Storage stable, formic acid-containing polyol compositions and methods of making polyurethane foams therefrom

Abstract

A formulated polyol composition includes a polyol mixture that include a Novolac-initiated polyether and at least one other polyether, formic acid, a urethane catalyst and a surfactant having the empirical formula MD10-200DR 2-50M, where each M is R(CH3)2Si-O1 / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -O1 / 2-Si(CH3)2-O1 / 2-, and each DR is where PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups. This formulated polyol composition is surprisingly storage-stable. It is useful for making polyurethane foams, in particular laminated panels in a discontinuous process.

Description

STORAGE STABLE, FORMIC ACID-CONTAINING POLYOL COMPOSITIONS AND METHODS OF MAKING POLYURETHANE FOAMS THEREFROMCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and all advantages of Italian Patent Application No.102024000023454 filed on 22 October 2024, the content of which is incorporated herein by reference.FIELD

[0002] This invention relates to polyol compositions that contain formic acid and methods for making polyurethane foams from those polyol compositions.BACKGROUND

[0003] Formic acid is a beneficial blowing agent for manufacturing certain types of polyurethane foam. A specific example is laminated panels, which have a foam layer with attached facing layers on one or both sides. At industrial scale, these laminated panels can be made in a continuous or discontinuous process. In a continuous process, the facing layer or layers move through the process continuously, and a polyurethane-forming reaction mixture is applied to the bottom facing layer continuously and cured continuously as the facing layer / foam layer assembly moves through the process. The finished product is then cut to length. In the discontinuous process, facing layers are cut to length beforehand and mounted horizontally into a press cavity and separated by spacers that define the thickness of the foam layer. The reaction mixture is then introduced between the facing layers and cured there to produce the polyurethane foam. The facing layer(s) are held stationary in the press throughout the process of introducing the reaction mixture and curing it. In systems formulated for these applications, formic acid contributes to a superior aesthetic appearance of the foam, helping to form smooth, uniform exterior surfaces.

[0004] Novolac polyols are desirable in processes such as discontinuous laminated panel production because the formulations containing them process well and the resulting foams tend to adhere well to facers. However, foams made using a Novolac polyol often perform more poorly on flammability tests than do otherwise like foams made using an aromatic polyester polyol.

[0005] It is common practice to formulate the formic acid into a polyol composition that contains various polyols, catalysts, silicone surfactants, optionally other chemical blowing agents such as water and, quite typically, one or more flame retardants (which may themselves be polyols). The polyol composition may or may not also contain a physical blowing agent. The polyol composition is usually formulated ahead of time, to separate the step of producing the polyol composition from that of making the laminated panels. This simplifies the panel manufacturing process and helps avoid product inconsistencies due to imperfect metering or mixing of the various components.

[0006] A pre-formulated polyol composition is usually made at a systems house or other formulator and shipped and stored before it is used. As such, a period of several weeks to some months may elapse between the time the polyol composition is formulated and when it is used. A problem with formic acid-containing polyol compositions is that they are unstable when stored. A polyurethane foam made using an aged formic acid-containing polyol composition may exhibit poorer performance on flammability testing. It also may suffer from increased surface defects associated with a phenomenon known as “blow off”, in which surface bubbles form on the surface of the foam. These problems are especially prevalent when the polyol composition contains a Novolac polyol, i.e., a polyether polyol containing aromatic groups made by alkoxylating a Novolac resin.

[0007] In view of the otherwise desirable attributes of polyurethane foams made using Novolac polyols and formic acid, a solution to the problems of poorer performance on flammability testing and ageing stability is desired. This advantage is obtained with a foam formulation that also exhibits processing properties, notably a property called “flow” or “flow index”.BRIEF SUMMARY

[0008] Disclosed in one aspect is a method of method of making a rigid polyurethane foam, comprisingI) forming a reaction mixture comprising:(A) a polyol mixture comprising(A-1) 30 to 70 weight percent, based on the total weight of the polyol mixture (A), of a Novolac-initiated polyether polyol, the Novolac-initiated polyether polyol having a nominal hydroxyl functionality of 2 to 6 and a hydroxyl number of 140 to 400 mg KOH / g;(A-2) 25 to 70 weight percent, based on the total weight of the polyol mixture (A), of one or more aliphatic polyether polyols; and(A-3) 0 to 5 weight percent, based on the total weight of the polyol mixture (A), of one or more additional polyols, different from polyether polyols (A-1) and (A-2);(B) 1 to 4 parts by weight formic acid per 100 parts by weight of the polyol mixture (A); (C) 1.5 to 6 parts by weight, per 100 parts by weight of the polyol mixture (A), of a silicone surfactant having the empirical formula MDIO-2OODR2-SOM, where each M is R(CH3)2Si-Oi / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis CH3— Of72— Si-OfT?p4nrQ-PE

[0009] where R4is hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups;(D) a catalytically effective amount of at least one urethane catalyst;(E) 3 to 10 parts by weight of a physical blowing agent per 100 parts by weight of the polyol mixture (A);and(F) an aromatic polyisocyanate, the aromatic polyisocyanate being provided in an amount sufficient to produce an isocyanate index of 80 to 200,wherein the reaction mixture contains 0.25 to 2% by weight phosphorus and 0 to 3% by weight bromine and,(II) curing the reaction mixture to produce the polyurethane foam.

[0010] In a method of particular interest, the polyurethane foam is produced as a layer of a laminated panel, by forming a layer of the reaction mixture formed in step I on a facer or between two facers and curing the layer of the reaction mixture on the facer or between the two facers to produce a laminated panel comprising a polyurethane foam layer adhered to the facer or facers.

[0011] The polyurethane foam performs significantly better on flammability testing such as the DIN 4102 flammability test, as indicated by lower maximum flame height and / or burn pattern, than an otherwise like polyurethane foam made with a surfactant in which the hydroxyl-terminated polyethylene oxide)s of the -Oi / 2-Si(CH3)(R4-O-PE)-Oi / 2- units are replaced with a hydroxyl-terminated copolymer of ethylene oxide and propylene oxide. This improvement in flammability testing performance is quite surprising in view of the structural similarity of the silicone surfactant (E) to those of previously-used silicone surfactants.

