MX2008010574A - Compatibilizing surfactants for polyurethane polyols and resins - Google Patents

Abstract

A resin blend composition is provided containing a polyol, an ethoxylate propoxylate surfactant initiated by a short chain compound, and a hydrocarbon blowing agent. The solubility and/or compatibility of the hydrocarbon carbon blowing agent in the polyol is increased and the phase stability of the resin blend composition is improved by the ethoxylate propoxylate surfactant. The resin blend is suitable for reaction with polyfunctional organic isocyanates to make cellular polyurethane and polyisocyanurate foams.

Description

TENSOACTIVE AGENTS OF COMPATIBILIZATION FOR RESINS AND POLYURETHANE POLYOLS FIELD OF THE INVENTION The present invention relates to rigid polyurethane / polyisocyanurate foams and to polyol-based resin blends used to make said foams. In particular, the invention relates to polyol-based resin blends containing a polyol, a surfactant ethoxylate propoxylate initiated by a short chain compound, and a hydrocarbon blowing agent.

BACKGROUND OF THE INVENTION The polyurethane and polyisocyanurate foams are produced by the reaction between a polyol and a polyisocyanate. Said foams are commonly used for thermal insulation. In a common procedure, the polyol is incorporated in a "resin" or "component B" which usually contains a polyol or a mixture of polyols, catalysts, silicone or other cell stabilizing surfactants, and one or more blowing agents which evaporate due to the heat of the reaction, resulting in expansion of the foam. The resin may also contain water, as an additional blowing agent that works by chemical generation of carbon dioxide during the reaction with isocyanate; flame retardants; and other additives. In said foam production process, the resin combination is, importantly, of stable phase, thus resisting the separation into layers of different composition. The resin combination is often packaged for sale or later use, instead of being used immediately. Even if the ingredients of the resin combination are combined only by the end user, it may take some time before the combination is completely consumed in the course of the normal foam process. In some cases, this elapsed time can go up to several days. In any case, if the ingredients of the resin combination are separated into discrete layers, the resin combination will not perform correctly in use. In an alternative process for producing polyurethane and polyisocyanurate foams, all the ingredients of the resin combination, except the blowing agent, are combined in a pre-combination. The blowing agent is then added to the pre-combination and mixed as the combination is transferred to the final mixing head, by using an in-line mixer, or, the blowing agent is added to the final mixing head itself . The isocyanate, or a mixture of isocyanate and blowing agent, together with other optionally preferred ingredients, are transferred simultaneously to the mixing head, where they are mixed with the pre-combination and discharged to produce the polyurethane or polyisocyanurate foam. Although it is not necessary to maintain phase stability for more than a few seconds in said process, however, the pre-combination is ideally mixed easily and uniformly with the blowing agent. Due to environmental legislation that restricts the use of chlorofluorocarbons and hydrochlorofluorocarbons as blowing agents, hydrocarbons are used in increasing amounts as viable alternative blowing agents in the manufacture of rigid polyurethane or polyisocyanurate foams. Hydrocarbons, such as isomers of pentanes and butanes, are readily available and provide a cost-effective alternative to chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs). Unfortunately, due to the non-polar hydrophobic characteristics of the hydrocarbons, they are only partially soluble in many polyols used in the manufacture of rigid polyurethane or polyisocyanurate foams. Problems may arise due to the low solubility and / or compatibility of the hydrocarbon in the polyol, the resin, or the foaming mixture consisting of resin and polyisocyanate. The low solubility in the resin can lead to stratification, with different concentrations of blowing agent at different depths, or phase separation. The stratification and separation result in a material of different compositions that is fed to the mixing head of the foaming machine, resulting in a loss of control of the process. Therefore, phase stability, i.e., resistance to stratification and separation, is a desirable proy of the resin combination. The low solubility of the blowing agent in the foaming mixture can also result in the development of voids and a rough cellular structure of the foam. The voids can be caused by vaporization of separate hydrocarbon globules, and will therefore be more frequent with a low solubility of blowing agent. The voids can also be caused by the breaking of the cellular structure of the ascending foam, which seems to be exacerbated by the low solubility. The voids and the rough cellular structure result in a lower insulation value in the final foam product. The increased compatibility can be verified through a greater degree of solubility and / or at least temporary stability of the combination of hydrocarbon with polyol or resin. It can also be verified by an improved emulsification, with the emulsion taking the form of either a microemulsion (which can be clear or translucent) or a macroemulsion (which will appear opaque). In any case, an improved emulsion will reduce the speed of phase separation. Many efforts have been made and there is a lot of technique in the field of rigid foams of polyurethane and polyisocyanurates, with respect to additives to make the hydrocarbons more compatible with standard mixtures of formulation of rigid foams. This invention raises other novel additives and admixtures of additives that make hydrocarbon blowing agents more compatible with formulation mixtures of rigid foams. The patent of E.U.A. No. 4,751, 251 (Dow Corning Corp. Midland, MI) discloses a combination of silicone, organic surfactant and water or Ci to C3 alcohols as a generic compatibilizer package. The document claims that there is no negative effect on foam reaction catalysis, even with functional organic surfactant, and observes an increasing height of foam when these mixtures are used. It is reported that the preferred organic surfactant agent is sodium dodecylbenzenesulfonate. The patents of E.U.A. Nos. 5,470,501 and 5,504,125 (both to BASF Corp., Mt. Olive, NJ) describe polyurethane foam formulations utilizing a C4-C7 hydrocarbon blowing agent and a compatibilizer. The aforementioned compatibilizer is an optionally alkoxylated alkyl aromatic monol or a derivative. The patents of E.U.A. Nos. 5,488,071, 5,484,817 and 5,464,562 (all for BASF Corp., Mt. Olive, NJ) describe a method for preparing a rigid closed cell polyisocyanurate foam comprising reacting polyisocyanate and polyol having ester linkages with a C4 hydrocarbon. C7 and a polyoxyalkylated C8-C24 alcohol additive. This additive is referred to as a polyoxyalkylene polyol monolide (ie, a monohydroxy compound) based on a C8-C24 fatty hydrocarbon with an active hydrogen atom.

