Polyols and foams made therefrom

Abstract

Embodiments relate to a liquid aromatic polyester polyol composition for preparing a polyurethane foam product comprising at least one polyalicyclic structure, the aromatic polyester polyol composition being a clear liquid at room temperature, the aromatic polyester polyol composition having a viscosity of 100 Pa·s or less at room temperature and a shear rate of 10 sec-1, and an OH number in the range of 100 mg KOH / g to 500 mg KOH / g; a process for preparing the liquid aromatic polyester polyol composition; and isocyanate-reactive compositions and foam-forming compositions comprising the liquid aromatic polyester polyol.

Description

[Technical Field]

[0001] Embodiments relate to polyol compositions useful for preparing polyurethane products, and more particularly to aromatic polyester polyol compositions for preparing polyurethane or polyisocyanurate foam products that exhibit improved thermal insulation performance properties.

[0002] Preface Polyurethane foam continues to be the material of choice for many applications requiring thermal insulation and lightweight construction. Some applications of polyurethane insulation foam include building and construction, appliances, and refrigerated transportation. With increasing global energy consumption, end users of foam products are demanding products with better thermal insulation performance and ease of processing and manufacturing. Additionally, as stringent energy efficiency regulations are promulgated, the industry is seeking foam products with better thermal insulation performance to meet such regulations. Over the years, various attempts have been made to improve the thermal insulation performance of polyurethane foam. Typically, polyurethane foam products are prepared by reacting an isocyanate component with an isocyanate-reactive component in the presence of a blowing agent and various other foaming additives. The thermal insulation performance of polymer foams is generally considered to be affected by three components: (1) the type and amount of blowing agent, (2) the thermal conductivity of the solid polymer, and (3) the foam cell size. However, most efforts to date to improve the insulating performance of foams have focused on using and / or optimizing various additives, such as surfactants, catalysts, or nucleating additives, to create foams with smaller cell sizes (thereby reducing thermal conductivity). It would be desirable to prepare foam products with improved insulating performance without relying solely on additive optimization. Summary of the Invention

[0003] While various polyester polyol structures have been used to produce polyurethane and polyisocyanurate foams, most of the known structures are aimed at addressing fire performance characteristics and general foam manufacturing processes. However, it is difficult to improve the thermal insulation performance of polyurethane and polyisocyanurate foams by varying the type and amount of polyol used in foam production. Surprisingly, it has been discovered that novel modified liquid aromatic polyester polyols containing polyalicyclic ring structures of the present invention are suitable for use in preparing rigid polyisocyanurate (PIR) or polyurethane (PUR) foams (collectively referred to herein as "PU foams") that exhibit improved thermal insulation performance compared to conventional aromatic polyester polyols. Furthermore, the novel aromatic polyester polyols exhibit excellent compatibility with various hydrocarbon blowing agents, such as cyclopentane, n-pentane, and isopentane, resulting in easily processable foams.

[0004] In addition to providing improved thermal insulation performance, the novel aromatic polyester polyols used in producing foam products provide the foam products with superior physical properties, such as dimensional stability, compressive strength, and density, among other properties, to meet the requirements for use in specific insulation applications. Thus, the novel aromatic polyester polyols can be used in the production of polymer foams to achieve best-in-class insulation performance for, for example, insulated metal panels, polyiso boards, appliances, and discontinuous panel applications.

[0005] One embodiment relates to novel liquid aromatic polyester polyols containing at least one polyaliphatic structure that are surprisingly effective in improving thermal insulation performance when used to make PU foams. The liquid aromatic polyester polyol composition contains at least one polyaliphatic structure of the following general chemical structure (I):

[0006] [ka] wherein m is an integer equal to 1 or 2, n is an integer equal to 0, 1, 2, 3, or 4, R1 and R2 are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n≧1, R2 is (CH2) n is attached to a ring having

[0007] In addition, the novel aromatic polyester polyols, which exist as clear liquids at room temperature (e.g., 20°C to 26°C), are further characterized by having the following properties: (1) a shear rate of 10 s -1 and a viscosity of ≦100 Pa·s at room temperature, and (2) an OH value in the range of 100 mg KOH / g to 500 mg KOH / g.

[0008] Another embodiment includes a process for preparing the liquid aromatic polyester polyol described above, wherein the aromatic polyester polyol is the reaction product of at least one aromatic dicarboxylic acid and / or one aromatic dicarboxylic acid anhydride and / or one aromatic tricarboxylic acid and / or aromatic tricarboxylic acid anhydride and / or an aromatic carboxylic acid source with at least one polyhydric alcohol having a polyaliphatic ring structure.

[0009] Another embodiment includes novel isocyanate-reactive compositions comprising the aromatic polyester polyols described above, which can be reacted with an isocyanate component to produce PU foams with improved thermal insulation performance. In this embodiment, the novel isocyanate-reactive compositions comprise at least 10 parts (pts) of the novel aromatic polyester polyols of the present invention, based on the total amount of polyols in the isocyanate-reactive composition equal to 100 parts (pts).

[0010] Yet another embodiment includes a foam-forming composition that includes (a) at least one isocyanate component; (b) at least one isocyanate-reactive component that is the isocyanate-reactive composition described above; and (c) any other additional foaming component and / or any other auxiliary additive.

[0011] Yet another embodiment includes a PU foam product prepared using the foam-forming composition described above. DETAILED DESCRIPTION OF THE INVENTION

[0012] As used herein, the term "liquid" means a nearly incompressible fluid that conforms to the shape of its container at room temperature.

[0013] Temperatures herein are in degrees Celsius (°C).

[0014] "Room temperature" and / or "ambient temperature" in this specification means a temperature between 20°C and 26°C, unless otherwise specified.

[0015] "Thermal insulation performance" herein means thermal conductivity, also known as "λ value" or "K factor," in units of mW / m·K at a given temperature.

[0016] As used herein, "polyisocyanate," "monomeric isocyanate," or "isocyanate-containing material" refers to an isocyanate compound having two or more isocyanate groups. As used herein, "polymeric isocyanate" refers to a higher molecular weight homolog and / or isomer of any monomeric isocyanate and is a subset of "polyisocyanate." For example, polymeric methylene diphenyl isocyanate refers to a higher molecular weight homolog and / or isomer of methylene diphenyl isocyanate and is a polymeric isocyanate.

[0017] As used herein, "polyester polyol" refers to a polyol compound having at least one ester bond.

[0018] By "polyalicyclic" herein is meant a polycyclic ring system that is aliphatic, including fused rings, bridged fused rings, bridged rings, polycyclic rings, and spiro rings.

[0019] As used herein, "aromatic carboxylic acid source" refers to ester and acid halide derivatives of aromatic dicarboxylic acids, aromatic dicarboxylic dianhydrides, aromatic tricarboxylic acids, aromatic tricarboxylic anhydrides, aromatic tetracarboxylic acids, and aromatic tetracarboxylic anhydrides.

[0020] As used throughout this specification, the following abbreviations have the following meanings, unless the context clearly dictates otherwise: "=" means "equal to" or "equal to", "<" means "less than", ">" means "greater than", "≦" means "less than or equal to", "≧" means "greater than or equal to", "@" means "at", μm = micrometer, g = gram, mg = milligram, mW / mK = 1 meter, milliwatt per degree Kelvin, L = liter, mL = milliliter, g / mL = gram per milliliter, g / L = gram per liter, kg / m 3 = kilograms per cubic meter, ppm = parts per million by weight, pbw = parts by weight, rpm = revolutions per minute, m = metres, mm = millimetres, cm = centimetres, μm = micrometres, min = minutes, s = seconds, ms = milliseconds, hr = hours, Pa·s = pascal seconds, mPa·s = millipascal seconds, g / mol = grams per mole, g / eq = grams per equivalent, mg KOH / g = milligrams of potassium hydroxide per gram, M n = number average molecular weight, M w = weight average molecular weight, pts = parts by weight, 1 / s or seconds -1 = reciprocal of seconds [s -1 ], °C = degrees Celsius, mmHg = millimeters of mercury, psig = pounds per square inch, kPa = kilopascals, % = percent, vol% = volume percent, mol% = mole percent, and wt% = weight percent.

[0021] Unless otherwise specified, all percentages, parts, ratios, and other amounts are defined by weight. For example, all percentages set forth herein are weight percentages (wt %) unless otherwise indicated.

[0022] In one broad embodiment, a novel isocyanate-reactive component is a polyol-containing composition that includes a novel liquid aromatic polyester polyol. The liquid aromatic polyester polyol is used in the isocyanate-reactive component to form a reactive foam-forming composition or system with the isocyanate component. The reactive foam-forming composition, including the isocyanate component and the isocyanate-reactive component containing the liquid aromatic polyester polyol, can then be used to form a foam product.

[0023] In one embodiment, the liquid aromatic polyester polyol comprises at least one polyalicyclic structure. In another embodiment, the liquid aromatic polyester polyol comprises at least one polyalicyclic structure, wherein the polyalicyclic structure is a fused ring. In yet another embodiment, the liquid aromatic polyester polyol comprises at least one polyalicyclic structure, wherein the polyalicyclic structure contains at least one bridged fused ring structure. In yet another embodiment, the liquid aromatic polyester polyol comprises at least one polyalicyclic structure, wherein the polyalicyclic structure contains at least one bridged ring structure. In yet another embodiment, the liquid aromatic polyester polyol comprises at least one polyalicyclic structure, wherein the polyalicyclic structure comprises at least one compound having the following general chemical structure as shown in Structure (I):

[0024] [ka] wherein m is an integer equal to 1 or 2, n is an integer equal to 0, 1, 2, 3, or 4, R1 and R2 are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n≧1, R2 is (CH2) n The aromatic polyester polyol is a transparent liquid at room temperature, and the viscosity of the aromatic polyester polyol composition is -1and the hydroxyl number (OH number) of the aromatic polyester polyol ranges from 100 mg KOH / g to 500 mg KOH / g. Structure (I) can also include one or more alkyl substituents at any position on the ring structure, where the alkyl substituents are C1 to C6 carbon groups (e.g., methyl, ethyl, propyl, isopropyl, etc.).

[0025] Examples of polyalicyclic structures having the above structure (I) include one or more of the following compounds: (1) tricyclo[5.2.1.0 2,6 (2) compounds where m is 1, n is 0, R1 is -CH2-, and R2 is -CH2-, such as bicyclo[2.2.1]heptane-2,3-dimethanol; and (3) compounds where m is 2, n is 0, R1 is -CH2-, and R2 is -CH2-, such as bicyclo[2.2.2]octane-1,4-dimethanol and bicyclo[2.2.2]octane-2,5-dimethanol.

[0026] In one embodiment, the liquid aromatic polyester polyol containing the polyalicyclic structure (I) is, for example, (i) at least one compound selected from the group consisting of aromatic dicarboxylic acids, aromatic dicarboxylic anhydrides, aromatic tricarboxylic acids, aromatic tricarboxylic anhydrides, aromatic tetracarboxylic acids, aromatic tetracarboxylic anhydrides, aromatic carboxylic acid sources, and mixtures thereof, wherein the amount of carboxylic acid groups and / or carboxylic acid equivalent groups directly bonded to the aromatic ring structure in component (i) is at least 25 mol %, based on the total number of moles of carboxylic acid groups and / or carboxylic acid equivalent groups used in preparing the aromatic polyester polyol; (ii) at least one polyhydric alcohol, wherein the at least one polyhydric alcohol comprises a polyalicyclic ring structure as shown in structure (I) and / or a diol compound having the following general chemical structure (II):

[0027] [ka] wherein m is an integer equal to 1 or 2, n is an integer equal to 0, 1, 2, 3, or 4, R1 and R2 are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n≧1, R2 is (CH2) n wherein the amount of the at least one polyhydric alcohol having a polyalicyclic ring of Structure (I) and / or Structure (II) is at least 10 percent based on the total moles of hydroxyl groups of all polyhydric alcohols used in preparing the aromatic polyester polyol, the aromatic polyester polyol composition is a clear liquid at room temperature, and the viscosity of the aromatic polyester polyol composition is at room temperature and 10 seconds -1 and the OH number of the aromatic polyester polyol composition is in the range of 100 mg KOH / g to 500 mg KOH / g. In another embodiment, structure (II) also includes one or more alkyl substituents on the ring structure, wherein the alkyl substituents are C1 to C6 carbon groups.