[0012] In a second aspect, this disclosure provides a formulated polyol composition comprising (A) a polyol mixture comprising(A-1) 30 to 70 weight percent, based on the total weight of the polyol mixture (A), of a Novolac-initiated polyether polyol, the Novolac-initiated polyether polyol having a nominal hydroxyl functionality of 2 to 6 and a hydroxyl number of 140 to 400 mg KOH / g;(A-2) 25 to 70 weight percent, based on the total weight of the polyol mixture (A), of one or more aliphatic polyether polyols; and(A-3) 0 to 5 weight percent, based on the total weight of the polyol mixture (A), of one or more additional polyols, different from polyether polyols (A-1) and (A-2);(B) 1 to 4 parts by weight formic acid per 100 parts by weight of the polyol mixture (A); (C) 1.5 to 6 parts by weight, per 100 parts by weight of the polyol mixture (A), of a silicone surfactant having the empirical formula MDIO-2OODR2-SOM, where each M is R(CH3)2Si-Oi / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis iO OQ i I x_z fTfR:O-PEwhere R4is hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups; and(D) a catalytically effective amount of at least one urethane catalyst;wherein the formulated polyol composition contains 0.55 to 2.5% by weight phosphorus and 0 to 6% by weight bromine.

[0013] In addition to providing the aforementioned improvements in flammability testing performance, the formulated polyol composition of this aspect of the invention exhibits improved ageing stability, as indicated by a lack of blow-off and good flammability test performance when used to make polyurethane foam after the formulated polyol composition is aged.DETAILED DESCRIPTION

[0014] Disclosed in one aspect is a method of method of making a rigid polyurethane foam, comprisingII) forming a reaction mixture comprising:(A) a polyol mixture comprising(A-1) 30 to 70 weight percent, based on the total weight of the polyol mixture (A), of a Novolac-initiated polyether polyol, the Novolac-initiated polyether polyol having a nominal hydroxyl functionality of 2 to 6 and a hydroxyl number of 140 to 400 mg KOH / g;(A-2) 25 to 70 weight percent, based on the total weight of the polyol mixture (A), of one or more aliphatic polyether polyols; and(A-3) 0 to 5 weight percent, based on the total weight of the polyol mixture (A), of one or more additional polyols, different from polyether polyols (A-1) and (A-2);(B) 1 to 4 parts by weight formic acid per 100 parts by weight of the polyol mixture (A); (C) 1.5 to 6 parts by weight, per 100 parts by weight of the polyol mixture (A), of a silicone surfactant having the empirical formula MDIO-2OODR2-SOM, where each M is R(CH3)2Si-Oi / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis

[0015] where R4is hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups;(D) a catalytically effective amount of at least one urethane catalyst;(E) 3 to 10 parts by weight of a physical blowing agent per 100 parts by weight of the polyol mixture (A);and(F) an aromatic polyisocyanate, the aromatic polyisocyanate being provided in an amount sufficient to produce an isocyanate index of 80 to 200,wherein the reaction mixture contains 0.25 to 2% by weight phosphorus and 0 to 3% by weight bromine and,(II) curing the reaction mixture to produce the polyurethane foam.

[0016] In a method of particular interest, the polyurethane foam is produced as a layer of a laminated panel, by forming a layer of the reaction mixture formed in step I on a facer or between two facers and curing the layer of the reaction mixture on the facer or between the two facers to produce a laminated panel comprising a polyurethane foam layer adhered to the facer or facers.

[0017] In a second aspect, this disclosure provides a formulated polyol composition comprising (A) a polyol mixture comprising(A-1) 30 to 70 weight percent, based on the total weight of the polyol mixture (A), of a Novolac-initiated polyether polyol, the Novolac-initiated polyether polyol having a nominal hydroxyl functionality of 2 to 6 and a hydroxyl number of 140 to 400 mg KOH / g;(A-2) 25 to 70 weight percent, based on the total weight of the polyol mixture (A), of one or more aliphatic polyether polyols; and(A-3) 0 to 5 weight percent, based on the total weight of the polyol mixture (A), of one or more additional polyols, different from polyether polyols (A-1) and (A-2);(B) 1 to 4 parts by weight formic acid per 100 parts by weight of the polyol mixture (A); (C) 1.5 to 6 parts by weight, per 100 parts by weight of the polyol mixture (A), of a silicone surfactant having the empirical formula MDIO-2OODR2-5OM, where each M is R(CH3)2Si-Oi / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis CH3— Si-CW□ FT4-where R4is hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups; and(D) a catalytically effective amount of at least one urethane catalyst;wherein the formulated polyol composition contains 0.55 to 2.5% by weight phosphorus and 0 to 6% by weight bromine.

[0018] The polyol mixture (A) includes all compounds having two or more hydroxyl groups in the reaction mixture or formulated polyol composition, but excludes silicone compounds such as surfactants. The polyol mixture includes Polyol A-1, Polyol A-2, and optionally up to 5 weight percent of one or more other polyols A-3, based on the total weight of the polyol mixture.

[0019] Polyol A-1 is a Novolac-initiated polyether polyol. It has a nominal hydroxyl functionality of 2 to 6, alternatively 2.5 to 4 or 3 to 4. It has a hydroxyl number, as measured according to ASTM D6342-22, of 140 to 400 mg KOH / g, alternatively 180 to 400 mg KOH / g or 180 to 300 mg KOH / g. The Novalac-initiated polyol is made by polymerizing at least one alkylene oxide onto astarting Novolac resin. The starting Novolac resin is a phenol-formaldehyde condensation product, generally represented by the structure:where each R5independently is hydrogen or C1-18 alkyl and n is 0 to 4, especially 0.5 to 2 or 1 to 2. The methylene bridges may be bonded to the 2-, 4- or 6-positions of the aromatic rings, the hydroxyl group in each case occupying the 1 -position. The starting Novolac resin is reacted with about 1 to 9 moles of ethylene oxide and / or propylene oxide per phenolic group to produce the Novolac-initiated polyether polyol. In a preferred embodiment, the starting Novolac is reacted with propylene oxide or both propylene oxide (simultaneously or sequentially) to produce the Novolac-initiated polyether polyol.

