US20030216483A1

US20030216483A1 - Urethane polymer foam composites in sized particulate form with controlled release of agents and additives

Info

Publication number: US20030216483A1
Application number: US10/406,301
Authority: US
Inventors: Paul Hermann; Wayne Celia
Original assignee: HH Brown Shoe Technologies Inc
Current assignee: HH Brown Shoe Technologies Inc
Priority date: 2002-04-02
Filing date: 2003-04-03
Publication date: 2003-11-20
Also published as: AU2003218302A1; CN1302818C; WO2003084579A1; EP1494725A1; US6706775B2; JP2005533132A; JP2008248261A; EP1494725A4; CN1658910A; US20030191204A1; US20030207954A1

Abstract

Granulated hydrophilic urethane polymer foam products with controlled release or contact of agents and additives, formed from the reaction product of an aqueous formulation comprising limited quantities of an absorbent polymer, an agent or additive from the group of detergents, soaps, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, chemicals, water emulsions, water mixture with solid particles and optionally selective additives with adequate water and a predetermined ratio of hydrophilic urethane prepolymer to provide the polymerized solid. The agents and additives if any, are homogenously incorporated strands, fibers and intercellular structures of the matrix for the formed urethane polymer foam product to materially increase mass transfer between the agents and additives and a target in the effluent. The hydrophilic urethane polymer will allow intimate contact between agent/additive and effluent target.

Description

This application is a continuation-in-part of U.S. Application No. 10/115,338, filed Apr. 2, 2002.[0001]

BACKGROUND OF THE INVENTION

The present invention relates generally to hydrophilic polyurethane foam composites used for various types of industrial, commercial, residential, personal care, cleaning and other products, and more particularly to such products formed, generated or granulated in predetermined particle sizes of the formed hydrophilic polyurethane foam product which contains limited quantities of superabsorbent polymers to control the release or contact with an agent or agents such as detergents, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, odor control compositions, polyoxometalates (POMS) and chemicals or optionally and selectively other additives when such foam product composite is brought into contact with water or an aqueous effluent during application and use of the sized particulate foam product.

When an aqueous formulation of the present invention including superabsorbent polymer, agents and adequate water is mixed with a hydrophilic urethane prepolymer, as described in U.S. Pat. No. 5,976,847, the reaction produces polymerization and forms a hydrophilic polyurethane foam composite.

Conventional prior art urethane polymer foam is mostly resistant and non-permeable to water. Some compositions have been treated with a surfactant in the formula to render the resultant urethane polymer foam products more acceptable to water. This type of surfactant-treated urethane polymer foam products will allow water to run along the supporting strands, fibers and intercellular gaps of the matrix for the foamed foam but will still disallow penetration into the strands and fibers forming the matrix of the formed urethane polymer foam.

Conventional prior art urethane polymer foams require a stochiometric balance of water to isocyanate below approximately 0.05% addition of water or water-bearing agent in the formulation. This limits the amount of agent addition to the final composite. A further limitation of agent addition is the starting viscosity of conventional polyol components of the formula. Most additions of agent are added to the polyol component based on the high reactivity of the isocyanate component. The polyol component is typically relatively high in viscosity prior to any agent addition. Increasing its viscosity further by addition of agent quickly renders the resultant viscosity too high to pump and disallows the processing requirements of metering machinery. In addition to limited amounts of agent capable to be added is the major objection of conventional prior art urethane foams, that is, its water resistance. A composite foam product made with water-resistant or water-impermeable urethane coats or blocks the agent with its intended contact with an aqueous effluent. This defeats the original effort in adding the agent to the composite. The agent was added and intended to be available to interact with moisture bearing effluents in use.

Hydrophilic urethane polymer foams in the prior art are described in U.S. Pat. Nos. 4,137,200; 4,339,550; 5,976,847 and others, as well as in Polyurethane's Chemistry and Technology by Saunders and Frisch, Volume XVI Part 2, High Polymer Systems. The primary departure from conventional prior art non-hydrophilic urethane foam is in the polyol component. Utilizing a hydrophilic polyol reacted with isocyanate provides a hydrophilic urethane prepolymer. Mixing this hydrophilic urethane prepolymer with water results in a hydrophilic urethane polymer foam product. Adding an agent into the water results in a formed hydrophilic urethane polymer foam composite or product containing the agent. If the formed hydrophilic urethane polymer foam composite including agent is subsequently contacted with an outside aqueous-based effluent, the agent may interact with the effluent for an intended purpose. In this prior art hydrophilic urethane polymer foam composite technology, the contact between the agent and the effluent, or the expression of agent into effluent, is controlled by the inherent hydrophilicity of the urethane polymer foam carrier. However, hydrophilic urethane polymer foam composites in accordance with such prior art techniques lack and do not provide any controlled release of the agent or agents on contact with water or an aqueous-based effluent.

It has been discovered that an improved controlled release urethane polymer or co-polymer foam composite or product in accordance with the present invention can be formed or obtained by combining an aqueous formulation consisting of a limited amount of superabsorbent polymer or copolymer, an agent or agents, optionally and selectively additives and adequate water with a hydrophilic urethane prepolymer. The agent or agents include, without limitation, detergents, soaps, waxes, polishes, abrasives, solid particles, drugs, cosmetics, biologicals, volatiles and chemicals. This improved composition slows and materially reduces the release of such agent or agents to a much greater extent than the known prior art products. Further, granules or particulate compositions formed with such compositions are adapted for cleaning, scrubbing, abrasion, waxing, polishing, bonding, odor-controlling, catalyzing, absorption and other chemical mass transfer applications, purposes and uses.

SUMMARY OF THE INVENTION

Thus, in one aspect, the controlled release urethane polymer foam product when used herein is a granulated or particulate composition of formed hydrophilic polyurethane foam, containing a limited quantity of superabsorbent polymer or copolymer and up to ninety percent (90%) solid agent or agents and optionally and selectively additives which, when exposed to an aqueous effluent, will enable the agent or agents, and additives if any, to be gradually released or exposed for at least one or more given reactions or functions with the aqueous effluent.

