HK1131591A

HK1131591A - Composition and articles containing cross-linked polymer matrix and immobilized active liquid, and methods of making same

Info

Publication number: HK1131591A
Application number: HK09111200.4A
Authority: HK
Inventors: 马克‧史丹利‧帕夫林
Original assignee: 阿利桑那化学公司
Priority date: 2006-12-19
Filing date: 2007-12-19
Publication date: 2010-01-29

Description

Compositions and articles containing a crosslinked polymer matrix and immobilized active liquid, and methods of making and using the same

Technical Field

The present invention relates to compositions and articles comprising a polymer matrix and an immobilized active liquid, and methods of making and using the same.

Background

Curing and/or crosslinking of polymer systems, such as Epoxy systems, is described in textbooks and in Industry manuals, for example "Handbook of Epoxy resins" by Henry Lee and Kris Neville (McGraw Hill, 1967), "The Epoxy formulations Manual" by Society of Plastics Industry, Inc. (1984), and Encyclopedia of Science and Technology (Kirk-Othmer, John Wiley & Sons, 1994). Until recently, it has been very difficult to cure such systems and other systems associated therewith, such as those with and/or containing fragrances, in a manner that would enable the active liquid to set, especially when durability and performance of such systems under a dynamic range of operating conditions is required.

For example, JP 032558899A requires the use of a solid powder system, whereas JP07145299 requires the use of a preformed urethane-containing epoxy resin which is crosslinked in the absence of polyamines and/or fragrance-containing active liquids. Furthermore, the JP references mentioned above refer specifically and exclusively to perfumed articles, such as air fresheners. The reactions and reaction products described herein do not have the properties of dynamic range due to the narrow goals of making such articles. Furthermore, they do not provide a product that is durable without a support. Thus, there is a need for controlled reaction conditions that produce a dynamic reaction product containing a persistent matrix that is capable of immobilizing any and/or all types of reactive liquids therein.

Compositions such as perfumed objects, and even in particular air fresheners, are well known devices for releasing perfume into the air in a room of a house, an area of a public building (e.g., a toilet), or the interior of a car, to make the air in that area more pleasant to the occupants. Only substantially non-aqueous gels, such as the thermoplastic polyamide-based products described in US 6,111,655 and 6,503,577 and the thermosetting poly (amide-acid) described in US5,780,527 and US 6,846,491, are homogeneous, transparent solids that can be easily loaded into molds in liquid form and thereby formed into visually appealing solid shapes without the use of supports. However, in the preparation of thermoplastic gels, these components must be heated to a temperature above the gelation temperature of the mixture, a procedure that is detrimental to volatile and sometimes temperature sensitive active liquids such as fragrances, insecticides, or surfactants. These gels must not be exposed to low temperatures during storage or use, as they can turn unsightly hazy. In addition, these gels must not be exposed to high temperatures, as they will become liquid, lose their shape, or leak from their containers. These disadvantages are serious for air fresheners, such as car interior fresheners, that require exposure to a dynamic range of temperatures. Automotive interior fresheners are often exposed to low temperatures in winter, and often to temperatures in excess of 110 ° F when the automobile is parked directly in the sun. In addition, these thermoplastic gels are soft solids that are easily deformed if scratched, dropped, pricked, or wiped. Thus, these conventional gels do not provide compositions and/or articles that are easily durable and capable of operating over a wide range of operating parameters.

Disclosure of Invention

The inventors of the present invention have found a more efficient solution providing a thermoset, i.e. cross-linked, polymer matrix containing a homogeneous distribution of immobilized active liquid that is durable and stable over a wide range of use conditions.

It is an object of the present invention to provide a reaction product simply obtained by mixing a compound having at least one, preferably at least two, functional groups selected from the group consisting of epoxy, isocyanate, anhydride and acrylate with a polyamine in the presence of an effective amount of a reactive liquid.

It is another object of the present invention to provide compositions comprising the reaction product obtained by mixing a compound having at least one, preferably two or more, functional group selected from the group consisting of epoxy, isocyanate, anhydride and acrylate with a polyamine in the presence of an effective amount of a reactive liquid, and articles comprising the reaction product. By way of non-limiting example, the article may be an air freshener, a laundry fragrance sheet, a laundry fabric softener sheet, a laundry antistatic sheet, a storage fragrance article, a pharmaceutical composition, a neutraceutical (neutraceutical) composition, a bioneutraceutical (bioceutical) composition, an anti-mold (mold) composition, a bactericide composition, a pesticide composition, a decorative article, a biomedical sensor, and/or an analytical instrument. Methods of making the above-described reaction products, compositions and/or articles are also further objects of the present invention.

One aspect of the present invention optionally relates to the solution when the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride and acrylate, and a polyamine in the presence of a reactive liquid and a reaction rate modifier (e.g., an accelerator (i.e., a catalyst) or a retarder). Other embodiments include methods of making and using such compositions and articles.

It is a further object of the present invention to provide compositions and/or articles comprising a cured polymer matrix and a reactive liquid wherein the reactive liquid is uniformly immobilized within the cured polymer matrix and the cured polymer matrix is the reaction product of mixing a compound having at least two non-aromatic isocyanate functional groups. Other embodiments include methods of making and using such compositions and articles.

It is a further object of the present invention to provide compositions and/or articles containing a cured polymer matrix and a reactive liquid wherein the reactive liquid is uniformly immobilized within the cured polymer matrix and the cured polymer matrix is the reaction product of mixing a compound having at least one but preferably more than one isocyanate functional group with a polyamine and the polyamine is a polymer terminated by residues from an aminobenzoic acid molecule. Other embodiments include methods of making and using such compositions and articles.

It is a further object of the present invention to provide a composition and/or article comprising a cured polymeric matrix and a reactive liquid, wherein the reactive liquid is immobilized within the cured polymeric matrix and the cured polymeric matrix is the reaction product of a liquid comprising a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine-containing liquid in the presence of the reactive liquid and water. Other embodiments include methods of making and using such compositions and articles.

It is a further object of the present invention to provide compositions and/or articles comprising a cured polymer matrix and a reactive liquid, wherein the reactive liquid is immobilized within the cured polymer matrix and the cured polymer matrix is the reaction product of mixing a liquid comprising a compound having two or more isocyanate functional groups with a polymeric polyamine in the presence of the reactive liquid; wherein the polymeric polyamine has an amine value of 1 to 100meqKOH/g and has a viscosity of no more than about 500cP measured at 150 ℃. Other embodiments include methods of making and using such compositions and articles.

It is a further object of the present invention to provide compositions and/or articles comprising a cured polymeric matrix and a reactive liquid, wherein the reactive liquid is immobilized within the cured polymeric matrix and the cured polymeric matrix is the reaction product of mixing a liquid comprising a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate with a polyamine in the presence of the reactive liquid or water or mixtures thereof; wherein the polyamine is a liquid at room temperature. Other embodiments include methods of making and using such compositions and articles.

It is therefore another object of the present invention to provide a transparent, flexible, and stable solid useful in air care, therapeutic, insecticidal, nutritional, surface treatment products, and other products prepared by uniformly immobilizing an active liquid within a polymer matrix by reaction of a liquid polyepoxide or polyisocyanate compound with a liquid polyamine. In addition, it is another object of the present invention to provide air care, therapeutic, nutritional, surface treatment and pesticidal products prepared therefrom which overcome the disadvantages of the heretofore known compositions of this general type.

With the above objects in view, there is provided in accordance with the present invention a process for the preparation of air care, therapeutic, neutraceutical and biocidal compositions and other useful articles. The method comprises uniformly immobilizing an active liquid, such as a fragrance oil, insecticide, surfactant, drug, nutraceutical, surfactant, tracer dye, or other active volatile or non-volatile liquid, in a cross-linked matrix selected from the reaction product of a polyamine and a liquid polyepoxide or liquid polyisocyanate material, the reaction being carried out in the presence of the active liquid. Products of the type described can be prepared by the following steps: (1) blending the polyamine, the active liquid, and any desired optional components including diluents, plasticizers, fillers, stabilizers, and colorants; (2) blending the mixture and a polyepoxide or polyisocyanate component optionally diluted with additional amounts of plasticizers, fillers, stabilizers, and colorants; (3) pouring the final blend into the form of a sheet or plate or into a support, form, container, or mold; (4) optionally covering or sealing the poured blend to prevent it from being contaminated and to prevent evaporation of the volatile components; (5) optionally storing it until the blend is cured; and (6) optionally removing the cured, fixed liquid article from the sheet, plate, form, container, or mold and cutting it into shape or using it in a form prepared in the container.

One invention of the present application relates to providing a solid air freshener that is transparent or nearly transparent (e.g., "matte") and robust and visually appealing, particularly a room, drawer, bag, container, area, or car interior freshener. According to this object of the invention, the active liquid is a fragrance composition (i.e. a perfume oil, perfume or essence). By "strong" is meant that the article can be inexpensively packaged and handled without deformation. The composition containing the fragrance material may be supported (i.e. located within a container or support) or free-standing. In particular, no special care is required when the air freshener is removed from its packaging or packaging material. Furthermore, the air freshener according to the invention is intended to withstand changes in temperature, humidity and exposure to light throughout its service life, or, in the case of reasonable protection thereof using suitable packaging, is intended to withstand changes in temperature, humidity and exposure to light throughout its storage and service life. The air care composition is substantially free of dehydration condensation (also known as "sweating"). The base material of the product is effectively non-toxic and does not cause irritation to the skin if treated outside of its packaging material. The air care compositions of the present invention are conveniently suitable for, but do not require the use of, porous powders, fabrics or fibers as a support for the perfume oil.

Another aspect of the invention is: the components of the article may be rendered water insoluble without losing any of the desired end properties of the article (e.g., perfume release, stability) so that if water is added to the cross-linked composition, the water may optionally be used for some suitable purpose, such as causing shrinkage to indicate end of life or introducing a water soluble active ingredient such as a dye or salt.

According to another object of the invention, the active liquid may be and/or contain a biologically active material such as a deodorant, germicide, sanitizer, insecticide, insect repellent, or pheromone. For the latter four cases, the product will be a pest control device.

According to another object of the invention, the active liquid may be and/or contain a surface treatment agent such as a sizing, a cross-linking or catalytic substance, a surfactant, a coloring or other coloring agent or dedicated dye, a fabric softener or a lubricant.

According to another object of the invention, the active liquid may be and/or contain a therapeutic, neutraceutical, and/or neutraceutical agent. As such, the invention may relate to a device, such as a patch (batch), for transporting a biomedical product to a human and/or animal patient, or to a device, such as a bait, for attracting an animal to a trap or hook.

According to another object of the invention, the active liquid may be and/or contain biopolymers such as DNA, RNA, and/or proteins, and/or carbohydrates and/or steroids. All protected precursors thereof are contemplated by the present invention. Thus, the present invention relates in part to a bioanalytical article and/or biosensor for the diagnosis of patients, test targets and/or environmental factors.

According to another object of the invention, inert solid materials can be incorporated to make them more attractive and/or useful. Examples of such materials include, but are not limited to, flakes, filings, glitter, foil, mica beads or flakes, metal, plastic, shell or glass, polycarbonate flakes, glass beads, or natural materials such as coffee powder. A possible application of the product containing natural materials is as a novel coffee coaster. The material may be a transparent plastic film pre-printed with a design or logo. Other useful solid objects that may be added are magnets to allow the crosslinked article to adhere tightly to the metal surface. Other useful solid objects that can be added are pest bait materials such as sugar, peanuts, protein powder and salt.

The invention also includes a method. The method comprises the following steps: blending a reactive liquid such as a fragrance or insecticide, a liquid polyepoxide, a polyanhydride, or a polyisocyanate compound (referred to herein simply as "epoxy", "anhydride", or "isocyanate") and a liquid or low-melting polyamine, preferably at or near room temperature; pouring the mixture into a mold or porous support or into a sheet; optionally sealing the uncrosslinked (e.g. uncured) or partially crosslinked article in an impermeable foil or film or container to prevent loss of any active ingredient, and leaving the mixture undisturbed at room temperature or optionally at higher temperatures until it has been crosslinked (e.g. cured). The thermoset solid formed can be used as a component in a device for releasing an active component into the environment, where the rate of release depends on a number of factors, including the geometry of the product, the size of the exposed surface, the temperature surrounding it under conditions of use, the air flow and moisture movement, the wear of the product in use, and the concentration in the active liquid formulation.

Immobilizing an active material in the compositions and/or articles of the present invention provides a number of advantages, wherein the active liquid is immobilized within a cured polymer matrix and the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of the active liquid, which advantages may include any one or more of the following:

■ the heat sensitive oil need not be heated;

■ high loadings of active liquid in the product that can be used are possible;

■ the product components can be liquids that can be easily blended together using simple equipment;

■ the curing reaction does not require external reagents to initiate, does not produce volatile by-products that may cause bubbles, and occurs uniformly throughout the reactants;

■ shrinkage of the blend during curing is less likely to occur;

■ if not filled, the product is transparent;

■ a product component with little odor, color and toxicity is obtained;

■ product has excellent durability, is insoluble in water, and does not melt;

■ product does not adhere to any plastic packaging material and therefore can be wrapped in a material that is not a specialized release film;

■ the viscosity of the cured product can be adjusted so that the product is not tacky or is sufficiently tacky to temporarily stick to a vertical surface, such as a window;

■ the product can be easily colored with dyes and pigments; and/or

■ the fluid pre-solidified liquid completely fills the mold so that details are also captured as part of the final product, such as embossed logos or decorative designs.

Other features which are considered as characteristic for the invention are described herein and are set forth in the following claims.