[0020] The Novolac-initiated polyether polyol (A-1) comprises 30 to 70 weight percent, alternatively 40 to 60 of the total weight of the polyol mixture (A).

[0021] Polyol A-2 is one or more aliphatic polyether polyols. The aliphatic polyether polyols are alkoxylates of aliphatic starter compounds that have two or more hydroxyl, primary or secondary amino or thio groups. Preferred starters are polyols having 2 to 8 hydroxyl groups. Examples of starters include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butane diol, 1,6-hexane diol, 1,8-octane diol, cyclohexane dimethanol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, mannitol, sucrose and alkoxylates (such as ethoxylates and / or propoxylates) of any of these that have a hydroxyl equivalent weight less than that of the product of the polymerization.

[0022] The starter can also be water.

[0023] The starter may contain bromine and / or phosphorus atoms. Phosphorus atoms may be present in the form of, for example, phosphate, phosphonate and / or phosphine groups in the starter molecule.

[0024] The starter is alkoxylated with one or more alkylene oxides such as ethylene oxide, 1,2-propylene oxide, oxetane, 1,2-butylene oxide, 2,3-butylene oxide and 1,2-hexene oxide, with ethylene oxide, 1 ,2-propylene oxide or both ethylene oxide and 1 ,2-propylene oxide being preferred.

[0025] The hydroxyl number(s) of the aliphatic polyether polyol(s) may range from, for example, 28 to 500 mg KOH / g.

[0026] Polyol A-2 may include (i) at least one polyether having a nominal functionality of 2 to 4, alternatively 3, and a hydroxyl number of 150 to 500 mg KOH / g and / or ii) at least one polyether having a nominal functionality of 5 to 8 and a hydroxyl number of 250 to 500, and optionally mayfurther contain at least one bromine-containing aliphatic polyether polyol having a hydroxyl number of 150 to 400 mg KOH / g.

[0027] Polyol A-2 may include (i) at least one polypropylene oxide) having a nominal functionality of 2 to 4, alternatively 3, and a hydroxyl number of 150 to 500 mg KOH / g and / or ii) at least one polypropylene oxide having a nominal functionality of 5 to 8 and a hydroxyl number of 250 to 500 mg KOH / g, and may optionally further contain at least one bromine-containing aliphatic polyether polyol having a hydroxyl number of 150 to 400 mg KOH / g.

[0028] Polyol A-2 may include (i) at least one polypropylene oxide) having a nominal functionality of 2 to 4, alternatively 3, and a hydroxyl number of 150 to 225 mg KOH / g, (ii) at least one polypropylene oxide) having a nominal functionality of 2 to 4, alternatively 3, and a hydroxyl number of 226-400 mg KOH / g, and (iii) at least one polypropylene oxide) having a nominal functionality of 5-8, alternatively 6, and a hydroxyl number of 250 to 500 mg KOH / g, and optionally may further contain at least one bromine-containing aliphatic polyether polyol having a hydroxyl number of 150 to 400 mg KOH / g.

[0029] Polyol A-2 constitutes 25 to 70 weight percent of the polyol mixture (A), alternatively 40 to 60 weight percent thereof.

[0030] Optional Polyol A-3 is one or more additional compounds having two or more hydroxyl, primary amino and / or secondary amino groups, different from polyether polyols A-1 and A-2. Examples of Polyols A-3 include, for example, polyester polyols; polyether polyols different from Polyols A-1 and A-2, and crosslinkers and / or chain extenders having hydroxyl numbers of 501 to 187 mg KOH / g. Examples of such crosslinkers and chain extenders include but are not limited to ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanedimethanol, glycerin, trimethylolpropane, triethanolamine, diethanolamine, monoethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine. Polyol A-3 may be absent.

[0031] 1 to 4 parts by weight formic acid are present per 100 parts by weight of the polyol mixture (A). A preferred amount is 2 to 4 parts, on the same basis.

[0032] The silicone surfactant (C) has the empirical formula MDIO-2OODR2-5OM, where each M is R(CH3)2Si-Oi / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -Oi / 2-Si(CH3)2-O1 / 2-, and each DRisCH3where R4is hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups. The D and DRgroups in one embodiment are randomly distributed.

[0033] Each R may be, for example, methyl, ethyl or phenyl, alternatively methyl.

[0034] The R4group is typically is aliphatic and may have 2 to 10, especially 2 to 4 carbon atoms. A carbon atom of the R4group is bonded directly to the silicon atom of the -Oi / 2-Si(CH3)(R4-O-PE)-OI / 2- group. The PE group is a homopolymer of ethylene oxide having 6 to 50, alternatively 8 to 30 or 8 to 20 oxyethylene groups.

[0035] In a specific embodiment, the silicone surfactant has general formula MDIO-SODR2-2OM, wherein each M is (CH3)3Si-Oi / 2-, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRiswhere R4is C2-4 hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 8 to 30 oxyethylene groups and the D and DRgroups are randomly distributed.

[0036] In another specific embodiment, the silicone surfactant has the general formula MD20-3ODR5-IOM, where each M is (CH3)3Si-Oi / 2-,each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRiswhere R4is C2-4 hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 8 to 20 oxyethylene groups, and the D and DRgroups are randomly distributed.

[0037] It is preferred to exclude other silicone surfactants.

[0038] The silicone surfactant may be provided in the form of a solution or dispersion in a diluent. In such a case, it is preferred that the diluent constitute at most 50%, alternatively at most 30% of the total weight of the solution or dispersion.

