MX2008010300A - Anti-cancer pharmaceutical composition - Google Patents

Abstract

Disclosed is an anti-cancer pharmaceutical composition for use in the prevention or treatment of a carcinoma, a sarcoma or hematopoietic cancer. The composition comprises a compound represented by the general formula (I) or a salt thereof as an active ingredient:(I) wherein R represents a phenyl group substituted by 1 to 5 substituents selected from a halogen atom, a hydroxy group, a C1-C6alkyl group, a halogeno C1-C6alkyl group, a C1-C6alkoxy group, a C1-C6alkylthio group, an amino group which may be substituted, a C3-C10cycloalkyl group which may be substituted, a C1-C7aliphatic acyloxy group, a nitrogenated 4- to 7-membered saturated heterocyclic group, a nitrogenated 5- to 6-membered aromaticheterocyclic group, a nitro group and a cyano group;and X represents an oxygen or sulfur atom. Also disclosed is an anti-cancer pharmaceutical composition comprising an epidermal growth factor receptor (EGFR) inhibitor, a vascular endothelial growth factor receptor (VEGFR) inhibitor or a Raf kinase inhibitor and a composition represented by the general formula (I) above or a salt thereof as active ingredients.

Description

METHOD FOR THE PREPARATION OF PE POLYURETHANE FOAM DIMENSIONALLY STABLE SPRAY BASED ON POLYOL FTHALATE POLYESTER FIELD OF THE INVENTION This present technology discloses compositions based on polyester phthalate and fully hydrated polyurethane water-sprayed foams of high dimensional stability derived from said compositions. More particularly, it describes compositions based on polyester phthalate comprising a polyester polyol, a cell opening agent, a catalyst, and water. The present technology also discloses methods for the preparation of compositions based on polyester phthalate and production methods of spray foams thereof. In addition, the present technology describes the use of said foams as insulation materials, especially roof insulation materials.

BACKGROUND OF THE INVENTION In the manufacture of refrigeration boxes, cold meats coolers, doors, and other insulated containers, polyurethane foam is poured into place between two substrates defining a cavity. In the production of roof insulation, the polyurethane foam is usually sprayed on the place. There are several desirable criteria that polyurethane foam must possess. One requirement is that the polyurethane foam should flow well and / or spread evenly over a surface so that the entire cavity is filled with the foam or the entire surface area is evenly coated with the foam. If the foam gels prematurely, voids will form behind the gelled foam prematurely where the foaming mass can not reach or as in a spray foam application, the foam will not produce a uniform coating on a substrate. A second requirement is to use the least amount of foamed raw material to fill a particular cavity or cover a surface to save raw material costs. To adequately fill all the portions of the cavity and prevent the presence of voids, it is often necessary to overfill the cavity or to over-cover the surface. The lower the over-fill that is necessary to completely fill the mold, however, the greater the savings in the cost of the raw material. In this way, it is desired to form a container filled with polyurethane having the lowest possible density. A third criterion is that an alternative blowing agent for ozone depleting CFC and HCFC is needed. Several fully halogenated hydrocarbons (chlorofluorocarbons, usually referred to as CFCs) normally used as blowing agents for the preparation of rigid foams are believed to cause environmental problems. For example, CFC-1 1 (trichlorofluoromethane) and CFC-12 (dichlorodifluoromethane) have been implicated in stratospheric ozone layer deterioration and are no longer used in the preparation of polyurethanes. Many partially halogenated hydrocarbons currently in use will no longer be available for use of polyurethane foam beyond 2003. Water is clearly considered to be the safest alternative blowing agent, more economically and ecologically attractive for the spray foam industry and Many manufacturers of polyurethane foam are now returned to water as the exclusive source of blowing agent instead of CFC or HCFC. However, at this point, spray foam blown with water has not proven to be practical or effective due to a variety of significant limitations. For example, in the field of cooling containers where the foam is poured into place, rigid polyurethane foams blown with water present a unique problem. Rigid polyurethane foams blown with water tend to be closed cell foams which shrink and wrinkle for a period of time after foaming and during curing. This is partly due to the migration of carbon dioxide gas, produced by the reaction of water with polyisocyanate, outside the closed cells and leaving behind a vacuum which then tightly closes and shrinks the foamed mass with the passage of time. The foam that shrinks in foaming applications at the site will be pulled away from a substrate, or continue to adhere to the internal surface of the substrates causing undulation and surface deformities in the substrate. The problem of foam shrinkage in CFC-blown and HCFC-blown foams has not been so serious since CFC gases tend to migrate out of closed cells very slowly over a period of months or years, if migrating, resulting in a minimized pressure gradient inside the foam. The problem of foam shrinkage or dimensional stability is more severe in applications such as cold meats coolers where the coolers are frequently subjected to wide variations in temperature, from indoor temperatures of 21.1 to 1-26.67 ° C at beach temperatures in direct sunlight which can rise to 43.33-44.44 ° C, also causing the gas to expand and diffuse into the cells. In general, water blown foams have suffered from poor dimensional stability, narrow processing window, high reaction exotherm, poor interlaminar adhesion and substrate, and an inability to be processed in conventional spray foam equipment. The difficulty in processing in routine equipment has been the result of higher formulation viscosity; Due to the absence of blowing agent HCFC-141 b, thinning of the resin does not occur as is normally the case when said blowing agent is present. Additionally, the requirement for the use of increased isocyanate (due to the presence of significant water levels) has precluded use in conventional equipment that frequently requires processing in isocyanate / polyol volume ratios or 1: polyol mixture: 1.

Deficient adhesion characteristics are the result of increased foam friability associated with poor mixing (due to the higher resin viscosity) as well as extensive use of high functional polyether and / or Mannich type polyols. These high functional polyols are usually required in order to provide the foamed polymer with adequate interlacing density to resist shrinkage. The high reaction exotherm, a direct result of the water-isocyanate reaction and the absence of cooling of a physical blowing agent such as HCFC-141 b, contributes to cracking of the foam and surface blisters. The extensive heat also makes it difficult to control the reaction profile thereby limiting the range of environmental conditions under which the sprayed foam can be applied. It is, therefore, desirable to produce a foam having a lower density yet which completely fills the cavity or spreads on a surface and is dimensionally stable in order to decrease raw material costs. The decrease in density, however, especially in water blown foam which already has a tendency to shrink has the present disadvantage of further exacerbating the dimensional instability of the foam. Examples of open cell foams have been described in the US patent. Nos. 5,214,076; 5,219,893; 5,250,579; 5,262,447; 5,318,997; 5,346,928; 5,350,777; 6,066,681; and 6.21 1, 257, each of which is incorporated herein by reference in its entirety.

BRIEF DESCRIPTION OF THE INVENTION The present technology avoids many of all the limitations of water-blown spray foams excluded from commercial availability. The present technology provides a solution to the question of dimensional stability. By uniformly and homogeneously opening the cells of the sprayed foam, a rapid pressure equalization is allowed after the diversion of carbon dioxide, thereby limiting or eliminating the vacuum-induced shrinkage. Through the incorporation of the single cell opening technology of the present technology, modifications of the formulation component can be easily made without impacting the dimensional stability of the foam. In particular, the present technology makes it possible to adjust the polyol composition to reduce the safety of the polymer in higher functional polyester or Mannich type polyols. This results in lower formulation viscosity characteristics and improved adhesion. In one aspect of the present technology, a significant proportion of lower functional groups, i.e. functional groups 1-2, the polyester polyol is incorporated into the polyol formulation. The present technology also depends on the use of non-reactive diluents in the formulation. These non-reactive diluents (which are usually plasticizers) perform various functions including viscosity reduction, increased flammability performance, reduction in reaction exotherm, and the ability to process the resin in conventional spray foam equipment. In particular, the use of non-reactive diluents as provided herein allows the foam to be processed in an A / B volume ratio of approximately 1: 1 without adversely affecting the qualitative or physical properties of the polymer, where "side A" means materials comprising an isocyanate and "B side" means materials comprising a polyol or a mixture of polyol, such as terms used by those of skill in the art. A preferred isocyanate is an aromatic polymeric isocyanate. In summary, the present technology provides spray foam technology and spray foams that meet the physical and processing requirements stipulated by the industry; The present technology provides the first and only commercially viable, fully commercially available water-blown spray foam available. Thus, in one aspect, the present technology provides spray foams which are the product of a reaction mixture comprising a mixture of polyol and an aromatic polymeric isocyanate, preferably in a mixture / isocyanate volume ratio of about 1: 1. These mixtures comprise a polyol formulation, non-reactive diluent, cell opening agent, and blowing agent. Mixtures optionally include other components as necessary to adjust, for example, the viscosity and stability of the mixture. The polyol formulation, as discussed below, comprises any of a variety of polyols, ie, polyol polyester, polyol polyether, and / or Mannich type polyol. The present technology provides fully dimensionally stable, low density, water-blown polyurethane foams that are predominantly prepared with low functional polyester polyols. These foams have sufficient open cell content to prevent shrinkage of the foam. In addition, the inventive foams are of sufficient strength to prevent shrinkage of the foam. Accordingly, in at least one aspect of the present technology, a method is provided for the preparation of a polymeric foam comprising urethane units and having an open cell content sufficient to resist shrinkage. This method comprises mixing an aromatic polymeric isocyanate with a dispersed polyol mixture, wherein the polyol blend comprises: (a) from about 20%, preferably 25%, to about 90% based on the weight of the polyol blend of a formulation of polyol; (b) a blowing agent; (c) a cell opening agent which is a mono-, di- or polyvalent metal salt of a fatty acid; and (d) from about 0.05 to about 50% by weight of the polyol mixture of a non-reactive diluent, and by spraying the mixture of the aromatic polymeric isocyanate and the polyol mixture to react the aromatic polymeric isocyanate and the polyol mixture for form the foam polymeric Another aspect of the present technology provides blends of polyols, ie, polyol resins, suitable for the preparation of a polymer foam comprising urethane units and having an open cell content sufficient to resist shrinkage. These mixtures comprise: a. a polyol formulation comprising from about 25 to about 90% by weight of the mixture of a polyester polyol, a polyester polyol and / or a Mannich type polyol; b. a blowing agent; c. a cell opening agent which is a mono-, di-, or polyvalent metal salt of a fatty acid; and d. from about 0.05% to about 50% by weight of the mixture of a non-reactive diluent. In one aspect, the polyol blends are mixtures of dispersed polyols. With respect to the polyol or polyol mixtures of the present technology, in at least one embodiment a sprayable polyol mixture is provided to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage. The rigid foam made of a sprayable polyol mixture is the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH number of about 85 to about 125.

