I For a control sample, an unstabilized acrylic fiber is obtained by extruding an acrylic solution containing dimethylacetamide and 25% of a polymer being 93% acrylonitrile and 7% vinyl acetate into an aqueous coagulation bath containing of dimethylacetamide. The fiber is washed with water to remove the dimethylacetamide, oriented by stretching, passed through an aqueous finish bath containing 3% of a textile finishing agent consisting of sorbitan monopalmitate and 40% castor fatty acid, and is then dried over hot rolls. The fiber is then analyzed and is found to have a Basic Dye Acceptance (BDA) of 4.4%.

EXAMPLE II The procedure of Example I is repeated except the acrylic solution contains 1% of a reaction product of 3.5 moles of C H C H (OC H OH and 1 mole of P 0 the percent based on weight of the polymer. The fiber is analyzed and is found to have a BDA of 5.0%. This test sample indicates a 11% BDA improvement over the control sample of Example 1.

EXAMPLE III Four acrylic samples are prepared as described in Example I except one acrylic sample (control) does not contain any phosphate ester and the other three samples (test) contain the below indicated percents of a phosphate ester obtained as a reaction product of 3 moles of C 2H25C6H4(Oc2H4) OH 1 mole of P205, the percents based on weight of the polymer. The fiber samples are analyzed for BDA and the results are reported in Table 1.

TABLE 1 Sample: Percent BDA Control 4.5 Test, contains 1% of the phosphate ester 4.9 Test, contains 4% of the phosphate ester 5.3 Test, contains 8% of the phosphate ester 5.5

These above data indicate that the alkaryl polyethoxy phosphate ester improves the BDA of the acrylic samples and that incorporation of 8% of the ester in the acrylic polymer improves the BDA by 22%, as compared with the control sample.

EXAMPLE IV Fiber samples having improved basic dye acceptance are obtained by incorporating in the acrylic polymer of the acrylic fiber samples disclosed in Example I the following phosphate esters: a product obtained by the reaction Of moles Of C13H3'7C5H4(OC2H4)5OCH2CH2OH 1 mole of P 0 2 product obtained by the reaction of 4 moles Of C5H11C5H4(OC2H4)1OCH2CH2OH 1 mole of P 0 a product obtained by the reaction of 3 moles Of (C8H1PT)2C6H3(OCZH4)HOCHZCHQOH 1 mole of P 0 and a product obtained by the reaction of 4 moles Of C 2H25C5H4(OC2H4) qOCHgCHgOH 1 mole of P 0 The above examples are presented to specifically illustrate the invention. It will become obvious to persons skilled in the art various modifications, equivalents or variations thereof which are intended to be included within the scope of the invention.

What is claimed is:

1. A process of improving the basic dye acceptance of an acrylonitrile-polymer containing article comprising mixing prior to extrusioninto said acrylonitrile polymer from about 0.5 to about 10% of an alkaryl polyethoxy phosphate ester, the percent based on the Weight of the polymer, said alkaryl polyethoxy phosphate ester being defined by the formula:

wherein R is selected from the group consisting of hydrogen and R and R is an alkyl phenyl poly (oxyethylene) glycol residue defined by the formula:

alkyl phenyl poly (oxyethylene) glycol defined by the formula:

wherein R is an alkyl containing from about 5 to about 15 carbon atoms and is in a position ortho to the repeating oxyethylene group, and n is a whole integer from about 5 to about 20.

References Cited UNITED STATES PATENTS 3,222,118 12/1965 Coleman 855AB 3,416,877 12/1968 Gantz et al. 855AB 3,432,472 3/1969 Caldwell 26478X GEORGE F. LESMES, Primary Examiner J. R. MILLER, Assistant Examiner US. Cl. X.R.