Although illustrated and described herein as a process for preparing compositions and articles, such as clear, soft, and stable compositions, by immobilizing an active liquid within a cross-linked matrix, the present invention is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.

The polymer matrix immobilized active liquids can be used as air care, pest control, laundry care, treatment or other devices because they release the active ingredient into the surrounding environment. The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying examples and claims.

Detailed Description

The present invention relates to compositions and/or articles comprising a cross-linked polymer matrix and an active liquid, wherein the active liquid is homogeneously (i.e., homogeneously) immobilized by or within the matrix. The invention also relates to a method for immobilizing an active liquid within a polymer matrix. Furthermore, the present invention relates to a method for preparing a stable solid composition and/or article comprising a polymer matrix and an active liquid, wherein the active liquid is immobilized by the polymer matrix. The active liquid may be a solution of the active ingredient in a carrier liquid or may be inherently active. The carrier liquid may be an organic liquid or water.

The crosslinked polymer matrix is the reaction product of a compound having at least one, and preferably two or more, functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine compound in the presence of a reactive liquid. If present and compatible with the matrix, water will become part of the immobilized liquid. If present but not compatible with the matrix, the water may be trapped by the matrix and the immobilized liquid phase or suspended in the matrix/immobilized liquid phase as a dispersion of particles.

Although with preferably two orThe compound of multiple epoxy functional groups may be any epoxy, but it is preferably in liquid form. Although examples of Epoxy-containing compounds of The present invention can be found in "Handbook of Epoxy resins" of Henry Lee and KrisNeville (McGraw Hill, 1967), "The Epoxy formulations Manual" of Society of plastics industry, Inc. (1984), and Encyclopedia of science and Technology (Kirk-Othmer, John Wiley&Sons, 1994), specific examples of liquid epoxy resins that can be used in the present invention are, but are not limited to, the substances listed below. The examples used the following ingredients:828 (diglycidyl ethers of bisphenol A and F (available from resolution Performance Products, Inc.)828 and8620 commercially available), hydrogenated glycidyl ether of bisphenol A (which may be obtained as5000 and5001 Products commercially available from CVE specialty Chemicals including hydrogenated glycidyl ether of bisphenol A), butanediol glycidyl ether, cyclohexanedimethanol, neopentyl glycol, dimer acid, and trimethylolpropane (all of which are available from resolution Performance Products as their ProductsModifier product series).

The above epoxy-containing compounds are merely representative, and many other epoxy-containing compounds may be used in the present invention.

While the compound having preferably two or more anhydride functional groups may be any polyanhydride, it is preferred that it be in liquid form and not a maleic acid-based polyolefin rubber. More specifically, preferred anhydrides are solid polymers dissolved in a suitable carrier liquid, said polymers being selected from:

(a) maleic acid-based olefin polymers other than maleic acid-based rubbers such as polybutadiene or poly (isobutylene);

(b) olefin-maleic anhydride copolymers; and

(c) an alternating alpha-olefin-maleic anhydride copolymer,

specific examples of suitable anhydride-functional polymers of the present invention are styrene-maleic anhydride copolymers such as are available from NOVA Chemicals232 and332 and poly (1-octadecene-alt-maleic anhydride) available from Chevron Corporation. These anhydride-containing polymers are representative, and many other anhydride-containing polymers are suitable for use in the present invention.

While the compound having preferably two or more isocyanate functional groups may be any polyisocyanate, it is preferably a compound having a liquid form. Specific examples of the isocyanate-containing compound of the present invention may be any aliphatic difunctional isocyanate material, including liquid diisocyanates such as isophorone diisocyanate and bis (4-isocyanatocyclohexyl) methane. Preferred polyfunctional isocyanates have low volatility and thus reduced toxicity. An example thereof is available from Bayer Corporation, Industrial Chemicals DivisionThose available under the trade names of (1), includingBut are not limited toN-series aliphatic isocyanurates, in particularN-3300、N-3600 andn-3800, andz-series, especiallyAnd Z4470. The above-mentioned isocyanate-containing compounds are merely representative and many other isocyanate-containing compounds may be used in the present invention.

As will be discussed further below, the isocyanate functional groups react with the amine functional groups significantly faster than the epoxy functional groups, so that polyamine compounds suitable for crosslinking reactions with isocyanates are not necessarily suitable for use with epoxies. The preferred polyamine compounds of the present invention for reaction with epoxy functional compounds are liquids at 25 ℃, are soluble and compatible with many reactive liquids, have a viscosity of no more than about 100cP measured at 100 ℃, and have an amine value of 100-1200meq KOH/g. The amine number may be 100, 200, 500, 750, 1000, and 1200meq KOH/g, including any and all ranges therebetween and subranges therebetween. Preferred polyamines are, but not limited to: 1, 2-diaminocyclohexane, isophoronediamine, m-xylylenediamine, 1, 3-bis (aminomethyl) cyclohexane (1, 3-BAC). Particularly preferred are poly (alkylene oxide) polyamines (also known as polyether amines) which are liquid at 25 ℃ and comprise polyether segments such that more than 50% by weight of the amine is derived from oligomeric ethylene oxidePolyethers of propylene oxide, butylene oxide or tetrahydrofuran or combinations of the foregoing, such as supplied by Huntsman Corporation and BASF Corporation. Examples thereof areD-230, D-400, D-2000, T-5000, T-403 and XTJ 511, XTJ-511, all of which are polyether diamines (supplied by Huntsman Corporation). The liquid polyamine may also be selected from the family of polyamido-amines, examples of which are sold by Arizona ChemicalA series of amido amide-amine curing agents. These materials are known to impart adhesion and have reduced skin sensitivity. The amine may be a mixture of two or more blended polyamines to optimize viscosity, reaction rate and product performance.

Preferred polyamine compounds of the present invention for reaction with isocyanate functional compounds are materials having a macromolecular backbone comprising repeating monomer units that are capped with amine groups that are not part of the monomer units. Furthermore, the polymeric polyamine is preferably liquid below 50 ℃, such as a liquid amine or a low melting amine. More preferably, the polyamine is liquid at ordinary temperature. According to the present invention, the polyamine has a melting or softening point of less than 50 ℃, including up to 50 ℃, 45 ℃, 40 ℃, 30 ℃, 20 ℃ and 10 ℃, including any and all ranges and subranges therebetween. Most preferably, the polyamine is a liquid and/or viscous and/or semi-solid below 10 ℃.

Preferred polymeric polyamines are soluble and compatible in many active liquids, have a number average molecular weight greater than 1000, have an amine value of 10-100meq KOH/g, and have a viscosity of no more than about 500cP measured at 150 ℃. The amine number may be 10, 25, 50, 75, or 100meq KOH/g, including any and all ranges therebetween and subranges therebetween. Also, the amine may have a viscosity of no more than about 500cP measured at 150 ℃. The viscosity of the amine measured at 150 ℃ may be about 450, 350, 250, 150, and 100cP, including any and all ranges therebetween and subranges therebetween.

The most preferred polymeric polyamines for reaction with the isocyanate functional compounds of the present invention are polyamide polyether block copolymers obtained by reacting one or more polyalkylene oxide polyamines with one or more aliphatic polyacids, as described hereinafter and in the examples section of this application. These ether polyamide polyamines (or "PAPAs") useful in the present invention may be prepared by reacting a polyacid or mixture of polyacids with a stoichiometric excess of a polyether polyamine mixed with an optional lower diamine including piperazine, ethylenediamine, isophoronediamine, hexamethylenediamine, 2-methyl-1, 5-pentanediamine, and the like. Preferred polyacids for use in preparing PAPA are adipic acid, azelaic acid (azeleic acid), sebacic acid, dodecanedioic acid, or other aliphatic diacids or ester equivalents thereof. The use of polyazic acid and a large amount of poly (alkylene oxide) polyamine (determined as more than 50% of all amine equivalents present) ensures that the resulting polyamide has excellent solubility in a variety of liquids, including water in particular cases. The amine value of the PAPA, which is measured by titration with dilute hydrochloric acid (diluteolic hydrochloric acid) and expressed as mg KOH/g of sample, should be less than 100, preferably less than 80mg KOH/g, most preferably less than 70mg KOH/g, is also important for proper reactivity of the matrix component.

Another preferred PAPA of the present invention is polymerized fatty acid (also known as dimer acid, manufactured by Arizona Chemical Company under the trade name ″)"sold, by Unichema corporation and under the trade nameIs "sold" and is manufactured by Cognis CorpManufactured by corporation under the trade name"materials sold") with a stoichiometric excess of one or more poly (alkylene oxide) polyamines selected from Huntsman polyamines such that at the completion of the reaction, the polymeric polyamine product is liquid at room temperature, has an acid number of less than about 5 and an amine number of from about 10 to about 70, and has a viscosity of less than 500cP measured at 150 ℃Polyamines, including for example D-400, D-2000, T-403, and XTJ-500. The most preferred PAPAs are liquid at room temperature, have an acid number of less than about 2 and an amine number of 20-60, and have a viscosity of less than 300cP at 150 ℃. Thus, for example, particularly preferred polymeric polyamines are obtained by reacting at 215 ℃ under a purge of dry nitrogen until the acid number is reduced to about 1.0 and the amine number is adjusted to about 30-40:1009 hydrogenated dimer acid, 29.5 wt.%;d-2000, 44.5 wt%;d-400, 22.5 wt%; andt-403, 3.5% by weight (see example #21 below). The material is a viscous liquid at room temperature having a viscosity of about 100 at 130 ℃ and a weight average molecular weight of about 25000.

The reaction rate for forming the matrix of the present invention varies with the type of amine present at the end of the polymeric polyamine component. The shortest curing time is obtained using compounds in which the polymer chain ends with a primary or secondary aliphatic amine. Hindered amines that are partially substituted by bulky groups such as t-butyl react more slowly. The longest cure times are obtained using polymeric polyamines that are capped with a specific type of aromatic amine with a carbonyl group, particularly an ester or amide group, or other strong electron-withdrawing group on the aromatic ring. While it is contemplated that carbonyl-substituted aromatic amines may be used in the reaction with any of the functional groups of the present invention, the aromatic amines are particularly useful when the functional group is a highly reactive isocyanate functional group.

Although any of the terminal carbonyl-substituted aromatic amines are believed to be suitable, non-limiting examples of preferred polyamines include those derived from para-aminobenzoic acid and ortho-aminobenzoic acid. These compounds are readily introduced into the polyamine termini described herein by reaction with specific polyamines and specific diacids. Preferred PAPAs of the invention are polymers obtained by reacting any of the above diacids and ether diamines in the presence of p-aminobenzoic acid and/or anthranilic acid. For example, a particularly preferred PAPA is obtained by reacting the following at 215 ℃ under a purge of dry nitrogen until the acid number drops to about 1.0 and the amine number is adjusted to 15 by non-potentiometric titration and to 30-35 by potentiometric titration:1009 hydrogenated dimer acid, 24.0 wt.%;d-400, 11.5 wt%; andt-403, 5.5% by weight (see example #36 below). The material was a viscous liquid at room temperature having a viscosity of about 250cP at 130 ℃ and a weight average molecular weight of about 13000 daltons.

In all of these PAPA embodiments, the weight average molecular weight (Mw) and/or number average molecular weight (Mn) of the PAPA may be as high as desired, but limited by the desired amine value and viscosity. For example, the Mw is preferably 5,000-35,000, more preferably 10,000-30,000 daltons. Thus, the degree of polymerization can be any number, but desirably is greater than 1.5 and less than 6, preferably 2.0 to 4.0, including any and all ranges and subranges therebetween.

Co-diacid and co-diamine may be used in small amounts, i.e., less than 50% on an equivalent basis, in preparing the PAPA of the present invention, so long as the desired properties of the PAPA are obtained. The co-diacid can be, for example, adipic acid and similar linear aliphatic diacids. The co-diamine can be, for example, ethylenediamine, piperazine, 1, 2-diaminocyclohexane, isophoronediamine, 1, 3-bis (aminomethyl) cyclohexane, dimer diamine (e.g.,551) hexamethylene diamine, 2-methyl-1, 5-pentamethylene diamine, and similar linear, branched and cyclic aliphatic diamines. The polyamidation (polyamidation) reaction can be carried out in the presence of catalysts known to increase the rate of reaction, such as acids, especially p-toluenesulfonic acid, phosphoric acid and sulfuric acid, by applying a vacuum to remove the water of reaction.

PAPAs (e.g., low melting polyamines) that are not liquid at room temperature but solid at room temperature and are compatible with the active liquids of the present invention are feasible in the present invention. Such a PAPA is prepared from a majority of diacid moieties of 1, 4-cyclohexanedicarboxylic acid with a stoichiometric excess of a polyamine (a majority of which is a poly (alkyleneoxy) polyamine selected from Huntsman polyaminesPolyamines including, for example, D-400, D-2000, T-403, and XTJ-500) such that after completion of the reaction, the PAPA is a solid at 25 ℃, has an acid number of less than 5 and an amine number of about 10 to about 70, and has a Ring below 50 ℃&Ball softening point. For these polyamides, the dimer acid may optionally be combined with other co-diacids such as those mentioned aboveThose are used together as a co-diacid. Co-diamines are also optional and undesirable ingredients because they are present at even low levels sufficient to raise the softening point of the resin above 50 ℃.

The polymeric polyamines of the present invention may also be those described in U.S. Pat. Nos. 6,870,011 and 6,399,713 and U.S. patent application Ser. No. 10/395,050, all of which are incorporated herein by reference in their entirety.

