Polyester polyol composition containing HF0-1336MZZM(Z)

Abstract

The present invention provides blends, polyol premix compositions, methods for forming such compositions, foaming compositions using premix compositions, methods for preparing foams containing premix compositions, and foams produced using premix compositions. [Solution] The polyol premix composition comprises a polyester polyol, a halogenated olefin blowing agent, and a distribution-enhancing component. In the polyol premix composition, the blowing agent, the polyester polyol, and the distribution-enhancing component form a substantially homogeneous composition.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority to U.S. Application No. 15 / 631,709, filed Jun. 23, 2017, which claims the benefit of priority of U.S. Provisional Application No. 62 / 366,437, filed Jul. 25, 2016, the contents of which are hereby incorporated by reference.

[0002] The present invention relates to polyurethane and polyisocyanurate foams and methods for their preparation. More specifically, the present invention relates to rigid, semi - rigid, and flexible polyurethane and polyisocyanurate foams, and halogenated olefins as blowing agents including cis - 1,1,1,4,4,4 - hexafluorobut - 2 - ene (HFO - 1336mzzm(Z)), and methods for their preparation using polyester polyols.

Background Art

[0003] The class of foams known as low-density, rigid, semi-rigid, and flexible polyurethane or polyisocyanurate foams is useful in a wide range of insulation applications, including roofing systems, building panels, building envelope insulation, refrigerators and freezers, seat cushions, mattresses, shoe soles, and packaging materials. A key factor in the large-scale commercial acceptance of rigid polyurethane foams is their ability to provide a good balance of properties. Rigid closed-cell polyurethane and polyisocyanurate foams are known to offer excellent thermal insulation, excellent fire resistance, and excellent structural properties at reasonably low densities. Semi-flexible and flexible polyurethane foams are known to offer excellent cushioning and energy absorption properties. The foam industry has historically used certain liquid fluorocarbon materials as blowing agents because they are easy to use under typical processing conditions. Certain fluorocarbons can act as blowing agents not only due to their volatility, but also, in the case of closed-cell foams, are conjugated into the closed-cell structure of rigid foams and are a major cause of the low thermal conductivity of rigid polyurethane foams. The use of certain fluorocarbon materials as preferred commercial expanders or blowing agents in insulating foam applications is partly based on the resulting k-factor associated with the foam produced. The k-factor is defined as the rate of thermal energy transfer by conduction through a 1-inch thick, 1-square-foot homogeneous material with a 1°F difference across two surfaces perpendicularly. Since the use of many closed-cell polyurethane foams is partly based on the foam's thermal insulation properties, it is advantageous to identify materials that produce foams with lower k-factors. In the case of flexible polyurethane foams, certain fluorocarbon-containing physical blowing agents are used to reduce the density of these foams to levels that are difficult to achieve with water alone.

[0004] It is known in the art that polyurethanes and polyisocyanurate foams can be produced by reacting polyisocyanates with polyols in the presence of blowing agents, catalysts, surfactants, and optionally other components. For many applications, the blowing agent should be substantially homogeneously distributed within the polyol components. The heat generated when the polyisocyanate reacts with the polyol volatilizes the blowing agent contained in the liquid mixture, forming bubbles within it. As the polymerization reaction proceeds, the liquid mixture becomes a polymeric, cellular solid, encapsulating the blowing agent within the cells of the foam in the closed-cell foam. In many applications, if a surfactant is not used in the foaming composition, the bubbles either simply pass through the liquid mixture without forming a foam, or form a foam with large, irregular cells that are unsuitable for a rigid foam. Also, if the blowing agent is not substantially homogeneously distributed in the foaming composition during foaming, an irregular and inconsistent foam is formed.

[0005] Suitable blowing agents include certain fluorinated carbon, chlorocarbon, chlorofluorocarbon, hydrohaloolefin, hydrocarbons, ethers, esters, aldehydes, ketones, acetals, organic acids, atmospheric gases, materials that produce gases, such as CO2, through decomposition or chemical reactions (such as, but not limited to, water, formic acid, and azodicarbonamide), and mixtures of two or more of these. Preferred blowing agents have a low potential for global warming. These blowing agents include certain hydrohaloolefins, including hydrofluoroolefins (HFO) (including hydrochlorofluoroolefins (also known as HFCO)). Of particular interest are trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz(Z)), and trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)). The process for producing 1,3,3,3-tetrafluoropropene is disclosed in U.S. Patents 7,230,146 and 7,189,884. The process for producing 1-chloro-3,3,3-trifluoropropene is disclosed in U.S. Patents 6,844,475 and 6,403,847. As used herein, "(E)" represents the trans isomer of the molecule, and "(Z)" represents the cis isomer.

[0006] Providing components for polyurethane or polyisocyanurate foams in pre-blended formulations is convenient in many applications. Most typically, the foam formulation is pre-blended into two components. Polyisocyanates and any isocyanate-compatible raw materials comprise a first component, commonly referred to as component "A". Polyols or mixtures of polyols, surfactants, catalysts, blowing agents, and other isocyanate-reactive and non-reactive components comprise a second component, commonly referred to as component "B". Thus, polyurethane or polyisocyanurate foams can be easily prepared by combining subcomponents A and B by either manual mixing for small-scale preparations, and preferably by mechanical mixing techniques, to form blocks, slabs, laminates, in-situ injection panels, flexible foams, soles, and other items, spray foams, floss, molded articles, etc. Optionally, all or part of the blowing agent may be added to the mixing head or reaction site together with other components such as flame retardants, colorants, auxiliary blowing agents, and other polyols. However, for the most convenience, they are all incorporated into a single component B.

[0007] For a physical blowing agent to produce a foam with uniform density and cellular structure, the blowing agent must be substantially uniformly distributed, for example, by dissolving, dispersing, and / or emulsifying in a polyol, thereby forming a substantially homogeneous blend of the polyol and the blowing agent. The mixture must remain homogeneous rather than foaming when stirred during transport. Many types of polyols are used in the production of polyurethane or polyisocyanurate foams. Most polyurethane or polyisocyanurate foams are prepared from blends of polyols with different structures and properties. The polyol directly used directly affects the physical properties of the polyurethane or polyisocyanurate foam. In each polyurethane or polyisocyanurate foam application, the choice of polyol differs, as do the concentrations of the blowing agent. The majority of polyols used are classified into two classes: polyethers and polyesters. The structures of polyols in each class differ. The use of polyester polyols is important for many applications. In some formulations, 100% of the polyol used is polyester polyol. The applicants have come to understand that a key consideration in the development of the formulation is how uniformly the blowing agent can be distributed in the polyol blend over the temperature range in which the blend is formed, stored, and transported (e.g., -20°C to 50°C), and / or the temperature range in which foam is formed (e.g., 10°C to 55°C). In addition to uniformity, the blend must not foam. do not have. [Overview of the project]

[0008] The applicants have come to understand that certain polyols do not readily form a uniform distribution using certain blowing agents under conventionally used conditions and in the presence of other conventionally used materials. Blends can cause problems with foaming, transport, and use. The applicants have found that including certain materials in the blend can overcome these drawbacks and improve or enhance the degree of uniform distribution achieved when the blowing agent is otherwise inadequately and substantially not uniformly distributed in the polyol.

[0009] One aspect of the present invention relates to a polyol premix composition, the polyol premix composition comprising (a) a polyester polyol, (b) a blowing agent comprising a halogenated olefin blowing agent, preferably a C3 or C4 halogenated olefin, and more preferably cis-1,1,1,4,4,4-hexafluorobuta-2-ene, also known as HFO-1336mzzm(Z), and (c) at least one distribution-enhancing component that enables and / or improves the uniformity of the distribution of the haloolefin blowing agent in the polyester polyol. Where used herein, the distribution-enhancing component selected according to the present invention may also be referred to herein for convenience as a “compatibilizer.” One sign that substantially uniform distribution of the blowing agent has not been achieved is preferably visual observation of phase separation after attempting to blend / mix the components, under conditions such as those described in the examples herein. Conversely, one sign in a preferred embodiment of the presence of a substantially uniform distribution is, preferably, visual observation of a substantially consistent liquid phase without any signs of phase separation, under conditions such as those described in the examples herein.

[0010] Other aspects of the present invention include blends, methods for preparing effervescent compositions, effervescent compositions, and foams.

[0011] One aspect of the present invention is the selection of an organic compatibilizer, preferably an organic hydroxyl-containing compound having 1 to 40 carbon atoms, more preferably 1 to 25 carbon atoms. In certain preferred embodiments, the selection is made from the group consisting of acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms, alkylphenols and alkylphenol ethoxylates, dipropylene glycol, diisopropylene glycol, dipropylene glycol methyl ether, methylal (methylene dimethyl ether), ethylene glycol mono-butyl ether, 1,3-diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, trans-1,2-dichloroethylene, 2-chloropropane, trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene, tris(1-chloro-2-propyl) phosphate, and any combination of two or more of these.

[0012] In certain embodiments, the present invention comprises a blend comprising a distribution-enhancing component, preferably one as identified in the preceding paragraph or as described elsewhere herein, and either (a) a halogenated olefin blowing agent or (b) a polyester polyol. In preferred embodiments, the halogenated blowing agent comprises or may essentially consist of cis-1,1,1,4,4,4-hexafluorobuta-2-ene. Preferably, the blend is formed as a substantially homogeneous blend or mixture of components, and more preferably, the blowing agent or polyester polyol, in either case, is solvated and / or substantially homogeneously dispersed therein and / or substantially homogeneously emulsified therein; in alternative methods, the compatibilizer is solvated by the blowing agent or polyester polyol (in either case). The solution / dispersion / emulsion is substantially uniformly dispersed and / or substantially uniformly emulsified therein. In such embodiments, it is also very preferable that the solution / dispersion / emulsion is stable during storage in a sealed container at a storage temperature under expected ambient temperature conditions, preferably for a period of 4 months, more preferably for 6 months, and even more preferably for 1 year. In certain preferred embodiments, stable storage exists according to the invention at a temperature of about -20°C to about 55°C.

