Stabilization of incompatible polyol blends

Abstract

The present disclosure provides for a composition that includes a nonionic poloxamer and a polyol blend that is shelf stable. The composition includes a nonionic poloxamer having a linear triblock copolymer poloxamer structure with at least one block formed from ethylene oxide monomers (EO) and at least one block formed from propylene oxide monomers (PO), and a polyol blend that includes two or more incompatible polyols, where each of the two or more incompatible polyols has a weight average molecular weight of 200 to 10,000 g / mol and the wt.% values are based on the total weight of the composition. The present disclosure also provides for a polyurethane article formed with the composition of the present disclosure and an isocyanate.

Description

[0001] STABILIZATION OF INCOMPATIBLE POLYOL BLENDS

[0002] Technical Field

[0003] The present disclosure relates generally to polyol blends and more specifically to the stabilization of incompatible polyol blends.

[0004] Background

[0005] When making polyurethane-based materials, many components are needed, in particular one or more polyols and one or more polyisocyanates along with the possibility of a catalyst(s) and other additives. Some producers of polyurethanes are equipped to handle more than two components. For example, some producers maintain each component in its own tank (e.g. , a first tank for a first polyol, a second tanks for a second polyol, etc. and therefore adjusting the components used in forming the polyurethanes can be done as needed. But there are other producers who are limited to just two component tanks, which usually means one tank will be for the polyisocyanate and the second tank will be for all the other components. This means that the one or more polyol along with the possible catalyst(s) and additives all need to be premixed along with being reasonably blend stable to be useful in producing the polyurethane. The longer that such a mixture can remain blend stable, the more convenient it is for the producer, as re-agitation / re-mixing can be avoided. If stability cannot be achieved, however, there can be problems. For example, the use of phase separated polyol side is detrimental for the resultant polyurethane part due to a false concentration of the target blend in the final product. In addition, certain polyol(s) are also incompatible resulting in liquid-liquid macrophase separation due to difference in their polarity, molecular structure(s), composition(s) of backbone, functionality, concentration (s), viscosity, and molecular weight(s).

[0006] Set against the backdrop of the above discussion, blends of incompatible polyols are often required to produce a desired polyurethane foam of target properties. For example, this can be true in forming high air permeability viscoelastic memory foams. Another example is polyurethane crosslinked elastomer systems that uses a very short chain polyol (e.g., less than about 300 g / mol MW) and a very long chain polyol (e.g., greater than about 4500 g / mol MW). These examples of incompatible polyol blends are problematic in terms of storage and processing due to the need and cost of any of the following: (a) either maintain individual storage tanks for each polyol, and meter the individual components to be blended at the mixer head; (b) have one storage tank with a blend of incompatible polyols that needs to be continuously stirred; and / or (c) the need to stir the polyol blend just prior to PU foam formation. Attempts to stabilize incompatible blends of polyols like the ones discussed above have taken different approaches. For example, co-solvents have been used with incompatible polyols in an attempt to stabilize the blend. Other attempts to stabilize incompatible blends of polyols have included the use of larger amounts of additive(s) and / or compatibilizers. These approaches, however, often negatively impact foam formation be it in form of interference with reaction or hindering bubble stabilization, and the physical or mechanical properties of the resultant foam or non-foam material due to the large amount of additive(s) and / or compatibilizers incorporated into the formulation. As such, there is a continuing need in the art to identify more effective stabilizer or compatibilizer materials that can be used at low loading levels to improve foam formulation stability but not hinder the final foam performance.

[0007] Summary

[0008] The present disclosure provides for stabilizing incompatible polyol blends. Stabilizing incompatible polyol blends in turn allows for the storage of such polyols (e.g., incompatible polyols) without the need for additional storage tanks (e.g., only one tank required for polyol-side) and / or mixing apparatus that can lead to additional costs and time requirements for the manufacturer. In addition to fewer capital costs (e.g., reduced need for mixing and storage systems), there can also be fewer potential quality issues with the resulting polyurethane of the present disclosure due in part to maintaining a stable polyol blend versus having a macroscopic phase separation. The present disclosure allows incompatible polyol blends to be processable (e.g., pumpable) but can dramatically increase their shelf life (ex: sitting in a tank) from 0.5 - 7 days to greater than 3 months. In addition, the stabilizer of the present disclosure, a nonionic poloxamer, is used at a low enough level(s) that it has little to no impact on the formation of the polyurethane product (e.g., the foaming of the polyurethane). In the end, the present disclosure provides a composition that imparts significant advantages in producing a polyurethane (e.g., a polyurethane foam) with fewer required resources due to the stability of the composition and its ability to generate polyurethane (e.g., polyurethane foams) from complex polyol blends containing incompatible materials.

[0009] For the various embodiments, the present disclosure provides for a composition that includes a nonionic poloxamer and a polyol blend that includes two or more incompatible polyols. Specifically, the present disclosure provides for a composition that includes 0.5 to 10 weight percent (wt.%) of the nonionic poloxamer having a linear triblock copolymer poloxamer structure with at least one block formed from ethylene oxide monomers (EO) and at least one block formed from propylene oxide monomers (PO), where the at least one block formed from EO comprises 50 to 90 mole percent (mol.%) of the nonionic poloxamer and the at least one block formed from PO comprises 10 to 50 mol.% of the nonionic poloxamer, and where the nonionic poloxamer has a number average molecular weight of 6,000 to 25,000 gram / mole; and 70 to 90 wt.% of a polyol blend that includes two or more incompatible polyols, where each of the two or more incompatible polyols has a weight average molecular weight of 200 to 10,000 g / mol and the wt.% values are based on the total weight of the composition.

