Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1999-09-22
2001-08-07
Aulakh, Charanjit S. (Department: 1612)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C504S250000, C504S116100, C510S337000, C510S361000, C524S099000, C524S457000, C524S458000, C525S191000, C525S205000, C525S218000, C525S329400, C525S333300, C528S50200C, C528S503000, C546S341000, C546S340000
Reexamination Certificate
active
06271386
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to novel quaternized, dye-complexable vinlpyridine carboxylate polymers, and to the process for their preparation involving water based, suspension polymerization of 4-vinyl pyridine monomer and subsequent quaternization of the resulting vinyl pyridine polymer.
2. Description of the Prior Art
Dye complexing polymers have been used in laundry detergent and fabric softener compositons to stabilize and minimize leaching of dyes in colored fabrics. During washing of colored and white fabrics, some of the dyes can bleed out of a colored fabric and a portion of the leached dye may deposit on white or lighter colored fabrics. The degree of bleeding is influenced by the character of the dye, the type of cloth and the pH, temperature and mechanical efficiency of the agitation process. Although is some cased the bled dye in the wash liquor can be washed off without altering the color of lighter colored fabrics, the dyed fabric looses a degree of brilliance resulting in a somewhat faded appearance. Often it is found that the fugitive dye deposits either onto the same fabric or onto another fabric leading to patches and streaks in the washed material. This deposition of the bled dye can be inhibited in several ways. One method involves the use of a dye transfer inhibitor (DTI) compound which can complex with the dye and minimize leaching or at least prevent redeposition on the same or other fabrics.
Polyvinylprrolidone (PVP), by virtue of its dye complexation ability, has been used to inhibit dye deposition during washing of colored fabrics under laundry conditions. The performance of PVP as a DTI, however, is adversely affected by the presence of anionic surfactants usually present in the washing process.
Vinylpyridine polymers such as those disclosed in U.S. Pat. No. 4,824,910 and in our previous U.S. patent application, Ser. No. 932,448, now U.S. Pat. No. 5,776,879, were formerly synthesized in alcoholic media; however, the product of this process contains significantly high unreacted monomer for a given period of reaction time and requires separation of organic solvent to recover pure polymer product. Costly and time consuming treatments are employed to remove impurities with the organic solvent in order to recover a purified product having no objectionable color.
Accordingly, it is an object of this invention to provide quaternized, complexable vinyl pyridine carboxylate polymers and an improved process for the preparation of the non-quaternized polymers, subsequent to their quaternization, which polymers are soluble in water.
Another object is to provide an economical and commercial process for the preparation of a water soluble dye transfer inhibitor and polymers for agrochemical or pharmaceutical formulations which have superior complexing properties and which are obtained in high purity suitable for immediate use.
A further feature of the invention is the provision of a water soluble poly (vinylpyridine polymer) containing a quaternary nitrogen and a carboxylate salt in high yield and purity.
Another object of the invention is to provide a laundry detergent composition which effectively resists fabric dye transfer during the washing and rinsing cycles, even in the presence of anionic surfactants. These and many other benefits and advantages of this invention will become apparent from the following description and disclosure.
SUMMARY OF THE INVENTION
This invention is directed to an a quaternized water soluble vinyl pyridine carboxylate polymer and to an economic and commercially desirable process for synthesizing the water soluble, quaternized vinlylpridine carboxylate polymer product in high yield and purity which product possesses superior complexing properties and is stable in aqueous and water media. The quaternized polymeric product of this invention, which can be obtained in water solution or in powder form, contains (a) from 30 to 100 wt. % of a quaternized monomer having 20 to 5,000 quaternized units, preferably 100 to 2,500 units, of the structure
(b) 0 to 30 wt. of a non-quaternized vinylpyridine unit having the structure
and (c) 0 to 70 wt. % of an unsaturated polymerizable comonomer wherein X is an anion; M is a cation, preferably an alkali or alkaline earth metal, most preferably sodium or potassium; at least one of R
1
and R
2
in the expression (CR
1
R
2
)
n
is a radical having a —C—O— containing moiety, which radical is selected from the group consisting of alkoxy, carboxyl, an alkali or alkaline earth metal salt of a carboxylic acid and a C
2
to C
13
carboxylate optionally substituted with halogen and any remaining R
1
and R
2
in the expression (CR
1
R
2
)
n
is selected from the group consisting of hydrogen, lower alkyl and aryl; S and T are each independently hydrogen or C
1
to C
4
alkyl; and n has a value of from 1 to 5 . The copolymer containing 70-95% (a) and 5-30% (c), with at least 0.5 wt. % of (b), is an exceptionally good complexing agent for many pharmaceuticals, personal care components and agrochemicals requiring film forming properties.
The above quaternized unit is polyfunctional and is chacterized as having a —C—O— containing group between the quaternized nitrogen and the terminal carboxylate salt moiety. The intervening carbonoxy group (—C—O—) provides an additional reactive site for stronger bonding to an active dye, pharmaceutical, agrochemical or hair and skin treating agent and therefore provides a polymer having significantly increased complexability for use in a wide variety of applications. Particularly its dye complexing property provides excellent dye transfer inhibition in printing, laundry and rinse formulations for the cleansing or dying of fabrics.
The comonomers of the above polymers are free radical polymerizable comonomers including styrene, alkyl styrene, N-vinylpyrrolidone, N-vinyl caprolactam, vinyl imidazole, N-vinyl amide, a lower alkyl acrylate, a lower alkyl methacrylate, acrylamide, methacrylamide and the like and mixtures thereof.
The preferred product of the invention are polymers where, in monomer moiety (a), n has a value of 1 to 3, X is a halide, particularly chloride or bromide, M is a metal such as sodium, potassium or calcium and at least one of said R
1
and R
2
is —COOY; wherein Y is hydrogen, an alkali or alkaline earth metal or C
1
to C
4
alkyl; S and T are both hydrogen and the polymer is 75-100% quaternized.
The polymer products of the present invention have a weight average molecular weight of from about 5,000 to about 1,000,000, preferably from 20,000 to 500,000.
The present polymers are most preferably those containing from 100 to 2,000 monomer units; which homo-, co- or ter-polymers are particularly useful at a concentration of from about 2 to about 1,000 ppm in laundry detergent or rinse, a drug, cosmetic or agrichemical formulations, ink and paint compositions etc. to inhibit the migration of dye or to complex with an active chemical for controlled release of the active component.
In general, the vinyl pyridine polymer reactant of the present invention, containing 0 to 70 wt. % comonomer(s), can be obtained by several types of polymerization, i.e.solution, suspenison, emulsion and precipitation polymerization processes in which a suitable solvent such as a C
1
to C
4
alkanol, water or a mixture thereof is employed as un U.S. Pat. Nos. 5,627,151 . and 5,458,809; EP 0664332 A and J. of Polymer Science 26/No.113/pp25-254/1957, incorporated herein by reference. Surprisingly it is now discovered that the vinyl pyridine polymer prepared by suspension polymerization has advantages over other types of polymerization. However, the polymerized products can be obtained as an emulsion, suspension, dispersion or as dry particles or powder. As feed to the quaternization zone of the present process, the vinylpyridine polymer is employed as a water mixture containing from about 20 to about 50 wt. % solids. The quaternization is effected under constant agitation at a temperature of between 40° and about 140° C., optionally under
Hornby John C.
Shih Jenn S.
Srinivas Bala
Yap Eduardo T.
Aulakh Charanjit S.
Davis William J.
ISP Investments Inc.
Katz Walter
Maue Marilyn J.
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