[0013] Another aspect of the present invention is a polyol premix composition. In one embodiment, the polyol premix composition comprises at least one polyester polyol, a cis-1,1,1,4,4,4-hexafluorobuta-2-ene foaming agent, and the distribution-enhancing components of the present invention, preferably acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms, alkylphenols and alkylphenol ethoxylates, dipropylene glycol, diisopropylene glycol, dipropylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1,3-diisopropylbenzene, isopropylbenzene, 1,3-diisopropenylbenzene, isopropenylbenzene The foaming agent and distribution-enhancing components are preferably distributed substantially uniformly as a blend or in a polyol premix by being substantially uniformly dispersed in and / or emulsified in and / or solvated therein in the polyol.

[0014] Another aspect of the present invention is a method for forming a polyol premix composition. In one embodiment, the method comprises (a) a polyester polyol, and (b) a blowing agent comprising, more preferably at least about 50% by weight thereof, and more preferably essentially therefrom, acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms, alkylphenols and alkylphenol ethoxylates, ethylene glycol, dipropylene glycol, diisopropylene glycol, dipropylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1,3-diisopropylbenzene, isopropylbenzene, 1,3-diisopropenylbenzene, isopropenylbenzene, and A distribution-enhancing component selected from the group consisting of cetone, methyl ethyl ketone, trans-1,2-dichloroethylene, 2-chloropropane, trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene, tris(1-chloro-2-propyl) phosphate, and any two or more combinations thereof, wherein the foaming agent and distribution-enhancing component are preferably substantially uniformly distributed in the polyol by being substantially uniformly dispersed in the polyol and / or emulsified therein and / or solvated therein, and the combination of (d) an amine catalyst and (e) a silicone surfactant.

[0015] Another aspect of the present invention is a foaming composition. In one embodiment, the foaming composition comprises a mixture of an organic polyisocyanate and a polyol premix composition according to the present invention.

[0016] Another aspect of the present invention is a method for preparing polyurethane or polyisocyanurate foams. In one embodiment, the method comprises reacting an organic polyisocyanate with a polyol premix composition according to the present invention.

[0017] Another aspect of the present invention is a foam produced according to a method utilizing the compatibilizer blend and / or polyol premix and / or foaming composition of the present invention. [Modes for carrying out the invention]

[0018] HFO-1336mzzm(Z) is a hydrohaloolefin developed in recent years. As discussed below, the ability of HFO-1336mzzm(Z) to uniformly distribute in various polyester polyols was compared with the abilities of two other commonly used blowing agents, 1,1,1,3,3-pentafluoropropane (HFC-245fa) and trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), at different concentrations and temperatures. It was found that the ability of HFO-1336mzzm(Z) to achieve uniform distribution varied significantly with respect to the polyester polyol, concentration, and temperature used, and that, surprisingly, in the absence of the present invention as described herein, HFO-1336mzzm(Z) was at best poorly distributed in many commonly used polyester polyols. This significantly limits its use as a substantial component of blowing agents in polyurethane or polyisocyanurate foams. The applicants have found that HFO-1233zd(E) appears to have a superior ability to provide a uniform distribution with several polyol esters compared to HFO-1336mzzm(Z), but they have also found that it is possible to achieve an improved or enhanced distribution of foaming agents, including less solution foam, with HFO-1233zd(E), and that such foaming agents can be used according to the teachings contained herein. The applicants have also found that certain compounds can enhance the degree to which halogenated olefins, more preferably C3 and C4 halogenated olefins, such as HFO-1336mzzm(Z), are uniformly distributed in certain polyester polyols used in polyol premix compositions. As described above, these compounds and blends of compounds are referred to herein as compatibilizers. The compatibilizer is preferably solvated and / or dispersed in a halogenated olefin, such as HFO-1336mzzm(Z), and / or a polyester polyol, and / or preferably both, and / or emulsified in the same. Furthermore, the uniform distribution thus formed is preferably a stable and substantially uniform distribution of the blowing agent in the polyol.As used herein, a stable and substantially uniform distribution means that a substantially uniform distribution is maintained at at least one temperature, preferably over the entire temperature range of about -20°C to about 55°C, when stored for a period of four months, preferably six months, and more preferably one year. In preferred embodiments, the stable and substantially uniform distribution comprises a stable solution, and / or dispersion, and / or emulsion of the blowing agent in the polyol. Preferably, the compatibilizer can be used with a wide variety of polyester polyols over a wide range of concentrations, and storage stability is demonstrated over at least the preferred temperature range described herein.

[0019] Preferably, the compatibilizer may be combined with HFO-1336mzzm(Z), or a polyester polyol, or a mixture of HFO-1336mzzm(Z), a polyester polyol, and any other component in the polyol premix composition.

[0020] Various materials were studied to determine their effectiveness as compatibilizers in various polyols. The distributed enhancement components typically have 1 to 40 carbon atoms. In some embodiments, the distributed enhancement components have one or more hydroxyl groups. The distributed enhancement components may include one of many: alcohols, glycols, ethers, acetals, benzenes, ketones, chlorinated solvents, carbonates, solvents, and surfactants.

[0021] Preferred compatibilizers include acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms (preferably about 6 to about 15 carbon atoms), alkylphenols and alkylphenol ethoxylates, ethylene glycol, and dipropylene. The applicants found that the compounds include, but are not limited to, glycols, diisopropylene glycol, dipropylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1,3-diisopropylbenzene, isopropylbenzene, 1,3-diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, trans-1,2-dichloroethylene, 2-chloropropane, trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, toluene, tris(1-chloro-2-propyl)phosphate (TCPP), and any combination of two or more of these.

[0022] Preferred acyclic alcohols may be linear or branched, and preferably have 1 to 10 carbon atoms, or 1 to 9 carbon atoms, or 1 to 8 carbon atoms, or 1 to 7 carbon atoms, or 1 to 6 carbon atoms, or 1 to 5 carbon atoms, or 2 to 5 carbon atoms, or 2 to 4 carbon atoms. Preferred acyclic alcohols are monofunctional alcohols. Preferred monofunctional alcohols are ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2-butanol, and 2-methyl-1-propanol.

[0023] Preferred cyclic alcohols preferably have 6 to 40 carbon atoms, or 6 to 35 carbon atoms, or 6 to 30 carbon atoms, or 6 to 25 carbon atoms, or 6 to 20 carbon atoms, or 6 to 15 carbon atoms, or 6 to 14 carbon atoms, or 6 to 12 carbon atoms, or 6 to 10 carbon atoms, or 6 to 9 carbon atoms, or 6 to 8 carbon atoms.

[0024] In some embodiments, the compatibilizer includes alkylphenols, and in preferred embodiments, alkylphenol alkoxylates, including, for example, alkylphenol ethoxylates. Specific preferred embodiments include, but are not limited to, nonylphenols and nonylphenol ethoxylates.

[0025] One aspect of the present invention provides a blend of a compatibilizer and either HFO-1336mzzm(Z) or a polyester polyol. Another aspect provides a polyol premix composition comprising a compatibilizer, HFO-1336mzzm(Z), and a polyester polyol. Other aspects provide a method for preparing a polyol premix composition, a method for preparing a polyurethane or polyisocyanurate foam using the polyol premix composition, and a foaming composition using the polyol premix composition.

[0026] One aspect of the present invention is a compatibilizer blend. In some embodiments, the compatibilizer blend comprises a compatibilizer according to the present invention and HFO-1336mzzm(Z). The compatibilizer blend can comprise a compatibilizer and a polyester polyol. The compatibilizer blend can optionally comprise one or more compatibilizers.

[0027] The compatibilizer can be present in an amount of about 0.5 wt% to about 10 wt%, or about 0.5 wt% to about 9 wt%, or about 0.5 wt% to about 8 wt%, or about 0.5 wt% to about 7 wt%, or about 0.5 wt% to about 6 wt%, or about 0.5 wt% to about 5 wt%, or about 1 wt% to about 10 wt%, or about 2 wt% to about 10 wt%, or about 3 wt% to about 10 wt%, or about 4 wt% to about 10 wt% based on the amount of the compatibilizer and the blowing agent, or based on the amount of the compatibilizer and the polyester polyol, as needed.

[0028] Another aspect of the present invention is a polyol premix composition. The polyol premix composition comprises a polyester polyol and a halogenated olefin blowing agent, preferably C3 or It contains a C4 halogenated olefin, more preferably cis-1,1,1,4,4,4-hexafluorobut-2-ene blowing agent and a compatibilizer. The blowing agent, or the polyester polyol, or both together form a stable and substantially homogeneous combination of components, and in a preferred embodiment, this is achieved by a combination of components that form a stable solution, dispersion, and / or emulsion.

[0029] The compatibilizer can be present in an amount of at least about 1.7% by weight of the polyol premix composition.