The patent of E.U.A. No. 5,684,092 (BASF Corp. Mt. Olive, NJ) discloses polyurethane foams which employ as blowing agents a hydrocarbon and a monol of 1-4 carbons other than t-butanol. The patent of E.U.A. No. 5,736,588 (Bayer Aktrengesellschaft6, Leverkusen, DE) utilizes solution promoters from a group consisting of dialkyl carbonates, certain esters of dicarboxylic acid, certain triesters of phosphoric acid, certain fatty acid / diamine reaction products, and certain quaternary ammonium salts. The patent of E.U.A. No. 5,578,651 (Bayer Aktiengesellschaft, Leverkusen, DE) discloses similar solubilizers used in polyurethane foams employing halohydrocarbon blowing agents. The patent of E.U.A. No. 5,786,400 (Sumitomo Bayer Urethane Co., Ltd., Japan) describes the use of t-butanol as a hydrocarbon emulsifier in rigid foams. The data in Table 3 of the citation show that it is a more efficient compatibilizer than a nonylphenol ethoxylate additive or that no additive. The patent of E.U.A. No. 5,922,779 (Stepan Company, Northfield, III.) Teaches the use of a combination of nonionic surfactants and reacted hydrophobic materials (e.g., soybean oil) as compatibilizers for hydrocarbon blowing agents. The patent of E.U.A. No. 6,034,145 (Imperial Chemical Industries PLC, London, UK) teaches the use of at least two different polyoxyethylene polyether monools (eg, ethoxylated fatty alcohols) to solubilize hydrocarbon blowing agents in polyol compositions for rigid polyurethane foams. The patents of E.U.A. Nos. 6,245,826 and 6,268,402 (both for BASF Corp., Mt. Olive, NJ) describe the use of a fatty acid compatibilizing agent or fatty alcohol ethoxylate to produce rigid isocyanate-based foam utilizing a hydrocarbon blowing agent of C4-C6 The patent of E.U.A. No. 6,420,443 (Crompton Corp., Middlébury, CT) describes a process for preparing rigid hydrocarbon-blown polyurethane foam using an alkoxylated triglyceride as a compatibilizing agent. The patent of E.U.A. 6,472,446 (BASF Corp., Mt. Olive, NJ) discloses a stable phase polyol combination composition containing a sucrose and polyether polyol of propylene oxide co-initiated with dipropylene glycol, a polyester polyol, a compatibilizing agent and a hydrocarbon blowing agent. The compatibilizing agent is a polyether surfactant of propylene oxide initiated with butanol. WO 98/42764 (Imperial Chemical Industries PLC, London, UK) discusses the use of a mixture of two different polyoxyethylene polyether monools to solubilize hydrocarbon blowing agents in resins for rigid polyurethane foams. Monols of C-12-C15 with hydroxyl values of 120-80 are discussed as solubilizing agents. WO 96/12759 (Dow Chemical Company, Midland, NJ) discloses a closed cell polyurethane foam comprising reacting in the presence of a hydrocarbon blowing agent, a polyisocyanate with a mixed polyol composition. This polyol blend comprises a standard rigid polyol plus a compatibilizing agent containing the CnH2n + i fragment, wherein n is greater than or equal to 5, which contains at least one active hydrogen and no more than one aromatic group. A preferred compatibilizing agent, described in WO 96/12759, is castor oil. The compatibilizing agents can be alkoxylated derivatives of fatty oils. No mention or suggested transcendence for alkoxylation. The patent of E.U.A. No. 5,451, 615 (Dow Chemical Company, Midland, NJ), a related patent, details compatibilization agents which are fatty acids with hydroxyl values of 100-200. Skowronski and Londrigan, (Jim Walter Research Inc., Birmingham, AL) SPI 29th Poiyurethane Conference, 1985 pages 76-83 describe foams based on surfactants prepared from castor oil ethoxylates on which maleate esters were grafted and fumarate through chemical coupling of free radicals. These surfactants were allegedly used in closed-cell phenolic foams as well as polyurethane foams and were substitutes for traditional silicone surfactants. A related patent, the patent of E.U.A. No. 4,529,745 (Jim Walter Research Inc., Birmingham, AL) discloses surfactants which are free-radical reaction products of polyoxyalkylene adducts of organic triglycerides with esterified dibasic acids possessing unsaturated C4-C5 diacid cores and tails derived from alcohol of Cs-Cie. Tridecyl fumarate and ethoxylated castor oil are preferred building blocks of these grafted surfactants.

BRIEF DESCRIPTION OF THE INVENTION It has now been discovered that certain nonionic surfactants and combinations of these surfactants are very effective in reducing the problems that result from the low solubility or compatibility of hydrocarbon blowing agents in polyols, resins, or foaming mixtures to make rigid foams. based on isocyanate. In a first aspect, the presently disclosed technology provides a stable phase resin combination composition comprising a polyol, a compatibilizing agent, and a hydrocarbon blowing agent. The compatibilizing agent of the present technology comprises a surfactant ethoxylate propoxylate agent produced by reacting propylene oxide (PO) and ethylene oxide (EO) with an initiator selected from the group consisting of compounds having an active hydrogen atom of oxide of alkylene and an aliphatic or alicyclic hydrocarbon group of Ci.Ce, compounds having an active hydrogen atom of alkylene oxide and an aryl or alkylaryl group of C6-C10, and combinations thereof. The initiator of preference is selected from the group consisting of aliphatic or alicyclic alcohols of Ci-C6, phenol, alkylphenols of C1-C4, and combinations thereof. An example of the surfactant ethoxylate propoxylate is a surfactant of propylene oxide-ethylene oxide initiated with butanol ("butanol-PO-EO"). Alternatively, the compatibilizing agent of the present technology may further comprise an alkoxylated triglyceride adduct (e.g., a castor oil ethoxylate) and / or an alkoxylated sorbitan ester adduct (e.g., ethoxylated derivative of a sorbitan ester. ). In one embodiment of the present technology, the polyol comprises at least 50% by weight of one or more aromatic polyester polyols based on the total weight of the polyol. An example of the aromatic polyester polyols is a polyol initiated with italic anhydride. The hydrocarbon blowing agents in the composition can be C4-C7 aliphatic hydrocarbons, C4-C7 cycloaliphatic hydrocarbons, and combinations thereof. For example, pentanes have been widely used in the industry. In another aspect, the presently disclosed technology provides a polyurethane or polyisocyanurate foam comprising the reaction product of a polyisocyanate and the resin combination composition of the present technology as described above. Compared to a combination of resin and foam made without a nonionic surfactant, one or more of the following improvements can be observed when adding a compatibilizing agent of the present technology: (1) greater compatibility of the hydrocarbon blowing agent in the resin combination; (2) greater compatibility of the hydrocarbon blowing agent in the polyol itself, property which is often taken as a measure of the relative compatibility in the resin combination; (3) higher phase stability of the resin combination (due to a reduced rate of separation of the hydrocarbon); and (4) after mixing the resin and isocyanate combination, better stabilization of the rising foam, as indicated with thinner cells and less voiding.

BRIEF DESCRIPTION OF THE DRAWINGS Does not apply.

DETAILED DESCRIPTION OF THE INVENTION The resin combination of the present technology includes a polyol, a compatibilizing agent as described herein and a hydrocarbon blowing agent. Depending on the specific foam production process used in the production, the hydrocarbon blowing agent can be premixed with the polyol and the compatibilizing agent before production begins; it can be added to a pre-combination containing the polyol and the compatibilizing agent and mixed as the combination is transferred to a final mixing head, by the use of an in-line mixer; or it can be added in the final mixer head.

