Isocyanate-reactive components with improved hydrocarbon compatibility

Abstract

The present disclosure relates to an isocyanate-reactive component comprising a soybean oil-modified aromatic polyester polyol, a terephthalic acid-based polyester polyol, a first EO / PO block copolymer nonionic surfactant, a phosphorus-based flame retardant, a C1-C3 carboxylic acid (e.g., formic acid), a silicone-based surfactant, a blowing / gelling catalyst, and a trimerization catalyst.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate to isocyanate-reactive components for forming rigid polyurethane (PU) foams, and more particularly, to isocyanate-reactive components with improved hydrocarbon compatibility for rigid PU foams. [Background technology]

[0002] Rigid polyurethane (PU) foams are often used as insulation in construction products such as preformed building panels. Rigid PU foams are typically produced by the reaction of an isocyanate with a polyol component, and the reaction mixture is then expanded with a blowing agent to provide the foam for the rigid PU foam. The isocyanate, polyol component, and blowing agent, along with a catalyst and other optional ingredients, are all contacted in a dispensing head that dispenses the rigid PU foam formulation. The blowing agent, typically dissolved or emulsified in the polyol component, volatilizes above its boiling point during the exothermic reaction between the polyol and the isocyanate compound, generating the pore or cell structure of the foam.

[0003] In forming rigid PU foam, the isocyanate is provided in what is called the "A-side" reagent stream, while the polyol component is provided in the "B-side" reagent stream. In addition to the polyol component, the B-side also contains a blowing agent that is mixed with the polyol component. Among the many blowing agents, some are preferred due to their low ozone depletion potential. These blowing agents include pentane isomers, such as normal pentane, isopentane, and cyclopentane. Normal pentane and isopentane are the least expensive of the isomers but are the least soluble in the polyol component. Cyclopentane is relatively soluble in the polyol component, but is expensive, and PU foam boards made with it can exhibit poor dimensional stability in colder environments. As a result, blends of these various pentane isomers are often used.

[0004] Pentane isomers present other challenges. For example, at least one problem with using pentane isomers is their tendency to rapidly phase separate in the B-side. This can be problematic when a blowing agent is mixed with the B-side and then added to a dispensing tank of a polyurethane foaming machine, and the mixture is allowed to sit in the tank. This can occur, for example, when operations are suspended between work shifts (e.g., overnight) or over the weekend. Once separated, the B-side and phase-separated blowing agent (e.g., pentane isomer) must be removed from the storage tank and associated supply lines so that the properly mixed B-side and blowing agent can be used to form PU foam.

[0005] Thus, there is a need in the art for polyol components that have improved compatibility (e.g., do not phase separate) with hydrocarbon blowing agents such as pentane isomers for use in producing rigid PU foams. Summary of the Invention

[0006] The present disclosure provides an isocyanate-reactive component that improves compatibility with hydrocarbon blowing agents, such as pentane isomers, for use in producing rigid PU foams. Specifically, the disclosure provides a composition comprising: (i) 5 to 20 wt. % of a soybean oil-modified aromatic polyester polyol having a hydroxyl number of 250 to 270 mg KOH / g and a functionality of at least about 1.8; and (ii) 30 to 65 wt. % of a soybean oil-modified aromatic polyester polyol having a hydroxyl number of 200 to 340 mg KOH / g. (viii) 0.5-5 wt. % of a trimerization catalyst; and (vii) 0.1-3 wt. % of a blowing / gelling catalyst. The present invention provides an isocyanate-reactive component comprising: a terephthalic acid-based polyester polyol having a hydroxyl number of 1000 KOH / g and a functionality of at least about 2; (iii) 1-5 wt. % of a first EO / PO block copolymer nonionic surfactant having a weight average molecular weight of 2000-3000 g / mol; (iv) 10-20 wt. % of a phosphorus-based flame retardant; (v) 2-5 wt. % of a C1-C3 carboxylic acid; (vi) 1-5 wt. % of a silicone-based surfactant; (vii) 0.1-3 wt. % of a blowing / gelling catalyst; and (viii) 0.5-5 wt. % of a trimerization catalyst, wherein the percentages of (i)-(viii) are based on the total weight of the isocyanate-reactive component, and the total weight of (i)-(viii) does not exceed 100%. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present disclosure provides an isocyanate-reactive component that exhibits improved compatibility with hydrocarbon-based blowing agents, such as pentane isomers, for use in the production of rigid polyurethane (PU) foams. Specifically, the present disclosure provides an isocyanate-reactive component useful for forming rigid PU foams for use in insulation applications, such as steel-plated construction panels, among others. Surprisingly, the isocyanate-reactive component exhibits improved solubility and stability when mixed with hydrocarbon-based blowing agents known in the art to rapidly separate from the so-called "B-side." As discussed herein, such blowing agents include, but are not limited to, pentane isomers. As a result, the isocyanate-reactive component of the present disclosure may be useful in rigid PU foam processes where the isocyanate-reactive component may be left undisturbed due to the rigid PU foam being formed in a discontinuous process (e.g., with overnight or weekend breaks between work shifts).

[0008] For various embodiments, the isocyanate-reactive component includes, among other things, a soybean oil-modified aromatic polyester polyol having a dicarboxylic acid phthalate backbone and a first ethylene oxide / propylene oxide (EO / PO) block copolymer nonionic surfactant, both of which serve to improve the solubility and stability of the blowing agent in the isocyanate-reactive component. Additional components in the isocyanate-reactive component include, among other things, a C1-C3 carboxylic acid (e.g., formic acid) and water, which also serve to enhance the solubility and stability of the blowing agent in the isocyanate-reactive component. Furthermore, it has been recognized that formic acid can also assist in the aesthetic performance of rigid PU foams formed in a discontinuous injection process. It has also been surprisingly discovered that an isocyanate-reactive component containing both a soybean oil-modified aromatic polyester polyol and a first EO / PO block copolymer nonionic surfactant has a significant effect on the flammability of rigid PU foams formed in accordance with the present disclosure.