[0028] In one embodiment, a suitable aromatic carboxylic acid or anhydride useful in preparing the aromatic polyester polyol, component (i), can include, for example, at least one aromatic carboxylic acid or anhydride selected from the group consisting of: (1) a dicarboxylic acid or dicarboxylic acid anhydride containing one aromatic ring; (2) a dicarboxylic acid or carboxylic acid anhydride containing two or more aromatic rings; (3) a tricarboxylic acid or tricarboxylic acid anhydride containing one or more aromatic rings; (4) a tetracarboxylic acid or tetracarboxylic acid anhydride containing one or more aromatic rings; or (5) a mixture thereof.

[0029] For example, the first carboxylic acid or anhydride containing one aromatic ring can include one or more of the following compounds: terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2.5-furandicarboxylic acid, tetrachlorophthalic acid, pyridinedicarboxylic acid and its isomers, and mixtures thereof.

[0030] For example, the second carboxylic acid or anhydride containing two or more aromatic rings can include one or more of the following compounds: 2,6-naphthalenedicarboxylic acid and its positional isomers, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalic anhydride, 4,4'-bibenzoic acid and its positional isomers, 4,4'-carbonyldibenzoic acid and its positional isomers, 4,4'-dicarboxydiphenyl ether and its positional isomers, 4,4'-dicarboxydiphenyl sulfone and its positional isomers, and mixtures thereof.

[0031] For example, the third carboxylic acid or anhydride containing at least one aromatic ring can include one or more of the following compounds: 1,3,5-benzenetricarboxylic acid, trimellitic acid, trimellitic anhydride, and mixtures thereof.

[0032] For example, the fourth carboxylic acid or anhydride containing at least one aromatic ring can include one or more of the following compounds: pyromellitic acid, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(isopropylidene)diphthalic anhydride, or mixtures thereof.

[0033] To prepare aromatic polyester polyols, one or more of the above-mentioned first, second, third, and fourth carboxylic acids or anhydrides can be used. As known to those skilled in the art, various derivatives of aromatic carboxylic acids can be used instead of aromatic carboxylic acids as the aromatic carboxylic acid source for preparing aromatic polyester polyols. Such derivatives include, but are not limited to, alkyl esters such as dimethyl terephthalate, dimethyl isophthalate, and dimethyl phthalate; aromatic polyesters such as polyethylene terephthalate (PET), recycled polyethylene terephthalate (rPET), polybutylene terephthalate, polyethylene naphthalate, aromatic polyester polyols, polycarboxylic acid anhydrides, and acid halides such as terephthaloyl chloride, isophthaloyl chloride, and phthaloyl chloride, and mixtures thereof.

[0034] In another embodiment, the at least one aromatic carboxylic acid or anhydride of component (i) is selected from terephthalic acid, isophthalic acid, phthalic anhydride, and / or mixtures thereof.

[0035] In yet another embodiment, an aliphatic polycarboxylic acid or anhydride may be used in combination with at least one aromatic carboxylic acid or anhydride of component (i) to prepare an aromatic polyester polyol. Aliphatic polycarboxylic acids and anhydrides suitable for use in the present invention include oxalic acid, malonic acid, glutaric acid, adipic acid, adipic anhydride, succinic acid, succinic anhydride, sebacic acid, pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, citric acid, isocitric acid, 1,4-cyclohexanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, and the like.

[0036] When an aliphatic polycarboxylic acid or anhydride is used in combination with at least one aromatic carboxylic acid in component (i), the molar amount of carboxylic acid groups and / or carboxylic acid equivalent groups derived from the aromatic carboxylic acid, aromatic anhydride, or aromatic carboxylic acid source relative to the total moles of carboxylic acid groups in component (i) is in one embodiment 25 mol% to 100 mol%, in another embodiment 35 mol% to 100 mol%, in another embodiment 50 mol% to 100 mol%, in yet another embodiment 60 mol% to 100 mol%, and in yet another embodiment 75 mol% to 100 mol%, based on the total moles of carboxylic acid groups used in preparing the aromatic polyester polyol, where each anhydride group in component (i) is equivalent to two carboxylic acid groups. In the above combinations, when a polyester polyol is prepared using more than 75 mol% of aliphatic carboxylic acid groups, the polyester polyol tends to have inferior fire performance properties when used to make PU foams, compared to aromatic polyester polyols prepared from a lower amount of aliphatic carboxylic acid groups.

[0037] When an aliphatic polycarboxylic acid or anhydride is used in combination with at least one aromatic carboxylic acid in component (i), the total aromatic content of the carboxylic acid and / or anhydride is, in one embodiment, at least 7 wt%, in another embodiment, at least 10 wt%, in another embodiment, at least 15 wt%, in yet another embodiment, at least 20 wt%, in yet another embodiment, at least 25 wt%, in yet another embodiment, at least 30 wt%, in another embodiment, at least 35 wt%, in yet another embodiment, at least 40 wt%, in yet another embodiment, at least 45 wt%, but in yet another embodiment, ≦65 wt%. The wt% of the aromatic carboxylic acid or anhydride (including their ester or halide derivatives, including mixtures with non-aromatic carboxylic acids or anhydrides) is calculated by taking the combined molecular weight of the aromatic carbon and the hydrogen bonded to the aromatic carbon, dividing by the formula molecular weight of the polycarboxylic acid and / or anhydride (including derivatives), and multiplying by 100. For example, terephthalic acid has a formula molecular weight of 166.1 with an aromatic content of CH of 76.1. Therefore, the wt% aromatic content of terephthalic acid = (76.1 / 166.1) = 45.8 wt%. For example, 2,6-naphthalenedicarboxylic acid has a formula molecular weight of 216.2 g / mol and a C 10 H6. Thus, the wt% aromatic content of 2,6-naphthalenedicarboxylic acid = (126.2 / 216.2) = 58.4 wt%. For example, for a 75 / 25 wt / wt ratio of terephthalic acid / adipic acid, the wt% aromatic content of the combined polycarboxylic acid = [(45.8% x (75 / 100)] = 34.4 wt%.

[0038] Generally, the concentration of component (i) used to make the aromatic polyester polyol ranges from 15 wt. % to 65 wt. % in one embodiment, from 20 wt. % to 60 wt. % in another embodiment, and from 25 wt. % to 55 wt. % in yet another embodiment, based on the total amount of components (i) and (ii) used to prepare the novel liquid aromatic polyester polyol.

[0039] Suitable polyalicyclic alcohols, component (ii), useful in preparing the aromatic polyester polyols of the present invention include, for example, (1) polyalicyclic alcohols (containing one or more alkyl substituents on the ring structure, the alkyl substituents having C1 to C6 carbon atoms, Structure II), (2) ethoxylates or propoxylates of polyalicyclic alcohols, or (3) mixtures thereof. Suitable polyalicyclic alcohols have at least two but no more than four alcohol groups.

[0040] As a specific example, the polyalicyclic alcohol may include one or more of the following compounds: tricyclo[5.2.1.0 2,6 ]decanedimethanol, bicyclo[2.2.1]heptane-2,3-dimethanol, bicyclo[2.2.2]octane-1,4-dimethanol, and their isomers, as well as tricyclo[3.3.1.1 3,7 ]decane-1,3-dimethanol, or mixtures thereof. "Tricyclo[5.2.1.0 2,6 ]-Decanedimethanol" is known (among other names) as octahydro-4,7-methano-1H-indenedimethanol, tricyclodecanedimethanol, and as bis(hydroxymethyl)tricyclo[5,2,1,0 2,6 ]decane, which can be used interchangeably, and includes various positional isomers individually and in combination. For example, some of the positional isomers are 3,8-bishydroxymethyltricyclo[5.2.1.0 2,6 ]decane, 3,9-bishydroxymethyltricyclo[5.2.1.0 2,6 ]decane, 4,8-bishydroxymethyltricyclo[5.2.1.0 2,6 ]decane, and 4,9-bishydroxymethyltricyclo[5.2.1.0 2,6 ] includes decane and can be named as such.

[0041] In one embodiment, a useful polyalicyclic alcohol is tricyclodecane dimethanol / tricyclo[5.2.1.0], which has the following chemical structure: 2,6 ] decanedimethanol (TCDDM),

[0042] [ka] This includes positional isomers (and mixtures thereof).

[0043] Other polyalicyclic alcohols that may be useful include one or more of the following compounds: 2,2-bis(4-hydroxycyclohexyl)propane and its positional isomers, (3-hydroxymethyl)-1-adamantanol and its positional isomers, isosorbide, 1,3-adamantanediol, 4,4'-bicyclohexanol and its positional isomers, 1,3,5-adamantatetriol and its positional isomers, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)2,4,8,10-tetraoxaspiro[5.5]undecane, and mixtures thereof.

[0044] In one embodiment, optionally, at least one diol or triol of a non-polyalicyclic structure may be used in combination with the at least one polyalicyclic alcohol of component (ii) to prepare the aromatic polyester polyol. For example, the non-polyalicyclic structure may be ethylene glycol (EG), diethylene glycol (DEG), dipropylene glycol (DPG), triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG), such as PEG 200 (nominal M n =200g / mol), PEG 400 (nominal M n = 400 g / mol), and / or PEG 600 (nominal M n= 600 g / mol), polypropylene glycol (PPG), polytetramethylene glycol, 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,4-butenediol, 1,4- and 2,3-butylene glycol, 1,4-butynediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, dibutylene glycol, polybutylene glycol, both available from Dow Inc., VORANOL™ CP 450 and VORANOL™ CP The polyols may include one or more diols and triols, such as polyols having a hydroxyl equivalent weight of 85 g / mol to 1100 g / mol, such as polyether polyols like 260, aromatic polyester polyols, aliphatic polyester polyols, polyester-ether polyols, polycarbonate polyols, and the like, and mixtures thereof.

[0045] In yet another embodiment, the diols and / or triols of polyethylene glycol, PEG 200, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and glycerol, optionally used in conjunction with component (i), which is at least one aromatic carboxylic acid or anhydride, in combination with component (ii), which is a polyalicyclic alcohol, are useful in preparing the novel liquid aromatic polyester polyols of the present invention.

[0046] In yet another embodiment, the non-polyalicyclic diol PEG 200, optionally used with component (i), an aromatic carboxylic acid or anhydride, is useful in combination with component (ii), a polyalicyclic alcohol, to prepare the novel liquid aromatic polyester polyols of the present invention.