Polyol Component The polyols used in the resin combinations of the present technology are compounds having two or more hydroxyl groups. They generally have a molecular weight between 50 and 12,000, more narrowly from about 200 to about 1,000. They can be polyether polyols, polyester polyols or other polyol compounds. It is also possible to use mixtures of polyols of various structures, molecular weights and / or functionalities. In addition, the polyols may include reacted hydrophobic materials (e.g., soybean oil) as described in U.S. Patents. Nos. 5, 922,779 and 6, 359,022 (both for Stepan Company, Northfield, III) The amount of the polyol component in the resin blend can be from about 65 to about 95% by weight. Preferably, the amount of polyol component is from about 70 to about 90% by weight, based on the total weight of the resin blend. Preferably, the amount of polyol component is from about 75 to about 85% by weight, based on the total weight of the resin blend. The polyol component can be a polyol of any type. For example, the polyol component may comprise only one or more polyester polyols, or may comprise a mixture of one or more polyester polyols and one or more polyether polyols. Optionally, the polyol component can additionally comprise other polyoids. The polyester polyol of the present technology is preferably an aromatic polyester polyol. According to at least one embodiment of the currently described technology, the polyol component contains at least about 20%, preferably at least about 50% by weight, of aromatic polyester polyoids based on the total weight of the polyol component. Aromatic polyester polyoids can be prepared directly through interesterification of reagents including materials based on italic acid and a hydroxylated material. The reagents may further include a hydrophobic material. Examples of italic acid based materials include italic acid; isophthalic acid; terephthalic acid; methyl esters of phthalic acid, soft or terephthalic; phthalic anhydride; dimethyl terephthalate; polyethylene terephthalate; trimellitic anhydride; and pyromellitic dianhydride. Examples of hydroxylated materials include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, butylene glycols, 1,2-cyclohexanediol, poly (oxyalkylene) polyols derived from the condensation of ethylene oxide, propylene oxide, or any combination thereof. , glycerol, 1,1-trimethylolpropane, 1,1-trimethylolethane, 2,2-dimethyl-1,3-propanediol and pentaerythritol. Examples of hydrophobic materials include castor oil, coconut oil, corn oil, cottonseed oil, linseed oil, olive oil, palm oil, palm kernel oil, peanut oil, soybean oil, Sunflower oil, wood oil and bait. The aromatic polyester polyol for the present technology advantageously has an average functionality of from about 1.5 to about 8.0, preferably from about 1.6 to about 6.0, and particularly from about 1.8 to about 4.0. Generally, the aromatic polyester polyol contains an amount of italic acid-based material relative to an amount of hydroxylated material to give an average acid value of from about 0 to about 10 and an average hydroxyl value of from about 100 to about 600, preferably from about 100 to about 400, and in particular from about 150 to about 350, taking into account that free glycols may be present. The aromatic polyester polyol generally has a free glycol content, based on the total weight of aromatic polyester polyol, from about 1 to about 30% by weight, and usually from about 2 to about 20 by weight. The polyol component can also include a polyether polyol. A particularly preferred polyether polyol is a polyoxyalkylene polyether polyol. Polyoxyalkylene polyether polyols useful in the polyol component include but are not limited to one or more of polyoxyalkylated sucrose, polyoxyalkylated glycerol, and polyoxyalkylene glycols. The polyoxyalkylene polyether polyols can be prepared through anionic or cationic polymerization of starting materials such as one or more alkylene oxides, preferably containing from 2 to 4 carbons in the alkylene radical. Any suitable alkylene oxide can be used, and examples include 1, 3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, amylene oxides, styrene oxide, and preferably, oxide of ethylene and 1,2-propylene oxide and mixtures thereof. Alternatively, the polyoxyalkylene polyether polyols can be polymerized from other starting materials such as tetrahydrofuran, alkylene oxide-tetrahydrofuran mixtures, or epihalohydrins such as epichlorohydrin. The polyoxyalkylene polyether polyols may have hydroxyl groups either primary or secondary. The polyoxyalkylene polyether polyols can be produced by anionic polymerization of said starting materials with alkaline hydroxides as catalysts, including sodium hydroxide or potassium hydroxide, or with alkali alcoholates as catalysts, including sodium methylate, sodium or potassium ethylate, or potassium isopropylate, and in addition to the catalysts, at least one initiator molecule containing from 2 to 8, and preferably from 3 to 8 reactive hydrogens. The polyoxyalkylene polyether polyols can also be produced by cationic polymerization of said starting materials with Lewis acids as catalysts, including antimony pentachloride or boron trifluoride etherate, or with bleaching earth as a catalyst. Included among the polyoxyalkylene polyether polyols are polyoxyalkylene glycols, such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, and polytetramethylene glycol.; block copolymers, such as combinations of polyoxypropylene and polyoxyethylene glycols, or poly-1,2-oxybutylene and polyoxyethylene glycols, or poly-1,4-tetramethylene and polyoxyethylene glycols; and copolymer glycols prepared from combinations or consecutive addition of two or more alkylene oxides. The polyoxyalkylene polyether polyols can be prepared by any known method such as, for example, the process described by Wurtz in 1859 and Encyclopedia of Chemical Technology, Vol. 257-262, published by Interscience Publishers, Inc. (1951) or in the patent of E.U.A. No. 1, 922.459 (I.G. Farbenindustrie Aktiengesellschaft, Frankfurt, Germany). Preferred polyoxyalkylene polyethers include the alkylene oxide addition products of polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. , hydroquinone, resorcinol, glycerol, 1,1-trimethylolpropane, 1,1-trimethylolethane, pentaerythritol, 1,2,6-hexanetriol, alpha-methylglucoside, sucrose and sorbitol. Other useful polyhydric alcohols in which to perform the addition of alkylene oxide include phenol-derived compounds such as 2,2-bis (4-hydroxyphenyl) -propane, commonly known as Bisphenol A. When included in the polyol component, the Polyether polyol is combined in an advantageous ratio with the reaction product of aromatic polyester polyol. The amount of polyether polyol used in the polyol component is determined by the requirements of the application and the physical properties required of the resulting foam. For example, in applications involving isocyanate rates close to 120, for example, preparation of typical polyurethane foams, the polyether polyols can be used in an amount up to 80% by weight, based on the total weight of the polyol component . Conversely, in applications involving isocyanate rates close to 300, eg, preparation of typical polyisocyanurate foams, less or no polyether polyol is incorporated into the polyol component. Other types of polyols can also be used in the polyol component. Examples of other types of polyols include: thioether polyols, polyester amides, polyacetals, and aliphatic polycarbonates containing hydroxyl groups; amine terminated polyoxyalkylene polyethers; non-aromatic polyester polyols, graft dispersion polyols, and preferably polyester polyether polyols. Mixtures of two or more of the aforementioned polyols can be used as long as the combination produces a polyol component containing an average hydroxyl number within the aforementioned scale.