[0009] The above-mentioned advantages of the present disclosure have surprisingly been achieved by combining (i) 5 to 20 wt. % of a soybean oil-modified aromatic polyester polyol having a hydroxyl number of 250 to 270 mg KOH / g and a functionality of at least about 1.8, (ii) 30 to 65 wt. % of a terephthalic acid-based polyester polyol having a hydroxyl number of 200 to 340 mg KOH / g and a functionality of at least about 2, (iii) 1 to 5 wt. % of a first EO / PO block copolymer nonionic surfactant having a weight average molecular weight of 2000 to 3000 g / mol, (iv) 10 to 20 wt. % of a phosphorus-based flame retardant, (v) 2 to 5 wt. % of a C1 to C3 carboxylic acid (e.g., formic acid), (vi) 1 to 5 wt. % of a silicone-based surfactant, (vii) 0.1 to 3 wt. % of a blowing / gelling catalyst, and (viii) 0.5 to 5 wt. % of a trimerization catalyst. wherein the percentages of (i) through (viii) are based on the total weight of the isocyanate-reactive components, and the total weight of (i) through (viii) does not exceed 100%.

[0010] The present disclosure further provides a rigid PU foam formed from a reaction mixture including: (A) an isocyanate component having a functionality of 2.7 to 2.9; (B) an isocyanate-reactive component provided herein; and (C) at least one hydrocarbon blowing agent, wherein the stoichiometric index of the isocyanate component to the isocyanate-reactive component is 1.0 to 3.0.

[0011] Each of the above components of the isocyanate-reactive components, along with other optional components, are discussed below. For various embodiments, hydroxyl number (OH number, as KOH) can be determined by ASTM D4274; ASTM D 1957 and ASTM E222-10 also describe methods for determining hydroxyl number provided herein, and acid number (as KOH) was determined by ASTM D4662. The weight percent (wt%) values ​​provided for the isocyanate-reactive components (e.g., (i)-(xii)) are based on the total weight of the isocyanate-reactive components, where the total weight percent never exceeds 100 wt%.

[0012] (i) - Soybean oil modified aromatic polyester polyol The isocyanate-reactive component includes (i) 5 to 20 weight percent of a soybean oil-modified aromatic polyester polyol having a hydroxyl number of 250 to 270 mg KOH / g and a functionality of at least about 1.8. As used herein, functionality is the number of chemically active atoms or groups (e.g., -H, -OH, -NCO) per molecule for the reaction being considered. This is used as an average value for the soybean oil-modified aromatic polyester polyol.

[0013] The soybean oil-modified aromatic polyester polyol is a reaction product of phthalic anhydride (phthalic polyester) or phthalic dicarboxylic acid, diethylene glycol (DEG), and soybean oil. The soybean oil-modified aromatic polyester polyol contains greater than 0 and up to 11% by weight of soybean oil. The soybean oil-modified aromatic polyester polyol may have a hydroxyl equivalent weight of 208 to 224 g / eq. As used herein, hydroxyl equivalent weight is the weight of compound per reactive site and is calculated according to the formula: equivalent weight = (56.1 x 1000) / OH number. All individual values ​​and subranges between 208 and 224 g / eq are included herein. For example, the soybean oil-modified aromatic polyester polyol may have a hydroxyl equivalent weight ranging from lower limits of 208, 210, 212, or 214 g / eq to upper limits of 224, 222, 220, or 218 g / eq.

[0014] Soybean oil-modified aromatic polyester polyols can be prepared using known equipment and reaction conditions. Further, methods for forming soybean oil-modified aromatic polyester polyols are provided in the Examples section. Briefly, soybean oil-modified aromatic polyester polyols were produced by mixing 30-40 weight percent (wt%) phthalic anhydride and 45-55 wt% diethylene glycol in a stirred reactor (e.g., a glass reactor with stirring) under an internal environment (e.g., a nitrogen atmosphere). The mixture was heated to a temperature of 100-130°C and stirred until a homogeneous mixture was obtained. Titanium acetylacetonate catalyst was then added (0.01-0.05 wt%), and the mixture was further heated to 210°C and stirred until an acid value of 3-5 mg KOH / g was achieved. 1-11 wt% refined soybean oil was then added to the reaction mixture and allowed to react until an acid value of less than 1 mg KOH / g was reached. The wt% values ​​are based on the total weight of the reaction mixture for the soybean oil-modified aromatic polyester polyol.

[0015] Conversion progress was monitored by acid value measurements according to the method in Table 2 in the Examples section below. The product was then cooled to 50-60°C and filtered through a 25 μm filter before use. The final product has an acid value of 0.30-0.40, a hydroxyl value of 250-270 mg KOH / g, and a functionality of at least about 1.8. Product functionality was calculated by multiplying the functionality of each building block by its weight percent in the formulation: f = 2 × (wt% phthalic anhydride + 2 × wt% DEG + 0 × wt% soybean oil) = functionality.

[0016] The soybean oil-modified aromatic polyester polyol has a functionality of at least about 1.8. For various embodiments, the functionality of the soybean oil-modified aromatic polyester polyol can be about 1.8 to 2.0. All individual values ​​and subranges between 1.8 and 2.0 are included for the functionality of the soybean oil-modified aromatic polyester polyol. For example, the soybean oil-modified aromatic polyester polyol can have a functionality from 1.8 or 1.85 to 2.0, 1.95, or an upper limit of 1.95 (e.g., 1.8 to 2.0). It is also understood that higher functionality glycols, such as glycerin, can provide higher functionality with the same amount of soybean oil.

[0017] For various embodiments, the isocyanate-reactive component comprises 5 to 20 weight percent soybean oil-modified aromatic polyester polyol. All individual values ​​and subranges of 5 to 20 weight percent soybean oil-modified aromatic polyester polyol are included herein, for example, the soybean oil-modified aromatic polyester polyol can be from a lower limit of 5 or 6 weight percent to an upper limit of 20, 17, 15, 12, 10, or 7 weight percent of the total weight of the isocyanate-reactive component. For example, the soybean oil-modified aromatic polyester polyol can be 5 to 15 weight percent, 5 to 10 weight percent, 5 to 7 weight percent, or 6 to 7 weight percent soybean oil-modified aromatic polyester polyol, based on the total weight of the isocyanate-reactive component.