Such controlled release urethane polymer foam products in granular or particulate composition in accordance with the present invention differ from the impermeable characteristic of conventional hydrophilic urethane polymer foam products formed in accordance with the prior art technology and are easily identifiable because of their water absorption capability in that they will swell up to one hundred fifty percent (150%) of their dry volume.

It is another aspect of the present invention that the compositions of the controlled release urethane polymer foam products formulated and generated in accordance with the present invention, which include a specific agent or agents or additives such as biological or bacterial additives, can be ground or granulated or formed in a predetermined size and, when enclosed in a filter housing, serve as a filter, for example, of noxious waste water.

It is another aspect of the present invention that a granulated or sized particle form of the controlled release urethane polymer foam product embodying a homogeneous mixture of odor control and absorption agents, and a selected additive or additives if any, will provide a litter composition for absorbing animal urine and semi-solids and for controlling noxious odors in animal litter boxes or, when placed in a suitable perforated housing or container, will control noxious odors from garbage, tobacco, diapers, vomit, liquor, gasoline, fish and other odoriferous substances.

In still another aspect, the present invention covers hydrophilic polyurethane foam products with agents such as detergents, soaps, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, chemicals and the like and optionally and selectively additives, formed into granules or sized particles in which the agents, and/or additives if any, are incorporated generally uniformly into the matrix or supporting strands, fibers and intercellular gaps of the formed foam, and will provide a granular or sized particulate controlled release urethane polymer foam product from the reaction product obtained by combining an aqueous formulation having a limited quantity of a superabsorbent polymer or copolymer, an agent or agents and optionally and selectively additives and adequate water with a hydrophilic urethane prepolymer to produce a formed hydrophilic urethane polymer foam product having unique properties such that, when wetted, or subjected to an aqueous effluent, the formed hydrophilic polyurethane foam product will act to slow the release of the agent or agents, and any selected additive if any, with or into the wetting effluent, to enable the formed product to provide extra and additional applications or more intimate mass transfer of the agents, and the selected additives if any, during use than those presently obtainable from similar products now known in the prior art.

It is another aspect of the present invention to provide a method for formulating and forming such granular or sized particulate controlled release urethane polymer foam products including the steps of:

a) metering and mixing an aqueous formulation having at least a limited quantity of superabsorbent polymer, an agent or agents and adequate water, with a predetermined ratio of hydrophilic urethane prepolymer to provide a polymerizing mixture for forming the controlled release urethane foam product;

b) depositing the polymerizing mixture on releasable bottom paper disposed on a movable carrier and covering the upper surface of the polymerizing mixture with releasable top paper as the polymerizing mixture is moved with the carrier;

c) advancing the polymerizing mixture in the top and bottom release paper by moving the carrier;

d) sequentially removing the top and bottom releasable paper while simultaneously drying the sized and formed product to remove residual moisture; and

e) passing the sized and formed controlled release urethane polymer foam product to secondary operations such as granulation or particulate sizing to provide shaped and sized particulate compositions and products for particular applications and uses.

In still another aspect of the present invention to provide a method for formulating and forming the granulated or sized particulate controlled release urethane polymer composition or products, in which all the steps are the same as those above described except that step c is modified as follows:

c) advancing the polymerizing mixture in the top and bottom release paper by moving the carrier and sizing the foam layer being formed to the desired thickness until it is tack free;

It is another aspect of the present invention to provide formed shaped and sized granules or particulate of controlled release urethane polymer foam compositions or products with abrasive characteristics from a polymerized combination of an aqueous mixture having, a limited quantity of a superabsorbent polymer, agents from the group of a sized quantity of abrasive particles and adequate water with a predetermined quantity of hydrophilic urethane prepolymer, in which the agent or agents including the abrasive particles are incorporated into the matrix or supporting strands and fibers and the intercellular structure of the formed foam to provide unique properties, applications and uses such as animal litter, and filling devices.

It is another aspect of the present invention to provide a method for formulating and forming such granular or sized particles of the controlled release urethane polymer foam compositions or products with abrasive particles homogeneously dispersed therethrough including the steps of:

a) metering and mixing an aqueous formulation having at least a quantity of superabsorbent polymer, an agent or agents, a sized quantity of abrasive particles and adequate water with a predetermined ratio of hydrophilic urethane prepolymer to provide a polymerizing mixture for forming the controlled release urethane foam product with abrasive characteristics;

e) passing the sized and formed controlled release urethane polymer foam composition or product with abrasive characteristics to secondary operations such as granulation or particle sizing, to provide shaped and sized products for particular applications and uses.

It is a still further aspect of the present invention to provide a ground or granulated or sized particles of the controlled release urethane polymer foam compositions or products in accordance with the present invention to absorb and retain various liquids and semi-solids and to control noxious odors from a polymerized combination of an aqueous mixture having, a limited quantity of superabsorbent polymer, a selected acid, neutral and alkaline odor control agent or agents and optionally and selectively additives and adequate water with a predetermined quantity of hydrophilic urethane prepolymer to provide the formed composite formulated and comminuted to the desired particle size for the given application and use.

It is a still further aspect of the present invention to provide a method for formulating a ground or granulated or sized particulate controlled release urethane polymer foam composition or product for the control of obnoxious odors and adapted to absorb various liquids or semi-solids and for the control of noxious odors including the steps of:

a) metering and mixing an aqueous formulation having at least a limited quantity of superabsorbent polymer, at least one acid, neutral and alkaline odor control agent or agents, optionally and selectively additives and adequate water with a predetermined quantity of hydrophilic urethane prepolymer to provide a polymerizing mixture for forming the controlled release urethane foam product with absorption characteristics and the control of noxious odors;

e) passing the sized and formed controlled release urethane polymer foam composition or product to a comminuting or sizing device set to provide the desired particle size of the formed composition or product for the particular applications and uses.