[0010] For the various embodiments, the present disclosure provides for a variety of structures for the linear triblock copolymer poloxamer. For example, in specific embodiments the linear triblock copolymer poloxamer structure consists essentially of at least one block formed from EO and the at least one block formed from PO. For the various embodiments, the linear triblock copolymer poloxamer structure can include one block formed from PO positioned between two blocks formed from EO to provide an EO / PO / EO configuration. In additional embodiments, the linear triblock copolymer poloxamer structure can include one block formed from EO positioned between two blocks formed from PO to provide an PO / EO / PO configuration. With respect to being linear, the linear triblock copolymer poloxamer structure can have a degree of branching value of less than 1 percent. For the various embodiments, the linear triblock copolymer poloxamer structure can also have a number average molecular weight of 6,000 to 15,000 g / mol. For the various embodiments, each of the at least one block of the linear triblock copolymer poloxamer structure formed from EO and the at least one block formed from PO is not a random copolymer.

[0011] For the various embodiments, the nonionic poloxamer of the composition can further include 0.5 to 10 wt.% of an inorganic stabilizer, where the wt.% is based on the total weight of the nonionic poloxamer and the inorganic stabilizer. For the various embodiments, the inorganic stabilizer can be selected from the group consisting of silica, fumed silica, metal carbonates, metal sulphates, metal hydroxides, metal hydrates, metal nitrates, silicates, silica fibers and combinations thereof. For the various embodiments, the inorganic stabilizer can 9 2 have a specific surface area 2 m / g to 500 m / g.

[0012] For the various embodiments, the two or more incompatible polyols can include a first polyol having a weight average molecular weight of less than 500 g / mol and a second polyol having a weight average molecular weight of greater than 1000 g / mol. For the various embodiments, the two or more incompatible polyols include at least one tri-functional polyol and at least one di-functional polyol each having a weight average molecular weight in a range of 200 g / mol to 8,000 g / mol. For the various embodiments, the composition of the present disclosure can further include up to 25 wt.% of one or more additives selected from the group consisting of a filler (e.g., micron and / or nano sized), silica, water, a surfactant (e.g., a silicone polyether), a catalysts (e.g., an amine-based, metal-based, blocked, delayed action, and others), a plasticizer, a chemical blowing agent other than water, a physical blowing agent (e.g., a gas or low boiling point liquid such as CFC, HFC, HFO, various alkanes, acetone, other volatile chemicals) and combinations thereof. For the various embodiments, the shelf stability of the composition of the present disclosure is at least 21 days at room temperature (23 °C), where the wt.% is based on the total weight of the composition. For the various embodiments, the composition of the present disclosure can have an instability index, as determined according to the Examples section herein, of less than (<) 0.65. The composition can also have a complex viscosity at 0.1 % strain, 1 rad / s of less than 75 and a viscosity measured from high to low shear of less than 12.5 at 1 s'1, as determined according to the Examples section herein.

[0013] The present disclosure also provides for a polyurethane article, that is formed with an isocyanate component and an isocyanate-reactive component comprising the composition of the present disclosure. In addition, the present disclosure provides for a method of forming the polyurethane article that includes forming the isocyanate-reactive component comprising the composition as provided herein and mixing the isocyanate-reactive component with an isocyanate component under reaction conditions to form the polyurethane article.

[0014] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list.

[0015] Detailed Description

[0016] The present disclosure provides for stabilizing incompatible polyol blends. Stabilizing incompatible polyol blends in turn allows for the storage of such polyols e.g., incompatible polyols) without the need for additional storage tanks e.g., only one tank required for polyol-side) and / or mixing apparatus that can lead to additional costs and time requirements for the manufacturer. In addition to fewer capital costs (e.g., reduced need for mixing and storage systems), there can also be fewer potential quality issues with the resulting polyurethane of the present disclosure due in part to maintaining a stable polyol blend versus having a macroscopic phase separation. The present disclosure allows incompatible polyol blends to be processable (e.g., pumpable) but can dramatically increase their shelf life (ex: sitting in a tank) from 0.5 - 7 days to greater than 3 months. In addition, the stabilizer of the present disclosure, a nonionic poloxamer, is used at a low enough levels that it has little to no impact on the formation of the polyurethane (e.g., the foaming of the polyurethane). In the end, the present disclosure provides a composition that imparts significant advantages in producing a polyurethane (e.g., a polyurethane foam) with fewer required resources due to the stability of the composition and its ability to generate polyurethane (e.g., polyurethane foams) from complex polyol blends containing incompatible materials.

[0017] As used herein, the term "nonionic poloxamer" refers to a block copolymer made of at least one chain or block of polyoxypropylene (the term "propylene oxide" may be used interchangeably herein) and at least one chain or block of polyoxyethylene (the term "ethylene oxide" may be used interchangeably herein). The nonionic poloxamer of the present disclosure can have a variety of configurations in which one of either of (a) the chain or block of polyoxypropylene or chain or (b) block of polyoxyethylene is flanked by two of the other (a) or (b). So, for example, in one embodiment, the nonionic poloxamer can have one chain or block of polyoxypropylene flanked by two chains of polyoxyethylene. In an alternative embodiment, the nonionic poloxamer can have one chain or block of polyoxyethylene flanked by two chains of polyoxypropylene. Nonionic poloxamers can be prepared by polymerizing either ethylene oxide or propylene oxide on the ends of a preformed polymeric base of either polyoxypropylene or polyoxyethylene as provided in the Pluronic Grid Approach, vol. II, Wyandotte Chemicals Corp., 1957). Nonionic poloxamers may also be sold under trade names including PLURONIC® (BASF), KOLLIPHOR® (BASF), LUTROL® (BASF), and SYNPERONIC® (Croda International), among others. Unless a particular nonionic poloxamer species is specified, references to " nonionic poloxamer" or “poloxamer” herein may generically refer to multiple nonionic poloxamer species. Nonionic poloxamer and poloxamer can be used interchangeably herein.