The spray polyol mixture contains from about 20% to about 90% by weight of the mixture of a polyol formulation consisting essentially of a diethylene glycol polyester polyether phthalate having an OH value of about 195 to about 400, and a polyol of Mannich having an OH value of about 315 to about 550, and optionally, diethylene glycol, water as a primary blowing agent; from about 0.01% to about 2.0% by weight of the polyol mixture of a cell opening agent consisting essentially of calcium stearate; and from about 0.05% to about 50% by weight of at least one non-reactive diluent consisting essentially of a tris-isopropylchlorophosphate, a propylene carbonate, a dibasic ester or dibasic esters, or a mixture thereof. In another embodiment a spray polyol mixture is provided to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage made from the reaction product of an aromatic polymeric isocyanate and a polyol mixture having a NCO / OH number from about 85 to about 125. Additionally, the spray polyol mixture contains about 25% to about 40% by weight of a diethylene glycol polyester phthalate polyol having an OH value of about 230 to about 250.; about 20% to about 35% by weight of a Mannich polyol having an OH value of about 415 to about 435, and optionally, about 5.5% to about 9% by weight of a diethylene glycol; about 1% to about 3.5% by weight of water; about 0.1% to about 1% by weight of the mixture of a cell opening agent consisting essentially of calcium stearate, lithium stearate, magnesium stearate, strontium stearate, zinc stearate, calcium myristate, its derivatives, or its combinations; and about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of a tris-isopropylchlorophosphate, a propylene carbonate, a dibasic ester or dibasic esters and a mixture thereof. In another aspect of the present technology, the optional inclusion of compatibilizing surfactants is provided. For example, at least one embodiment of the present technology provides a spray polyol mixture comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture dispersed at an NCO / OH index of from about 85 to about 125. The spray polyol mixture is suitable for use in a rigid polymer spray foam and comprises a polyol formulation consisting essentially of a polyester polyol phthalate diethylene glycol having an OH value of about 230 to about 250, and a Mannich polyol having an OH value of about 415 to about 435; water as a primary blowing agent; an opener of calcium stearate cell, a mixture of non-reactive diluent consisting of tris-isopropylchlorophosphate, propylene carbonate, and a dibasic ester or dibasic esters; a catalyst selected from the group consisting of dimethylethanolamine, dimethylcyclohexylamine, a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol or its mixture; and an alkoxylated polysiloxane surfactant. In another embodiment of this aspect of the present technology a spray polyol mixture is provided to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of a polymeric isocyanate. aromatic and a polyol mixture having an NCO / OH number of from about 85 to about 125. The spray polyol mixture contains about 25% to about 40% by weight of a diethylene glycol polyester polyether phthalate having an OH value of about 290 to about 325; about 20% to about 35% by weight of an annich polyol having an OH value of about 415 to about 435; optionally, about 6% to about 8% by weight of a diethylene glycol; about 1% to about 3.5% by weight of water; about 0.1% to about 2.5% by weight of a cell opening agent consisting essentially of calcium stearate, lithium stearate, magnesium stearate, strontium stearate, zinc stearate, calcium myristate, its derivatives, or combinations thereof; about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of tris-isopropylchlorophosphate, a propylene carbonate, a dibasic ester or mixtures thereof; and up to about 15% by weight of at least one compatibilizing surfactant comprising a nonyl phenol alkoxylate. In a further embodiment of this aspect of the present technology a sprayable polyol mixture is also provided for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an isocyanate. aromatic polymer and a polyol mixture having an NCO / OH number of from about 85 to about 125. The spray polyol mixture comprises about 25% to about 40% by weight of a diethylene glycol polyester polyether phthalate having an OH value from about 230 to about 250; about 20% to about 35% by weight of a Mannich polyol having an OH value of from about 415 to about 435; optionally, about 6% to about 8% by weight of diethylene glycol; about 1% to about 3.5% by weight of water; about 0.1% to about 2.5% by weight of a mono-, di- or polyvalent metal salt of a fatty acid as a cell-opening agent; about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester and mixtures thereof; and up to about 15% by weight of at least one compatibilizing agent comprising a nonyl phenol alkoxylate. In yet a further embodiment a spray polyol mixture is provided for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture. having an NCO / OH number of from about 85 to about 125. The spray polyol mixture comprises about 46.1 1 wt% of a diethylene glycol polyester phthalate polyol having an OH value of about 290 to about 325; about 23.05% by weight of a high functional alkoxylated sucrose polyol having an OH value of about 380 to about 420, about 2.1 1% by weight of an alkoxylated polysiloxane surfactant; about 0.21% by weight of a calcium stearate cell opener; about 5.77% by weight of a catalyst mixture comprising dimethylcyclohexylamine, dimethylethanolamine, and an isocyanate polymerization catalyst; about 0.15% by weight of 30% lead catalyst; about 0.38% by weight of 2-ethylhexanoic acid; about 11.5% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters and their mixtures; about 3.01% by weight of water; and up to about 15% by weight of a compatibilizing agent consisting essentially of a nonyl phenol alkoxylate. In a further embodiment a sprayable polyol mixture is provided for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture which it has an NCO / OH number of from about 85 to about 125. The spray polyol mixture contains about 35% to about 50% by weight of a diethylene glycol polyester phthalate polyol having an OH value of about 290 to about 325; (b) from about 20% to about 30% by weight of a Mannich-type polyol having an OH value of about 460 to about 480; about 2% to about 10% by weight of a diethylene glycol; about 1% to about 3% by weight of an alkoxylated polysiloxane surfactant; about 0.1% to about 1% by weight of a calcium stearate cell opener; about 1% to about 5% by weight of a catalyst mixture comprising dimethylcyclohexylamine, dimethylethanolamine, and an isocyanate polymerization catalyst; about 10% to about 25% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters and mixtures thereof; about 1% to about 3% by weight of water, and up to about 15% by weight of a nonyl phenol alkoxylate as a compatibilizing agent. In yet a further aspect the present technology involves a mixture of sprayable polyol to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH number of about 85 to about 125. The spray polyol mixture contains about 30.83% by weight of a diethylene glycol polyester polyether phthalate having an OH value of about 230 to about 250; (b) about 32.00% by weight of a Mannich type polyol having an OH value of about 415 to about 435; about 5.80% by weight of a diethylene glycol; about 1.30% by weight of an alkoxylated polysiloxane surfactant; about 0.60% by weight of a calcium stearate cell opener; about 3.85% by weight of a catalyst mixture comprising dimethylcyclohexylamine, dimethylethanolamine, an isocyanate polymerization catalyst, and a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol; about 28.12% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters and mixtures thereof; about 3.30% by weight of water; and optionally up to about 15% by weight of a compatibilizing agent consisting essentially of a nonyl phenol alkoxylate. Alternatively, another aspect of the present technology involves a mixture of sprayable polyol to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH number of from about 85 to about 125. The spray polyol mixture comprises about 30.44% by weight of a diethylene glycol polyester polyether phthalate having an OH value of about 230 to about 250; about 31.44% by weight of a Mannich-type polyol having an OH value of about 415 to about 435; about 5.80% by weight of a diethylene glycol; about 1.91% by weight of an alkoxylated polysiloxane surfactant; about 0.70% by weight of calcium stearate cell opener, about 4.27% by weight of a catalyst mixture comprising amine and isocyanate polymerization catalysts; about 1.08% by weight of a lead catalyst; about 27.58% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters, or mixtures thereof; about 2.58% by weight of water; and optionally up to about 15% by weight of an agent of compatibilization consisting essentially of a nonyl phenol alkoxylate. Inventive foams made with the polyol or blends of polyols of the present technology are produced using cell opening agents having melting points or softening points between about 100 ° and about 180 ° C. When formulated according to the present technology, these cell opening agents form part of a dispersed polyol mixture having a droplet size or dispersion particle of less than about 50 μ. Without being bound by a particular theory, it is believed that during the polymerization reaction, the dispersion containing the cell openers stops working by releasing the cell opener in this way allowing the controlled cell opening. Without linking to a particular theory, it is believed that the cell opening takes place immediately before the gelation of the polymer. The resulting low density, water-blown foam is primarily an open cell foam and exhibits dimensional stability in the spray-free ascending condition as well as within a packaged cavity. By "primary open cell" is meant a foam having a sufficient amount or percentage of open cells to resist shrinkage. In this way, the present technology includes methods and compositions for the preparation of polyurethane foams having strength and an open cell content sufficient to prevent or resist shrinkage comprising reacting an aromatic polymeric isocyanate with a dispersed polyol mixture. The dispersed polyol blend of the present technology comprises a polyol formulation, a blowing agent, a cell opening agent, and a non-reactive diluent. The polyol formulation of the present technology may optionally contain an acid. It has been unexpectedly discovered that the addition of an acid to a combination of a polyol, a blowing agent such as water, and a specific cell opening agent provides a dispersed polyol mixture having surprising stability. Mixtures of dispersed polyols, when reacted with aromatic polymeric isocyanates, form sputtered and poured urethane foams on the open cell site having excellent dimensional stability at low densities. The present technology also provides blends of polyols comprising a polyol formulation, preferably containing high levels, i.e., up to about 100% by weight of the formulation, of a polyester polyol, together with a blowing agent and an opening agent. of cell. Optionally, the polyol blends of the present technology may comprise an emulsifier.

DETAILED DESCRIPTION OF THE INVENTION In this document, all temperatures are set in degrees Celsius unless otherwise stated. All quantities, ratios, concentrations, proportions and the like are established in units of weight, unless otherwise stated, except for solvent ratios, which are in units of volume. Percentages are by weight unless otherwise indicated. By OH value is meant the hydroxyl value, a quantitative measure of the concentration of hydroxyl groups, usually stated as mg KOH / g, that is, the number of milligrams of potassium hydroxide equivalent to the hydroxyl groups in 1 g of substance . By NCO / OH index is meant the molar ratio, multiplied by 100, of isocyanate groups to hydroxyl groups (including those contributed by water) in the reaction between the polyol mixture and the aromatic polymeric polyisocyanate. Functionality means the number of reactive groups, for example, hydroxyl groups, in a chemical molecule. By uniform open cell content is meant a polyurethane foam having an average open cell content that does not vary substantially between two or more samples removed from the same foamed material and is separated in the foam material by a distance of at least about 2 hours. cm.

The polyol blends of the present technology are preferably "dispersed polyol mixtures". By the term "dispersed polyol mixture" is meant a mixture of polyol or polyol resin, i.e., a mixture comprising a polyol formulation, a cell opening agent, a non-reactive diluent and a blowing agent, together with any of the optional components, wherein the cell opening agent, preferably as particles, and more preferably as particles having an average diameter of less than about 50 μ, is stably suspended in the polyol mixture. Said dispersion is stable for a period of time sufficient to allow reaction with aromatic polymeric polyisocyanate to form an open cell foam having an open cell content sufficient to prevent or resist shrinkage. Preferably, the dispersed polyol blends are stable at a temperature of about 25 ° C for at least about 1 week, more preferably, the blends are stable at about 25 ° C for at least about 3 months. By softening point as used herein means a temperature at which a material becomes more liquid, less rigid, softer, or more elastic; that is, a temperature at or above its transition temperature. As used herein, the shrinkage resistance means less than about 5% shrinkage of a polyurethane foam material.

The polyol blends of the present technology preferably have particles having average diameters of less than about 50 μ, more preferably less than about 25 μ, still more preferably less than about 10 μ, and more preferably less than about 1 μ. Smaller particles are believed to result in improved stability of the polyol blends which in turn result in improved uniformity of the open cell content of the final polyurethane foams. The present technology provides polyurethane foams suitable for use as disposed insulation materials or among a variety of substrates. Suitable substrate materials comprise metal such as aluminum or metal foil, wood, including mixed composite wood, rubber acrylonitrile-butadiene-styrene (ABS) triblock, optionally modified with styrene-butadiene diblock, styrene-ethylene triblock / butylene styrene, optionally functionalized with maleic anhydride and / or maleic acid; polyethylene terephthalate, polycarbonate, polyacetals, high impact polystyrene modified with rubber (HIPS), mixtures of HIPS with polyphenylene oxide; copolymers of ethylene and vinyl acetate, ethylene and acrylic acid, ethylene and vinyl alcohol; homopolymers or copolymers of ethylene and propylene such as polypropylene, high density polyethylene, high molecular weight high density polyethylene, polyvinyl chloride, nylon 66, or amorphous thermoplastic polyesters, glass fiber or glass fiber composite; roof floor materials such as gypsum board, Dens-deck, Isoboard, cement wood wool (Tectum Deck), lightweight concrete, modified asphalt, and a variety of rubber-based membranes. The foams of the present technology have densities in place of about 32.04 to about 80.1 kg / m3 and, in one embodiment, the foams of the present technology have densities in place of about 36.85 to about 56.07 kg / m3. The spray foams of the present technology have densities in place sprayed from about 32.04 to about 56.07, and preferably from about 36.85 to about 52.87, kg / m3. As explained in more detail below, the foams of the present technology can be water blown foams. Water blown foams according to the present technology have K-factors of at least about 0.16 to about 0.24. The polyurethane foam of the present technology comprises the reaction product of aromatic polymeric polyisocyanate with at least one polyol component in a polyol mixture. The polyurethane foam is rigid, meaning that the ratio of tensile strength to compressive strength is high, in the order of about 0.5 to about 1 or greater, and has less than about 10 percent elongation. The blends described herein are generally free of CFCs and / or hydrocarbon blowing agents and are highly suitable for use in Spray foam applications, for example, spray foams for insulated roofs. Although not critical to the present technology, blends of the present technology may optionally contain from about 0.01 to about 50.0 wt% of an entanglement agent. Suitable entangling agents are, for example, high functionality alcohols such as triols or pentaerythritol. In a preferred aspect, the present technology provides blends of polyols suitable for the preparation of a urethane foam, comprising: (a) from about 28% to about 85%, more preferably about 80% by weight, based on the weight of the composition, of a polyol formulation; (b) from about 0.05% to about 3%, preferably less than about 2.0% by weight, based on the weight of the composition, of a cell opening agent; (c) from about 3.5%, preferably about 5% to about 50%, preferably about 45% by weight, more preferably about 15% to about 30% based on the weight of the composition, of a non-reactive diluent; and (d) from about 0.5% to about 5% by weight, based on the weight of the composition, of water.