The active liquid of the present invention may be any liquid that imparts functionality to the formed composition and/or article. That is, the active liquid may be a volatile and/or non-volatile organic liquid or semi-solid or a solid dissolved in a carrier liquid (diluent). Examples of such active liquids include perfume oils, surface treatment chemicals, neutraceuticals, pharmaceuticals, radiotracers, pesticides, and surfactants.

One non-limiting example of an active liquid is a perfume oil (also known as perfume or fragrance). The flavor oil can be any blend of a variety of aromatic chemicals and aromatic natural oils known to those skilled in the art. Some of the types of chemicals that can be used in the present invention are esters such as linalool acetate and butyl acetate (present in banana oil), phenols such as methyl salicylate (present in wintergreen oil), esters such as 1, 8-cineole (present in eucalyptus oil), alcohols such as geraniol (present in rose oil), aldehydes such as cinnamaldehyde (present in cinnamon oil), and ketones such as menthone (present in spearmint oil).

Specific examples of hundreds of commercially available perfume oils that may be used in the present invention are "Ocean" (N-123-03), "countryWildflower" (N-122-03), "Spring Meadow" (N-124-03), and "moving Rain" (Q-119-03), supplied by continuous industries of Hawthorne, NJ; "Evergreen" (#42441) and "Green Apple" (#50520) supplied by Belle arms of Mundelein, IL; "Cherry" (#124559), "Vanilla" (#122745), and "Mulberry" (#124561) supplied by Aromatic Fragrances and Flavrors International of Marietta, GA; "Garnet" by International Fragrances Technology, Inc. of Canton, GA (# 242926); and "Crisp Breeze", "nutritional Fragrance", "Oceanside Mist" supplied by Atlas Products of Tinley Park, IL. A list of these examples is provided below.

There are hundreds of commercially available perfume oils from a large number of suppliers. The present invention is not limited to any particular fragrance, but the list provided below illustrates a number of selected oils that can be used to prepare the fixed oils of the present invention and to achieve the dynamic operability of the polymer matrix of the present invention:

the active liquid may be used at a level that imparts efficacy to the composition for the intended application. The active ingredient may be of very potent efficacy and need to be present only at very low levels, possibly less than 0.1%, but must be immobilized as an active liquid by dilution with a carrier liquid in accordance with the present invention. In this case, the active liquid may be said to be a solution of the potent agent in the carrier. With this in mind, the active liquid (or potent agent dissolved in a carrier) may be used in the compositions and/or articles of the present invention in an amount of from about 1% (for small loads) to about 90% or more. The loading is of course a function of the particular active liquid, the polymer matrix and any other compounds present. It may also depend on the final configuration of the formed product, i.e., whether the formed product is free-standing, contained, or supported. The active liquid may be used in an amount of 1, 2, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, or 90%, including all ranges and subranges therebetween.

By way of non-limiting example, the preferred amount of perfume oil for use in air fresheners is about 15-75% and most preferably 30-70% by weight, based on the weight of the final article, without calculating the weight of any embedded object. The amount of perfume oil may be 15, 20, 25, 30, 40, 50, 60 and 75% by weight of the composition (not counting the weight of any support or embedded object), including all ranges and subranges therebetween. The non-reactive diluent or plasticizer may be present in an additional amount such that the total amount of liquid may be from about 20% to about 90% by weight of the composition, preferably from about 40% to about 80% by weight of the composition.

Similarly, the mixture of reaction components, reactive liquid and optional liquid, while still uncured, may be dispersed in water or other aqueous medium and the resulting oil-in-water emulsion may be stabilized by means of a surfactant. The droplets of the composition of the present invention are thus emulsion solidified. The result is a dispersion of solid immobilized active liquid particles in water. The surfactant may be anionic, cationic or nonionic. Examples are the anionic salts sodium lauryl sulfate; cationic quaternary ammonium salts di (hydrogenated tallow) dimethyl ammonium chloride, cocamidopropyl betaine, and dibenzyl dimethyl ammonium chloride; and a nonionic polyethoxylated sorbitan monooleate. Such emulsions are milky liquids and are themselves capable of penetrating into porous media such as paper, cardboard, cellulose pads, cellulose pulp, blankets, fabrics, porous synthetic foams, porous ceramics, activated carbon, soil, diatomaceous earth (diatomaceous earth), diatomaceous earth (kieselguhr), charcoal, silica, clay, and the like or coated onto non-porous substrates including, but not limited to, plastic films, metal foils, rubber, ceramics, wood, glass, and leather.

The surfactant compound may itself be an active compound of the invention when used in excess as needed to stabilize the gel dispersion. They may be used with or without water. The surfactants thus immobilized are slowly released into their environment of use, together with the perfume or other active ingredient, and can therefore be used, for example, as toilet air fresheners/cleaners, insecticides/disinfectants, or as fabric softeners for dryers in liquid form or, if impregnated into a porous medium, in sheet form.

The active liquid of the present invention may be a liquid insecticide or a solid insecticide dissolved in a carrier liquid. A pesticide is any substance or mixture of substances intended to prevent, destroy, repel, or reduce any organism that causes or may cause damage to or distress people, valuable animals (e.g., livestock), or valuable plants (e.g., flowers, trees, and food crops).

The pesticide may be a chemical or biological agent (e.g., a virus or bacterium) used to control food competition with humans, destroy property, transmit disease and nuisance insects, phytopathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microorganisms. Since many pesticides are toxic to humans, it is useful to control their application and release, for example, by dissolving them in a non-hazardous carrier liquid and then immobilizing them with the matrix of the invention.

The pesticide may be natural or synthetic. Among the synthetic insecticides are the following:

1. organic phosphates. These insecticides affect the nervous system by interfering with enzymes that regulate acetylcholine (neurotransmitter). They are generally not persistent in the environment. Immobilization enables them to be effective for longer periods of time without compromising the environment.

2. A carbamate ester. They also affect the nervous system by interfering with enzymes that modulate acetylcholine.

3. An organic chloride. They have been common in the past, but many have disappeared from the market due to their impact on health and environment and their persistence (e.g., DDT and chlordane).

4. A pyrethroid. They have been developed as a naturally occurring pyrethrin composition. The compositions are modified to increase their stability in the environment and to reduce their cost.

Some insecticides are derived from natural sources such as animals, plants, bacteria, examples being the naturally occurring raw material pyrethrin, which is extracted from chrysanthemum. The biopesticides include microbial insecticides composed of a microorganism (e.g., a bacterium, a fungus, a virus, or a protozoan) as an active ingredient. Microbial pesticides are capable of controlling many different species of pests, but each individual active ingredient is relatively specific for its target pest. For example, there are fungi that control certain weeds and other fungi that kill certain insects. The most widely used microbial insecticides are subspecies and strains of bacillus thuringiensis or Bt.

Pesticides can be classified according to the type of pest they attack. Among the types of insecticides that can be used in the present invention are: seaweed removers for controlling seaweed in lakes, ditches, swimming pools, sinks and other locations; antifouling agents that kill or repel organisms adhering to an underwater surface, such as the bottom of a ship; bactericides that kill microorganisms (e.g., bacteria and viruses); attractants that attract pests (e.g., insects or rodents to the trap), including foods, such as sugar; biopesticides as active agents derived from natural sources such as animals, plants, bacteria and specific minerals; a biocide that kills microorganisms; disinfectants and sanitizers that kill or render non-living organisms that produce disease on their surfaces; fungicides that kill fungi (including blight, mildew, mold, rust); herbicides that kill weeds and other plants that grow in undesired locations; insecticides that kill insects and other arthropods; acaricides that kill mites that feed on plants and animals; microbial pesticides which are microorganisms that kill, inhibit or repel pests such as insects or other microorganisms; molluscicides that kill snails and slugs; nematicides that kill nematodes (tiny, worm-like organisms that feed on plant roots); ovicides that kill eggs of insects and mites; pheromones that interfere with mating behavior of insects; are insect repellents that are chemicals that repel pests, including insects (e.g., mosquitoes) and birds, from surfaces, such as skin or seeds; rodenticides which cause illness, repel or kill rats and other rodents; insect growth regulators that interfere with moulting, maturation, or other life processes from pupal stage to adult stage of an insect; and plant growth regulators that are substances that alter the expected growth, flowering, or reproductive rate of a plant (excluding fertilizers or other plant nutrients).

Not intended to be exhaustive, the insecticides that can be used in the articles of the present invention are: 2, 4-Dichlorophenoxyacetic Acid (2, 4-D), 2, 4-D butyric Acid (2, 4-DB), propanil (DCPA), 2-Methyl-4-chlorophenoxyacetic Acid (MCPA), Abamectin (Abamectin), Acephate (Acephosphate (Orthene), Acetochlor (Acetochlor), Acifluorfen (Acifluor), Alachlor (Alachlor), Aldicarb, Allethrin (Allenthrin), Ametryn (Ametryn), Amitraz (Amitraz), Atrazine (Atrazine), toosendanin (Azadirachtin), glutathione (Azinophos-Methyl), Bacillus thuringiensis (Bacillus), Bendiocarb (Bendicarb), Benomyl (Benzophyl), fenpyrane (Benzopyridine (Benzopyr), fenpyracetin (Benzafenozide), fenpyracetin (Benthiazyl), fenpyrathion (Benthiabendazole), fenpyrauxin (Benzamide), Bromacil (Benzid), pyrauxin (Benzid), pyrazocarb (Benzid), Benzid (Ben, Captan (Captan), monocrotaline (Carbaryl), Carbofuran (Carbofuran), thiophosphor (Carbophenothion), Carboxin (Carboxin), chloramphenium (chlomet), Chlordane (Chloramben), diclofen (chlorarane), Dicofol (chlobenzilate), Chloropicrin (chlorpicrin), tetrachlorodicyanobenzene (Chlorothalonil), Chlorpyrifos (Chlorpyrifos), chlorpropropropham (chlopropham), Clethodim (Clethodim), chloramine T (Clomazone), Coumaphos (Coumaphos), Cyanazine (Cyanazine), Cyfluthrin (Cyfluthrin), Cypermethrin (Cypermethrin), Dalapon (Dalapon), dimethylsuccinate (Diminozide), Diethyltoluide (DET), dichlorflufen), Deltamethrin (DDfenthion), dichlorvofenozide (DDS), dichlorvofenozide (dichlorphenazone), dichlorvophos (Deltamethrin), dichlorvofenozide (Deltamethrin), dichlorvofenozide (Deltamethrin), dichlorvofenozide), dichlorvofenoxas (dinotefuran (difenon (chlorpyris (Chlorpyrifos), dichlorvofenozide), dichlorvofenoxas (Chlorpyrifos), Deltamethrin (Deltamethrin), deltameth, Aldicarb sulfone (Dimetomorph), fenamiprop (Dinocap), dimethomorph (Dinoseb), norathyriol (dinosine), Diquat (Diquat Dibromide), ethoprophos (Disulfoton), Diuron (Diuron), dodecylguanidineacetate (Dodine), dibromoethane (Ethylene Dibromide), Endosulfan (endosufan), Endothall (endosulfal), S-Ethyldipropylthiourea (EPTC), Esfenvalerate (esfenvalant), Ethephon (Ethephon), Ethion (Ethion), Fenamiphos (fennamis), Fenitrothion (fenpyrothion), Fenoxycarb (Fenoxycarb), Fenthion (Fenthion), flupyraflufen (flufenthiuron), flufenoxate (flumuron), fluazinam (flumuron), fluazin (flumuron), flufenoxafen (flumuron), flufenoxate (flumethonal), flufenoxyfen (Fenoxycarb), flufenoxycarb (fenoxate), flufenoxaprop-p (fenoxaprop-ethyl, flufenoxyfen), flufenoxyfen (fenoxyfen), fenoxyfen (fenoxyfen), imazaquin (Imazaquin), Imazethapyr (Imazethapyr), Imidacloprid (Imidacloprid), Iprodione (Iprodione), isoprofos (Isofenphos), Lactofen (Lactofen), lambda-Cyhalothrin (lambda-Cyhalothrin), Lindane (Lindane), Linuron (Linuron), Malathion (Malathion), Mancozeb (Mancozeb), Maneb (Maneb), 2-Methyl-4-chloropropionic acid (Mecoprop), Metalaxyl (Metalaxyl), snail (Metaldehyde), Methamidophos (methamphos), Methidathion (Methidathion), Methoprene (Methoprene), methochlor (metocloprid), metosul (Methyl), metosulam (Methyl), metosulpon (Methyl), metosulpon (Methyl), metosulpons (Methyl), metosulpons (Methyl-Methyl, metosulbensul (Methyl), metosul (Methyl-Methyl, metosul-Methyl, metosul (Methyl-Methyl, metosul, Oryzalin (Oryzalin), Oxamyl (Oxamycin), Oxyfluorfen (Oxyfluorfen), Paraquat (Paraquat), Parathion (Parathion), Pendimethalin (Pendimithalin), Pentachlorophenol (Pentachlorophyllenol), promethilin (Permethrin), Phorate (Phorate), Phosmet (Phosphotone), Phosmet (Phoxim), epithion (Picloram), Primisulfuron (Methylon-Methyl), Prometryn (Prometyn), propyzate (Pronamide), Propanil (Propanil), promazine (Propazine), amisul (Propetiolos), Propoxur (Propoxur), pyrethrin (Pyrethrin) and Pyrethroids (Pyrethyos), Quinol (Quinoquinone), quindox (Oxythrox), fentezine (Tetramethrin), Roxithrone (Thifenzine), Roxithrone (Thifenprox), Roxithrone (Thifentin (Thiofluran), tetramethrin (Thiofluran (Oxyphone), tetramethrin (Thiofluran), tetramethrin (Oxyphone (Thiofluran), Thiofluran (R (Robinin), Thiofluran (Roxithrone), Thiofluran (, Temephos (Temephos), Terbacil (Terbacil), Terbufos (terbutos), Terbutryn (Terbutryn), Thiabendazole (Thiabendazole), seleam (Thiram), triazolone (triadimifon), Triallate (triallete), Trichlorfon (Trichlorfon), Triclopyr (Triclopyr), Trifluralin (Trifluralin), trimetrex (Triforine), Validamycin (Validamycin), imazamox (Vernollate), Vinclozolin (Vinclozolin), Warfarin (Warfarin), Zineb (Zineb) and Ziram (Ziram).

