Compositions for forming foams

Abstract

Embodiments of the present disclosure are directed towards compositions for forming foam including an isocyanate-reactive composition including a first aromatic polyester polyol, a second aromatic polyester polyol, a third aromatic polyester polyol, and a carboxylate ionic liquid, and an isocyanate composition.

Description

COMPOSITIONS FOR FORMING FOAMSField of Disclosure

[0001] This disclosure relates to compositions for forming foams. These compositions include an isocyanate-reactive composition and an isocyanate composition.Background

[0002] Foam can used as thermal insulation material in buildings, vehicles, and appliances, among other applications. Foam can be made by reacting one or more polyols and one or more isocyanates.Summary

[0003] The present disclosure provides various embodiments, including the following. A composition for forming foam including an isocyanate-reactive composition including a first aromatic polyester polyol, a second aromatic polyester polyol, a third aromatic polyester polyol, and a carboxylate ionic liquid, and an isocyanate composition.Detailed Description

[0004] Compositions for forming foams are disclosed herein. The compositions for forming foams include an isocyanate-reactive composition and an isocyanate composition. Advantageously, the isocyanate-reactive compositions can remain clear and without phase separation. For instance, after a number of components of the isocyanate-reactive composition have been combined, the isocyanate-reactive compositions can remain clear and without phase separation for at least 24 hours, while being maintained at ambient conditions.

[0005] The compositions for forming foams, as disclosed herein, can provide a combination of desirable properties, as discussed further herein. The compositions for forming foams disclosed herein can advantageously be utilized to make a foam having an improved, i.e. reduced, thermal conductivity, as compared to other foam formulations that include similar polyols.

[0006] Further, the compositions for forming foams disclosed herein can provide foam having an improved, i.e. reduced, friability, as compared to other foam formulations that include similar polyols. Reduced friability is desirable for a number of applications, such as insulation applications. A foam with reduced friability is less likely to break down and / or generate dust over time, thereby maintaining structural integrity and insulating properties, as compared to a foam with a relatively greater friability.

[0007] Further, the compositions for forming foams disclosed herein can provide an improved, i.e. faster, gel time as compared to other foam formulations that include similar polyols. A faster gel time is desirable for a number of applications. A faster gel time can help to reduce production times, help reduce shrinkage and / or deformation during curing, and / or help to reduce the occurrence of surface defects of the foam.

[0008] As mentioned, the compositions for forming foams disclosed herein include an isocyanate-reactive composition and an isocyanate composition. Embodiments of the present disclosure advantageously provide that the compositions for forming foams include a carboxylate ionic liquid.

[0009] Embodiments provide that the isocyanate-reactive composition includes a first aromatic polyester polyol, a second aromatic polyester polyol, and a third aromatic polyester polyol. As used herein, “polyol” refers to a molecule having an average of greater than 1.0 hydroxyl groups per molecule, e.g., an average hydroxyl functionality of greater than 1 .0.

[0010] Embodiments provide that the first aromatic polyester polyol is terephthalic acid initiated. The first aromatic polyester polyol can have a functionary from 2 to 4. As used herein, “functionality” refers to an average hydroxyl functionality, unless stated otherwise. One or more embodiments provide that the first aromatic polyester polyol has a functionality of 2.

[0011] Embodiments provide that the first aromatic polyester polyol has an average hydroxyl number from 200 to 225 mg KOH / g. All individual values and subranges from 200 to 225 mg KOH / g are included; for example, the first aromatic polyester polyol can have an average hydroxyl number from a lower limit of 200, 205, or 210 mg KOH / g to an upper limit of 225, 220, or 218 mg KOH / g. Hydroxyl number can be determined by ASTM D4274-21.