[0030] In relation to the polyol premix composition, the compatibilizer can be present in the polyol premix in an amount of about 0.01% to about 10% by weight, or about 0.01% to about 9% by weight, or about 0.01% to about 8% by weight, or about 0.01% to about 7% by weight, or about 0.01% to about 6% by weight, or about 0.01% to about 5% by weight, or about 0.05% to about 10% by weight, or about 0.05% to about 9% by weight, or about 0.05% to about 8% by weight, or about 0.05% to about 7% by weight, or about 0.05% to about 6% by weight, or about 0.05% to about 5% by weight, or about 0.1% to about 10% by weight, or about 0.1% to about 9% by weight, or about 0.1% to about 8% by weight, or about 0.1% to about 7% by weight, or about 0.1% to about 6% by weight, or about 0.1% to about 5% by weight, or about 0.3% to about 10% by weight, or about 0.3% to about 9% by weight, or about 0.3% to about 8% by weight, or about 0.3% to about 7% by weight, or about 0.3% to about 6% by weight, or about 0.3% to about 5% by weight, or about 0.5% to about 9% by weight, or about 0.5% to about 8% by weight, or about 0.5% to about 7% by weight, or about 0.5% to about 6% by weight, or about 0.5% to about 5% by weight, or about 1% to about 10% by weight, or about 2% to about 10% by weight, or about 3% to about 10% by weight, or about 4% to about 10% by weight, based on the total weight of the components in the premix composition.

[0031] In relation to the polyol premix composition, based on the total weight of the components in the polyol premix composition, polyester polyol can be present in the polyol premix in an amount of about 50% to about 98% by weight, and the blowing agent can be present in an amount of about 0.25% to about 50% by weight.

[0032] In relation to polyol premix compositions, the polyester polyol is present in approximately 55% to approximately 98% by weight of the polyol premix composition, or approximately 60% to approximately 98% by weight, or approximately 65% ​​to approximately 98% by weight, or approximately 70% to approximately 98% by weight, or approximately 75% to approximately 98% by weight, or approximately 80% to approximately 98% by weight, or approximately 85% to approximately 98% by weight, or approximately 90% to approximately 98% by weight, or approximately It can be present in the polyol premix composition in amounts of 50% to about 95% by weight, or about 50% to about 90% by weight, or about 50% to about 85% by weight, or about 60% to about 95% by weight, or about 60% to about 90% by weight, or about 60% to about 85% by weight, or about 60% to about 80% by weight, or about 65% to about 95% by weight, or about 65% to about 90% by weight, or about 65% to about 85% by weight, or about 65% to about 80% by weight.

[0033] The amount of foaming agent is based on the total weight of the components of the polyol premix composition, in amounts of approximately 0.25% to approximately 45% by weight, or approximately 0.25% to approximately 40% by weight, or approximately 0.25% to approximately 35% by weight, or approximately 0.25% to approximately 30% by weight, or approximately 0.25% to approximately 25% by weight, or approximately 0.25% to approximately 20% by weight, or approximately 0.25% to approximately 15% by weight, or approximately 0.25% to approximately 10% by weight, or approximately 0.25% to approximately 5% by weight, or approximately 0.25% to approximately 2% by weight, or approximately 1% to approximately 50% by weight, or approximately 1% to approximately 45% by weight, or approximately 1% to approximately 40% by weight, or approximately 1% to approximately 35% by weight, or approximately 1% to approximately 30% by weight Quantity %, approximately 1% to approximately 25% by weight, or approximately 1% to approximately 20% by weight, or approximately 1% to approximately 15% by weight, or approximately 1% to approximately 10% by weight, or approximately 1% to approximately 5% by weight, or approximately 1% to approximately 2% by weight, or approximately 5% to approximately 50% by weight, or approximately 5% to approximately 45% by weight, or approximately 5% to approximately 40% by weight, or approximately 5% to approximately 35% by weight, or approximately 5% to approximately 30% by weight, approximately 5% to approximately 25% by weight, or approximately 5% to approximately 20% by weight, or approximately 5% to approximately 15% by weight, or approximately 5% to approximately 10% by weight, or approximately 10% to approximately 40% by weight, or approximately 10% to approximately 35% by weight, or approximately 10% to approximately 30% by weight It can exist in amounts of %, approximately 10% to 25% by weight, or approximately 10% to 20% by weight, or approximately 10% to 15% by weight, or approximately 15% to 50% by weight, or approximately 15% to 45% by weight, or approximately 15% to 40% by weight, or approximately 15% to 35% by weight, or approximately 15% to 30% by weight, or approximately 15% to 25% by weight, or approximately 15% to 20% by weight, or approximately 20% to 50% by weight, or approximately 20% to 45% by weight, or approximately 20% to 40% by weight, or approximately 20% to 35% by weight, or approximately 20% to 30% by weight, or approximately 20% to 25% by weight.

[0034] The polyol premix composition may contain a catalyst and a surfactant.

[0035] The polyol premix composition may contain one or more of the following: flame retardants, dyes, fillers, pigments, dispersants, cell stabilizers, and nucleating agents.

[0036] Polyol premix compositions can be formed by combining a polyester polyol, a halogenated olefin blowing agent, and a compatibilizer. The blowing agent, or the polyester polyol, or both, are preferably substantially uniformly distributed in the compatibilizer by forming a stable solution, dispersion, and / or emulsion of the compatibilizer, blowing agent, and / or polyol.

[0037] In general, the order and method of adding components in the compatibilizer blend and in the formation of the polyol premix can vary considerably within the scope of the present invention. The compatibilizer may be added to the blowing agent before being added to the remaining components of the premix composition. Alternatively, the compatibilizer may be added to the polyester polyol before being added to the remaining components of the premix composition. Alternatively, the compatibilizer may be added to a mixture of the blowing agent, polyester polyol, and any other components. Alternatively, all components may be added simultaneously.

[0038] Polyester polyols may contain one or more polyester polyols. A wide variety of polyester polyols can be used. Suitable polyester polyols include, but are not limited to, aromatic polyester polyols, aromatic polyethylene terephthalate polyols, aromatic carboxylic acid anhydrides, linear poly(diethylene adipate) glycol-based polyester polyols, dipropylene glycol, and combinations thereof.

[0039] In addition to polyester polyols, one or more additional polyols may be present. The additional polyols may be any polyols that react with isocyanates in a known manner when preparing polyurethane or polyisocyanurate foams. Useful additional polyols include sucrose-containing polyols, phenol-formaldehyde-containing polyols, glucose-containing polyols, sorbitol-containing polyols, methyl glucoside-containing polyols, toluenediamine-containing polyols, Mannich base polyols, glycerin-containing polyols, ethylene glycol-containing polyols, diethylene glycol-containing polyols, propylene glycol-containing polyols, graft copolymers of polyether polyols and vinyl polymers, copolymers of polyether polyols and polyurea, and (b) One or more of the (a) that are condensed with one or more:

[0040] ((a) Glycerin, ethylene glycol, diethylene glycol, trimethylolpropane, ethylenediamine, pentaerythritol, soybean oil, lecithin, tall oil, palm oil, castor oil,

[0041] (b) comprising one or more of the following: ethylene oxide, propylene oxide, butylene oxide, a mixture of ethylene oxide and propylene oxide, or a combination thereof.