[0047] In another embodiment, the amount of at least one polyalicyclic alcohol relative to the amount of all polyhydric alcohols used to prepare the aromatic polyester polyol of the present invention ranges from 10 mol% to 90 mol% in one embodiment, from 15 mol% to 85 mol% in another embodiment, and from 20 mol% to 80 mol% in still another embodiment, where mol% is calculated by dividing the number of moles of hydroxyl groups from the at least one polyalicyclic alcohol by the number of moles of hydroxyl groups from all polyhydric alcohols (i.e., both polyalicyclic and non-polyalicyclic) used to prepare the aromatic polyester polyol. If the amount of at least one polyalicyclic alcohol used exceeds 90 mol%, the viscosity of the aromatic polyester polyol tends to be too high for practical purposes such as handling and mixing, while if the amount of at least one polyalicyclic alcohol used is less than 10 mol%, the resulting aromatic polyester polyol will exhibit weaker viscosity.

[0048] In yet another embodiment, the amount of the at least one polyalicyclic alcohol of component (ii) used to make the aromatic polyester polyol ranges from 4 wt % to 70 wt % in one embodiment, from 6 wt % to 60 wt % in another embodiment, and from 12 wt % to 50 wt % in yet another embodiment, based on the combined amount of components (i) and (ii) used to prepare the novel liquid aromatic polyester polyol.

[0049] Generally, the concentration of component (ii), which comprises at least one polyalicyclic alcohol and, optionally, at least one diol or triol of non-polyalicyclic structure, to make the aromatic polyester polyols of the present invention, ranges from 35 wt % to 85 wt % in one embodiment, from 40 wt % to 80 wt % in another embodiment, and from 45 wt % to 75 wt % in yet another embodiment, based on the combined amount of components (i) and (ii) used to prepare the novel liquid aromatic polyester polyols.

[0050] Other optional components, component (iii), can be used in preparing the aromatic polyester polyols. In one embodiment, other optional components, component (iii), can include, but are not limited to, esterification catalysts, transesterification catalysts, antioxidants, and mixtures thereof.

[0051] Esterification catalysts and transesterification (i.e., transesterification, glycolysis) catalysts include compounds containing metal elements belonging to Groups 1 to 14 of the periodic table excluding hydrogen and carbon, as well as Lewis acids or Bronsted acids. Specific examples include organic group-containing compounds such as carboxylates, alkoxy salts, organic sulfonates, and β-diketonates, each containing at least one metal such as titanium, zirconium, or germanium; inorganic compounds such as oxides or halides of the aforementioned metals; and mixtures thereof. For example, in one embodiment, titanium compounds include titanium acetylacetonate and / or tetraalkyl titanates such as tetra-n-propyl titanate. In another embodiment, zirconium compounds include zirconium tetraacetate. In yet another embodiment, germanium compounds include inorganic germanium compounds such as germanium oxide and organic germanium compounds such as tetraalkoxygermanium. Other examples of catalysts useful in the present invention are described, for example, in U.S. Pat. No. 10,619,000.

[0052] Generally, the other additional optional component (iii), when used, used to prepare the aromatic polyester polyols can range from 0 wt % to 5 wt % in one embodiment, from 0.001 wt % to 2 wt % in another embodiment, and from 0.01 wt % to 1 wt % in yet another embodiment, based on the total amount of components (i) and (ii) used to prepare the liquid aromatic polyester polyols of the present invention.

[0053] Additionally, the aromatic polyester polyols of the present invention can be further modified by adding a different polyol, such as a different polyester polyol, a polyether polyol, or a polycarbonate polyol, and / or a thermoplastic polymer, such as a polyester or a polycarbonate, along with an optional transesterification catalyst, and applying heat in the range of 50°C to 290°C for a time period in the range of 1 minute to 12 hours.

[0054] In a broad embodiment, the process for producing the liquid aromatic polyester polyols of the present invention comprises mixing, combining, or blending (i) a predetermined amount of at least one aromatic carboxylic acid, aromatic carboxylic anhydride, or aromatic carboxylic acid source suitable for preparing the aromatic polyester polyols of the present invention, (ii) a predetermined amount of at least one polyalicyclic alcohol suitable for preparing the aromatic polyester polyols of the present invention, and optionally at least one diol or triol of a non-polyalicyclic structure, and (iii) any other additional optional components, such as an esterification catalyst, a transesterification catalyst, and / or an antioxidant, if desired, under process conditions such that the compounds are thoroughly mixed and react to form the liquid aromatic polyester polyol containing at least one polyalicyclic structure. As previously mentioned, specific examples of aromatic carboxylic acid sources include liquid or solid aromatic polyester polyols that are separate and distinct from the aromatic polyester polyols of the present invention, solid thermoplastic aromatic polyesters such as polyethylene terephthalate (PET), recycled PET, etc.

[0055] In one embodiment of the above process, the water content of component (i) and / or component (ii) is in one embodiment 0 ppm to ≦20,000 ppm, in another embodiment 0.01 ppm to <10,000 ppm, and in yet another embodiment 0.1 ppm to <1,000 ppm. In other embodiments, the water content may be in one embodiment <500 ppm, and in another embodiment <250 ppm.

[0056] In another embodiment, the process for producing liquid aromatic polyester polyols comprising at least one polyaliphatic structure is carried out at a temperature of at least 130° C. in one embodiment, at least 150° C. in another embodiment, and 180° C. in yet another embodiment. In other embodiments, the process for producing liquid aromatic polyester polyols comprising at least one polyaliphatic structure is carried out at a temperature of ≦240° C. in one embodiment, ≦260° C. in another embodiment, and ≦290° C. in yet another embodiment.

[0057] In yet another embodiment, the process for producing liquid aromatic polyester polyols comprising at least one polyaliphatic structure is carried out under an inert atmosphere using an inert gas such as N2, argon, etc., at pressures from atmospheric pressure (760 Torr / 101 kPa) to pressures > 1 Torr / 0.1 kPa in one embodiment, and from atmospheric pressure to pressures > 10 Torr / 1 kPa in another embodiment, and from atmospheric pressure to pressures > 100 Torr / 13 kPa in another embodiment. The reaction time can be from a few minutes to several hours, as is known in the art.

[0058] In yet another embodiment, a process for producing liquid aromatic polyester polyols containing at least one polyalicyclic structure utilizes a molar excess of alcohol from a polyalicyclic alcohol in combination with optional diols and / or triols relative to the carboxylic acid equivalents, with the respective molar ratios being ≦4.00 in one embodiment, ≦3.00 in another embodiment, ≦2.50 in another embodiment, and ≦2.10 in yet another embodiment. In other embodiments, the molar ratio is ≧1.10 in one embodiment, ≧1.20 in another embodiment, ≧1.50 in another embodiment, and ≧1.70 in yet another embodiment. When alternative sources of carboxylic acid are used to prepare the liquid aromatic polyester polyols of the present invention, the molar amounts of carboxylic acid for those alternative sources must be treated differently from typical polycarboxylic acids, as follows: each anhydride group is equivalent to two carboxylic acid groups, each pre-formed ester bond in a material such as PET is equivalent to one carboxylic acid group and one hydroxyl group, etc. The calculation of the molar ratio of hydroxyl groups to carboxylic acid groups must consider all sources of hydroxyl and carboxylic acid groups in components (i) and (ii).

[0059] In yet another embodiment, the liquid aromatic polyester polyols comprising at least one polyalicyclic structure of the present invention can be prepared by the steps of: (1) charging a reactor with agitation a predetermined amount of at least one aromatic carboxylic acid, or at least one aromatic carboxylic acid anhydride, or at least one aromatic carboxylic acid source, at least one polyalicyclic alcohol, at least one optional diol or triol, and at least one optional esterification / transesterification catalyst; (2) providing an inert atmosphere to the reactor contents with an inert gas (e.g., N2 or argon) with the optional application of reduced pressure (<760 Torr / 101 kPa); and (3) stirring / mixing the reactor contents while heating to a temperature of 130°C to 290°C to react the condensation products from the reaction of the carboxylic acid (including its derivatives) with the alcohol, diol, and / or triol. (4) optionally, upon completion of the reaction of step (3) based on the amount of distillate, hydroxyl number measurement, acid number measurement, and / or molecular weight moment measurement, adding a polyalicyclic alcohol, diol, and / or triol to transesterify under N2 without distillative removal of any products or by-products; and (5) transferring the resulting liquid aromatic polyester polyol comprising at least one polyalicyclic structure from the reactor to a storage vessel at a temperature ranging from room temperature to a process temperature of 290°C.

[0060] Typically, aromatic carboxylic acids or anhydrides are used in the process because the condensation by-product formed is water (and water is not flammable). In another embodiment, due to some monomer stability concerns or if diacid purity is poor, the production process can be run at lower temperatures in the range of 130°C to 290°C (e.g., <240°C), and esters such as dimethyl terephthalate can be used. In addition, titanate catalysts are typically used in this process; however, in another embodiment, ethylene glycol can be used in combination with a different catalyst type, such as germanium oxide. In one embodiment, the catalyst is added to the reaction mixture at the beginning of the reaction when the other components are charged; in another embodiment, the catalyst is added to the reaction mixture while the reaction mixture is warming to the reaction temperature; in yet another embodiment, the catalyst is added to the reaction mixture after a quantity of condensation by-products has been removed from the reaction mixture; and in yet another embodiment, the catalyst is added to the reaction mixture during any combination of two or more of the above periods, i.e., at the beginning of the reaction, while the reaction is warming to the reaction temperature, and / or after a quantity of condensation by-products has been removed from the reaction.

[0061] Some of the advantageous properties exhibited by the resulting liquid aromatic polyester polyols of the present invention produced according to the above-described process can include, for example, (1) pourable viscosity of <100 Pa·s at 20°C-50°C, (2) hydroxyl number of <500 mg KOH / g, (3) acid number of <10 mg KOH / g, (4) number average molecular weight of <2,000 g / mol, (5) hydroxyl functionality of <4.0, (6) optical clarity or transparency at ambient temperature, (7) glass transition temperature <0°C, and (8) improved miscibility with physical blowing agents such as cyclopentane, iso-pentane, and the like.

[0062] For example, 26°C and 10 seconds -1The viscosity of the aromatic polyester polyol at 200°C may be in the range of 0.5 Pa·s to 100 Pa·s in one embodiment, 1.0 Pa·s to 90 Pa·s in another embodiment, and 2.0 Pa·s to 75 Pa·s in still another embodiment. The viscosity of the aromatic polyester polyol can be measured, for example, by a rotational rheometer according to the procedure described in ISO 3219.

[0063] Another characteristic of aromatic polyester polyols particularly useful for making polyurethane or polyisocyanurate foams is the hydroxyl number (OH#) of the polyester polyol. The OH# characteristic of the polyol can range from 100 mg KOH / g to 500 mg KOH / g in one embodiment, from 150 mg KOH / g to 450 mg KOH / g in another embodiment, from 175 mg KOH / g to 425 mg KOH / g in yet another embodiment, and from greater than 200 mg KOH / g to 400 mg KOH / g in yet another embodiment. The OH# of the polyol can be determined according to conventional processes, such as, for example, the procedure set forth in ASTM E1899-16.

[0064] Another property of the aromatic polyester polyol that may be improved or maintained is the acid number of the polyester polyol. The acid number property of the aromatic polyester polyol may range from 0 mg KOH / g to 10 mg KOH / g in one embodiment, from 0.01 mg KOH / g to 7.5 mg KOH / g in another embodiment, from 0.1 mg KOH / g to 5.0 mg KOH / g in yet another embodiment, and from 0.1 mg KOH / g to 2.0 mg KOH / g in yet another embodiment. The acid number (acid#) of the aromatic polyester polyol may be determined, for example, by potentiometric titration of the polyol dissolved in a solvent such as toluene or methanol with standardized 0.01 N sodium hydroxide using a conventional titration system.