[0018] It is understood that soybean oil is a natural product containing a mixture of different fatty acids (e.g., linoleic acid, oleic acid) that are also found in other natural oils, such as, for example, sunflower oil and safflower oil. Thus, the recitation of soybean oil can and does include other natural oils that share such overlap with the fatty acids found in soybean oil.

[0019] (ii)-Terephthalic acid-based polyester polyol The isocyanate-reactive component comprises (ii) 30 to 65 weight percent of a terephthalic acid-based polyester polyol having a hydroxyl number of 200 to 340 mg KOH / g and a functionality of at least about 2. As noted above, functionality is the number of chemically active atoms or groups per molecule for the reaction being considered, which is an average value for the terephthalic acid-based polyester polyol.

[0020] The terephthalic acid-based polyester polyols can have a hydroxyl equivalent weight of 165 to 280 g / eq, where hydroxyl equivalent weight is calculated as described herein. All individual values ​​and subranges from 165 to 280 g / eq are included herein; for example, the terephthalic acid-based polyester polyols can have a hydroxyl equivalent weight from a lower limit of 165, 175, 185, 195, or 205 g / eq to an upper limit of 280, 270, 260, or 250 g / eq.

[0021] The terephthalic acid-based polyester polyol has a functionality of at least about 2. For various embodiments, the functionality of the terephthalic acid-based polyester polyol can be from 2 to 2.7. All individual values ​​and subranges from 2 to 2.7 for the functionality of the terephthalic acid-based polyester polyol are included herein; for example, the terephthalic acid-based polyester polyol can have a functionality from a value of 2.0 or 2.2 to an upper limit of 2.7, 2.5, or 2.3.

[0022] The terephthalic acid-based polyester polyol has a hydroxyl number of 200 to 340 mg KOH / g. All individual values ​​and subranges between 200 and 340 mg KOH / g are included herein. For example, the terephthalic acid-based polyester polyol can have a hydroxyl number from a lower limit of 200, 220, 240, or 250 mg KOH / g to an upper limit of 340, 320, 300, or 280 mg KOH / g. Preferably, the terephthalic acid-based polyester polyol is a polyester polyol from an aromatic terephthalic diacid or diester and a glycol or polyhydric alcohol, and is produced according to known techniques. For example, terephthalic acid-based polyester polyols can be prepared by reacting an aromatic polyester polyol containing at least one acid component (e.g., terephthalic acid) with at least one glycol, glycerin, and / or polyol component (e.g., ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide of bisphenol A). Preferably, the terephthalic acid-based polyester polyol is a polyester polyol from aliphatic or aromatic terephthalic diacid, diethylene glycol, and polyethylene glycol, and is produced by a polycondensation reaction according to known techniques. An esterification catalyst may be present during the reaction, and the reaction can be carried out in an inert gas atmosphere, such as nitrogen, carbon monoxide, helium, or argon, at a temperature of 150 to 280°C, optionally under reduced pressure, until the desired acid value is reached.

[0023] For various embodiments, the isocyanate-reactive component comprises 30 to 65 weight percent terephthalic acid-based polyester polyol. All individual values ​​and subranges of 30 to 65 weight percent terephthalic acid-based polyester polyol are included herein, for example, the terephthalic acid-based polyester polyol can be from a lower limit of 30, 35, or 40 weight percent to an upper limit of 65, 60, 55, 50, or 45 weight percent of the total weight of the isocyanate-reactive component. For example, the terephthalic acid-based polyester polyol can be 35 to 65 weight percent, 35 to 55 weight percent, 35 to 45 weight percent, or 40 to 45 weight percent terephthalic acid-based polyester polyol, based on the total weight of the isocyanate-reactive component.

[0024] (iii)—First EO / PO block copolymer nonionic surfactant The isocyanate-reactive component includes (iii) 1 to 5 wt. % of a first EO / PO block copolymer nonionic surfactant having a weight average molecular weight of 2000 to 3000 g / mol. Examples of the first EO / PO block copolymer nonionic surfactant include products sold under the trade names Tergitol™ L-61, Tergitol™ L-64, Tergitol™ L-81, and combinations thereof.

[0025] For various embodiments, the isocyanate-reactive component comprises 1-5 wt. % of the first EO / PO block copolymer nonionic surfactant. All individual values ​​and subranges of 1-5 wt. % of the first EO / PO block copolymer nonionic surfactant are included herein, for example, the first EO / PO block copolymer nonionic surfactant can be from a lower limit of 1, 1.5, or 2 wt. % to an upper limit of 5, 4, or 3 wt. % of the total weight of the isocyanate-reactive component. For example, the first EO / PO block copolymer nonionic surfactant can be 1-4 wt. %, 1.5-4 wt. %, or 2-4 wt. % of the first EO / PO block copolymer nonionic surfactant, based on the total weight of the isocyanate-reactive component.

[0026] Preferably, the isocyanate-reactive component of the present disclosure may include 5 to 15 wt. % of a soybean oil-modified aromatic polyester polyol and 2 to 4 wt. % of a first EO / PO block copolymer nonionic surfactant.