[0042] When a mixture of polyester polyols and one or more additional polyols is used, the polyester polyols (total amount of all polyester polyols) generally exist in an amount of about 1% to about 99% by weight of the total amount of polyols (polyester polyols and additional polyols), and the additional polyols generally exist in an amount of about 1% to 99% by weight of the total amount of polyols. Polyester polyols are present in the polyol premix composition in amounts of approximately 5% to approximately 99% by weight, or approximately 10% to approximately 99% by weight, or approximately 15% to approximately 99% by weight, or approximately 20% to approximately 99% by weight, or approximately 25% to approximately 99% by weight, or approximately 30% to approximately 99% by weight, or approximately 35% to approximately 99% by weight, or approximately 40% to approximately 99% by weight, or approximately 45% to approximately 99% by weight, or approximately 50% to approximately 99% by weight, or approximately 55% to approximately 99% by weight, or approximately 6% by weight. 0% to approximately 99% by weight, or approximately 65% ​​to approximately 99% by weight, or approximately 70% to approximately 99% by weight, or approximately 75% to approximately 99% by weight, or approximately 80% to approximately 99% by weight, or approximately 85% to approximately 99% by weight, or approximately 90% to approximately 99% by weight, or approximately 95% to approximately 99% by weight, or approximately 5% to approximately 95% by weight, or approximately 10% to approximately 95% by weight, or approximately 15% to approximately 95% by weight, or approximately 20% to approximately 95% by weight, or approximately 25% to approximately 95% by weight, or approximately 30% to approximately 95% by weight, or approximately 35% to approximately 95% by weight, or approximately 40% to approximately 95% by weight, or approximately 45% to approximately 95% by weight, or approximately 50% to approximately 95% by weight, or approximately 55% to approximately 95% by weight, or approximately 60% to approximately 95% by weight, or approximately 65% ​​to approximately 95% by weight, or approximately 70% to approximately 95% by weight, or approximately 75% to approximately 95% by weight, or approximately 80% to approximately 95% by weight, or approximately 85% to approximately 95% by weight, or approximately 90% to approximately 95% by weight, or Approximately 5% to 90% by weight, or approximately 10% to 90% by weight, or approximately 15% to 90% by weight, or approximately 20% to 90% by weight, or approximately 25% to 90% by weight, or approximately 30% to 90% by weight, or approximately 35% to 90% by weight, or approximately 40% to 90% by weight, or approximately 45% to 90% by weight, or approximately 50% to 90% by weight, or approximately 55% to 90% by weight, or approximately 60% to 90% by weight, or approximately 65% ​​to 90% by weight.Or approximately 70% to 90% by weight, or approximately 75% to 90% by weight, or approximately 80% to 90% by weight, or approximately 85% to 90% by weight, or approximately 5% to 85% by weight, or approximately 10% to 85% by weight, or approximately 15% to 85% by weight, or approximately 20% to 85% by weight, or approximately 25% to 85% by weight, or approximately 30% to 85% by weight, or Approximately 35% to approximately 85% by weight, or approximately 40% to approximately 85% by weight, or approximately 45% to approximately 85% by weight, or approximately 50% to approximately 85% by weight, or approximately 55% to approximately 85% by weight, or approximately 60% to approximately 85% by weight, or approximately 65% ​​to approximately 85% by weight, or approximately 70% to approximately 85% by weight, or approximately 75% to approximately 85% by weight, or approximately 80% to approximately 85% by weight, and Approximately 85% by weight to approximately 85% by weight, or approximately 90% by weight to approximately 85% by weight, or approximately 5% by weight to approximately 80% by weight, or approximately 10% by weight to approximately 80% by weight, or approximately 15% by weight to approximately 80% by weight, or approximately 20% by weight to approximately 80% by weight, or approximately 25% by weight to approximately 80% by weight, or approximately 30% by weight to approximately 80% by weight, or approximately 35% by weight to approximately 80% by weight, or approximately 40% by weight to approximately 80% by weight, or Approximately 45% to 80% by weight, or approximately 50% to 80% by weight, or approximately 55% to 80% by weight, or approximately 60% to 80% by weight, or approximately 65% ​​to 80% by weight, or approximately 70% to 80% by weight, or approximately 75% to 80% by weight, or approximately 5% to 75% by weight, or approximately 10% to 75% by weight, or approximately 15% to 75% by weight, or Approximately 20% to 75% by weight, or approximately 25% to 75% by weight, or approximately 30% to 75% by weight, or approximately 35% to 75% by weight, or approximately 40% to 75% by weight, or approximately 45% to 75% by weight, or approximately 50% to 75% by weight, or approximately 55% to 75% by weight, or approximately 60% to 75% by weight, or approximately 65% ​​to 75% by weight, or approximately 70% to 75% by weight, or approximately 5% to 70% by weight, or approximately 10% to 70% by weight, or approximately 15% to 70% by weight, or approximately 20% to 70% by weight, or approximately 25% to 70% by weight Weight %, or approximately 30% to 70% by weight, or approximately 35% to 70% by weight, or approximately 40% to 70% by weight, or approximately 45% to 70% by weight, or approximately 50% to 70% by weight, or approximately 55% to 70% by weight, or approximately 60% to 70% by weight, or approximately 65% ​​to 70% by weight, or approximately 5% to 65% by weight, or approximately 10% to 65% by weight, or approximately 15% to 65% by weight, or approximately 20% to 65% by weight, or approximately 25% to 65% by weight, or approximately 30% to 65% by weight, or approximately 35% to 65% by weight, or approximately 40% by weight %~approximately 65% ​​by weight, or approximately 45%~approximately 65% ​​by weight, or approximately 50%~approximately 65% ​​by weight, or approximately 55%~approximately 65% ​​by weight, or approximately 60%~approximately 65% ​​by weight, or 5%~approximately 60% by weight, or approximately 10%~approximately 60% by weight, or approximately 15%~approximately 60% by weight, or approximately 20%~approximately 60% by weight, or approximately 25%~approximately 60% by weight, or approximately 30%~approximately 60% by weight, or approximately 35%~approximately 60% by weight, or approximately 40%~approximately 60% by weight, or approximately 45%~approximately 60% by weight, or approximately 50%~approximately 60% by weight, or approximately 55%~approximately 60% by weight, or approximately 5% by weight to approximately 55% by weight, or approximately 10% by weight to approximately 55% by weight, or approximately 15% by weight to approximately 55% by weight, or approximately 20% by weight to approximately 55% by weight, or approximately 25% by weight to approximately 55% by weight, or approximately 30% by weight to approximately 55% by weight, or approximately 35% by weight to approximately 55% by weight, or approximately 40% by weight to approximately 55% by weight, or approximately 45% by weight to approximately 55% by weight, or approximately 50% by weight to approximately 55% by weight, or approximately 5% by weight to approximately 50% by weight, or approximately 10% by weight to approximately 50% by weight, or approximately 15% by weight to approximately 50% by weight, or approximately 20% by weight to approximately 50% by weight, or approximately 25% by weight to approximately 50% by weight, or approximately 30% by weight to approximately 50% by weight,Alternatively, it may be present in amounts of about 35% to about 50% by weight, or about 40% to about 50% by weight, or about 45% to about 50% by weight. The polyester polyol constitutes at least about 20% by weight, more preferably at least about 50% by weight, of the polyols in the blend. The remainder of the total polyols is additional polyols.

[0043] The amount and composition of polyols used depend in part to the type of foam being produced. Flexible foams, for example, may contain about 80% to about 95% by weight of total polyols (polyester polyols and additional polyols (if present)) depending on the weight of the polyol premix composition. In spray foams, for example, about 65% to about 85% by weight of total polyols may be present depending on the weight of the polyol premix composition. For foams for electrical appliances, for example, about 65% to about 85% by weight of total polyols may be present depending on the weight of the polyol premix composition. For polyurethane (PUR) panel foams, for example, about 65% to about 80% by weight of total polyols may be present depending on the weight of the polyol premix composition. In polyisocyanurate (PIR) panel foams, for example, about 65% to about 85% by weight of total polyols may be present depending on the weight of the polyol premix composition. PIR panel foams can be, for example, substantially all polyester polyols.

[0044] The halogenated olefin blowing agent preferably comprises a C3 or C4 halogenated olefin, and more preferably comprises cis-1,1,1,4,4,4-hexafluorobuta-2-ene (cis-HFO-1336mzzm(Z)).

[0045] Auxiliary blowing agents may be present. Suitable auxiliary blowing agents include other hydrohaloolefins, carbon fluorides, chlorocarbons, chlorofluorocarbons, hydrocarbons, ethers, esters, Examples of gas-generating materials include, but are not limited to, aldehydes, ketones, acetals, organic acids, atmospheric gases, gas-generating materials, or combinations thereof. By gas-generating materials, we mean materials that produce gas, such as CO2, through decomposition or chemical reactions. Examples of gas-generating materials include, but are not limited to, water, formic acid, or azodicarbonamides. Water reacts with isocyanates to form carbon dioxide. Formic acid reacts with isocyanates to form carbon dioxide and carbon monoxide.

[0046] Other hydrohaloolefins preferably contain at least one haloalkene, such as a fluoroalkene or chloroalkene containing 3 to 4 carbon atoms and at least one carbon-carbon double bond. Suitable hydrohaloolefins non-exclusively include trifluoropropene; tetrafluoropropene, e.g., trans-HFO-1234ze or cis-HFO-1234ze; pentafluoropropene, e.g., HFO-1225; hexafluorobutene, e.g., trans-HFO-1336mzz; or chlorotrifluoropropene, e.g., trans-HFO-1233zd, cis-HFO-1233zd, HFO-1233xf; chlorodifluoropropene; chlorotetrafluoropropene; and combinations thereof. Tetrafluoropropene, pentafluoropropene, and chlorotrifluoropropene compounds having one or fewer F or Cl substituents at the unsaturated terminal carbon are preferred. trans-1,3,3,3-tetrafluoropropene (HFO-1234ze); 2,3,3,3-tetrafluoropropene (HFO-1234yf); 1,1,3,3-tetrafluoropropene; cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye); trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye); 1,1,1-trifluoropropene; 1,1,1,3,3-pentafluoropropene (HFO-1225zc); 1,1,1,3,3,3-hexafluorobuta-2-ene, 1 This includes 1,2,3,3-pentafluoropropene (HFO-1225yc); cis-1,1,1,2,3-pentafluoropropene (HFO-1225ye); trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd); 2-chloro-3,3,3-trifluoropropene (HFO-1233xf); trans-1,1,1,4,4,4-hexafluorobuta-2-ene (HFO-1336mzz), or combinations thereof, and any and all structural, geometric, or stereoisomers of each of these.

[0047] Preferred hydrohaloolefins have a Global Warming Potential (GWP) of 150 or less, more preferably 100 or less, and even more preferably 75 or less. As used herein, "GWP" refers to "The Scientific Assessment of Ozone Depletion, 2002, a report of the World," which is incorporated herein by reference. As defined in the Meteorological Association's Global Ozone Research and Monitoring Project, the Ozone Depletion Potential (ODP) is measured relative to the Global Ozone Wage (GWP) of carbon dioxide and over a 100-year planned period. Preferred hydrohaloolefins also have an Ozone Depletion Potential (ODP) of preferably 0.05 or less, more preferably 0.02 or less, and even more preferably about zero. As used herein, "ODP" is as defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project," which is incorporated herein by reference.

[0048] Other suitable blowing agents include HCFC-141b(CH3CCl2F), HCFC-142b(CH3CClF2), HCFC-22(CHClF2), HFC-245fa( Examples include CHF2CH2CF3), HFC-365mfc(CH3CF2CH2CF3), HFC-227ea(CF3CHFCF3), HFC-134a(CH2FCF3), HFC-152a(CH3CHF2), trans-1,2-dichloroethylene, propane, butane, isobutane, n-pentane, isopentane, cyclopentane, dimethyl ether, methyl formate, methyl acetate, acetone, methylal, ethylal, carbon dioxide, water, formic acid, acetic acid, and mixtures thereof, or two or more of these.