[0018] In addition, the term " nonionic poloxamer" may encompass many distinct compounds as discussed above and herein because different lengths for the polyoxypropylene and polyoxyethylene chains may be used in combination. The particular combination of polyoxypropylene and polyoxyethylene chains present in a nonionic poloxamer may give rise to particular chemical properties. In some embodiments, the nonionic poloxamer has the chemical formula of HO(C2H4O)n(C3H6O)m(C2H4O)nH (Formula I) or HO(C3H6O)m(C2H4O)n(C3H6O)mH (Formula II). In some embodiments, n (i.e., the nonionic polyoxyethylene chain length) has a value from about 60 to about 150. In some embodiments, m (i.e., the nonionic polyoxypropylene chain length) has a value from about 25 to about 60.

[0019] Nonionic poloxamers are often described by a numbering system that designates their approximate molecular weight and percentage of polyoxyethylene content. These values may refer to an average value in a nonionic poloxamer composition, rather than an absolute value of each poloxamer molecule in the composition. Under this system, the first two digits are multiplied by 100 to give the approximate molecular weight of the polyoxypropylene block, and the third digit is multiplied by 10 to give the percentage by weight of the polyoxyethylene block. For example, poloxamer 188 ( CAS No. 9003-11-6 ) may refer to a poloxamer with n having a value of about 80 and with m having a value of about 27 as in Formula I depicted above. Poloxamer 237 may refer to a poloxamer with n having a value of about 64 and with m having a value of about 37. Poloxamer 338 may refer to a poloxamer with n having a value of about 141 and with m having a value of about 44. Poloxamer 407 may refer to a poloxamer with n having a value of about 101 and with m having a value of about 56. In some embodiments, the poloxamer has an average molecular weight of from about 6,000 to about 18,000 g / mol. In some embodiments, poloxamer 188 may refer to a poloxamer with n having a value of about 80, with m having a value of about 27 as in Formula I depicted above, and with the poloxamer having an average molecular weight of from about 7680 to about 9510 g / mol. In some embodiments, poloxamer 188 may refer to a poloxamer with n having a value of about 80, with m having a value of about 27 as in Formula I depicted above, and with the poloxamer having an average molecular weight of from about 7000 to about 10000 g / mol.

[0020] Poloxamers sold under trade names, e.g., PLURONIC®, may be named under a different system. A letter may be used to indicate the physical state (e.g., F for solid, P for paste, or L for liquid). A 2 or 3 digit number may be used to indicate the chemical properties. The first one or two digits are multiplied by 300 to give the approximate molecular weight of the polyoxypropylene block, and the third digit is multiplied by 10 to give the percentage by weight of the polyoxyethylene block. For example, PLURONIC® F68 may refer to a solid poloxamer with n having a value of about 80 and with m having a value of about 27 as in Formula I depicted above. PLURONIC® F87 may refer to a solid poloxamer with n having a value of about 64 and with m having a value of about 37. PLURONIC® Fl 08 may refer to a solid poloxamer with n having a value of about 141 and with m having a value of about 44. PLURONIC® F127 may refer to a solid poloxamer with n having a value of about 101 and with m having a value of about 56. Since nonionic poloxamers have both hydrophobic (polyoxypropylene) and hydrophilic (polyoxyethylene) moieties of various lengths, different poloxamers may possess different hydrophilic-lipophilic balances (HLBs). The HLB of a compound is determined by calculating the relative proportion of the compound that is hydrophilic or lipophilic, and the HLB value is used to predict the properties of a compound. For example, a compound with an HLB less than 10 is predicted to be water insoluble, and a compound with an HLB greater than 10 is predicted to be water soluble. Tn preferred embodiments, nonionic poloxamers of the present disclosure can have an HLB of 10 or above. The HLB of a poloxamer may be calculated according to methods well known in the art, including those described in Griffin, W.C. (1954) J. Soc. Cosmet. Chemists 5(4):249-56 and Davies, J.T. (1957) Gas / Liquid and Liquid / Liquid Interfaces: Proc, of 2nd Inti. Congress Surface Activity, Butterworths (London): 426-38.

[0021] For the various embodiments, the nonionic poloxamer of the present disclosure can have a linear triblock copolymer poloxamer structure with at least one block formed from ethylene oxide monomers (EO) and at least one block formed from propylene oxide monomers (PO). For the various embodiments, the at least one block formed from EO of the nonionic poloxamer can comprise 50 to 90 mole percent (mol.%) of the nonionic poloxamer and the at least one block formed from PO can comprise 10 to 50 mol.% of the nonionic poloxamer. Preferably, the at least one block formed from EO of the nonionic poloxamer can comprise 70 to 80 mol.% of the nonionic poloxamer and the at least one block formed from PO can comprise 20 to 30 mol.% of the nonionic poloxamer.

[0022] For the various embodiments, the present disclosure provides for a variety of structures for the linear triblock copolymer poloxamer, where examples have been provided above and herein. For example, in specific embodiments the linear triblock copolymer poloxamer structure of the present disclosure can consist essentially of the at least one block formed from EO and the at least one block formed from PO. In other words, the linear triblock copolymer poloxamer structure of the present disclosure only includes at least one block formed from EO and the at least one block formed from PO. With respect to various configurations for the nonionic poloxamer on the present disclosure, in various embodiments the linear triblock copolymer poloxamer structure can include one block formed from PO positioned between two blocks formed from EO to provide an EO / PO / EO configuration. In additional embodiments, the linear triblock copolymer poloxamer structure can include one block formed from EO positioned between two blocks formed from PO to provide an PO / EO / PO configuration. For the various embodiments, each of the at least one block of the linear triblock copolymer poloxamer structure formed from EO and the at least one block formed from PO is not a random copolymer. Rather, the linear triblock copolymer poloxamer structure is a block copolymer where each block is formed only from its respective monomer.