These and other aspects and advantages of the present invention will be better understood from the detailed description which follows below when taken with the FIGURES of the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of a portion of the strands, fibers and intercellular gaps in the matrix or supporting structure for a formed foam granulated or sized particulate controlled released urethane polymer foam composite or product in accordance with the present invention having an agent or agents and selected additives homogenously dispensed therethrough. [0036]
FIG. 2 is an enlarged cross-section taken on line [0037] 2-2 of the strands of the supporting structure of the matrix shown in FIG. 1 of the drawings.
FIG. 3 is a schematic diagram showing the mechanical steps for one method of formulating a sized particulate controlled release urethane polymer composite or product in accordance with the present work. [0038]
FIG. 4 is a further schematic illustration for selecting the sized particulate controlled release urethane polymer foam composition or product with means to add liquids or solids to the sized formed particles in conjunction with the formulation, size selection and packaging of the commercial product for marketing purposes.[0039]

DETAILED DESCRIPTION

Controlled release urethane foam products in accordance with the present invention take various forms because of the myriad of agents that can be embodied into the matrix or supporting strands, fibers and intercellular structure of the formed foam compositions or product and the multiplicity of applications and uses to which such products can be applied or adapted. [0040]
One basic form of the controlled release urethane foam products in accordance with the present invention is formulated and formed, as hereinafter more fully described, by combining an aqueous mixture of a limited quantity of superabsorbent polymer, one or more agents from the group, detergents, soaps, abrasives, waxes, polishes, biologicals, volatiles and the like materials, and additionally optionally and selectively additives if any, with a predetermined ratio of a hydrophilic urethane prepolymer to provide a polymerizing mixture so that during polymerization the agent or agents and any additive, if any, will be incorporated and bound into the matrix or supporting structure of the formed urethane foam product. [0041]
The absorbent polymers or superabsorbent polymers or copolymers in such formulations are preferably sodium polyacrylate/polyalchohol polymers and co-polymer sorbents described in U.S. Pat. Nos. 5,763,335 and 4,914,170, purchasable in the commercial marketplace. [0042]
The detergent agents used in the formulation of the granulated or sized particulate controlled release urethane polymer foam compositions or products are those surfactant chemicals commonly available and known to those skilled in the art to satisfy hard surface cleansing, skin cleansing, rug cleansing and other cleaning tasks such as in detergents sold as “LYSOL APC, SIMPLE GREEN, 409, MR. CLEAN, SOFT-SCRUB, RESOLVE CARPET CLEANSER”, etc. all registered trademarks. These trademarked products illustrate a combination of surfactants, solvents and other miscellaneous ingredients. Any soaps or detergent formulations may thus be considered as the agent. In some cases, more than one agent may be utilized in the formulation of the granulated or sized particulates controlled release urethane polymer form compositions or products in accordance with the present invention as a function of the application or use for the particular composition or product. [0043]
The abrasive agents used in the formulation of the granulated or sized particulate controlled release urethane polymer foam compositions or products are classified into at least two groups. The first group would be particles that have (a) low abrasive qualities such as diatomaceous earth, (b) medium abrasive qualities such as feldspar, and (c) high-abrasive qualities such as silica. The second group would be sheet stock abrasives in the form of (a) non-woven fiber such as those commercially available as Scotchbrite®, floor cleaning pads and Buf-Puff®; (b) woven or paper adhesively bonded sheets such as sandpaper; and (c) naturally occurring abrasive materials such as Loofah, Apricot Seed, crushed Walnut shell, crushed Jojoba shell and the like. Abrasives will function to polish, abrade or remove substrate materials over which the foam composite is rubbed. [0044]
The wax agents used in the formulations of the granulated or sized particulate controlled release urethane polymer foam compositions or products are materials which impart a shine on a secondary surface with which they are brought in contact and include crystalline waxes, paraffin waxes, wax emulsions and silicone fluids such as: [0045]

POLISHING APPLICATION

WAX AGENT Vinyl Furniture Metal Shoe Auto

Crystalline X X X

wax

Paraffin X X X

wax

Wax X X

emulsions

Silicone X X X X X

fluids

The drug agents used in the formulation of the granulated or sized particulate of controlled release urethane polymer foam compositions or products may be any medicament or pharmaceutical used to alter the body response such as vitamins, analgesics, vaccines, spermicides and the like.



	DRUG AGENT	APPLICATION

	Ben Gay	Analgesic wrap
	Desitin	Diaper rash protective pad
	Vitamin C	Skin enhancement
	Nonoxynol 9	Contraceptive
	Iodine	Germ Kill

The cosmetic agents used in the formulation of the granulated or sized particles of controlled release urethane polymer foam products are those chemical materials established to alter the external appearance, feel or smell of a human or animal body such as, by way of illustration and not limitation, skin conditioners, hair color dyes, hair shampoos, fragrances, lip glosses, nail polishes, aqueous dispersible body powders and liquid emulsions, etc.



	COSMETIC AGENT	APPLICATION

	Sodium laurol sarcosinate	maximizes suds
	Sodium laureth sulphate	copious suds
	Anionic surfactants	skin cleaning
	Citric acid	PH modifier
	Isothionate	skin softener

The biological agents used in the formulation of the granular or sized particles of controlled release urethane polymer foam compositions or products are those materials produced by or consisting of live cells that react with aqueous effluent which include, by way of illustration and not limitation, bacteria, plant cells, viruses, algae and fungi.



	BIOLOGICAL AGENT	APPLICATION

	Azolla (plant)	scrub heavy metals
	Jimson weed (plant)	scrub radioactivity
	Chlorella (green algae)	scrub heavy metals
	Pseudomonas (bacteria)	scrub heavy metals
	Yeast strain R14 (yeast)	scrub heavy metals

The chemical agents used in the formulation of the granulated or sized particles of controlled release urethane polymer foam compositions or products not specifically embodied in the agents as above identified include materials intended to enable a secondary reaction when the formed foam product is contacted by an aqueous effluent such, for example:



	THE AGENT OR
	ADDITIVE	APPLICATION OR USE

	Human Blood	Absorb oxygen from water
	Odor Absorbent	Destroy noxious odor
		materials
	Phase Change Agents	Absorb and release BTUs
	Baking Soda Agents	Alkalize acid solutions
	Cellulose Fibers	Absorption and tensile
		strength