The invention may also be used to immobilize liquid pheromones or solid pheromones dissolved in a carrier liquid and thus to make articles that can be used as baits in insect traps, fish-trapping baits, rodent traps, and the like. Pheromones are typically esters, aldehydes, alcohols and ketones of six to twenty carbon atoms and are therefore similar to aromatic compounds and can be immobilized as described above for aromatic compounds. Hundreds of such compounds have been identified for many animal and insect species, many of which are not considered pests. Representative examples of articles useful in the present invention include, but are not exhaustive of, the following: e or Z-13-octadecenyl acetate, E or Z-11-hexadecenal; e or Z-9-hexadecenal; hexadecene aldehyde; e or Z-11-hexadecenyl acetate; e or Z-9-hexadecenyl acetate; e or Z-11-tetradecenal; e or Z-9-tetradecenal; tetradecenal; e or Z-11-tetradecenyl acetate; e or Z-9-tetradecenyl acetate; e or Z-7-tetradecenyl acetate; e or Z-5-tetradecenyl acetate; e or Z-4-tridecyl acetate; e or Z-9-dodecenyl acetate; e or Z-8-dodecenyl acetate; e or Z-5-dodecenyl acetate; dodecenyl acetate; 11-dodecenyl acetate; dodecyl acetate; e or Z-7-undecylenyl acetate; e or Z-5-undecylenyl acetate; e or Z-3-undecylenyl acetate; octadecanal, Z or E, Z or octadecadienyl E3, 13-acetate; z or E, Z or E2, 13-octadecadienyl acetate; z, Z or E-7, 11-hexadecadienyl acetate; tetradecadienyl Z, E9, 12-acetate; e, E-8, 10-dodecenyl acetate; z, E6, 8-heneicosane diene 11-one; e, E7, 9-heneicosane-11-one; z-6-heneicosene-11-one; 7, 8-epoxy-2-methyloctadecane; 2-methyl-7-octadecene, 7, 8-epoxyoctadecane, Z, Z, Z-1, 3, 6, 9-nonadecatetraene; 5, 11-dimethylheptadecane; 2, 5-dimethylheptadecane; 6-ethyl-2, 3-dihydro-2-methyl-4H-pyran-4-one; methyl jasmonate; alpha-pinene; beta-pinene; terpinolene; limonene; 3-carene; p-isopropylphenyl methane; crotonic acid ethyl ester; (ii) myrcene; camphor terpene; camphor; 1, 8-cineole; alpha-cubeberry bitter; allyl anisole; undecalaldehyde; nonanal; heptanal; e-2-hexenal; e-3-hexenal; hexanal; verbenadine; verbenone; verbenol; 3-methyl-2-cyclohexenone; 3-methyl-3-cyclohexenone; the ips typographus pheromone (1, 5-dimethyl-6, 8-dioxabicyclo [3.2.1] octane (frontalin)); exo-and endo-western bark beetle collectins pheromone (7-ethyl-5-methyl-6, 8-dioxabicyclo [3.2.1] octane (brevicomin)); trimethyldioxytricyclononane (lineatin); a multistriatin; the intermediate cave beetle aggregation pheromone (chalcogran); 7-methyl-1, 6-dioxaspiro (4.5) -decane; 4, 8-dimethyl-4(E), 8(E) -decadienolide (4, 8-dimethyl-4(E), 8(E) -decadienolide); 11-methyl-3(Z) -undecenolide (11-methyl-3(Z) -undecenolide); z-3-dodecen-11-olide; z, Z-3, 6-dodecen-11-olide; z-5-tetradecen-13-olide; z, Z-5, 8-tetradecen-13-olide; z-14-methyl-8-hexadecenal; 4, 8-dimethyldecanal; gamma-caprolactone; hexyl acetate; e-2-hexenyl acetate; butyl-2-methylbutyrate; propyl caproate; hexyl propionate; butyl caproate; hexyl butyrate; butyl butyrate; e-butylene hexylene butyl ester; z-9-tricosene; eugenol methyl ether; alpha-ionone; 4- (p-hydroxyphenyl) -2-butanone acetate; e-beta-farnesene (E-beta-farnesene); nepetalactone (nepetalactone); 3-methyl-6-isopropenyl-9-decenyl acetic acid; z-3-methyl-6-isopropenyl-3, 9-decadienylacetic acid; e or Z-3, 7-dimethyl-2, 7-octadecadienylpropionate; 2, 6-dimethyl-1, 5-heptadien-3-ylacetate; z-2, 2-dimethyl-3-isopropenylcyclobutanemethylethyl; e-6-isopropyl-3, 9-dimethyl-5, 8-decadieneacetic acid ester; z-5- (1-decenyl) dihydro-2 (3H) -furanone; 2-phenylethyl propionate; 3-methylene-7-methyl-7-octenylpropionate; 3, 11-dimethyl-2-nonacosanone; 8-methylene-5- (1-methylethyl) spiro (11-oxabicyclo) 8.1.0-undecene-2, 2-oxiran-3-one; 2-propylcycloalkylsulfanyl; 3-propyl-1, 2-dithiolane; 3, 3-dimethyl-1, 2-dithiolane; 2, 2-dimethylsulfolane; e or Z-2, 4, 5-trimethylthiazoline; 2-sec-butyl-2-thiazoline; and isopentenyl methyl sulfide. Specific pheromones include the following: 8-methyl-2-decyl-propionate; 14-methyl-1-octadecene; 9-tricosene; tridecenyl acetate; dodecyl acetate; dodecenyl acetate; tetradecenyl acetate; tetradecanedienyl acetate; cetyl acetate; hexadecadienyl acetate; hexadecatrienyl acetate; octadecenyl acetate; dodecenyl acetate; octadecadienyl acetate; z, E-9, 12-tetradecadien-1-ol.

The active liquid may be an active ingredient in liquid form, or may be an active ingredient in solid, liquid or gas form dissolved (contained) in and diluted by the carrier liquid. The active liquid may consist of water and an active agent dissolved in the water. The active liquid may consist of an organic liquid and an active agent dissolved in the liquid.

Examples of active ingredients contained in the active liquid may be therapeutically active ingredients (for humans or animals), e.g. drugs, quasi-drug organisms, which may optionally be combined with a biologically acceptable carrier. Furthermore, examples of active ingredients comprised in the active liquid may be biological compounds, such as amino acids, vitamins, sugars and/or steroids. Examples of biological compounds may be biopolymers or biological copolymers or chimeras comprising DNA, RNA, oligonucleotides, modified DNA, modified RNA, proteins, polypeptides, and modified polypeptides.

In addition to the preferred embodiments described above, other embodiments are possible by adding/changing optional components including: plasticizers, diluents, accelerators, retarders, thickeners, fillers and colorants. Phthalates, benzoates, salicylates, lactates, alcohols, polyols, polyalkylene glycols, and alcohols, polyols, alkyl ethers and aryl ethers of polyalkylene glycols are examples of useful plasticizers/diluents. These materials can produce flexibility, improve active release and reduce product cost.

Factors that can be used to influence the epoxy-based product may also be used in the invention to which this application relates. These materials may well impart benefits to the air freshener of the present invention. Reactive and inert diluents may also be used to reduce the viscosity of the initial blend. Possible diluents include, but are not limited to, various mono-and diglycidyl ethers, glycols, and N-methylpyrrolidone. Phenols such as nonylphenol and 2, 4, 6-tris (dimethylaminomethyl) phenol are examples of known accelerators for epoxy-amine curing reactions. Thus, they can benefit the system by reducing the time required to cure the air freshener of the present invention. The reaction promoter may be any alcohol-containing compound and/or water and/or mixtures thereof. Dissolving specific resins in epoxy or diluent/plasticizer and adding them to the system can impart tack to the final product. These resins include those sold under the trade name Arizona ChemicalAndfor saleRosin esters and polyterpenes.

The compositions and/or articles of the present invention may be prepared by contacting, mixing or blending a compound containing preferably two or more functional groups selected from epoxy, isocyanate, anhydride and acrylate with a polyamine compound in the presence of a reactive liquid. The mixture formed before and after curing is preferably homogeneous. Such contacting, mixing and blending of the reactive component with the reactive liquid may occur at a temperature in the range of 10-50 ℃. The temperature of the blending operation may preferably be 10, 15, 20, 25, 30, 35, 40, 45, and 540 ℃, including all ranges and subranges therebetween. The components may be added continuously in any order provided that the active liquid cannot be added after the time at which the matrix-forming reaction has progressed to the point where its high viscosity and increased elasticity prevent the blending operation. The optional ingredients may also be added to the mixture in any order, again subject to the above conditions. In case the amine is a solid, it is preferably first dissolved in a diluent liquid or an active liquid or a mixture of both.

The temperature and blending conditions must be controlled to prevent premature curing, which is extensive curing during the contacting, mixing or blending steps. Preferably, the mixture becomes a homogeneous thermoset solid after early cure. The curing temperature may be different from the temperature of the blending operation and may be in the range of 10-100 ℃, preferably 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100 ℃, including all ranges and subranges therebetween.

The rate of cure is a function of at least six factors: curing temperature, functional group and amino group concentrations and ratios, amine structure, accelerator/retarder concentrations, perfume oil/diluent composition. Accordingly, the curing time can be varied within wide limits.

Mixing and/or curing may occur in the mold. For example, a low temperature procedure may include blending at room temperature, pouring the blend into a mold, sealing, and maintaining the blend at room temperature. Such procedures may take from a few minutes to a few days depending on the functional groups and reaction conditions selected. For example, isocyanate-amine matrix reaction rates are significantly higher than epoxy-amine matrices. Another example is a pre-cure procedure, which is more applicable to epoxy-amine matrices, which involves blending at room temperature, tight sealing, heating to 70 ℃ for 30-90 minutes to obtain a partially cured but gel-free composition, and then pouring the resulting partially cured product into a mold, allowing it to cool and stand at room temperature. Such a procedure may take from 1 hour to 2 days. Finally, another example is a high temperature procedure, which may include blending at room temperature, pouring into a pouch or mold, hermetically sealing it, and heating it to a temperature range of 60-100 ℃. Such a procedure may take from a few minutes to a few hours.

The method of the invention is not limited to the above-described steps in the above order and a person skilled in the art may very well wish to combine different steps therein. Additionally, the curing time may vary from 0.01 hour to 60 hours, more preferably from 5 minutes to 20 hours, and most preferably from 10 minutes to 100 minutes, i.e., 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100 hours, including all ranges and subranges therebetween.

One preferred embodiment of the present invention includes blending the reactive liquid, the liquid polyepoxide, and the liquid polyamine to form a mixture. Blending of these components may occur at 10-40 ℃. However, the blending is performed without causing any loss of temperature sensitive active components. The temperature of blending may preferably be 10, 15, 20, 25, 30, 35, and 40 ℃, including all ranges and subranges therebetween. When an epoxy-containing compound is used, the curing temperature may be room temperature, i.e., 25 ℃, but may be higher depending on the temperature sensitivity of the active liquid component and its volatility. If the reactive liquid is not readily degraded and curing is carried out in a sealed mold, the preferred curing temperature is about 60 ℃. Curing of a typical formulation occurs in about 3-6 hours at such temperatures, and in a shorter time if accelerators are used.

Another preferred embodiment of the present invention includes blending a reactive liquid, a liquid diluent, a liquid polyisocyanate, and a liquid polyamine to form a mixture that cures to a liquid fixed polyurea composition. Blending of these components may occur at 10-40 ℃. However, the blending is carried out without causing any loss of temperature sensitive active components. The temperature of blending may preferably be 10, 15, 20, 25, 30, 35, and 40 ℃, including all ranges and subranges therebetween.

Even in the absence of a catalyst, the reaction between the polyamine and the isocyanate is rapid at room temperature. Preferably no catalyst is present, rather it is preferred to use a rate modifier or "retarder" to slow the reaction, leaving sufficient time for the ingredients to be blended and poured into the mold. Useful rate modifiers are, for example, aldehydes which are usually present in the customary essential and flavor oils. Other useful rate modifiers are those that are mild in odor or enhance the odor of the active liquid. Examples of useful retarders are aromatic aldehydes, such as benzaldehyde, vanillin, and salicylaldehyde; α, β unsaturated aromatic aldehydes such as cinnamaldehyde and methyl cinnamaldehyde; terpene aldehydes such as citral, cyclocitral, citronellal; and C₄-C₁₈Aliphatic and alicyclic aldehydes such as isobutyraldehyde, lyral (lyral), 2-phenylpropionaldehyde; and so on. Although the above-mentioned blocking agents are preferred when using the isocyanate-containing mixtures according to the invention, said blocking agents can optionally be used in all reactions according to the invention.

Another method to increase cure time is to use PAPA terminated with a carbonyl-substituted aromatic amine, prepared as described above. The following table lists the set times (time from mixing to loss of fluidity) for four commercially available fragrances derived from PAPA and PAPA at a concentration of 50%Immobilization of the reacted substrate of N-3300, the PAPA being terminated with a non-aromatic primary amine or a carbonyl-substituted aromatic amine, i.e., thePAPA is end-capped by reaction with p-aminobenzoic acid.