[0023] With respect to having a “linear” triblock copolymer poloxamer structure, the linear triblock copolymer poloxamer structure can have a degree of branching value of less than 1 percent. Degree of branching percent is based on the total number of monomer units in the linear triblock copolymer poloxamer structure. The degree of branching can be measured using known techniques, which can include gel permeation chromatography where comparing the chromatograms of a branched polymer with those of the linear triblock copolymer poloxamer structure can provide the degree of branching. Other techniques are also known in the art (e.g., NMR spectroscopy, DSC and light scattering techniques).

[0024] For the various embodiments, the nonionic poloxamer of the present disclosure can have a number average molecular weight of 6,000 to 25,000 gram / mole. Preferably, the nonionic poloxamer can have a number average molecular weight of 7,000 to 15,000 gram / mole. The number average molecular weight can be measured using known techniques, such as gel permeation chromatography or size exclusion chromatography with suitable standards used for calibration.

[0025] For the various embodiments, the present disclosure provides for a composition that includes the nonionic poloxamer and a polyol blend that includes two or more incompatible polyols. Specifically, the present disclosure provides for a composition that includes 0.5 to 10 weight percent (wt.%) of the nonionic poloxamer having the linear triblock copolymer poloxamer structure, as described herein, with at least one block formed from ethylene oxide monomers (EO) and at least one block formed from propylene oxide monomers (PO) and 70 to 90 wt.% of a polyol blend that includes two or more incompatible polyols. For the various embodiments, the composition can further include 0.5 to 10 wt.% of the nonionic poloxamer having the linear triblock copolymer poloxamer structure with at least one block formed from ethylene oxide monomers (EO) and at least one block formed from propylene oxide monomers (PO) and 80 to 90 wt.% of the polyol blend that includes two or more incompatible polyols. The above wt.% values are based on the total weight of the composition.

[0026] For the various embodiments, the polyol blend of the present disclosure can include two or more incompatible polyols. As used herein, “incompatible” polyols include those polyols, as described herein or as known in the art, that do not or are incapable of forming a homogeneous mixture or blend with each other, but rather form a heterogeneous mixture in that one or more of the polyols are phase separated. Such a heterogeneous mixture can be formed at a temperature in the range of those typically used in forming polyurethane and polyurethane foams, such as, for example, 10 °C to 90 °C. As appreciated by one skilled in the art, the lack of compatibility in the polyols in the production of, for example, a polyurethane or polyurethane foam can lead to undesirable effects in the final product. This lack of compatibility can result in issues such as poor dispersion, reduced mechanical properties, or compromised performance of the resulting polyurethane or polyurethane foam.

[0027] For the various embodiments, the polyol blend of the present disclosure can include from two to seven incompatible polyols. Such a polyol blend, however, can also include one or more compatible polyols, where such a compatible polyol(s) are capable of homogeneously mixing or blending with the other incompatible polyols. For the various embodiments, each of the two or more incompatible polyols can have a weight average molecular weight of 200 to 10,000 g / mol. The weight average molecular weight can be measured using gel permeation chromatography (GPC) with appropriate standards (e.g., polystyrene standards) as is known in the art.

[0028] For the various embodiments, the polyol blend of the present disclosure can be formed by one or more of the following polyols: polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, hydroxyl-terminated polybutadiene (HTPB) polyols, silicone polyols, polyether ester polyols, amide polyols, natural oil polyols, water-blown polyols and combinations thereof. For the various embodiments, each of the above polyols are known in the art and so will only be briefly described herein. Examples of polyether polyols can include those produced by the polymerization of one or more epoxides with at least one initiator, where such epoxides can include ethylene oxide, propylene oxide, and / or butylene oxide. Examples of polyester polyols can include those synthesized by the condensation polymerization of diols with dicarboxylic acids, such as adipic acid, phthalic acid, or isophthalic acid. Examples of polycarbonate polyols can include those produced through the reaction of diols with phosgene and / or diphenyl carbonate. Examples of acrylic polyols can include those produced from acrylic or methacrylic monomers with hydroxyl-functional groups. Examples of HTPB polyols can include those based on hydroxyl-terminated polybutadiene, synthesized by the polymerization of butadiene with a bifunctional initiator. Examples of silicone polyols can include silicone functional group modified polyols. Examples of polyether ester polyols can include polyols having copolymers of polyether and polyester segments. Examples of amide polyols can include polyols that include amide groups. Examples of natural oil polyols (NOPs) can include those derived from renewable resources such as soybean oil, castor oil, or palm oil, among others. Preferably, the polyol blend of the present disclosure can be formed by one or more polyether polyols, as provided herein. For the various embodiments, the two or more incompatible polyols of the present disclosure can include a first polyol having a weight average molecular weight of less than or equal to 500 g / mol and a second polyol having a weight average molecular weight of greater than or equal to 1000 g / mol. For example, the two or more incompatible polyols of the present disclosure can include a first polyol having a weight average molecular weight of > 50 to < 500 g / mol and a second polyol having a weight average molecular weight of > 1000 g / mol to < 8000 g / mol. For the various embodiments, the two or more incompatible polyols can include at least one tri-functional polyol and at least one di-functional polyol each having a weight average molecular weight in a range of 200 g / mol to 8,000 g / mol. The first and second polyol(s) described above could range in concentration^ ) anywhere from 5% by weight to 95% by weight in the total polyol side causing incompatibility at a specific concentration range. For the various embodiments, the two or more incompatible polyols due their oxide compositions, include at least one or polyol contains an EO capping of 5% to 75% by mol, where this polyol(s) is in a concentration of 10 to 85 by weight in the polyol side. For the various embodiments, the two or more incompatible polyols include at least one or polyol with an EO content hetero-fed with PO such that final resultant concentration of EO is 5% to 85% by mol, where this polyol(s) is in a concentration anywhere in the range of 10% to 85% by weight in the polyol side. Incompatible polyol(s) also could be a result of inherent difference in viscosity of the polyols wherein the viscosity difference could be greater than 500 cP and less than 10000 cP at temperature of 10 °C to 60 °C during the blending.

