POLYURETHANE FOAM ADDITIVES TO IMPROVE FOAM ADHESION TO ORGANIC

POLYMERS

FIELD OF THE INVENTION

[0001] The field of invention is the composition and application of additives useful for the production of rigid polyurethane foams utilized in insulation of commercial and residential enclosures as well as polyurethane insulating materials used in appliances such as refrigerators, freezers as well as hot water heaters, insulation panels, garage doors, entry doors, and other various applications where insulation is desired.

BACKGROUND OF THE INVENTION

[0002] Polyurethane foam compositions are typically prepared by reacting an isocyanate and a premix which consists of isocyanate-reactive components such as a polyol. The premix optionally also contains other components such as water, flame retardants, blowing agents, foam-stabilizing surfactants, and catalysts to promote the reactions of isocyanate with polyol to make urethane, with water to make C0 ₂ and urea, and with excess isocyanate to make isocyanurate (trimer). The presence of isocyanurate in PIR/PUR foam products provides excellent thermal stability and flame resistance. Isocyanurates are stable to temperatures of about 160°C and are resistant to most organic solvents, acids, alkali, ultraviolet light, and humidity.

[0003] The blowing agent in the premix is usually a liquid or gas with a boiling point sufficiently low to be vaporized by the heat released during the polymerization reaction. Examples of blowing agents useful in the production of insulating polyurethane foam include but are not limited to hydrofluorocarbons, hydrofluoroolefins (HFOs),

hydrofluorochloroolefins, hydrochlorofluorocarbons, formates, ketones such as acetone, and hydrocarbons. Unlike simple hydrocarbons, such as pentane, halogen containing molecules such as chrolofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are far less flammable and safer to use in foam production. However, some of the halogen containing blowing agents can either harm the ozone layer or contribute to global warming. In contrast, HFOs are very efficient and environmentally friendly blowing agents with a much lower global warming potential (GWP). However, the higher reactivity of HFO that makes them low GWP also causes them to chemically react and decompose in formulation premixes containing amine catalyst. Considering the wide use of amine catalysts in polyurethane foam production, this has limited the use of HFOs.

[0004] Thus, proper selection and combination of the components in the premix and the isocyanate can be useful for the production of polyurethane foam that is spray applied, poured in place, and used in applications such as refrigerators, freezers, hot water heaters, insulation panels, garage doors, entry doors, and other various applications where insulation is desired. For some of these applications, the premix is stored for one day up to one year before being reacted with isocyanate to generate polyurethane foam. This is common in spray foam applications, where drums of premix and isocyanate are shipped to field locations for on-site application. Thus, it is desirable for the premix of an insulating foam formulation to be both chemically and physically stable. Flowever, in some cases, the catalysts that are useful to promote the

polyurethane reaction can also participate or induce undesired hydrolysis reactions with the blowing agents present in the premix resulting in reduced storage stability. Common amine catalysts useful for the production of polyurethane foam include tertiary amines which are known to accelerate the urethane reaction promoting the formation of polyurethane polymers. Flowever, in some cases, tertiary amines can catalyze the hydrolysis of esters causing the formation of carboxylic acids which in turn can neutralize the tertiary amine catalysts in the systems causing a slowdown in the reactivity of the mixture towards isocyanate. This reactivity slowdown can also result in various quality issues such as sagging during spray foam applications and it can also produce polyurethane foam with poor physical properties.

[0005] These undesired reactions are typically observed in spray foam systems containing polyester polyol as well as spray foam systems containing halogenated components that can act as flame retardants or blowing agent.

[0006] Rigid polyurethane spray foam is widely used in construction and building industries as rigid foam insulation, which reduces energy consumption. Rigid

polyurethane spray foam is typically applied directly onto the surface of substrates. Examples of substrates include oriented strand board (OSB), gypsum, concrete, wood, steel and various other metal surfaces. Rigid polyurethane spray foam requires to be applied under a variety of conditions and depending on weather fluctuations of temperature and humidity can affect the adhesion of the polyurethane product to the substrate. Rigid polyurethane spray foam typically cracks from the substrate when spraying is carried out at relatively low temperature (less than 10°C). Cracking between the substrate and the rigid polyurethane spray foam allows air and moisture to enter the interface of foam and substrate reducing the thermal insulation efficiency of the foam. In some extreme cases, cracking could even prevent the foam layer to adhere to the substrate effectively making the foam layer to further pull away from the substrate causing complete failure of spray foam application.

[0007] Similarly, during the manufacture of appliance parts, polyurethane material is injected as liquid mixture in a steel outer case that is coated with a plastic inner liner typically made of high impact polystyrene polymer (HIPS). The liquid reacting

polyurethane polymer is injected over a short period of time normally about 30 seconds and its volume expands over 25 to 35 times filling the space between the liner-outer case walls. The polyurethane polymer expands from its initial liquid state to a flowable foaming mass that fills every cavity and crevice in the mold creating an airtight environment needed for high performing insulating materials. The polyurethane rigid foam also provides mechanical strength and structural integrity to appliances besides thermal insulation. In order to achieve an airtight insulating structure where air or gas convection is minimized to reduce thermal conductivity, it is essential to have strong adhesive bonding between the polyurethane material and the liner-outer case wall. Promoting good adhesion between the inner liner and the polyurethane foam requires a good balance between polymerization reaction kinetics, ability of the polyurethane polymer to wet the surface, control over the rate of viscosity change as well as chemical affinity between the polyurethane polymer and the liner material.

[0008] Current available solutions to this problem include using special catalysts such as 1 -methylimidazole, 1 ,2-dimethylimidazole and N,N-dimethylbenzylamine. However, these catalysts have certain limitations including undesired emanations and odor from foam particularly when spraying at lower temperatures where the required use level is higher.

[0009] Appliance manufacturers typically use N, N-dimethylbenzylamine to promote adhesion between polyurethane foam and the appliance mold liner but this product has high vapor pressure and strong amine odor. Other compounds used include 1 - methylimidazole and 1 ,2-dimethylimidazole but they are more costly and they do not provide a solution to the amine odor. Furthermore, these solutions are based on amine catalysts that can be potentially detrimental to premixes and polyurethane foam systems containing low GWP blowing agents such as hydrofluoroolefins and hydrochloroolefins.