More preferred polyol formulations of the present technology comprise from about 1% to about 100% by weight of a polyester polyol or mixtures of said polyols. More preferably, the polyol formulation or mixtures thereof comprise polyester polyols having an OH value of from about 195 to about 400 and a molecular weight of from about 390 to about 800. Even more preferred polyol formulations comprise from about 30% to about 48. % polyester polyol by weight of the polyol mixture, and more preferably from about 30% to 45% polyester polyol by weight of the polyol mixture. The blends of the present technology may further comprise: (e) from about 0.25% to about 5% by weight, based on the weight of the composition, of a urethane catalyst; and / or (f) from about 0% to about 1% by weight, based on the weight of the composition, of an acid; and / or (g) from about 0% to about 3% by weight, based on the weight of the composition, of a surfactant. In a preferred embodiment, the polyol formulation comprises from about 1% to about 100%, more preferably about 75% to about 100% by weight, based on the weight of the polyol formulation, of a diethylene glycol polyester phthalate polyol having an OH value of about 150 to about 350 and that comprises: (a) the reaction product of a mixture comprising a phthalic acid compound and a low molecular weight aliphatic diol and (b) an optional nonionic surfactant, and wherein the polyol polyester diethylene glycol phthalate has a molecular weight from about 350 to about 700. In a particularly preferred embodiment, the polyol blend comprises from about 50% to about 85% by weight of a polyol formulation comprising a polyol diethylene glycol phthalate having an OH value of about 195. to about 400, a Mannich-type polyol having an OH value from about 315 to about 550, and diethylene glycol. In another particularly preferred embodiment, the polyol blend comprises from about 50% to about 85% by weight of a polyol formulation comprising a polyol diethylene glycol phthalate having an OH value of about 23 to about 350, a polyol type Mannich having an OH value from about 415 to about 435, and diethylene glycol. In another particularly preferred embodiment, the polyol blend of the present technology comprises: (a) from about 30% to about 35% by weight of a diethylene glycol polyester phthalate polyol having an OH value of from about 290 to about 325 or a polyol polyester phthalate diethylene glycol having an OH value of about 230 to about 250; (b) from about 20% to about 30% by weight of a Mannich-type polyol having an OH value of from about 415 to about 435; (c) optionally from about 5.5% to about 9% by weight of diethylene glycol; (d) from about 1% to about 3.5% by weight of water; (e) from about 0.1% to about 1% by weight of cell opener; and (f) from about 15% to about 34% by weight of the non-reactive diluent. In another preferred embodiment, the polyol blend comprises, based on the weight of the mixture, about 30% to about 35% by weight of the diethylene glycol polyester polyether phthalate having an OH value of about 290 to about 325, or the polyol diethylene glycol polyester phthalate having an OH value of from about 230 to about 250; from about 20% to about 30% by weight of the Mannich-type polyol having an OH value of from about 415 to about 435, optionally from about 6% to about 8% by weight of diethylene glycol, from about 1% to about 3.5% by weight of water, from about 0.15% to about 2.5% by weight of the cell opener, and from about 15% to about 34% by weight of the non-reactive diluent. In one aspect, the present technology discloses a urethane foam made of a reaction mixture comprising: (a) a polyol blend of the present technology, and (b) an aromatic polymeric isocyanate, an aromatic polymeric polyisocyanate, or its mixture . In this embodiment, the aromatic polymeric isocyanate is preferably 2,4- and / or 2, 4/2, 6-toluene, isocyanate, diphenyl methane 4,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or mixture thereof. Also in this embodiment, the aromatic polymeric polyisocyanate is alternatively a polyphenylene polymethylene polyisocyanate. The present technology also contemplates in another embodiment a mixture of sprayable polyol to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a mixture of polyol having an NCO / OH number of from about 85 to about 125. The spray polyol mixture contains from about 25% to about 40% by weight of a diethylene glycol polyester phthalate polyol having an OH value of from about 290 to about 325; about 20% to about 35% by weight of a Mannich polyol having an OH value of from about 315 to about 550, optionally, up to about 9% by weight of diethylene glycol; about 1% to about 3.5% by weight of water; about 0.1% to about 1% by weight of a cell-opening people selected from the group consisting of mono-, di- or polyvalent fatty acid metal salts; and about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters and mixtures thereof. In a further aspect a mixture of sprayable polyol for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having a NCO / OH ratio of about 85 to about 125 is also contemplated. The spray polyol mixture comprises from about 20% to about 90% by weight of the mixture of a polyol formulation consisting essentially of a diethylene glycol polyester polyether phthalate having an OH value of from about 195 to about 325, a polyol of Mannich that has an OH value of from about 315 to about 550, and diethylene glycol; water as a primary blowing agent; a cell opening agent consisting essentially of calcium stearate, lithium stearate, magnesium stearate, strontium stearate, zinc stearate, calcium myristate, derivatives thereof, or combinations thereof; and from about 0.05% to about 50% by weight of the mixture of at least one non-reactive diluent consisting essentially of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters, or their mixture. In yet a further aspect of the present technology a spray polyol mixture comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a dispersed polyol mixture is contemplated. at an NCO / OH index of about 85-125, wherein the spray polyol mixture is suitable for use in a rigid polymer spray foam. The spray polyol mixture comprises a polyol formulation consisting essentially of a diethylene glycol polyester phthalate polyol having an OH value of about 290 to about 325 and a Mannich polyol having an OH value of about 415 to about 435, and optionally diethylene glycol; water as a primary blowing agent; a divalent metal salt of a fatty acid cell opener; a non-reactive diluent mixture consisting essentially of tris-isopropylchlorophosphate, propylene carbonate, or a dibasic ester or dibasic esters; a catalyst selected from the group consisting of dimethylethanolamine, dimethylcyclohexylamine, a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol or its mixture; and an alkoxylated polysiloxane surfactant. Additionally, another aspect of the present technology also describes sprayable rigid foams. As a result, in at least one embodiment of the present technology a rigid foam is provided having a volumetric ratio of aromatic polymeric isocyanate to approximately 1: 1 polyol mixture made of a spray polyol mixture to make a foam comprising urethane units and having an open cell content sufficient to withstand shrinkage made of the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH number of about 85 to about 125. The polyol blend sprayable contains from about 20% to about 90% by weight of the mixture of a polyol formulation consisting essentially of a diethylene glycol polyester polyether phthalate having an OH value of about 230 to about 250, a Mannich polyol having an OH value from about 415 to about 425, and diethylene glycol; water as a primary blowing agent; a sufficient amount of calcium stearate as a cell opening agent; and from about 0.05% to about 50% by weight of the mixture of at least one diluent not reagent selected from the group consisting of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters and mixtures thereof. The present technology further discloses a method for the preparation of polyol compositions which is suitable for the preparation of a urethane foam. This method comprises the combination of: (a) from about 38% to about 90% by weight, based on the weight of the composition, of a polyol formulation; (b) from about 0.05% to about 2.0% by weight, based on the weight of the composition, of a cell opening agent; (c) from about 5% to about 45% by weight, based on the weight of the composition, of a non-reactive diluent; and (d) from about 0.5% to about 5% by weight, based on the weight of the composition, of water. The methods of the present technology may additionally include the addition of the following optional components: (e) from about 0.25% to about 5% by weight, based on the weight of the composition, of a urethane catalyst; and / or (f) from about 0% to about 1% by weight, based on the weight of the composition, of an acid; and / or (g) from about 0% to about 3% by weight, based on the weight of the composition, of a surfactant. In another embodiment, the present technology provides a foam of polyurethane comprising from about 0.01% to about 1% by weight of a cell opening agent which is a mono-, di- or polyvalent metal salt of a fatty acid, preferably a divalent metal salt of a fatty acid, where the foam has an open cell content sufficient to resist shrinkage and exhibits less than about 5% shrinkage when stored at about 70 ° C and about 100% relative humidity for about 28 days. These foams comprise the reaction product of an aromatic polymeric isocyanate with a polyol mixture of the present technology. Preferably, the polyurethane foam exhibits less than about 3% shrinkage when stored at about -28.89 ° C for 28 days. In yet another embodiment, the present technology discloses a method for the preparation of a urethane foam comprising reacting the polyol composition with an aromatic polymeric isocyanate, an aromatic polymeric polyisocyanate, or its mixture, to produce the foam. According to this embodiment, the NCO / OH index of the foam is about 85 to about 125. The foam produced according to the embodiments described herein is pourable and / or sprayable. Accordingly, the present technology also discloses spraying foam application methods, which are derived from the mixtures described herein, to various substrates, particularly roofs.

Polyols or blends of polyols Polyols or blends of polyols suitable for use in the present technology are polyester polyols, polyether polyols, Mannich-type polyols and combinations thereof. Preferred polyol mixtures are those comprising a polyester polyol. In these preferred blends, the polyester polyol can be up to about 100% of the polyol formulation. In other preferred polyol blends, the polyol formulation is a mixture of polyols, for example, (a) polyol polyester and polyol polyether, (b) polyol polyester and Mannich type polyol, (c) polyol polyether and Mannich type polyol, or (d) polyether polyol, polyester polyol, and Mannich type polyol. In this way, the polyol formulation can be up to about 100% by weight of the polyether polyol, that is, it can be free of polyester polyol, or it can contain a mixture of polyether polyols and polyester. Suitable starting polyol components for use in blends of polyols or blends according to the present technology include polyesters containing at least two hydroxyl groups, as a rule having a molecular weight of from about 300 to about 10,000, in particular, polyesters containing from 2 to 8 hydroxyl groups, and, in some embodiments of the present technology, having a molecular weight of from about 390 to about 800, wherein the acid component of these polyesters comprises at least about 50% by weight in one embodiment, and at least about 70% by weight in another embodiment, of acid residues italic. These polyesters containing hydroxyl groups include, for example, reaction products of polyhydric alcohols, such as dihydric and trihydric, with italic acids and other polybasic carboxylic acids, such as dibasic. Instead of using the free italic acids or polycarboxylic acids, the corresponding acid anhydrides or corresponding acid esters of lower alcohols or their mixtures can be used for the preparation of polyesters. Orthophthalic acids, isophthalic acids and / or terephthalic acids can be used as the italic acid. The optional polybasic carboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and can be substituted, for example, with halogen atoms and / or can be saturated. The following are mentioned as examples; succinic acid, atypical acid, suberic acid, azelaic acid, sebacic acid, trimellitic acid, trimellitic anhydride, tetrahydroitic acid anhydride, hexahydro thalic acid anhydride, endomethylene tetrahydro-italic acid anhydride, glutaric acid anhydride, maleic acid, acid anhydride maleic acid, fumaric acid, dimeric and trimeric fatty acids, such as oleic acid, optionally mixed with monomeric fatty acids. Suitable polyhydric alcohols include, for example, ethylene glycol, propylene glycol, - (1, 2) and - (1, 3), diol- (1, 8), neopentyl glycol, cyclohexane dimethanol (1,4-bis-hydroxymethylcyclohexane), -methyl-1, 3-propane diol, glycerol, trimethylolpropane, hexametriol- (1, 2,6), butane triol- (1, 2,4), trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dibutylene glycol, and polybutylene glycols. The polyesters can also contain carboxyl end groups. Polyesters of lactose, such as e-caprolactone, or hydroxycarboxylic acids, such as d-hydroxycaproic acid, may also be used. In one embodiment, polyester polyols for use in the present technology comprise the reaction products of (a) italic acid compounds, (b) low molecular weight aliphatic diol compounds, (c) and nonionic surfactant compounds. Said polyester polyols are described in US Patents. Nos. 4,644,047 and 4,644,048, each of which is incorporated herein by reference in its entirety. Suitable polyols for the present technology also include Mannich type polyols. Mannich-type polyols are prepared by reacting, for example, nonylphenol, formaldehyde, and mono and dialkanolamines or mixtures thereof. This intermediate is then usually reacted with alkylene oxide to produce the final "Mannich polyol". The preparation of Mannich-type polyols are also described in the patents of E.U.A. Nos. 3,297,597; 4,137,265; 4,383,102; 4,247,655; 4,654,376, each of which is incorporated herein in its entirety. According to the present technology, polyesters containing at least one, generally 2 to 8, and in one embodiment of the present technology, 3 to 6 hydroxyl groups and having a molecular weight of from about 100 to about 10,000 can be used in the polyol mixture. These are prepared, for example, by the polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin, either by itself, for example in the presence of BF3, or by the chemical addition of these epoxides, optionally as mixtures or successively, for starting components having reactive hydrogen atoms, such as alcohols or amines, for example water, ethylene glycol, propylene glycol- (1, 3) or - (1, 2) ), trimethylol propane, 4,4-dihydroxy diphenylpropane aniline, ethanolamine ammonia or ethylenediamine. Sucrose polyethers that have been described, for example in Auslgeschrift German Nos. 1, 176,358 and 1, 064,938 can also be used according to the present technology. Among the corresponding polythioethers that can be used are the condensation products obtained from thiodiglycol itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or aminoalcohols should be particularly mentioned. The products obtained are ethers mixed with polythio, polythioether esters or polythio ether ether amides, depending on the co-components. Polyhydroxyl compounds which themselves contain urethane or urea groups and modified and unmodified natural polyols, such as castor oil, carbohydrates or starch can also be used. Addition products of alkylene oxides and phenyl / formaldehyde resins or of alkylene oxides and urea / formaldehyde resins are also suitable in accordance with the present technology.