[0049] The foaming agent according to the present invention may exist in a range of concentrations based on the type and / or use of the foam, and all such concentrations are within the scope of the present invention. For example, the foaming agent may be present in a polyol premix composition in amounts of about 0.25% to about 50% by weight, or 0.5% to about 50% by weight, or about 1% to about 50% by weight, or about 2% to about 50% by weight, or about 0.5% to about 40% by weight, or about 1% to about 40% by weight, or about 2% to about 40% by weight, or about 0.5% to about 30% by weight, or about 1% to about 30% by weight, or about 2% to about 30% by weight, or about 0.5% to about 25% by weight. It is present in the polyol premix composition in amounts of approximately 1% to approximately 25% by weight, or approximately 2% to approximately 25% by weight, or approximately 0.5% to approximately 20% by weight, or approximately 1% to approximately 20% by weight, or approximately 2% to approximately 20% by weight, or approximately 0.5% to approximately 15% by weight, or approximately 1% to approximately 15% by weight, or approximately 2% to approximately 15% by weight, or approximately 0.5% to approximately 10% by weight, or approximately 1% to approximately 10% by weight, or approximately 2% to approximately 10% by weight.

[0050] Those skilled in the art will be able to select the amount of blowing agent to be used for the type of foam to be produced based on the teachings contained herein. For example, flexible foams are generally produced using a relatively low concentration of blowing agent, preferably HFO-1336mzzm(Z), in amounts of preferably about 0.25% to about 10% by weight, or about 0.5% to about 8% by weight, or about 0.5% to about 6% by weight, or about 0.5% to about 5% by weight, or 0.5% to about 4% by weight. Spray foams preferably contain a blowing agent, preferably HFO-1336mzzm(Z), in amounts of preferably about 4% to about 25% by weight, or about 4% to about 20% by weight, or about 4% to about 15% by weight, or about 6% to about 12% by weight. The foam for electrical appliances, PIR panel foam, and PUR panel foam preferably contain a foaming agent, preferably HFO-1336mzzm(Z), in an amount of about 5% to about 30% by weight, or about 10% to about 30% by weight, or about 15% to about 30% by weight.

[0051] When both HFO-1336mzzm(Z) and an auxiliary blowing agent are present, the amount of HFO-1336mzzm(Z) is preferably about 1% to about 99% by weight, or about 5% to about 99% by weight, or about 10% to about 99% by weight, or about 15% to about 99% by weight, or about 20% to about 99% by weight, or about 25% to about 99% by weight, or about 30% to about 99% by weight. Weight %, or approximately 35% to 99% by weight, or approximately 40% to 99% by weight, or approximately 45% to 99% by weight, or approximately 50% to 99% by weight, or approximately 55% to 99% by weight, or approximately 60% to 99% by weight, or approximately 65% ​​to 99% by weight, or approximately 70% to 99% by weight, or approximately 75% to 99% by weight, or approximately 80% to 99% by weight, or approximately 85% to The total amount of the blowing agent is preferably about 99% by weight, or about 90% to about 99% by weight, and the auxiliary blowing agent is preferably about 99% to about 1% by weight, or about 95% to about 1% by weight, or about 90% to about 1% by weight, or about 85% to about 1% by weight, or about 80% to about 1% by weight, or about 75% to about 1% by weight, or about 70% to about 1% by weight, or about 65% to about 1% by weight, or It exists in amounts of approximately 60% to 1% by weight, or approximately 55% to 1% by weight, or approximately 50% to 1% by weight, or approximately 45% to 1% by weight, or approximately 40% to 1% by weight, or approximately 35% to 1% by weight, or approximately 30% to 1% by weight, or approximately 25% to 1% by weight, or approximately 20% to 1% by weight, or approximately 15% to 1% by weight, or approximately 10% to 1% by weight.

[0052] The overall composition of the blowing agent blend can vary considerably within the broad scope of the present invention, and those skilled in the art will be able to adjust the components and amounts of specific blowing agents to suit their particular needs based on the teachings contained herein, including based on the type of foam to be produced and the desired foam properties.

[0053] The polyol premix composition may contain a surfactant. The surfactant is used to form a foam from the mixture and to control the size of the foam's bubbles (cells) so that a foam with a desired cell structure is obtained. Preferably, the foam has small bubbles or cells of uniform size because it has the most desirable physical properties, such as compressive strength and thermal conductivity. Furthermore, the foam should have stable cells that do not collapse before formation or during foaming.

[0054] Suitable surfactants include silicone surfactants and non-silicone surfactants. The surfactant components are preferably present in the polyol premix composition in an amount of about 0.1% to about 10% by weight, or about 0.2% to about 5% by weight, or about 0.2% to about 3.0% by weight, or about 0.5% to about 3.0% by weight, depending on the weight of the polyol premix composition.

[0055] The polyol premix composition contains a catalyst. Suitable catalysts include amine catalysts and non-amine catalysts. Preferably, the catalyst is present in the polyol premix composition in an amount of about 0.2% to about 8.0% by weight, or about 0.4% to about 7.0% by weight, or about 0.5% to about 6.0% by weight, depending on the weight of the polyol premix composition.

[0056] Conventional flame retardants may be optionally incorporated, preferably in amounts of about 20% by weight or less, or about 15% by weight or less, or about 10% by weight or less of the polyol premix. Some embodiments, such as foams for electrical appliances, typically do not contain flame retardants. Examples of optional flame retardants include, but are not limited to, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(3-dichloropropyl) phosphate, tri(2-chloroisopropyl) phosphate, tricresyl phosphate, tri(2,2-dichloroisopropyl) phosphate, diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonate, dimethylmethylphosphonate, tri(2,3-dibromopropyl) phosphate, tri(1,3-dichloropropyl) phosphate, and tetra-cis-(2-chloroethyl)ethylenediphosphate, triethyl phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and melamine.

[0057] In addition to the components already described, other components such as dyes, fillers, pigments, dispersants, cell stabilizers, and nucleating agents (such as 3M perfluoro compounds, PF-5056 and FA-188) may be included in the preparation of the foam. These other components are typically included in the polyol premix composition in amounts of up to 20% by weight in total, or 15% or less by weight, or 10% or less by weight, or 5% or less by weight. Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fiber, carbon black, and silica. Pigments that may be used herein may be any conventional pigments, such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chromium green, chromium yellow, iron blue sienna, molybdenum orange, and organic pigments, such as para red, benzidine yellow, toluidine red, toner, and phthalocyanine.

[0058] The polyol premix composition may contain about 50% to about 98% by weight of polyester polyol and any additional polyols. If additional polyols are present, there may be about 10% to about 99% by weight (based on the total weight of the polyol components) of polyester polyol and about 1% to about 90% by weight (based on the total weight of the polyol components) of additional polyols, such as polyether polyols and Mannich polyols. The polyol premix composition may contain about 0.25% to about 50% by weight of blowing agent (based on the total polyol premix). The blowing agent may be HFO-1336mzzm(Z) or a mixture of HFO-1336mzzm(Z) and an auxiliary blowing agent. HFO-1336mzzm(Z) may be present in an amount of about 40% to about 99% by weight, depending on the weight of the blowing agent components, and the auxiliary blowing agent may be present in an amount of 1% to 60% by weight, depending on the weight of the blowing agent components. The compatibilizer may be an alcohol and may be present in an amount of about 0.01% to about 10% by weight. A surfactant may be present in an amount of about 0.2% to about 5% by weight. The polyol premix composition may contain about 0.1% to about 8.0% by weight of catalyst. The polyol premix may contain up to about 20% by weight of flame retardant and up to about 20% by weight of other additives.

[0059] Preferred formulations for foams used in electrical appliances, PIR panels, and PUR panels are based on a total polyol premix composition and include about 65% to about 85% by weight of polyester polyols and optional additional polyols (about 20% to about 99% by weight of polyester polyols and about 1% to about 80% by weight of additional polyols (if present) (based on the total weight of polyols)). The polyol premix composition may contain about 15% to about 30% by weight of a blowing agent (based on the total polyol premix) (cis-HFO-1336mzzm(Z), or a mixture of about 92% to about 97% by weight of cis-HFO-1336mzzm(Z) and about about 3% to about 8% by weight of water). A compatibilizer may be an alcohol and may be present in an amount of about 0.01% to about 10% by weight. About 0.2% to about 5% by weight of a surfactant and about 0.1% to about 6% by weight of a catalyst may be present. The polyol premix composition may optionally contain about 15% by weight of a flame retardant and about 10% by weight of other additives.

[0060] A preferred formulation for spray foam applications is based on a total polyol premix composition and comprises about 65% to about 85% by weight of polyester polyol and optional additional polyols (about 40% to about 99% by weight of polyester polyol and about 1% to about 60% by weight of additional polyol (if present) (based on the total weight of polyols)). The polyol premix composition preferably contains about 6% to about 12% by weight of a blowing agent (based on the total polyol premix composition) (cis-HFO-1336mzzm(Z), or a mixture of about 60% to about 85% by weight of cis-HFO-1336mzzm(Z) and about about 15% to about 40% by weight of water). A compatibilizer may be an alcohol and may be present in an amount of about 0.01% to about 10% by weight. About 0.2% to about 5% by weight of a surfactant and about 0.1% to about 8% by weight of a catalyst may be present. The polyol premix composition may contain 15% by weight of a flame retardant and 10% by weight of other additives.