[0012] Embodiments provide that the first aromatic polyester polyol has a hydroxyl equivalent weight from 175 to 350 g / eq. All individual values and subranges from 175 to 350 g / eq are included; for example, the first aromatic polyester polyol can have a hydroxyl equivalent weight from a lower limit of 175, 200, or 250 g / eq to an upper limit of 350, 300, or 275 g / eq. Hydroxyl equivalent weight can be determined dividing the molecular weight of the polyol by the number of equivalents contributed by the reactive groups.

[0013] The first aromatic polyester polyol can be made with known equipment, known components, and known conditions. The first aromatic polyester polyol may be obtained commercially.

[0014] The first aromatic polyester polyol can be from 20 to 50 weight percent (wt%) of the isocyanate-reactive composition based upon a total weight (100 wt%) of the isocyanate-reactive composition. All individual values and subranges from 20 to 50 wt% are included; for example, the first aromatic polyester polyol can be from a lower limit of 20, 25, or 30 wt% to an upper limit of 50, 45, or 40 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0015] Embodiments provide that the second aromatic polyester polyol is terephthalic acid initiated. The second aromatic polyester polyol can have a functionary from 2 to 4. One or more embodiments provide that the second aromatic polyester polyol has a functionality of 2.4.

[0016] Embodiments provide that the second aromatic polyester polyol has an average hydroxyl number from 310 to 400 mg KOH / g. All individual values and subranges from 310 to 400 mg KOH / g are included; for example, the second aromatic polyester polyol can have an average hydroxyl number from a lower limit of 310 or 315 mg KOH / g to an upper limit of 400, 375, 350, or 325 mg KOH / g.

[0017] Embodiments provide that the second aromatic polyester polyol has a hydroxyl equivalent weight from 100 to 300 g / eq. All individual values and subranges from 100 to 300 g / eq are included; for example, the second aromatic polyester polyol can have a hydroxyl equivalent weight from a lower limit of 100, 125, or 150 g / eq to an upper limit of 300, 250, or 200 g / eq.

[0018] The second aromatic polyester polyol can be made with known equipment, known components, and known conditions. The second aromatic polyester polyol may be obtained commercially.

[0019] The second aromatic polyester polyol can be from 5 to 25 wt% of the isocyanatereactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 5 to 25 wt% are included; for example, the second aromatic polyester polyol can be from a lower limit of 5, 8, or 10 wt% to an upper limit of 25, 20 or 15 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0020] Embodiments provide that the third aromatic polyester polyol is ortophthalic acid initiated. Embodiments provide that the third aromatic polyester polyol can have afunctionary from 2 to 4. One or more embodiments provide that the third aromatic polyester polyol has a functionality of 2.

[0021] Embodiments provide that the third aromatic polyester polyol has an average hydroxyl number from 230 to 290 mg KOH / g. All individual values and subranges from 230 to 290 mg KOH / g are included; for example, the third aromatic polyester polyol can have an average hydroxyl number from a lower limit of 230 or 235 mg KOH / g to an upper limit of 290, 275, or 250 mg KOH / g.

[0022] Embodiments provide that the third aromatic polyester polyol has a hydroxyl equivalent weight from 175 to 350 g / eq. All individual values and subranges from 175 to 350 g / eq are included; for example, the third aromatic polyester polyol can have a hydroxyl equivalent weight from a lower limit of 175, 200, or 225 g / eq to an upper limit of 350, 300, or 250 g / eq.

[0023] The third aromatic polyester polyol can be made with known equipment, known components, and known conditions. The third aromatic polyester polyol may be obtained commercially.

[0024] The third aromatic polyester polyol can be from 10 to 35 wt% of the isocyanatereactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 10 to 35 wt% are included; for example, the third aromatic polyester polyol can be from a lower limit of 10, 13, or 15 wt% to an upper limit of 35, 30, or 25 wt% of the isocyan ate- reactive composition based upon the total weight of the isocyanate-reactive composition.

[0025] Embodiments provide that the isocyanate-reactive composition includes a carboxylate ionic liquid. As used herein, “carboxylate ionic liquid” refers to an ionic carboxylate composition that is liquid at Standard Ambient Temperature and Pressure (SATP: 25 °C; 101.325 kPa).