Compatibilization agent The compatibilization agent of the present technology contains a propoxylate ethoxylate ethoxylated surfactant which is produced by reacting propylene oxide and ethylene oxide with an initiator. The initiator may be one or more short chain compounds having an active hydrogen atom of alkylene oxide and an aliphatic or alicyclic hydrocarbon group of CrC6 or an aryl or aryl hydrocarbon group of C6-C 0. Suitable monofunctional initiators include , for example, aliphatic or alicyclic alcohols, secondary amines, phenol, alkylphenols, and aliphatic or aromatic monocarboxylic acids. Preferably, the initiator is an aliphatic or alicyclic C 1 -C 6 alcohol, a phenol, a C 1 -C 4 alkylphenol, or a combination thereof. A particularly suitable initiator for the currently described technology is butanol, which will give a non-ionic propoxylate ethoxylate compound initiated with butanol having both propylene oxide (PO) and ethylene oxide (EO) in the alkylene oxide moiety. The surfactant ethoxylate propoxylate initiated with butanol may be referred to as a butanol-PO-EO surfactant. In the preparation of the propoxylate ethoxylate surfactant of the present technology, for each mole of initiator (eg, butanol), preferably at least about 3 moles of propylene oxide and at least about 1 mole of ethylene oxide are used; preferably, at least about 10 to about 100 moles of propylene oxide and at least about 10 to about 100 moles of ethylene oxide are used. According to at least one embodiment of the present application, PO and EO are reacted with the initiator separately in order to produce block polymers. For example, the initiator can react first with the entire PO, and then with the whole EO, or vice versa. As another example, by reacting the initiator with PO and EO in order in a repeated manner, multiple alternate blocks of PO and EO can be formed. According to at least one other embodiment of the present application, PO and EO can be premixed and then reacted simultaneously with the initiator to produce random copolymers. The compatibilizing agent of the present technology may contain other compatibilizers (either now known or to be discovered) that can improve the solubility of hydrocarbon blowing agents in polyol compositions. For example, the compatibilizing agent of the present technology may be a combination of the surfactant ethoxylate propoxylate initiated with alcohol with an alkoxylated triglyceride adduct and / or an alkoxylated sorbitan ester adduct. The preparation and application of adducts of alkoxylated triglyceride are known in the art, and are described, for example, in the patent of E.U.A. No. 6,420,443 (Clark et al.). Examples of alkoxylated triglyceride adducts illustrated in the U.S.A. No. 6,420,443 include a variety of castor oil ethoxylates. The level of the coupling of the alkoxylated triglyceride adduct is not important for the present technology. According to at least one embodiment, the level of alkoxylation is in the range of about 5 to about 100 moles of alkylene oxide (eg, ethylene oxide) per mole of triglycerides (eg, those of castor oil) . As is known to one skilled in the art, an alkoxylated sorbitan ester adduct can be easily produced by reacting a sorbitan precursor ester with alkylene oxide (for example, ethylene oxide). The precursor ester of the alkoxylated sorbitan ester adduct may be a mono-, di- or tri-ester of sorbitol, sorbitan, or a mixture thereof with any C12-C2o fatty acid or a mixture of Ci2-C20 fatty acids. Examples of adducts of alkoxylated sorbitan ester include ethoxylated sorbitan triesters of wood oil fatty acids. The level of alkoxylation of the alkoxylated sorbitan ester adducts is not important for the present technology. According to at least one modality, the level of alkoxylation is within the range of about 2 to about 50 moles of alkylene oxide (eg, ethylene oxide) per mole of sorbitan ester precursor (eg, sorbitan triesters of wood oil fatty acids) ). A series of alkoxylated sorbitan esters is available from Stepan Company (Northfield, III) under the trade names Toximul® SEE-340 and SEE-341. The use of these types of materials alone as compatibilizers in resins is described for example in S.N. Singh et al, Proceedings of the Polyurethanes World Congress '97, Methods of Increasing the Solubility of Hydrocarbons and HFCs in Polyurethane Raw Materials and the Effects on the Performance and Processing Characteristics of Construction Foams, p. 136. The general amount of the compatibilizing agent can be from about 2 to about 30% by weight; alternatively from about 5 to about 20% by weight, based on the total weight of the polyol component and the compatibilizing agent. It has been observed that the compatibilizing agent of the present technology can increase the compatibility of a hydrocarbon blowing agent in a resin combination; increasing the compatibility of a hydrocarbon blowing agent in a polyol, which property is often taken as a measure of the relative compatibility in a resin combination made from the polyol; increase the phase stability of a resin combination (due to a reduced rate of separation of the hydrocarbon to form a separate phase); and / or after mixing the resin and isocyanate combination, better stabilize the rising foam, as indicated with thinner cells and less gap formation.

Blowing agent The resin combination of the present technology also contains an aliphatic or cycloaliphatic C4-C7 hydrocarbon blowing agent. Said hydrocarbons have a boiling point of 70 ° C or less at 1 atmosphere, and preferably have a boiling point of 50 ° C or less at 1 atmosphere. The hydrocarbon blowing agent is physically active and has a sufficiently low boiling point to evaporate and become gaseous at the exothermic temperatures caused by the reaction between the isocyanate and the polyols. The vaporizing hydrocarbon blowing agent provides foaming action within the resulting polyurethane matrix. The hydrocarbon blowing agents consist exclusively of carbon and hydrogen and therefore are not halogenated by definition. Exemplary C4-C7 hydrocarbon blowing agents include, alone or in combination: linear or branched alkanes, such as butane, isobutane, 2,3-dimethylbutane, n-pentane, isopentane, mixtures of pentane technical grade, n-hexane , isohexane, n-heptane, isoheptane, or mixtures thereof; alkenes, such as 1-pentane, 2-methylbutene, 3-methylbutene, 1-hexene, or mixtures thereof; and cycloalkanes, such as cyclobutane, cyclopentane, cyclohexane or mixtures thereof. Preferred C4-C hydrocarbon blowing agents include cyclopentane, n-pentane, isopentane, and mixtures thereof. Other blowing agents can be used in conjunction with C4-C7 hydrocarbon blowing agents. Said auxiliary blowing agents can be divided into the classes of: (1) chemically active blowing agents, which react chemically with isocyanate or other formulation ingredients to produce a gas which is subsequently released, thus generating the foaming action; and (2) physically active blowing agents which are gaseous at or below the exothermic foaming temperatures, thus providing a blowing gas without the need to chemically react with the foam ingredients. Included within the meaning of physically active blowing agents are decomposition materials that are thermally unstable and which decompose at elevated temperatures, releasing a gas. The preferred auxiliary chemically active blowing agents are those that react with isocyanate to liberate a gas such as CO2. Suitable chemically active blowing agents include, but are not limited to water, mono- and polycarboxylic acids having a molecular weight of 46 to 300, salts of said polycarboxylic acids and tertiary alcohols. Water can be classified and used as a chemically active blowing agent because water reacts with isocyanate to produce and release C02 gas, the actual resulting blowing agent. However, because water consumes isocyanate groups, the use of water as a chemically active blowing agent requires the addition of an equivalent molar excess of isocyanate to compensate for the amount of isocyanates consumed by water.

More information about auxiliary chemically active blowing agents and physically active auxiliary blowing agents for use in combination with hydrocarbon blowing agents, can be found in the US patent. No. 6,359,022 (Stepan Company, Northfield, III.). The total and relative amounts of blowing agent will depend on the desired foam density, the type of hydrocarbon, and the amount and type of additional blowing agents employed. Polyurethane foam densities typical of products intended for rigid polyurethane insulation applications encompass free increase densities from about 20.81 to about 40.02 g / l, preferably from about 20.81 to about 33.62 g / l and general molded densities of about 24.01 a approximately 48.03 g / i- The total amount of blowing agent, based on the weight of all foaming ingredients (i.e., the combination of resin and socianate), is preferably from about 3 to about 15 weight percent. The amount of hydrocarbon blowing agent, based on the weight of all the foaming ingredients, is preferably from about 3 to about 15 weight percent, and in particular from about 5 to about 10 weight percent. The amount by weight of all the blowing agents in the resin blend is generally from 5 to about 35 parts by weight per one hundred parts of all the polyols and the compatibilizing agents (php), and preferably from about 10 to about 30. php The amount of hydrocarbon blowing agent in the resin blend of the currently described technology is from about 1 to about 35 weight percent, alternatively from about 5 about 30 weight percent, based on the total weight of the combination of resin. Particularly, the amount of hydrocarbon blowing agent is from about 10 to about 20 weight percent, based on the total weight of the resin blend. As described above, the hydrocarbon spraying agent in the resin blend can be augmented with chemically active auxiliary blowing agents and / or physically active blowing agents. A smaller amount of water in polyols can be found as a reaction byproduct, and said water may be sufficient to act as a single auxiliary chemically active blowing agent. However, optionally, water can be added to the resin blend in an amount of about 0.05 to about 5 php, and preferably about 0.25 about 1.0 php. Other auxiliary chemically active blowing agents can be used in place of or in addition to water. Physically active auxiliary blowing agents can also be used in place of or in addition to auxiliary chemically active blowing agents.