Any of the agents from the groups enumerated may first be formed in an aqueous premix solution with a typical surfactant material and then added to the aqueous mixture to be combined with the hydrophilic urethane prepolymer. Surfactants may be used with the agents in the aqueous mixture to increase the concentration of the selected agent or agents in the aqueous mixture. The surfactants are preferably present in amounts of about 0.5% to about 3.5% by weight of the aqueous mixture. The surfactants may be prepared from anionic polyoxyethylene and polyoxypropylene oxides such as BASF surfactant, available under the trademark “PLURONIC”. Other surfactants known as anionics, cationics and or zwitterionics, singularly or in combination, can be added to the formulation, as known by those skilled in the art, to satisfy specific needs. [0050]
The aqueous mixture may further consist of various combinations of other selected additives without departing from the scope of the present invention, including, for example, germicides, bactericides and fungicides. Such products are provided in the commercial marketplace by a myriad of suppliers for controlling germs, or bacterial and fungal growth. One preferred material available in the commercial marketplace is supplied by Lauricidin Co. of Galena, Ill. 61036, under the trademark “LAURICIDIN”. [0051]
In those applications desiring biocidal protection, the selected agent is added into the aqueous phase at the proper rate so as to function yet be safe to handle. Typical prior art volume of such agent when added is less than 1% by weight of the aqueous mixture. However, it has been discovered that up to ten percent (10%) by weight of an active anti-bacterial may be added in the formulations in accordance with the present invention without adverse results. It is believed that the controlled release characteristics of the composition and products so formulated prevents any skin irritation or problems. [0052]
In addition, volatile agents and volatile additives may be used in the formulation of the granulated or sized particles of controlled release urethane polymer foam compositions or products in accordance with the present invention. Such volatiles are materials having a low boiling or subliming temperature at atmospheric pressure that vaporize to produce a secondary reaction as is the case with fragrances and solvents. [0053]
Thus, an agent or agents, when used herein, are any active ingredients added into the aqueous formulation for composites or products in accordance with the present invention prior to polymerization that will provide a desired end result for the application and use of the formed controlled release urethane polymer foam composites or products. Accordingly, the agents as set forth above are only by way of illustration and not limitation of the formed granulated or sized particulate controlled release urethane foam composites or products in accordance with the present invention. [0054]
During polymerization, water soluble agents and the selected additives if any, are incorporated homogenously into the matrix or strands, fibers and intercellular supporting structure of the granulated or sized particulates of the formed foam compositions or products. These agents and additives, if any, remain bound in position in the matrix until the granulated or sized particulate of the formed foam composition or products are wetted or contacted by sufficient moisture to activate the agents in the granules or sized particles of such formed foam compositions or products, at which time one or more of the agents and such additives if any, present are slowly released from the matrix or supporting strands, fibers or intercellular structure of the formed foam granulated or sized particulates compositions or product and diffuse toward the surface, where they can be put to use for cleaning, scrubbing, waxing, polishing, controlling noxious odors, as the case may be, for a given agent or agents and the selected additive, if any, for a given application or use. Non-water soluble solid agents such as abrasives incorporated in the granules or size particulates of the formed controlled release urethane polymer foam composition or products remain bound in situ for contact with and to effect a change in the aqueous effluent such as binding a component of the aqueous effluent to the agent. It is noted that in some cases, the agent may be added to the prepolymer rather than the aqueous mixture during formulation, particularly when the agent is anhydrous or oil-based. [0055]
FIG. 1 of the drawings shows diagrammatically an enlarged fragment of the foam matrix generally designated [0056] 10 for a granule or sized particle of the controlled release urethane polymer foam of a composite or product formulated in accordance with at least one of the methods of the present invention.
[0057] Matrix 10 from the polymerizing step for formulating the foam composition or product is a mesh of interconnected strands and fibers 11 defining the supporting structure for the matrix, and formed therein are intercellular air spaces or gaps 12.
FIGS. 1 and 2 also show that the agent or [0058] agents 13 and additives 14 are generally uniformly deposited and bonded in, out, along and through the strands and fibers 11 and the intercellular air spaces or gaps 12 formed by and in the supporting structures for the matrix.
The aqueous mixture is prepared by conventional batch mixing in blending [0059] apparatus 15 where the selected agent or agents, and optionally and selected additives are mixed in a volume to satisfy the intended application and use. Thus the water is added first into the blender 15, the agent is blended in or emulsified in with a surfactant, then the superabsorbent polymers and the additives if any, are added and the aqueous mixture is intimately mixed.
This aqueous mixture includes, the superabsorbent polymer in a range from 0.05% to 10% by weight, and preferably about 0.6% by weight, at least one or more of the group of agents from 0.1 to 15% by weight and preferably 6% by weight, water in a range from 15% to 85% by weight and preferably about 30% by weight with hydrophilic urethane prepolymer in a range from 0.25% to 80% by weight and preferably 30% by weight. [0060]
The hydrophilic urethane prepolymer is dispensed from a [0061] storage tank 16 through line 17 into a mixing and dispensing apparatus 18. The blended aqueous mixture is also passed from blending apparatus 15 through line 19 to the mixing and dispensing apparatus 18 in the proper stoichiometric quantity to initiate polymerization. The polymerizing mixture 20 is dispensed through the dispensing head or outlet 21 for the mixing and dispensing apparatus 18 onto releasable bottom paper 22 traveling on a continuous conveyer 23 where it first passes the releasable bottom paper 22 enter dispensing outlet 21 to secure a layer of the polymerizing mixture thereon. Now, the polymerizing mixture and releasable bottom paper 22 traveling with this continuous conveyer 23 are moved through a drying oven 24.
Hydrophilic urethane prepolymer available in the commercial marketplace is a water reactive 10,000-20,000 cps liquid and must be intimately mixed with the above described aqueous mixture of a limited quantity of superabsorbent polymer, agent or agents, and optionally selected additives to initiate polymerization. [0062]