[0065] Yet another property of the aromatic polyester polyol that may be improved or maintained is the average hydroxyl (OH) functionality of the polyester polyol (i.e., the average number of hydroxyl groups per molecule). In one embodiment, the average OH functionality of the aromatic polyester polyol may range from at least 1.8 to 4.0, from at least 2.0 to 3.5 in another embodiment, from at least 2.0 to 3.0 in yet another embodiment, and from at least 2.0 to 2.7 in yet another embodiment.

[0066] Yet another property of the aromatic polyester polyol that is improved or maintained is the molecular weight of the polyester polyol. n ) property may range from 250 g / mol to 2,000 g / mol in one embodiment, from 275 g / mol to 1,750 g / mol in another embodiment, from 300 g / mol to 1,500 g / mol in yet another embodiment, from 300 g / mol to 1,250 g / mol in yet another embodiment, from 300 g / mol to 1,000 g / mol in yet another embodiment, and from 325 g / mol to 900 g / mol in yet another embodiment. The molecular weight (e.g., number average molecular weight (M n ), weight average molecular weight (M w ), and polydispersity index (PDI) = M w / M n )) can be determined, for example, according to the procedure set forth in ASTM D5296.

[0067] Yet another property of the aromatic polyester polyol that is improved or maintained is a glass transition temperature (T) below ambient room temperature. g ) T of aromatic polyester polyol g In one embodiment, the property is <0°C, in another embodiment <-10°C, in yet another embodiment <-20°C, and in yet another embodiment <-30°C. In yet another embodiment, the Tg of the aromatic polyester polyol is >-75°C. The glass transition temperature is T g It is measured in accordance with ASTM E1356-08(2014) using the midpoint temperature.

[0068] Reaction schemes for preparing PU foams are well known in the art and generally involve reacting an "A-side material" with a "B-side material," where the A-side material comprises at least one isocyanate-containing material (herein component (a)), and the B-side material comprises a blend of materials (herein component (b)), where at least one isocyanate-reactive material, such as a polyol, typically at least one of the materials is a polyol. Component (c), which are optional other additional foaming ingredients, such as foaming catalysts, blowing agents, and surfactants, can be added to the A-side and / or B-side materials or mixed with the A-side and B-side materials as a separate stream to provide a reactive foam-forming composition useful for forming PU foams.

[0069] Generally, the PU foam-forming compositions of the present invention are produced by mixing a polyol-containing material (B-side) comprising the novel liquid aromatic polyester polyol having at least one polyaliphatic structure described above with an isocyanate-containing material (A-side). The resulting reactive PU foam-forming composition is then used in a process to produce a polyurethane foam article. For example, in preparing a PU foam article or product, an A-side material and a B-side material are first prepared, with the A-side material comprising at least one isocyanate-containing material and the B-side comprising at least one aromatic polyester polyol of the present invention. The A-side material and the B-side material are then mixed together to form a PU foam-forming reaction mixture. The reactive blend is then subjected to conditions sufficient to cure the reactive blend to form a PU foam. Other optional foaming ingredients, auxiliary additives, or compounds can be added to the A-side material, the B-side material, or both the A-side and B-side materials, or can be mixed with the A-side and B-side materials as separate streams.

[0070] Generally, suitable isocyanate-containing materials / polyisocyanate compounds (side A) or component (a) for use in preparing PU foams can include any organic isocyanate known in the art containing two or more isocyanate (NCO) groups for preparing polyurethanes, including aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates. In one embodiment, aromatic polyisocyanates are generally preferred based on cost, availability, reactivity, and the properties they impart to the polyurethane product. Exemplary polyisocyanates useful in the present invention include, for example, m-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), various isomers of diphenylmethane diisocyanate (MDI), hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI (H 12 MDI), naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4',4"-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate or mixtures thereof with MDI (polymeric MDI), hydrogenated polymethylene polyphenylisocyanate, toluene-2,4,6-triisocyanate, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, naphthyl diisocyanate, isocyanate prepolymers, and mixtures of two or more of the above isocyanates.

[0071] The isocyanate compounds useful in the present invention may be modified polyfunctional isocyanates, i.e., products obtained by chemical reaction of isocyanate compounds. Illustrative are polyisocyanates containing esters, ureas, biurets, allophanates, and carbodiimides and / or uretonimines. In one embodiment, polyisocyanates that may be used to form the polyurethane foam-forming compositions of the present invention may include MDI and derivatives of MDI, such as uretdione-, isocyanurates-, carbodiimides-, uretonimines-, allophanates-, and biuret-modified "liquid" MDI products and polymeric MDI, as well as mixtures of the 2,4- and 2,6-isomers of MDI.

[0072] In one embodiment, the polyisocyanate is a polymerized or oligomerized compound of a monomeric isocyanate, commonly referred to as a polymeric isocyanate. As used herein, "polymeric" refers to higher molecular weight homologs and / or isomers in describing the isocyanate. For example, polymeric methylene diphenyl isocyanate refers to higher molecular weight homologs and / or isomers of methylene diphenyl isocyanate. VORANATE (Trademark) M229, VORANATE (Trademark) M600, and PAPI™ 580N are examples of some commercially available polymeric MDI materials useful in the present invention. The above-mentioned VORANATE™ and PAPI™ products are available from Dow Inc. In another embodiment, the isocyanates useful in the present invention may be prepared by any process known to those skilled in the art for producing polyisocyanates.

[0073] Alternatively, or in addition, the isocyanate component may also include an isocyanate prepolymer. Isocyanate prepolymers are known in the art and are generally prepared by reacting (1) at least one isocyanate compound, in which the molar amount of isocyanate groups is greater than the molar amount of hydroxyl groups, with (2) at least one polyol compound. The isocyanate prepolymer can be obtained by reacting the above-mentioned monomeric isocyanate compound or polymeric isocyanate with one or more polyols.

[0074] In one embodiment, the polyisocyanate or mixture thereof may generally have an average of at least 1.8 isocyanate groups per molecule. In another embodiment, the isocyanate functionality may be from 1.9 to 4, from 1.9 to 3.5 in another embodiment, from 2.0 to 3.5 in yet another embodiment, from 2.2 to 3.5 in yet another embodiment, and from 2.5 to 3.3 in yet another embodiment.

[0075] The isocyanate component can have an isocyanate equivalent weight of 80 g / eq to 300 g / eq, including all individual values ​​and subranges between 80 g / eq and 300 g / eq, for example, the isocyanate can have a lower isocyanate equivalent weight of 80 g / eq, 90 g / eq, or 100 g / eq to an upper limit of 300 g / eq, 290 g / eq, or 280 g / eq.

[0076] In certain embodiments, the isocyanate has a viscosity of 5 mPa·s to 10,000 mPa·s, measured at 25°C according to ASTM D4889-15. Other viscosity values ​​may be possible. For example, in other embodiments, the isocyanate compound may have a viscosity value at 25°C ranging from a lower limit of 5 mPa·s, 10 mPa·s, 25 mPa·s, 50 mPa·s, or 100 mPa·s to an upper limit of 1,000 mPa·s, 2,000 mPa·s, 3,500 mPa·s, 5,000 mPa·s, or 10,000 mPa·s.

[0077] Generally, the amount of isocyanate component used in the foam-forming composition of the present invention can vary based on the end use of the rigid PU foam. For example, the concentration of the isocyanate component can be from 20 wt. % to 80 wt. % in one general embodiment, from 25 wt. % to 80 wt. % in another embodiment, and from 30 wt. % to 75 wt. % in yet another embodiment, based on the total weight of all components in the reactive foam-forming composition for preparing the rigid PU foam.

[0078] The stoichiometric ratio of isocyanate groups in the isocyanate component to hydroxyl groups in the isocyanate-reactive component (e.g., polyol, water, etc.) is 1.0 to 6. This ratio multiplied by 100 is typically referred to as the Isocyanate Index. The Isocyanate Index of the foam-forming compositions of the present invention can be 100 to 600 in one embodiment, 120 to 575 in another embodiment, 150 to 550 in yet another embodiment, 175 to 500 in yet another embodiment, 200 to 475 in yet another embodiment, and 250 to 450 in yet another embodiment.

[0079] The isocyanate-reactive component, or component (b), of the foam-forming composition of the present invention comprises a novel liquid aromatic polyester polyol having at least one polyaliphatic structure, as described above, which is combined with the isocyanate component (side A) or component (a) to produce the foam-forming composition. The novel aromatic polyester polyols of the present invention provide PU foams with improved thermal insulation performance, smaller cell size, and other superior properties.

[0080] In another embodiment, the isocyanate-reactive component, or component (b), may further comprise at least one other polyol different from the novel aromatic polyester polyols having at least one polyalicyclic structure of the present invention, where such other polyol is selected from polyester polyols, polyether polyols, polycarbonate polyols, or mixtures thereof. When at least one other polyol different from the aromatic polyester polyols of the present invention is used in component (b) of the foam-forming compositions of the present invention, the amount of the novel aromatic polyester polyols having at least one polyalicyclic structure is in one embodiment at least 10 parts (pts), in another embodiment at least 15 pts, in another embodiment at least 25 pts, in yet another embodiment at least 35 pts, in yet another embodiment at least 45 pts, in yet another embodiment at least 50 pts, and in another embodiment at least 55 pts, all parts being parts by weight and based on the total amount of polyols in isocyanate-reactive component (b) equal to 100 parts.

[0081] Generally, non-polyalicyclic polyols useful in the foam-forming compositions of the present invention can have an average hydroxyl functionality ranging from 1.8 to 7.5, an average hydroxyl number from 75 mg KOH / g to 650 mg KOH / g, a number average molecular weight from 100 g / mol to 1,500 g / mol, and a hydroxyl equivalent molecular weight from 50 g / eq to 750 g / eq.

[0082] Other optional additional foaming components useful in preparing the foam-forming compositions of the present invention, component (c), can include, for example, one or more additional types of other materials that may be useful (or may be used) in the manufacturing process used to make the foam-forming composition or to impart desired properties to the resulting foam product, including, but not limited to, blowing catalysts, surfactants, physical or chemical blowing agents, flame-retardant (FR) additives, and the like, and mixtures thereof.

[0083] For various embodiments, the foaming catalyst can be a blowing catalyst, a gelling catalyst, a trimerization catalyst, or a combination thereof. In one embodiment, a combination of the above catalysts is used. Any conventional foaming catalyst, for example, a catalyst that tends to favor the urea (blowing) reaction, can be used in accordance with the present invention, such as bis-(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylene-triamine, triethylamine, tributylamine, N,N-dimethylaminopropylamine, dimethylethanolamine, N,N,N',N'-tetramethylethylenediamine, and combinations thereof. An example of a commercially available foaming catalyst is POLYCAT® 5, available from Evonik. When used, the blowing catalyst may be present in an amount of 0.05 pts to 5 pts in one general embodiment (e.g., 0.1 pts to 3.5 pts in one embodiment, 0.2 pts to 2.5 pts in another embodiment, and 0.5 pts to 2.5 pts in yet another embodiment), based on 100 pts of the total polyol in the isocyanate-reactive component.