The blowing agent can be added and incorporated into the polyol combination for storage and subsequent use in a foaming apparatus or can be added to a pre-mix tank in the foaming apparatus and incorporated into the polyol combination before pumping the ingredients of foaming to the mixing head. Alternatively, the blowing agent can be added to the pre-mix and mixed as the combination is transferred to the final mixer head, by using an in-line mixer, or it can be added to the foaming ingredients in the mixing head as a separate current.

Other optional ingredients Optionally preferred ingredients include cell stabilizing surfactants, flame retardants, and catalysts.

A. Cell Stabilizing Surfactants Resin combinations of the currently described technology optionally contain cell stabilizing surfactants. Examples of cell stabilizing surfactants include but are not limited to Niax Silicone L-6900, commercially available from GE Silicones (Friendly, WV); silicone surfactant Dabco DC-5598, commercially available from Air Products and Chemicals, Inc. (Allentown, PA); silicone surfactant Tegostab B 8512, commercially available from Goldschmidt Chemical Corp. (Essen, Germany); and Vorasurf 504, a non-silicone surfactant available from Dow Chemical Co. (Midland, Michigan). The cell stabilizing surfactants, if employed, are preferably added to the resin blend in an amount of about 0.5 to about 5 php, and preferably about 1 to about 3 php. The amount of cell stabilizing surfactant based on the weight of all the foaming ingredients is preferably from about 0.2 to about 2.5 weight percent, and in particular from about 0.4 to about 1.5 weight percent.

B. Flame Retardants Flame retardant additives can be added to obtain foams that have a particular flame retardancy rating. Preferred flame retardants are solid or liquid compounds that contain one or more of the elements phosphorus, chlorine, bromine, and boron. Examples of flame retardants include but are not limited to tri- (2-chloro isopropyl) phosphate, tetrakis- (2-chloro ethyl) ethylene diphosphate, tris- (beta-chloro ethyl) phosphate, and tris- (2,3 -dibromo propyl) phosphate. Tris- (2-chloro isopropyl) phosphate is a particularly preferred flame retardant. If employed, flame retardants are added to the resin blend in an amount of from about 2 to about 50 php, and preferably from about 5 to about 25 php. The amount of flame retardant based on the weight of all the foaming ingredients is from about 1 to about 25 weight percent, and preferably from about 2 to about 12 weight percent.

C. Catalysts The resin blends of the invention optionally contain catalysts to accelerate the reaction with the polyisocyanate. Suitable catalysts, include but are not limited to salts of organic carboxylic acids, for example sodium salts, ammonium salts, and preferably potassium salts. Examples include trimethyl-2-hydroxypropyl ammonium formate, trimethyl-2-hydroxypropyl ammonium octanoate, potassium formate, potassium 2-ethylhexanoate, and potassium acetate. Tin (II) salts of organic carboxylic acids are often also used as catalysts, which include, for example, tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate and tin laurate. (II), and the dialkyltin (IV) salts of organic carboxylic acids, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. The organic metal compounds can be used alone or preferably in combination with strongly basic amines. Tertiary amines are often used to promote the formation of urethane bonds and the reaction of isocyanate with water to generate carbon dioxide. Tertiary amines include but are not limited to triethylamine, 3-methoxypropyl dimethylamine, triethylenediamine, pentamethyl diethylenetriamine, and bis (dimethylaminopropyl) urea. Other examples that may be mentioned are amines such as 2-3-dimethyl-3,4,516-tetrahydropyrimidine or tertiary amines such as triethylamine.; tributylamine; dimethylbenzylamine; N-methylmorpholine; N-ethylmorpholine; N-cyclohexylmorpholine; ?,?,? ',?' - tetramethylethylenediamine; ?,?,? ',?', - tetramethylbutanediamine; N, N, N ', N'-tetramethylethylhexan-1,6-diamine; pentamethyl ethylenetriamine; bis (dimethylaminoethyl) ether; bis (dimethylaminopropyl) urea; dimethylpiperazine; 1,2-dimethyl imidazole; 1-azabicyclo (3,3,0) octane and preferably 1,4-diazabicyclo (2,2,2) octane. Additionally, alkanolamine compounds such as triethanolamine; triisopropanolamine; N-methyldiethanolamine and N-ethyldiethanolamine and dimethylethanolamine. Particularly preferred catalysts include potassium 2-ethylhexanoate, commercially available from Air Products and Chemicals under the tradename Dabco K-15 Catalyst; pentamethyl ethylenetriamine, commercially available Air Products and Chemicals under the trade name Polycat 5 Catalyst; and dimethylcyclohexylamine, commercially available from Air Products and Chemicals under the trade name Polycat 8 Catalyst. Additional suitable catalysts include tris (dialkylaminoalkyl) -s-hexahydrotriazines, in particular tris (N, N-dimethylaminopropyl) -s-hexahydrotriazine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; alkali metal hydroxide such as sodium hydroxide and alkali metal alkoxides such as sodium methoxide and potassium isopropoxide and also alkali metal salts of long chain fatty acids having from 10 to 20 carbon atoms and possibly OH side groups in combinations of organic metal compounds and strongly basic amines. If employed, the catalysts are added to the resin blend in an amount of about 0.5 to about 10 php, and preferably about 1 to about 8 php. The amount of catalyst based on the weight of all the foaming ingredients is from about 0.5 to about 5 weight percent, and preferably from about 1 to about 4 weight percent. The resin blend of the present technology can be mixed with an isocyanate to produce a polyurethane or polyisocyanurate foam. The isocyanate component is preferably a polyisocyanate, herein defined as having two or more isocyanate functionalities. Examples of these include conventional aliphatic, cycloaliphatic, and preferably aromatic isocyanates. Specific examples include: alkylene diisocyanates with 4 to 12 carbons in the alkylene radical such as 1, 12-dodecane diisocyanate, 2-ethyl-1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate , 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate, cycloaliphatic isocyanates such as 1,3- and 1,4-cyclohexane diisocyanate as well as any mixture of these isomers, 1-isocyanate-3,3,5 -trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding isomeric mixtures, 4,4'-2,2'- and 2,4'-dicyclohexylmethane diisocyanate and as the corresponding isomeric mixtures and preferably aromatic isocyanates and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomer mixtures, and 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures, mixtures of isocyanates of 4,4'-. 2,4'-, and 2,2-diphenylmethane and polyphenylenepolymethylene polyisocyanates (crude MDI). In one embodiment, the polyisocyanate component that is used in conjunction with the resin blend of the present technology is a polymeric diphenylmethane diisocyanate (MDI) having a nominal functionality of about 3, and an NCO content of about 31% by weight . Generally, the isocyanate and the resin combination are combined at an isocyanate index of from about 80 to about 1000, alternatively from about 100 to about 400. A preferred isocyanate index for polyurethane foams is in the range of about 100 to about 150; a preferred isocyanate index for the polyisocyanurate foams is in the range of about 200 to about 300. When the isocyanate index is in the range of about 150 to about 200, foams with intermediate characteristics are produced between the polyurethane foams and foams. of polyisocyanurate. Normally rigid polyurethane / polyisocyanurate foam is a closed and thin cell foam material with a broad physical integrity in batch and a self-supporting character to be used as laminated building panels, structural components in electronic devices, etc. This foam often also has a high thermal resistance and good insulation properties, with only a relatively low increase in thermal conductivity over time. It may also be required to have low friability, high compressive strength, and low flammability. The technology described herein and its advantages will be better understood with reference to the following examples. These examples are provided to describe specific modalities of the present technology. In providing these specific examples, the inventors do not limit the scope and spirit of the present technology. Those skilled in the art should understand that the full scope of the present disclosed technology encompasses the subject matter defined by the claims appended to this specification, and any alteration, modification or equivalent to these claims.