[0027] (iv)-Phosphorus-based flame retardants The isocyanate-reactive component includes (iv) 10 to 20 weight percent of a phosphorus-based flame retardant. For the embodiments provided herein, the phosphorus-based flame retardant is preferably halogen-free and selected from the group consisting of phosphates, phosphonates, phosphinates, and combinations thereof. Examples of phosphate-based flame retardants include trialkyl phosphates, triaryl phosphates, phosphate esters, and resorcinol bis(diphenyl phosphate). As used herein, a trialkyl phosphate has at least one alkyl group having 2 to 12 carbon atoms and an optional halogen atom. The other two alkyl groups of the trialkyl phosphate, including linear or branched alkyl groups, cyclic alkyl groups, alkoxyethyl, hydroxyl alkyl, hydroxyl alkoxy alkyl groups, and linear or branched alkylene groups, may independently be the same as or different from the first alkyl group and contain 1 to 8 carbon atoms. Examples of the other two alkyl groups of the trialkyl phosphate include, for example, methyl, ethyl, propyl, butyl, n-propyl, and isopropyl. Examples of trialkyl phosphates include N-butyl, isobutyl, sec-butyl, tert-butyl, butoxyethyl, isopentyl, neopentyl, isohexyl, isoheptyl, cyclohexyl, propylene, 2-methylpropylene, neopentylene, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl. Blends of different trialkyl phosphates can also be used. The three alkyl groups of the trialkyl phosphate can be the same. The trialkyl phosphate can be tris(2-chloro-1-methylethyl)phosphate (TCPP), tris[2-chloro-1-(chloromethyl)ethyl]phosphate (TDCP), tris(p-tert-butylphenyl)phosphate (TBPP), and tris(2-chloroethyl)phosphate (TCEP). The trialkyl phosphate is preferably triethyl phosphate (TEP).

[0028] Examples of phosphonates include diethyl (hydroxymethyl) phosphonate, dimethyl methyl phosphonate, and diethyl ethyl phosphonate. Examples of phosphinates include metal salts of organic phosphinates such as aluminum methyl ethyl phosphinate, aluminum diethyl phosphinate, zinc methyl ethyl phosphinate, and zinc diethyl phosphinate. Examples of additional halogen-free flame retardant compounds include resorcinol diphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, ammonium polyphosphate, and combinations thereof.

[0029] For various embodiments, the isocyanate-reactive component comprises 10-20 wt. % phosphorus-based flame retardant. All individual values ​​and subranges of 10-20 wt. % phosphorus-based flame retardant are included herein, for example, the phosphorus-based flame retardant can be from a lower limit of 10, 12, or 13 wt. % to an upper limit of 20, 18, or 15 wt. % of the total weight of the isocyanate-reactive component. For example, the phosphorus-based flame retardant can be 10-18 wt. %, 12-18 wt. %, or 13-15 wt. % phosphorus-based flame retardant, based on the total weight of the isocyanate-reactive component.

[0030] (v) -C1-C3 Carboxylic Acid The isocyanate-reactive component comprises (v) 2 to 5 weight percent of a C1-C3 carboxylic acid (i.e., formic acid, acetic acid, and / or lactic acid). In various embodiments, the isocyanate-reactive component comprises 2 to 5 weight percent of a C1-C3 carboxylic acid. All individual values ​​and subranges of 2 to 5 weight percent of a C1-C3 carboxylic acid are included herein, for example, the C1-C3 carboxylic acid can be from a lower limit of 2, 2.5, or 2.8 weight percent to an upper limit of 5, 4.5, or 4 weight percent of the total weight of the isocyanate-reactive component. For example, the C1-C3 carboxylic acid can be 2 to 4.5 weight percent, 2.5 to 4 weight percent, or 2.8 to 4 weight percent of a C1-C3 carboxylic acid, based on the total weight of the isocyanate-reactive component. Preferably, the C1-C3 carboxylic acid is formic acid.

[0031] (vi) Silicone surfactants The isocyanate-reactive component includes (vi) 1 to 5 weight percent of a silicone surfactant. The silicone surfactant can help provide stabilization during the polyurethane reaction to prevent cell collapse, especially in the case of low-density rigid PU foams. For example, the surfactant can help stabilize the cells formed by the blowing agent during the foaming process until the polymer cures. Examples of suitable surfactants include silicone surfactants such as polyether polysiloxanes, including polysiloxane polyoxylalkylene block copolymers, and organic surfactants containing polyoxyethylene-polyoxybutylene block copolymers. Examples of such silicone surfactants are commercially available under the trade names TEGOSTAB® (Evonik Industries AG), NIAX® (Momentive), and VORASURF® (The Dow Chemical Company). Specific examples of useful surfactants include VORASURF® DC193, VORASURF® RF 5374, VORASURF® DC 5604, VORASURF® SF 2937, VORASURF® DC 5098, VORASURF® 504, TEGOSTAB® B 8418, TEGOSTAB® B 8491, TEGOSTAB® B 8421, TEGOSTAB® B 8461, and TEGOSTAB® B 8462, NIAX® L-6988, NIAX® L-6642, and NIAX® L-6633 surfactants.

[0032] For various embodiments, the isocyanate-reactive component comprises 1-5 wt. % silicone surfactant. All individual values ​​and subranges from 1-5 wt. % silicone surfactant are included herein, for example, the silicone surfactant can be from a lower limit of 1, 1.5, or 2 wt. % to an upper limit of 5, 4, or 3 wt. % silicone surfactant based on the total weight of the isocyanate-reactive component. For example, the silicone surfactant can be 1-4 wt. %, 1.5-4 wt. %, or 2-3 wt. % silicone surfactant, based on the total weight of the isocyanate-reactive component.

[0033] (vii)—Blowing / Gelling Catalyst The isocyanate-reactive component comprises (vii) 0.1 to 3 weight percent of a blowing / gelling catalyst. As used herein, blowing catalysts and gelling catalysts may be distinguished by their tendency to favor either a urea (blow) reaction in the case of a blowing catalyst, or a urethane (gel) reaction in the case of a gelling catalyst. For various embodiments, the blowing / gelling catalyst may include any one or more of the blowing catalysts and / or gelling catalysts provided herein or known in the art.

[0034] Examples of blowing catalysts, e.g., catalysts that may tend to favor the blow reaction, include, but are not limited to, short-chain tertiary amines or tertiary amines containing oxygen. For example, blowing catalysts include, among others, bis-(2-dimethylaminoethyl)ether, pentamethyldiethylene-triamine, triethylamine, tributylamine, N,N-dimethylaminopropylamine, dimethylethanolamine, N,N,N',N'-tetramethylethylenediamine, and combinations thereof.