[0084] Any conventional gelling catalyst, e.g., a catalyst that tends to favor a urethane (gel) reaction, can be used in accordance with the present invention, such as (1) organometallic compounds including tin(II) salts of organic carboxylic acids (e.g., tin(II) diacetate), salts of organic carboxylic acids (e.g., dibutyltin diacetate), and bismuth salts of organic carboxylic acids (e.g., bismuth octanoate), and (2) cyclic tertiary amines and / or long-chain amines, including dimethylbenzylamine, triethylenediamine, and combinations thereof. Examples of commercially available gelling catalysts are POLYCAT® 8, DABCO® 33-LV, and DABCO® T-12, all available from Evonik. When used, the gelling catalyst may be present in an amount of from 0.05 pts to 5 pts in one general embodiment (e.g., from 0.1 pts to 3.5 pts in one embodiment, from 0.2 pts to 2.5 pts in another embodiment, and from 0.5 pts to 2.5 pts in yet another embodiment), based on 100 pts of the total polyol in the isocyanate-reactive component.

[0085] Any conventional trimerization catalyst, e.g., a catalyst utilized to promote the formation of isocyanurate structures in compositions, can be used in accordance with the present invention, such as N,N',N"-tris(3-dimethylaminopropyl)hexahydro-S-triazine, potassium acetate, tetraalkylammonium hydroxides (e.g., tetramethylammonium hydroxide), alkali metal hydroxides (e.g., sodium hydroxide), alkali metal alkoxides (e.g., sodium methoxide), and combinations thereof. Some commercially available trimerization catalysts include, for example, DABCO® TMR-2, DABCO® TMR-20, DABCO® TMR-30, DABCO® TMR-7, DABCO® K, and the like. 2097, DABCO® K15, POLYCAT® 41, and POLYCAT® 46, each available from Evonik. When used, the trimerization catalyst may be present in an amount of from 0.05 pts to 5 pts in one general embodiment (e.g., from 0.1 pts to 3.5 pts in one embodiment, from 0.2 pts to 2.5 pts in another embodiment, and from 0.5 pts to 2.5 pts in yet another embodiment), based on 100 pts of total polyol in the isocyanate-reactive component.

[0086] For various embodiments, the foam-forming composition of the present invention can include at least one blowing agent. The blowing agent can be selected based, for example, at least in part, on the desired density of the final foam, the miscibility of the blowing agent in the foam-forming composition, such as in the polyol component, and the compatibility of the blowing agent with other components in the foam-forming composition. Any conventional chemical and / or physical blowing agent can be used in producing PU foams, including, for example, water, formic acid, methyl formate, various low-boiling hydrocarbons (e.g., heptane, hexane, n-pentane, iso-pentane, butane, cyclopentane, cyclohexane, etc., and mixtures thereof), various low-boiling ketones, such as acetone and methyl ethyl ketone, various hydrochlorofluorocarbons (HCFCs), such as 1,1-dichloro-1-fluoroethane, various hydrofluorocarbons (HFCs), such as 1,1,1,3,3-pentafluoropropane, various hydrofluoroolefins (HFOs), such as trans-1,3,3,3-tetrafluoroprop-1-ene and 1,3,3,3-tetrafluoropropene, and mixtures thereof. Some commercially available hydrofluoroolefin blowing agents useful in the present invention include Solstice® LBA and Solstice® GBA available from Honeywell, and Opteon™ 1100 and Opteon™ 1150 available from Chemours. Mixtures of these low boiling point liquids with each other and / or with other substituted or unsubstituted hydrocarbons may also be used. In various embodiments, the amount of at least one blowing agent is from 0.1 pts to 40 pts (e.g., from 0.5 pts to 35 pts, from 1 pts to 30 pts, or from 5 pts to 25 pts) based on 100 pts of total polyol in the isocyanate-reactive component.

[0087] For various embodiments, the foam-forming composition of the present invention may include a surfactant. The surfactant may be a cell-stabilizing surfactant, i.e., a surfactant used in an amount sufficient to stabilize the foaming reaction against collapse and the formation of large, non-uniform cells. Examples of suitable surfactants include silicone-based surfactants such as the polysiloxane polyoxyl alkylene block copolymers disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458, as well as organic surfactants containing polyoxyethylene-polyoxybutylene block copolymers, such as those described in U.S. Pat. No. 5,600,019. Other surfactants useful in the present invention include polyethylene glycol ethers of long-chain alcohols, tertiary amine or alkanolamine salts of long-chain aryl acid sulfates, alkyl sulfonates, alkylaryl sulfonic acids, and combinations thereof. Some commercially available surfactants useful in isocyanate-reactive compositions include VORASURF™ DC 193, VORASURF™ RF 5374, VORASURF™ DC 5604, VORASURF™ SF 2937, VORASURF™ SF 2938, VORASURF™ DC 5098, and VORASURF™ 504 (all available from Dow Inc.), TEGOSTAB® B8418, TEGOSTAB® B8491, TEGOSTAB® B8421, TEGOSTAB® B8461, and TEGOSTAB® B8462 (all available from Evonik Industries AG), and NIAX * L-6988, NIAX * L-6642 and NIAX *L-6633 (all available from Momentive). The amount of surfactant, if used, can be from 0.1 pts to 10.0 pts in one general embodiment, based on 100 pts of total polyols present in the isocyanate-reactive component. All individual values ​​and subranges within the range of 0.1 pts to 10.0 pts are included, for example, surfactant concentrations can be from a lower limit of 0.1 pts, 0.2 pts, or 0.3 pts to an upper limit of 10.0 pts, 9.0 pts, 7.5, or 6 pts, based on 100 pts of total polyols present in the isocyanate-reactive component.

[0088] For various embodiments, the foam-forming compositions of the present invention may include halogenated or non-halogenated flame-retardant (FR) additives such as tris(1,3-dichloropropyl)phosphate, various halogenated aromatic compounds, aryl phosphates such as triethyl phosphate, diethyl(hydroxymethyl)phosphonate, diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate, resorcinol bis(diphenylphosphate) (e.g., FYROLFLEX RDP available from ICL Industrial), antimony oxide, alumina trihydrate, and combinations thereof. When used, the flame retardant may be present in an amount of 0.1 pts to 30 pts, 1 pts to 25 pts, 2 pts to 25 pts, or 5 pts to 25 pts, based on 100 pts of total polyol in the isocyanate-reactive component.

[0089] As noted above, component (c) may include any other optional additional foaming components and / or any number of various other optional auxiliary additives useful in producing the foam-forming compositions of the present invention, which are then used to form PU foams. Other optional auxiliary additives may include, for example, liquid nucleating additives, solid nucleating agents, Ostwald ripening inhibitor additives, reactive or non-reactive diluents, expandable graphite, pigments, rheology modifiers, emulsifiers, antioxidants, mold release agents, dyes, pigments, fillers, and the like, and mixtures thereof. The amount of each of the other optional auxiliary additives used in the foam-forming compositions of the present invention will depend on the specific application and foam processing conditions. When used, each of the other optional auxiliary additives may be added to one or both of the A-side and B-side materials prior to mixing of the A-side and B-side, or may be mixed online with the A-side and B-side as a separate stream during foam production. The other optional auxiliary additives are used in amounts known to those skilled in the art for their function and use, and may also be added directly to the isocyanate-reactive component (B-side) along with the aromatic polyester polyol. Generally, other optional auxiliary additives in the foam-forming composition, if used, can range from 0.01 pts to 25 pts in one general embodiment, from 0.1 pts to 20 pts in another embodiment, and from 0.5 pts to 15 pts in yet another embodiment, all based on 100 pts of total polyol in the isocyanate-reactive component.

[0090] As described above, the process for producing the PU foam-forming composition of the present invention generally involves mixing (a) a predetermined amount of at least one isocyanate component as an A-side component, and (b) a predetermined amount of at least one isocyanate-reactive component as a B-side component, where the B-side component includes at least one isocyanate-reactive compound that is a liquid aromatic polyester polyol having at least one polyaliphatic structure, and, optionally, (c) any other additional foaming components and / or other optional auxiliary additives. The above components are typically prepared and stored separately until foam processing equipment is ready to thoroughly mix each individual component and extemporaneously pour, spray, or deposit the resulting reactive foam composition into a mold, onto a surface, or onto a substrate, followed by foaming and curing into an article. Some or all of the components / additives of optional component (c), including any other additional foaming components and / or other optional auxiliary additives, can be added to any one of the components of the foam-forming composition or added as a separate stream during foam production. For example, optional component (c) can be added to one or both of the A-side and B-side materials prior to mixing the A-side and B-side; i.e., optional component (c) can be premixed into the isocyanate-reactive component (B-side) or the isocyanate component (A-side) before the A-side and B-side are mixed together. Alternatively, each component (c), when used in the present invention, can be introduced as a separate stream and mixed with the A-side and B-side to produce the reactive foam-forming composition; i.e., each component (c) can be mixed online with the A-side and B-side as a separate stream during foam production. For example, in one embodiment, optional component (c) can be added directly to the isocyanate-reactive component (B-side) along with the aromatic polyester polyol. Regardless of any particular method and order of mixing each individual component to produce the foam-forming composition, the reactive foaming mixture generally has high reactivity at room temperature and should be used immediately for foam article production after the foam-forming composition is prepared.

[0091] In one broad embodiment, the process for producing the polyurethane foam-forming composition of the present invention comprises the steps of: (1) providing a reactor vessel or container for receiving the above-described components and forming a reaction mixture therein; and (2) mixing the components in the reactor vessel or container to form a homogeneous reaction mixture. The ingredients that make up the foam-forming composition may be mixed together by any known mixing process and equipment typically used in producing polyurethane foams. The order in which the ingredients are mixed is not important; two or more compounds may be mixed together followed by the addition of the remaining ingredients.

[0092] Generally, the process for making a reactive foam composition comprises mixing components (a) and (b) above, and optionally adding component (c) to the foam composition, which optionally includes one or more of the other optional additional foaming components, such as blowing agents, catalysts, surfactants, flame retardant additives, and / or one or more of the other optional co-additives, and mixtures thereof. The blowing agents, catalysts, surfactants, flame retardant additives, and other optional co-additives of component (c) are added to the foam formulation and can be in either (1) the isocyanate component or A-side, (2) the isocyanate-reactive component or B-side, or (3) both the isocyanate component (A-side) and the isocyanate-reactive component (B-side), and each of the optional foaming components and / or optional co-additives of component (c) can be added before components (a) and (b) are mixed together or at the same time as components (a) and (b) are mixed together.

[0093] In preparing the foam-forming compositions of the present invention, the A-side and B-side, along with any other optional ingredients (if any), can be prepared separately and independently, and all of these components can be mixed together at the desired concentrations discussed above to prepare the foam-forming composition. Generally, the molar ratio of isocyanate groups on the A-side to isocyanate-reactive groups on the B-side can range from 1.0:1 to 6:1 in one embodiment, from 1.2:1 to 5.75:1 in another embodiment, from 1.5:1 to 5.5:1 in yet another embodiment, from 1.75:1 to 5:1 in yet another embodiment, from 2:1 to 4.75:1 in yet another embodiment, and from 2.5:1 to 4.5:1 in yet another embodiment. Mixing of components (a) and (b) can be carried out at a temperature of from 5°C to 80°C in one embodiment, from 10°C to 60°C in another embodiment, and from 15°C to 50°C in yet another embodiment. Typical times for mixing components (a), (b) and other optional component (c) into a reactive foam-forming composition at room temperature range from as short as 10 ms to 100 ms to as long as 20 s.