[0039] 1.5 to 6 parts by weight of the silicone surfactant is provided per 100 parts by weight of the polyol mixture (A). A preferred lower amount is at least 1.75 parts and preferred upper amounts are up to 5 parts or up to 4.5 parts, on the same basis. The weight of the silicone surfactant is on an active basis, excluding the weight of any solvent or diluent.

[0040] Urethane catalysts (Component D) for purposes of this invention catalyze the reaction between an isocyanate group and an alcohol group and / or water. Among suitable urethane catalysts are tin (II) and tin (IV) catalysts, catalysts that contain other Group III to Group XV metals, tertiary amine compounds, amidines, tertiary phosphines, and the like. Among the useful urethane catalysts are, for example, trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, dimethyl cyclohexyl amine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, dialkylimidazole compounds, 2,2’-dimorpholinodiethylether, N,N,N',N'-tetramethyl-1 ,4-butanediamine, N,N-dimethylpiperazine, 1 ,4-diazobicyclo-2,2,2-octane, tetraalkyl guanidine compounds, 2,2,2-dimethylaminoethoxyethyl methylaminoethanol, N,N-dimethylcyclohexylamine, 1 ,3,5-tris[3-(dimethylamino)propyl]hexahydro-1 ,3,5-triazine, triethylenediamine, dimethylalkylamines where the alkyl group contains from 4 to 18 carbon atoms, pentamethyldiethylene triamine, tetramethyl ethylene diamine, dibutyl tin dilaurate, dimethyltin dilaurate, stannous octoate, stannous oleate, stannic chloride, stannous chloride, di-n-butyl tin bis(mercaptoacetic acid isooctyl ester) and other organotin compounds of the formula SnRn(OR)4-n, wherein R is alkyl or aryl and n is 0-2. A mixture of two or more urethane catalysts may be used.

[0041] The urethane catalyst is present in a catalytically effective amount. Tertiary amine and amidine catalysts, for example, may be present when used in an amount of 0.1 to 5 parts or 0.25 to 2 parts by weight per 100 parts by weight of the polyol mixture (A). Tin catalysts may be present (when used) in an amount of 0.01 to 1 or 0.1 to 0.25 parts by weight per 100 parts by weight of the polyol mixture (A).

[0042] The physical blowing agent (E) is a compound that is not reactive toward isocyanate groups under the conditions of the curing step and which volatilizes under the conditions of the curing step to produce a gas that expands the reaction mixture and produces cells in the cured polyurethane. Examples of suitable blowing agents include n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, methyl cyclopentane, n-hexane, 2- and / or 3-methyl pentane, cyclohexane, n-heptane, 2-, 3- and / or 4-methyl hexane, methylcyclohexane, 1 -butene, 2-butene, 1 -pentene, 2-pentene, 1 -hexene, 2-hexene, 1 -heptene, 2-heptene, 3-heptene, 1.1.1.3.3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1.1.1.2.3.3.3-heptafluoropropane (HFC-227ea), 1,1,1,2-tetrafluoroethane (HFC-134a), trifluoropropene, 1 ,3,3,3-tetrafluoropropene (1234ze), 1,1,3,3-tetrafluoropropene, 2, 2,3,3-tetrafluoropropene (1234yf), 1,2,3,3,3-pentafluoropropene (1225ye), 1,1,1 -trifluoropropene, 1.1.1.3.3-pentafluoropropene (1225zc), 1,1,2,3,3-pentafluoropropene (1225yc), (Z)- 1,1, 1,2,3-pentafluoropropene (1225yez), 1-chloro-3,3,3-trifluoropropene (1233zd) and 1, 1,1, 4,4,4-hexafluorobut-2-ene (1336mzzm). 3 to 10, alternatively 4 to 8, parts by weight of a physical blowing agent are provided per 100 parts by weight of the polyol mixture (A).

[0043] The reaction mixture comprises one or more aromatic polyisocyanates. The one or more organic polyisocyanates typically have an average isocyanate functionality of 2.0 to 3.2, alternatively 2.1 to 2.8. The one or more polyisocyanates may have an isocyanate equivalent weight of up to 200 g / equivalent, such as 80 to 175 g or 80 to 150 g / equivalent, as measured according to ASTM D2572. Examples of useful organic polyisocyanates include m-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, naphthylene-1 ,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4’-diisocyanate 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4-4'-biphenyl diisocyanate, 3,3-dimethyldiphenyl methane-4,4'-diisocyanate, 4, 4', 4"-triphenyl methane tri isocyanate, a polymethylene polyphenylisocyanate (PMDI), toluene-2,4,6-triisocyanate, 4,4,-dimethyldiphenylmethane-2,2,,5,5,-tetraisocyanate or a so-called polymeric MDI, which is mixture of diphenylmethane diisocyanate and PMDI. In specific embodiments, the polyisocyanate is diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, PMDI, polymeric MDI toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or mixtures thereof. Polyisocyanate products made by modifying any of the foregoing may be modified to produce urea, urethane, carbodiimide, biuret, uretonimine or other linkages are also useful.

[0044] The one or more isocyanates are provided in an amount sufficient to produce an isocyanate index of 80 to 200. A preferred isocyanate index is at least 100 and up to 175 or up to 150. Isocyanate index is 100 times the ratio of the number of isocyanate groups to the number of isocyanate-reactive groups in the reaction mixture, prior to any reaction.

[0045] A preferred optional ingredient is water. The amount of water may be at least 0.5 parts, at least 1 part or at least 2 parts per 100 parts by weight of polyol mixture (A), and up to 5.5 parts, up to 5 parts or up to 4 parts.

[0046] The reaction mixture may further contain optional ingredients such as a flame retardant, one or more fillers and / or reinforcing agents such as fiber glass, carbon fibers, flaked glass, mica, talc, melamine and calcium carbonate; one or more pigments and / or colorants such as titanium dioxide, iron oxide, chromium oxide, azo / diazo dyes, phthalocyanines, dioxazines and carbon black; one or more biocides; one or more preservatives; one or more antioxidants; one or more flame retardants; and the like.