[0010] Thus, there is a need in the polyurethane industry for additives able to provide premixes that are stable towards polyester polyols, flame-retardants, halogen containing blowing agents and in particular premixes that are stable towards HFOs. There is also a need in the industry to provide additives able to improve adhesion of polyurethane towards various substrates such as wood, concrete, gypsum, composite materials such as oriented strand boards, steel and other metals to give finished products characterized by having low emissions or no emissions and low amine odor or no amine odor.

Furthermore, there is a need for additives able to promote good adhesion between the inner liner and the polyurethane foam in appliance manufacturing to provide insulating parts that are airtight and with excellent insulation performance.

[0011] The focus of the present invention is on additives that can enhance the adhesion of polyurethane foam polymers to various sources using additives that are not based on volatile amines or compounds that can be detrimental to the polyurethane premix or system and therefore have no amine odor and have no impact on low GWP blowing agent degradation.

[0012] US Patent No. 5,100,927 discloses a process for producing rigid polyurethane foam by reducing the amount of CFC in the presence of water as blowing agent. The patent does not teach the use of low GWP blowing agents such as HFOs, haloolefins and hydrohaloolefins together with the catalysts of the present invention.

[0013] US Patent No. 8,513,318 discloses a process for producing a rigid polyurethane foam using HFC together with water as a blowing agent. The patent does not teach the use of HFOs, haloolefins and hydrohaloolefins and other low GWP blowing agents together with the catalysts of the invention.

[0014] US Patent No. 5,104,907 discloses a process for producing flexible high resilience polyurethane foam by using imidazole compounds as catalysts.

[0015] The disclosure of the previously identified patents are hereby incorporated by reference.

BRIEF SUMMARY OF THE INVENTION

[0016] The instant invention can solve problems associated with conventional foam precursors by permitting the use of the inventive additives thereby improving the storage stability of an isocyanate reactive mixture comprising polyester polyols, and various blowing agents including pentane, halogen containing molecules such as

chrolofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrochloroolefins (HCOs), hydrochlorofluoroolefins (HCFOs), haloolefins and hydrohaloolefins in general. The invention is particularly useful when using HFOs and haloolefin blowing agents in general. [0017] The present invention provides a novel polyurethane additive composition having the following benefits: a) promoting adhesion of spray polyurethane foam onto substrates under cold weather conditions as well as promoting adhesion with liner in appliance parts; b) minimizing polyester polyol, flame retardant and blowing agent degradation in the premix mixture; c) minimizing HFOs, haloolefins and hydrohaloolefins degradation of the premix allowing the use of low GWP blowing agents; and d) minimizing or eliminating amine odor due to the replacement of adhesion promoting amine catalysts.

[0018] The additive composition is defined as at least one compound selected from the following groups:

a. Aromatic ethers of general formula R-(CH2)x-Z-(CH ₂ )y-R’ where R = substituted or unsubstituted aryl group; Z = O or R”-N with R” = CrC ₈ alkyl group, and preferentially methyl or benzyl; x = 0-3; y = 0-3; and R’ = substituted or unsubstituted aryl group where the substituents are non isocyanate reactive groups or a CrC ₈ alkyl group;

b. Aromatic ethers of general formula R-O-Aryl-O-R’ where R = CrC ₈ hydrocarbon; R’ = CrC ₆ hydrocarbon; and aryl = alkyl/aryl substituted or unsubstituted where the substituents are non-isocyanate reactive groups; c. Aromatic esters of general formula R-0 ₂ C-Aryl-C0 ₂ -R’ where R = CrC ₆ hydrocarbon; R’ = CrC ₆ hydrocarbon; and aryl = substituted or unsubstituted aryl group where the substituents are non-isocyanate reactive groups; and

d. Substituted aromatic compounds of the general formula R _x -Aryl where R = Ci-C ₆ hydrocarbon; x = 1 -6; and aryl = substituted or unsubstituted aromatic derived from benzene, naphthalene, anthracene, or phenanthrene.

[0019] The various aspects and embodiments herein can be used alone or in combinations with each other.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 shows a rigid polyurethane sample prepared according to example 2 for adhesion testing.

[0021] Figure 2 shows the peeling force for various organic aromatic compounds according to example 3.

[0022] Figure 3 shows the peeling force for DBA (di-benzylamine) at various use levels according to example 4. [0023] Figure 4 shows the peeling force for BA (benzylamine), DBA (di-benzylamine), TBA (tri-benzylamine) and BE (di-benzylether) at a constant use level according to example 5.

DEFINITIONS

[0024] The following definitions are provided in order to aid those skilled in the art in understanding the detailed description of the present invention.

PUR - Polyurethane.

Isocyanate Index - The actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100. Also known as (Eq NCO/Eq of active hydrogen)x100.

pphp - parts by weight per hundred weight parts polyol.

DMI - 1 ,2-dimethylimidazole

BDMA - Benzyl dimethylamine

DABCO® 2039 catalyst from Evonik Corp. is a 50% solution of 1 ,2- dimethylimidazole in dipropylene glycol.

Polycat®-77 catalyst from Evonik Corp. is a polyurethane catalyst, known chemically as pentamethyldipropylenetriamine.

DETAILED DESCRIPTION OF THE INVENTION

[0025] The present invention is directed to a novel additive composition comprising at least one compound defined according to the general formula described below under a, b, c and d.

[0026] Thus, the additive composition is defined as at least one compound selected from the following groups:

a. Aromatic ethers of general formula R-(CH ₂ )x-Z-(CH ₂ )y-R’ where R = substituted or unsubstituted aryl group; Z = O or R”-N with R” = CrC ₈ alkyl group, and preferentially methyl or benzyl; x = 0-3; y = 0-3; and R’ = substituted or unsubstituted aryl group where the substituents are non isocyanate reactive groups or a CrC ₈ alkyl group;

b. Aromatic ethers of general formula R-O-Aryl-O-R’ where R = CrC ₈ hydrocarbon; R’ = CrC ₆ hydrocarbon; and aryl = alkyl/aryl substituted or unsubstituted where the substituents are non-isocyanate reactive groups; c. Aromatic esters of general formula R-0 ₂ C-Aryl-C0 ₂ -R’ where R = CrC ₆ hydrocarbon; R’ = CrC ₆ hydrocarbon; and aryl = substituted or unsubstituted aryl group where the substituents are non-isocyanate reactive groups; and

d. Substituted aromatic compounds of the general formula R _x -Aryl where R = Ci-C ₆ hydrocarbon; x = 1 -6; and aryl = substituted or unsubstituted aromatic derived from benzene, naphthalene, anthracene, or phenanthrene.