[0029] For the various embodiments, the nonionic poloxamer of the present disclosure can further include 0.5 to 10 wt.% of an inorganic stabilizer, where the wt.% is based on the total weight of the nonionic poloxamer and the inorganic stabilizer. Preferably, the nonionic poloxamer of the present disclosure can include 0.75 to 8 wt.% of the inorganic stabilizer. More preferably, the nonionic poloxamer of the present disclosure can include 1 to 7 wt.% of the inorganic stabilizer. Most preferably, the nonionic poloxamer of the present disclosure can further include 2 to 7 wt.% of the inorganic stabilizer, where 2.75 wt.% is commonly used.

[0030] For the various embodiments, the inorganic stabilizer can be selected from the group consisting of silica, fumed silica, ceramics(s), clay(s), minerals, metal oxides, metal carbonates, metal sulphates, metal hydroxides, metal hydrates, metal nitrates, metal chlorides, silicates, metal phosphates, silica fibers and combinations thereof. Metals for the aforementioned inorganic stabilizers can include but not limited to aluminum, magnesium, manganese, iron, calcium, potassium, sodium, cobalt, nickel, tin, silver, rhodium, palladium, bismuth, gold, titanium, and copper, among others known in the art. For the various embodiments, specific examples of such inorganic stabilizer can include but not limited to colloidal silica, fumed silica, carbon black, calcium carbonate, magnesium carbonate, aluminum trihydrate, titanium dioxide, aluminum hydroxide, copper oxide, aluminum oxide, ammonium polyphosphate, boron nitride, copper chloride, copper sulphates, glass powder, glass beads, glass microspheres, alumina, kaolinite, dolomite, zeolites, calcite, talc, carbon black, oxide-based pigments (titania, zirconia etc.).

[0031] For the various embodiments, the inorganic stabilizer can have a specific surface area in a range of 2 m2 / g to 500 m2 / g . Preferably, the inorganic stabilizer can have a specific surface area in a range of 10 m2 / g to 400 m2 / g . More preferably, the inorganic stabilizer can have a specific surface area in a range of 50 m2 / g to 400 nr / g . The inorganic stabilizer(s) can be a combination of different surface in the said ranges above in multi-modal distribution form. The inorganic stabilizer(s) can have functionalization(s) or modification(s) with several organic molecule(s) and / or polymeric chain(s) on its surface to improve its moisture pickup, enhance the ease of dispersion in the organic polyol side, and potentially synergistic improvement in the polyol blend stability.

[0032] For the various embodiments, the composition of the present disclosure can further include up to 25 wt.% of one or more additives selected from the group consisting of a filler, silica, water, a surfactant, a catalyst, a plasticizer, flame retardant molecule(s), a chemical blowing agent other than water, a physical blowing agent and combinations thereof, wherein the wt.% is based on the total weight of the composition. Examples of the additives can include, but are not limited to, micron and / or nano sized fillers comprising carbon black, recycled materials, hollow microspheres, cellulosic fillers and / or mineral fillers (e.g., calcium carbonate); surfactant can include, but are not limited to silicone polyethers, silicone glycols; nonionic surfactants such as alkylphenol ethoxylates, alcohol ethoxylates, and polysorbates; catalysts can include amine catalyst, tin catalysts, and organic catalysts, including blocked and delayed action catalysts as are known in the polyurethane art; plasticizers can include phthalate plasticizers, polymeric plasticizers, trimellitate esters, adipate esters, and citrate esters, among others; chemical blowing agents can include, among others, azodicarbonamide (ADC), hydrazine derivatives such as N,N'-dinitrosopentamethylenetetramine (DNPT) or 4,4'- oxybis(benzenesulfonylhydrazide) (OBSH), sodium bicarbonate / adipic acid, and carbonates as are known in the art; physical blowing agents can include gas or low boiling point hydrocarbons such as chlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, various alkanes, acetone, other volatile chemicals as are known in the polyurethane art. Other additives can include organic particles, such as wood flour and cellulose ether among others. As used herein, the composition of the present disclosure is shelf stable, as illustrated in the Examples section below. As used herein, shelf stable means that there are no visible macrophase separations within the composition as a function of time as provided herein. Specifically, the present disclosure allows incompatible polyol blends to be processable (e.g., pumpable) by dramatically increasing their shelf life (ex: sitting in a tank) from 0.5 to greater than 3 months. For example, the shelf stability of the composition of the present disclosure can be at least 7 days at room temperature (23 °C). Preferably, the shelf stability of the composition of the present disclosure can be at least 21 days at room temperature (23 °C). For the various embodiments, the composition of the present disclosure can have an instability index, as determined according to the Examples section herein, of less than (<) 0.65.

[0033] The composition of the present disclosure can be formed by mixing the above described components using, for example, a mechanical mixer, such as an overhead mixer or dual mixer. The use of other mixers as are known in the art is also possible. The composition and / or the components of the composition of the present disclosure can also be heated either before or during the mixing process, where heating in a temperature range of 60 to 70 °C to solubilize any of the above components (e.g., the additives) in the two or more incompatible polyols is possible. In addition, the typical time to solubilize any of the components of the composition can vary with the amount of polyols and / or the type of mixing used.

[0034] The present disclosure also provides for a polyurethane article formed with an isocyanate component and an isocyanate-reactive component comprising the composition of the present disclosure. The present disclosure also provides for a method of forming the polyurethane article that includes forming the isocyanate-reactive component comprising the composition as provided herein and mixing the isocyanate -reactive component with an isocyanate component under reaction conditions to form the polyurethane article, as described herein. For the various embodiments, the polyurethane article can be obtained by mixing at least: the isocyanate component (“A-side”) and the isocyanate-reactive component (“B-side” or “polyol side” or “polyol blend”), where the isocyanate-reactive component includes the composition of the present disclosure. In forming the polyurethane article, the isocyanate component, isocyanatereactive components, and optional components and / or additives (if needed and as discussed herein) are mixed, creating a curing reaction mixture that is processed to form the polyurethane article, material, or composite. Where the isocyanate component and the isocyanate-reactive component are combined in the presence of aqueous fluids and / or blowing catalysts, the curing reaction mixture that generates a polyurethane article can have a density ranging from 0.05 g / mL to 2.5 g / mL measured using ASTM D792 upon cure. Other examples of forming the polyurethane article are also possible based on the present disclosure.