Suitable hydrophilic urethane prepolymer for use in the present invention are known and will be readily recognized by those of ordinary skill in the art from U.S. Pat. Nos. 5,763,335; 4,209,605; 4,160,076; 4,137,200; 3,805,532; 2,999,013; as are the general procedures for the preparation and formation of such prepolymers which can be found in Polyurethane's Chemistry and Technology by J. H. Saunders and K. C. Frisch published by John Wiley & Sons, New York, N.Y., at Vol. XVI Part 2. High Polymer Series. “Foam Systems”, pages 7-26, and “Procedures for the Preparation of Polymers”, pages 26 et seq. One preferred prepolymer for use in the present invention is sold under the trademark BIPOL 6 by Mace Adhesives and Coatings. Another prepolymer suitable for use in the present invention is sold under the trademark HYPOL by The Dow Chemical Company. Still another prepolymer for use in the present invention is sold under the trademark PREPOL by Lendall Manufacturing Incorporated. These prepolymers are suitable for the present invention because of their strong hydrophilic characteristic and reasonable cost. [0063]
Admixing the aqueous mixture with a predetermined ratio of the precise amounts of the hydrophilic urethane prepolymer initiates polymerization. The physical characteristics such as density and tensile strength are controlled by the ratio of prepolymer in the aqueous mixture to produce controlled release urethane polymer foam composition or product, which composition or product can be granulated, ground, comminuted or sized to provide granular or sized particulate controlled release urethane foam compositions or products in accordance with the present invention. [0064]
The formulation of the granules or sized particles of controlled release urethane polymer foam composite or products is schematically illustrated in FIGS. 3 and 4 of the drawings. [0065]
Thus, referring further to FIG. 3, the releasable bottom paper is removed from the formed controlled release urethane polymer foam composition or product and continues to travel on the [0066] roller type conveyer 25 where it is discharged onto a grinder or comminuting apparatus 26 which delivers the comminuted or ground controlled release urethane polymer foam composition or product to one end of an auger type feed assembly 27 for passing the comminuted or ground composition or product to the upper or inlet end of a rotary screener 28.
[0067] Rotary screener 28 has outlets for three sizes of the comminuted or ground composition or product, an oversized outlet at 29; an undersized outlet at 30 and an acceptable or desired sized outlet as at 31.
FIG. 4 schematically shows the further steps for preparing the acceptable sized granular or particulate controlled release urethane polymer foam composition or product for packaging and marketing into the commercial marketplace. Thus, the acceptable sized compositions or products from the acceptable [0068] sized outlet 31, are dispensed into one end of an auger feed and metering device 32 which passes the comminuted or ground composition or product past liquid metering spray head 33A and 33B. Any liquid or solid additions to the granular or sized particulates can even be applied to the granular or sized particles after the controlled release urethane polymer foam composite or products have been formed, subjected to moisture removal and comminution is complete.
The [0069] weight packer 34 has filling buckets 35 a, 35 b, 35 c and 35 d which deposit a pre-determined quantity of the granular or sized particulate controlled release urethane foam composition or product into marketing containers as at 36 a, 36 b, 36 c and 36 d. These marketing containers can be delivered by conveying apparatus 37 to the delivery point for transport into the commercial marketplace.
The present invention may be formulated as a composition of dry particles with odor control agents uniformly dispersed therethrough so that the formed controlled release urethane foam product in the sized and shaped particulate form can act both to absorb and retain noxious liquids such as urine and semi-solid waste materials such as feces and also control or modify noxious odors. [0070]
While the particulate form of the controlled release urethane foam product with odor control agent is particularly adapted for use as an animal litter for the absorption and retention of animal urine and feces and for controlling or modifying the noxious odors associated therewith, it also can be applied for the absorption, adsorption, retention, control and modification of pleasant odors or for noxious odors emanating from garbage, tobacco, kitchens, bathrooms, bedding and other sources, for example, by the use in filters or perforated containers containing quantities of the granular materials or when possible by direct sprinkling or contact. [0071]
Prior art animal litters composed of clays, shredded paper, wood chips and inorganic fiber have claimed the ability to remove odor and agglomerate urine. Control of odor in prior art is attempted by masking or absorbing. Masking is defined as overpowering the objectionable odor with an acceptable odor. Absorbing is defined as trapping the odor in a porous shell. It has been discovered that both solutions represent problems: [0072]
Masking Agent Problems [0073]
1. hard to distribute uniformly in each particle [0074]
2. ceases to function after evaporation [0075]
3. high volume required to make up for evaporation [0076]
4. known to create animal aversion to using litter [0077]
Absorbent Agent Problems [0078]
1. differential density and particle size causing separation [0079]
2. odor releases with stress or temperature [0080]
Also, prior art litter suffers from maintaining its structural integrity wherein urine excretions in the form of a liquid stream dissolve particles, leaving a puddle of urine on the floor of the litter box. The puddle is then prevented from contact with any means of odor control in prior art litter. This uncontrollable odor generation can necessitate a change of the entire box of animal litter. Clumping agents, such as superabsorbent polymers, gums, borax and alginates, have been added to prior art animal litter to minimize this problem by increasing the integral strength and clumping ability of the prior art materials. However, such clumping agents, due to differences in their specific gravity and particle size, tend to separate from the prior art animal litter materials. As a result, the prior art litter materials with such additives create a non-homogenous end product, which does not make uniform contact with the urine and thus fails to overcome the offensive or noxious odor. [0081]
In addition to the above, another major problem encountered by the prior art animal litter materials is their potential for —dusting—. Inappropriate handling, during shipment or the action of the animals using the animal litter, creates frictional rubbing forces between the particles, which reduce particle size and generate dust. This dust can be picked up and tracked by the animal's paws and transferred to other surfaces throughout the house, such as floors and furniture. Further, handling such dust-laden animal litter exposes the environment and the user to objectionable and potentially harmful contaminants. [0082]
It has been conveniently discovered that the preferred method of the present invention animal litter for controlling or modifying odors from the deposited urine and fecal matter is by neutralization of the noxious odors. Neutralization is the permanent chemical conversion of the noxious odor into a non-toxic stable compound. The key to chemical conversion is contact of the neutralizer with the offensive odor. [0083]
The particulate form of the controlled release urethane foam product with odor control agents meets and overcomes prior art problems, particularly odors that produce objectionable olfactory sense reactions. The objectionable odors are overcome by providing agents, which react with the odors and convert them into harmless non-toxic stable chemical compounds in accordance with the following formulae: [0084]