[0094] The ingredients that make up the foam composition may be mixed together by any known mixing process and equipment. For example, the isocyanate component (side A) and the isocyanate-reactive component (side B) can be mixed together by any known urethane foaming equipment, such as a sprayer, high-pressure impingement mixer, static mixer, liquid dispense gun, mix head, or vessel. High-pressure impingement mixers and sprayers are most commonly used to mix the A-side and B-side and the optional ingredients / additives of component (c). Immediately after mixing (e.g., within less than 5 seconds), the foam foam mixture can be sprayed or otherwise deposited, injected, or poured onto a substrate or into a mold. Regardless of any particular method of foam production, the amount of foam mixture introduced into a mold or onto a substrate is sufficient to completely fill the mold or assume the shape of a panel or any other functional shape as the foam expands and cures. A degree of overpack can be introduced by using a slight excess of the reacting mixture over the minimum required amount. For example, the cavity may be overpacked by 5% to 35%, i.e., 5% to 35% by weight more reaction system may be introduced than is minimally required to fill the cavity as the reaction mixture expands. The cavity may optionally be maintained at atmospheric pressure or may be partially evacuated to a pressure below atmospheric pressure.

[0095] The thoroughly mixed reactive foam-forming composition is subjected to conditions sufficient to cause the foaming reaction inside the cavity or mold, or on the substrate, to occur and cure to form a rigid foam product. Upon reaction, the foamed mixture takes the shape of the mold or adheres to the substrate, producing a PU foam, which is then either partially or fully cured. Suitable conditions for accelerating the cure of the polymer include temperatures of 20°C to about 150°C in one general embodiment. In some embodiments, curing is carried out at temperatures of 30°C to 80°C. In other embodiments, curing is carried out at temperatures of 35°C to 65°C. In various embodiments, the temperature for curing can be selected based, at least in part, on the duration required for the PUR / PIR polymer to gel and / or cure at that temperature. The cure time will also depend on other factors, including, for example, the amount of particular components used (e.g., the type and amount of catalyst), and the size and shape of the article being produced. Different articles produced may include, but are not limited to, foam boards for roofing, insulation panels for building and construction applications, door panels for appliances, and the like.

[0096] In various embodiments, PU foams are prepared by mixing all of the individual components, including at least one isocyanate-reactive component comprising a novel liquid aromatic polyester polyol having at least one polyaliphatic structure, the at least one isocyanate component, and optional ingredients and / or auxiliary additives of component (c), such as catalysts, surfactants, blowing agents, flame retardant additives, and / or any other auxiliary additives. Mixing can be carried out at room temperature or at temperatures between 5°C and 80°C for a duration of 10 ms to 20 s, followed by immediate pouring, spraying, injection, or placement of the resulting mixture into a mold cavity or substrate for foaming. In some embodiments, optional ingredients and / or auxiliary additives of component (c), such as catalysts, surfactants, blowing agents, and flame retardants, can be added to the isocyanate-reactive component or the isocyanate component prior to mixing with the other components, or can be mixed online with the other components as a separate stream.

[0097] A variety of methods can be used to manufacture insulation products incorporating rigid polyurethane foams prepared from the foam-forming compositions of the present invention, including, for example, a continuous double-belt lamination process for making insulated metal panels with rigid metal facers (such as steel facers) on both the top and bottom of the panel; a continuous process for making boardstock foam with flexible facers, such as aluminum foil or paper, on both sides of the foam; a discontinuous process for making three-dimensionally shaped insulation panels or articles by injecting a reactive formulation into a mold cavity followed by subsequent curing of the formulation in the mold at temperatures ranging from 25°C to 80°C for a desired time; and other processes. Those skilled in the art can adjust the reaction rates of the current information to achieve the best mold filling and foam cure for the most economical production.

[0098] The foam-forming composition of the present invention may, in one typical embodiment, be applied to a mass of 20 kg / m 3 ~200kg / m 3 In an exemplary embodiment, the rigid PU foam has a density of 25 kg / m 3 ~150kg / m 3 , and in another embodiment 25 kg / m 3 ~100kg / m 3 and in another embodiment 25 kg / m 3 ~75kg / m 3 and in yet another embodiment 25 kg / m 3 ~60kg / m 3 and in yet another embodiment, 30 kg / m 3 ~60kg / m 3 Some of the advantageous properties exhibited by the resulting foam products produced in accordance with the present invention can include, for example, (1) lower thermal conductivity, (2) smaller cell size, (3) excellent compressive strength, and (4) good mechanical toughness, such as low foam crushability.

[0099] The aromatic polyester polyol compositions used in the isocyanate-reactive compositions, i.e., foam-forming compositions for making rigid PU foams, provide PU foams with improved thermal insulation performance. For example, the PU foam products of the present invention exhibit low thermal conductivity at 10°C of ≦20.3 mW / m·K in one embodiment, from 13.0 mW / m·K to 20.0 mW / m·K in another embodiment, from 14.0 mW / m·K to 19.8 mW / m·K in yet another embodiment, and from 15.0 mW / m·K to 19.5 mW / m·K in yet another embodiment. The thermal insulation performance of rigid foams, as measured by thermal conductivity (or “K-factor”), is defined and determined by the procedure set forth in ASTM C518-17.

[0100] The PU foams of the present invention advantageously exhibit good mechanical properties, as measured by compressive strength determined by the procedure described in ASTM D1621-16. For example, in a typical embodiment, the PU foam exhibits a compressive strength value of 100 kPa or greater. PU foams having a compressive strength of less than 100 kPa are generally considered to lack sufficient mechanical strength for long-term use.

[0101] Additionally, the PU foams of the present invention exhibit good mechanical toughness, with a physical crushability measured according to ASTM C421-08 of 20% or less. PU foams with a crushability of more than 30% are generally considered unacceptable for most applications described herein. The PU foams of the present invention also advantageously exhibit small cell sizes, with the average cell size of the foam being less than 170 μm in one embodiment, ≦160 μm in another embodiment, and ≦150 μm in yet another embodiment.

[0102] The polyurethane foam products produced by the novel foam-forming compositions and methods of the present invention can be used in various types of insulation applications, such as building and construction applications, appliances, refrigerated shipping containers, cryogenic storage, and similar applications. The liquid aromatic polyester polyols of the present invention can also be used in non-foam applications, such as coatings, adhesives, and packaging applications. [Example]

[0103] The following examples are presented to further illustrate the invention, but should not be construed as limiting the scope of the claims. Unless otherwise indicated, all parts and percentages are by weight.

[0104] The various materials used in the preparation of the inventive examples (Inv. Ex.) and comparative examples (Comp. Ex.), described below, are set forth in Table I.

[0105] [Table 1]

[0106] Example 1 - Polyols prepared with polyalicyclic alcohols In a 2,000 mL four-neck round-bottom flask, add tricyclo[5.2.1.0 2,6 ] Decane-dimethanol (TCDDM) (522.02 g), polyethylene glycol 200 (PEG 200) (531.89 g), and terephthalic acid (TA) (441.81 g) are charged. A nitrogen (N2) inlet adapter equipped with a thermocouple is inserted along with a glass stir shaft equipped with a half-moon blade, and a stir bearing with a stopper is placed in the remaining neck of the flask. The flask is degassed three times by circulating N2 between 100 Torr / 13.3 kPa and atmospheric pressure through a Firestone valve. The flask is placed under a gentle N2 sweep through a Dean-Stark trap and condenser attached to the flask outlet. The apparatus is completed with a heating mantle for heating the flask, and the flask temperature is controlled by a temperature controller. The upper reactor surfaces of the flask and Dean-Stark trap are insulated with heat tracing and thermal insulation. An air motor is used to drive the stir shaft.

[0107] The flask is heated to a set temperature of 220°C over 2 hours with stirring, and TYZOR AA105 (0.443 g) is injected into the flask at approximately 80°C as the flask warms to the set temperature. The flask is maintained at 220°C for 4.5 hours while the distillate is collected and discharged through the Dean-Stark trap. The flask temperature is increased and maintained at 230°C for 3.5 hours while the distillate is collected and discharged through the Dean-Stark trap. The Dean-Stark trap and condenser are then removed from the flask, and the flask is cooled to 200°C over 0.5 hours. The flask is stoppered under positive N pressure via a Firestone valve. To replace excess distillate from the flask, the flask temperature is reduced and maintained at 180°C for 1.0 hour while polyethylene glycol 200 (43.0 g, 120 ppm water in PEG 200) is injected into the flask. The flask is then slowly cooled and maintained at 50°C overnight (approximately 12 hours) and the product is transferred while still warm. The final product obtained is 25.6°C (10 seconds). -1 ) viscosity η of 54.1 Pa s, GPC M of 584 n , 1,004 M w , a polydispersity index of 1.72, a hydroxyl number (OH#) of 214 mg KOH / gram, and an acid number (acid#) of less than 2 mg KOH / g. The detailed synthesis recipe and characterization results of the obtained product (Inv.Ex.1) are listed in Table II.

[0108] [Table 2] Notes for Table II: PESP = prepared from PEG200 (348.33 g), terephthalic acid (193.66 g), TYZOR AA105 (0.1374 g), M n = 942, Mw = 1,993, and nm = not measured or not measurable. a 1,000 mL round-bottom flask. 220°C for 4 hours, then 230°C for 4 hours. b250 mL round bottom flask. Transesterification reaction under positive N2 pressure: 1.75 hours to 180°C, 2 hours at 180°C, 2 hours to / at 190°C. c 1,000 mL round-bottom flask. 9 hours at 220°C, then 3.5 hours at 230°C.

[0109] Comparative Examples A and B - Polyols prepared with polyalicyclic alcohols The same basic synthetic protocol as that for P1 (Inv. Ex. 1) above was followed, except that h-BPA (Comp. Ex. A) and a spiroacetal alcohol (Comp. Ex. B) were used as the polyaliphatic alcohols to prepare each polyester polyol (with the differences noted in the footnotes in Table II). Interestingly, neither of these two polyester polyols is a clear liquid at room temperature. Instead, the two polyester polyols are in the form of a white paste or a white wax-like solid that does not become a clear liquid below 200°C. The detailed synthesis recipes and characterization results for the two resulting polyester polyol products (Comp. Ex. A and Comp. Ex. B) are listed in Table II.

[0110] Comparative Example C - Polyols Prepared with Polyalicyclic Alcohols Comp.Ex.C is prepared according to the same synthetic protocol (time and temperature details are given in the footnotes) as described for the preparation of P1 (Inv.Ex.1), except that isosorbide is used as the polyaliphatic alcohol for the preparation of Comp.Ex.C. The reaction yielded a clear and transparent liquid at room temperature. The obtained final product was eluted at 25.6°C (10 s). -1 ) viscosity η of 32.9 Pa·s, GPC M of 450 n , 1,118 M wThe polyol of Comp.Ex.C had a polydispersity index of 2.48, a hydroxyl number (OH#) of 281 mg KOH / g, and an acid number (acid#) of less than 2 mg KOH / g. However, the polyol of Comp.Ex.C failed to improve the thermal insulation performance when incorporated into foam formulations. The detailed synthesis recipe and characterization results of the resulting product (Comp.Ex.C) are listed in Table II.

[0111] Examples 2-6 - Polyols prepared with TCDDM Polyols Inv.Ex.2-6, designated as P2-P6, respectively, were prepared in a manner similar to the process for preparing P1 (Inv.Ex.1), with the differences noted in the footnotes of Table III. Details of the preparation and properties of the polyols (Inv.Ex.2-6) are given in Table III, and the reaction flask dimensions and temperature profile used when the setpoint was >200°C are given in the footnotes.

[0112] Comparative Example D - Polyols Prepared with Polyalicyclic Alcohols Polyol Comp.Ex.D was prepared according to the same synthesis protocol (with the differences noted in the footnotes in Table III) as described for the preparation of inventive polyol example P6, except that h-BPA was used to prepare Comp.Ex.D. Although the resulting polyester polyol was liquid at room temperature, the viscosity of this polyester polyol was measured to be extremely high, at 486 Pa·s. This viscosity is more than 10 times higher than that of inventive polyol P6. The extremely high viscosity of Comp.Ex.D makes mixing this viscous polyol with other materials very difficult to handle and process. The detailed synthesis recipe for Comp.Ex.D and the results of polyol characterization are listed in Table III.