[0035] For the various embodiments, the polyurethane article can be formed from a polyurethane foam formed from the isocyanate component and the isocyanate-reactive component comprising the composition of the present disclosure as described herein. As is known in the art, a polyurethane can be formed with one or more of the above identified components included in the composition of the present disclosure with a desired stoichiometric index of the isocyanate to the composition of the present disclosure. For the various embodiments, the curing reaction mixture can be mixed at a temperature of from 10 to 90 °C, preferably from 20 to 60 °C and in particular from 20 to 50 °C, and introduced onto a work piece (e.g., a steel panel), into the open mold or, optionally under elevated pressure, into the closed mold. Mixing can be carried out mechanically by means of a stirrer or a stirring screw. Reaction temperature for the curing reaction mixture once dispensed can be from 15 to 110 °C, preferably from 25 to 70 °C and in particular from 25 to 60 °C.

[0036] For the various embodiments, the isocyanate component can include at least one polyisocyanate. As used herein, “polyisocyanate” refers to a molecule having an average of greater than 1.0 isocyanate groups / molecule, e.g., an average functionality of greater than 1.0. The isocyanate component can be an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aril- aliphatic polyisocyanate, an aromatic polyisocyanate, or combinations thereof, for example. Examples of isocyanates include, but are not limited to, toluene 2,4- / 2,6-diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), polymeric MDI, triisocyanatononane (TIN), naphthyl diisocyanate (NDI), 4,4’-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3,3,5- trimethylcyclohexyl isocyanate (isophorone diisocyanatellPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HD1), 2-methylpentamethylene diisocyanate, 2,2,4- trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1,4- diisocyanatocyclohexane, 4,4’-diisocyanato-3,3’ -dimethyldicyclohexylmethane, 4,4’- diisocyanato-2,2-dicyclohexylpropane, 3-isocyanatomethyl-l-methyl-l-isocyanatocyclohexane (MCI), l,3-diisooctylcyanato-4-methylcyclohexane, l,3-diisocyanato-2-methylcyclohexane, and combinations thereof, among others. As well as the isocyanates mentioned above, partially modified polyisocyanates including uretdione, isocyanurate, carbodiimide, uretonimine, allophanate or biuret structure, and combinations thereof, among others, may be utilized.

[0037] The isocyanate component can be polymeric. As used herein "polymeric", in describing the isocyanate component, refers to higher molecular weight homologues and / or isomers. For instance, polymeric methylene diphenyl isocyanate refers to a higher molecular weight homologue and / or an isomer of methylene diphenyl isocyanate.

[0038] For the various embodiments, the stoichiometric index of the isocyanate component to the isocyanate reactive groups (e.g., hydroxyl groups) in the composition of the present disclosure can be 0.5 to 3.0. For the various embodiments, the nonionic poloxamers present in the composition of the present disclosure also contribute to the number of isocyanate reactive groups (e.g., terminal hydroxyl groups) that can react with the isocyanate component. As a result, preferably the nonionic poloxamers in the composition of the present disclosure are present in the isocyanate-reactive component of the of the curing reaction mixture, as provided herein.

[0039] As known in the art, when the number of isocyanate groups of the isocyanate component equals the number of hydroxyl groups in an isocyanate reactive component the result is a stoichiometric index of the isocyanate component to the isocyanate reactive component of 1.0. When the number of isocyanate groups of the isocyanate component is greater than the number of hydroxyl groups in the isocyanate reactive component (e.g., three times as many) the result is a stoichiometric index of the isocyanate component to the isocyanate reactive component that is greater than 1.0 (e.g. , 3.0 for the example).

[0040] The isocyanate component can have an isocyanate equivalent weight 130 g / eq to 200 g / eq. All individual values and subranges from 130 g / eq to 200 g / eq are included herein; for example, the isocyanate component can have an isocyanate equivalent weight from a lower limit of 130 or 132 g / eq to an upper limit of 200, 198 or 196 g / eq.

[0041] The isocyanate component may be prepared by a known process. For instance, the polyisocyanate can be prepared by phosgenation of corresponding polyamines with formation of polycarbamoyl chlorides and thermolysis thereof to provide the polyisocyanate and hydrogen chloride, or by a phosgene-free process, such as by reacting the corresponding polyamines with urea and alcohol to give poly carbamates, and thermolysis thereof to give the polyisocyanate and alcohol, for example.

[0042] The isocyanate component may be obtained commercially. Examples of commercial isocyanates include, but are not limited to, polyisocyanates under the trade names VORANATE™, such as VORANATE™ M 220, and PAPI™ such as PAPI™ 27, available from DOW®, among other commercial isocyanates.

[0043] The polyurethane article can be prepared from the curing reaction mixture by using known methods and conditions, which may vary for different applications. One or more embodiments of the present disclosure provide a process for forming a polyurethan foam product. The process includes curing the curing reaction mixture disclosed herein. The process may utilize known equipment and conditions, such as a one shot process, among others.

[0044] One or more embodiments of the present disclosure provide that the composition for producing the polyurethane foam can include one or more additional components. Different additional components and / or different amounts of additional components may be utilized for various applications. Examples of additional components include pigments, colorants, additional flame retardants as are known in art, crosslinkers, chain extenders, antioxidants, bioretardant agents, and combinations thereof, among others.