[0026] One or more embodiments provide that the carboxylate ionic liquid can be reactive with one or components of the composition for forming foam disclosed herein. Advantageously, utilizing the reactive carboxylate ionic liquid can reduce plasticizing that may occur when utilizing non-reactive additives.

[0027] Embodiments provide that the carboxylate ionic liquid is 1 -ethyl-3- methylimidazolium acetate (CAS 143314-17-4).

[0028] The carboxylate ionic liquid can be from 0.1 to 8 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 0.1 to 8 wt% are included; for example, thecarboxylate ionic liquid can be from a lower limit of 0.1 , 0.5, 1 , 1 .5, or 2.0 wt% to an upper limit of 8, 7, 6, 5, 4, or 3 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0029] Embodiments provide that the isocyanate-reactive composition can include a surfactant. Surfactants for use in the preparation of foams are known and many are commercially available. The surfactant may be a silicone surfactant. Examples of suitable silicone surfactants include, but are not limited to, TEGOSTAB B-8421 , B-8427, B-8454, B-8404, B-8407, B-8409, B-8715, and B-8462 from Evonik; NIAX L-2171 , L- 5130, L-5180, L-5340, L-5440, L-6100, L-6900, L-6980, and L-6988 from MOMENTIVE, and VORASURF SF 2937, VORASURF 5374, VORASURF DC 5164, from The Dow Chemical Company. The surfactant may be an organosilicone copolymer. The surfactant may be a non-hydrolysable polyether-polydimethyl-siloxane-copolymer. The surfactant may comprise octamethyl cyclotetrasiloxane.

[0030] The surfactant, when utilized, can be from 0.5 to 4 wt% of the isocyanatereactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 0.5 to 4 wt% are included; for example, the surfactant can be from a lower limit of 0.5, 0.75, or 1 .0 wt% to an upper limit of 4, 3.5, or 3 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0031] Embodiments provide that the isocyanate-reactive composition can include a catalyst. The catalyst may be a blowing catalyst, a gelling catalyst, a trimerization catalyst, or a combination thereof.

[0032] Examples of blowing catalysts, include, but are not limited to, short chain tertiary amines or tertiary amines containing an oxygen. The amine-based catalyst may not be sterically hindered. For instance, blowing catalysts include bis-(2- dimethylaminoethyl)ether, pentamethyldiethylene-triamine, triethylamine, tributyl amine, N,N-dimethylaminopropylamine, N,N-dimetilciclohexilamina, dimethylethanolamine, N,N,N',N'-tetra-methylethylenediamine, and combinations thereof, among others. Examples of commercial blowing catalysts are POLYCAT 5 and POLYCAT 8 from Evonik, among other commercially available blowing catalysts.

[0033] Examples of gelling catalysts include, but are not limited to, organometallic compounds, cyclic tertiary amines and / or long chain amines, e.g., that contain several nitrogen atoms, and combinations thereof. Organometallic compounds include organotin compounds, such as tin(ll) salts of organic carboxylic acids, e.g., tin(ll) diacetate, tin(ll)dioctanoate, tin(ll) diethylhexanoate, and tin(ll) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. Bismuth salts of organic carboxylic acids may also be utilized as the gelling catalyst, such as, for example, bismuth octanoate. Cyclic tertiary amines and / or long chain amines include dimethylbenzylamine, triethylenediamine, and combinations thereof. Examples of a commercially available gelling catalysts are POLYCAT SA-2LE, DABCO 33 LV, DABCO BL-11 , DABCO EG, and DABCO T-12 from Evonik, among other commercially available gelling catalysts.

[0034] Examples of a commercially available trimerization catalysts are POLYCAT 41 , DABCO K 2097, and DABCO TMR 30, from Evonik, among other commercially available trimerization catalysts.