Representative of these compounds which can be used according to the present technology have been described, for example, in higher polymers, volume XVI, "Polyurethanes, Chemistry and Technology", by Saunders and Frisch, Interscience Publishers, New York; London, Volume I, 1962, pages 32-34 and pages 44 and 54 and Volume II, 1964, pages 5 and 6 and 198-199, and in Kunstsoff-Handbuch, Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, for example, on pages 45 to 71. In certain embodiments, the polyol formulation comprises a polyester polyether ether phthalate. These polyester-ether polyols are the reaction product of a polyol polyester phthalate ("intermediate polyester polyols"), and a polyhydric polyol. The intermediate polyester phthalate polyol is the reaction product of: (1) about 2% to about 60% by weight, based on the weight of the polyester polyol of phthalic anhydride or phthalic acid; and (2) about 40% to about 98% by weight, based on the weight of the polyester polyol, of at least one polyol of the formula: wherein R1 represents: (a) alkylene groups of from about 2 to about 10 carbon atoms; or (b) -CH2-R2-CH2- wherein R2 represents: (c) its mixture. The alkylene group R1 can be straight or branched chain, saturated or unsaturated, and when R2 contains a hydroxyl radical, said hydroxyl group can be optionally alkoxylated. Preferably, the polyester phthalate polyol is of general formula wherein R represents: (a) alkylene groups of from about 2 to about 0 carbon atoms; or where R2 represents: or (c) its mixture. Suitable polyhydric polyols include (i) alkoxylated glycerin, such as propoxylated glycerin, (ii) alkoxylated sucrose, and (iii) alkoxylated glycols, such as diethylene glycol, ethylene glycol, propylene glycol, butylene glycol, and the like, or mixtures of any of these polyhydric alcohols. . Typical alkoxylation agents of any of these polyhydric alcohols are ethylene, propylene and / or butylene oxide. In a preferred aspect, the polyester and polyhydric alcohol are combined together in the polyol mixture and before reacting the mixture with the "side A" of isocyanate. In these blends, the polyester polyol and polyhydric alcohols can be present in a variety of suitable ratios. Suitable ratios of polyol polyester to polyhydric alcohol are from about 25: 1 to about 1: 1. More preferred ranges are higher ratios from about 20: 1 to about 15: 1 at lower ratios of about 1.5: 1. Higher even more preferred ratios are approximately 8: 1. More preferred lower ratios are about 3: 1 or about 2: 1. The polyester-ether polyols of the present technology can be the reaction product of phthalic anhydride (PA), a polyhydroxyl compound, and an alkoxylation agent, for example, propylene oxide, as shown below: wherein R is C2-io, cycloalkyl, alkenyl, alkynyl, aromatic, polyoxyethylene, saturated or unsaturated, branched or linear polyoxypropylene alkyl; wherein R may contain pendant secondary functionality such as hydroxyl, aldehyde, ketone, ether, ester, amide, nitrile, amine, nitro, thiol, sulfonate, sulfate, and / or carboxylic groups. Where pendant secondary hydroxyl functionality is present, said hydroxyl groups may be optionally alkoxylated. In some embodiments of the present technology, phthalic anhydride is reacted with a polyol, i.e., a diol such as diethylene glycol to form a polyester polyol. Preferred polyester polyols can be made as follows: where n = 2-10, x = 1-500. According to this embodiment, polyester polyol PA intermediates for use in the present technology are derived from the condensation of phthalic anhydride and ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, triethylene glycol, and tetramethylene glycol and mixtures thereof. Specific polyester polyols for use in the compositions of the present technology include for example diethylene glycol polyester polyols of phthalic acid. Suitable diethylene glycol polyester polyols of phthalic acid are commercially available from Stepan Company, Northfield Illinois. Representative auxiliary polyols are StepanPol® PS-2002 (a diethylene glycol polyester polyol of phthalic anhydride having an OHv of about 195 and a functionality of about 2.0), StepanPol® PS-2352 (a diethylene glycol polyester polyol of phthalic anhydride having a OHv of about 230 and a functionality of about 2.0), StepanPol® PS-3152 (a diethylene glycol polyester polyol of phthalic anhydride having an OHv of about 315 and a functionality of about 2.0), StepanPol® PS-4002 (a polyester polyol of diethylene glycol of phthalic anhydride having an OHv of about 400 and a functionality of about 2.0), StepanPol® PS-2502A (an aromatic polyester polyol having an OHv of about 245) and mixtures thereof. In the present technology, by value of OH (OHv) means the hydroxyl value, a quantitative measurement of the concentration of hydroxyl groups, usually stated as mg of KOH / mg, that is, the number of milligrams of the equivalent of potassium hydroxide to the hydroxyl groups in 1 g of substance. By functionality means the number of reactive groups, for example, hydroxyl groups, in a chemical molecule. In this manner, the diethylene glycol polyester polyols of the anionic acid representative of the present technology can have an OHv of about 195 to about 400 and a functionality of about 1.5 to about 2.5. However, it should be appreciated by those skilled in the art that the OHV of polyester polyols of the present technology may vary from about 195 to about 205, from about 205 to about 215, from about 215 to about 225, from about 225 to about 235, from about 235 to about 245, from about 245 to about 255, from about 255 to about 265, from about 265 to about 275, from about 275 to about 285, from about 285 to about 295, from about 295 to about 305, from about 305 to about 315, from about 315 to about 325, from about 325 to about 335, from about 335 to about 345, from about 345 to about 355, from about 355 to about 365, from about 365 to about 375 , from approximately 375 to about 385, from about 385 to about 395, and about 395 to approximately 400 or slightly higher. Additionally, it should be appreciated by those skilled in the art that the functionality of the polyester polyols of the present technology may vary from about 1.5 to about 1.6, from about 1.6 to about 1.7, of about 1.7. at about 1.8, from about 1.8 to about 1.9, from about 1.9 to about 2.0, from about 2.0 to about 2.1, from about 2.1 to about 2.2, from about 2.2 to about 2.3, from about 2.3 to about 2.4, of about 2.4 to approximately 2.5 or slightly higher. Other auxiliary polyester polyols, ie, polyester polyols based on non-italic anhydride, include, for example, polyester polyols derived from the condensation of caprolactone and a polyalcohol, and polyester terato polyols (e.g., Terato-203) a polyol polyester diethylene glycol terephthalate which has an OHv of 315 and a functionality of 2.3, commercially available from Kosa). Specific auxiliary polyether polyols suitable for use in the methods and compositions of the present technology include for example the condensation products of propylene glycol / propylene oxide, trimethylolpropane / ethylene oxide / propylene oxide, trimethylolpropane / propylene oxide, sucrose / propylene glycol / propylene oxide, alkylamine / propylene oxide, and glycerin / propylene oxide, and mixtures thereof.

Mannich Polyol or Polyols Specific Mannich polyols suitable for use in the compositions of the invention include for example those obtained by the alkoxylation of a Mannich condensation product as described in the US patent. No. 3,297,597 (Production of rigid polyurethane foam, G.D. Edwards, R.L. Soulen, 1967); Patent of E.U.A. No. 4,137,265 (water-insoluble nitrogen-containing polyols, G.D. Edwards, D.M. Rice, R.L. Soulen, 1979); Patent of E.U.A. No. 4,383,102 (Method for the production of a low viscosity spray polyol by reacting an alkylene oxide with reaction product of a phenol, an amine and a smaller formaldehyde portion, K.G. McDaniel, G.P. Speranza, 1983); Patent of E.U.A. No. 4,654,376 (Polyurethane foams based on amino polyols, M.E. Brennan, K.G. McDaniel, H.P. Klein, 1987); Patent of E.U.A. No. 6,495,722 B1 (Mannich polyols for rigid spray foams, R.L. Zimmerman, M.P. Devine, P.l., Weaver, 2002); and Patent of E.U.A. No. 6,281, 393 B1 (Useful polyols for the preparation of rigid polyurethane foam for blowing in water, N.F. Molina, S.E. Moore, 2001). Mannich polyols suitable for use in the practice of the present technology are commercially available from Huntsman polyurethanes, Houston, Texas as JEFFOL® R-350X (a Mannich polyol having an OHV of 530), JEFFOL® R-425X (a polyol of Mannich having an OHV of 425), JEFFOL® R-466X (a Mannich polyol having an OHV of 470), JEFFOL® R-.650X (a Mannich polyol having an OHV of 450), JEFFOL® R-315X (a Mannich polyol having an OHV of 325); from Siltech Corporation, Toronto, Canada as SILPOL® SIP-425LV (a Mannich polyol having an OHV of 425); from PUMEX, INC., Georgetown, Texas as MARKOL® RB-214 (a Mannich polyol having an OHV of 470), MARKOL® RB-216 (a Mannich polyol having an OHV of 470); from Dow Chemical, Midland, Michigan as VORANOL® 350X (a Mannich polyol having an OHV of 530), VORANOL® 470X (a Mannich polyol having an OHV of 470).

Aromatic Polymer Polyisocyanate Aromatic polymeric polyisocyanate starting components used in accordance with the present technology include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie 562: 75 -136. Examples include ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate; dodecane-1, 12-diisocyanate; Cyclobutane-1,3-diisocyanate, cyclohexane-1, 3-, and 1,4-diisocyanate and mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (German Ausiegeschrift No. 1, 202.785, U.S. Patent No. 3,401, 190); hexahydrotylene-2,4- and 2,6-diisocyanate and mixtures of these isomers; hexahydrophenylene-1, 3- and / or -1,4-diisocyanate; perhydrodiphenylmethane-2,4'- and / or 4,4'-diisocyanate; phenylene-1, 3- and 1,4-diisocyanate; toluene-2,4- and 2,6-diisocyanate and mixtures of these isomers; diphenylmethane-2,4'- and / or 4,4'- diisocyanate; naphthylene-1, 5-diisocyanate; triphenylmethane-4,4 ', 4"-triisocyanate; polyphenylpolymethylene polyisocyanate obtainable by condensation of aniline / formaldehyde followed by phosgenation and which can be described, for example, in British Patent Nos. 874,430 and 848,671; isocyanate of m- and p-isocyanatophenyl sulfonyl according to U.S. Patent No. 3,454,606; perchlorinated aryl polyisocyanate as described, for example, in U.S. Patent No. 3,227,138, polyisocyanate, containing carbodiimide groups as described in U.S. Pat. No. 3,152,162, the diisocyanates described in U.S. Patent No. 3,492,330, polyisocyanates containing allophanate groups as described, for example, in British Patent No. 994,890, Belgian Patent No. 761, 626 and Dutch Patent Application. No. 7,102,524, polyisocyanates containing acrylated urea groups according to German Patent No. 1, 230,778, polyisocyanates containing Biuret reaction groups as described above. for example, in the Patents of the U.S.A. Nos. 3,124,605 and 3,201, 372; and in British Patent No. 889,050; polyisocyanates prepared by telomerization reactions as described, for example, in the U.S. Patent. No. 3,654,016; polyisocyanates containing ester groups as mentioned, for example, in British Patents Nos. 965,474 and 1, 072,956, in the US patent. No. 3,567,763 and in German Patent No. 1, 231, 688; reaction product of the aforementioned isocyanates with acetals according to German Patent No. 1, 072,385, and polyisocyanates containing polymeric fatty acid groups described in U.S. Pat. No, 3,455,883. As well Suitable for use in the present technology are isocyanate-terminated prepolymers using hydroxy containing reagents of any of the foregoing. The distillation residues obtained from the commercial production of isocyanates and which will contain isocyanate groups can also be used, optionally dissolved in one or more of the aromatic polymeric polyisocyanates mentioned above. Mixtures of aromatic polymeric polyisocyanates mentioned above can also be used. In some embodiments of the present technology, the polyisocyanates that are readily available are used, for example, toluene-2,4- and -2,6-diisocyanate and mixtures of these isomers ("TDI"); polyphenylene polymethylene polyisocyanates obtainable by aniline / formaldehyde condensation followed by phosgenation ("crude MDI"); and, polyisocyanates containing carbodiimide groups, alofenate groups, urea groups or Biuret reaction groups ("modified polyisocyanates"), and mixtures thereof. In some embodiments of the present technology, polyisocyanates are 2,4- and / or 2,4-2,6-toluene diisocyanate, 4,4'-diphenyl methane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and their mixtures In one embodiment of the present technology, the polyisocyanate is methylene bis (phenyl isocyanate). In a rigid spray application in the usual place, the aromatic polymeric polyisocyanate mixture is reacted with a mixture of polyol in a ratio of about 0.9 to about 1.1: 1 ratio (v / v). The reaction can be achieved using a spray gun or other suitable mixing devices. Alternatively, the reaction can be achieved using a high pressure shock machine provided with a nozzle capable of filling a void volume. As another alternative, the reaction can be achieved using a static low pressure mixing machine equipped with a nozzle to fill a void volume.

Acid component Some embodiments of the polyol formulation used in the present technology comprise a polyester polyol and an acid. While not wishing to be bound by any particular theory, it is believed that the acid is used in an amount capable of maintaining the stability of the cell opener dispersion within the polyol mixture for a sufficient period of time to allow production of a polyurethane foam and preferably a foam having a uniform open cell content. Preferably, the foam is made by reacting the polyol mixture with an aromatic polymeric polyisocyanate. The amount of acid optionally present is generally up to about 5% by weight of the polyol mixture. In one embodiment, the amount of the acid is from about 0.05 to about 5% by weight of the polyol mixture. In another modality, the amount of acid is from about 0.1% to about 1%. Suitable acids are generally Bronsted acids, that is, substances that can donate protons. In one embodiment of the present technology, the acids are organic acids. In another embodiment, the acids are various alkanoic acids or alkenoic acids of the formula RCO2H, where R is hydrogen, a straight or branched chain alkyl group having from about 1 to about 18 carbon atoms, or a straight-chain alkenyl group or branched having from about 2 to about 18 carbon atoms. Representative acids include, for example, formic, oleic, acetic, isobutyric, and 2-ethylhexanoic acids. In a preferred embodiment, the acid is 2-ethylhexanoic acid.

Blowing Agent In accordance with the present technology, the reaction of the polyol mixture dispersed as set forth above with an aromatic polymeric polyisocyanate is provided with an open cell rigid polyurethane foam as desired. In a preferred embodiment of the present technology, water is used as a primary blowing agent in the dispersed polyol mixture. In this embodiment, the amount of water as a blowing agent is from about 0.5% to about 5% and can be from about 1% to about 4% and additionally it can be from about 1.5% to about 2.5%, based on the weight of the composition. When the amount of water is insufficient, you can not produce a low density foam. Although the preparation of the foam is usually carried out using a dispersed polyol mixture having water as a blowing agent, in another embodiment, the blowing agent comprises a secondary blowing agent, either alone, or preferably in combination with the primary blowing agent, water. Suitable secondary blowing agents include both CFC and non-CFC blowing agents. Secondary blowing agents are usually liquids that have low boiling points. Suitable secondary blowing agents include, but are not limited to, halogenated hydrocarbons such as, for example, 2,2-dichloro-2-fluoroethane (HCFC-1 b), water, and hydrocarbons such as pentane, hydrofluorocarbons (HFC) and perfluorocarbons for example. Other suitable organic blowing agents include, for example, acetone, ethyl acetate, halogenated alkanes, such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, and also butane, pentane, hexane, heptane or diethyl ether. The effect of a blowing agent can also be obtained by adding compounds that decompose at room temperature above room temperature to release gases, such as nitrogen, for example, azo compounds, such as azoisobutyric acid nitrile. Other examples of blowing agents and details about the use of blowing agents can be found in Kunststoff-handbuch, Volume VII, published by Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, for example, in pages 108 and 109, 453 to 455 and 507-510. Additional examples of suitable optional blowing agents are described in US Patents. Nos. 5,346,928, which are hereby incorporated by reference in their entirety.

