Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
1999-09-22
2001-03-13
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S457000, C524S458000, C524S459000, C525S191000, C525S205000, C525S218000, C525S329400, C525S333300, C528S310000, C528S50200C, C528S503000
Reexamination Certificate
active
06201046
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the synthesis of quaternized, dye-complexable vinylpyridine carboxylate mono-, co- and ter- polymers in high yield and purity, employing suspension polymerization and subsequent quaternization of the resulting vinyl pyridine polymer.
2. Description of the Prior Art
Dye completing polymers have been used in laundry detergent and fabric softener compositions 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 in some cases 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.
Polyvinylpyrrolidone (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. Pat. Nos. 5,776,879 and 5,929,175, 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.
Emulsion polymerization of vinylpyridine prior to quaternization has also been considered; however, this system requires the presence of a surfactant which is objectionable in certain formulations. For example, in cosmetic or pharmaceutical formulations which require specialized wetting agents for the active component, interactions with any remaining amount of surfactant in the polymer product can lead to an undesirable side reaction and/or a discoloration of the formulation. Also, certain dyes are sensitive to and interact with surfactants; thus their presence can cause problems in laundering compositions particularly when used in hot washing and rinsing cycles.
Accordingly, it is an object of this invention to provide a process for the preparation of water stable, quaternized, complexable vinyl pyridine carboxylate polymers which are not subject to the above objections and disadvantages.
Another object is to provide an economical and commercially feasible process for the preparation of a water soluble dye transfer inhibitor and stabilizing component for agrochemical, cosmetic or pharmaceutical formulations which are obtained in high purity suitable for immediate use.
A further feature of the invention is a process for providing a water soluble vinylpyridine polymer containing a quaternary nitrogen and a carboxylate salt in high yield and purity which is free of surfactant.
Another object of the invention is to provide a laundry detergent composition which effectively resists fabric dye transfer or discoloration during the washing and rinsing cycles.
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 a method for the preparation of a quaternized, water soluble vinyl pyridine carboxylate polymer by an economical and commercially feasible process in high yield and purity. The quaternized polymeric product produced by the present suspension polymerization process can be obtained in water solution or in powder form and contains from about 20 to about 5,000 quaternized units, preferably from 100 to 2,500 units. The quaternized product comprises (a) between about 30 and about 100 wt. % of the quaternized unit having the structure
(b) between 0 and about 30 wt. of a non-quaternized poly(vinylpyridine) unit having the structure
and (c) between 0 and about 70 wt. % of an olefinically unsaturated polymerizable comonomer wherein
X is an anion;
M is a cation, preferably an alkali or alkaline earth metal, most preferably sodium or potassium;
R is a divalent hydrocarbon radical selected from the group consisting of a C
1
to C
12
alkylene optionally substituted with monocyclic aryl and
S and T are each independently hydrogen or C
1
to C
4
alkyl.
The above products have a weight average molecular weight of from 5,000 to 1,000,000, preferably from 20,000 to 500,000.
The product polymer, containing a hydrocarbon group interposed between the quaternized nitrogen and the terminal carboxylate salt moiety, results in a polymer having dual functionality 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; whereas its complexability with an active cosmetic, pharmaceutical or agrichemical component provides for gradual and controlled release of the active component.
The comonomers of the above polymers are free radical polymerizable comonomers containing olefinic unsaturation and include, for example, 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 products of the invention are 75-100% quaternized polymers where, X is a halide, particularly chloride or bromide; M is a metal such as sodium, potassium or calcium; R is C
1
to C
4
alkylene and S and T are both hydrogen.
The present homo-, co- or ter- polymers are particularly useful at a concentration of from about 2 to about 1,000 ppm in a laundry detergent or rinse, a cosmetic, drug or agrichemical formulation, ink and paint compositions etc. to inhibit the migration of dye or to promote the formation of a complex with an active chemical for controlled release of the active component.
In general, the process for the preparation of the present quaternized vinyl pyridine polymer containing 0 to 70 wt. % comonomer(s) involves charging a 20 to 50 wt. % solids mixture of water and the vinylpyridine monomer, optionally with a desired amount of comonomer to a reactor and adding a water soluble suspension agent and a free radical polymerization initiator while intimately mixing the components under constant agitation and under a blanket of an inert gas, i.e. nitrogen. The mixture is then polymerized at a temperature of between about 70° and about 120° C. The suspension agent and the free radical catalyst each can be introduced in the initial charge or can be added gradually or in increments throughout the reaction. The polymerization is continued until the concentration of vinylpyridine monomer is reduced to a desired concentration, less than 1 wt. % of the reaction mixture, most preferably to less than 0.5 wt. %. In the present process the water suspension containing non-quaternized polymer is an intermediate product which can be recovered as an aqueous suspension or dried to a wet cake or a particulate solid for reconstitution prior to quaternization.
The vinylpyridine homo- or co- polymer is then subjected to quaternization with a suitable metal salt of a halogenated, branched chain or linear, monobasic carboxylic
Hornby John C.
Shih Jenn S.
Srinivas Bala
Yap Eduardo T.
Davis William J.
ISP Investments Inc.
Katz Walter
Maue Marilyn J.
Truong Duc
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