[0027] In one embodiment, the aromatic ether of general formula R-(CH ₂ )x-Z-(CH ₂ )y-R’ is selected from the group consisting of di(benzyl) ether, di(phenyl) ether, di(mesityl) ether, di(xylene) ether, benzyl methyl ether, phenyl methyl ether, phenyl ethyl ether, phenyl propyl ether, dibenzylamine, N-methyldibenzylamine, and tribenzylamine.

[0028] In one embodiment, the aromatic ether of general formula R-O-Aryl-O-R’ is selected from the group consisting of 1 ,2-dimethoxybenzene, 1 ,3-dimethoxybenzene and 1 ,4-dimethoxybenzene.

[0029] In one embodiment, the substituted aromatic compound of the general formula R _x -Aryl is selected from the group consisting of mesitylene and xylene.

[0030] The composition provides a novel polyurethane additive composition having the following benefits: a) promoting adhesion of spray polyurethane foam onto substrates under cold weather conditions as well as promoting adhesion with liner in appliance parts; b) minimizing polyester polyol, flame retardant and blowing agent degradation in the premix mixture; c) minimizing HFOs, haloolefins and hydrohaloolefins degradation of the premix allowing the use of low GWP blowing agents; and d) minimizing or eliminating amine odor due to the replacement of adhesion promoting amine catalysts.

[0031] Adhesion to a typical rigid foam formulation was measured in accordance with the procedure described in Example 1 .

[0032] Further, the present invention also is directed to novel compositions comprising the contact product of at least one active hydrogen-containing compound, at least one blowing agent, and an additive composition comprising compounds as defined above in a, b, c and/or d.

[0033] Additionally, the present invention is directed to novel compositions comprising the contact product of at least one polyisocyanate, at least one blowing agent, and an additive composition as defined above in a, b, c and/or d in combination with a tertiary amine having or not an isocyanate reactive group. These novel compositions can be used together with additional components to produce polyurethane foams. [0034] Also, the present invention provides a method for preparing a polyurethane foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of an additive composition as defined above in a, b, c and/or d in combination with a tertiary amine having or not an isocyanate reactive group.

[0035] Additionally, polyurethane foams can be produced with the additive combination and novel compositions resulting from them by several methods known within the art.

[0036] A chemical composition comprising additives as defined above in a, b, c and/or d in combination with a tertiary amine having or not an isocyanate reactive group can be used to catalyze the reaction between isocyanates and polyols to produce polyurethane foam.

[0037] Generally, any amount of additives as defined above in a, b, c and/or d can be used in the compositions of the present invention.

[0038] Applicants disclose several types of ranges in the present invention. These include, but are not limited to, a range of temperatures; a range of number of atoms; a range of foam density; a range of isocyanate indexes; and a range of pphp for the blowing agent, water, surfactant, flame retardant, and additive composition as defined above in a, b, c and/or d

[0039] When Applicants disclose or claim a range of any type, Applicants’ intent is to disclose or claim individually each possible number that such a range could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein. For example, when the Applicants disclose or claim a chemical moiety having a certain number of carbon atoms, Applicants’ intent is to disclose or claim individually every possible number that such a range could encompass, consistent with the disclosure herein.

[0040] For example, the disclosure that R is each independently CrC ₆ alkyl group cycloalkyl, alkenyl, alkynyl, aryl, or aralkyl, any of which are substituted or unsubstituted mean for example that an alkyl group having up to 6 carbon atoms, or in alternative language a Ci to C ₆ alkyl group, as used herein, refers to a“R” group that can be selected independently from an alkyl group having 1 , 2, 3, 4, 5 or 6 carbon atoms, as well as any range between these two numbers (for example, a Ci to C ₄ alkyl group), and also including any combination of ranges between these two numbers (for example, a Ci to C ₃ and C ₄ to C ₆ alkyl group).

[0041] Similarly, another representative example follows for the parts by weight of the additive composition as defined above in a, b, c and/or d per hundred weight parts of the at least one active hydrogen-containing compound in a composition or a foam formulation. If the at least one active hydrogen-containing compound is an at least one polyol, the parts by weight per hundred weight parts polyol is abbreviated as pphp.

Hence, by the disclosure that the additive composition as defined above in a, b, c and/or d is present in an amount from about 0.05 to about 10 pphp, for example, Applicants intend to recite that the pphp can be selected from about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.1 , about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1 , about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these two examples.

[0042] Applicants reserve the right to proviso out or exclude any individual members of any such group, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application. Further, Applicants reserve the right to proviso out or exclude any individual substituents, analogs, compounds, ligands, structures, or groups thereof, or any members of a claimed group, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application.

[0043] In another aspect of the invention, the additive compositions can be used to make rigid foams (foam that is unable to bend or be forced out of shape) having a density of about 0.5 lb/ft ³ to about 5 lb/ft ³ , about 1 lb/ft ³ to about 4 lb/ft ³ and in some cases about 2 lb/ft ³ to about 3 lb/ft ³ . The additive compositions were used to make close celled spray foam having desirable adhesion to wood. Foam adhesion was measured using the protocol described in Example 1 using standards 1 ,2-dimethylmidazole and dimethylbenzylamine. In a further aspect, the additive compositions can be used to make spray foams having a density of about 0.5 lb/ft ³ to about 5 lb/ft ³ , about 1 lb/ft ³ to about 4 lb/ft ³ and in some cases about 2 lb/ft ³ to about 3 lb/ft ³ . Density was measured in accordance with ASTM D3574 Test A.