Cell opening agent Suitable cell opening agents for use in the present technology include known mono-, di-, or polyvalent metal salts of long chain fatty acids of about 1 to about 22 carbon atoms. Preferably, the present technology utilizes divalent metal salts of long chain fatty acids. Examples of such agents may include calcium stearate, lithium stearate, magnesium stearate, strontium stearate, zinc stearate, calcium ministat, its derivatives, or combinations thereof. Examples of divalent metal salts of stearic or myristic acid, such as calcium stearate, magnesium stearate, strontium stearate, zinc stearate or calcium myristate, are preferred, as well as other metal salts such as those described in Japanese Patent Application. of open to the public No. 61 -153480. However, it should be appreciated by those of skill in the art that additional mono- or polyvalent cell opening agents can be used in the practice of the present technology such as lithium stearate. The cell opening agent is used in an amount from about 0.01% to about 2.0% based on the weight of the composition. The cell opening agent is usually capable of forming a stable dispersion with the polyester polyol. In preferred embodiments of the present technology, cell opening agents having melting or softening points of about 100 to about 180 ° C are used. In one embodiment, mixtures of dispersed polyols comprise from about 0.05% to about 1.5% cell opening agent based on the weight of the composition. In another embodiment, mixtures of dispersed polyols comprise from about 0.1% to about 0.8% cell opening agent based on the weight of the composition.

Isocyanate polymerization catalysts Compounds which readily initiate a polymerization reaction of NCO groups at temperatures as low as room temperature are used as the catalyst system for polymerization.

Compounds of this type are described, for example, in French Patent No. 1, 441, 565, Belgian Patents Nos. 723,153 and 723,152 and German Patent No. 1, 112.285. Said catalyst systems are, in particular, Mannich mononuclear or polynuclear bases of condensable phenols, oxo compounds and secondary amines which are optionally substituted with alkyl groups, aryl groups or aralkyl groups, and, in one embodiment of the present technology, those in the which formaldehyde is used as the compound oxo and dimethylamine as the secondary amine. According to the present technology, catalysts that can be used as the catalyst for the polyurethane reaction include, for example, tertiary amines, such as triethylamine, tributylamine, N-methyl morpholine, N-ethyl-morpholine, N-co-comorpholine, ?,?,? '?' - tetramethylethylenediamine, 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethyl-aminoethyl-piperazine, N, N-dimethylbenzylamine, bis- ( N, N-diethylaminoethyl) -adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine,?,? - dimethylcyclohexylamine, N, N, N'N'-tetramethyl-1,3-butane diamine,?,? - dimethyl-beta-phenylethylamine , 1,2-dimethylimidazole and 2-methylimidazole and Curithane 52 (available from Air Products). Tertiary amines containing isocyanate-reactive hydrogen atoms used as catalysts include, for example, triethanolamine, triisopropylamine, N-methyl-diethanolamine, N-ethyldiethanolamine, α, β-dimethylethanolamine and their reaction products with alkylene oxides, such as oxide of propylene and / or ethylene oxide. Silaamines having carbon-silicon bonds as described, for example, in German Patent No. 1, 229,290 (corresponding to US Patent No. 3,620,984) can also be used as catalysts, for example, 2,2,4- trimethyl-2-silamorpholine and 1,3-diethylaminomethyl-tetramethyl-disiloxane. The catalysts used can also be basic nitrogen compounds, such as tetralkylammonium hydroxides, alkali metal hydroxides, such as sodium hydroxide, alkali metal phenolates, such as sodium-phenolate, or alkali metal alcoholates, such as sodium methylate. Hexahydrotriazines can also be used as catalysts. Usually, the amine catalyst is used in excess of the required acid. However, any of the amine-derived catalysts can be used in the present technology as the corresponding ammonium salts or quaternary ammonium salts. Thus, in the practice of the present technology, amine-derived catalysts can be present in the polyol mixtures as their corresponding acid blocked form. Accordingly, in certain embodiments, said catalyst and the requisite acid may conveniently be added simultaneously as the amine salt of the acid. According to the present technology, organic metal compounds, in particular organic tin compounds, can also be used as catalysts. Suitable organic tin compounds are, in some embodiments of the present technology, tin (II) -carboxylic acid salts, such as tin (II) -acetate, tin (II) -octoate, tin (II) -ethylhexoate and tin ( ll) -laurate, and tin (IV) -compounds, for example dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate. Lead organ compounds suitable for use as primary catalysts include lead naphthanate and lead octoate. All the catalysts mentioned above can be use as mixtures. Additional representatives of catalysts that can be used in accordance with the present technology, as well as details on the manner of operation of the catalyst, are described in Kunststoff-Handbuch, Volume III, published by Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1996 , for example, on pages 96 to 102. Other catalysts include N, N-dimethyl-cyclohexylamine, lead naphthanate, tin octanoate and tin dilaurate. Still other catalysts suitable for use in the present technology include amino acid salt catalysts, for example, those derived from sarcosine. Suitable amino salts derived from sarcosine include various N- (2-hydroxy or 2-alkoxy-5-alkylphenyl) alkyl sarconates. Alkyl groups are independently Ci8 alkyl groups and alkoxy groups are CrC6 alkoxy groups. Of course, each of the sarcosinate derivatives includes a suitable counter-ion, such as, for example, sodium, potassium, magnesium, lithium, etc. In one embodiment of the present technology, the amino acid salt is sodium sarcosinate N- (2-hydroxy-5-nonylphenyl) methyl. Each of the amino acid derivatives can be prepared according to the procedures outlined in the U.S. Patent. No. 3,903,018. Representative amino acid salt catalysts are, for example, sodium sarcosinate N- (2-hydroxy-5-methylphenyl) methyl, sodium sarcosinate N- (2-hydroxy-5-ethylphenyl) methyl, sodium sarcosinate N- (2 -hydroxy-5-butylphenyl) methyl; Sodium sarcosinate N- (2-hydroxy-5-heptylphenyl) methyl; Sodium sarcosinate N- (2-hydroxy-5-nonylphenyl) methyl; Sodium sarcosinate N- (2-hydroxy-5-dodecylphenyl) methyl; potassium sarcosinate N- (2-hydroxy-5-nonylphenyl) methyl; lithium sarcosinate N- (2-hydroxy-5-nonylphenyl) methyl; and its mixtures. Other suitable catalysts include, for example, the disodium salt of 2,6-bis- (N-carboxymethyl-N-methylaminomethyl) -p-ethylphenol and 2,6-bis- (N-carboxymethyl-N-methylaminomethyl) disodium salt. ) -p-nonylphenol; and its mixtures. The catalysts are generally used in an amount of about 0.001% to about 10% by weight, based on the amount of polyesters used in accordance with the present technology.

Non-reactive diluents As used herein, the terms "non-reactive diluent" or "non-reactive diluents" include within their scope plasticizing materials. By the term "non-reactive diluent" or "non-reactive diluents", it means that the diluent does not react with the isocyanate (for example, an aromatic polymeric isocyanate) of the present technology described herein, or will not be incorporated (eg, covalently bound) into the resulting polymer chain. Preferably the non-reactive diluent (s) is dissolved within polymer, for example. Non-reactive diluents suitable for use in the present technology include those described in US Patents. 3,773,697, 5,929,153, 3,929,700 and 3,936,410, the descriptions of each of which are incorporated herein by reference in their entirety. Suitable non-reactive diluents include, for example: (a) italic plasticizers such as di-n-butyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisooctyl phthalate, di-octyldecyl phthalate, phthalate of di-butylbenzyl, and di-2-ethylhexyl isophthalate, aliphatic ester plasticizers such as di-2-ethylhexyl adipate, di-n-decyl adipate, diisodecyl adipate, dibutyl sebacate and di-2- sebacate. ethylhexyl trimellitic plasticizers such as triocyl trimellitate and tridecyl trimellitate, phosphoric ester plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate and tricresyl phosphate, epoxy plasticizers such as epoxy soybean oil , high molecular plasticizers based on polyester, and the like. Other non-reactive diluents suitable for use in the present technology include, for example: (b) propylene carbonate, (c) dialkyl esters of dibasic acids wherein each alkyl group is independently a straight or branched chain alkyl having 1- 20 carbon atoms (hereinafter "dibasic esters"), (d) dialkyl ethers of alkylene (C Ce) or polyalkylene glycols, (e) diacid esters of α, β-diols wherein the acid is a straight or branched chain alkanoic acid having 1-6 carbon atoms and the diol is a straight or branched chain aliphatic diol (hereinafter "diol esters") "), (f) tris-isopropylchlorophosphate, tris chloroethyl phosphate, tris dichloropropyl phosphate, their derivatives, or combinations thereof, and (g) mixtures of any of (a) - (f). Suitable diesters of dibasic acids for use in the present technology include, for example, dimethyl adipate, dialkyl adipate, dimethyl glutarate, dimethyl succinate, H 3 CO (CO) (CH 2) n (CO) OCH 3, wherein n is an integer between 1 and 10, and di (2-ethylhexyl) adipate. A preferred aspect of the present technology employs a mixture of dibasic esters. A particularly preferred mixture contains about 20% by weight of dimethyl succinate, about 21% by weight of dimethyl adipate and about 59% by weight of dimethyl glutarate. A diacid ester representative of an α, β-diol is diisobutyrate of 2,2,4-trimethyl-1,3-pentanediol. Preferred non-reactive diluents include, for example, propylene carbonate, a mixture of dibasic ester, and tris-isopropylchlorophosphate. In preferred embodiments of the present technology, non-reactive diluents are of low viscosity (less than about 50 centipoise at 25 ° C) and act as plasticizers within the polymer.

Comparative Agents Suitable compatibilizing agents for use in the present technology include, for example, alkoxylated nonyl phenols, more preferably Makon 10® (nonyl phenol ethoxylate) commercially available from Stepan Company (Northfield, Illinois).

Surfactants and Additives Surfactants suitable for use in the present technology include nonionic surfactants and amphoteric surfactants such as those described in the U.S. Pat. No. 6,017,860, the description of which is incorporated herein for reference in its entirety. Suitable nonionic surfactants according to the present technology are also generally described in the column, line 14 to column 16, line 6 of US Pat. 3,929,678, the description of which is incorporated herein for reference in its entirety. Generally, the nonionic surfactant is selected from the group consisting of polyoxyethylenated alkylphenols, polyoxyethylenated straight chain alcohols, polyoxyethylenated branched chain alcohols, polyoxyethylenated polyoxypropylene glycols, polyoxyethylenated mercaptans, fatty acid esters, glycerol acid acid esters, polyglyceryl fatty acid esters. , propylene glycol esters, sorbitol esters, polyoxyethylenated sorbitol esters, polyoxyethylene glycol esters, polyoxyethylenated fatty acid esters, primary alkanolamides, ethoxylated primary alkanolamides, secondary alkanolamides, ethoxylated secondary alkanolamides, tertiary acetylenic glycols, polyoxyethylenated silicones, N-alkylpyrrolidones, alkylpolyglycosides, alkylpolysaccharides, EO-PO block polymers, polyhydroxy fatty acid amides, oxides of amine and its mixtures. Suitable amphoteric surfactants are selected from the group comprising alkyl glycinates, propionates, imidazolines, anfoalkylsulfonates, sold as "Miranol" by Rhone Poulenc, N-alkylaminopropionic acids, N-.alkyliminodipropionic acids, imidazoline carboxylates, N-alkylbetaines, amidopropyl betaines, sarcosinates, cocoanfocarboxiglycinates, amine oxides, sulphobetaines, sultaines and mixtures thereof. surfactants Additional suitable amphoteric include cocoamphoglycinate, cocoamphocarboxyglycinate, lauranfocarboxiglicinato, cocoamphopropionate, lauranfopropionato, estearanfoglicinato, cocoamphocarboxypropionate, seboanfopropionato, seboanfoglicinato, oleoanfoglicinato, caproanfoglicinato, caprilanfopropionato, caprilanfocarboxiglicinato, cocoylimidazoline, lauryl imidazoline, stearyl imidazoline, behenyl imidazoline, behenilhidroxietil imidazoline, caprilanfopropilsulfonato, cocoanfopropilsulfonato, steampropyl sulfonate, oleoanopropyl sulfonate and the like. Other surfactants suitable for use in the present technology include, but are not limited to, alkoxylated polyether siloxanes or polysiloxanes such as Niax L-5440 (available from OSI specialties, Crompton), Tegostab B-8404 (available from Goldschmidt), Dabco DC-5357 (available from Air Products), and their mixtures. Active surface additives and foam stabilizers can also be used in the present technology. Suitable materials include, for example, the sodium salts of ricinoleic sulfonates, or salts of fatty acids and amines, such as diethyl amine of oleic acid or diethanolamine stearic acid. Alkali metal or ammonium salts of sulfonic acids, such as dodecyl benzene sulphonic acid or dinaphthylmethane disulfonic acid, or of fatty acids, such as ricinoleic acid, or of polymeric fatty acids can also be used as surface active additives. The foam stabilizers used are preferably polyether siloxanes, especially those which are soluble in water. These compounds generally have a polydimethyl siloxane group attached to a copolymer of ethylene oxide and propylene oxide. Foam stabilizers of this type have been described, for example, in U.S. Patents. Nos. 2,834,748; 2,917,480 and 3,629,308. According to the present technology, it is also possible to use known cell regulators such as paraffin or fatty alcohols or dimethyl polysiloxanes, as well as pigments or inks and known anti-flame agents, for example, trischloroethylphosphate, tricresylphosphate or ammonium phosphate or polyphosphate , also stabilizers against aging, wear and tear on the environment, plasticizers, fungistatic and bacteriostatic substances and fillers, such as barium sulfate, diatomite, carbon black or calcium carbonate. Other examples of active surface additives, foam stabilizers, cell regulators, reaction retarders, stabilizers, anti-flame substances, plasticizers, inks, fillers and fungistatic and bacteriostatic substances which may also be used in accordance with the present technology and the details concerning the use of the action of these additives can be found in Kunststoff-Handbuch, Volume-Val, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 103 and 113.