When an isocyanate-containing compound is used, the preferred curing temperature is room temperature, i.e. 25 ℃, but it may be higher or lower depending on the desired curing time. For example, if the reactive liquid does not readily degrade and very rapid curing is required, curing can be carried out in a sealed mold, and the preferred curing temperature is about 50 ℃. For typical formulations based on PAPA terminated with aliphatic primary amines and curing in the presence of little or no catalyst at room temperature, the typical set time is from less than 1 second to about 30 minutes. The time may be 0.1, 0.5, 1, 5, 10, 20, and 30 minutes, including any and all ranges and subranges therebetween. For typical formulations based on carbonyl-substituted aromatic amine-terminated polyamines, the cure takes about 10 minutes to 2 days when cured in the presence of a retarder, but preferably the cure takes 20-600 minutes in the absence of a retarder. The time may be 20, 50, 100, 200, 300, and 600 minutes, including any and all ranges and subranges therebetween.

The present invention relates in part to compositions and/or articles containing a crosslinked polymeric matrix and a reactive liquid, wherein the reactive liquid is immobilized within the crosslinked polymeric matrix and the crosslinked polymeric matrix is the reaction product of a compound having at least one and preferably two or more functional groups selected from the group consisting of epoxy, anhydride, and isocyanate, and a polyamine compound, in the presence of the reactive liquid. Immobilizing the active liquid in this manner has several advantages, including:

■ the heat sensitive oil need not be heated;

■ shrinkage of the blend during curing is less likely to occur;

■ if not filled, the product is transparent;

■ a product component with little odor, color and toxicity is obtained;

■ product has excellent durability, is insoluble in water, and does not melt;

■ the product can be easily colored with dyes and pigments; and/or

When the composition of the invention contains a crosslinked polymeric matrix based on the reaction of compounds bearing epoxy functional groups, there are also two advantages:

■ even in the case of aliphatic primary amine-terminated polyamine compounds, the blend cures slowly at room temperature, leaving sufficient time for degassing of the mixture, optional filler and/or icon addition, transfer or pumping of uncured material and pouring into a mold, and storage of the mold before the matrix-liquid blend cures.

■ A wide variety of amines are available to allow the properties of the final crosslinked product to be controlled.

When the composition according to the invention comprises a crosslinked polymeric matrix based on the reaction of a compound bearing isocyanate functional groups with a PAPA, the following two advantages are also obtained:

■ the blends cured rapidly at room temperature, typically within 30 minutes.

■ unlike other polyamine compounds, PAPA is a high molecular weight polymer with little or no odor, high viscosity, light color, and low toxicity.

The method for immobilizing an active liquid may be adapted to overcome or avoid the disadvantages exemplified below:

■ curing is exothermic, but the heat generated in the blend of which the active liquid of the invention is the major component is not significant, especially when the blend is cured in a small mold with good heat dissipation properties.

■ epoxy cures very slowly, typically requiring 1-3 days at 25 ℃, but desirably in a mold after the product is sealed and packaged. The curing time can be significantly reduced by using an accelerator and by heating the article to about 60 ℃.

■ in some cases the isocyanate cured too quickly to pour the blend into a mold. This can be avoided by appropriate selection of blending temperature, retarder, PAPA and reactant concentrations.

■ all amine compounds are themselves somewhat toxic and require care during handling, but are used in relatively low amounts and are irreversibly incorporated into the crosslinked polymer matrix during the curing step. Only very small amounts of free amine groups are present in the crosslinked product.

■ all isocyanate compounds are themselves somewhat toxicAnd requires care during handling, but is used in relatively low amounts in the compositions of the invention. Only very small amounts of free isocyanate are present in the crosslinked product and can be eliminated by further reaction with reactive liquids, diluents or alcohols in water. The epoxy resin is5001. The curing agents were T-403, IPDA and 1, 3-BAC. The perfume oil is "Evergreen" supplied by Belle Aire Fragrances of Mundelein I11.

The purpose of many of the materials described above is to make the article more visually appealing. Although these materials are not essential to the present invention, they may well provide benefits to the articles of the present invention, such as improving the release rate of the active ingredient contained therein.

Articles of manufacture of the present invention include, but are not limited to, pharmaceutical devices having an active liquid that is pharmaceutically active, pesticide devices having an active liquid that is a pesticide, laundry care devices having an active liquid for laundry care (i.e., softeners, perfumes, conditioners, cleaners, soil repellents, surface treatment agents, etc.), or air fresheners having an active liquid that is a perfume.

The articles of the present invention can be processed into any desired shape that is appealing to potential consumers. Such shapes may be 3-D shapes molded in a mold or flat shapes die cut from a pre-formed sheet. These shapes may include those of natural geometries such as triangular, square, circular, spherical, elliptical, regular geometric or irregular geometric shapes, and the like. The above examples are not meant to limit the articles of the present invention, as a large number of 3-D shapes may be formed.

The compositions of the present invention as described above comprise a perfume oil or other active liquid immobilized with a matrix. A significant advantage of the present invention is that the essential component is a liquid that remains fluid for a certain period of time after mixing and before curing into a solid thermoset form. This allows for the preparation of a wide variety of forms of air care articles. The invention also includes such articles, particularly articles suitable for use in air care articles, particularly air fresheners. The air freshener may include a room air freshener; a closet air freshener; a container air freshener for use in: such as boxes, jars, storage containers, bags, boxes, cabinets, warehouses, trash cans and/or drums; a vehicle air freshener; and zone/zone air fresheners for the following zones or zones: such as sidewalks in front of stores, sidewalks in malls, etc.

The air care articles of the present invention can have, for example, a wide variety of geometric and aesthetic shapes such as, but not limited to, disk, circular, cylindrical, square, rectangular, pentagonal, hexagonal, star, heart, hemispherical, spherical, cubic, flower, animal, letter, number, logo, trademark, and face. These shapes are limited only by the known methods of making suitably shaped molds.

These articles may be colored with soluble dyes or with pigments. These colorants are preferably dissolved or dispersed prior to final mixing of the reactive components. These colorants can be conventional, fluorescent, pearlescent, temperature sensitive, light sensitive, pH sensitive or moisture sensitive. The latter four colorants allow the preparation of new products that change color when environmental conditions change or indicate the consumption of active ingredients in the preparation.

Since the composition is fluid prior to curing, it can be easily poured into a mold and thus obtain precise shapes such as depressions, curves, logos, etched patterns, and any other embossed or engraved images. It is particularly advantageous to design the product to be directly contained in a support body so as to adhere to surfaces of complex shape, such as body parts, curved surfaces, such as heated braille disks (potpourri dish), bulbs, or to adhere to the inside of the package.

Various insoluble materials may be suspended in the reaction mixture prior to curing, such that the system entraps the suspended materials upon crosslinking. The suspended substance may be a decorative object such as an icon, bead, glitter, gemstone, debris, or the like; plant materials (botanicals) such as leaves, seeds, stems, needles, nuts, and the like; insoluble powder substances such as waxes, sugars, coffee powder, bait granules, insoluble plain weave (plain), coloured or flavoured salts, water, glycerine, silicone fluids, aqueous solutions of dyes, actives, acids, bases and the like, with or without the aid of surfactants for stabilizing the dispersion formed; or air or other gas generated by the whipping action or other deliberate mixing with the gas used to form the bubbles in the matrix-forming liquid. Alternatively, the gas may be generated in the matrix-forming composition by a chemical process, such as thermal decomposition of a nitrogen, oxygen or carbon dioxide generating species. Examples of these compounds are carboxylic acids, azobisisobutyronitrile, hydrogen peroxide and sodium carbonate or bicarbonate. Preferred carboxylic acids for use in this manner are polymeric fatty acids.

The article of the invention may consist solely of perfume oil or other active liquid and a component selected from those listed above which is immobilized by the cross-linked matrix, or the article of the invention may consist of an immobilized liquid and a support, whether the support is a container, a scaffold or a support, into which a mixture of reactive, active and other liquids and optional components is poured before curing takes place or into which the mixture is loaded after curing takes place.

If not poured into a container, the cured article may be coated, printed, or otherwise decorated, packaged or otherwise supported by a stand, plate, bowl, pan, support, or other support device. If poured into a container, the container may be made of glass, ceramic, metal, paper, plastic, or any other oil-impermeable material, and may have any convenient shape, such as cylindrical, tubular, bowl-like, disk-like, and the like. The container itself may be shaped to fit within a support, chamber or body designed to fit within a fragrance delivery device that may house a heater, fan, blower or other auxiliary mechanical device. If it is intended to heat the article, the heater may be disposed outside the reactive liquid immobilized by the cross-linked matrix or may be disposed inside, e.g., surrounded by or embedded within, the cross-linked article. One example of such a device is a reactive composition of the invention poured into a container arranged with electrical resistance heating wires that can be energized after the matrix has cured to heat the crosslinked composition from within.

Similarly, the composition, which is still fluid, may be impregnated into porous materials such as paper, cardboard, cellulose pads, cellulose pulp, blankets, fabrics, porous synthetic foams, porous ceramics, activated carbon, soil, diatomaceous earth, sand, charcoal, silica, clay, and the like, or coated onto non-porous substrates including, but not limited to, plastic films, metal foils, rubber, ceramics, wood, glass, and leather.

Similarly, a mixture of reactive components, reactive liquid and optional liquid, which are still uncured, may be dispersed in water or other aqueous medium, the resulting emulsion optionally being stabilized with a surfactant. The droplets of the composition of the invention thus emulsified may then be solidified to give a dispersion of solid gel particles. This may be considered a method of preparing the encapsulated active oil in a dispersed form. The material is an emulsion and may be so impregnated into porous media such as paper, cardboard, cellulose pad, cellulose pulp, felt, fabric, porous synthetic foam, porous ceramic, activated carbon, soil, diatomaceous earth, sand, charcoal, silica, clay, etc., or coated on non-porous substrates including, but not limited to, plastic films, metal foils, rubber, ceramic, wood, glass, and leather.

Another embodiment of the article of the invention is a container nearly filled with a volatile active liquid, which is then filled with the composition of the invention and sealed, trapping the volatile material behind a barrier or film of the cross-linked matrix. This arrangement is advantageous because the volatile liquid is released very slowly and continuously as it diffuses through the barrier of the liquid-impregnated substrate.

When the article of the present invention is an air freshener, it may be "active" and/or "passive". Active air fresheners comprise relatively complex devices having moving parts including heaters and fans for dispensing concentrated or diluted fragrance compounds or spray cans containing fragrance chemicals, carrier liquids, and propellants. Active air fresheners require an occupant to dispense the material to the area to be treated. Passive air fresheners are available in a variety of forms, but are essentially "fixed" liquid chemicals: a multi-component article comprising a fixed perfume oil and/or a solid support. The support material may be simple, such as a sheet of cardboard, blotter paper, cotton or other fibrous material. The support material may be complex, such as an aqueous dispersion (gelatin) or a non-aqueous gel (e.g., gelled by a polyamide resin). Preferably, the air freshener of the present invention is transparent, but may be opaque.

The invention is explained in more detail below by means of the following examples, which are not intended to limit the scope of the invention in any way.

Examples

Examples 1 to 4

Example 1

Air freshener components containing a small amount of green dye (the name and amount are listed below) were weighed into a glass vial and manually stirred together at ambient temperature with a wooden stir bar. A portion of the mixture (8.0g) was then poured into a flat, rectangular, 2.50 inch by 3.25 inch uncoated polystyrene mold:

■ epoxy TreeFat:5001，10.00g；55.1％

■ curing agent: 1, 3-BAC, 3.55 g; 19.6 percent

■ spice oil: belle Aire "Evergreen", 4.55 g; 25.1 percent

■ dye: green, 0.05 g; 0.3 percent of

The next day, the samples were firm, transparent, non-tacky, and soft. It can be removed from the mold by hand with only a small amount adhering to the mold. It was stored in polyethylene "pouches" at room temperature and showed no syneresis even after several weeks.

Example 2

A total of 100 parts by weight of these air freshener components were treated using the procedure of example 1:5001(53.6 parts), 1, 3-BAC (19.0 parts), Belle Aire "Evergreen" perfume oil (25.1 parts), nonyl phenol (2.2 parts). After one day of curing at room temperature, the resulting article was clear, strong, soft and non-tacky.

Example 3

A total of 100 parts by weight of these air freshener ingredients were treated using the procedure of example 1: cyclohexanedimethanol diglycidyl ether (22.8 parts),828(22.8 parts), Huntsman T-403 polyamine (24.2 parts), continuous Aromatics "Country Meadow" perfume oil (30.0 parts), plastic glitter (0.1 part) and trace amounts of green dye. After curing at room temperature for three days, the resultingThe article is transparent, strong, soft, non-tacky and exhibits the ability to lightly adhere to a vertical and flat glass surface, be easily removed from the glass surface and be reapplied without damaging the surface.

Example 4

By reacting adipic acid (20.0g, 274meq of acid),T-403 polyamine (20g, 132meq amine) and Huntsman XTJ-500(80g, 254meq amine) were poured into a 250mL glass flask equipped with a stirrer and the pour was heated to 210 ℃ and 220 ℃ under a stream of dry nitrogen to prepare polyamidopolyamine. After holding the mixture under these conditions for 5 hours, the reaction mixture was poured into a vessel. The product was a clear, viscous, nearly water-white liquid with an acid number of 1.4, an amine number of 42.2, and a Brookfield viscosity of 340cP at 150 ℃. A portion of the product (11.63g) was dissolved in water (27.5g) and then blended with polyethylene glycol diglycidyl ether (EEW 195; 3.40 g). Perfume oil ("Sunshine liquids", Firmenich perfume oil #190196) and a few drops of tween 80 surfactant were then added to a portion of the mixture (20.0g) in a small plastic bottle with a screw cap to form a milky emulsion which gelled to a non-flowing solid white homogeneous solid which gradually released the perfume upon opening after sealing and standing.