[0035] Examples of gelation catalysts, such as catalysts that tend to favor gelation reactions, include, but are not limited to, organometallic compounds, such as cyclic tertiary amines and / or long-chain amines containing several nitrogen atoms, and combinations thereof. Organometallic compounds include organotin compounds such as tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate. Bismuth salts of organic carboxylic acids can also be used as gelation catalysts, such as bismuth octanoate. Cyclic tertiary amines and / or long chain amines include dimethylbenzylamine, N,N,N',N'-tetramethylbutanediamine, N,N-dimethylcyclohexylamine, triethylenediamine, and combinations thereof.

[0036] For various embodiments, the isocyanate-reactive component comprises 0.1 to 3 weight percent blowing / gelling catalyst. All individual values ​​and subranges from 0.1 to 3 weight percent blowing / gelling catalyst are included herein, for example, the blowing / gelling catalyst can be from a lower limit of 0.1, 0.12, or 0.14 weight percent to an upper limit of 3, 2, or 1.6 weight percent of the total weight of the isocyanate-reactive component. For example, the blowing / gelling catalyst silicone can be 0.12 to 3 weight percent, 0.12 to 2 weight percent, or 0.14 to 1.6 weight percent blowing / gelling catalyst, based on the total weight of the isocyanate-reactive component.

[0037] (viii)-Trimerization catalyst The isocyanate-reactive component includes (viii) 0.5 to 5 weight percent of a trimerization catalyst. A trimerization catalyst is a material that promotes the reaction of an isocyanate group with another isocyanate group to form an isocyanurate ring. Useful trimerization catalysts include strong bases such as alkali metal phenolates, alkali metal alkoxides, alkali metal hydroxides, alkali metal carboxylates, and quaternary ammonium salts. The alkali metal can be sodium or potassium. Examples of trimerization catalysts include tris(dialkylaminoalkyl)-s-hexahydrotriazines, such as 1,3,5-tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine; [2,4,6-tris(dimethylaminomethyl)phenol]; N-(2-hydroxypropyl)-N-trimethylammonium formate, potassium acetate, potassium octanoate; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, alkali metal hydroxides such as sodium hydroxide, alkali metal alkoxides such as sodium methoxide and potassium isopropoxide; and alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms, and combinations thereof. Some commercially available trimerization catalysts include DABCO® TMR, DABCO® TMR-2, DABCO® TMR-30, DABCO® K 2097; DABCO® K15, POLYCAT® 41, POLYCAT® 43, and POLYCAT® 46, among others.

[0038] In various embodiments, the isocyanate-reactive component comprises 0.5 to 5 weight percent trimerization catalyst. All individual values ​​and subranges from 0.5 to 5 weight percent trimerization catalyst are included herein, for example, the trimerization catalyst can be from a lower limit of 0.5, 1, 1.2, or 1.4 weight percent to an upper limit of 5, 3, or 2 weight percent of the total weight of the isocyanate-reactive component. For example, the trimerization catalyst can be 0.5 to 3 weight percent, 1 to 2 weight percent, or 1.2 to 2 weight percent trimerization catalyst, based on the total weight of the isocyanate-reactive component.

[0039] For various embodiments, the percentages of (i)-(viii) are based on the total weight of the isocyanate-reactive component, and the total weight of (i)-(viii) does not exceed 100%. In one embodiment, the isocyanate-reactive component can include components (i)-(viii). In additional embodiments, the isocyanate-reactive component can consist essentially of components (i)-(viii). In further embodiments, the isocyanate-reactive component can consist of components (i)-(viii). The isocyanate-reactive component of the present disclosure can also include other components, such as components (ix)-(xii), as discussed herein. For various embodiments, when other components (e.g., (ix)-(xii) as provided herein) are present along with (i)-(viii), the percentages of components (e.g., (i)-(xii)) are based on the total weight of the isocyanate-reactive component, and the total weight of (i)-(xii) does not exceed 100%.

[0040] (ix)—A second EO / PO block copolymer nonionic surfactant The isocyanate-reactive component may optionally include (ix) 0.5 to 1.5 wt. % of a second EO / PO block copolymer nonionic surfactant having a weight average molecular weight of greater than 3000 to 5000 g / mol. In various embodiments, the second EO / PO block copolymer nonionic surfactant is different (i.e., not identical) to the first EO / PO block copolymer nonionic surfactant. The second EO / PO block copolymer nonionic surfactant may include a linear EO / PO block copolymer. The second EO / PO block copolymer nonionic surfactant may act as a defoamer / antifoaming agent and a low-foaming surfactant. An example of a commercially available second EO / PO block copolymer nonionic surfactant includes, but is not limited to, DOWFAX™ 92N40, available from DOW.

[0041] For various embodiments, the isocyanate-reactive component can comprise 0.5 to 1.5 wt. % of the second EO / PO block copolymer nonionic surfactant. All individual values ​​and subranges of 0.5 to 1.5 wt. % of the second EO / PO block copolymer nonionic surfactant are included herein, for example, the second EO / PO block copolymer nonionic surfactant can be from a lower limit of 0.5, 0.55, or 0.6 wt. % to an upper limit of 1.5, 1.3, or 1 wt. % of the total weight of the isocyanate-reactive component. For example, the second EO / PO block copolymer nonionic surfactant can be 0.5 to 1.3 wt. %, 0.5 to 1 wt. %, or 0.6 to 1 wt. % of the second EO / PO block copolymer nonionic surfactant, based on the total weight of the isocyanate-reactive component.

[0042] (x)-Aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol The isocyanate-reactive component may optionally further comprise up to 25% by weight of an aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol having a hydroxyl number of 195 mg KOH / g, an equivalent weight of 286 g / mol, and an average functionality (as defined herein) of 3.3. In one embodiment, the aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol may be a novolac-type polyol; a suitable commercially available example may include Voranol® IP 585, available from The Dow Chemical Company.