[0061] A preferred flexible foam formulation is based on the total polyol premix composition and comprises about 80% to about 95% by weight of polyester polyol and optional additional polyols (about 10% to about 99% by weight of polyester polyol and about 1% to about 90% by weight of additional polyol (if present) (based on the total weight of polyols)). The polyol premix composition may contain about 0.5% to about 4% by weight of a blowing agent (based on the total polyol premix composition) (cis-HFO-1336mzzm(Z), or a mixture of about 40% to about 50% by weight of cis-HFO-1336mzzm(Z) and about about 50% to about 60% by weight of water). The compatibilizer may be an alcohol, and may be about 0.01% to about 10% by weight. It can be present in weight percent. Approximately 0.2 to 5% by weight of surfactant and approximately 0.1 to 3.5% by weight of catalyst may be present. The polyol premix composition may contain approximately 10% by weight of flame retardant and approximately 10% by weight of other additives.

[0062] Preferred distribution-enhancing components for aromatic polyester polyols and cis-HFO-1336mzzm(Z) include alcohols, alkylphenol ethoxylates, ethers, and chlorinated solvents.

[0063] One preferred polyol premix comprises a monofunctional acyclic alcohol having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably ethanol.

[0064] One preferred polyol premix comprises an aromatic polyester polyol, cis-HFO-1336mzzm(Z), and nonylphenol ethoxylate.

[0065] One preferred polyol premix comprises an aromatic polyester polyol, cis-HFO-1336mzzm(Z), and ethylene glycol mono-butyl ether.

[0066] One preferred polyol premix comprises an aromatic polyester polyol, cis-HFO-1336mzzm(Z), and 2-chloropropane.

[0067] Preferred distribution-enhancing components for aromatic carboxylic acid anhydride (phthalic acid) polyester polyols and cis-HFO-1336mzzm(Z) include alcohols, alkylphenol ethoxylates, glycols, ethers and acetals, benzenes, ketones, chlorinated solvents, carbonates, and other solvents.

[0068] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and a monofunctional acyclic alcohol having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably ethanol.

[0069] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and nonylphenol ethoxylate.

[0070] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and dipropylene glycol.

[0071] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and dipropylene glycol methyl ether.

[0072] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and methylal.

[0073] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and ethylene glycol mono-butyl ether.

[0074] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and 1,3-diisopropenylbenzene.

[0075] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and isopropenylbenzene.

[0076] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and acetone.

[0077] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and methyl ethyl ketone.

[0078] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and methyl formate.

[0079] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and trans-1,2-dichloroethylene.

[0080] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and 2-chloropropane.

[0081] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and propylene carbonate.

[0082] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and dioctyl phthalate.

[0083] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and toluene.

[0084] One preferred polyol premix comprises an aromatic carboxylic acid anhydride (phthalic acid) polyester polyol, cis-HFO-1336mzzm(Z), and 1-propoxy-2-propanol.

[0085] Preferred distribution-enhancing components for aromatic polyester polyol diols and cis-HFO-1336mzzm(Z) include alcohols, glycols, and ethers.

[0086] One preferred polyol premix comprises an aromatic polyester polyol diol, cis-HFO-1336mzzm(Z), and a monofunctional acyclic alcohol having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably ethanol.

[0087] One preferred polyol premix comprises an aromatic polyester polyol diol, cis-HFO-1336mzzm(Z), and ethylene glycol.

[0088] One preferred polyol premix comprises an aromatic polyester polyol diol, cis-HFO-1336mzzm(Z), and ethylene glycol mono-butyl ether.

[0089] Preferred distribution-enhancing components for aliphatic adipate diethylene glycol-based polyester polyols and cis-HFO-1336mzzm(Z) include alcohols, alkylphenol ethoxylates, ethers and acetals, chlorinated solvents, and ketones.

[0090] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate polyester polyol, cis-HFO-1336mzzm(Z), and a monofunctional acyclic alcohol having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and even more preferably ethanol.

[0091] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and nonylphenol ethoxylate.

[0092] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and dipropylene glycol methyl ether.

[0093] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and methylal.

[0094] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and ethylene glycol mono-butyl ether.

[0095] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and isopropenylbenzene.

[0096] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and acetone.

[0097] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and methyl ethyl ketone.

[0098] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate-based polyester polyol, cis-HFO-1336mzzm(Z), and trans-1-chloro-3,3,3-trifluoropropene.

[0099] One preferred polyol premix comprises a linear aliphatic diethylene glycol adipate polyester polyol, cis-HFO-1336mzzm(Z), and methyl formate.

[0100] The preparation of polyurethane or polyisocyanurate foams using the compositions described herein may be carried out by any of the methods well known in the art, see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and Technology, 1962; John Wiley and Sons, New York, NY; or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, NY; or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, Ohio. Generally, polyurethane or polyisocyanurate foams are prepared by combining isocyanates, polyol premix compositions, and other materials such as optional flame retardants, colorants, or other additives. These foams may be rigid, flexible, or semi-rigid, and may have a closed-cell structure, an open-cell structure, or a mixture of open-cell and closed-cell structures.

[0101] Providing components for polyurethane or polyisocyanurate foams in pre-blended formulations is convenient in many applications. Most typically, foam formulations are pre-blended with two components. An isocyanate and optionally other isocyanate-compatible raw materials constitute a first component, commonly referred to as component "A". A polyol mixture composition containing a surfactant, catalyst, blowing agent, and any other component constitutes a second component, commonly referred to as component "B". In any given application, component "B" does not have to contain all of the components listed above. For example, some formulations omit flame retardants if flame retardancy is not a required foam property. Thus, polyurethane or polyisocyanurate foams are readily prepared by combining subcomponents A and B by either manual mixing for small-scale preparations, and preferably by mechanical mixing techniques, to form blocks, slabs, laminates, in-situ injection panels, and other items, spray foams, floss, etc. Optionally, other components such as flame retardants, colorants, auxiliary foaming agents, water, and even other polyols may be added as a flow to the mixing head or reaction site. Most conveniently, they are all incorporated into one component B as described above.

[0102] A foaming composition suitable for forming polyurethane or polyisocyanurate foams can be formed by reacting an organic polyisocyanate with the above-mentioned polyol premix composition. Any organic polyisocyanate, including aliphatic and aromatic polyisocyanates, can be used in the synthesis of polyurethane or polyisocyanurate foams. Suitable organic polyisocyanates include aliphatic, alicyclic, aromaticaliphatic, aromatic, and heterocyclic isocyanates, which are well known in the field of polyurethane chemistry. These are described, for example, in U.S. Patents 4,868,224, 3,401,190, 3,454,606, 3,277,138, 3,492,330, 3,001,973, 3,394,164, 3,124,605, and 3,201,372. Aromatic polyisocyanates are preferred as a class.

[0103] Typical organic polyisocyanates are given by formula: R(NCO)z Corresponding to the formula, where R is an aliphatic group, an aromatic group, or a mixture thereof, and z is an integer corresponding to the valency of R, and is at least 2. Representative organic polyisocyanates intended herein include, for example, aromatic diisocyanates, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanates, crude toluene diisocyanate, methylenediphenyl diisocyanate, crude methylenediphenyl diisocyanate; aromatic triisocyanates, such as 4,4',4''-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanate; aromatic tetraisocyanates, such as 4,4'-dimethyldiphenylmethane-2,2'5,5-'tetraisocyanate; arylalkyl polyisocyanates, such as xylene diisocyanate; aliphatic polyisocyanates, such as hexamethylene-1,6-diisocyanate, lysine diisocyanate methyl ester, and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, m-phenylenediisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate. Typical aliphatic polyisocyanates are alkylenediisocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorene diisocyanate, and 4,4'-methylenebis(cyclohexyl isocyanate).Typical aromatic polyisocyanates include m- and p-phenylenediisocyanates, polymethylene polyphenyl polyisocyanates, 2,4- and 2,6-toluene diisocyanates, dianisidine diisocyanates, vitoleene isocyanates, 1,4-diisocyanates, bis(4-isocyanatophenyl)methane, and bis(2-methyl-4-isocyanatophenyl)methane. Preferred polyisocyanates are polymethylene polyphenyl polyisocyanates, particularly mixtures containing about 30 to about 85% by weight of methylene bis(phenyl isocyanate), with the remainder of the mixture being polymethylene polyphenyl polyisocyanates with a higher functionality than 2. In certain cases, so-called isocyanate prepolymers may also be used. Prepolymers are formed by combining excess diisocyanate with a polyol (polyester polyol, or polyether polyol). These polyisocyanates are prepared by conventional methods known in the art. In the present invention, polyisocyanates and polyols are used in amounts that yield an NCO / OH stoichiometric ratio in the range of about 0.9 to about 5.0. In the present invention, the NCO / OH equivalent ratio is preferably about 0.9 to about 4, or about 0.95 to about 3. Suitable organic polyisocyanates include polymethylene polyphenyl polyisocyanate, methylene bis(phenyl isocyanate), toluene diisocyanate, or combinations thereof.

[0104] In the preparation of polyisocyanurate foams, trimerization catalysts are preferably used to convert the blend, along with excess A component, into a polyisocyanurate-polyurethane foam. Trimerization catalysts used include, but are not limited to, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, alkali metal carboxylates, and mixtures of various types of catalysts, and may be any catalyst known to those skilled in the art. Preferred species within this class are potassium acetate, potassium octanoate, and N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

[0105] The resulting polyurethane or polyisocyanurate foams may have densities ranging from 0.5 lbs / cubic foot to approximately 60 lbs / cubic foot, or approximately 0.5 to approximately 20.0 lbs / cubic foot, or approximately 0.5 to approximately 15 lbs / cubic foot. The resulting density is a function of the amount of blowing agent or blowing agent mixture, plus auxiliary blowing agents such as water or co-blowing agents, present in or added when the foam is prepared. These foams may be rigid, flexible, or semi-rigid foams and may have closed-cell, open-cell, or a mixture of open-cell and closed-cell structures. These foams are used in a variety of well-known applications, including but not limited to thermal insulation, cushioning, flotation, packaging, adhesives, void filling, craft and decoration, and shock absorption.