[0113] [Table 3] Notes for Table III: a 1,000 mL round-bottom flask. 220°C for 4 hours, then 240°C for 4 hours. b 2,000 mL round-bottom flask. 220°C for 3.75 hours, then 240°C for 4.5 hours. c 1,000 mL round-bottom flask. 220°C for 3.75 hours, then 240°C for 5.75 hours. d 1,000 mL round-bottom flask. 4.67 hours at 220°C, 3.5 hours at 230°C. e 1,000 mL round-bottom flask. 220°C for 3.5 hours, then 230°C for 4 hours. f 1,000 mL round-bottom flask. 200°C for 4 hours, then 220°C for 4 hours.

[0114] The results set forth in Tables II and III demonstrate that TCDDM is particularly useful as a polyalicyclic alcohol for the preparation of the liquid aromatic polyester polyols of the present invention.

[0115] Test Method Polyol Measurement viscosity Viscosity (η) measurements for the polyols used in the examples and comparative examples were performed using a TA Instrument AR2000 rheometer with a 40 mm cone at a temperature of 25.6° C. and a 10 s -1 The test was carried out using the procedure described in ISO 3219 at a shear rate of 100 rpm.

[0116] Hydroxyl Number Hydroxyl number (OH#) is determined according to the procedure described in ASTM E1899-16, Standard Test Method for Hydroxyl Groups Using Reaction with p-Toluenesulfonyl Isocyanate and Potentiometric Titration with a Mettler T70 Titration System Using Tetrabutylammonium Hydroxide.

[0117] Acid value Acid number (acid#) is determined by potentiometric titration of polyol (approximately 1 g specimen size) dissolved in 25.0 mL of toluene / methanol (2 / 1, vol / vol) with standardized 0.01 N potassium hydroxide using a Mettler T70 titration system, along with titration of a blank.

[0118] molecular weight Number average molecular weight (M n ), weight average molecular weight (M w ), and polydispersity index (PDI) = M w / M n The molecular weight (Mw) is determined according to the procedure described in ASTM D5296-19. The method uses gel permeation chromatography (GPC) on an Agilent 1200 HPLC system (5 μm, 300 mm × 7.5 mm) equipped with a PLgel Guard Column and four PLgel narrow pore columns (50 angstroms (Å), 100 Å, 1,000 Å, and 10,000 Å), and a ReadyCal Polyethylene Glycol Calibrant Set (44000-238 Mp) utilizing unsuppressed tetrahydrofuran (THF). The specimens used for molecular weight determination were prepared at a concentration of 0.1 g / 10 mL THF.

[0119] Isocyanate-reactive compositions and materials for use in polyurethane foam compositions The inventive polyols and comparative polyols prepared above are used in the preparation of polyurethane foam examples.

[0120] In addition, two aromatic polyester polyols, Polyol A and Polyol B, which do not contain polyalicyclic structures, were also used in the preparation of foams. Both Polyol A and Polyol B are prepared using terephthalic acid and polyglycols such as DEG, PEG200, and glycerol. Polyol A has an OH value of 220 mg KOH / g, a number average molecular weight of 510 g / mol, and an OH functionality of 2.0. Polyol B has an OH value of 315 mg KOH / g, a number average molecular weight of 427, and an OH functionality of 2.4.

[0121] Various foaming additives, such as catalysts, surfactants, flame retardant (FR) additives, and physical blowing agents, were also used to make the foams. For example, DABCO® K-2097 (catalyst A) is a trimer catalyst available from Evonik, POLYCAT® 5 (catalyst B) is a blowing catalyst available from Evonik, surfactant A is TEGOSTAB® B8421, a silicone polyether surfactant commercially available from Evonik, surfactant B is a silicone polyether surfactant available from Dow, and TEP (FR additive) is a triethyl phosphate flame retardant available from ICL-IP.

[0122] The physical blowing agent used in the foam examples and comparative examples is a 70 / 30 blend of cyclopentane and isopentane, ie, a c / i-pentane blend (70 / 30).

[0123] Preparation of foams Two different methods are used to prepare foams: (1) hand mixing using an overhead mixer, and (2) high-pressure machine operation using an impingement mixer. Several polyester polyols were prepared in kg quantities that allowed for foam preparation by high-pressure machine. The two methods are referred to herein as hand mixing (HM) and high-pressure machine (HP) operation.

[0124] General protocol for manual mixing foam preparation: The polyol, surfactant, flame retardant, catalyst, and water were added to a 1,000 mL plastic cup, and the plastic cup with its contents was weighed. The contents of the cup were then mixed in an overhead mixer to prepare a "polyol mixture" (side B). The target amount of blowing agent was then added to the cup and thoroughly mixed with the polyol package. Subsequently, the desired amount of polyisocyanate component (side A) was added to the compound mixture in the cup. The resulting compound was immediately mixed in a high-speed overhead mixer at a mixer speed of 3,000 rpm for 5 seconds, and then the compounded compound was poured into a preheated mold preheated to 55°C. The mold dimensions were 30 cm (height) x 20 cm (length) x 5 cm (thickness). The mold was positioned vertically along the "height" direction of the mold for foaming. After approximately 20 minutes, the foam was removed from the mold and allowed to sit on a lab bench overnight before the resulting foam product was tested for physical properties.

[0125] General protocol for HP mechanical foam preparation: The appropriate amounts of polyol, surfactant, flame retardant, catalyst, physical blowing agent, and water were weighed and added into a 5-gallon (19 liter) plastic bucket, followed by thorough mixing with an air mixer. The resulting formulation, designated as the "polyol mixture" (B-side), was then charged to the polyol tank of a foaming machine (Cannon A40 high-pressure (HP) foaming machine). A polyisocyanate, such as VORANATE™ M 600, designated as the "A-side," was charged to the isotank of the Cannon A40 HP machine. The appropriate amounts of the foam formulation, consisting of the A-side and B-side, were mixed together using an impingement mixer and immediately introduced into the mold cavity, where the components were allowed to react and expand. The pump pressure for both the isocyanate pump stream and the polyol pump stream was 1,500 psi (10,342 kPa), and the temperatures for both the polyol stream and the isocyanate stream were set at 70°F (21°C).

[0126] A flat mold was used for foam preparation by HP machine operation. The flat mold had dimensions of 30 cm (length) × 30 cm (width) × 10 cm (thickness or height). The "thickness or height" direction of this mold corresponds to the foam rise direction during foam preparation. The flat mold was preheated to 55°C and maintained at a constant temperature of 55°C throughout the entire foam preparation period. The reactive foaming mixture was poured into the mold and allowed to cure in the mold for 5 minutes, after which a foam specimen was removed from the mold. All foams produced by HP machine operation were left on a lab bench overnight before physical property testing.

[0127] Test methods and foam property measurements Various tests were performed on foam products made according to the examples and comparative examples described herein.

[0128] Creaming time, gelling time, tack-free time Creaming time, gel time, and tack-free time are determined according to the test procedures described in ASTM D7487(2013). The general procedure for measuring creaming time and gel time is as follows: Free-rise foam is made using the plastic cup method described in the ASTM procedure above. Using this method, polyol, surfactant, flame retardant, catalyst, and water are weighed into a plastic cup. The polyol component is thoroughly mixed using an overhead mixer at 200 rpm to 500 rpm. The appropriate amount of blowing agent is then added to the cup and thoroughly mixed into the polyol component. The isocyanate component is then added to the cup, followed by immediate mixing for 5 seconds using an overhead mixer at approximately 3,000 rpm. The time recording begins when mixing of the isocyanate with the polyol component is triggered. When the foam formulation in the cup exhibits a distinct color or appearance change based on increased bubble formation (or more commonly known to those skilled in the art as creaming), the time is recorded as the "creaming time." The tip of the wooden tongue depressor is then dipped into the foam formulation and quickly withdrawn to determine whether the foam mixture becomes stringy. The time when the foam formulation becomes stringy based on the wooden tongue depressor test is recorded as the "gel time." The time when the top surface of the foam is not tacky when tapped lightly with the wooden tongue depressor is recorded as the "tack-free time." The "tack-free time" is reached when lifting the wooden tongue depressor does not result in a dent or rupture of the foam surface.

[0129] Thermal conductivity (K factor or lambda value) Within 24 hours of foam preparation (and after standing overnight on the lab bench), foam samples measuring 20 cm x 20 cm x 2.5 cm were cut from the central interior section of the molded foam for thermal conductivity measurements. Measurements were performed at 50°F (10°C) according to the procedure described in ASTM C518-17. For each example and comparative example, the average K-factor measurement across at least two specimens was reported.

[0130] Foam Core Density The density of rigid foams was measured according to the procedure described in ASTM 1622-03(2008). Cube samples measuring 5 cm x 5 cm x 5 cm were cut from the central interior section of the molded foam for measurement. The density of each sample was calculated by weighing the mass and measuring its exact dimensions. Measurements were performed on at least three samples for each foam specimen, and the average value was reported.

[0131] Free-rise density Free-rise density was also measured for foams produced by high-pressure machine operation. A predetermined amount of reactive foaming mixture was poured into a 20 cm x 20 cm x 20 cm open wooden box with a plastic liner. The foaming mixture was allowed to react, expand, and cure in the open wooden box at room temperature for approximately two hours. Rectangular blocks of foam specimens were then cut, approximately 14 cm x 12 cm x 10 cm in size, weighed, and their exact dimensions determined to calculate density. Three free-rise foam measurements from each foam formulation were taken, and the average values ​​reported.

[0132] Compression strength The compressive strength (CS) of foam specimens measures the mechanical resistance of the foam to compressive stress. Measurements are taken parallel to the foam rise direction (z-axis) and / or perpendicular to the foam rise direction (x-axis). Testing was performed according to ASTM D1621 method on 5 cm x 5 cm x 2.5 cm foam samples taken from the central interior section of the mold foam.

[0133] Physical crushability The physical crushing properties of the foams were measured by testing foam samples in a tumbling machine according to the procedure described in ASTM C421-08. The apparatus included an oak cube box with interior dimensions of 7 1 / 2 inches by 7 3 / 4 inches by 7 3 / 4 inches (190 mm x 197 mm x 197 mm). The box shaft was motor-driven at a constant speed of 60 rpm. Twenty-four 3 / 4-inch (19 mm) cubes of room-dried solid oak were placed in the box containing the test sample. Test samples were prepared by cutting the interior portion of the molded foam into 1-inch (25.4 mm) cubes with a fine-tooth saw.

[0134] Foam Cell Size Cell size analysis was measured for several foams by analyzing 2 cm x 1 cm x 0.5 cm foam specimens with a Porescan® system. Porescan® is an automated cell size analyzer manufactured by Goldlucke Ingenieurleistungen. The system includes a camera and software components. A contrast fluid (provided by Goldlucke Ingenieurleistungen) was deposited onto the foam specimens by spray coating and consisted of carbon black in pentane with propane and butane as propellants. The contrast-treated foam specimens were imaged with the camera and processed with software. At least 5,000 cells were imaged and analyzed for each specimen.

[0135] Foam prepared by manual mixing Comparative Example: E-Form FA 180 grams of foaming mixture was prepared according to the "General Protocol for Manual Mix Foam Preparation." The mixture was then immediately poured into a 5 cm x 20 cm x 30 cm upright mold. Approximately 135 g of foaming mixture was poured into the mold. After 20 minutes, the foam was removed from the mold and allowed to sit on a lab bench overnight before testing the resulting foam product for physical properties. The results of the foam property characterization are summarized in Table IV.