[0043] For various embodiments, the isocyanate-reactive component can include up to 25 weight percent aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol. All individual values ​​and subranges for up to 25 weight percent aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol are included herein, for example, the aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol can be from a lower limit of 5, 10, 15, or 20 weight percent to an upper limit of 25 or 23 weight percent of the total weight of the isocyanate-reactive component. For example, the aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol can be 10-25 weight percent, 15-25 weight percent, or 20-23 weight percent blowing / gelling catalyst, based on the total weight of the isocyanate-reactive component.

[0044] (xi)-Glycerin propoxylated polyether triol The isocyanate-reactive component optionally further comprises 1 to 7 weight percent (xi) of a glycerin propoxylated polyether triol having an average molecular weight of 1000 g / mol. The glycerin propoxylated polyether triol is a glycerin-initiated polytriol ether polyol prepared using known equipment and reaction conditions, having a hydroxyl number of 165 mg KOH / g and a functionality (as defined herein) of 3. Suitable commercially available polyether polyols include VORANOL™ 220-110, VOLATEC™ SD301, VORANOL™ CP 260, VORANOL™ CP 450, VORANOL™ CP 755, VORANOL™ CP 1000, VORANOL™ CP 1050, and VORANOL™ CP 1055, all available from The Dow Chemical Company.

[0045] For various embodiments, the isocyanate-reactive component can include 1 to 7 weight percent glycerin propoxylated polyether triol. All individual values ​​and subranges of 1 to 7 weight percent glycerin propoxylated polyether triol are included herein, for example, the glycerin propoxylated polyether triol can be from a lower limit of 1, 2, or 3 weight percent to an upper limit of 7, 6, or 5 weight percent of the total weight of the isocyanate-reactive component. For example, the glycerin propoxylated polyether triol can be 2 to 7 weight percent, 2 to 6 weight percent, or 3 to 5 weight percent trimerization catalyst, based on the total weight of the isocyanate-reactive component.

[0046] (xii) - Water The isocyanate-reactive component can further comprise 0.2 to 1 weight percent (xii) water. All individual values ​​and subranges from 0.2 to 1 weight percent water are included herein, for example, the water can be from a lower limit of 0.2, 0.4, or 0.6 weight percent to an upper limit of 1, 0.9, or 0.8 weight percent of the total weight of the isocyanate-reactive component. For example, the water can be 0.2 to 1 weight percent, 0.4 to 0.9 weight percent, or 0.6 to 0.8 weight percent water, based on the total weight of the isocyanate-reactive component.

[0047] (xiii) Hydrocarbon blowing agents The isocyanate-reactive component of the present disclosure can further include 1 to 15 parts by weight of (xiii) a hydrocarbon blowing agent. In various embodiments, the hydrocarbon blowing agent can be selected from the group consisting of at least one of alkanes such as butane, isobutane, 2,3-dimethylbutane, pentane isomers such as n-pentane and i-pentane, hexane isomers, heptane isomers; cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365 mfc (1,1,1,3,3-pentafluorobutane), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane), HFC-134a (1,1,1,2-tetrafluoroethane), trans-1-chloro-3,3,3-trifluoropropene, or a combination thereof.

[0048] An embodiment of the present disclosure provides that the isocyanate reaction system further comprises 1 to 15 parts by weight of a hydrocarbon blowing agent, based on the weight of the isocyanate reaction system. All individual values ​​and subranges from 1 to 15 parts by weight of hydrocarbon blowing agent are included herein, for example, the hydrocarbon blowing agent can be from a lower limit of 1, 3, or 5 parts by weight, to an upper limit of 15, 12, or 10 parts by weight, based on the weight of the isocyanate reaction system.

[0049] In addition to the embodiments provided herein, embodiments of the present disclosure include an isocyanate-reactive component having the following embodiment: the isocyanate-reactive component comprises: (i) 6 to 15 weight percent of a soybean oil-modified aromatic polyester polyol provided herein, (ii) 35 to 62 weight percent of a terephthalic acid-based polyester polyol, (iii) 2 to 4 weight percent of a first EO / PO block copolymer nonionic surfactant, (iv) 12 to 16 weight percent of a phosphorus-based flame retardant, (v) 2 to 5 weight percent of a C1 to C3 carboxylic acid (e.g., formic acid), (vi) 2 to 3 weight percent of a silicon-based surfactant, (vii) 0.1 to 1 weight percent of a blowing / gelling catalyst, and (viii) 1 to 3 weight percent of a trimerization catalyst, wherein the percentages of (i) through (viii) are based on the total weight of the isocyanate-reactive component, and the total weight of (i) through (viii) does not exceed 100%. This embodiment may optionally further comprise components (ix)-(xiii) as follows: 0 or 0.7-1 parts by weight of (ix) second EO / PO block copolymer nonionic surfactant; 0 or 20-25 parts by weight of (x) aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol; 0 or 1-7 parts by weight of (xi) glycerin propoxylated polyether triol; 0 or 0.6-0.9 parts by weight of (xii) water; and 1-15 parts by weight of (xiii) hydrocarbon blowing agent. The percentages of (i)-(xii) are based on the total weight of the isocyanate-reactive components, and the total weight of (i)-(xii) does not exceed 100%.

[0050] The isocyanate-reactive component comprises (i) 6 to 7 weight percent of a soybean oil-modified aromatic polyester polyol provided herein, (ii) 40 to 62 weight percent of a terephthalic acid-based polyester polyol, (iii) 2 to 4 weight percent of a first EO / PO block copolymer nonionic surfactant, (iv) 12 to 16 weight percent of a phosphorus-based flame retardant, (v) 2 to 5 weight percent of a C1 to C3 carboxylic acid (e.g., formic acid), (vi) 2 to 3 weight percent of a silicone-based surfactant, (vii) 0.1 to 0.5 weight percent of a blowing / gelling catalyst, and (viii) 1 to 2 weight percent of a trimerization catalyst, wherein the percentages of (i) to (viii) are based on the total weight of the isocyanate-reactive component, and the total weight of (i) to (viii) does not exceed 100%. This embodiment may optionally further comprise components (ix)-(xiii) as follows: 0 or 0.7-1 parts by weight of (ix) second EO / PO block copolymer nonionic surfactant; 0 or 20-25 parts by weight of (x) aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol; 0 or 1-7 parts by weight of (xi) glycerin propoxylated polyether triol; 0 or 0.6-0.9 parts by weight of (xii) water; and 1-15 parts by weight of (xiii) hydrocarbon blowing agent. The percentages of (i)-(xii) are based on the total weight of the isocyanate-reactive components, and the total weight of (i)-(xii) does not exceed 100%.