[0047] Polyurethane foam is made by combining the various ingredients to form a reaction mixture which is then cured. The order of mixing is generally not critical although it is preferred to combine the poly isocyanate after mixing the other ingredients, or at least simultaneously with the mixing of the other ingredients.

[0048] However, it is often convenient to produce a formulated polyol composition that comprises the polyol mixture (A), the formic acid (B), the silicone surfactant (C), the urethane catalyst (D), water (if used) and optionally the physical blowing agent (E), each as described above. Such a formulated polyol composition may be packaged separately from the polyisocyanate (F) and optionally separated from the the physical blowing agent (E) as well, being stored in a tank or other suitable container for a period ranging from a few days to many months (such as seven days to six months or seven days to 3 months), before being combined with the polyisocyanate and physical blowing agent (if not already in the formulated polyol composition) to produce foam. Aging is generally performed at moderate temperatures such as 10°C to 40°C, typical of storage and transportation conditions. The formulated polyol composition may be maintained under an inert atmosphere such as nitrogen during the aging period. An advantage of this invention such a formulated polyol composition is surprisingly storage-stable. Foam made from the aged formulated polyol composition exhibit properties very similar to foam made using a freshly-prepared formulated polyol composition that is not aged. In particular, flame properties asmeasured according to DIN 4102 exhibit little or no change, and “blow off”, which is an indicator of surfactant degradation, is not seen when the aged formulated polyol composition is used to produce foam.

[0049] To make the foam, the formulated polyol composition and polyisocyanate (F) are brought together in suitable mixing equipment, combined and dispensed. The physical blowing agent (E), if not already in the formulated polyol composition, is conveniently mixed with the formulated polyol composition just prior to or simultaneously with combining the formulated polyol composition with the polyisocyanate. For example, the formulated polyol composition, physical blowing agent and polyisocyanate may be fed into the mixing equipment as separate streams and combined therein. An important advantage of this invention that such a formulated polyol composition exhibits excellent stability upon ageing, which allows the formulated polyol composition to be formulated, packaged, transported and stored for extended periods prior to being processed into foam.

[0050] No special foaming conditions are necessary; therefore, foaming conditions and equipment described in the art for making polyurethane foam are entirely suitable. In general, the isocyanate compounds will react spontaneously with the polyols even at room temperature (23°C) and therefore in some embodiments curing is accomplished without heating to an elevated temperature (apart from a temperature rise associated with a reaction exotherm that takes place during the curing). If necessary, heat can be applied to the reaction mixture to speed the curing reaction. Curing is continued until the reaction mixture has expanded and cured sufficiently to form a stable foam.

[0051] In some embodiments, the curing step is performed in a closed mold. In such a process, the reaction mixture is either formed in the mold itself or formed outside the mold and then introduced into the mold, where it cures. The expansion of the reaction mixture as it cures is therefore constrained by the internal surfaces of the mold, as are the size and geometry of the molded part. Enough of the reaction mixture is introduced into the mold such that the resulting foam achieves the wanted density as it expands and fills the mold.

[0052] The invention is especially useful in making laminated panels that comprise a polyurethane foam layer adhered on one or both sides to a facer. Such panels are made by forming a layer of the reaction mixture formed in step I on a facer or between two facers and curing the layer of the reaction mixture on the facer or between the two facers to produce a laminated panel comprising a polyurethane foam layer adhered to the facer or facers.. The curing step (step II of the invention) is then performed on the layer of reaction mixture on the facer to produce the laminated panel.

[0053] Such laminated panels may be manufactured industrially in either a continuous or discontinuous process. In a continuous process, the reaction mixture is formed and passed through a distribution system that defines multiple flow paths and has multiple outlets throughwhich the reaction mixture is dispensed onto a moving bottom facing layer. This produces parallel strips of reaction mixture that combine as they expand to form a continuous layer of reaction mixture on the bottom facer. A top facing layer may be continuously laid on top of the layer of reaction mixture. The assembly is then cured continuously by passing it through a heated zone while maintaining mechanical pressure on it to control the thickness of the foam layer that forms as the reaction mixture cures. The resulting laminate is then cut to length. The process of forming the laminated panel may be performed on a heated conveyor, such as a double band laminator in which one or both bands are heated, to provide a suitable curing temperature.

[0054] Examples of such continuous laminated panel processes are described, for example, in US Published Patent Application Nos. 2014 / 00417412, 2017 / 0285619, US 2010 / 0080900, US Patent No. 9,718,223, German Utility Models 202011 001 109 U1 and 202009015838U1, WO 2008 / 018787 and WO 2021 / 045888.

[0055] In a discontinuous process, the facer layer(s) are cut to the desired shape and size in a preliminary step, before producing the laminated panel. Top and bottom facers are inserted onto the cavity of a press and separated by spacers that define the thickness of the foam layer. The reaction mixture is introduced between the facing layers. The reaction mixture is then cured in the press while applying mechanical pressure to prevent excessive expansion of the foam layer. The cured laminated panel is then taken out and the next successive panel is produced. Suitable equipment for making laminated panels in a discontinuous process is sold by Cannon PlasTec and Weihua Machinery (Wuxi City, China).

[0056] The facers may be, for example, a metal (which may have an applied coating) such as steel or aluminum, kraft or other paper, a fiber-reinforced paper, a metal foil-paper composite layer or a plastic sheet or film.

[0057] A continuous or discontinuous process for making laminated panels may and typically does include various additional steps (and associated apparatus) as are needed to produce a laminated panel product. The facing layers, particularly metal ones, may be pre-treated to promote good adhesion to the polymer foam or otherwise to facilitate panel manufacture. Examples of pre-treatment steps include decoiling, corona discharge treatment, profiling, heating to the process temperature, and application of a layer of an adhesion promoter. The facings, especially metal facers, may be preheated to between 20°C and 80°C to increase the adhesion to the foam. The laminated panel may be cut or trimmed, stacked, packaged and labeled.