Materials used in the examples The main materials used in the examples are described below: Active surfactant 1: produced by reacting one mole of butanol with 50 moles of propylene oxide and 56 moles of ethylene oxide. Surfactant 2: produced by reacting 1 mol sorbitan triester of fatty acids of bait oil with 20 moles of ethylene oxide. Surfactant 3: produced by reacting 1 mol of castor oil with 36 moles of ethylene oxide. Surfactant 4: produced by reacting 1 mol of castor oil with 16 moles of ethylene oxide. Surfactant 5: produced by reacting 1 mole of tridecyl alcohol with 12 moles of ethylene oxide. Ortegol® 410 is a compatibilizer produced by Degusta Corporation (Parsippany, New Jersey), which is claimed in the patent of E.U.A. 6,472,446 (BASF Corp., Mt. Olive, NJ) which is a polyether surfactant of propylene oxide initiated with butanol. The butanol in Ortegol® 10 is only propoxylated (ie it is not ethoxylated). Polyol A: the polyol A which is used in the examples was a polyester polyol having a hydroxyl value of 236, an acid value of 1.1, and a content of soybean oil of 8.03%. To make the polyol A according to the method described in the patent of E.U.A. No. 5,922,779 (Stepan company), combine 3,495 g of phthalic anhydride, 4,285 g of diethylene glycol, and 1.6 g of tetrabutyl titanate, in a 12-liter reaction flask and react at 210 ° C to produce a polyol with a hydroxyl value of 257 and an acid value of 1.0. Then 642 g of soybean oil is added, and the mixture is maintained at 210 ° C for 4 hours with stirring, to effect esterification. The resulting polyol had a hydroxyl value of 236, an acid value of 1.1, and a soybean oil content of 8.03%. Polyol B: the polyol B used in the examples was another polyester polyol, which had a hydroxyl value of 262, an acid value of 1.1, and a soybean oil content of 8.33%. To make the polyol B according to the method described in the patent of E.U.A. No. 5,922,779 (Stepan Company), combine 3.356 g of phthalic anhydride, 4.384 g of diethylene glycol and 1.6 g of tetrabutyl titanate, in a 12-liter reaction flask and allow to react at 210 ° C to produce a polyol with a hydroxyl value of 285 and an acid value of 1.0. Then 666 g of soybean oil are added, and the mixture is maintained at 210 ° C for 4 hours with stirring, to effect internal esterification. The resulting polyol had a hydroxyl value of 262, an acid value of 1.1, and a soybean oil content of 8.33%.

Voranol 360 is a polyether polyol based on sucrose / glycerol as an initiator, distributed by the Dow Chemical Company (Midland, Michigan). Fyrol®CEF is a tris (beta-chloroethyl) phosphate, a flame retardant provided by Akzo Nobel Chemicals, Inc. (Dobbs Ferry, NY). Pel-Cat® 9540A is potassium 2-ethyl exanoate, a catalyst provided by Pelron Corporation (Lyons, IL). PMDETA is a pentamethyl diethylene triamine. Tegostab® B-8512 is a silicone surfactant provided by Goldschmidt Chemical Corporation (Essen, Germany). Mondur® 489 is a polymeric isocyanate provided by Bayer Corporation (Pittsburgh, PA). In the examples and tests described below, polyol A was used for the comparative examples and polyol B was used in the examples of the present technology to mix them with the nonionic surfactants of the present technology. The reason why different polyols are used was to achieve approximately the same hydroxyl value for the polyol / surfactant mixtures in the examples of the present technology, as presented in the comparative examples. In addition to the hydroxyl values, the two polyester polyols used in the examples were essentially equivalent.

EXAMPLES 1 TO 8 Compatibility of the blowing agent in the polyol or in the combinations of polyol / surfactant In Examples 1 to 8 the compatibility of n-pentane, which is a widely used hydrocarbon blowing agent, in polyol was tested (see Table 1). Examples 1 to 6 used only polyester polyol, while examples 7 and 8 contained the two polyester and polyether polyols. Example 1 is a comparative example testing polyol A without the addition of any compatibilizing agent. Example 2 is another comparative example testing polyol B (90 parts by weight) with the addition of Ortegol® 410 compatibilizer (10 parts by weight). Example 7 is also a comparative example in this group testing a mixture of polyol B (60 parts by weight) and Voranol® 360 (40 parts by weight) without the addition of any compatibilizing agent. In Examples 3 to 6, 90 parts by weight of the polyol B were mixed with 10 parts by weight of the surfactant 1 or a mixture of the surfactant 1 with 1 of the surfactants 2 to 4. In Example 8, one was made mixture of 54 parts by weight of polyol B and 40 parts by weight of Voranol® 360, with 6 parts by weight of surfactant 1 of the present technology. The procedure for measuring the compatibility of the blowing agent in the polyol or in the polyol / surfactant blends included the following steps: adding a heavy amount of polyol or mixture to a jar; adding the blowing agent in portions, with mixing after each; it was observed if the mixture had signals indicative of the incompatibility / compatibility grades (blue color, fog or opacity) after each addition of the blowing agent; and noting the weight of the blowing agent (after agitation) and clarity after each addition. Without limiting the scope of the term or of the present invention for the purposes of this test, an estimate of the degree of compatibility with respect to the maximum amount of the blowing agent producing a semi-transparent haze was identified, a little less than the amount resulting in opacity. It is expressed in parts of the blowing agent per one hundred parts of the polyol or the polyol / surfactant mixture, and is determined in the nearest part per hundred. The results are shown in table 1.

TABLE 1 Compatibility tests of the polyol and the polyol / surfactant Comparative examples In the mixtures in which only one polyester polyol (polyol A or B) is used, the comparison of examples 1 and 3 shows that the use is only 10% by weight of the surfactant 1 of the present technology , based on the total weight of the polyol / surfactant mixture, significantly increased the compatibility of n-pentane in the polyol from 5 parts to 18 parts. Examples 2 and 3 demonstrate that the surfactant 1 of the present technology worked much better than the commercially available Ortegol® 410 compatibilizer to improve the compatibility of the n-pentane in the polyol B. a mixture of the surfactant 1 with the surfactant 2 , 3 or 4, also increased blowing agent compatibility. In the examples containing both the polyester and the polyether polyols, Example 8, with the surfactant 1, demonstrated improved compatibility over example 7, without any compatibilizer.

EXAMPLES 9 TO 16 Compatibility of the blowing agent in the resin combinations Examples 9 to 16 (table 2) tested the compatibility of n-pentane in resin combinations that included polyol and some commercially available ingredients that are commonly used in resin combinations to produce polyurethane / polyisocyanurate foams. Examples 9 to 14 used a polyester polyol (polyol A or B) as the sole polyol, while examples 15 to 16 contained both polyester and polyether polyols. Example 9 is a comparative example in which the resin combination does not include any compatibilizing agent. Example 10 is another comparative example, which included 90 parts by weight of polyol B and 10 parts by weight of Ortegol® 410 in the resin combination. Example 15 is also a comparative example, which used a mixture of polyol B and Voranol® 360, but did not include any compatibilizing agent in its resin combination. Examples 11 to 14 used the surfactant 1 or a mixture of the surfactant 1 and one of the surfactants 2 to 4 as the compatibilizing agent. Example 16 was based on a mixture of polyol B and Voranol® 360 and included surfactant 1 in its resin combination. The formulations of the resin combinations of examples 9 to 16 are recorded in table 2.