[0136] Examples 7-15 - Forms F-1 to F-9 The Comp.Ex. Foam FA protocol was repeated by replacing a portion of Polyol A in Comp.Ex. FA with one of the polyester polyols of the present invention synthesized from TCDDM in the respective amounts shown in Table IV. Foam properties of F-1 through F-9 were measured. The results are shown in Table IV.

[0137] [Table 4]

[0138] The results, set forth in Table IV, show that the thermal conductivity or K-factor measured for foams prepared from formulations containing the liquid aromatic polyester polyols of the present invention is significantly lower than that of Comp. Ex. E (FA). There is no measurable difference in foam reaction rate between the foam formulations of the present invention and the reference formulation. No degradation in foam mechanical properties was observed for all foams from Inv. Ex. 7 to 15.

[0139] Foam prepared by high pressure machine operation Example 16 (Form F-10) and Comparative Example G (Form FB) These examples were prepared from the respective formulations shown in Table V using a high-pressure foaming machine equipped with an impingement mixer (model: Cannon A40). Comp. Ex. FB and F-10 differ only in the type of aromatic polyester polyol used, in that F-10 used 50 pts of P1 (Inv. Ex. 1) per 100 pts of total polyol. To mold the foams, a flat mold with dimensions of 30 cm (length) x 30 cm (width) x 10 cm (height) was used. The mold was preheated to 55°C and maintained at a constant temperature of 55°C for foam curing. The foams prepared in the mold were removed from the mold after 5 minutes of curing. Detailed properties of Comp. Ex. FB and F-10 are reported in Table V.

[0140] The results in Table V show that foam preparation from polyol P1 of the present invention (Inv. Ex. 1) gives better foam properties than the comparative foam examples: lower thermal conductivity, smaller cell size, and similar mechanical properties in terms of compressive strength and physical crushability.

[0141] [Table 5]

[0142] Taken together, the results set forth in Tables IV and V clearly demonstrate that the novel liquid aromatic polyester polyols of the present invention are surprisingly and uniquely advantageous for use in polyurethane foam formulations to achieve lower thermal conductivities and smaller cell sizes than comparative foams, while still maintaining properties such as excellent mechanical strength and foam toughness. Examples of the invention of this application include the following. [1] A liquid aromatic polyester polyol composition comprising at least one polyalicyclic structure having the following general chemical structure (I): [ka] wherein m is an integer equal to 1 or 2, n is an integer equal to 0, 1, 2, 3, or 4, and R 1 and R 2 are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n is 1 or greater, R 2 is (CH 2 ) n The aromatic polyester polyol composition is a transparent liquid at room temperature, and the viscosity of the aromatic polyester polyol composition is -1 a shear rate of 100 Pa·s or less, and an OH value of the aromatic polyester polyol composition is in the range of 100 mg KOH / g to 500 mg KOH / g. [2] (i) at least one compound selected from the group consisting of aromatic dicarboxylic acids, aromatic dicarboxylic anhydrides, aromatic tricarboxylic acids, aromatic tricarboxylic anhydrides, aromatic tetracarboxylic acids, aromatic tetracarboxylic anhydrides, and aromatic carboxylic acid sources, wherein the total amount of carboxylic acid groups and / or carboxylic acid equivalent groups directly bonded to the aromatic ring structure in compound (i) is at least 25 mol% based on the total number of moles of carboxylic acid groups and carboxylic acid equivalent groups used in the preparation of the aromatic polyester polyol; (ii) at least one polyhydric alcohol, wherein the at least one polyhydric alcohol comprises a polyalicyclic ring of structure (I) above and / or a compound having the following general chemical structure (II): [ka] wherein m is an integer equal to 1 or 2, n is an integer equal to 0, 1, 2, 3, or 4, and R 1 and R 2 are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n is 1 or greater, R 2 is (CH 2 ) n wherein the amount of the at least one polyhydric alcohol having a polyalicyclic ring of Structure (I) and / or Structure (II) is at least 10 percent based on the total moles of hydroxyl groups of all polyhydric alcohols used in preparing the aromatic polyester polyol, the aromatic polyester polyol composition is a clear liquid at room temperature, and the viscosity of the aromatic polyester polyol composition is at room temperature and 10 seconds -1 and the OH value of the aromatic polyester polyol composition is 100 mg / kg or less at a shear rate of 100 Pa·s or less. The aromatic polyester polyol composition according to the above item [1], wherein the KOH / g is in the range of 500 mg KOH / g to 500 mg KOH / g. [3] The polyester polyol composition according to [2] above, wherein the component (ii) is tricyclodecane dimethanol, an isomer of tricyclodecane dimethanol, or a mixture thereof. [4] A process for producing a polyester polyol composition, comprising: (i) at least one compound selected from the group consisting of aromatic dicarboxylic acids, aromatic dicarboxylic anhydrides, aromatic tricarboxylic acids, aromatic tricarboxylic anhydrides, aromatic tetracarboxylic acids, aromatic tetracarboxylic anhydrides, and aromatic carboxylic acid sources, wherein the total amount of carboxylic acid groups and / or carboxylic acid equivalent groups directly bonded to an aromatic ring structure in compound (i) is at least 25 mol % based on the total number of moles of carboxylic acid groups and carboxylic acid equivalent groups used in preparing the aromatic polyester polyol; (ii) reacting at least one polyhydric alcohol, wherein the at least one polyhydric alcohol comprises a polyalicyclic ring of structure (I) above and / or a compound having the following general chemical structure (II):

change

[10] The polyurethane or polyisocyanurate foam product according to [9] above, wherein the polyurethane product has a thermal conductivity (K-factor or lambda value) of 20.3 mW / m·K or less when measured at 10°C according to the procedure described in ASTM C518-17.

Claims

1. 1. A liquid aromatic polyester polyol composition for preparing polyurethane insulating foam, comprising at least one polyalicyclic structure having the following general chemical structure (I): 【Chemical 1】 where m is an integer equal to 1 or 2, n is an integer equal to 1, 2, 3, or 4, and R １ and R ２ are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n is 1 or greater, R ２ is (CH ２ ) ｎ The aromatic polyester polyol composition is a transparent liquid at room temperature, and the viscosity of the aromatic polyester polyol composition is －１ and the OH number of the aromatic polyester polyol composition is in the range of 100 mg KOH / g to 500 mg KOH / g.

2. (i) at least one compound selected from the group consisting of aromatic dicarboxylic acids, aromatic dicarboxylic anhydrides, aromatic tricarboxylic acids, aromatic tricarboxylic anhydrides, aromatic tetracarboxylic acids, aromatic tetracarboxylic anhydrides, and aromatic carboxylic acid sources, wherein the total amount of carboxylic acid groups and / or carboxylic acid equivalent groups directly bonded to an aromatic ring structure in compound (i) is at least 25 mol % based on the total number of moles of carboxylic acid groups and carboxylic acid equivalent groups used in preparing the aromatic polyester polyol; (ii) at least one polyhydric alcohol, wherein the at least one polyhydric alcohol comprises a polyalicyclic ring of structure (I) and / or a compound having the following general chemical structure (II): 【Chemistry 2】 where m is an integer equal to 1 or 2, n is an integer equal to 1, 2, 3, or 4, and R １ and R ２ are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n is 1 or greater, R ２ is (CH ２ ) ｎ wherein the amount of the at least one polyhydric alcohol having a polyalicyclic ring of Structure (I) and / or Structure (II) is at least 10 percent based on the total moles of hydroxyl groups of all polyhydric alcohols used in preparing the aromatic polyester polyol, the aromatic polyester polyol composition is a clear liquid at room temperature, and the viscosity of the aromatic polyester polyol composition is at room temperature and 10 seconds －１ At a shear rate of 100 Pa·s or less, the OH value of the aromatic polyester polyol composition is The aromatic polyester polyol composition of claim 1, wherein the aromatic polyester polyol has a solubility in the range of from 500 mg KOH / g to 500 mg KOH / g.

3. 3. The polyester polyol composition of claim 2, wherein component (ii) is tricyclodecane dimethanol, an isomer of tricyclodecane dimethanol, and mixtures thereof.

4. A process for producing a polyester polyol composition for preparing polyurethane insulating foam, comprising: (i) at least one compound selected from the group consisting of aromatic dicarboxylic acids, aromatic dicarboxylic anhydrides, aromatic tricarboxylic acids, aromatic tricarboxylic anhydrides, aromatic tetracarboxylic acids, aromatic tetracarboxylic anhydrides, and aromatic carboxylic acid sources, wherein the total amount of carboxylic acid groups and / or carboxylic acid equivalent groups directly bonded to an aromatic ring structure in compound (i) is at least 25 mol % based on the total number of moles of carboxylic acid groups and carboxylic acid equivalent groups used in the preparation of the aromatic polyester polyol; (ii) with at least one polyhydric alcohol, wherein the at least one polyhydric alcohol comprises a polyalicyclic ring of structure (I) and / or a compound having the following general chemical structure (II): 【Chemistry 3】 where m is an integer equal to 1 or 2, n is an integer equal to 1, 2, 3, or 4, and R １ and R ２ are each independently a divalent hydrocarbon group selected from 1 to 6 carbon atoms, and when n is 1 or greater, R ２ is (CH ２ ) ｎ wherein the amount of the at least one polyhydric alcohol having a polyalicyclic ring of Structure (I) and / or Structure (II) is at least 10 percent based on the total moles of hydroxyl groups of all polyhydric alcohols used in preparing the aromatic polyester polyol, the aromatic polyester polyol composition is a clear liquid at room temperature, and the viscosity of the aromatic polyester polyol composition is at room temperature and 10 seconds －１ At a shear rate of 100 Pa·s or less, the OH value of the aromatic polyester polyol composition is The process ranges from 500 mg KOH / g to 500 mg KOH / g.

5. An isocyanate-reactive composition for preparing polyurethane insulating foam, comprising the aromatic polyester polyol composition of claim 1.

6. 6. The isocyanate-reactive composition of claim 5, further comprising at least one other polyol different from the aromatic polyester polyol having a polyalicyclic structure, wherein such other polyol is selected from polyester polyols, polyether polyols, polycarbonate polyols, or mixtures thereof, and the amount of the aromatic polyester polyol having a polyalicyclic structure is at least 10 parts, based on the total amount of polyols in the isocyanate-reactive composition equal to 100 parts.

7. 1. A foam-forming composition comprising: (a) at least one isocyanate component; and (b) at least one isocyanate-reactive component, wherein the at least one isocyanate-reactive component comprises the isocyanate-reactive composition of claim 5 or claim 6, and wherein the foam-forming composition has an Isocyanate Index of 100 to 600.

8. 1. A process for producing a foam-forming composition comprising: (a) at least one isocyanate component; (b) reacting with at least one isocyanate-reactive component, wherein the at least one isocyanate-reactive component comprises the isocyanate-reactive composition of claim 5 or claim 6.

9. 1. A polyurethane or polyisocyanurate foam product comprising: (I) at least one isocyanate component having an isocyanate index of 100 to 600; (II) a polyurethane or polyisocyanurate foam product comprising the reaction product of:

10. 10. The polyurethane or polyisocyanurate foam product of claim 9, wherein the polyurethane product has a thermal conductivity (K-factor or lambda value) of 20.3 mW / m K or less, when measured at 10°C according to the procedure set forth in ASTM C518-17.

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