[0035] The catalyst, when utilized, can be from 0.1 to 4 wt% of the isocyan ate- reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 0.1 to 4 wt% are included; for example, the catalyst can be from a lower limit of 0.1 , 0.5, 0.75, or 1 .0 wt% to an upper limit of 4, 3.5, or 3 wt% based upon the total weight of the isocyanate-reactive composition.

[0036] Embodiments provide that the isocyanate-reactive composition includes a blowing agent. The blowing agent can be a chemical blowing agent, a physical blowing agent, or combinations thereof. Examples of chemical blowing agents include water and formic acid. Examples of physical blowing agents include methyl formate, low boiling hydrocarbons, e.g., heptane, hexane, n-pentane, iso-pentane, butane, cyclopentane, cyclohexane, and the like; and mixtures thereof, low boiling ketones such as acetone and methyl ethyl ketone, hydrochlorofluorocarbons (HCFCs) such as 1 , 1 -dichloro-1 - fluoroethane, hydrofluorocarbons (HFCs) such as 1 ,1 ,1 ,3,3-pentafluoropropane, hydrofluoroolefins (HFOs) such as trans-1 ,3,3,3-tetrafluoroprop-1 -ene, 1 , 3,3,3- tetrafluoropropene, and the like; and mixtures thereof. Commercially available hydrofluoroolefin blowing agents include SOLSTICE LBA and SOLSTICE GBA, available from Honeywell; and OPTEON 1100 and OPTEON 1150, available from Chemours. Linear, branched and / or cyclic C4-C6 alkanes such as cyclopentane, isopentane, n- pentane and neopentane can be utilized. One or more embodiments provide that the blowing agent includes n-pentane and water. One or more embodiments provide that the blowing agent includes a cyclopentane / isopentane blend and water.

[0037] The blowing agent can be from 3 to 20 wt% of the isocyanate-reactive composition based a total weight of the isocyanate-reactive composition. All individualvalues and subranges from 3 to 20 wt% are included; for example, the blowing agent can be from a lower limit of 3, 5, or 10 wt% to an upper limit of 20, 18, or 16 wt% of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

[0038] One or more embodiments provide that the isocyanate-reactive composition includes a flame retardant. The flame retardant can be a phosphate, a phosphonate, a phosphazenes or derivatives thereof, a metal phosphinic acid salt, a metal phosphinic acid salt: zinc diethyl phosphinate and aluminum diethyl phosphinate, a melamine derivative, or combinations thereof. Examples of the flame retardant include triethylphosphate, resorcinol bis(diphenyl phosphate), triphenyl phosphate, trimethyl phosphate, triphenylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide and derivative, red phosphorus, inorganic phosphinates, aluminum phosphate, melamine orthophosphate, dimelamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, oligomeric ethyl ethylene phosphate, dimethyl methylphosphonate, diethyl ethylphosphonate, diethyl propylphosphonate, cyclic phosphonates, pentaerythrtol phosphonate, cyclic neopentyl thiophosphoric anhydride, metal phosphinic acid salts such as zinc diethyl phosphinate and aluminum diethyl phosphinate, tricresyl phosphate, t-butylphenyl phosphates including t-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, varous phosphazene compounds, and combinations thereof. Polymeric or oligomeric phosphorus-containing compounds such as oliogomeric alkyl phosphate ester (e.g., LEVAGARD 2000 and LEVAGARD 3000, from Lanxess) are also suitable. One or more embodiments provide that the flame retardant is triethylphosphate.

[0039] The flame retardant can be from 5 to 20 wt% of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition. All individual values and subranges from 5 to 20 wt% are included; for example, the flame retardant can be from a lower limit of 5, 8, or 10 wt% to an upper limit of 20, 18, or 15 wt% based upon the total weight of the isocyanate-reactive composition.

[0040] One or more embodiments provide that the isocyanate-reactive composition includes an additive. Additives for use in the preparation of foams are known. Different additives and / or different amounts of the additive may be utilized for various applications. Examples of additives include pigments, colorants, antioxidants, bioretardant agents, and combinations thereof, among others.