[0044] In one aspect of the invention, the additive composition as defined above in a, b, c and/or d comprises at least one member selected from the group consisting of 1 ,2- di(methoxy)benzene, 1 ,3-di(methoxy)benzene, 1 ,4-di(methoxy)benzene,

di(methyl)phthalate, dimethylisophthalate, di(methyl)terephthalate, 1 ,2- di(ethoxy)benzene, 1 ,3-di(ethoxy)benzene, 1 ,4-di(ethoxy)benzene, di(ethyl)phthalate, diethylisophthalate, di(ethyl)terephthalate,1 ,2-di(propoxy)benzene, 1 ,3- di(propoxy)benzene, 1 ,4-di(propoxy)benzene, di(propyl)phthalate, di(propyl)isophthalate, di(propyl)terephthalate,1 ,2-di(butoxy)benzene, 1 ,3-di(butoxy)benzene, 1 ,4- di(butoxy)benzene, di(butyl)phthalate, di(butyl)isophthalate, di(butyl)terephthalate, di(phenyl)ether, di(benzyl)ether, di(mesityl)ether, di(xylene)ether, di(phenylethyl)ether, di(phenylpropyl)ether, di(phenylbutyl)ether, phenyl-methyl-ether, benzyl-methyl-ether, phenylethyl-methyl-ether, phenylpropyl-methyl-ether, phenylbutyl-methyl-ether, phenyl- ethyl-ether, benzyl-ethyl-ether, phenylethyl-ethyl-ether, phenylpropyl-ethyl-ether, phenylbutyl-ethyl-ether, phenyl-propyl-ether, benzyl- propyl-ether, phenylethyl- propyl- ether, phenylpropyl- propyl-ether, phenylbutyl-propyl -ether, phenyl-butyl-ether, benzyl- butyl-ether, phenylethyl- butyl-ether, phenylpropyl- butyl-ether, phenylbutyl- butyl-ether, mesitylene, 2-ethyltoluene, 3-ethyltoluene, 2-propyltoluene, 3-propyltoluene, xylene, 1 ,3- diethylbenzene, 1 ,3,5-triethylbenzene, dibenzylamine, N-methyldibenzylamine, tribenzylamine and the like. Such compounds can be employed individually or in any combination thereof.

[0045] The additive composition as defined above in a, b, c and/or d can be used in combination with at least one tertiary amine having at least one isocyanate reactive group comprising a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group or an amide group. Examples of tertiary amine catalysts having an isocyanate reactive group include, but are not limited to N, N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N, N-dimethylaminoethyl-N'- methyl ethanolamine, N, N, N'-trimethylaminopropylethanolamine, N, N- dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethyl-N', N'-2-hydroxy(propyl)- 1 ,3-propylenediamine, dimethylaminopropylamine, (N, N-dimethylaminoethoxy) ethanol, methyl-hydroxy-ethyl-piperazine, bis(N, N-dimethyl-3-aminopropyl) amine, N, N- dimethylaminopropyl urea, diethylaminopropyl urea, N, N'-bis(3- dimethylaminopropyl)urea, N, N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2- propanol, 6-dimethylamino-1 -hexanol, N-(3-aminopropyl) imidazole), N-(2-hydroxypropyl) imidazole, and N-(2-hydroxyethyl) imidazole, 2-[N-(dimethylaminoethoxyethyl)-N- methylamino] ethanol, N, N-dimethylaminoethyl-N'-methyl-N'-ethanol,

dimethylaminoethoxyethanol, N, N, N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, or a combination thereof. The weight ratio of suitable tertiary amines to the inventive additive can range from about 0 to about 100, about 0.1 to about 50 and in some cases about 1 to about 10. [0046] The inventive additive can also be acid blocked with an acid including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acids or any other organic or inorganic acid. Examples of carboxylic acids include mono-acids, di acids or poly-acids with or without isocyanate reactive groups. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid and the like. An acid blocked additive can be obtained by known methods using conventional equipment.

[0047] Illustrative examples of alkali metal, alkaline earth metal, and quaternary ammonium carboxylate salts include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium pivalate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium neodecanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octoate, lithium stearate, sodium caprioate, lithium octoate,

tetramethylammonium pivalate (commercially available as the Dabco® TMR7 catalyst), 2-hydroxypropyltrimethylammonium octoate solution, and the like, or any combination thereof.

[0048] The amount of the other catalytic materials and salts can range from about 0 pphp to about 20 pphp, about 0.1 pphp to about 15 pphp and in some cases about 0.5 pphp to about 10 pphp.

[0049] It is also within the scope of the additive composition of this invention to include mixtures or combinations of one or more catalysts added to the additive composition as defined above in a, b, c and/or d . Additionally, the catalyst system or the novel compositions of the present invention can also further comprise at least one urethane catalyst having no isocyanate reactive groups.

[0050] The term“contact product” is used herein to describe compositions wherein the components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. Further, contacting of any component can occur in the presence or absence of any other component of the compositions or foam formulations described herein. Combining catalyst components to the additive composition can be done by any method known to one of skill in the art. For example, in one aspect of the present invention, catalyst compositions can be prepared by combining or contacting the additive composition as defined above in a, b, c and/or d with at least one tertiary amine having or not at least one isocyanate reactive group and optionally with an alkali metal carboxylate salt. This typically occurs in solution form.

[0051] While compositions and methods are described in terms of“comprising” various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components or steps.

POLYISOCYANATES

[0052] Polyisocyanates that are useful in the PIR/PUR foam formation process include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyante, toluene diisocyanate (TDI), diphenyl methane diisocyanate isomers (MDI), hydrated MDI and 1 ,5-naphthalene diisocyanate. For example, 2,4-TDI, 2,6-TDI, and mixtures thereof, can be readily employed in the present invention. Other suitable mixtures of diisocyanates include, but are not limited to, those known in the art as crude MDI, or PAPI, which contain 4,4’-diphenylmethane diisocyanate along with other isomeric and analogous higher polyisocyanates. In another aspect of this invention, prepolymers of polyisocyanates comprising a partially pre-reacted mixture of

polyisocyanates and polyether or polyester polyol are suitable. In still another aspect, the polyisocyanate comprises MDI, or consists essentially of MDI or mixtures of MDIs.

[0053] The catalyst system, compositions, and methods of producing PIR/PUR foam of the present invention can be used to manufacture many types of foam. This catalyst system is useful, for example, in the formation of foam products for rigid and flame retardant applications, which usually require a high Isocyanate Index. As defined previously, Isocyanate Index is the actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture, multiplied by 100. For purposes of the present invention, Isocyanate Index is represented by the equation: Isocyanate Index = (Eq NCO/Eq of active hydrogen)x100, wherein Eq NCO is the number of NCO functional groups in the polyisocyanate, and Eq of active hydrogen is the number of equivalent active hydrogen atoms. [0054] Foam products which are produced with an Isocyanate Index from about 10 to about 800 are within the scope of this invention. In accordance with other aspects of the present invention, the Isocyanate Index ranges from about 20 to about 700, from about 30 to about 650, from about 50 to about 600, or from about 70 to about 500.