TABLE 2 Compatibility tests of the resin "Comparative examples To measure the compatibility of the blowing agent in the resin, all the ingredients, except the blowing agent, were added to a jar and mixed; and then the procedure described in the compatibility of the polyol above was followed. The compatibility limit in this test is also expressed in parts per 100 of the polyol or the polyol / nonionic surfactant mixture, and is determined to the nearest part per hundred. The results are shown in table 2. Comparing examples 11 to 14 with examples 9 to 10, the results show that the compatibilizing agent consisting solely or partially of the surfactant butane-PO-EO of the present technology, improved from Substantially the compatibility of n-pentane in the resin combinations and performed much better than the Ortegol® 410 compatibilizer that is commercially available. In Examples 15 and 16 using mixtures of polyester and polyether polyols, the formulation of Example 16 with the butanol-PO-EO surfactant in the same manner more compatibilized the n-pentane than the formulation of Example 15 without this surfactant .

EXAMPLES 17 TO 23 Resin stability tests and foam stabilization In examples 17 to 23 (table 3), the resin combinations were formulated and then reacted with polymeric isocyanate to make foams. To investigate the contribution of the compatibilizing agent of the present technology in the stabilization of the resin foam, these foams were made using a normally low level of silicone. The level chosen was that which provided a minimum foam stabilization, just enough to prevent the foam from collapsing during foaming. The stability of the resin combinations and the reactivity of the resin combinations with polymeric isocyanate were tested. Some of the physical properties of the foams were also observed or measured in these examples. Examples 17 and 18 are comparative examples in this group.

The resin combination of example 17 used was polyol A and does not contain any compatibilizing agent. The resin combination of Example 18 used 90 parts by weight of polyol B and 10 parts by weight of the commercially available compatibilizer, Ortegol® 410. The formations of the resin combinations of examples 17 to 23 are shown in Table 3.

Resin stability To test the phase stability of the resin combination, the resin components were combined in an oven and mixed for about 1 minute with a motor-driven mixing blade rotating at 3600 rpm, placed in a covered jar, and put in a constant temperature bath at 20 ° C. After 3 hours the jar was removed and the depth of the clear or almost clear blowing agent layer was measured on top, with a machinist's rule. This depth is expressed as a percentage of the total depth of the material in the jar.

Reactivity test To test the reactivity of the resin combination with a Polymeric socianate, resin and polymeric isocyanate quantities were combined to give 300 g of the total mixture, in a paper cup of 907184 g at 20 ° C, mixed for 8 seconds with a motor-driven mixing blade rotating at 3600 rpm, was poured into a 4,677 kg paper cup, and allowed to rise. The cream time (initiation of the elevation) and the gel time (time at which the polymer chains can be perceived from the mass in reaction) were observed. The density was calculated from the weight of the foam remaining in the body of the cup after having cut the foam protruding above the upper edge of the cup.

Cell structure and hollow depth The cup containing foam resulting from the reactivity test was cut vertically through the center, and the foam was observed. The cell structure was judged based on the relative average cell size. The formulations with a reduced content of silicone that were used resulted in the formation of a hollow in the bottom of the cup, extending over most or over the entire area of the bottom surface. The average depth of this hole was measured with a ruler, and expressed in centimeters. The results of examples 17 to 23 are recorded in the table 3.

TABLE 3 Resin stability and foam stabilization tests * Comparative examples As can be seen in table 3, the foams of examples 19 to 23 had an improved cell structure compared to comparative example 17, in which the cell structure ratio improved from "very poor" to "bad" These proportions are compared to the cell structures obtained at much higher levels of silicone than are normally used in the production of foam. The very low silicon level that was used in Examples 17 to 23 resulted in a relatively low cell structure, but was used to allow the effect of the surfactants of the present technology to be easily seen in the cell structure. . The effects were also evident at the average hollow depth, where the larger hollow depth is interpreted as an indication of less foam stability during elevation. Examples 19 to 23 also demonstrated an improvement over example 17. Therefore, it was observed in these two tests that the compatibilizing agents of the present technology contribute to a more uniform and finer cell foam. The separation in the resin is also reported in Table 3. Examples 19 to 23, with the surfactants of the present technology, displayed a reduced separation at the start compared to Example 17, without the compatibilizing surfactant. Example 18, with Ortegol® 410 as compatibilizer, actually demonstrated a faster separation than in example 17. A slower rate of separation of the resin increases the amount of time in which the resin can be used to foam with a uniform density through a run of production, especially in the processes in which the agitation of the resin after the incorporation of the blowing agent is slow or does not exist.

EXAMPLES 24 and 25 Foam tests and physical properties In Examples 24 and 25 resin blends were prepared with normal levels of silicone, and foams were made therefrom. Examples 24 and 25 used combinations of polyol B resin containing a mixture of surfactants 1 and 2 or surfactants 1 and 3. The resin combination formulations of examples 24 and 25 are shown in Table 4 The reactivities of the resin combinations of Examples 24 and 25 are tested in these examples in Table 4. In these examples the reactivities of the resin combinations of Examples 24 and 25 and some of the physical properties were tested. of the foam produced from the resin combination of example 24. The method for testing the reactivity of the resin was the same as that described above for examples 17 to 23.

Foam molding To produce foam samples to test the properties of the molded foam, the resin and the isocyanate were combined and mixed in the same manner as for the reactivity test, and immediately poured into a rectangular mold of 5.08. cm by 33.02 by 63.5 cm, whose surfaces were maintained at 51.666 ° C. The 5.08 cm dimension was oriented vertically. The minimum amount of foaming mixing that was required to fill the mold was used. After 15 min. The mold foam panels were removed and placed in an oven at 93,333 ° C for 24 hours to complete the cure. The blocks were cut from the interiors of the panels that would be used as test pieces.

Compression strength The procedure that was used to measure the resistance to compression was the ASTM C-158 method. According to this method, the 5.08 x 5.08 x 2.54 cm test pieces were cut from the interiors of the test panels in such a way that a compressive force could be applied in each of the three specified directions. The directions were indicated with reference to the elevation direction (5.08 cm). The compressive strengths were determined on a test machine. The compressive strength was defined as a maximum force per unit area (kg / cm2) indicated at a deflection of 10% or less.

K factor The procedure that was followed to measure the K factors was the ASTM method C-518. Test pieces of 27.94 x 27.94 x 3.175 cm were cut from the interiors of the test panels, and the K factors were measured on a LaserComp Heat Flow Meter instrument (LaserComp, Saugus, MA). The test results of examples 24 and 25 are recorded in table 4.

TABLE 4 Foaming tests and physical properties The foams of examples 24 and 25 had a fine and regular cell structure and a normal overall appearance. The compressive strengths and K factors of example 24 are typical of a commercially acceptable polyisocyanurate foam. The present technology has been described in complete, clear, concise and exact terms so that one skilled in the art to which it belongs can practice it. It should be understood that the foregoing describes the preferred embodiments of the present technology and that modifications may be made thereto without departing from the spirit or scope of the present technology as represented in the following claims.