[0041] One or more embodiments provide that the isocyanate-reactive composition includes one or more other polyols. ‘Other polyols” refers to polyols other than the first aromatic polyester polyol, the second aromatic polyester polyol, and the third aromatic polyester polyol discussed herein. One or more embodiments provide that one or more of the other polyols is utilized rather than the first aromatic polyester polyol, the second aromatic polyester polyol, and / or the third aromatic polyester polyol discussed herein. Examples of other polyols include other aromatic polyester polyols than the first aromatic polyester polyol, the second aromatic polyester polyol, and the third aromatic polyester polyol discussed herein, non-aromatic polyester polyols, polyether polyols, and combinations thereof. Different amounts of the one or more other polyols may be utilized for various applications.

[0042] Components of the isocyanate-reactive composition can be combined utilizing known equipment and known conditions.

[0043] As mentioned, advantageously, the isocyanate-reactive compositions can remain clear and without phase separation. For instance, after a number of the components of the isocyanate-reactive composition have been combined, the isocyanate-reactive compositions disclosed herein can remain clear and without phase separation for at least 24 hours, while being maintained at ambient conditions. Cloudiness and phase separation can be determined by visual inspection.

[0044] One or more embodiments provide that the compositions for forming foams disclosed herein are non-fluorinated and halogen free. In other words, the compositions for forming foams do not include a fluorine compound or a halogen. Non-fluorinated and halogen free compositions for forming foams are desirable for a number of applications.

[0045] As mentioned, the compositions for forming foams disclosed herein include an isocyanate-reactive composition and an isocyanate composition. The isocyanatereactive composition can be combined with the isocyanate composition to make a foam. The isocyanate-reactive composition and the isocyanate composition can be combined utilizing known equipment and known conditions.

[0046] The isocyanate composition includes an isocyanate. The isocyanate may be a polyisocyanate. As used herein, “polyisocyanate" refers to a molecule having an average of greater than 1.0 isocyanate groups per molecule, e.g., an average functionality of greater than 1.0.

[0047] The isocyanate can be an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate, or combinations thereof, for example.Examples of isocyanates include, but are not limited to, polymethylene polyphenylisocyanate, toluene 2,4- / 2,6-diisocyanate (TDI) , methylenediphenyl diisocyanate (MDI), polymeric MDI, triisocyanatononane (TIN), naphthyl diisocyanate (NDI), 4,4'-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3,3,5- trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1 ,4- diisocyanatocyclohexane, 4,4'-diisocyanato-3,3'-dimethyldicyclohexylmethane, 4,4'- diisocyanato-2,2-dicyclohexylpropane, 3-isocyanatomethyl-1 -methyl-1 - isocyanatocyclohexane (MCI), 1 ,3 -diisooctylcyanato -4 -methylcyclohexane, 1 ,3 - diisocyanato-2-methylcyclohexane, and combinations thereof, among others. As well as the isocyanates mentioned above, partially modified polyisocyanates including uretdione, isocyanurate, carbodiimide, uretonimine, allophanate or biuret structure, and combinations thereof, among others, may be utilized.

[0048] The isocyanate can be polymeric. As used herein “polymeric”, in describing the isocyanate, refers to higher molecular weight homologues and / or isomers. For instance, polymeric methylene diphenyl isocyanate refers to a higher molecular weight homologue and / or an isomer of methylene diphenyl isocyanate.

[0049] As mentioned, the isocyanate can have an average functionality of greater than 1 .0 isocyanate groups per molecule. For instance, the isocyanate can have an average functionality from 1 .5 to 8.0. All individual values and subranges from 1.5 to 8.0 are included; for example, the isocyanate can have an average functionality from a lower limit of 1 .5, 1 .7, 2.0, 2.3, 2.5, 2.7, or 3.0 to an upper limit of 8.0, 7.5, 7.0, 6.7, 6.5, 6.3, 6.0, 5.7 or 5.5.