[0058] Laminated panels produced in accordance with the invention are useful, for example: in building applications, such as walls, ceilings, roofs, doors and ductwork; cold storage such as walls, flooring and ceilings for warehouses and cold room; in transportation applications such as refrigerated trucks and trailers and ships; as well as other uses.

[0059] The following examples are provided to illustrate the invention and are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.

[0060] In the following examples:

[0061] The Novolac Polyol is prepared by polymerizing a mixture of propylene oxide and ethylene oxide onto an aromatic Novolac resin. It has a hydroxyl number of 196 mg KOH / g and an average hydroxyl functionality of 3.3.

[0062] Polyether Polyol 1 is a nominally trifunctional polypropylene oxide) having a hydroxyl number of 165 mg KOH / g.

[0063] Polyether Polyol 2 is a sorbitol-initiated polypropylene oxide) having a hydroxyl number of 480 mm KOH / g.

[0064] Polyether Polyol 3 is a nominally trifunctional polypropylene oxide) having a hydroxyl number of about 375 mg KOH / g.

[0065] TCPP is tris (1-chloro-2-propyl) phosphate.

[0066] The Amine Catalyst is a mixture of dimethyl cyclohexyl amine and dimethyl benzyl amine.

[0067] The Brominated Polyol is a brominated aliphatic polyether triol containing 31.5% bromine and having a hydroxyl number of 330 mg KOH / g, sold as Ixol™ B251 by Solvay.

[0068] Surfactant A is a trimethylsilyl-terminated poly(dimethylsiloxane) having hydroxylterminated ethylene oxide / propylene oxide side chains, commercially available from Dow Inc. as Dowsurf® 5604 additive. It corresponds to the general formula MD2O-3ODR5-IOM where each M is -Oi / 2-Si(CH3)3, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis -0i / 2Si(CH3)(PE / P0)-0 2- where PE / PO is a hydroxyl-terminated random copolymer having 5-15 oxyethylene groups and 2-6 oxypropylene groups. The D and DRgroups are randomly distributed.

[0069] Surfactant B is a trimethylsilyl-terminated poly(dimethylsiloxane) having hydroxyl-terminated ethylene oxide / propylene oxide side chains, commercially available from Evonik as Tegostab® B84711.

[0070] Surfactant 1 is a trimethylsilyl-terminated poly(dimethylsiloxane) having hydroxyl-terminated polyethylene side chains. It corresponds to the general formula MD2O-3ODR5-IOM, where each M is -Oi / 2-Si(CH3)3, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis -Oi / 2-Si(CH3)(PE)-Oi / 2-where PE is a hydroxyl-terminated polypthylene oxide) consisting of 8 to 12 oxyethylene groups. The D and DRgroups are randomly distributed.

[0071] Surfactant 2 is a trimethylsilyl-terminated poly(dimethylsiloxane) having hydroxyl-terminated polyethylene side chains. It corresponds to the general formula MD2O-3ODR5-IOM1, where each M is -Oi / 2-Si(CH3)3, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis -Oi / 2-Si(CH3)(PE)-O1 / 2- where PE is a hydroxyl-terminated polypthylene oxide) consisting of 13 to 20 oxyethylene groups. The D and DRgroups are randomly distributed.

[0072] PMDI is a polymeric MDI having an isocyanate content of about 31.4% and an average isocyanate functionality of 2.7.

[0073] Examples 1-6 and Comparative Samples A-CPolyurethane foams are made from formulations as indicated in Table 1 :Table 1Ingredient Parts by WeightA* Ex. 1 Ex. 2 Ex. 3 B* Ex. 4 Ex. 5 Ex. 6 C* Novolac Polyol 36 36 36 36 36 36 36 36 36 Polyether Polyol 1 10 10 11 11.5 12 10 11 11.5 12 Polyether Polyol 2 25 25 25 25 25 25 25 25 25 Polyether Polyol 3 5 5 5 5 5 5 5 5 5 TCPP 12 12 12 12 12 12 12 12 12 Amine Catalyst 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Surfactant A 3 0 0 0 0 0 0 0 0 Surfactant 1 0 3 2 1.5 1 0 0 0 0 Surfactant 2 0 0 0 0 0 3 2 1.5 1 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Formic Acid 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Trans-1 chloro- 3.65 3.65 3.65 3.65 3.65 3.65 3.65 3.65 3.65 3,3,3-trifluoropropenePMDI 121 121 121 121 121 121 121 121 121Surfactant 3.94 3.94 2.60 1.93 1.28 3.94 2.60 1.93 1.28 loading, pphp1% P in reaction 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5mixture•Comparative.1The weight of surfactant per 100 parts by weight polyols.

[0074] Foams are made by combining all ingredients except the PMDI to produce a formulated polyol composition. The formulated polyol composition and PMDI are then combined at room temperature and poured into a plastic-lined 20 cm x 20 cm x 20 cm box, where the ingredients react and cure to produce the foam.

[0075] Gel time is measured on Comparative Sample A and Examples 1 and 4 as the foam rises and cures by periodically touching a spatula to the surface of the foam; gel time is the time after pouring at which the reaction mixture no longer adheres to the spatula. The free-rise density of Comparative Sample A and Examples 1 and 4 is measured one hour after pouring according to ASTM D3574. The cured foams are evaluated for flame properties according to DIN 4102. The maximum flame height is recorded. Results are as indicated in Table 2.Table 2Test A* Ex. 1 Ex. 2 Ex. 3 B* Ex.4 Ex. 5 Ex. 6 c* Gel time, s 136 136 - - - 140 - - - Density, g / L 30.2 30.5 - - - 29.9 - - - Max Flame 150 105 105 110 150 105 105 110 155Height, mm

[0076] The data in Table 1 shows the effect of the choice of surfactant and its amount. When the surfactant (Surfactant A) has EO / PO copolymer side chains as in Comparative Sample A, the max flame height on the DIN 4102 is 150 mm. Replacing Surfactant A with equal amounts of either of Surfactants 1 or 2 (each of which has ethylene oxide homopolymer side chains), as in Example 1 and 4, leads to a large and desirable reduction in maximum flame height. Equivalent results are obtained even when the amount of Surfactant 1 or 2 is reduced to as low as 1.93 pphp, as shown by Examples 2-3 and 5-6. However, greater flame heights are seen again when the amount of Surfactant is reduced to 1.28 pphp, as shown in Comparative Samples B and C.