[0051] The present disclosure further provides a rigid PU foam formed from a reaction mixture comprising (A) an isocyanate component having a functionality of 2.7 to 2.9, (B) an isocyanate-reactive component, and (C) at least one hydrocarbon blowing agent, wherein the stoichiometric index of the isocyanate component to the isocyanate-reactive component is 1.0 to 3.0. For various embodiments, (B) the isocyanate-reactive component and (C) the at least one hydrocarbon blowing agent are as described above and herein. For various embodiments, the reaction mixture is mixed at a temperature of 15 to 90°C, preferably 20 to 60°C, and particularly 20 to 35°C, and can be introduced onto a workpiece (e.g., a steel panel) into an open mold or, optionally, into a closed mold under high pressure. Mixing can be performed mechanically with a stirrer or stirring screw. The reaction temperature of the reaction mixture at the time of dispensing can be 20 to 110°C, preferably 30 to 70°C, and particularly 40 to 60°C.

[0052] For various embodiments, the isocyanate component includes at least one 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 greater than 1.0. The isocyanate component can be, for example, an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an arylaliphatic polyisocyanate, an aromatic polyisocyanate, or a combination thereof. Examples of isocyanates include, among others, 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 IIPDI), tetramethylene diisocyanate, hexamethylene diisocyanate, 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.Similar to the isocyanates mentioned above, partially modified polyisocyanates containing uretdione, isocyanurate, carbodiimide, uretonimine, allophanate, or biuret structures, and combinations thereof, among others, may also be utilized.

[0053] The isocyanate component can be polymeric. As used herein, "polymeric" refers to higher molecular weight homologs and / or isomers in describing the isocyanate component. For example, polymeric methylene diphenyl isocyanate refers to higher molecular weight homologs and / or isomers of methylene diphenyl isocyanate.

[0054] For various embodiments, the stoichiometric index of the isocyanate component to the isocyanate-reactive component is between 1.0 and 3.0. As is known in the art, when the number of isocyanate groups in the isocyanate component is equal to the number of hydroxyl groups in the isocyanate-reactive component, the resulting stoichiometric index of the isocyanate component to the isocyanate-reactive component is 1.0. When the number of isocyanate groups in the isocyanate component is greater than the number of hydroxyl groups in the isocyanate-reactive component (e.g., by a factor of three), the resulting stoichiometric index of the isocyanate component to the isocyanate-reactive component is greater than 1.0 (e.g., 3.0, for example).

[0055] The isocyanate component can have an isocyanate equivalent weight of from 130 g / eq to 140 g / eq. All individual values ​​and subranges between 130 g / eq and 140 g / eq are included herein, for example, the isocyanate component can have an isocyanate equivalent weight from a lower limit of 130 or 132 g / eq to an upper limit of 140, 138, or 136 g / eq.

[0056] The isocyanate component can be prepared by known processes, for example, polyisocyanates can be prepared by phosgenation of the corresponding polyamine with the formation of a polycarbamoyl chloride and its thermal decomposition to provide a polyisocyanate and hydrogen chloride, or by a phosgene-free process, for example, by reacting the corresponding polyamine with urea and an alcohol to give a polycarbamate, which is then thermally decomposed to give, for example, a polyisocyanate and an alcohol.

[0057] The isocyanate component can be obtained commercially. Examples of commercially available isocyanates include, but are not limited to, polyisocyanates available from DOW® under the trade names VORANATE™, such as VORANATE™ M 220, and PAPI™, such as PAPI™ 27, among other commercially available isocyanates.

[0058] The isocyanate component can be utilized such that the composition for producing rigid PU foams has an Isocyanate Index ranging from 100 to 300. The Isocyanate Index can be determined as the quotient of the actual amount of isocyanate used and the theoretical amount of isocyanate required to completely react all active hydrogen groups present in the isocyanate reaction system, multiplied by 100. All individual values ​​and subranges from 100 to 300 are included herein; for example, foam formulations can have Isocyanate Indexes from lower limits of 100, 120, or 150 to upper limits of 300, 250, or 200.

[0059] The compositions disclosed herein for producing rigid PU foams cure to yield foams of 30 kg / m 3Rigid PU foams having a core density greater than 1 / 2 can be formed. As used herein, the core density of a PU foam is determined from the central interior section of the molded foam as its mass per unit volume. The foam core density is generally lower than the apparent density calculated by dividing the foam mass by its total volume due to the density change from the skin to the core in a molded foam. Rigid PU foams can be prepared using known methods and conditions, which may vary for different applications. One or more embodiments of the present disclosure provide a process for forming a rigid polyurethane foam product. The process includes curing the reaction mixture disclosed herein. The process may utilize known equipment and conditions, such as a one-shot process, among others.

[0060] One or more embodiments of the present disclosure provide that the composition for producing rigid PU foams can include one or more additional ingredients. Different additional ingredients and / or different amounts of the additional ingredients can be utilized for various applications. Examples of additional ingredients include pigments, colorants, additional flame retardants known in the art, crosslinkers, chain extenders, antioxidants, bioinhibitors, and combinations thereof. [Example]

[0061] The following examples are provided for illustrative purposes only and are not intended to define or limit the embodiments in any way. Unless otherwise specified, all compounds were obtained from Sigma-Aldrich. In the examples (EX) and comparative examples (CE) of the present invention, various terms and notations for materials are used, including, for example, the following:

[0062] [Table 1]