[0045] Examples

[0046] All components purchased from commercial vendors and used as received unless otherwise noted. Amounts provided for the compositions of the Examples (EX) and Comparative Examples (CE) are in weight percent (wt.%) based on the total weight of the composition, unless otherwise noted.

[0047] The components used in forming the EX and CE are provided in Table 1. Mixing of the EX and the CE was done with a lab scale speed mixer. As used herein, EO stands for ethylene oxide; PO stands for propylene oxide. Test methods for the following are provided at the end of the Examples section.

[0048] Table 1 - Components for EX and CE

[0049] Product Formulations

[0050] Table 2 - Two Incompatible Polyol Blends *the shelf life for these samples was only monitored over 28 days

[0051] The EX and CE presented in Table 2 highlight the impact that small amounts (e.g. 0.5 wt.%) of the polymeric stabilizer of the present disclosure had on the sample stability, increasing from < 1 day with no (CE A) or 0.1 wt.% polymeric stabilizer (CE B) to > 28 days with 0.5 wt.% (EX 1 and EX 2) or polymeric stabilizer when the polymeric stabilizer was formed with 50 to 90 mol.% EO and had a molecular weight of 6,000 g / mol up to preferably as high as 15,000 g / mol.

[0052] Table 3 provides additional EX and CE to support the composition of the present disclosure. The examples in Table 3 show the response when the polymeric stabilizer does not meet the molecular weight or EO content criteria for different polyol blends (CE C - CE H).

[0053] Table 3 - Two Incompatible Polyp Blends

[0054] *the shelf life only monitored over 28 days

[0055] The storage stability improvement of the EX of the present disclosure were clearly shown in 3-polyol system as seen in Table 4. Table 4 - Three Incompatible Polyol Blends

[0056] * contained bubbles, which impacted plane polarized measurement ** only monitored for 14 days

[0057] CE K and CE L did not contain poloxamer, where the shelf life for each was less than 7 days. CE M and CE N contained low levels of poloxamer, but lacked some of the structural formation seen in the EX with higher loadings of poloxamer.

[0058] EX 5 through EX 9 contained > 0.1 wt.% Poloxamer 3 or Poloxamer 4, which had 50-90 mol.% EO content and number average molecular weights of 6,000 g / mol up to preferably as high as 15,000 g / mol. In addition to the high complex viscosity, EX 5 through EX 9 showed reasonable viscosities at 1 s’1, generally of the same order of magnitude as CE K, which is considered to be processable. Furthermore, EX 5 through EX 9 containing poloxamer for the formulations given in Table 4 showed additional brightness under plane polarized imaging, which further supports the formation of a microstructure within the EX. This same brightness is not seen for the CE without poloxamer, suggesting that the poloxamer contributes to the change in microstructure.

[0059] Table 8 - All EO low MW Polyol versus all PO low MW Polyol CE K, EX 6, EX 7, and EX 9 are repeated from Table 7, above. “CE” means comparative example, and “IE” means inventive example. “EO” being used as a placeholder until sample designation is competed based on experimental data.

[0060] In addition to formulations in which the low molecular weight polyol is all PO (Polyol 1), this approach also applies to formulations in which the low molecular weight polyol species is all EO (Polyol 11). One main difference between the CE from Table 7 and the CE from Table

[0061] 8 is the presence of brightness for plane polarized images for CE without poloxamer. This could be the result of structure formation by Polyol 11. However, despite this difference, the complex viscosity is not further increased for the no poloxamer cases containing Polyol 11 (CE O and CE P) compared to the corresponding examples containing Polyol 1 (CE K and CE 3, respectively).

[0062] Experimental Procedures

[0063] Formulation

[0064] Poloxamers were warmed on a hotplate or in an oven to melt (selected oven temperature could be between 40 °C and 80 °C to ensure the poloxamer melted but was usually ~60 °C). The polyol blend master batch was weighed out and mixed at 2000 rpm for 1 minute and then dispensed into smaller speedmixer cups. The cups were placed in an oven to warm; each sample was pulled from the oven to add poloxamer, mixed at 2000 rpm for 30 seconds (under vacuum if possible) and put back in the oven for ~30 minutes. Then each sample was pulled from the oven to add silica, mixed again at 2000 rpm for 30 seconds, hand mixed to scrape down sides and placed back in the oven for ~30 minutes. Upon removing from the oven each sample was mixed a final time (under vacuum if possible) at 800 rpm for 30 s followed by 2000 rpm for 30 s. Samples were dispensed into different containers for analysis / storage.

[0065] LUMiSizer

[0066] The LUMiSizer is an analytical centrifuge that measures transmitted light across the sample length with spatial and temporal resolution (LUM GmbH, LUMiSizer). Approximately 460 ,uL of sample were dispensed in each 2 mm polycarbonate rectangular cell (110-131xx from LUM Americas). Each cell was loaded on the LUMiSizer 6110-77 (LUM GmbH), which uses an 865 nm wavelength light source. The samples were then measured at 25 °C at a speed of 4000 rpm with a profile interval of 60 seconds and a light factor of 1.00, collecting a total of 300 profiles per sample.

[0067] Instability Index

[0068] Accelerated stability test was run at LUMiSizer 6110-77 instrument from LUM GmbH. Samples were loaded into a transparent plastic cell and then centrifuged at a rate of 4000 rpm for 5 hours. The transmission profile was recorded by the CCD sensor over time. Instability index is calculated by the SEPView Explorer software. It quantifies the change of transmission profile for the selected sample range (18.27 mm) within the selected time slot (1800 s).

[0069] 1) Calculation of clarification (difference between first and subsequent transmission profiles) :

[0070] Tdiff= T. _Tifor i> 2

[0071] 2) The total clarification change is calculated by summing up all incremental for the ROI (region of interest - range of the sample analyzed) from rmm to rmax-

[0072] 3) Maximum clarification possible:

[0073] The difference between mean transmission, TEnd, or a cell with water only and the mean transmission, T1?of first profile (= arithmetic average of the transmission values along the ROI of the sample) is multiplied with the number of transmission values (position increments) nd minimum of the position range.