Emulsifiers Polyol blends may optionally include emulsifiers to prolong the shelf life stability of the dispersed polyol blends. Examples of suitable emulsifiers include sodium sarcosinate N- (2-hydroxy-5-nonylphenyl) methyl and soybean oil. All documents, for example, patents and articles of publications, cited above or later are incorporated herein for reference in their entirety. A person skilled in the art will recognize that modifications can be made in the present technology without deviating from the essence and scope of the present technology. The present technology is further illustrated by the following examples that are not constructed as limitations of the present technology or scope of the specific procedures described herein. The following is a description of certain materials used in the following examples: Stepanpol® PS-2352: A low functional diethylene glycol polyester phthalate (functionality of 2) having an OH value of about 220 to about 250, sold by Stepan Company, Northfield, Illinois. Stepanpol® PS-3152: A low functional diethylene glycol polyester phthalate (functionality of 2) having an OH value from about 290 to about 325, sold by Stepan Company, Northfield, Illinois. Stepanpol® PS-2502-A A low functional diethylene glycol polyester phthalate (functionality of 2) having an OH value of about 230 to about 250, sold by Stepan Company, Northfield, Illinois. Dabco® DC5357: A polysiloxane surfactant composed of dimethyl, methyl (polyethylene oxide) siloxane copolymer, sold by Air Products Corporation of Allentown, Pennsylvania. Tegostab® B8404: A polysiloxane surfactant composed of dimethyl, methyl (polyethylene oxide) siloxane copolymer, sold by Goldschmidt Niax ® A-1: A catalyst containing approximately 70% bis (2-dimethylaminoethyl) either in 30 % dipropylene glycol, sold by OSI Specialty Chemical Mondur® MR®: Polymethylene polyphenyl isocyanate having an isocyanate content of about 31.5%, commercially available from Bayer, Pittsburgh, Pennsylvania Thanol® R-360: Alkoxylated glycerin sucrose polyether polyol having an OH value of about 345 to about 375, sold by Eastman. Polycat® 8: Dimethylcyclohexylamine Catalyst, sold by Air Products Jeffeat® ZR-70: A catalyst containing 2- (2- (dimethylamino) ethoxy) ethanol, sold by Huntsman Pluracol® P-975: A high functional alkoxylated sucrose diol having an OH value of about 380-420, sold by BASF Voranol®-270 Alkoxylated glycerin having an OH value of 230-250, sold by Dow Chemical Voranol ®-470X: A Mannich-type polyol having an OH value of 460-480, sold by Dow Chemical arkol® RB 216 A Mannich-type polyol having an OH value of 470-490, sold by Chemistry, Pumex Silpol® SIP -425LV: A Mannich-type polyol having an OH value of 415-435, sold by Siltech Corp. Carbowax® 400: Polyethylene glycol of approximately 400 MP sold by Union Carbide Makon 10® Nonyl phenol ethoxylated with an average of 10 oxide units Ethylene sold by Stepan Company Terato-203® A diethylene glycol polyester polyurethane terephthalate having an OH value of 300-330, sold by Kosa Surfactant A 5440 alkoxylated polysiloxane surfactant sold by Crompton OSI Curithane 52® A catalyst Isocyanate polymerization available from Air Products.

General experimental section Quantities of components in later examples are percentages by weight of the polyol (resin) mixture unless otherwise indicated another way. The individual resin components are added and mixed until a homogeneous homogeneous polyol dispersion is obtained. The polyol mixtures subsequently exposed are prepared according to the present technology and are reacted upon mixing and / or mixing. spray manually with an aromatic polymeric polyisocyanate (Mondur MR®).

The manually mixed foams are reacted in an amount of 150 g of total material in an isocyanate / resin weight ratio of 52/48 (approximately ratio of aromatic polymeric isocyanate / polyol or polyol mixture 1: 1 by volume). Unless otherwise indicated, the isocyanate and resin components are conditioned at 25 ° C before mixed. The pre-weigh isocyanate in a No. 2 cup of 0.907 Kg. desired amount of resin component is then added to the isocyanate and two are mixed vigorously for 3 seconds using a palette of mixed Cohn double that rotates at approximately 3500 rpm. The foam is let rise and cure in the cup used for mixing. The properties of the manually mixed foams are indicated later. Foams machine sprays use a Gusmer machine or GlasCraft machine with parameters for particular examples.

EXAMPLE 1 Polyester phthalate (Stepanpol PS-3152) 37.26% polyester terato (Terato-203) 14.90% Glycerol propoxylated (Voranol-270) 22.35% Surfactant (L-5440) 1.49% Opener cell (Calcium Stearate) 0.33% Catalysts amine * 5.23% Lead catalyst (30% Pb Naftanate) 0.22% 2-ethyl hexanoic acid 0.37% Non-reactive diluents ** 14.90% Water 2.94% * Amine catalysts: Polycat 8 = 2.24%; dimethylethanolamine = 2.24%; Curithane 52 = 0.75%.

** Non-reactive diluents: tris-isopropylchlorophosphate Manual mixing properties Mixing ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Start time 4 sec. Adhesion free time 1 1 sec. Cup density 39.89 kg / m3 Resin viscosity (25 ° C) 580 cps Machine spray properties (Gusmer H-2: GX-7 Gun; temperatures 48.89 ° C: pressures of 54.43 atm dim stability (37.78 ° C / 95% RH, 28, ASTM D-2126) Water absorption (weight gain 28) Permeability of water vapor (with surface skin, ASTM E 96) Perm (2.54 cm) ( permeability X (2.54 cm)) Water vapor permeability (without surface skin, ASTM E 96) 4.59 perm x (2.54 cm) EXAMPLE 2 phthalate polyester (Stepanpol PS-3152) 37.02% terrato polyester (Terato-203) 14.81% Glycerol propoxylated (Voranol-270) 22.21% Surfactant (L-5440) 2.04% Opener cell (Calcium Stearate) 0.30% Catalysts amine * 5.18% Lead catalyst (30% Pb Naftanate) 0.22% 2-ethyl hexanoic acid 0.37% Non-reactive diluents ** 14.81% Water 3.04% * Amine catalysts: Polycat 8 = 2.22%; dimethylethanolamine = 2.22%; Curithane 52 = 0.74%.

** Non-reactive diluents: tris-isopropylchlorophosphate Manual mixing properties Mixed ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Start time 5 sec. Free time of adhesion 12 sec. Cup density 40.53 Kg / rrr Resin viscosity (25 ° C) 550 cps Machine spray properties (Gusmer H-2; GX-7 Gun: temperatures 48.89 ° C; pressures 54.43 atm) Density (with line of passage, ASTM D-1622) 44.22 Kg / m3 Density without line of passage, ASTM D-1622) 35.08 Kg / m3 Compressive resistance (with pass line, ASTM D-1621) 1.83 atm Compressive resistance (without line of passage, ASTM D-1621) 1.55 atm Cutting resistance (with line of passage, ASTM C-273) 2.05 atm Cut resistance (without line of passage, ASTM C-273) 1.81 atm Tensile strength (with line of passage, ASTM D-1623) 2.64 atm Tensile strength (are step line, ASTM D-1623) 3.71 atm Friability (with passline, loss wt%, ASTM C421 0.21%) Friability (passline without loss% by weight, 0.45% ASTM C 421) Stability Dim. (With passline, -28.89 ° C, day 28, ASTM -0.01% D-2 26) Stability Dim. (/ with line of passage, 70 ° C, day 28, ASTM D- -0.36% 2126) Stability Dim. (with / line of passage, 37.78 ° C / 95% RH, 0.91% ASTM D-2126) EXAMPLE 3 phthalate polyester (Stepanpol PS-3152) 46.1 1% Sucrose propoxylated (Pluracol P-975) 5.23% Surfactant (L-5440) 2.1% Opener cell (Calcium Stearate) 0.21% Catalysts amine * 5.77% lead catalyst ( 30% Pb Naftanate) 0.15% 2-ethyl hexanoic acid 0.38% Non-reactive diluents ** 1 1.53% Water 3.01% Compatibility agent (Makon 10®) 7.68% * Amine catalysts: Polycat 8 = 2.50%; dimethylethanolamine .fifty%; Curithane 52 = 0.77%.

** Non-reactive diluents: tris-isopropylchlorophosphate = 1 1.53% Manual mixing properties Mixed ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Start time 5 sec. Free time of adhesion 12 sec. Cup density 41.01 kg / m3 Resin viscosity (25 ° C) 680 cps Machine spray properties (Gusmer H-2; GX-7 Gun; temperatures 48.89 ° C; pressures 54.43 atm) Density (with line of passage, ASTM D-1622) 42.29 kg / m3 Density without line of passage, ASTM D-1622) 36.05 kg / m3 Compressive resistance (with line of passage, ASTM D-1621) 2.06 atm Compressive resistance (without line of passage, ASTM D-1621) 1.17 atm Cutting resistance (with line of passage, ASTM C-273) 1.52 atm Cutting resistance (without line of passage, ASTM C-273) 1 .42 atm Tensile strength (with line of passage, ASTM D-1623) 2.91 atm Tensile strength (without line of passage, ASTM D-1623) 2.49 atm EXAMPLE 4 Polyester phthalate (Stepanpol PS-3152) 45.27% Poliol Mannich (Voranol 470X) 20.89% Diethylene glycol 3.48% Surfactant (L-5440) 2.09% Opener cell (Calcium stearate) 0.35% Amine catalysts * 3.55% Non-reactive diluents ** 14.62% Water 2.79% Compatibility agent (MACOM 10®) 6.96% * Amine catalysts: Polycat 8 = 1 .25%; dimethylethanolamine = 1.95%; Curithane 52 = 0.35%.

** Non-reactive diluents: tris-isopropylchlorophosphate = 14.62% Manual mixing properties Mixed ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Initiation time 6 sec. Adherence free time 13 sec. Cup density 45.02 Kg / m3 Resin viscosity (25 ° C) 600 cps Machine spray properties (Gusmer H-2; GX-7 Gun: temperatures 48.89 ° C; pressures 54.43 atm) Cutting resistance (with line of passage, ASTM C-273) 2.22 atm Cutting resistance (without line of passage, ASTM C-273) 3.17 atm Tensile strength (with line of passage, ASTM D-1623) 4.4 atm Tensile strength (are through line, ASTM D-1623) 6.75 atm Friability (with line of passage, loss% in weight, ASTM C-421) 0.61% Friability (without line of passage, loss% in weight, ASTM C-421) 1 .35% Dim stability (with line of passage, -28.89 ° C, day 28, ASTM D-0.20% 2126) Stability dim. (without line of passage, -28.89 ° C, day 28, ASTM D-0.20% 2126) Stability dim. (with line of passage, 70 ° C, day 28, ASTM D-2126) 1.12% Dim stability (without line of passage, 70 ° C, day 28, ASTM D-2126) -0.91% Dim stability (c / pass line, 37.78 ° C / 95% H.R., ASTM 3.37% D-2126) Stability dim. (without line of passage, 37.78 ° C / 95% of H.R., ASTM -0.05% D-2126) Stability dim. (c / pass line, 70 ° C / 95% of H.R., ASTM D- 0.45% 2 26) Stability dim. (without line of passage, 70 ° C / 95% of H.R. ASTM D- -2.60% 2126) Water absorption (Gusmer H-2, GX-7, 54.43 atm, D-2842) 2.56% Water absorption (Gus H-2000, GX-7, 102.06 atm, D-2842) 0.08% EXAMPLE 5 Polyester phthalate (Stepanpol PS-3152) 36.93% Mannich Polyol (Voranol 470X) 26.87% Diethylene glycol 6.72% Surfactant (L-5440) 2.02% Cell opener (Calcium stearate) 0.32% Amine catalysts * 3.77% Non-reactive diluents ** 14.1 1% Water 2.54% Compatibility agent (Makon 10®) 6.72% * Amine catalysts: polycat 8 = 1.21%; dimethylethanolamine .88%; Curithane 52 = 0.34%; Niax A-1 = 0.34%.