[0050] The isocyanate can have an isocyanate equivalent weight 80 g / eq to 500 g / eq. All individual values and subranges from 80 to 500 g / eq are included; for example, the isocyanate can have an isocyanate equivalent weight from a lower limit of 80, 82, 84, 90, or 100 to an upper limit of 500, 450, 400, 375, or 350 g / eq.

[0051] The isocyanate may be prepared by a known process. For instance, the polyisocyanate can be prepared by phosgenation of corresponding polyamines with formation of polycarbamoyl chlorides and thermolysis thereof to provide the polyisocyanate and hydrogen chloride, or by a phosgene-free process, such as by reacting the corresponding polyamines with urea and alcohol to give polycarbamates, and thermolysis thereof to give the polyisocyanate and alcohol, for example.

[0052] The isocyanate may be obtained commercially. Examples of commercial isocyanates include, but are not limited to, polyisocyanates under the trade names VORANATE, such as VORANATE M 600, VORACOR, such as VORACOR CL 100 and VORACOR CE 101 , and PAPI, such as PAPI 27, available from The Dow Chemical Company, among other commercial isocyanates.

[0053] The isocyanate composition can be utilized such that the composition for forming foam has an isocyanate index from 250 to 600. Isocyanate index can be determined as a quotient, multiplied by one hundred, of an actual amount of isocyanate utilized and a theoretical amount of isocyanate for curing. All individual values and subranges from 250 to 600 are included; for example, the composition for forming foam can have an isocyanate index from a lower limit of 250, 300, 350, 375, or 400 to an upper limit of 600, 550, or 500.

[0054] The isocyanate composition can be utilized such that the isocyanate composition is from 200 wt% to 350 wt% based upon 100 wt% of isocyanate-reactive composition. In other words, a greater mass of isocyanate composition is utilized as compared to a mass of isocyanate-reactive composition utilized. All individual values and subranges from 200 wt% to 350 wt% are included; for example, the isocyanate composition be from a lower limit of 200 or 205 wt% to an upper limit of 350, 325, 300, or 250 wt% based upon 100 wt% of isocyanate-reactive composition.

[0055] The compositions for forming foams disclosed herein can be utilized to make a foam. The foam formulations disclosed herein can be cured by utilizing known equipment and known conditions. The foam can have a number of desirable properties. One or more embodiments provide that the foam is a polyisocyanurate foam. One or more embodiments provide that the foam is a polyurethane / polyisocyanurate (PUR / PIR) foam.

[0056] As mentioned, the compositions for forming foams can advantageously provide an improved, i.e. reduced, gel time, as compared to other foam formulations that include similar polyols. For instance, one or more embodiments provide that the compositions for forming foams have a gel time less than 18 seconds, e.g., from 8 to 17 seconds. All individual values and subranges from 8 to 17 seconds are included; for example, the compositions for forming foams have a gel time from a lower limit of 8 9, or 10 seconds to an upper limit 17 or 16 seconds. Gel Time can be determined according to ASTM D7487.

[0057] As mentioned, the foam can advantageously provide an improved, i.e. reduced, thermal conductivity, as compared to other foams made from formulations that include similar polyols. For instance, one or more embodiments provide that the foam has a thermal conductivity less than 20 mW / m- K, e.g., from 10 to 19.9 mW / m-K. All individual values and subranges from 10 to 19.9 mW / m- K are included; for example, the polyisocyanurate foam can have a thermal conductivity from a lower limit 10, 12, or 15 mW / m- K to an upper limit 19.9, 19.7, or 19.5 mW / m-K. Thermal conductivity can be determined in accordance with ISO 22007-2.