ACID ODOR CONTROL NEUTRALIZERS

H2S + R—COONa = Na2S + NaHS

Hydrogen Salt in Odor Sodium Sodium

Sulfide Control Agent Sulfide Hydrosulfide
[0085]

ALKALINE ODOR CONTROL NEUTRALIZERS

NH3 + R—COOH = R—COONH4

Ammonia Acid in Odor Organic Salt

Control Agent
The preferred odor control agent is a proprietary amphoteric formulation using naturally occurring materials, which react with odor-causing gases of organic and inorganic materials, and converts them into odorless, stable and non-toxic compounds. It is sold in the commercial marketplace under the brand name APPTECSORB. Other odor control agents, which may operate in a different manner, such as the products sold in the commercial marketplace under the brand names ODOR-X, FEBREZE, or dio-esters from Robertet, may also be used without departing from the scope of the present invention. [0086]
The most important aspect of any odor-controlling agent is that it must be homogenously incorporated to insure contact and maximum mass transfer with the noxious odor. In addition, the litter must contain means to spread urine or other waste materials radially through the litter to prevent puddling and to insure that each formed homogenous particle will have sufficient integral strength, wet or dry, to insure that it remains dust-free during normal use. [0087]
The comminuted or sized particulate controlled release urethane polymer foam composition or product with odor-controlling agents obtained from a polymerized combination of an aqueous formulation having a limited quantity of superabsorbent polymer, at least one odor control agent from the group of acidic and alkaline odor control neutralizers, optionally and selectively at least one additive and adequate water with a predetermined ratio of hydrophilic urethane prepolymer, provides a product in which the odor control agent or agents, and additives if any, are uniformly and homogeneously disposed throughout the matrix or supporting structure of the dried and formed foam product so this product can be ground or comminuted to reduce the product to dry particles having a predetermined size in which the odor-controlling agents, if any, are uniformly and homogeneously disposed. The dry particles of this formed foam product can be packaged and sold and applied in this form for various applications and uses. [0088]
The superabsorbent polymer or copolymers in the aqueous formulation will be the same ones as above described for the earlier forms of the granular or sized particulate forms of the controlled release urethane polymer foam compositions and products and therefore requires no additional comments. [0089]
Dependent on the particular application and use, the preferred odor control agent to react with acidic, neutral or alkaline gaseous odors can be selected from a plurality of products available from APPTECSORB. Because these commercially available products are water soluble and the hydrophilic urethane prepolymer is water activated to establish the formed foam product, variable loading of the odor control agent selected is easily obtained by changing the ratio of the selected odor control agent in the aqueous formulation mixed with the hydrophilic prepolymer to establish polymerization. Thus, active loadings in a range from 0.5% to over 90% by weight of the selected odor control agent can be obtained. [0090]
The hydrophilic urethane prepolymers are also the same as those above described for the earlier form of the controlled release urethane foam products and therefor require no further description for this comminuted form of the formed foam product in accordance with the present invention. [0091]
After the solid homogeneous controlled release urethane foam product with the odor control agents, and optionally and selectively additives, has been formed and dried, it can be comminuted to a size to satisfy the particular application or use. Particle sizes generally can be in a range from 60 mesh to 4 mesh and, preferably for animal litter, about 50 mesh. However, those skilled in the art will recognize the mesh size of the particles can be smaller or larger depending on the application or use for the dry homogeneous controlled release urethane foam product. [0092]
The density of the dry formed foam product created by admixing the aqueous formulation with the hydrophilic urethane prepolymer is approximately 3 lbs./cu. ft. This density can be increased by the addition of any solid fillers which aid the particular application or use. For example, clays, feldspar, sand, ground fibers etc. may be added to the odor control agent and water of the aqueous mixture to effect higher densities. Densities approaching 50 lbs./cu. ft. have been achieved. In order to lower densities for an application where the product wants to float on water, for example, a solids filler such as hollow micro spheres such as 3M's K1 hollow glass beads may be added. Densities are selected based on the particular application or use. For example, a product used in a cat litter box may be designed to be lighter than conventional litter but not so light as to pick up on paws or tracked out of the animal litter box. Applications which do not require weight, such as those for controlling odor from vents in septic systems, are prepared with no filler additions. Solid filler additions are incorporated into the formed foam particles and will not wash out of the particles when they are saturated. To enhance this binding, a coupling agent such as silane A1120 from OSI may be utilized as an optional additive in the makeup of the aqueous formulation. If silane is used, it is added to the aqueous formulation at approximately one percent (1%) by weight of the solids filler. [0093]
The following examples will aid in demonstrating controlled release urethane foam granulated or sized particulate products in accordance with the present invention. [0094]

EXAMPLE 1

A controlled release granulated urethane foam product for use as a garbage disposal cleaner was prepared by combining a aqueous mixture containing the following ingredients by weight:



	Ingredients	Percent by Weight

	Water	46.55
	Superabsorbent HS-80	.45
	Stockhausen
	Wollastonite 325 mesh	25.00
	abrasive Nyco, N.Y
	Silane A1120 OSA	.195
	Pluronic F-88, BASF	2.00
	Color	.05
	Lauricidin Med-Chem Labs MI	.75
	EDTA Akzo Nobel	.0075
	With
	Hydrophilic urethane	25.00
	Prepolymer

The mixed aqueous and prepolymer was deposited directly onto release paper and advanced downstream till cured. Excess residual moisture was driven off in an oven at approximately 250° F., the release paper was removed and the sheet was granulated into particles of 6-14 mesh in a Cumberland grinder. The lot of foam particles was split into two halves and continued processing included: [0096]
First Lot [0097]
To the weight of foam particles was intimately blended 1% by weight of N 300A odor control Agent AppTec N.J. To this was added 3% by weight of citric acid powder. [0098]
Second Lot [0099]
To the weight of foam particles was intimately blended 1% by weight of N 300S odor control AppTec, and 10% by weight of sodium bicarbonate, Arm Hammer RTM Baking Soda. [0100]
Lots 1 and 2 were blended to provide a dry granulated particulate which, when placed into a running in-sink garbage disposal with water, would clean and disinfect the unit. [0101]