POLYOLS

[0055] Active hydrogen-containing compounds for use with the foregoing

polyisocyanates in forming the polyisocyanurate/polyurethane foams of this invention can be any of those organic compounds having at least two hydroxyl groups such as, for example, polyols. Polyols that are typically used in PIR/PUR foam formation processes include polyalkylene ether and polyester polyols. The polyalkylene ether polyol includes the poly(alkyleneoxide) polymers such as poly(ethyleneoxide) and poly(propyleneoxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols, These include, but are not limited to, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, cyclohexane diol, and sugars such as sucrose and like low molecular weight polyols.

[0056] Amine polyether polyols can be used in the present invention. These can be prepared when an amine such as, for example, ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, or triethanolamine is reacted with ethylene oxide or propylene oxide.

[0057] In another aspect of the present invention, a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols, such as mixtures of different multifunctional materials and/or different molecular weight or different chemical composition materials can be used.

[0058] In yet another aspect of the present invention, polyester polyols can be used, including those produced when a dicarboxylic acid is reacted with an excess of a diol. Non-limiting examples include adipic acid or phathalic acid or phthalic anhydride reacting with ethylene glycol or butanediol. Polyols useful in the present invention can be produced by reacting a lactone with an excess of a diol, for example, caprolactone reacted with propylene glycol. In a further aspect, active hydrogen-containing compounds such as polyester polyols and polyether polyols, and combinations thereof, are useful in the present invention. [0059] The polyol can have an OH number of about 5 to about 600, about 100 to about 600 and in some cases about 50 to about 100 and a functionality of about 2 to about 8, about 3 to about 6 and in some cases about 4 to about 6.

[0060] The amount of polyol can range from about 0 pphp to about 100 pphp, about 10 pphp to about 90 pphp and in some cases about 20 pphp to about 80 pphp.

BLOWING AGENTS

[0061] In accordance with the compositions, foam formulations, and methods of producing PIR/PUR foam within the scope of the present invention, suitable blowing agents that can be used alone or in combination include, but are not limited to, water, methylene chloride, acetone, hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrofluoroolefins (HFOs), chlorofluoroolefins (CFOs), hydrochloroolefins (HCOs), hydrofluorochloroolefins (HFCOs), hydrochlorofluorocarbons (HCFCs), chloroolefins, formates, and hydrocarbons. Examples of HFCs include, but are not limited to, HFC- 245fa, HFC-134a, and HFC-365; illustrative examples of HCFCs include, but are not limited to, HCFC-141 b, HCFC-22, and HCFC-123. Exemplary hydrocarbons include, but are not limited to, n-pentane, iso-pentane, cyclopentane, and the like, or any combination thereof. In one aspect of the present invention, the blowing agent or mixture of blowing agents comprises at least one hydrocarbon. In another aspect, the blowing agent comprises n-pentane. Yet, in another aspect of the present invention, the blowing agent consists essentially of n-pentane or mixtures of n-pentane with one or more blowing agents. Examples of hydrohaloolefin blowing agents are HFO-1234ze (trans-1 ,3,3,3- Tetrafluoroprop-1 -ene), HFO-1234yf (2,3,3,3-Tetrafluoropropene) and HFCO-1233zd (1 - Propene,1 -chloro-3,3,3-trifluoro), among other HFOs.

[0062] Due to the discovery that chlorofluorocarbons (CFCs) can deplete ozone in the stratosphere, this class of blowing agents is not desirable for use in general. A chlorofluorocarbon (CFC) is an alkane in which all hydrogen atoms are substituted with chlorine and fluorine atoms. Examples of CFCs include trichlorofluoromethane and dichlorodifluoromethane.

[0063] The amount of blowing agent used can vary based on, for example, the intended use and application of the foam product and the desired foam stiffness and density. In the compositions, foam formulations and methods for preparing a

polyisocyanurate/polyurethane foam of the present invention, the blowing agent is present in amounts from about 5 to about 80 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. In another aspect, the blowing agent is present in amounts from about 10 to about 60, from about 15 to about 50, or from about 20 to about 40, parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. If the at least one active hydrogen-containing compound is an at least one polyol, the blowing agent is present in amounts from about 5 to about 80 parts by weight per hundred weight parts polyol (pphp), from about 10 to about 60 pphp, from about 15 to about 50 pphp, or from about 20 to about 40 pphp.

[0064] If water is present in the formulation, for use as a blowing agent or otherwise, water is present in amounts up to about 60 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound. Likewise, if the at least one active hydrogen-containing compound is an at least one polyol, water can range from 0 to about 15 pphp. In another aspect, water can range from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, or from 0 to about 4 pphp.

URETHANE CATALYST

[0065] Conventional urethane catalysts having no isocyanate reactive group can be employed to accelerate the reaction to form polyurethanes, and can be used as a further component of the catalyst systems and compositions of the present invention to produce polyisocyanurate/polyurethane foam. Urethane catalysts suitable for use herein include, but are not limited to, metal salt catalysts, such as organotins, and amine compounds, such as triethylenediamine (TEDA), N-methylimidazole, 1 ,2-dimethyl-imidazole, N- methylmorpholine (commercially available as the DABCO ^® NMM catalyst), N- ethylmorpholine (commercially available as the DABCO ^® NEM catalyst), triethylamine (commercially available as the DABCO ^® TETN catalyst), N,N’-dimethylpiperazine, 1 ,3,5- tris(dimethylaminopropyl)hexahydrotriazine (commercially available as the Polycat ^® 41 catalyst), 2,4,6-tris(dimethylaminomethyl)phenol (commercially available as the DABCO TMR ^® 30 catalyst), N-methyldicyclohexylamine (commercially available as the Polycat ^® 12 catalyst), pentamethyldipropylene triamine (commercially available as the Polycat ^® 77 catalyst), N-methyl-N’-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl- diethylenetriamine (commercially available as the Polycat ^® 5 catalyst), hexamethyl- triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl- amine (commercially available as the Polycat ^® 8 catalyst), pentamethyldipropylene- triamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether

(commercially available as the DABCO ^® BL19 catalyst), tris(3-dimethylamino)- propylamine (commercially available as the Polycat ^® 9 catalyst), 1 ,8-diazabicyclo[5.4.0] undecene (commercially available as the DABCO ^® DBU catalyst) or its acid blocked derivatives, and the like, as well as any mixture thereof. Particularly useful as a urethane catalyst for foam applications related to the present invention is the Polycat ^® 5 catalyst, which is known chemically as pentamethyldiethylenetriamine.