Claims (3)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A combination of polyol-based resin comprising: (a) a polyol; (b) a compatibilizing agent comprising a propoxylate ethoxylate surfactant which is produced by reacting propylene oxide and ethylene oxide with an initiator selected from the group consisting of compounds having an active hydrogen atom of alkylene oxide and a aliphatic or alicyclic C1-C6 hydrocarbon group, compounds having an active hydrogen atom of alkylene oxide and an alkylaryl or aryl hydrocarbon group of Ce-Cio, and combinations thereof; and (c) a hydrocarbon blowing agent.
2. 2. The resin combination according to claim 1, further characterized in that the compatibilizing agent also comprises an alkoxylated triglyceride adduct.
3. 3. The resin combination according to claim 1, further characterized in that the compatibilizing agent also comprises an alkoxylated sorbitan ester adduct. 4 - The resin combination according to claim 3, further characterized in that the alkoxylated sorbitan ester adduct is made from a sorbitan ester comprising a mono, di, or triester of sorbitol or sorbitan, or a mixture of the same, with a C12-C20 fatty acid or a mixture of C- | 2-C20 fatty acids. 5. - The resin combination according to claim 1, further characterized in that the initiator is selected from the group consisting of aliphatic or alicyclic alcohols of Ci-C6, phenol, alkyl phenols of Ci-C4, and combinations thereof. 6. - The resin combination according to claim 1, further characterized in that the initiator comprises butanol. 7. - The resin combination according to claim 1, further characterized in that the blowing agent is selected from the group consisting of C4.C7 hydrocarbons and combinations thereof. 8 - The resin combination according to claim 1, further characterized in that the compatibilizing agent is present in an amount of about 2 to about 30% by weight based on the total weight of the components (a) and (b). 9 - The resin combination according to claim 1, further characterized in that the hydrocarbon blowing agent is present in an amount of about 5 to about 35 parts by weight per hundred parts of the total weight of the components (a) and ( b) 10. The resin combination according to claim 1, further characterized in that the polyol comprises at least 50% by weight of one or more aromatic polyester polyols, based on the total weight of the polyol. 11. The resin combination according to claim 1, further characterized in that for each mole of the initiator, at least 3 moles of propylene oxide and at least one mole of ethylene oxide are used. 12 - The resin combination according to claim 1, further characterized in that for each mole of the initiator, about 10 to about 100 moles of propylene oxide and about 10 to about 100 moles of ethylene oxide are used. 13 - A polyurethane or polyisocyanurate foam comprising a reaction product of an isocyanate and a resin combination, wherein the resin combination comprises: (a) a polyol; (b) a compatibilizing agent comprising a propoxylate ethoxylate surfactant produced by reacting propylene oxide and ethylene oxide with an initiator selected from the group consisting of compounds having an active hydrogen atom of alkylene oxide and a hydrocarbon group aliphatic or alicyclic C1-C6, compounds having an active hydrogen atom of alkylene oxide and a hydrocarbon group of alkylaryl or C6-C10 aryl, and combinations thereof; and (c) a hydrocarbon blowing agent. 14 -. 14 - The foam according to claim 13, further characterized in that the compatibilizing agent also comprises an alkoxylated triglyceride adduct. 15. The foam according to claim 13, further characterized in that the compatibilizing agent also comprises an alkoxylated sorbitan ester adduct. 16 - The foam according to claim 15, further characterized in that the alkoxylated sorbitan ester adduct is made from a sorbitan ester comprising a mono, di, or triester of sorbitan or sorbitol, or a mixture thereof , with a C12-C20 fatty acid or a mixture of Ci2-C2o-17 fatty acids. - The foam according to claim 13, further characterized in that the initiator is selected from the group consisting of C1-C6 alcohols, phenol, C1-C4 alkyl phenols, and combinations thereof. 18. - The foam according to claim 13, further characterized in that the initiator comprises butanol. 19. - The foam according to claim 13, further characterized in that the blowing agent is selected from the group consisting of C4-C7 hydrocarbons and combinations thereof. 20. - The foam according to claim 13, further characterized in that the compatibilizing agent is present in the resin blend in an amount of about 2 to 30% by weight based on the total weight of the components (a) and ( b) The foam according to claim 13, further characterized in that the hydrocarbon blowing agent is present in the resin combination in an amount of about 5 to 35 parts by weight per hundred parts of the total weight of the components ( a) and (b) 22. - The foam according to claim 13, further characterized in that the polyol comprises at least 50% by weight of one or more aromatic polyester polyols based on the total weight of the polyol. 23. - The foam according to claim 13, further characterized in that the resin combination comprises from about 65 to about 99% by weight of the polyol based on the total weight of the resin combination. 24. - The foam according to claim 13, further characterized in that for each mole of the initiator, at least 3 moles of propylene oxide and at least 1 mole of ethylene oxide are used. 25. The foam according to claim 13, further characterized in that for each mole of the initiator, from about 10 to about 100 moles of propylene oxide and from about 10 to about 100 moles of ethylene oxide are used. 26 -. 26 - A method for making a polyol based on a resin combination, comprising: providing a polyol; providing a compatibilizing agent comprising a propoxylate ethoxylate surfactant which is produced by reacting propylene oxide and ethylene oxide with an initiator selected from the group consisting of compounds having an active hydrogen atom of alkylene oxide and a hydrocarbon group aliphatic or alicyclic of CrC6, compounds having an active hydrogen atom of alkylene oxide and a hydrocarbon group of alkylaryl or aryl of C6-Cio, and combinations thereof; provide a hydrocarbon blowing agent; and combining the polyol, the compatibilizing agent, the hydrocarbon blowing agent to form a resin combination. 27. - The method according to claim 26, further characterized in that the compatibilizing agent also comprises an alkoxylated triglyceride adduct. 28. - The method according to claim 26, further characterized in that the compatibilizing agent also comprises an alkoxylated sorbitan ester adduct. 29. - The method according to claim 26, further characterized in that the initiator is selected from the group consisting of C1-C6 alcohols, phenol, C1-C4 alkyl phenols, and combinations thereof. 30 -. The method according to claim 26, further characterized in that the initiator comprises butanol. 31 - A method for making a polyurethane or polyisocyanurate foam, comprising: providing an isocyanate; provide a polyol; providing a compatibilizing agent comprising a propoxylate ethoxylate surfactant produced by reacting propylene oxide and ethylene oxide with an initiator selected from the group consisting of compounds having an active hydrogen atom of alkylene oxide and an aliphatic hydrocarbon group or alicyclic of C C6, compounds having an active hydrogen atom of alkylene oxide and an alkylaryl or aryl C6-C10 hydrocarbon group, and combinations thereof; provide a hydrocarbon blowing agent; making a mixture comprising the isocyanate, the polyol, the compatibilizing agent, and the hydrocarbon blowing agent; and reacting the mixture to produce the polyurethane or polyisocyanurate foam. 32. - The method according to claim 31, further characterized in that the isocyanate comprises a polyisocyanate. 33. - The method according to claim 31, further characterized in that the mixture has an isocyanate index of about 100 to about 400. The method according to claim 31, further characterized in that the compatibilizing agent also comprises a alkoxylated triglyceride adduct. 35. - The method according to claim 31, further characterized in that the compatibilizing agent also comprises an alkoxylated sorbitan ester adduct. 36. - The method according to claim 31, further characterized in that the initiator is selected from the group consisting of C1-C6 alcohols, phenol, C1-C4 alkyl phenols, and combinations thereof. 37. The method according to claim 31, further characterized in that the initiator comprises butanol.