EXAMPLE 2

A controlled release urethane foam product for use as a litter material was prepared by combining a formulation containing the following ingredients by weight:



	Ingredients	Percent by Weight

	Water	30.91
	F88 Pluronic surfactant	.28
	BASF
	Feldspar filler Feldspar	46.68
	Corp.
	Silane coupling agent A1120	.49
	OSI
	Color pigment Vivitone	1.67
	Germaben II bacteriacide	.83
	Germall
	Guar gum	2.00
	Superabsorbant HS80	.48
	Stockhausen
	Prepolymer	16.66

The foam sheet was processed as in EXAMPLE 1, dried, granulated and separated by weight into two batches. To each batch was then added a 0.5% by weight of Apptec “S” or Apptec “A”, odor control agent. The difference being in the control of acidic or basic odors. The two batches were then blended together to produce a litter material to control odor, agglomerate or clump liquids, maintain wet integrity, remain dust free, be homogenous, and absorb more liquid than prior art litter. The function of the superabsorbent aids in agglomeration of liquids or semi-solids for removal. [0103]

EXAMPLE 3



	INGREDIENTS	PERCENT BY WEIGHT

	Water	54.36
	F88 Pluronic surfactant	.48
	BASF
	Feldspar filler Feldspar	20.00
	Corp.
	Silane coupling agent A1120	.20
	OSI
	V-Gum Regular thickener	1.6
	Vanderbilt
	Color pigment Vivitone	1.88
	Germaben II bacteriacide	1.00
	Germall
	Superabsorbent HS80	.48
	Stockhausen
	with
	Hydrophilic Urethane	20.00
	Prepolymer

The foam sheet was processed as in EXAMPLE 1 dried, granulated and separated into two batches. To each batch was then added a 0.5% by weight of Apptec “S” or Apptec “A”, odor control agent. The difference being in the control of acidic or basic odors. The two batches were then blended together to produce a litter material to control odor, maintain wet integrity, remain dust-free, be homogenous, and absorb more liquid than prior art litter. The function of the superabsorbent is to agglomerate liquids or semi-solids for removal. [0105]

EXAMPLE 4

A controlled granulated urethane foam product for use as a mass transfer complexing material to complex with and absorb toluene in a gas stream was prepared by combining an aqueous mixture containing the following ingredients by weight: [0106]

Ingredients Percent by Weight

1% F88 solution BASF 15.4

Ultra I Ultra One Corp. 15.4

Feldspar NC 4 Feldspar 38.5

Corp.

Hydrophilic Urethane 30.7

Prepolymer
Foam was processed by combining the first three components listed, described as the aqueous phase. The aqueous phase was then metered in a ratio simultaneously into a mix head. The mix was dispensed onto a releasable paper traversing on a movable conveyer. After foam rise and cure excess moisture was driven off in an oven at 250° degrees F. The paper was stripped off and the foam sheet was continuously fed to a Cumberland Grinder for granulation. The granulated foam was then sized through vibratory screens to separate the granules into proper mesh particles. [0107]
In use the particles were suspended onto a screen in a filter housing. An effluent gas stream laden with toluene was run through the particles and tested for breakthrough toluene at the output side of column. Test results showed that the granules of the present invention were superior to a similar volume of activated carbon. [0108]
The embodiments described in the Examples above should provide adequate details of the invention. However, it should be noted by those skilled in the art that the disclosures herein are exemplary only and that various other alternative adaptations and modification may be made within the scope of the present invention. Accordingly, the present invention in not limited by the specific embodiments of the Examples as illustrated. It is therefore to be understood that numerous modifications may be made to the illustrated embodiments of the Examples and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. [0109]

Claims

1. A controlled release comminutent urethane polymer foam product comprising the reaction composition of an aqueous formulation including, a limited quantity of absorbent polymer, at least one agent from the group detergents, soaps, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, odor absorption or control compositions and or other active ingredients such as polyoxometalates, water soluble chemicals, water emulsions, water mixtures with solid particles and adequate water with a predetermined ratio of hydrophilic urethane prepolymer whereby the at least one agent is generally dispersed uniformly throughout the foam product and slowly released or contacted with a water effluent, and the formed foam product is sized, comminutent and particles.

2. The sized comminutent and particles of the controlled release urethane polymer foam product in claim 1 including, optionally and selectively, at least one additive from the group of cellulose fibers, phase change materials, vaccines, spermicides, coloring and dyes.

3. The sized comminutent and particulate controlled release urethane polymer foam product as in claims 1 or 2, wherein the detergent is from the group of anionic, cationic, nonionic, and zwitterionic surfactants, soaps or combinations of same.

4. The sized comminutent and particulate of the controlled release urethane polymer foam product as in claims 1 or 2, wherein the wax is from the group of crystalline wax, paraffin wax, wax emulsions and silicone fluids.

5. The sized comminutent and particulate of the controlled release urethane polymer foam product as in claims 1 or 2, wherein the polish is from the group of light mineral abrasives less than 3 on the moh hardness scale and less than 20 micron particle size.

6. The sized comminutent and particulate of the controlled release urethane polymer foam product as in claims 1 or 2, wherein the drugs are from the group including animal, human, and environmental or plant species drugs, compounds or formulations of the same prepared to alleviate or control disease.

7. The sized comminutent and particulate of the controlled release urethane polymer foam product as in claims 1 or 2, wherein the cosmetics are from the group of materials made to improve or enhance the appearance such as vitamin E, retinol, aloe vera, hair conditioners, bath oils, suntan oils and U.V. protectants, etc.

8. The sized comminutent and particulate of the controlled release urethane polymer foam product as in claims 1 or 2, wherein the biologicals are from the group Monera, Protista, Fungi, Plantae or Animalia.