** Non-reactive diluents: tris-isopropylchlorophosphate = 14.1 1% Manual mixing properties mixed (A / B in volume) 1: 1 Component temperatures 25 ° C Initiation time 5 sec. Free time of adhesion 12 sec. Cup density 47.1 kg / m3 Resin viscosity (25 ° C) 550 cps Machine spray properties (Gusmer H-2; GX-7 Gun; temperatures 48.89 ° C; pressures 54.43 atm) Density (with line of passage, ASTM D-1622) 43.89 kg / m3 Compressive resistance (with line of passage, ASTM D-1621) 2.36 atm Cutting resistance (with line of passage, ASTM C-273) 2.59 atm Tensile strength (with line of passage, ASTM D-1623) 4.46 atm Friability (with line of passage, loss% in weight, ASTM C- 0.33% 421) Stability dim. (with line of passage, -28.89 ° C, day 28, ASTM D- -0.44 %% 2126) Stability dim. (with line of passage, 70 ° C, day 28, ASTM D- -1.49% 2126) Stability dim. (c / line of passage, 70 ° C / 95% of H.R., ASTM D- -3.3% 2126) Permeability of water vapor (with line of passage, ASTM E-2.01 96) perm x (2.54 cm) Machine spray properties (Gusmer H-2000; GX-7 Gun; temperatures 54.44 ° C; pressures 102.06 atm) Density (with line of passage, ASTM D-1622) 50.94 kg / m3 Density (without line of passage, ASTM D-1622) 46.94 kg / m3 Compressive resistance (with line of passage, ASTM D-1621) 2.81 atm Compressive resistance (they are line of passage, ASTM D-1621) 2.72 atm Water vapor permeability (with line of passage) ASTM 1.23 perm x E-96 (2.54 cm) EXAMPLE 6 Polyester phthalate (Stepanpol PS-3152) 42.54% Mannich polyol (Markol RB 216) 15.47% Diethylene glycol 5.80% Surfactant (L-5440) 1.90% Cell opener (Calcium stearate) 0.48% Amine catalysts * 3.46% Diluents non-reactive ** 16.25% Water 2.49% Compatibility agent (Makon 10®) 1 1.60% * Amine catalysts: polycat 8 = 1.06%; dimethylethanolamine .66%; Curithane 52 = 0.39%; Niax A-i = 0.35%.

** Non-reactive diluents: tris-isopropylchlorophosphate = 16.25% Manual mixing properties Mixing ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Start time 5 sec. Adherence free time 1 sec. Cup density 47.9 Kg / m3 Resin viscosity (25 ° C) 520 cps Machine spray properties (Gusmer H-2; GX-7 Gun; temperatures 48.89 ° C; pressures 54.43 atm) Density (with line of passage, ASTM D-1622) 61.2 Kg / m3 Density without line of passage, ASTM D-1622) 51.58 Kg / m3 Compressive strength (with pass line, ASTM D-1621) 4.2 atm Compressive resistance (without pass line, ASTM D-1621) 3.54 atm Cutting resistance (with line of passage, ASTM C-273) 2.88 atm Cutting resistance (without pass line, ASTM C-273) 3.56 atm Tensile strength (with line of passage, ASTM D-1623) 4.69 atm Tensile strength (are step line, ASTM D-1623) 4.95 atm Friability (with line of passage, loss% in weight, ASTM 0.31% C421) Friability (without line of passage, loss% in weight, ASTM C- 0.34% 421) Absorption of water (without line of passage, ASTM D-2842 0.58 % EXAMPLE 7 Phthalate Polyester (Stepanpol PS-3152) 32.47% Mannich Polyol (Silip SIP-425LV) 21.65% Diethylene Glycol 7.22% Surfactant (L-5440) 1.77% Cell Opener (Calcium stearate) 0.39% Amine catalysts * 3.36% Non-reactive diluents ** 20.15% Water 2.16% Compatibility agent (Makon 10®) 10.82% * Amine catalysts: Polycat 8 = 1 .04%; dimethylethanolamine = 1.63%; Curithane 52 = 0.36%; Niax A-1 = 0.33%.

** Non-reactive diluents: tris-isopropylchlorophosphate = 15.15%; propylene carbonate = 5.00%.

Manual mixing properties Mixing ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Start time 5 sec. Adherence free time 3 sec. Cup density 49.34 Kg / m3 Resin viscosity (25 ° C) 320 cps Machine spray properties (GlasCraft; Probler Gun: temperatures 48.89 ° C; pressures 102.06 atm) Density (with line of passage, ASTM D-1622) 50.3 Kg / m3 Compressive strength (with line of passage, ASTM D-1621) 2.93 atm Cutting resistance (with line of passage, ASTM C-273) 3.18 atm Tensile strength (with line of passage, ASTM D-1623) 5.2 atm Friability (with line of passage, loss% in weight, ASTM C- 0.71% 421) Stability dim. (with line of passage, 70 ° C, day 28, ASTM D- 0.58 %% 2126) Stability dim. (c / pass line, 37.78 ° C / 95% RH, -0.32% ASTM D-2 26) Dimensional stability (c / pass line, 70 ° C / 95% RH, -2.44% ASTM D -2126) Water vapor permeability (with line of passage, ASTM 2.09 perm) E-96) x (2.54 cm) Water Absorption (without line of passage, ASTM D-2842) 0.79% Machine spray properties (Gusmer H-2000; GX-7 Gun; temperatures 54.44 ° C; pressures 102.06 atm) Density (with line of passage, ASTM D-1622) 50.94 Kg / m3 Compressive resistance (with line of passage, ASTM D-1621) 2.85 atm EXAMPLE 8 Polyethylene glycol (Carbowax 400) 32.70% Mannich polyol (Silpol SIP-425LV) 21.80% Diethylene glycol 7.27% Surfactant (L-5440) 0.75% Cell opener (Calcium stearate) 0.40% Amine catalysts * 3.36% Non-reactive diluents ** 20.26% Water 2.55% Compatibility agent (Makon 10®) 10.90% * Amine catalysts: Polycat 8 = 1.04%; dimethylethanolamine = 1 .63%; Curithane 52 = 0.36%; Niax A-1 = 0.33%.

** Non-reactive diluents: tris-isopropylchlorophosphate = 15.26%; dibasic asters = 5.00%.

Manual mixing properties Mixing ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Start time 4 sec. Free time of adhesion 12 sec. Cup density 47.58 Kg / i Resin viscosity (25 ° C) 130 cps Cup open cell content 95.7% Dimensional stability of manual mixing < 2.0% (70 ° C / 95% H.R., 7 days) EXAMPLE 9 Polyethylene glycol (Carbowax 400) 39.79% Mannich Polyol (Silpol SIP-425LV) 26.53% Surfactant (L-5440) 0.75% Cell opener (Calcium stearate) 0.40% Amine catalysts * 3.36% Non-reactive diluents ** 15.56% Water 2.55% Compatibility agent (Makon 10®) 1.05% * Amine catalysts: Polycat 8 = 1.04%; dimethylethanolamine .63%; Curithane 52 = 0.36%; Niax A-1 = 0.33%.

** Non-reactive diluents: tris-isopropylchlorophosphate = 15.56%.

Manual mixing properties Mixed ratio (A / B in volume) 1: 1 (in volume) Component temperatures 25 ° C Initiation time 4 sec. Free time of adhesion 12 sec. Cup density 48.38 Kg / m3 Resin viscosity (25 ° C) 180 cps Cup open cell content 92.4% Dimensional stability of manual mixing < 2.0% (70 ° C / 95% H.R., 7 days) EXAMPLE 10 Phthalate Polyester (Stepanpol PS-2502-A 30.83% Mannich Polyol (Silpol SIP-425LV) 32.00% Surfactant (L-5440) 1.30% Cell Opener (Calcium stearate) 0.60% Amine catalysts * 3.85% Diluents ** 28.12% Water 3.30% * Amine catalysts: Polycat 8 = 1.15%; dimethylethanolamine = 2.20%; Niax A-1 = 0.50%.

** Diluents: tris-isopropylchlorophosphate = 15.11%; Esters dibasic = 13.01% Manual mixing properties Mixed ratio (A / B in volume) 1: 1 Component temperatures 25 ° C Initiation time 4 sec. Adherence free time 9 sec. Cup density 32.84 Kg / m3 Resin viscosity (25 ° C) 300 cps Cup open cell content 96.5% Dimensional stability of manual mixing < 2.0% (70 ° C / 95% H.R., 7 days) EXAMPLE 11 Phthalate Polyester (Stepanpol PS-2502-A 30.44% Mannich Polyol (Silpol SIP-425LV) 31.44% Surfactant (L-5440) 1.91% Cell Opener (Calcium Stearate) 0.70% Amine Catalyst * 4.27% Lead Catalyst (30% naphthana Pb) 1.08% Thinners ** 27.58% Water 2.58% * Amine catalysts: Polycat 8 = 1.13%; dimethylethanolamine = 2.16%; Curithane 52 = 0.49%; Niax A-1 = 0.49%.

** Diluents: tris-isopropylchlorophosphate = 14.82%; Esters dibasic = 12.76% Manual mixing properties Mixed ratio (A / B in volume) 1: 1 Component temperatures 10 ° C Initiation time 3 sec. Adherence free time 5 sec. Cup density 36.85 Kg / m3 Resin viscosity (25 ° C) 200 cps Cup open cell content 96.5% Dimensional stability of manual mixing < 2.0% change (70 ° C / 95% H.R., 7 days) volume The present technology and the way and procedure of doing and use it, now it is described in such complete, concise and exact terms to allow any person with experience in the technique to which belongs, make and use it. It must be understood that the modalities preferred described above of the present technology and these Modifications can be made without departing from the essence and scope of the present invention as outlined in the claims. To particularly point out and clearly claim the subject matter with respect to the present technology, the following claims conclude this specification.

Claims (27)

NOVELTY OF THE INVENTION CLAIMS

1. A mixture of sprayable polyol to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an index of NCO / OH from about 85 to about 125, the sprayable polyol mixture comprising: (a) about 20% to about 90% by weight of the mixture of a polyol formulation consisting essentially of a diethylene glycol polyester polyether phthalate having an OH value of about 195 to about 400, and a Mannich polyol having an OH value of about 315 to about 550, and optionally, diethylene glycol; (b) water as a primary blowing agent; (c) about 0.01% to about 2.0% by weight of the polyol mixture of a cell opening agent consisting essentially of calcium stearate, and (d) about 0.05% to about 50% by weight of at least one non-reactive diluent consisting essentially of a tris-isopropylchlorophosphate, a propylene carbonate, a dibasic ester or dibasic esters, or their mixture.

2. The sprayable polyol mixture according to claim 1, further characterized in that the non-reactive diluent has a viscosity of less than about 50 centipoise at 25 ° C.

3. The sprayable polyol mixture according to claim 1, further characterized in that the non-reactive diluent is a plasticizer within the polyol mixture.

4. The sprayable polyol mixture according to claim 1, further characterized in that the sprayable polyol mixture comprises about 50% to about 85% by weight of the polyol formulation.

5. The sprayable polyol mixture according to claim 1, further characterized in that the sprayable polyol mixture further comprises: (a) a catalyst selected from the group consisting of dimethylethanolamine, dimethylcyclohexylamine, a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol or its mixture; and (b) an alkoxylated polysiloxane surfactant.

6. The sprayable polyol mixture according to claim 1, further characterized in that the non-reactive diluent is a mixture consisting essentially of tris-isopropylchlorophosphate, propylene carbonate, or dibasic esters.

7 - A rigid foam made of a sprayable polyol mixture according to claim 1, wherein the foam is processed with a volumetric ratio of aromatic polymeric isocyanate to polyol mixture of about 1: 1.

8. - A spray polyol mixture for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an NCO index / OH from about 85 to about 125; the sprayable polyol mixture comprising: (a) about 25% to about 40% by weight of a diethylene glycol polyester polyether phthalate having an OH value of about 230 to about 250; (b) about 20% to about 35% by weight of a Mannich polyol having an OH value of about 415 to about 435; (c) optionally, about 5.5% to about 9% by weight of diethylene glycol; (d) about 1% to about 3.5% by weight of water; (e) about 0.1% to about 1% by weight of the mixture of a cell opening agent consisting essentially of calcium stearate, lithium stearate, magnesium stearate, strontium stearate, zinc stearate, calcium myristate, derivatives, or combinations thereof; and (f) about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of a tris-isopropylchlorophosphate, a propylene carbonate, a dibasic ester or dibasic esters and mixtures thereof.

9. A mixture of sprayable polyol for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the product of reaction of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH number of about 85 to about 125; the sprayable polyol mixture comprising: (a) about 25% to about 40% by weight of a diethylene glycol polyester phthalate polyol having an OH value of about 290 to about 325; (b) about 20% to about 35% by weight of a Mannich-type polyol having an OH value of about 315 to about 550; (c) optionally, up to about 9% by weight of diethylene glycol; (d) about 1% to about 3.5% by weight of water; (e) about 0.1% to about 1% by weight of a cell opening agent selected from the group consisting of mono-, di-, or polyvalent fatty acid metal salts; and (f) about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters and mixtures thereof.