[0077] Examples 7-9 and Comparative Samples D and E

[0078] Molded foams are made from the formulations set forth in Table 3. These formulations include an additional flame retardant, a brominated polyol (Ixol B251). All ingredients except the n-pentane and PM DA are combined to form a formulated polyol composition that in each case (except Comparative Sample D) is aged for 2 months separately from the n-pentane and PMDA in a sealed container at 22°C.Table 3Ingredient Parts by WeightD* E* F* Ex. 7 Ex. 8 Formulated Polyol CompositionNovolac Polyol 36.6 36.6 36.6 36.6 36.6 Polyether Polyol 1 5.9 5.9 5.9 5.9 5.9 Polyether Polyol 2 24.4 24.4 24.4 24.4 24.4 Brominated Polyol 8 8 8 8 8 TCPP 16.4 16.4 16.4 16.4 16.4 Amine Catalyst 2.05 2.05 2.05 2.05 2.05 Surfactant A 0 0 3 0 0 Surfactant B 3 3 0 0 0 Surfactant 1 0 0 0 3 0 Surfactant 2 0 0 0 0 3 Water 1.25 1.25 1.25 1.25 1.25 Formic Acid 3.15 3.15 3.15 3.15 3.15 Aged? No 2 mo. 2 mo. 2 mo. 2 mo. Physical Blowing Agentn-Pentane 3 3 3 3 3 PolyisocyanatePMDI 107 107 107 107 107Surfactant loading, 4.0 4.0 4.0 4.0 4.0 PPhp% P in reaction mixture 0.8 0.8 0.8 0.8 0.8% Br in reaction mixture 1.25 1.25 1.25 1.25 1.25 ‘Comparative.

[0079] Foams are made from each of these formulations by separately bringing the formulated polyol composition, n-pentane and PMDI into a high-pressure mixing machine with a L-shaped mix-head. Component temperatures are 20-22°C, mixing pressure is 150-155 bar and output is 250 g / second. A portion of the output is discharged into a plastic-lined 20 cm x 20 cm x cm box for determination of cream and gel times and then free-rise density. The box foams are observed during cure for evidence of “blow-off”, which is an indicator of aging instability in the formulated polyol composition. Additional portions of the output are discharged into 40°C Brett molds of various sizes for measurement of minimum fill density, flow index (ratio of minimum fill density to free rise density) and post-demold expansion (with a demold time of 25 minutes). Foams made by overpacking the Brett mold by about 10% to produce 39 g / L foams are evaluated for lambda (average plate temperature 10°C, measured after 24 hours) and flame performance according to DIN 4102. Samples subjected to flame performance testing are inspected visually to determine the extent of flame damage. Results are as indicated in Table 4.Table 4Test D* E* F* Ex. 7 Ex. 8 Cream Time, s 6 6 6 6 6 Gel Time, s 96 99 88 98 96 Blow off? No Yes No No No Free-rise Density, g / L 28.4 29.3 28.4 28.9 - Minimum Fill Density, g / l 36.4 36.7 36.1 36.1 36 Flow index 1.28 1.21 1.21 1.25 - Lambda, mW / m-K 22.4 22.6 22.7 22.3 27.1 Post-Demold Expansion, % 1.0 0.7 - 1.0 - Flame Height, mm 131 133 145 138 130Flame Damage Normal Normal Extensive Normal Normal

[0080] These results demonstrate how different surfactants affect the performance of the polyol premix after aging. When Comparative Polyol Premix D is aged for 2 months (to produce comparative Polyol Premix E), “blow off” is seen in the box foams. The surfactant in each case is Surfactant B, a commercially available product that has EO / PO side chains. “Blow off” is quite undesirable in producing rigid polyurethane foam panels due to both aesthetic and performance reasons (notably, poorer adhesion to facings), and the blow off seen with Comparative Sample E is a significant drawback.

[0081] Replacing Surfactant B with Surfactant A (which also has EO / PO side chains) as in Comp. F leads to significantly poorer performance on flame testing. Not only does the flame height increase by about 10%, but the flame damage pattern indicates much greater burning. The burned area is wider and more deeply charred than the other foams tested.

[0082] Examples 7 and 8 demonstrate the greater aging stability of the polyol premix when Surfactant 1 or 2 replaces Surfactants A or B. There is no evidence of blow off, flame heights are comparable to those of Comp. D and E, and the normal burn patterns are observed.

Claims

CLAIMS1. A method of making a rigid polyurethane foam, comprisingI) forming a reaction mixture, comprising:(A) a polyol mixture, comprising:(A-1) 30 to 70 weight percent, based on the total weight of the polyol mixture (A), of a Novolac-initiated polyether polyol, the Novolac-initiated polyether polyol having a nominal hydroxyl functionality of 2 to 6 and a hydroxyl number of 140 to 400 mg KOH / g;(A-2) 25 to 70 weight percent, based on the total weight of the polyol mixture (A), of one or more aliphatic polyether polyols; and(A-3) 0 to 5 weight percent, based on the total weight of the polyol mixture (A), of one or more additional polyols, different from polyether polyols (A-1) and (A-2);(B) 1 to 4 parts by weight formic acid per 100 parts by weight of the polyol mixture (A); (C) 1.5 to 6 parts by weight, per 100 parts by weight of the polyol mixture (A), of a silicone surfactant having the empirical formula MDIO-2OODR2-5OM, where each M is R(CH3)2Si-Oi / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRis CH3— Of72~ Si-OfuD l l4vO-PEwhere PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups;(D) a catalytically effective amount of at least one urethane catalyst;(E) 3 to 10 parts by weight of a physical blowing agent per 100 parts by weight of the polyol mixture (A); and(F) an aromatic polyisocyanate, the aromatic polyisocyanate being provided in an amount sufficient to produce an isocyanate index of 80 to 200,wherein the reaction mixture contains 0.25 to 2% by weight phosphorus and 0 to 3% by weight bromine and,(II) curing the reaction mixture to produce the polyurethane foam.