9. The sized comminutent and particulate of the controlled release urethane polymer foam product as in claims 1 or 2, wherein the volatiles are from the group fragrances, decongestants, insecticides and solvents, etc.

10. The sized comminutent and particulate of the controlled release urethane polymer foam product as in claims 1 or 2, wherein the odor absorbing and controlling compositions are from the group odor neutralizers, enzymatic reactive, fragrances and anti-microbials.

11. The sized comminutent and particulate of the controlled release urethane polymer foam product of claims 1 or 2 wherein the absorbent polymer is at least 0.05% by weight of the aqueous formulation.

12. The sized comminutent and particulate of the controlled release urethane polymer foam product of claims 1 or 2 wherein the at least one agent from the selected group of agents is from about 0.5% to about 40% by weight of the aqueous formulation.

13. The sized comminutent and particulate of the controlled release urethane polymer foam product of claims 1 or 2 wherein the water present is in a range from about 15% to about 85% by weight of the aqueous formulation.

14. The sized comminutent and particulate of the controlled release urethane polymer foam product of claims 1 or 2 wherein the hydrophilic urethane prepolymer is about 0.25% to 80% by weight of the aqueous formulation.

15. A controlled release urethane polymer foam product comprising the reaction composition of an aqueous formulation including, at least less than 0.5% by weight of a absorbent polymer, at least one agent from the group detergents, soaps, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, odor absorbing and control compositions, and or other active ingredients, water soluble chemicals, water emulsions, water mixtures with solid particles in an amount from 0.5% to about 40% by weight of the aqueous formulation and water in an amount of 15% to 80% by weight of the aqueous formulation with a hydrophilic urethane prepolymer in a predetermined ratio in a range from 0.25% to 80% of the aqueous formulation whereby the at least one agent is dispersed throughout the matrix of the formed controlled release urethane foam product and slowly released on contact with a water effluent and the foam matrix is as formed by sized comminutent or particles.

16. A sized comminutent and particulate of the controlled release urethane polymer foam product as in claim 15, where the aqueous mixture includes at least one surfactant in an amount from 0.5% to 15% by weight of the aqueous mixture.

17. A controlled release urethane polymer foam product comprising:

a. the reaction composition of an aqueous formulation including, a limited quantity of absorbent polymer, at least one agent from the group detergents, soaps, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, odor absorbing and control compositions and or other active ingredients, water soluble chemicals, water emulsions water mixtures with solid particles and adequate water with a predetermined ratio of hydrophilic urethane prepolymer whereby the at least one agent is generally dispersed uniformly throughout the matrix of the formed controlled release urethane foam product and slowly released on contact with a water effluent; and

b. at least one addition from the group of abrasives material, and

c. the formed foam matrix is sized comminuting and particles.

18. The sized comminutent and particulate of the controlled release urethane polymer foam product in claim 17, including, optionally and selectively, at least one additive from the group of cellulose fibers, phase change materials, vaccines, spermicides, coloring and dyes.

19. The sized comminutent and particulate of the controlled release urethane polymer foam as in claims 17 or 18, where the aqueous formulations includes at least one surfactant in an amount from 0.5% to about 15% by weight of the aqueous mixture.

20. The controlled release urethane polymer foam product comprising:

a. the reaction composition of an aqueous formulation including, at least less than 0.5% by weight of a superabsorbent polymer, at least one agent from the group detergents, soaps, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, odor absorption or control compositions, and other active ingredients, water soluble chemicals, water emulsions, water mixtures with solid particles in an amount from 0.5% to about 40% by weight of the aqueous formulation and water in an amount of 15% to 80% by weight of the aqueous formulation with a hydrophilic urethane prepolymer in a predetermined ratio in a range from 0.25% to 80% of the aqueous formulation whereby the at least one agent is dispersed throughout the matrix of the formed controlled release urethane foam product and slowly released on contact with a water effluent; and

b. said formed controlled release urethane foam product is formed from predetermined sized comminutent and particle.

21. The controlled release comminutent urethane polymer foam product as in claim 20, wherein the granules and particle sizes are in a range from 0.010-0.500 inches diameter.

22. The controlled release urethane polymer foam product as in claims 20 or 21, wherein the density of the formed controlled release urethane foam sized comminutent and particles product is adjusted by solid fillers in amounts by weight and in ratio to the weight of the aqueous formulation.

23. The controlled release urethane polymer foam product as in claim 22, wherein the density of the formed controlled release urethane foam sized comminutent and particulate product is adjusted in a range from 1.5 lbs/cu. ft. to about 60 lbs/cu. ft. by adding solid fillers by weight and in ratio to the aqueous formulation.

24. The controlled release urethane polymer foam product as in claim 22, wherein the solid filler is selected from the group diatomaceous earths, feldspar, wollastonite or clay for higher densities and glass micro spheres for lower densities as a function of the required applications and uses.

25. The controlled release comminutent urethane polymer foam product as in claim 17 wherein the aqueous formulations contain solid particles, the solid particles are from the group of abrasives including natural materials.

26. The method for forming comminuted controlled release urethane polymer foam products comprising the steps of:

a. metering and mixing an aqueous formulation having at least a limited quantity of absorbent polymer, at least one agent from the group detergents, soaps, abrasives, waxes, polishes, drugs, cosmetics, biologicals, volatiles, odor absorbing and controlling compositions, water soluble chemicals, water emulsions, water mixture with solid particles and adequate water with a predetermined ratio of hydrophilic urethane prepolymer to provide a polymerizing mixture for forming the controlled release urethane foam product;

b. depositing the polymerizing mixture on releasable bottom paper disposed on a movable carrier;

c. covering the upper surface of the polymerizing mixture with releasable top paper as the polymerizing mixture is moved with the carrier;

d. advancing the polymerizing mixture in the top and bottom release paper by moving the carrier and sizing the foam layer being formed to the desired thickness until it is tack free;

e. sequentially removing the top and bottom release paper while simultaneously drying the formed foam product to remove residual moisture; and

f. passing the formed controlled release urethane foam product to secondary operations of comminuted the formed controlled release urethane polymer foam product into sized granules and particles for particular applications and uses.