[0066] The additive of the present invention can be used with tertiary amines catalysts having isocyanate reactive groups. Isocyanate reactive groups present in the alternative tertiary amine gelling co-catalyst consist essentially of primary amine, secondary amine, secondary-hydroxyl group, amide and urea. Examples of gelling catalysts include N,N- bis(3-dimethylamino-propyl)-N-(2-hydroxypropyl) amine; N,N-dimethyl-N’,N’-bis(2- hydroxypropyl)-1 ,3-propylenediamine;dimethylaminopropylamine (DMAPA); N-methyl-N- 2-hydroxypropyl-piperazine, bis(dimethylaminopropyl)amine (POLYCAT® 15), dimethylaminopropylurea and N,N’-bis(3-dimethylaminopropyl) urea (DABCO® NE1060, DABCO® NE1070, DABCO® NE1080 and DABCO® NE1082), 1 ,3-bis(dimethylamino)- 2-propanol, 6-dimethylamino-1 -hexanol, N-(3-aminopropyl)imidazole, N-(2- hydroxypropyl)imidazole, N,N’-bis(2-hydroxypropyl) piperazine, N-(2-hydroxypropyl)- morpholine, N-(2-hydroxyethylimidazole). Examples of blowing co-catalysts containing isocyanate reactive groups that can be used with the above mentioned gelling catalysts include 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol (DABCO® NE200), N,N,N’-trimethyl-N’-3-aminopropyl-bis(aminoethyl) ether (DABCO® NE300). The catalyst compositions may also include other components, for example transition metal catalysts such as organotin compounds or bismuth carboxylates. Metal catalysts can also comprise at least one member selected from the group consisting of dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin

dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-thylhexyl mercaptacetate), dibutyltin bi(2-thylhexyl mercaptacetate), stannous octate, other suitable organotin catalysts, or a combination thereof. Other metals can also be included, such as, for example, bismuth (Bi). Suitable bismuth carboxylate salts includes salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid,

neododecanoic acid, and other suitable carboxylic acids. Other salts of transition metals of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included. [0067] For preparing a polyisocyanurate/polyurethane foam of the present invention, the urethane catalyst can be present in the formulation from 0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, from 0 to about 4 pphp, from 0 to about 2 pphp, or from 0 to about 1 pphp. In another aspect, the urethane catalyst is present from 0 to about 0.8 pphp, from 0 to about 0.6 pphp, from 0 to about 0.4 pphp, or from 0 to about 0.2 pphp.

MISCELLANEOUS ADDITIVES

[0068] Depending on the requirements during foam manufacturing or for the end-use application of the foam product, various additives can be employed in the PIR/PUR foam formulation to tailor specific properties. These include, but are not limited to, cell stabilizers, flame retardants, chain extenders, epoxy resins, acrylic resins, fillers, pigments, or any combination thereof. It is understood that other mixtures or materials that are known in the art can be included in the foam formulations and are within the scope of the present invention.

[0069] Cell stabilizers include surfactants such as organopolysiloxanes. Silicon surfactants can be present in the foam formulation in amounts from about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 to about 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp, about 1 to about 5 pphp, or about 1.1 to about 4 pphp. Useful flame retardants include halogenated organophosphorous compounds and non- halogenated compounds. A non-limiting example of a halogenated flame retardant is trichloropropylphosphate (TCPP). For example, triethylphosphate ester (TEP) and DMMP are non-halogenated flame retardants. Depending on the end-use foam application, flame retardants can be present in the foam formulation in amounts from 0 to about 50 pphp, from 0 to about 40 pphp, from 0 to about 30 pphp, or from 0 to about 20 pphp. In another aspect, the flame retardant is present from 0 to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5 pphp. Chain extenders such as ethylene glycol and butane diol can also be employed in the present invention. Ethylene glycol, for instance, can also be present in the formulation as a diluent or solvent for the carboxylate salt catalysts of the present invention.

POLYURETHANE FOAM FORMULATION AND PROCESS

[0070] One aspect of the present invention provides for a composition comprising the contact product of at least one active hydrogen-containing compound, at least one blowing agent, and at least one additive composition as defined above in a, b, c and/or d.

[0071] Another aspect provides a composition comprising the contact product of at least one polyisocyanate, at least one blowing agent, and at least one additive composition as defined above in a, b, c and/or d used in combination with at least one tertiary amine having at least one isocyanate reactive group.

[0072] Another aspect provides a composition comprising the contact product of at least one polyisocyanate, at least one blowing agent, and at least one additive composition as defined above in a, b, c and/or d used in combination with at least one tertiary amine having no isocyanate reactive group.

[0073] The composition can further comprise additive composition as defined above in a, b, c and/or d with at least one urethane catalyst having no isocyanate reactive group and at least one urethane catalyst having an isocyanate reactive group. Likewise, the compositions can further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any

combination thereof.

[0074] The present invention provides a method for preparing a polyurethane foam as well as a polyisocyanurate/polyurethane (PIR/PUR) foam which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound, in the presence of at least one blowing agent and an effective amount of additive composition as defined above in a, b, c and/or d . In accordance with the method of the present invention, PUR as well as PIR/PUR foams can be produced having a density from about 16 Kg/m ³ to about 250 Kg/m ³ (about 0.5 lb/ft ³ to about 15.5 lb/ft ³ ), or from about 24 Kg/m ³ to about 60 Kg/m ³ (about 1 .5 lb/ft ³ to about 3.75 lb/ft ³ ).