Example 5

To a commercially available resealable polyethylene "pouch" was added a total of 100 parts by weight of the ingredients: cyclohexanedimethanol diglycidyl ether (13.9 parts),826(13.9 parts), Arizona's own proprietary liquid triethylenetetramine amido-amine # X54-327-004 (amine number 349, acid number 0.8, 22.2 parts), Atlas "Crisp Breeze "perfume oil (50.0 parts) and traces of blue dye. The "pouch" was massaged for several minutes to blend the components, the air bubbles were pressed out and the liquid mixture was left flat at room temperature for one week. At that time, the material cross-links to the point of being non-flowable, transparent and flexible.

Example 6

Adding Huntsman into a glass beaker provided with a magnetic stirring rodL24-5, liquid ethoxylated alcohol surfactant (12.0g), Atlas Products "Crisp Breeze" perfume oil (8.0g), Huntsman T-403 polyamine (8.4g), FD&C #3 blue-green dye (0.4g) and48 epoxy (14.0 g). The mixture was heated to 58 ℃ with stirring for about 3 hours to bring it to near solidification, then poured into a cylindrical mold and allowed to cool. After the material was allowed to stand at room temperature for 3 days, it was removed from the mold as a slightly rubbery, firm solid.

Example 7

A total of 100 parts by weight of these air freshener components were mixed at room temperature: cyclohexane dimethanol diglycidyl ether (25.3 parts),828(17.2 parts), Arizona has proprietary polyamido-amine curing agent # X54-327-. The blend was held at about 67 ℃ for about 45 minutes, at which time it was allowed to cool to room temperature. It was very sticky at this stage, but could still be poured out and stirred. Adding the whole cross-linked intermediate of the part by a gentle dispensing deviceAbout two dozen 1/4 "colored metal foil hearts. After 3 days of curing at room temperature, the resulting article was strong, soft, and non-tacky with the metal foil hearts clearly visible uniformly suspended therein.

Example 8

A total of 100 parts by weight of these components were treated using the procedure of example 1: poly (propylene glycol) diglycidyl ether (13.0 parts),828(22.0 parts), Arizona UNI-2801 amido-amines (14.0 parts), a "Vanilla" perfume oil from Aromatic Flavors and Fragrances, dipropylene glycol benzoate (19.5 parts), and commercial coffee powder (29.5 parts). The resulting article after curing is strong, slightly soft, non-tacky. These coffee powders are uniformly distributed and give the product a dark brown, opaque appearance, the bottom of the product being smooth in the case of a smooth mould and the top of the product being rough in the case of free settling of the coffee powders.

In the examples below, the abbreviations are as follows:

■ CHDA is 1, 4 cyclohexanedicarboxylic acid from Eastman Chemical;

■ Empol is available from Cognis Corporation1008 dimer acid;

■ Unidyme is supplied by Arizona Chemical Company18 dimer acid;

■ T-403 is supplied by Huntsman CorporationIs/are as followsT-403 poly (alkyleneoxy) diamine;

■ D-400 is also from HuntsmanD-400 poly (alkyleneoxy) diamine;

■ D-2000 is also from HuntsmanT-2000 poly (alkyleneoxy) diamine;

■ V-551 is supplied by Cognis Corporation551 dimer diamine;

■ N-3300 is available from Bayer Corporation, Industrial Chemicals DivisionN-3300 or N-3300A;

■ N-3800 isN-3800, also from Bayer;

■ Z-4470 isZ4470, also from Bayer.

Example 9

By mixing1008 polymerized fatty acid (63.0g, 219 m)eq acid (c) in the presence of a catalyst,t-403 polyamine (18g, 118meq amine) andd-400(45g, 205meq. amine) was poured into a 250mL glass flask equipped with a stirrer and the pour was heated to 210 ℃ and 220 ℃ under a stream of dry nitrogen to prepare a polyamide polyamine. After holding the mixture under these conditions for 5 hours, the reaction mixture was poured into a vessel. The product was a clear, viscous, nearly water-white liquid with an acid number of 0.3, an amine number of 41.8, a weight average molecular weight of 2,270, and a brookfield viscosity of 204cP at 150 ℃.

By heating 10.0g of the polyamidopolyamine with 5.0gTN benzoates and 10.0g of perfume oil ("Linen Fresh", Wessel Fragrances), cooling them to room temperature and reacting withA mixture of Z4470 and 5.1g of additional perfume oil was thoroughly blended to make a solution. A small amount of red dye and red glitter is then added to the composition. After a few minutes, 25g of the final formulation was poured into a flat, annular rose-shaped silicone rubber mold and the remaining formulation was left in the bottle. After a total of 33 minutes after blending the ingredients, the remaining material cured to a non-flowing gel. After standing at room temperature for 16 hours, the immobilized perfume oil preparation was removed from the mold. It does not adhere to the mold, is non-tacky, has the same flower shape as the mold, exhibits uniform color and glitter distribution, and can be handled without breaking. It also exhibits excellent adhesionAdhesion to various vertical surfaces including glass and plastic films.

Examples 10 to 15

Polyamide polyamine was prepared according to the procedure in example 9 by pouring the acids and amines of the kind listed in Table A (below) in the weight percentages indicated into the reactor and heating the pour under a stream of dry nitrogen to 200-220 ℃ for about 4-5 hours and pouring the product out. The properties of the products were then measured and they are also recorded in table a.

TABLE A polyamidopolyamines for examples 10-15

Example number	No.10	No.11	No.12	No.13	No.14	No.15
Example number	No.10	No.11	No.12	No.13	No.14	No.15	Components
Diacid(s)	Adipic acid	Empol	Empol	Empol	CHDA	Unidyme	Components
Diacid(s)	Adipic acid	Empol	Empol	Empol	CHDA	Unidyme	Diamines	T-5000	T-403	T-403	T-403	T-403	D-2000
Co-diamines	--	D-400	D-400	XTJ-500	D-400	Piperazine derivatives	Diamines	T-5000	T-403	T-403	T-403	T-403	D-2000
Co-diamines	--	D-400	D-400	XTJ-500	D-400	Piperazine derivatives	Tertiary diamines	--	D-2000	D-2000	--	D-2000	--
Component (wt%)							Tertiary diamines	--	D-2000	D-2000	--	D-2000	--
Component (wt%)							Diacid(s)	2.0％	41.2％	30.8％	43.3％	18.7％	82.3％
Diamines	98.0％	9.6％	4.2％	12.6％	17.8％	2.1％	Diacid(s)	2.0％	41.2％	30.8％	43.3％	18.7％	82.3％
Diamines	98.0％	9.6％	4.2％	12.6％	17.8％	2.1％	Co-diamines	0.0％	24.6％	16.7％	44.1％	35.5％	15.6％
Tertiary diamines	0.0％	24.6％	48.3％	0.0％	28.0％	0.0％	Co-diamines	0.0％	24.6％	16.7％	44.1％	35.5％	15.6％
Tertiary diamines	0.0％	24.6％	48.3％	0.0％	28.0％	0.0％	Product Properties
Neutralization	194.4％	139.5％	141.5％	148.2％	141.1％	131.7％	Product Properties
Neutralization	194.4％	139.5％	141.5％	148.2％	141.1％	131.7％	Acid value	0.4	0.5	0.4	0.4	1.4	0.6
Amine number	12.2	27.1	22.6	42.4	44.6	14.1	Acid value	0.4	0.5	0.4	0.4	1.4	0.6
Amine number	12.2	27.1	22.6	42.4	44.6	14.1	Colour(s)	Light yellow	Light yellow	Light yellow	Off-white color	Light yellow	Amber
Softening point (R)&B，℃)	Liquid, method for producing the same and use thereof	Liquid, method for producing the same and use thereof	Liquid, method for producing the same and use thereof	Liquid, method for producing the same and use thereof	128	Liquid, method for producing the same and use thereof	Colour(s)	Light yellow	Light yellow	Light yellow	Off-white color	Light yellow	Amber

Viscosity [ cP ] at 150 deg.C]	770	391	141	190	290	481
Viscosity [ cP ] at 150 deg.C]	770	391	141	190	290	481	Weight average molecular weight	6150	2150	17780	5650	1720	33760

A fixed perfume oil was prepared by heating a mixture consisting of 2.0 grams of the PAPA of the example and 2.0 grams of perfume oil to about 55 ℃, and then manually blending the heated mixture with a stir bar. The test Fragrances were "Ocean" (continuous Aromatics), "Linen Fresh" (Wessel Fragrances), and "Cherry" (Aromatic Flavors and Fragrances). After blending, one equivalent of the isocyanate curing agent dissolved in the same weight of oil was added with stirring, a stopwatch was started, and the consistency of the mixture was monitored. When the mixture was unable to flow under its own weight, the time (in minutes) was marked as "gel time". Table B shows that all of these polyamide polyamines effectively fix the target oil when crosslinked with polyisocyanates. The gel time is short, but not so short as to hinder the preparation of useful products, and the following consistency pattern (consistency pattern) is followed:

Ocean＜Linen Fresh Cherry＜＜Cherry

TABLE B gel time (minutes at 50 Wt% base) for the formulations of examples 10-15

40% polyurea-see example 9 conditions

Examples 16 to 20

Polyamide polyamine was prepared according to the procedure in example 9 by pouring the acids and amines of the kind listed in Table C (below) in the indicated weight percentages into the reactor and heating the pour under a stream of dry nitrogen to 200-220 ℃ for about 5 hours and pouring the product out. The properties of the products were then measured and they are also recorded in table C.

Watch CPolyamide polyamines in examples 8 to 20

Examples	No.16	No.17	No.18	No.19	No.20
Examples	No.16	No.17	No.18	No.19	No.20	Components
Diacid(s)	Empol	Adipic acid	Adipic acid	Empol 1008	Unidyme	Components
Diacid(s)	Empol	Adipic acid	Adipic acid	Empol 1008	Unidyme	Triamines (meth) acrylic acid esters)	T-403	T-403	T-403	--	--
Diamines	D-400	XTJ-500	D-400	D-400	V-551	Triamines (meth) acrylic acid esters)	T-403	T-403	T-403	--	--
Diamines	D-400	XTJ-500	D-400	D-400	V-551	Tertiary amines	D-2000	--	D-2000	D-2000	--
By weight%						Tertiary amines	D-2000	--	D-2000	D-2000	--
By weight%						Diacid(s)	30.6％	18.2％	15.2％	36.7％	41.7％
Triamines (meth) acrylic acid esters)	5.0％	9.1％	7.6％	--	--	Diacid(s)	30.6％	18.2％	15.2％	36.7％	41.7％
Triamines (meth) acrylic acid esters)	5.0％	9.1％	7.6％	--	--	Diamines	16.5％	72.7％	38.6％	22.9％	58.3％
Tertiary amines	47.9％	--	38.6％	40.4％	--	Diamines	16.5％	72.7％	38.6％	22.9％	58.3％
Tertiary amines	47.9％	--	38.6％	40.4％	--	Performance of
Acid value	0.6	2.2	0.7	0.7	1.1	Performance of
Acid value	0.6	2.2	0.7	0.7	1.1	Amine number	27.0	28.9	29.9	13.1	33.2
Colour(s)	Colorless and colorless	Colorless and colorless	Colorless and colorless	Colorless and colorless	Amber	Amine number	27.0	28.9	29.9	13.1	33.2
Colour(s)	Colorless and colorless	Colorless and colorless	Colorless and colorless	Colorless and colorless	Amber	Viscosity [ cP ] at 150 deg.C]	106	393	198	1340	656
Weight average molecular weight Mw	26380	12230	13490	31550	13180	Viscosity [ cP ] at 150 deg.C]	106	393	198	1340	656

The fixed perfume oil was prepared by heating a mixture consisting of 2.0 grams of the polyamidoamine of the example and 2.0 grams of perfume oil to about 55 deg.C, and then manually blending the heated mixture with a stir bar. The test Fragrances were Oceanside Mist, tropical (atlas products), Spring Meadow, CountryWildflower, Ocean (contextual Aromatics), Linen Fresh (Wessel Fragrances), Yankee Home (Belle air), Mulberry and Cherry (Aromatic Fragrances and Fragrances). After blending, one equivalent part of an isocyanate curing agent dissolved in the same weight of oil was added with stirring, a stopwatch was started, and the consistency of the mixture was monitored. When the mixture was unable to flow under its own weight, the time (in minutes) was marked as "gel time". Table D shows that all of these polyamide polyamines effectively fix the desired oils when crosslinked with polyisocyanates. The gel time was short, but not so short as to hinder the preparation of useful products, and the following consistency pattern was followed:

Spring Meadow＜Ocean＜Tropical＜Linen Fresh＜Yankee Home＜Mulberry＜Cherry

table D.Gel time of the formulations of examples 16-20 (curing agent is N3300， Minutes at 50 Wt% polyurea)

Example 21

The procedure of example 9 was followed, using the starting materials (weight percentages in parentheses)1008 or UNID12 (Low trimer content, hydrogenated dimer acid from Arizona Chemical) [ 29.5%]，T-403[3.7％]，D-400[22.6％]And D-2000[ 44.2% ]]Multiple batches of PAPA were prepared. This polymer used in examples 22-35 generally had an amine value (1800-1600 equivalents), a weight average molecular weight of 10,700-12,100, a number average molecular weight of 4300-4900, and a viscosity of 40-70cP at 150 ℃.