[0106] The following non-limiting embodiments are helpful in illustrating the present invention. [Examples]

[0107] Comparative Example 1: Distribution of foaming agent in polyol In the absence of any embodiment of the compatibilizer of the present invention, the ability of certain polyols to form a stable and uniform distribution of HFO-1336mzzm(Z) was tested. Each polyol identified in Table 1 was tested by placing a predetermined amount of polyol in a 3-ounce glass pressure vessel, and the height and weight of the polyol were recorded. For each test, each liquid blowing agent identified in Table 1, containing HFO-1336mzzm(Z), was then added in an amount that produced 5 wt% blowing agent and 95 wt% polyol in the vessel, with a total weight of 70 grams of polyol and blowing agent in the vessel. The tube assembly was sealed, and the height and weight of the polyol and blowing agent components were recorded together. The components were then thoroughly mixed to obtain a homogeneous distribution of the blowing agent in the polyol. Visual observation of the liquid height and the state of the component mixture was recorded against the test temperature. If a homogeneous mixture was produced, i.e., if the 5% by weight concentration of the blowing agent was uniformly distributed in the polyol by visual observation, this result was recorded as 5% by weight in the column titled "Weight % Uniform Distribution" in Table 2. For any test, if the sample did not show the presence of a visually homogeneous mixture, i.e., if phase separation was observed, the height of each layer was recorded, and the amount of blowing agent uniformly distributed in the polyol by weight was reported based on this height and known density information for the polyol and blowing agent. The tests were conducted at room temperature (RT), 32°C (90°F), and 54°C (130°F).

[0108] Table 1 shows the blowing agent, the concentration of the blowing agent, and the polyols tested.

[0109] [Table 1]

[0110] [Table 2]

[0111] As can be seen from Table 2 above, polyol D (1,4-butanediol chain extender diol) failed to form a homogeneous mixture with HFO-1336mzzm(Z) at any concentration for both room temperature and 32°C tests. Even at a high temperature of 54°C, the maximum amount of HFO-1336mzzm(Z) that could be uniformly distributed in polyol D was only 2%. In contrast, the other polyols were able to form a uniform distribution of approximately 5% by weight of HFO-1336mzzm(Z) even in the absence of a compatibilizer. Generally, the ability of all the blowing agents tested to achieve a uniform distribution improved at higher temperatures.

[0112] The tests were repeated with other polyols. Each liquid blowing agent identified in Table 3, including HFO-1336mzzm(Z), was tested by adding it in an amount that produced 21% by weight of blowing agent and 79% by weight of polyol in a container, with a total weight of polyol and blowing agent of 70 grams. If a homogeneous mixture was produced, i.e., if the 21% by weight blowing agent was uniformly distributed in the polyol by visual observation, this result was recorded as 21% by weight in the column of Table 4 titled "Weight % Uniform Distribution". For any test, if the sample did not show the presence of a visually homogeneous mixture, i.e., if phase separation was observed, the height of each layer was recorded, and the amount of blowing agent uniformly distributed in the polyol by weight was reported based on this height and known density information for the polyol and blowing agent. The tests were conducted at room temperature (RT), 32°C (90°F), and 54°C (130°F).

[0113] [Table 3]

[0114] Table 4 below shows the blowing agent, the concentration of the blowing agent, and the polyols tested.

[0115] [Table 4]

[0116] In the absence of the present invention, HFO-1336mzzm(Z) exhibited a significantly lower uniform distribution in polyols F-I at all temperatures compared to HFO-1233zd(E). HFO-1233zd(E) exhibited superior uniformity of distribution in polyols F-I compared to HFO-1336mzzm(Z) and HFC-245fa.

[0117] In the absence of the present invention, HFO-1336mzzm(Z) exhibited a significantly lower uniform distribution in polyol O than HFO-1233zd(E) at all temperatures. HFO-1233zd(E) exhibited superior uniformity of distribution in polyol K~O compared to HFO-1336mzzm(Z) and HFC-245fa.

[0118] From this test, HFO-1336mzzm(Z) showed a significantly lower level of uniform distribution of certain polyester polyols, while other polyester polyols did not appear to have a similar problem.

[0119] Example 1: Compatibilizer for use with HFO-1336mzzm(Z) We have initiated research to determine the extent to which a particular compatibilizer can enhance the ability of HFO-1336mzzm(Z), which is uniformly distributed in different classes of polyester polyols, specifically aromatic carboxylic acid anhydride (phthalic acid) polyester polyols (polyol F), aromatic polyester polyols (polyol O), aromatic polyester polyol diols (polyol P), and linear aliphatic diethylene glycol adipate polyester polyols (polyol Q).

[0120] To demonstrate the ability of various dispersants to uniformly distribute within the tested polyols, a first test set was performed. 17 grams of each tested polyol were transferred to a small vial, and the height of the polyol was recorded. 8 grams of an appropriate weight of the identified compatibilizer was added to the polyol, and it was reported whether a uniform distribution was formed upon mixing.

[0121] A second test set was conducted to demonstrate the ability of various distributing agents to be uniformly distributed in the foaming agent HFO-1336mzzm(Z). 8.5 grams of foaming agent were transferred to a small vial, and the height of the foaming agent was recorded. 1.5 grams of an identified compatibilizer was added to the foaming agent, and it was reported whether a uniform distribution was formed upon mixing.

[0122] A third test set was conducted to demonstrate the ability of various distributing agents to uniformly distribute with the foaming agent HFO-1336mzzm(Z) and the tested polyol. The mixtures shown in the first and second tests were repeated as shown above, and then 16 grams of the first mixture (polyol / compatibilizer mixture) and 4 grams of the second mixture (HFO-1336mzzm(Z) / compatibilizer mixture) were mixed to form a mixture of polyol, HFO-1336mzzm(Z), and the indicated compatibilizer (UDA). The presence or absence of uniform distribution of the foaming agent, polyol, and compatibilizer was reported by visual observation during mixing. For convenience, the uniform distribution agent is identified as UDA (uniform distribution agent) in Tables 5A-5F.

[0123] [Table 5A]

[0124] [Table 5B]

[0125] [Table 5C]

[0126] [Table 5D]

[0127] [Table 5E]

[0128] [Table 5F]

[0129] As shown in Tables 5A-F and Example 1 above, lower molecular weight alcohols are superior for HFO-1336mzzm(Z) among all the polyester polyols tested. These are compatibilizers. Regarding glycols and ethers, the only glycol or ether that is a general-purpose compatibilizer for HFO-1336mzzm(Z) in polyester polyols is ethylene glycol mono-butyl ether. Ethylene glycol, diisopropylene glycol, dipropylene glycol methyl ether, and methylal can be used as compatibilizers for several types of polyester polyols. Neither benzene nor ketones were general-purpose compatibilizers for HFO-1336mzzm(Z). However, this class of materials has been found to be effective compatibilizers for HFO-1336mzzm(Z) in polyester polyols with lower functionality (e.g., polyols F and Q). Oils and hydrocarbons did not provide the ability to act as compatibilizers to improve the miscibility of HFO-1336mzzm(Z) in polyester polyols. Most co-foaming agents do not function as compatibilizers at the levels tested. However, HFO-1233zd(E) was a compatibilizer for polyol Q, and methyl formate was a compatibilizer for polyester polyols with lower functionality (e.g., polyols F and Q). Many commonly used raw materials do not function as general compatibilizers for HFO-1336mzzm(Z) in polyester polyols. However, some are effective for polyester polyols with lower functionality. For example, trans-1,2-dichloroethylene, 2-chloropropane, propylene carbonate, and toluene are effective for both polyols F and Q, while tris(1-chloro-2-propyl) phosphate is effective for polyol Q, and 1-propoxy-2-propanol is effective for polyol F.

[0130] As can be seen from Tables 5A to 5F above, the compatibilizers and mixtures thereof according to the present invention formed a uniform distribution with polyols F and O and the compatibilizer HFO-1233zd(E), whereas, as reported in Comparative Example 1, a uniform distribution was not otherwise formed.

[0131] Example 2 - Minimum Concentration Range 27 grams of the polyol to be evaluated were added to a large vial, and the height of the polyol in the vial was measured. 8 grams of HFO-1336mzzm were added to the vial, and the height of the liquid was measured. The vial was sealed and thoroughly mixed. The height of the separation layer was measured (this is the HFO-1336mzzm that was not uniformly distributed in the solution). 0.2 grams of compatibilizer were added to the vial. The vial was sealed, and the solution was thoroughly mixed. The height of the layer in the vial was recorded. Additional compatibilizer was added to the solution until a homogeneous solution was obtained. The amount was then recorded. Table 6 shows the results.

[0132] Example 3A: Stability test: Ternary mixture at 4-6 months The mixtures of HFO-1336mzzm(Z) + polyol + UDA reported in Tables 5A-5F above were stored in sealed containers under ambient (room temperature) conditions for 4-6 months to evaluate their long-term stability. The presence or absence of uniform distribution of the foaming agent, polyol, and compatibilizer was reported by visual observation at the time of initial mixing and during storage for 4-6 months. Tables 7A-C show the results.