[0075] The instant invention can be used in a wide range of methods for making rigid closed-cell foams as well as rigid open cell foams. Examples of suitable methods comprise molding, spraying, among other rigid foam production methods. In one aspect the inventive method relates to a method for making a laminated foam. The inventive foam can be laminated to a wide range of substrates including wood, steel, paper and plastic.

[0076] The method for preparing PUR as well as PIR/PUR foams also can provide equivalent or faster surface cure when compared to other commercially available catalyst systems, such that the PUR as well as the PIR/PUR foam has enhanced surface adherence, useful for the production of articles such as laminated foam panels. [0077] Optionally, in yet another aspect, the method of the present invention can produce PUR as well as PIR/PUR foams with no or substantially no undesirable amine odor. In a still further aspect, the method of the present invention produces PIR/PUR foam that is substantially free of volatile amines and/or amine odors.

[0078] The additive composition as defined above in a, b, c and/or d should be present in the foam formulation in an effective amount. In PUR as well as in PIR/PUR foam formulations of the present invention, the additive composition is present in amounts from about 0.05 to about 20 parts by weight per hundred weight parts of the at least one active hydrogen-containing compound, excluding the weight contribution of the additive system diluent if applicable. In another aspect, the additive composition is present in amounts from about 0.4 to about 10 parts, or from about 0.8 to about 8 parts, by weight per hundred weight parts of the at least one active hydrogen-containing compound. If the at least one active hydrogen-containing compound is an at least one polyol, the catalyst composition is present in amounts from about 0.05 to about 10 parts by weight per hundred weight parts polyol (pphp). In another aspect, the additive composition is present in amounts from about 0.2 to about 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp, or about 0.8 to about 8 pphp.

[0079] In accordance with one aspect of the method of the present invention, the components of the foam formulation are contacted substantially contemporaneously.

For example, at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, an effective amount of catalyst composition and an effective amount of additive composition as defined above in a, b, c and/or d , are contacted together. Given the number of components involved in PUR and PIR/PUR formulations, there are many different orders of combining the components, and one of skill in the art would realize that varying the order of addition of the components falls within the scope of the present invention. As well, for each of the different orders of combining the aforementioned components of the foam formulation, the foam formulation of the present invention can further comprise at least one urethane catalyst. In addition, the method of producing PIR/PUR foams can further comprise the presence of at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof. In one aspect of the present invention, all of the components, including optional components, are contacted substantially contemporaneously. [0080] In another aspect of the present invention, a premix of ingredients other than the at least one polyisocyanate are contacted first, followed by the addition of the at least one polyisocyanate. For example, the at least one active hydrogen-containing compound, the at least one blowing agent, and the additive composition of the present invention are contacted initially to form a premix. The premix is then contacted with the at least one polyisocyanate to produce PUR or PIR/PUR foams in accordance with the method of the present invention. In a further aspect of the present invention, the same method can be employed, wherein the premix further comprises at least one urethane catalyst. Likewise, the premix can further comprise at least one additive selected from at least one cell stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0081] One aspect of the present invention provides a method for preparing a polyisocyanurate/polyurethane foam comprising (a) forming a premix comprising:

i) at least one polyol;

ii) about 10 to about 80 parts by weight per hundred weight parts of the polyol (pphp) blowing agent;

iii) about 0.5 to about 10 pphp silicon surfactant;

iv) zero to about 60 pphp water;

v) zero to about 50 pphp flame retardant;

vi) zero to about 10 pphp urethane catalyst; and

vii) about 0.05 to about 20 pphp of additive composition as defined above in a, b, c and/or d; and

(b) contacting the premix with at least one polyisocyanate at an Isocyanate Index from about 10 to about 800.

EXAMPLES

[0082] These Examples are provided to demonstrate certain aspects of the invention and shall not limit the scope of the claims appended hereto.

[0083]

Examples 1 and 2 describe the method and result of lab adhesion testing by using a lamination formulation. EXAMPLE 1

Use Levels for Lamination Formulation

[0084] Using the formulation shown in Table 1 below, a master batch of premix-1 (1 ,150 g) was prepared in a 1.89 L Nalgene container by mixing all the ingredients except the isocyanate, blowing agent and catalyst for 15 seconds with a 7.6 cm mixing blade at roughly 3000 rpms using an Indco Mixer, model HSL-4. A master batch premix- 2 (929.1 g) was prepared in a separate 950 mL Nalgene container by mixing isocyanate (Rubinate M, 900.6 g) and blowing agent (n-pentane, 28.5 g). The lid was tightly closed on the 950 mL container and the bottle was shaken vigorously for 30 seconds to blend the isocyanate and pentane. 149.5 g of premix-1 was weighed out into a 1.89 L paper cup and catalyst was added (the weight of catalyst varied and the final use level of each catalyst that provided matched activity was summarized in Table 2) and mixed for 15 seconds using the same blade at roughly 3000 rpms. 21 1.9 g of premix-2 was added to the paper cup containing the mixture of premix-1 and the catalyst. All components were then mixed using the same blade at roughly 3000 rpms, for 6 seconds. This mixture was then poured into a paper bucket (the mixing cup has a height of 20.2 cm and a bottom diameter of 15.5 cm and the top diameter is 21.8 cm), and then the bucket was placed under FOMAT sonar equipment (Format Messtechnik GmbFI) with standard software, to measure the change in height (mm) vs time (seconds) using FOAM software version 3.5/10. Using the FOMAT software, cream time (CT) was first recorded followed by top of the cup (TOC) in seconds once the foaming mass reach the top edge of the bucket. String gel time (SGT, defined as the time in seconds at which the polymerizing mass is able to form polymer strings when touched with a wooden tongue suppressor) was then determined and recorded. Dabco®2039 was the standard catalyst for the formulation in Table 1 and the use level of Dabco®2039 was 1 .70 pphp when SGT was 80 seconds. The use levels in pphp for the experimental catalysts were adjusted to match 80 second SGT. Results were summarized in Table 2.