Example 22

This example illustrates the preparation of an air freshener having a simple geometry. 13.1g of the PAPA of example 21 and 15g of "Cotton Fresh" perfume oil (Symrise Corp.) were added to a glass mixing flask and the mixture was gently stirred for 15 minutes at ambient temperature. Blue dye (2 drops) was added to the mixture, causing the solution to turn pale blue. To the homogeneous mixture was added 1.5gN3300A. The mixture was then stirred until a homogeneous phase was achieved, allowed to stand for a few minutes to dissipate the air bubbles, and a total of 13g of the mixture was poured into a rectangular flexible silicone mold having a uniform length of 1.87 inches, a height of 0.3 inches, and a width of 1.0 inch. The set time was recorded at 28 minutes. The mixture was covered with a polyethylene film and allowed to cure for 24 hours without interference. Thereafter the mould is freed from cross-linked airThe freshener object was removed, which was now firm, soft, transparent and non-tacky to the touch.

Example 23

This example illustrates the preparation of an air freshener having a complex shape. To a glass blender jar was added 13.1g of the polyamine of example 21 and 15g of "auggle Type" perfume oil (Alpha Aromatics) and the mixture was gently stirred at ambient temperature for 15 minutes. A red dye (3 drops) was added to the mixture, turning the solution to a pale pink/red color. To the homogeneous mixture was added 1.5gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 10g of the mixture was poured into an oval-shaped flexible silicone mold (circular-shaped branched flexible silicone mold) having a uniform top width of 1.875 inches, a height of 0.375 inches, and a bottom width of 1.625 inches. The set time was 6 minutes. The mixture was covered with a polyethylene film and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener article, which is now strong, soft, transparent and non-tacky to the touch.

Example 24

This example illustrates the preparation of an air freshener having a complex shape. 19g of the polyamine of example 21 and 20g of "cosmetic Splash" perfume oil (Symrise Corp.) were added to a glass mixing flask and the mixture was stirred gently at ambient temperature for 15 minutes. Blue dye (3 drops) was added to the mixture, turning the solution to a light green color. Then 2.0g of the homogeneous mixture was addedN3300A. The mixture was then stirred for a short time (until homogeneous phase was reached), allowed to stand for a few minutes to dissipate the bubbles, which amounted to 20The mixture in g was poured into a shell-shaped flexible silicone mold having a uniform top width of 2.375 inches, a height of 0.125 inches, and a bottom width of 2.25 inches. The set time was recorded at 24 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener article, which is now strong, soft, transparent and non-tacky to the touch.

Example 25

This example illustrates the preparation of an air freshener containing suspended insoluble particles. 19g of the polyamine of example 21 and 20g of "Clean Citrus" perfume oil (Symrise Corp.) were added to a glass mixing flask and the mixture was stirred gently at ambient temperature for 15 minutes. Yellow aluminum flake "glitter" (0.04g) was added to the mixture. Then 2.0g of the homogeneous mixture was addedN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 18g of the mixture was poured into a disc-shaped flexible silicone mold having a uniform circumference of 9.75 inches, a height of 0.75 inches, and a width of 3.0 inches. The set time was recorded at 30 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener article, which is now strong, soft, transparent and non-tacky to the touch, and exhibits a uniform distribution of glitter.

Example 26

19g of the polyamine of example 21 and 20g of "Sunshine mineral" perfume oil (Firmenich, Inc.) were added to a glass mixing flask and the mixture was gently stirred at ambient temperature for 15 minutes. A green "glitter" (0.03g) was added to the mixture. To the homogeneous mixture was added 2.0gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 28.0g of the mixture was poured into a heart-shaped flexible silicone mold having a uniform length of 2.5 inches, a height of 0.3 inches, and a width of 2.875 inches. The set time was recorded at 17 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch, and exhibits a uniform distribution of glitter.

Example 27

19g of the PAPA of example 21 and 20g of "Mandarin Grapefront" perfume oil (Givaudan Corp.) were added to a glass mixing flask and the mixture was gently stirred at ambient temperature for 15 minutes. Blue dye (1 drop) was added to the mixture, turning the solution to light yellow/green. To the homogeneous mixture was added 2.0gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 31.0g of the mixture was poured into a round cake-shaped (bundtcake-shaped) flexible silicone mold having a uniform top width of 1.75 inches, a height of 0.75 inches, and a bottom width of 2.5 inches. The set time was recorded at 67 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch.

Example 28

This example illustrates the preparation of a stationary phase transfer liquid. Into a glass mixing flask were charged 10.4g of the polyamine of example 21 and 18g of 1-decanol (freezing point, 5-7 ℃ C.) as an active oil, 0.6g as an odorant and a crosslinking reaction retarderBenzaldehyde and the mixture was stirred gently at ambient temperature for 15 minutes. To the homogeneous mixture was added 1.5gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 18.5g of the mixture was poured into a truncated pyramidal flexible silicone mold having a uniform top width of 0.75 inches, a height of 0.75 inches, and a bottom width of 1.0 inch. The set time was recorded at 30 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch. When placed in a freezer, the object hardens without splitting. When removed from the freezer and allowed to warm at room temperature, the object regains elasticity but is still a hard, firm, transparent solid.

Example 29

This example illustrates the preparation of a small air freshener for use in a purse or other small enclosed space. To a glass mixing bottle was added 5g of the polyamine of example 21 and 5g of "Ocean" perfume oil (Orlandi, Inc.) and the mixture was gently stirred at ambient temperature for 15 minutes. Blue dye (2 drops) was added to the mixture, causing the solution to turn pale blue. To the homogeneous mixture was added 0.6gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 5.0g of the mixture was poured into diamond polyethylene button head molds having a uniform middle perimeter of 1.5 inches, a height of 1.625 inches, and top and bottom widths of 0.5 inches. The set time was 7 minutes. The mixture was sealed and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong,Transparent and non-tacky to the touch.

Example 30

28g of the polyamine of example 21 and 30g of "Country Garden" perfume oil (Belle-Aire) are added to a glass mixing bottle and the mixture is stirred gently at ambient temperature for 15 minutes. Green dye (3 drops) and yellow crumb (0.02g) were added to the mixture to turn the solution yellow/green. To the homogeneous mixture was added 3.0gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the air bubbles, and a total of 50.0g of the mixture was poured into a hemispherical flexible silicone mold having a base perimeter of 7.25 inches, a height of 1.0 inch, and a base width of 3.75 inches. The set time was 260 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch.

Example 31

30g of the polyamine from example 21 and 30g of "Cotton Fresh" perfume oil (Symrise) are added to a glass mixing flask and the mixture is stirred gently at ambient temperature for 15 minutes. Autumn leaf metal flakes (6 flakes) were added to the clear mixture. To the homogeneous mixture was added 3.5gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 50g of the mixture was poured into a glass bottle having a uniform circumference of 7.25 inches, a height of 1.25 inches, and a top and bottom width of 2.25 inches. The set time was recorded at 28 minutes. The mixture was covered and allowed to cure for 24 hours without interference. Thereafter removing the mold from the cross-linked cavityThe air freshener object was removed, which was now solid, transparent and smooth to the touch.

Example 32

37g of the polyamine of example 21 and 40g of "Lemon Citrus" perfume oil (Alpha Aromatics) were added to a glass blender jar and the mixture was gently stirred at ambient temperature for 15 minutes. Green crumb (0.02g) was added to the mixture, turning the solution yellow/green. To the homogeneous mixture was added 4.0gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the air bubbles, and a total of 60.0g of the mixture was poured into a lemon-shaped flexible silicone mold having a uniform top and bottom width of 0.75 inches, a height of 2.75 inches, and a median perimeter of 5.5 inches. The set time was recorded at 42 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch.

Example 33

A glass mixing bottle was charged with 36g of the polyamine of example 21 and 40g of "Cherry Berry" perfume oil (Belle-Aire) and the mixture was stirred gently at ambient temperature for 15 minutes. A red dye (3 drops) was added to the mixture to turn the solution red. To the homogeneous mixture was added 4.0gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the air bubbles, and a total of 60.0g of the mixture was poured into a rosette-shaped flexible silicone mold having a uniform top and bottom width of 3.75 inches, a height of 0.75 inches, and a circumference of 12.25 inches. The set time was recorded at 155 minutes. CoveringThe mixture was allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch.

Example 34

19g of the polyamine of example 21 and 20g of "Cherry" perfume oil (Atlas, Inc.) were added to a glass mixing flask and the mixture was gently stirred at ambient temperature for 15 minutes. A red dye (3 drops) was added to the mixture to turn the solution red. To the homogeneous mixture was added 2.0gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and a total of 28.0g of the mixture was poured into a hollow polyethylene golf ball mold having a uniform perimeter of 5.25 inches. The set time was recorded at 75 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch.

Example 35

This example illustrates the preparation of a foamed article. To a glass mixing bottle was added 15g of the polyamine of example 21, 15g60 g of polymerized fatty acid (Arizona Chemical) and 30g of "Very Berry" perfume oil (Belmay Corp.) the mixture was stirred gently at ambient temperature for 15 minutes to give a slightly cloudy solution. A red dye (3 drops) was added to the mixture to turn the solution red. To the homogeneous mixture was added 4.0gN3300A. The mixture is then stirred for a short time (untilUntil homogeneous) was achieved, allowed to stand for a few minutes to dissipate the bubbles, and a total of 40g of the mixture was poured into a paper baking cup mold (bagging cupper mold) having a uniform top and bottom width of 2.0 inches, a height of 1.25 inches, and a circumference of 7.5 inches. The set time was 8 minutes. The mixture was allowed to cure for 24 hours without interference. During this time, the object is full of entrapped air bubbles (foam) and doubles in volume, forming a dome. The foam air freshener is now strong and non-tacky to the touch. When compressed (squeezed), it returns to a circular shape.

Example 36

By charging the following raw materials (figures in parentheses are weight percent) into a 3L round bottom glass reactor equipped with an overhead mechanical stirrer:1009 hydrogenated dimer acid [24.0 ]]P-aminobenzoic acid [5.0 ]]、D-2000[54.0]、D-400[11.5]AndT-403[5.5]and the above raw materials were heated to 215 ℃ under a dry nitrogen stream to prepare batches of the carbonyl-substituted aromatic amine-terminated polyamide polyamine. The mixture was maintained under the above conditions for about 25 hours, and then the reaction mixture was poured into a container. The product was a clear, viscous, light yellow liquid. The polymer has a titer amine value (non-potentiometric titration, or amine value by potentiometric titration 30-35, amine reactivity equivalent of 1,800-1,600), a weight average molecular weight of 13,000-14,000, a number average molecular weight of 4,500-5,500, and a viscosity of 250cP at 130 ℃. The material was used in a series of fixation experiments at 30 wt.%, test mediumIs a liquid (70 wt.%) without the use of active agents, catalysts or retarders. The results (table below) show that the set time for this modified PAPA varies up to about 1 day in the absence of the retarder aldehyde. The data also show the acceleration of cure rate using an alcoholic diluent such as polypropylene glycol or its alkyl ethers.

	Setting time	Once curing has occurred	Syneresis
	Setting time	Once curing has occurred	Syneresis	Experimental liquid Medium	(minutes)	Appearance of the product	(after 4 days)
Dipropylene glycol	60	Turbidity (haze)	Slightly syneresis	Experimental liquid Medium	(minutes)	Appearance of the product	(after 4 days)
Dipropylene glycol	60	Turbidity (haze)	Slightly syneresis	Isostearyl alcohol	60	Turbidity (haze)	Without syneresis
Tripropylene glycol	66	Slightly turbid	Apparent syneresis	Isostearyl alcohol	60	Turbidity (haze)	Without syneresis
Tripropylene glycol	66	Slightly turbid	Apparent syneresis	Dipropylene glycol monomethyl ether	90	Is transparent	Without syneresis
Castor oil	105	Slightly turbid	Without syneresis	Dipropylene glycol monomethyl ether	90	Is transparent	Without syneresis
Castor oil	105	Slightly turbid	Without syneresis	Salicylic acid methyl ester	400	Is transparent	Without syneresis
FINSOLV TN armor acid ester	440	Is transparent	Without syneresis	Salicylic acid methyl ester	400	Is transparent	Without syneresis

Adipic acidDibutyl ester	1014	Is transparent	Without syneresis
Adipic acidDibutyl ester	1014	Is transparent	Without syneresis	Dipropylene glycol dimethyl ether	1245	Is transparent	Without syneresis
Diethyl-m-toluamide (DEET)	1470	Is transparent	Without syneresis	Dipropylene glycol dimethyl ether	1245	Is transparent	Without syneresis
Diethyl-m-toluamide (DEET)	1470	Is transparent	Without syneresis	Isophorone	1845	Transparent, yellow	Without syneresis

Example 37

This example illustrates the preparation of another type of polyamide polyamine terminated with a carbonyl-substituted aromatic amine. Prepared according to the procedure of example 37 using the starting materials (numbers in parentheses are weight percent) T-5000[92.9] and p-aminobenzoic acid [7.1 ]. The polymer used in examples 38-41 had an amine equivalent of 1,950.