[0063] Production of polyester polyol 2. Polyester polyol 2 was prepared as follows. Phthalic anhydride (3755.3 g, 37.6 wt%) and diethylene glycol (5144.7 g, 51.4 wt%) were weighed into a glass reactor equipped with a mechanical stirrer, thermocouple, nitrogen inlet, and distillation bridge under a nitrogen atmosphere. The reactor was brought to a temperature range of 110-120°C and stirred until a homogeneous mixture was obtained. Titanium acetylacetonate catalyst (Tyzor AA-105 from Dorf Ketal) was then added (3.00 g, 0.03 wt%), and the mixture was further heated to 210°C and allowed to stir until an acid value of 3-5 mg KOH / g was achieved. Refined soybean oil (1100.0 g, 11.0 wt%) was then added to the reaction mixture, and the reaction was allowed to proceed until an acid value of less than 1 mg KOH / g was achieved. Conversion progress was monitored by acid value measurement according to the method in Table 2. The product was then cooled to 50-60°C and filtered through a 25 μm NO filter before use. The final product had an acid value of 0.37 and a hydroxyl value of 262.5 mg KOH / g. The functionality of the product was calculated by multiplying the functionality of each building block by its weight percent in the formulation: f = 2 × 37.6% (for phthalic anhydride) + 2 × 51.4% (for DEG) + 0 × 11.0% (for soybean oil) = 1.8.

[0064] [Table 2]

[0065] test NBS smoke chamber test (smoke optical density) performed according to ASTM E 662. Flame spread test performed according to DIN 4102-1.

[0066] sample Polyurethane Examples (EX) and Comparative Examples (CE) were formed as follows: Rigid foams were produced by the reaction of a compounded polyol containing a hydrocarbon blowing agent with a polymeric isocyanate (both maintained at 20°C). The two components were mixed to homogeneity using a suitable apparatus operating at 2500 revolutions per minute and poured into a 20 cm x 20 cm x 8 cm mold maintained at 50°C. Demolding occurred after 20 minutes. Foam specimens were then cut to the desired dimensions required for the flame test method.

[0067] [Table 3]

[0068] [Table 4]

[0069] Each of Comparative Examples A through D exhibited phase separation. In contrast, each example exhibited a fully formulated blend that was a clear liquid (i.e., homogeneous and did not separate), providing unexpectedly beneficial fire performance, as demonstrated by Example 8 (Table 2B). It is believed that the unexpected results were facilitated by the combination of Nonionic Surfactant 2 and the soybean oil derivative (the soybean oil derivative was used in the amount listed for the pre-formulated polyol mix), as compared to other examples containing the same type and amount of hydrocarbon blowing agent.

Claims

1. an isocyanate-reactive component, (i) 5 to 20 weight percent of a soybean oil modified aromatic polyester polyol having a hydroxyl number of 250 to 270 mg KOH / g and a functionality of at least about 1.8; (ii) 30 to 65 weight percent of a terephthalic acid-based polyester polyol having a hydroxyl number of 200 to 340 mg KOH / g and a functionality of at least about 2; (iii) 1 to 5 wt. % of a first EO / PO block copolymer nonionic surfactant having a weight average molecular weight of 2000 to 3000 g / mol; (iv) 10 to 20 wt. % of a phosphorus-based flame retardant; (v) 2 to 5 wt. % of a C1 to C3 carboxylic acid; (vi) 1 to 5 wt. % of a silicone surfactant; (vii) 0.1 to 3 wt. % of a blowing / gelling catalyst; (viii) 0.5 to 5 wt. % of a trimerization catalyst; wherein the percentages of (i) through (viii) are based on the total weight of said isocyanate-reactive component, and the total weight of (i) through (viii) does not exceed 100%.

2. 10. The isocyanate-reactive component of claim 1, further comprising: (ix) 0.5 to 1.5 wt. % of a second EO / PO block copolymer nonionic surfactant having a weight average molecular weight of greater than 3000 to 5000 g / mol, wherein the second EO / PO block copolymer nonionic surfactant is different from the first EO / PO block copolymer nonionic surfactant; and wherein the percentages of (i) through (ix) are based on the total weight of the isocyanate-reactive component, and the total weight of (i) through (ix) does not exceed 100%.

3. 3. The isocyanate-reactive component of any one of claims 1 to 2, further comprising up to 25 wt.% of (x) an aromatic resin-initiated polyoxypropylene-polyoxyethylene polyol having a hydroxyl number of 195 mg KOH / g, an equivalent weight of 286, and an average functionality of 3.

3.

4. The isocyanate-reactive component of any one of claims 1 to 3, further comprising 1 to 7 weight percent of (xi) a glycerin propoxylated polyether triol having an average molecular weight of 1000.

5. The isocyanate-reactive component of any one of claims 1 to 4, further comprising 0.2 to 1 wt% of (xii) water.

6. The isocyanate-reactive component of any one of claims 1 to 5, wherein the soybean oil-modified aromatic polyester polyol is a reaction product of phthalic anhydride, diethylene glycol, and soybean oil.

7. 7. The isocyanate-reactive component of claim 6, wherein the soybean oil-modified aromatic polyester polyol comprises up to 11% by weight of soybean oil.

8. 8. The isocyanate-reactive component of any one of claims 1 to 7, further comprising a hydrocarbon blowing agent selected from the group consisting of at least one of butane, isobutane, 2,3-dimethylbutane, n-pentane, i-pentane, hexane isomers, heptane isomers, cyclopentane, cyclohexane, cycloheptane, HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365 mfc (1,1,1,3,3-penta-fluorobutane), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane), HFC-134a (1,1,1,2-tetrafluoroethane), trans-1-chloro-3,3,3-trifluoropropene, or combinations thereof.

9. 9. The isocyanate-reactive component of any one of claims 1 to 8, comprising 5 to 15 weight percent of the soybean oil-modified aromatic polyester polyol and 2 to 4 weight percent of the first EO / PO block copolymer nonionic surfactant.

10. 1. A rigid polyurethane foam comprising: (A) an isocyanate component having a functionality of 2.7 to 2.9; (B) an isocyanate-reactive component according to any one of claims 1 to 9; and (c) at least one hydrocarbon blowing agent; wherein a stoichiometric index of said isocyanate component to said isocyanate-reactive component is from 1.0 to 3.0.

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