[0085] Table 1. Rigid Adhesion Lamination Formulation

[0086] Table 2. Catalyst Use Level to Get Approximately 80 Seconds SGT

EXAMPLE 2

Adhesion Testing of Rigid Molded Foam on Paper

[0087] A non-heated 50.8 cm x 50.8 cm x 5.1 cm mold was internally covered by a facer typically used in lamination applications with one side of the facer being aluminum foil and the other side of the facer being brown paper. When the mold is open, the paper side faces the internal part of the mold. Once foam was made, the brown paper side of the facer was in contact with the foam surface. The minimum fill of the mold was defined as the minimum weight of foaming material capable of filling the whole mold including its corners. Foams that are 20% over-pack means foam parts made with 20 % higher foaming mass than the minimum fill mass required to fill all mold space including its corners. These 20 % overpack foam were made and used for the adhesion testing. When making foam pads for actual adhesion testing, a paper/aluminum foil facer was used in lamination pads covering the top and bottom of the mold. Regular aluminum foil was used to cover the sides of the mold. Based on the formulation in Table 1 , catalyst use level in Table 2, and the needed foaming mass to make 20% overpack foam, a mixture of premix-1 , premix-2 and catalyst was prepared in a 1.89 L paper cup according to the same procedure described in example 1. After mixing, the foaming mass was poured into the mold and the mold lid was then closed to make the foam pad. After the 20% over-pack foam pad was made, the foam pad was removed from the mold after 12 minutes (12 minute de-mold time). After foam pad was de-molded, it was stored at constant temperature and humidity (20°C and 50% humidity) conditions for

approximately 24 hours. Foam pad were cut into samples that are 3.8 cm wide and 10 - 15 cm long for adhesion testing (Figure 1 ). Roughly 5 cm from the sides of the foam pad was cut away and discarded. Test samples came from the center of the foam block. Testing was done using a force-to-crush (FTC) machine. The indenter plate of the machine was removed. A spring scale (the scale set was ordered from MiniScience.com with a force range from 250 g to 5,000 g) was hung from a hook on FTC machine and clipped to top foam facer. Machine was turned on at 0.7 speed setting. Facer was pulled off of foam by spring scale and adhesion was measured by the reading on that scale. The unit of the reading is gram. Because the width of the foam sample is 3.8 cm, we used g/3.8 cm as the unit to denote the force required to pull the facer from the foam surface. Cohesive failure between the paper and aluminum foil due to adhesion to foam (paper side of facer being held onto the foam surface while aluminum foil being peeled off from paper) indicated good adhesion (Figure 1 ) and the maximum force recordable. The results were summarized in Table 3. The same procedure was repeated using a mixture of premix-1 , premix-2, catalyst and additive based on the formulation in Table 1 , catalyst use level in Table 4, additive use level in Table 4, and the needed foaming mass to make 20% overpack foam. The results were summarized in Table 4.

[0088] Table 3. Adhesion Testing Result of Standard Catalysts in Lamination Formulation

[0089] Table 4. Adhesion Testing Result of Additives in Lamination Formulation

Epodil®LV5 is an epoxy diluent commercially available from Evonik Corporation used as an adhesion promoter. EXAMPLE 3

Adhesion Testing of Rigid Appliance Formulation on High Impact Polystyrene Polymer (HIPS): Various Aromatic Compounds Including 1 ,2-Dimethoxybenzene, Acetophenone, Dimethylphthalate, Benzylalcohol and Dibenzylamine

[0090] The adhesion between polystyrene and polyurethane foam was measured using an aluminum mold 30 cm x 30 cm x 10 cm heated to 40°C with 3 pieces of HIPS foils 7.5 cm x 20 cm placed at the bottom of the mold. The polyol blend shown in Table 5 was mixed with the corresponding catalysts and blowing agent (cyclopentane) and the mixture was then mixed with polymeric MDI. Approximately 360 g of foaming mass was poured on the mold, over the HIPS foils and the mold was closed while the foaming mass expanded. After four minutes, the appliance foam was demolded and allowed to post-expand. The foil adhesion strength was measured using INSTRON equipment that measured the peeling force in Newtons (N) over the peeled distance (mm).

[0091] Table 5. Rigid Appliance Formulation

[0092] The polyol blend in Table 5 is a mixture of three different polyols: 60 weight % Polyol A sugar based polyol with OH# = 440 and functionality in the 4.0 to 4.5 range; 20 weight % Polyol B sorbitol based polyol with OH # 500 and functionality in the 4.3 to 4.8 range and 20 weight % Polyol C which is a o-toluenediamine based polyol OH# 410 and functionality = 4.

[0093] Adhesion testing measured using the formulation described above and at a constant use level of 2.0 pphp with the following list of compounds:

DMB = 1,2-dimethoxybenzene ATP = Acetophenone DMP = Dimethylphthalate

BA = Benzylalcohol DBA = Dibenzylamine

[0094] All the compounds tested having aromatic moieties provided positive impact on HIPS adhesion to foam but none of the candidates was better than the standard DABCO®BDMA at the same use level of 2.0 pphp. The peeling force for the compounds tested is shown in Chart 1 (see Figure 2).

EXAMPLE 4

Adhesion Testing of Rigid Appliance Formulation on High Impact Polystyrene Polymer (HIPS): Dibenzylamine (DBA) At Various Use Levels

[0095] Dibenzylamine showed an increase in adhesion as measured by an increasing peel force value with increasing use levels. At approximately 5.0 pphp dibenzylamine showed a peel force value of 5.2 N and comparable to benzyldimethylamine (BDMA) value of 4.7 pphp at 2.5 pphp use level. The peeling force at various use levels of dibenzylamine is shown in Chart 2 (see Figure 3).

EXAMPLE 5

Adhesion Testing of Rigid Appliance Formulation on High Impact Polystyrene Polymer (HIPS): Benzylamine (BA), Dibenzylamine (DBA), Tribenzylamine (TBA) and

Dibenzylether (BE)

[0096] Adhesion testing measured at a constant use level of 2.0 pphp in comparison to standard DABCO®BDMA at 2.5 pphp with the following list of compounds:

[0097] The performance of BA (benzylamine), DBA (di-benzylamine), TBA (tri- benzylamine) and BE (di-benzylether) all at the same use level of 2.0 pphp in

comparison to standard DABCO®BDMA at 2.5 pphp is shown in Chart 3 (see Figure 4). Adhesion to HIPS improves, as the central nitrogen atom is further benzylated despite the fact that the MW of the adhesion promoter increases. The presence of reactive =NH ₂ and =NH groups is detrimental for adhesion improvement. Dibenzylether (BE) provides the best adhesion and even superior adhesion than the standard.