[0074] Optical microscope

[0075] A small drop of a sample was applied to a pre-cleaned glass slide or glass slide with printed wells, topped with a cover slide and observed under 40x magnification in phase contrast mode using Zeiss Axiolmager z2.m microscope.

[0076] PICA

[0077] Samples were imaged under side light or backlight (intensity = 0.75) with plane polarized imaging using a custom-built imaging technology (Phase Identification and Characterization Apparatus, PICA). Samples were imaged at multiple time points (e.g. 0 days, 1 day, 7 days, 14 days, 28, days, 56 days) and monitored for macroscopic changes within the samples.

[0078] Rheology The flow curves were measured with shear sweeps from 0.01 to 500 s1and 500 to 0.01 s'1after a pre-shear of 100 s'1for 30 seconds on a TA Instruments AR-G2 rheometer using 25 mm parallel plates with -1 mm gap at 25 °C.

[0079] After pre-annealing the samples at 60°C for -20 minutes followed by cooling for -240 minutes, the complex viscosity of the formulations were evaluated at 25 °C using a frequency sweep from 100 to 0.02 rad / s at 0.1% oscillation strain on a TA Instruments AR-G2 rheometer using a cup and bob setup with -20 mL of sample.

[0080] Table 9 - Tested Property Results brightness (birefringence) under plane polarized imaging is indicative of some structure formation. See also birefringence images below.

[0081] Data Analysis Macrophase separation & birefringence

[0082] Macrophase separation (shelf stability) was visually analyzed for separation over the testing time.

[0083] Plane polarized images were evaluated in ImageJ version 1.52a for gray value intensity.

[0084] A value > 13 was considered to contain a “structure.”

[0085] Measurement Information

[0086] Instability index cutoff: 0.65. Structure formation: Image intensity > 13 when imaged w / plane polarizers. Stability > 28 days.

Claims

What is claimed is:

1. A composition, comprising:0.5 to 10 weight percent (wt.%) of a nonionic poloxamer having a linear triblock copolymer poloxamer structure with at least one block formed from ethylene oxide monomers (EO) and at least one block formed from propylene oxide monomers (PO), wherein the at least one block formed from EO comprises 50 to 90 mole percent (mol.%) of the nonionic poloxamer and the at least one block formed from PO comprises 10 to 50 mol.% of the nonionic poloxamer, and wherein the nonionic poloxamer has a number average molecular weight of 6,000 to 25,000 g / mol; and70 to 90 wt.% of a polyol blend that includes two or more incompatible polyols, wherein each of the two or more incompatible polyols has a weight average molecular weight of 200 to 10,000 g / mol and the wt.% values are based on the total weight of the composition.

2. The composition of claim 1 , wherein the linear triblock copolymer poloxamer structure consists essentially of the at least one block formed from EO and the at least one block formed from PO.

3. The composition of any one of claims 1-2, wherein the linear triblock copolymer poloxamer structure includes one block formed from PO positioned between two blocks formed from EO to provide an EO / PO / EO configuration.

4. The composition of any one of claims 1 -2, wherein the linear triblock copolymer poloxamer structure includes one block formed from EO positioned between two blocks formed from PO to provide an PO / EO / PO configuration.

5. The composition of any one of claims 1-4, wherein the linear triblock copolymer poloxamer structure has a degree of branching value of less than 1 percent.

6. The composition of any one of claims 1-5, wherein the linear triblock copolymer poloxamer structure has a number average molecular weight of 6,000 to 15,000 g / mol.

7. The composition of any one of claims 1-6, wherein each of the at least one block of the linear triblock copolymer poloxamer structure formed from EO and the at least one block formed from PO is not a random copolymer.

8. The composition of any one of claims 1-7, wherein the nonionic poloxamer further includes 0.5 to 4 wt.% of an inorganic stabilizer, wherein the wt.% is based on the total weight of the nonionic poloxamer and the inorganic stabilizer.

9. The composition of claim 8, wherein the inorganic stabilizer is selected from the group consisting of silica, fumed silica, metal carbonates, metal sulphates, metal hydroxides, metal hydrates, metal nitrates, silicates, silica fibers and combinations thereof.

10. The composition of any one of claims 8-9, wherein the inorganic stabilizer has a specific surface area 2 m2 / g to 500 m2 / g.

11. The composition of any one of claims 1-10, wherein the two or more incompatible polyols includes a first polyol having a weight average molecular weight of less than 500 g / mol and a second polyol having a weight average molecular weight of greater than 1000 g / mol.

12. The composition of any one of claims 1-11, wherein the two or more incompatible polyols include at least one tri -functional polyol and at least one di-functional polyol each having a weight average molecular weight in a range of 200 g / mol to 8,000 g / mol.

13. The composition of any one of claims 1-12, further including up to 25 wt.% of one or more additives selected from the group consisting of a filler, silica, water, a surfactant, a catalyst, a plasticizer, flame retardant molecule(s), a chemical blowing agent other than water, a physical blowing agent and combinations thereof, wherein the wt.% is based on the total weight of the composition.

14. The composition of any one of claims 1-12, wherein the shelf stability is 21 days or greater.

15. The composition of any one of the claims 1- 12, wherein the composition has an instability index of less than 0.65.

16. The composition of any one of the claims 1-12, wherein the composition has a complex viscosity at 0.1 % strain, 1 rad / s of less than 75 and a viscosity measured from high to low shear of less than 12.5 at 1 s1.

17. A polyurethane article formed by a reaction of: an isocyanate component; and an isocyanate-reactive component comprising the composition of any one of claims 1-16.

18. A method of forming a polyurethane article, comprising: forming an isocyanate-reactive component comprising the composition of any one of claims 1-16; and mixing the isocyanate-reactive component with an isocyanate component under reaction conditions to form the polyurethane article.

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