Example 38

This example illustrates the preparation of an article containing liquid fragrance trapped behind a matrix membrane. Mixing into glassA bottle was charged with 5.0g of the polyamine of example 36 and 5.0gTN, the mixture was stirred gently at ambient temperature for 15 minutes. To the homogeneous mixture was added 0.6gN3300A. The mixture was then stirred for a short time (until homogeneous phase was reached), allowed to stand for a few minutes to dissipate the bubbles, and then 1.0g portions were poured without stirring into 1oz glass bottles containing 10g of "Lily of the Valley" green perfume oil (Wellington Fragrances). The base solution floats above the perfume oil, which remains as a separate oil layer below the base solution. The set time for the top (film) layer, which typically absorbs some perfume oil, is 80 minutes. The bottle was capped and cured for 24 hours. After which the bottle is hung upside down. At this point, the perfume oil typically permeates through the film layer and evaporates, acting as a sustained release air freshener.

Example 39

This example illustrates the preparation of an article containing an aromatic filler. 15g of the polyamine from example 36, 6g of castor oil and 9g of commercial coffee powder are added to a glass mixing flask and the mixture is stirred gently at ambient temperature for 30 minutes. To the viscous slurry was added 2.0gN3300A. The mixture was then stirred for a short period of time (until homogeneous phase was achieved), allowed to stand for a few minutes to dissipate the bubbles, and (18.0 g was used) the mixture was poured into a disc-shaped flexible mold having a uniform perimeter of 8.25 inches, a height of 0.25 inches, and a top and bottom width of 2.5 inches. The set time was recorded at 165 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now aromatic (coffee-flavored), strong, soft, and non-contactIs sticky.

Example 40

This example illustrates the preparation of an aqueous article. 20g of the polyamine of example 36, 20g of "Snuggle Type" perfume oil (Alpha Aromatics) and 8g of deionized water were added to a glass blender jar and the mixture was gently stirred at ambient temperature for 15 minutes to give a milky suspension of water in the matrix-perfume solution. Blue dye (2 drops) was added to the mixture. To the light blue, milky mixture was added 2.5gN3300A. The mixture was then stirred for a short time (until homogeneous phase was reached) and allowed to stand for a few minutes to allow the bubbles to dissipate. The 31.0g portion was then poured into a doughnut-shaped flexible silicone mold having a uniform top width of 1.75 inches, a height of 0.75 inches, and a bottom width of 2.5 inches. The set time was recorded at 130 minutes. The mixture was covered and allowed to cure for 24 hours without interference. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and non-tacky to the touch. As the moisture evaporated over a month, the product gradually became transparent (starting from the edges and moving towards the center).

EXAMPLE 41

This example illustrates the preparation of an example dispersion. Solution A: to a glass mixing bottle was added 8g of the polyamine of example 36 and 8gTN, the mixture was stirred gently at ambient temperature for 15 minutes. To the homogeneous mixture was added 0.8gN3300A. The mixture was then stirred for a short time (until homogeneous phase was reached) and allowed to stand for a few minutes to allow the bubbles to dissipate. Solution B: adding 3 into another glass mixing bottle2g of deionized water and 0.8g of surfactant (T-DET A-136). The mixture was stirred (10 min). Solution a was then poured into solution B and stirred for 10 minutes. The blend of mixture a + mixture B was then poured into a metal evaporating dish and the water was allowed to evaporate (24 hours). A white smooth powder of fixed oil particles was obtained, which was insoluble in toluene.

Example 42

Representative articles containing pesticides which can be prepared according to the present invention are the following controlled release Diethyltoluamide (DEET) devices. The entire mixture was made from DEET (20 parts), dimethyl adipate carrier (50 parts), benzaldehyde as fragrance and retarder (1.6 parts), the polyamidopolyamine of example 21 (26.8 parts) and a trace of orange dye. Adding to the blend under stirringN3300 polyisocyanate (3.2 parts), the final mixture was poured into a shell-shaped silicone mold. After curing, the shell-shaped roundings (mediallions) formed were strong, soft, non-sticky solids.

Example 43

Representative articles containing pheromones that can be prepared according to the present invention are the following controlled release devices for pheromone octadecanal. The whole mixture is composed of octadecanal (30 parts) as carrierTN benzoate (30 parts) and the polyamide polyamine of example 21 (35.5 parts). Adding to the blend under stirringN3300 polyisocyanate (4.5 parts), the final mixture was poured into a cylindrical mold. After curing, the resulting material is a strong, soft, non-tacky solid that can be cut into small disks for use as bait.

Example 44

This example illustrates the use of a styrene-maleic anhydride copolymer and a polyamide polyamine as reaction ligands for the preparation of a low-odor disc-shaped air freshener. Adding 6.0g of 25% by weight of the polyamidopolyamine of example 21 to a glass mixing bottleTN solution, 7.5g 20 wt.%232 poly (styrene-co-maleic anhydride, NOVA Chemicals) solution, and about 2g "Ocean" perfume oil (Wellington, Inc.). The mixture was gently stirred at ambient temperature for a few minutes and the blue dye (4 drops) was added. The mixture was initially slightly cloudy, but became clear after a few minutes and remained clear and apparently homogeneous. The mixture (about 11g used) was poured into a disc-shaped polyethylene mold and allowed to stand without interference. After about 2 hours the mixture cures to a tacky elastomer and after 24 hours the mold can be removed. The mold is then removed from the cross-linked air freshener object, which is now strong, soft, transparent and slightly tacky to the touch.

Example 45

This example illustrates the use of a cationic surfactant to prepare a fixed fragrance emulsion for use as a fabric softener. A blend of these ingredients was first prepared by warming and stirring the following individual ingredients: PAPA (4.0g), "Cinnamon Chai" perfume oil (3.0g) andb1216 alkyl dimethyl benzyl ammonium chloride (80% active, Degussa Corporation, 1.0 g). To the blend was added water (9.0g) and 0.65g with stirringN3300A. The mixture quickly became viscous and uniformly cloudy. It is storage stable and can be diluted with water, indicating that it is an oil-in-water dispersion. Light scattering particle size measurements on this material determined that the particle size distribution was bimodal with about 50% by weight of the particles having a size of about 0.4 microns and the other 50% having a size of about 3.0 microns.

Example 46

This example illustrates the preparation of an immobilized cationic surfactant for use as a fabric softener. A blend of these ingredients was first prepared by warming and stirring the following individual ingredients: PAPA (3.0g) of example 21,DPM (1.0g) andb1216 alkyl dimethyl benzyl ammonium chloride (80% active, Degussa Corporation, 6.0g), which was then cooled to room temperature. Preparation ofDPM (4.2g) andN3300A (0.8 g). The two clear mixtures were then mixed together and immediately poured into a mold. The blended components cure almost immediately and are sufficiently strong that they can be removed from the mold in less than 30 minutes. The final product contained 32 wt% active quaternary ammonium compound.

Ranges used in this context are used as abbreviations to describe each and every value within the range, including all subranges therein.

Many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

All references cited herein, and the references cited therein, are incorporated herein by reference for all references cited herein, and for the portions of their cited references relevant to the subject matter of the present invention and all embodiments thereof.

Claims

1. An article comprising a porous support material and a composition disposed therein, the composition comprising a cured polymer matrix and an active liquid, wherein the active liquid is immobilized in the cured polymer matrix; and the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of the reactive liquid.

2. The article of claim 1, wherein the porous support material comprises at least one selected from the group consisting of paper, paperboard, cellulose pad, cellulose pulp, felt, fabric, porous synthetic foam, porous ceramic, activated carbon, soil, diatomaceous earth, charcoal, silica, and clay.

3. The article of claim 2, wherein the article is selected from the group consisting of a therapeutic article having a therapeutic active liquid, a neutraceutical article having a nutritive active liquid, a pesticide article having a pesticidal active liquid, a laundry care article having an active liquid for laundry care, and an air freshener having an active liquid that is a perfume oil.

4. The article of claim 3, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine in the presence of a reactive liquid and a reaction promoter.

5. The article of claim 3, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine in the presence of a reactive liquid and a reaction retarder.

6. The article of claim 3, wherein the cured polymer matrix is a reaction product of a compound having at least two anhydride functional groups and a polyamine in the presence of a reactive liquid, and the compound having at least two anhydride functional groups is not a maleic-based polyolefin rubber.

7. The article of claim 3, wherein the cured polymer matrix is a reaction product of a compound having at least two epoxy functional groups and a polyamine in the presence of a reactive liquid, and the polyamine is a non-aromatic polyamine.

8. The article of claim 3, wherein the cured polymer matrix is the reaction product of a compound having at least two isocyanate functional groups and a polyamine in the presence of a reactive liquid, and the at least two isocyanate functional groups may be the same or different.

9. The article of claim 8, wherein the reactive amine groups of the polyamine comprise amino groups derived from at least one of anthranilic acid or p-aminobenzoic acid.

10. The article of claim 3, wherein the cured polymer matrix is the reaction product of a compound having at least two non-aromatic isocyanate functional groups and a polyamine in the presence of a reactive liquid, and the at least two non-aromatic isocyanate functional groups may be the same or different.

11. The article of claim 3, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of a reactive liquid; wherein the polyamine has an amine value of 10-100meq KOH/g and has a viscosity of no more than about 500cP measured at 150 ℃.

12. The article of claim 3, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of a reactive liquid; wherein the polyamine is a liquid at room temperature.

13. An article comprising a part, component or assembly comprising a cured polymer matrix and an active liquid, wherein the active liquid is immobilized in the cured polymer matrix; and the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of the reactive liquid.

14. The article of claim 13, wherein the article is selected from the group consisting of a therapeutic article having a therapeutic active liquid, a neutraceutical article having a nutritive active liquid, a pesticide article having a pesticidal active liquid, a laundry care article having an active liquid for laundry care, and an air freshener having an active liquid that is a perfume oil.

15. The article of claim 14, wherein the cured polymer matrix is the reaction product of a compound having at least two isocyanate functional groups and a polyamine in the presence of a reactive liquid.

16. The article of claim 14, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine in the presence of a reactive liquid and a reaction retarder.

17. The article of claim 14, wherein the cured polymer matrix is a reaction product of a compound having at least two anhydride functional groups and a polyamine in the presence of a reactive liquid, and the compound having at least two anhydride functional groups is not a maleic-based polyolefin rubber.

18. The article of claim 14, wherein the cured polymer matrix is a reaction product of a compound having at least two epoxy functional groups and a polyamine in the presence of a reactive liquid, and the polyamine is a non-aromatic polyamine.

19. The article of claim 14, wherein the cured polymer matrix is the reaction product of a compound having at least two isocyanate functional groups and a polyamine in the presence of a reactive liquid.

20. The article of claim 19, wherein the reactive amine groups of the polyamine comprise amino groups derived from at least one of anthranilic acid or p-aminobenzoic acid.

21. The article of claim 14, wherein the cured polymer matrix is the reaction product of a compound having at least two non-aromatic isocyanate functional groups and a polyamine in the presence of a reactive liquid.

22. The article of claim 19, wherein the article comprises a shape selected from the group consisting of: triangular, square, circular, spherical, elliptical, regular geometric and irregular geometric shapes.

23. The article of claim 14, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of a reactive liquid; wherein the polyamine has an amine value of 10-100meq KOH/g and has a viscosity of no more than about 500cP measured at 150 ℃.

24. The article of claim 14, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of a reactive liquid; wherein the polyamine is a liquid at room temperature.

25. An article comprising a support component and a solid composition supported thereon, the solid composition comprising a cured polymer matrix and an active liquid, wherein the active liquid is immobilized in the cured polymer matrix; and the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of the reactive liquid.

26. The article of claim 25, wherein the article is selected from the group consisting of a therapeutic article having a therapeutic active liquid, a neutraceutical article having a nutritive active liquid, a pesticide article having a pesticidal active liquid, a laundry care article having an active liquid for laundry care, and an air freshener having an active liquid that is a perfume oil.

27. The article of claim 25, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine in the presence of a reactive liquid and a reaction promoter.

28. The article of claim 25, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine in the presence of a reactive liquid and a reaction retarder.

29. The article of claim 25, wherein the cured polymer matrix is a reaction product of a compound having at least two anhydride functional groups and a polyamine in the presence of a reactive liquid, and the compound having at least two anhydride functional groups is not a maleic-based polyolefin rubber.

30. The article of claim 25, wherein the cured polymer matrix is a reaction product of a compound having at least two epoxy functional groups and a polyamine in the presence of a reactive liquid, and the polyamine is a non-aromatic polyamine.

31. The article of claim 25, wherein the cured polymer matrix is the reaction product of a compound having at least two isocyanate functional groups and a polyamine in the presence of a reactive liquid.

32. The article of claim 31, wherein the reactive amine groups of the polyamine comprise amino groups derived from at least one of anthranilic acid or p-aminobenzoic acid.

33. The article of claim 25, wherein the cured polymer matrix is the reaction product of a compound having at least two non-aromatic isocyanate functional groups and a polyamine in the presence of a reactive liquid.

34. The article of claim 31, wherein the article comprises a shape selected from the group consisting of: triangular, square, circular, spherical, elliptical, regular geometric and irregular geometric shapes.

35. The article of claim 25, wherein the support assembly comprises at least one selected from the group consisting of: glass, ceramic, metal, paper, plastic, and oil impermeable materials.

36. The article of claim 25, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of a reactive liquid; wherein the polyamine has an amine value of 10-100meq KOH/g and has a viscosity of no more than about 500cP measured at 150 ℃.

37. The article of claim 25, wherein the cured polymer matrix is the reaction product of a compound having at least two functional groups selected from the group consisting of epoxy, isocyanate, anhydride, and acrylate, and a polyamine, in the presence of a reactive liquid; wherein the polyamine is a liquid at room temperature.