[0058] As mentioned, the foam can advantageously provide an improved, i.e. increased, compressive strength, as compared to other foams made from formulations that include similar polyols. For instance, one or more embodiments provide that the foam has a compressive strength equal to or greater than 215 kPa e.g., from 215 to 275 kPa. All individual values and subranges from 215 to 275 kPa are included; for example, the foam can have a compressive strength from a lower limit 215, 218, or 220 kPa to an upper limit 275, 265, or 250 kPa. Compressive strength was measured according to ASTM D1621.

[0059] As mentioned, the foam can advantageously provide an improved, i.e. reduced, friability, as compared to other foams made from formulations that include similar polyols. Reduced friability is desirable for a number of applications, such as insulation applications. A foam with reduced friability is less likely to break down and / or generate dust over time, thereby maintaining structural integrity and insulating properties, as compared to a foam with a relatively greater friability. Embodiments provide that the polyisocyanurate foam can provide a friability less than 12%. For instance, the foam can provide a friability from 1 to 12%. All individual values and subranges from 1 to 12% are included; for example, the foam can provide a friability from a lower limit of 1 , 2, or 3% to an upper limit of 12, 10, or 8%. Friability can be determined according to ASTM C 421 .

[0060] The foam can have a Free Rise Density from 20 to 100 kg / m3. All individual values and subranges from 20 to 100 kg / m3are included; for example, the foam be from a lower limit of 20, 25, or 30 kg / m3to an upper limit of 100, 80, 60, 50, or 45 kg / m3. Free Rise Density can be determined according to ASTM D 6226.

[0061] Foams, i.e. rigid foam, of the present disclosure are useful in various types of thermal insulation applications such as for building and construction use, walk-in cooler, refrigerated transport container, cryogenic storage, as well as other applications.

[0062] One or more embodiments provide that an insulated metal panel (IMP) can be made with the composition for forming disclosed herein, e.g., where the composition for forming foam has an isocyanate index from 250 to 600 or 350 to 600. Such insulated metal panels can be utilized for construction applications and / or cold storage applications, for instance.

[0063] The following examples are provided for illustration but are not intended to limit the scope. All parts and percentages are by weight unless otherwise indicated.EXAMPLES

[0064] In the Examples, various terms and designations for materials are used including, for instance, the following.

[0065] First aromatic polyester polyol (terephthalic acid initiated, average hydroxyl functionality 2.0, average hydroxyl number 213 mg KOH / g, equivalent weight 263 g / eq, obtained from The Dow Chemical Company).

[0066] Second aromatic polyester polyol (terephthalic acid initiated, average hydroxyl functionality 2.5, average hydroxyl number 315 mg KOH / g, equivalent weight 178 g / eq, obtained from The Dow Chemical Company).

[0067] Third aromatic polyester polyol (average hydroxyl functionality 2.0, average hydroxyl number 240 mg KOH / g, equivalent weight 234g / eq, obtained from Stepan).

[0068] Carboxylate ionic liquid (1 -ethyl-3-methylimidazolium acetate).

[0069] Flame retardant (triethylphosphate, obtained from ICL-IP).

[0070] Surfactant 1 (silicone surfactant, TEGOSTAB B 8421 , obtained from Evonik).

[0071] Surfactant 2 (silicone surfactant, VORASURF SF 2937, obtained from The Dow Chemical Company).

[0072] Catalyst 1 (blowing catalyst, pentamethyldiethylenetriamine, POLYCAT 5, obtained from Evonik).

[0073] Catalyst 2 (trimerization catalyst, 30% solution of potassium acetate in diethylene glycol, DABCO K2097, obtained from Evonik).

[0074] Foam Additive (fluoroalkene; Foam Additive FA-188, obtained from 3M).

[0075] Blowing agent 1 (70 wt% cyclopentane, 30 wt% isopentane).

[0076] Blowing agent 2 (water).

[0077] Isocyanate (PAPI 27, obtained from The Dow Chemical Company).