10. The mixture according to claim 9, further characterized in that the polyol mixture comprises (g) approximately 2.5 to about 4.5% by weight of at least one amine catalyst; and (h) about 1% to about 3% by weight of an alkoxylated polysiloxane surfactant. 1.

A mixture of sprayable polyol for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the product of reaction of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH number of about 85 to about 125; the sprayable polyol mixture comprising: (a) about 20% to about 90% by weight of the mixture of a polyol formulation consisting essentially of a diethylene glycol polyester polyether phthalate having an OH value of from about 195 to about 325 , a Mannich polyol having an OH value from about 315 to about 550, and diethylene glycol; (b) water as a primary blowing agent; (c) a cell opening agent consisting essentially of calcium stearate, lithium stearate, magnesium stearate, strontium stearate, zinc stearate, calcium myristate, derivatives thereof, or combinations thereof; and (d) about 0.05% to about 50% by weight of the mixture of at least one non-reactive diluent consisting essentially of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters, or their mixture.

12. A rigid foam having a volumetric ratio of aromatic polymeric isocyanate to a polyol mixture of about 1: 1 made from a spray polyol mixture to make a rigid foam comprising urethane units and having a sufficient open cell content to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH number of about 85 to about 125; the spray polyol mixture comprising: (a) about 20% a about 90% by weight of the mixture of a polyol formulation consisting essentially of a diethylene glycol polyester phthalate polyol having an OH value of about 230 to about 250, a Mannich polyol having an OH value of about 415 to about 435, and diethylene glycol; (b) water as a primary blowing agent; (c) a sufficient amount of calcium stearate to act as a cell opening agent; and (d) about 0.05% to about 50% by weight of the mixture of at least one non-reactive diluent selected from the group consisting of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or dibasic esters and mixtures thereof.

13. A sprayable polyol mixture comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture dispersed at an NCO / OH index of approximately 85-125, wherein the spray polyol mixture is suitable for use in a rigid polymer spray foam, the spray polyol blend comprising: (a) a polyol formulation consisting essentially of a diethylene glycol polyester polyether phthalate having a value OH from about 290 to about 325 and a Mannich polyol having an OH value from about 415 to about 435, and optionally diethylene glycol; (b) water as a primary blowing agent; (c) a divalent metal salt of a fatty acid cell opener; (d) a non-reactive diluent mixture consisting of essentially of tris-isopropylchlorophosphate, propylene carbonate, or a dibasic ester or dibasic esters; (e) a catalyst selected from the group consisting of dimethylethanolamine, dimethylcyclohexylamine, a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol or its mixture; and (f) an alkoxylated polysiloxane surfactant.

14. - A rigid foam made of a sprayable polyol mixture according to claim 13, wherein the foam is processed with a volumetric ratio of aromatic polymeric isocyanate to polyol mixture of about 1: 1.

15. The sprayable polyol mixture according to claim 13, further characterized in that the sprayable polyol mixture comprises about 50-85% by weight of a polyol formulation consisting essentially of a diethylene glycol polyester polyether phthalate having a OH value of about 230-250 and a Mannich polyol having an OH value of about 415 to about 435.

16. A sprayable polyol mixture comprising urethane units and having an open cell content sufficient to withstand shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture dispersed at an NCO / OH index of from about 85 to about 125; wherein the spray polyol mixture is suitable for use in a spray foam rigid polymer, the sprayable polyol mixture comprising: (a) a polyol formulation consisting essentially of a diethylene glycol polyester phthalate polyol having an OH value of about 230 to about 250 and a Mannich polyol having a value of OH from about 415 to about 425; (b) water as a primary blowing agent; (c) a calcium stearate cell opener; (d) a non-reactive diluent mixture consisting of tris-isopropylchlorophosphate, propylene carbonate, and a dibasic ester or dibasic esters; (e) a catalyst selected from the group consisting of dimethylethanolamine, dimethylcyclohexylamine, a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol or its mixture; and (f) an alkoxylated polysiloxane surfactant.

17. A mixture of sprayable polyol to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a mixture of polyol having a NCO / OH number from about 85 to about 125, the sprayable polyol mixture comprising: (a) about 25% to about 40% by weight of a diethylene glycol polyester phthalate polyol having an OH value of about 290 to about 325; (b) about 20% to about 35% by weight of a Mannich polyol having an OH value of about 415 to about 435; (c) optionally, approximately 6% a about 8% by weight of a diethylene glycol; (d) about 1% to about 3.5% by weight of water; (e) about 0.1% to about 2.5% by weight of a cell opening agent consisting essentially of calcium stearate, lithium stearate, magnesium stearate, strontium stearate, zinc stearate, calcium myristate, its derivatives, or its combinations; (f) about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester or mixtures thereof; and (g) up to about 15% by weight of at least one compatibilizing surfactant comprising a nonyl phenol alkoxylate.

18. The sprayable polyol mixture according to claim 17, further characterized in that the diethylene glycol polyester phthalate polyol having an OH value of about 290 to about 325 is about 32% to about 33% by weight of the mixture., the Mannich polyol having an OH value from about 415 to about 435 is about 21% to about 22% by weight of the mixture, diethylene glycol, is about 7% to about 8% by weight of the mixture, the water is about 1% to about 3.5% by weight of the mixture, the cell opener is about 0.15% to about 2.25% by weight of the mixture, the non-reactive diluent is about 15% to about 35% by weight of the mixture, the catalyst is about 2.5% to about 4% by weight of the mixture, and the surfactant is from about 1% to about 3% by weight of the mixture.

19. A mixture of sprayable polyol for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an index of NCO / OH from about 85 to about 125, the sprayable polyol mixture comprising: (a) about 25% to about 40% by weight of a diethylene glycol polyester polyether phthalate having an OH value of from about 230 to about 250; (b) about 20% to about 35% by weight of a Mannich polyol having an OH value of about 415 to about 435; (c) optionally, about 6% to about 8% by weight of diethylene glycol; (d) about 1% to about 3.5% by weight of water; (e) about 0.1% to about 2.5% by weight of a mono-, di- or polyvalent metal salt of a fatty acid as a cell-opening agent; (f) about 15% to about 34% by weight of at least one non-reactive diluent selected from the group consisting of tris-isopropylchlorophosphate, propylene carbonate, a dibasic ester and mixtures thereof; and (g) up to about 15% by weight of at least one compatibilizing agent comprising a nonyl phenol alkoxylate.

20. - The spray polyol mixture according to claim 19, further characterized in that the diethylene glycol polyester polyether phthalate having an OH value of from about 230 to about 250 is about 32% to about 33% by weight of the mixture, the polyol Mannich having an OH value from about 415 to about 435 is about 21% to about 22% by weight of the mixture, diethylene glycol, is about 7% to about 8% by weight of the mixture, the water is about 1%. % to about 3% by weight of the mixture, the cell opener is about 0.15% to about 2.25% by weight of the mixture, the non-reactive diluent is about 15% to about 35% by weight of the mixture, the catalyst is about 2.5% to about 4% by weight of the mixture, and the surfactant is from about 1% to about 3% by weight of the mixture.

21. A mixture of sprayable polyol for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an index of NCO / OH from about 85 to about 125, the sprayable polyol mixture comprising: (a) from about 35% to about 40% by weight of a diethylene glycol polyester polyether phthalate having an OH value of about 290 to about 325; (b) about 14% to about 15% by weight of a diethylene glycol polyester terephthalate polyol having an OH value of about 300 to about 330; (c) about 20% to about 25% by weight of an alkoxylated glycerin having an OH value of about 230 to about 250; (d) about 1% to about 3% by weight of an alkoxylated polysiloxane surfactant; (e) about 0.1% to about 1% by weight of a divalent metal salt of a fatty acid cell opener; (f) about 3% to about 7% by weight of a catalyst mixture comprising dimethylcyclohexylamine, and dimethylethanolamine, and an isocyanate polymerization catalyst; (g) about 0.1% to about 0.5% by weight of 30% lead catalyst; (h) about 0.1% to about 0.5% by weight of 2-ethylhexanoic acid; (i) about 10% to about 15% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate; and (j) about 1% to about 3.5% by weight of water.

22. A spray polyol mixture for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an index of NCO / OH from about 85 to about 125, the sprayable polyol mixture comprising: (a) about 46.1 1% in weight of a diethylene glycol polyester polyether phthalate having an OH value of from about 290 to about 325; (b) about 23.05% by weight of a high functional alkoxylated sucrose polyol having an OH value of about 380 to about 420; (c) about 2.1 1% by weight of an alkoxylated polysiloxane surfactant; (d) about 0.21% by weight of a calcium stearate cell opener; (e) about 5.77% by weight of a catalyst mixture comprising dimethylcyclohexylamine, dimethylethanolamine, and an isocyanate polymerization catalyst; (f) about 0. 5% by weight of 30% lead catalyst; (g) about 0.38% by weight of 2-ethylhexanoic acid; (h) about 1.5% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate; propylene carbonate, a dibasic ester or dibasic esters and their mixtures; (i) about 3.01% by weight of water; and (j) up to about 15% by weight of a compatibilizing surfactant consisting essentially of a nonyl phenol alkoxylate.

23. A sprayable polyol mixture for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an index of NCO / OH from about 85 to about 125, the sprayable polyol mixture comprising: (a) about 35% to about 50% by weight of a diethylene glycol polyester polyether phthalate having an OH value of from about 290 to about 325; (b) about 20% to about 30% by weight of a Mannich-type polyol having an OH value of about 460 to about 480; (c) about 2% to about 10% by weight of a diethylene glycol; (d) about 1% to about 3% by weight of an alkoxylated polysiloxane surfactant; (e) about 0.1% to about 1% by weight of a calcium stearate cell opener; (f) about 1% to about 5% by weight of a catalyst mixture comprising dimethylcyclohexylamine, dimethylethanolamine, and an isocyanate polymerization catalyst; (g) about 10% to about 25% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate; propylene carbonate, a dibasic ester or dibasic esters and their mixtures; (h) about 1% to about 3% by weight of water, and (i) up to about 15% by weight of a nonyl phenol alkoxylate as a compatibilizing agent.

24. The sprayable polyol mixture according to claim 23, further characterized in that the catalyst mixture comprises a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol.

25. A mixture of sprayable polyol for making a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the product of reaction of an aromatic polymeric isocyanate and a polyol mixture having an NCO / OH index of about 85 to about 125, the spray polyol mixture comprising: (a) about 42.54% by weight of a diethylene glycol polyester polyether phthalate which has an OH value of from about 290 to about 325; (b) about 15.47% by weight of a Mannich-type polyol having an OH value of about 470 to about 490; (c) 5.80% by weight of diethylene glycol; (d) about 1.90% by weight of an alkoxylated polysiloxane surfactant; (e) about 0.48% by weight of a calcium stearate cell opener; (f) about 3.46% by weight of a catalyst mixture comprising dimethylcyclohexylamine, dimethylethanolamine, and an isocyanate polymerization catalyst, and a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol; (g) about 16% by weight or more of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate; propylene carbonate, a dibasic ester or dibasic esters and their mixtures; (h) about 2.49% by weight of water; and (i) up to about 15% by weight of a compatibilizing agent consisting essentially of a nonyl phenol alkoxylate.

26.- A mixture of sprayable polyol to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture which has an NCO / OH number of about 85 to about 125, the spray polyol mixture comprising: (a) about 30.83% by weight of a diethylene glycol polyester polyether phthalate having an OH value of about 230 to about 250; (b) about 32.00% by weight of a Mannich type polyol having an OH value of about 415 to about 435; (c) about 5.80% by weight of diethylene glycol; (d) about 1.30% by weight of an alkoxylated polysiloxane surfactant; (e) about 0.60% by weight of a calcium stearate cell opener; (f) about 3.85% by weight of a catalyst mixture comprising dimethylcyclohexylamine, dimethylethanolamine, an isocyanate polymerization catalyst, and a catalyst containing about 70% bis (2-dimethylaminoethyl) ether in 30% dipropylene glycol; (g) about 28.12% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate; propylene carbonate, a dibasic ester or dibasic esters and their mixtures; (h) about 3.30% by weight of water; and (i) optionally up to about 15% by weight of a compatibilizing agent consisting essentially of a nonyl phenol alkoxylate.

27. A mixture of sprayable polyol to make a rigid foam comprising urethane units and having an open cell content sufficient to resist shrinkage comprising the reaction product of an aromatic polymeric isocyanate and a polyol mixture having an index of NCO / OH from about 85 to about 125, the sprayable polyol mixture comprising: (a) about 30.44% by weight of a diethylene glycol polyester polyether phthalate having an OH value of from about 230 to about 250; (b) about 31.44% by weight of a Mannich-type polyol having an OH value of about 415 to about 435; (c) about 5.80% by weight of diethylene glycol; (d) about 1.91% by weight of an alkoxylated polysiloxane surfactant; (e) about 0.70% by weight of a calcium stearate cell opener; (f) about 4.27% by weight of a catalyst mixture comprising amine and isocyanate polymerization catalysts; (g) about 1.08% by weight of a lead catalyst; (h) about 27.58% by weight of a non-reactive diluent mixture comprising tris-isopropylchlorophosphate; propylene carbonate, a dibasic ester or dibasic esters or their mixtures; (i) about 2.58% by weight of water; and (j) optionally up to about 15% by weight of a compatibilizing agent consisting essentially of a nonyl phenol alkoxylate.