2. The method of claim 1, wherein the reaction mixture further comprises 1 to 6 parts by weight water per 100 parts by weight of the polyol mixture (A).

3. The method of claim 1 or 2, wherein the reaction mixture comprises a phosphorus-containing flame retardant that does not contain hydroxyl, primary amino, secondary amino or thiol groups.

4. The method of claim 3 wherein the phosphorus-containing flame retardant includes tris(1-chloro-2-propyl)phosphate.

5. The method of any one preceding claim wherein the one or more aliphatic polyether polyols (A-2) includes at least one phosphorus- and / or bromine-containing polyol.

6. The method of claim 5 wherein the one or more aliphatic polyether polyols (A-2) includes a bromine-containing polyol.

7. The method of any one preceding claim wherein the surfactant has general formulaMDio-5oDR2-2oM, where each M -Oi / 2-Si(CH3)3, each D is -O-Si(CH3)2-Oi / 2-, and each DRis CH,iO • S i oO ~ PEwherePE jS ahydroxyl-terminated poly(ethylene oxide) consisting of 8 to 30 oxyethylene groups and the D and DRgroups are randomly distributed.

8. The method of any one preceding claim, wherein the surfactant has the general formula MD2O-3ODR5-IOM, where each M is -Oi / 2-Si(CH3)3, each D is -O-Si(CH3)2-Oi / 2-, and each DRis CH3— Of72— Si-Of77p4Q — PFw rwhere PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 8 to 20 oxyethylene groups, and the D and DRgroups are randomly distributed.

9. The method of any one preceding claim, wherein the reaction mixture formed in step I is formed into a layer on the facer or between two facers and step II is performed by curing the layer of the reaction mixture on the facer or between the two facers to produce a laminated panel comprising a polyurethane foam layer adhered to the facer or facers.

10. The method of any one preceding claim, wherein the reaction mixture is introduced between top and bottom facers which are inserted into the cavity of a press and are separated by spacers, and in step II the reaction mixture is cured between the top and bottom facers in the press while applying mechanical pressure to prevent excessive expansion of the foam layer.

11. The method of claim 9, wherein the top and bottom facers are each a metal.

12. The method of any one preceding claim, comprising a step of combining components (A), (B), (C), (D) and optionally (E) to produce a formulated polyol composition, then aging the formulated polyol composition under an inert atmosphere at a temperature of 10 to 40°C for a period of 7 days to 6 months, and then in step I forming the reaction mixture by combining the formulated polyol composition with component E and, if the formulated polyol composition does not contain component E, further combining the formulated polyol composition with component D.

13. A formulated polyol composition, comprising(A) a polyol mixture, comprising:(A-1) 30 to 70 weight percent, based on the total weight of the polyol mixture (A), of a Novolac-initiated polyether polyol, the Novolac-initiated polyether polyol having a nominal hydroxyl functionality of 2 to 6 and a hydroxyl number of 140 to 400 mg KOH / g;(A-2) 25 to 70 weight percent, based on the total weight of the polyol mixture (A), of one or more aliphatic polyether polyols; and(A-3) 0 to 5 weight percent, based on the total weight of the polyol mixture (A), of one or more additional polyols, different from polyether polyols (A-1) and (A-2);(B) 1 to 4 parts by weight formic acid per 100 parts by weight of the polyol mixture (A); (C) 1.5 to 6 parts by weight, per 100 parts by weight of the polyol mixture (A), of a silicone surfactant having the empirical formula MDIO-2OODR2-5OM1, where each M is R(CH3)2Si-Oi / 2- where R is hydrocarbyl having up to 10 carbon atoms, each D is -Oi / 2-Si(CH3)2-Oi / 2-, and each DRisO-PEwhere PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 6 to 50 oxyethylene groups; and(E) a catalytically effective amount of at least one urethane catalyst;wherein the formulated polyol composition contains 0.55 to 2.5% by weight phosphorus and 0 to 6% by weight bromine.

14. The formulated polyol composition of claim 13, further comprising 1 to 6 parts by weight water per 100 parts by weight of the polyol mixture (A).

15. The formulated polyol composition of claim 13 or 14, wherein the reaction mixture comprises a phosphorus-containing flame retardant that does not contain hydroxyl, primary amino, secondary amino or thiol groups.

16. The formulated polyol composition of claim 15, wherein the phosphorus-containing flame retardant includes tris(1-chloro-2-propyl)phosphate.

17. The formulated polyol composition of any one of claims 13-16, wherein the one or more aliphatic polyether polyols (A-2) includes at least one phosphorus- and / or brominecontaining polyol.

18. The formulated polyol composition of claim 17, wherein the one or more aliphatic polyether polyols (A-2) includes a bromine-containing polyol.

19. The formulated polyol composition of any one of claims 11-18, wherein the surfactant has general formula MDIO-5ODR2-2OM, where each M is -Oi / 2-Si(CH3)3, each D is -Oi / 2-Si(CH3)2-O1 / 2, and each DRiswhere R4is C2-4 hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 8 to 30 oxyethylene groups and the D and DRgroups are randomly distributed.

20. The formulated polyol composition of any one of claims 13-19, wherein the surfactant has the general formula MD2O-3ODR5-IO, where each M is -Oi / 2-Si(CH3)3, each D is -Oi / 2-Si(CH3)2-O1 / 2, and each DRisCH3—Ogj— Si-OfT?R4Q-Ptwhere R4is C2-4 hydrocarbyl and PE is a hydroxyl-terminated poly(ethylene oxide) consisting of 8 to 20 oxyethylene groups, and the D and DRgroups are randomly distributed.

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