[0078] Isocyanate-reactive composition 1 , was made as follows. Components shown in Table 1 , except blowing agent 1 , catalyst 2, and the isocyanate, were added to acontainer and mixed with a high-speed mixer at 3,000 rpm for 15 seconds to make the isocyanate-reactive composition. After 24 hours at ambient conditions, the contents of the container were visually observed for cloudiness and phase separation; the results are reported in Table 2.

[0079] Then blowing agent 1 , catalyst 2 were added to isocyanate-reactive composition 1 . Then Example 1 , a composition for forming foam was made by adding a desired amount of isocyanate to isocyanate-reactive composition 1 , and the contents of the container were mixed with at 3,000 rpm for 5 seconds. Then the mixed contents of the container were poured into a polyethylene bag and placed in a box (20 cm by 9 cm by 3 cm) for free rise foam formation. The polyisocyanurate foam was then cured for approximately 24 hours.

[0080] Isocyanate-reactive compositions 2-3, were made as isocyanate-reactive composition 1 with any changes shown in Table 1 .

[0081] Comparative Examples A-D were made as isocyanate-reactive composition 1 with any changes shown in Table 1 .Table 1Table 2

[0082] A number of properties were determined for the respective foam products made from Examples 1-3 and Comparative Examples A-D. The results are reported in Table 3.Table 3

[0083] The data of Table 3 illustrate that Examples 1 -3 each provided a polyisocyanurate foam having an improved, i.e. reduced, Friability percent, as compared to foams made from each of Comparative Examples A, B, C and D.

[0084] The data of Table 3 illustrate that Examples 1 -3 each provided a polyisocyanurate foam having an improved, i.e. reduced, Thermal Conductivity, as compared to foams made from each of Comparative Examples A, B, and D.

[0085] The data of Table 3 illustrate that Examples 1 -3 each provided a polyisocyanurate foam having an improved, i.e. reduced, gel time, as compared to foams made from each of Comparative Examples A, B, C, and D.

[0086] Free Rise Density was determined according to ASTM D 6226.

[0087] Friability was determined according to ASTM C 421 .

[0088] Thermal Conductivity was determined according to ISO 22007-2.

[0089] Gel Time was determined according to ASTM D7487.

[0090] Compressive strength was measured according to ASTM D1621 .

Claims

What is claimed is:1 . A composition for forming foam comprising: an isocyanate-reactive composition comprising: a first aromatic polyester polyol; a second aromatic polyester polyol; a third aromatic polyester polyol; and a carboxylate ionic liquid; and an isocyanate composition comprising an isocyanate.

2. The composition for forming foam of claim 1 , wherein the carboxylate ionic liquid comprises 1 -ethyl-3-methylimidazolium acetate.

3. The composition for forming foam of claim 2, wherein the carboxylate ionic liquid is 0.1 to 8 weight percent of the isocyanate-reactive composition based upon a total weight of the isocyanate-reactive composition.

4. The composition for forming foam of claim 3, wherein the first aromatic polyester polyol has an average hydroxyl number from 200 to 225 mg KOH / g, the second aromatic polyester polyol has an average hydroxyl number from 310 to 400 mg KOH / g, and the third aromatic polyester polyol has an average hydroxyl number from 230 to 290 mg KOH / g.

5. The composition for forming foam of claim 4, wherein the first aromatic polyester polyol is from 20 to 50 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition, the second aromatic polyester polyol is from 5 to 25 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition, and the third aromatic polyester polyol is from 10 to 35 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

6. The composition for forming foam of claim 5, wherein the composition for forming foam includes a flame retardant.

7. The composition for forming foam of claim 6, wherein the flame retardant is from 5 to 20 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

8. The composition for forming foam of claim 7, wherein the isocyanate-reactive includes a blowing agent that is from 3 to 20 weight percent of the isocyanate-reactive composition based upon the total weight of the isocyanate-reactive composition.

9. A foam made with the polyisocyanurate foam formulation of claim 9.

10. An insulated metal panel made with the composition for forming foam of any one of claims 1 -8, wherein the composition for forming foam has an isocyanate index from 250 to 600.

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