[0133] [Table 6]

[0134] [Table 7A]

[0135] [Table 7B]

[0136] [Table 7C]

[0137] Example 3B: Stability test: 1 year The ternary mixtures of HFO-1336mzzm(Z) + polyol + UDA, as reported in Tables 7A-7C above, were stored in sealed containers under ambient (room temperature) conditions for one year to evaluate their long-term stability. Visual observations were conducted to report the presence or absence of uniform distribution of the foaming agent, polyol, and compatibilizer at the time of initial mixing and during storage over the one-year period. Mixtures that showed stability at 4-6 months were observed to remain stable after one year.

[0138] Example 3C: Stability test: Binary mixture at 4-6 months and 1 year The binary mixtures of HFO-1336mzzm(Z)+UDA and polyol+UDA reported in Tables 5A-5F above will be stored in sealed containers under ambient (room temperature) conditions for 4-6 months and 1 year to evaluate their long-term stability. The presence or absence of uniform distribution of the foaming agent and compatibilizer, as well as the polyol and compatibilizer, will be reported by visual observation during storage for 4-6 months and 1 year. The binary mixtures will be observed to be stable at 4-6 months and 1 year.

[0139] Example 4: Compatibilizer for use with HFO-1336mzzm(Z) in 1,4-butanediol Specifically, we will begin research to determine the extent to which a particular compatibilizer can enhance the ability of HFO-1336mzzm(Z), which is uniformly distributed in butanediols, and more specifically in alkanediols containing 1,4-butanediol.

[0140] To demonstrate the ability of various dispersants to uniformly distribute in 1,4-butanediol, the first test set is performed. 17 grams of 1,4-butanediol to be tested are transferred to a small vial, and the height of the material is recorded. 8 grams of the identified compatibilizer are added to the material, and it is reported whether uniform distribution is formed upon mixing, and then during storage in a sealed container under ambient (room temperature) conditions for storage periods of 6 months and 1 year.

[0141] A second test set will be conducted to demonstrate the ability of various distributing agents to uniformly distribute within the foaming agent HFO-1336mzzm(Z). 8.5 grams of foaming agent will be transferred to a small vial, and the height of the foaming agent will be recorded. 1.5 grams of an identified compatibilizer will be added to the foaming agent, and it will be reported whether uniform distribution is formed upon mixing, and then during storage in a sealed container under ambient (room temperature) conditions for 6 months and 1 year.

[0142] A third test set is conducted to demonstrate the ability of various distributing agents to uniformly distribute with the blowing agent HFO-1336mzzm(Z) and 1,4-butanediol. The mixtures shown in the first and second tests are repeated as shown above, and then 16 grams of the first mixture (polyol / compatibilizer mixture) and 4 grams of the second mixture (HFO-1336mzzm(Z) / compatibilizer mixture) are mixed to form a mixture of the material, HFO-1336mzzm(Z), and the indicated compatibilizer, which is identified as "1336+polyol+UDA" in Table 8 below. The presence or absence of uniform distribution of the blowing agent, material, and compatibilizer is reported by visual observation in Table 8 below, at the time of initial mixing and during storage for periods of 6 months and 1 year. For convenience, the uniform distributing agent is identified as UDA in the table.

[0143] [Table 8]

[0144] As can be seen from Table 8 above, all of the compatibilizers and mixtures thereof according to the present invention were able to form a uniform distribution of 1,4-butanediol and HFO-1336mzzm(Z) with the compatibilizer, whereas, as reported in Comparative Example 1, a uniform distribution was not formed otherwise.

[0145] Example 5: Compatibilizer for use with HFO-1336mzzm(Z) in other polyols Polyol A, Polyol B, Polyol C, Polyol E, Polyol G, Polyol H, Polyol I, Polyol K, Polyol L, Polyol M, Polyol N, Fragrance The tests reported in Example 4 above were repeated for the polyols, with the exception of each of the polyols identified as polyethylene terephthalate polyol and dipropylene glycol polyol. Acceptable results were obtained both at the time of initial mixing and after the storage period shown in Example 2.

[0146] Polyols A-E can be used in a variety of foam applications, including but not limited to integral skin foam. Polyols F-I can be used in a variety of foam applications, including but not limited to board stock foam. Polyols K-O can be used in a variety of foam applications, including but not limited to spray foam. Polyol P can be used in a variety of foam applications, including but not limited to board stock foam. Polyol Q can be used in a variety of foam applications, including but not limited to flexible foam.

[0147] Example 6: Compatibilizer for use with HFO-1233zd(E) in polyols Repeat the tests for polyols reported in Example 4 above using each of the polyols identified as polyols A to Q and polyester terephthalate polyols excluding HFO-1233zd(E). Acceptable results are obtained both at the time of initial mixing and after the storage period shown in Example 2.

[0148] While the present invention has been shown and described with particular reference to preferred embodiments, it will be readily apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The claims are intended to be construed to encompass the embodiments disclosed, their substitutes described above, and all their equivalents.

Claims

1. A polyol premix composition, halogenated olefin blowing agent, Polyester polyol and A polyol premix composition comprising a distribution-enhancing component comprising at least one organic compound having 1 to 40 carbon atoms, wherein the at least one organic compound is present in the premix in an amount effective to enhance the ability of the halogenated blowing agent and the polyol to form a stable and substantially homogeneous blend that remains substantially homogeneous when stored under ambient conditions for a period of four months.

2. The polyol premix composition according to claim 1, wherein the distribution-enhancing component has one or more hydroxyl groups and 1 to 25 carbon atoms.

3. The polyol premix composition according to claim 2, wherein the distribution-enhancing component comprises an alcohol, glycol, ether, acetal, benzene, ketone, chlorinated solvent, carbonate, solvent, and surfactant.

4. The polyol premix composition according to claim 3, wherein the halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobuta-2-ene.

5. The distribution-enhancing component comprises one or more of the following: acyclic alcohols having 1 to 10 carbon atoms, cyclic alcohols having 6 to 40 carbon atoms, alkylphenols and alkylphenol ethoxylates, dipropylene glycol, diisopropylene glycol, dipropylene glycol methyl ether, methylal, ethylene glycol mono-butyl ether, 1,3-diisopropylbenzene, isopropylbenzene, 1,3-diisopropenylbenzene, isopropenylbenzene, acetone, methyl ethyl ketone, 2-chloropropane, trans-1-chloro-3,3,3-trifluoropropene, methyl formate, propylene carbonate, dioctyl phthalate, and toluene. The polyol premix composition according to claim 1, wherein the halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobuta-2-ene.

6. The polyol premix composition according to claim 5, wherein the distribution-enhancing component comprises one or more of ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2-butanol, and 2-methyl-1-propanol.

7. The polyol premix composition according to claim 1, wherein the distribution-enhancing component is present in an amount of 0.5% to 10% by weight based on the total amount of the blend.

8. A polyol premix composition, Polyester polyol and halogenated olefin blowing agent, A polyol premix composition comprising a distribution-enhancing component comprising at least one organic compound having 1 to 40 carbon atoms, wherein the distribution-enhancing component is present in the polyol premix composition in an amount effective in enhancing the ability of the halogenated olefin blowing agent and the polyester polyol to form a stable and substantially homogeneous composition.

9. The polyol premix composition according to claim 8, wherein the distribution-enhancing component has one or more hydroxyl groups and 1 to 25 carbon atoms.

10. The polyol premix composition according to claim 8, wherein the distribution-enhancing component comprises one or more of the following: alcohol, glycol, ether, acetal, benzene, ketone, chlorinated solvent, carbonate, solvent, and surfactant.

11. The polyol premix composition according to claim 8, wherein the halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobuta-2-ene.

12. The polyol premix composition according to claim 11, wherein the distribution-enhancing component is present in an amount of at least 1.7% by weight of the polyol premix composition and comprises one or more of ethanol, methanol, isopropanol, n-butanol, 2-propanol, 1-pentanol, 3-methyl-2-butanol, and 2-methyl-1-propanol.

13. The polyol premix composition according to claim 8, wherein the polyester polyol and any additional polyol are present in an amount of 50% to 98% by weight of the polyol premix composition, the halogenated olefin blowing agent is present in an amount of 0.25% to 50% by weight of the polyol premix composition, and the distribution strengthening component is present in an amount of 0.01% to 10% by weight of the polyol premix composition.

14. The polyol premix composition according to claim 8, wherein the polyester polyol and any additional polyol are present in an amount of 80% to 95% by weight of the polyol premix composition, the halogenated olefin blowing agent is present in an amount of 0.25% to 10% by weight of the polyol premix composition, and the distribution strengthening component is present in an amount of 0.01% to 10% by weight of the polyol premix composition.

15. The polyol premix composition according to claim 8, wherein the stable and substantially homogeneous composition remains a substantially homogeneous mixture when stored under ambient conditions for a period of four months.

16. A method for forming a polyol premix composition, A method comprising combining a polyester polyol, a halogenated olefin blowing agent, and a distribution-enhancing component comprising at least one organic compound having 1 to 40 carbon atoms, wherein the distribution-enhancing component is present in the polyol premix composition in an amount sufficient to enhance the ability of the halogenated olefin blowing agent and the polyester polyol to form a stable and substantially homogeneous composition.

17. The method according to claim 16, wherein the distribution-enhancing component comprises an alcohol, glycol, ether, acetal, benzene, ketone, chlorinated solvent, carbonate, solvent, and surfactant, and the halogenated olefin blowing agent comprises cis-1,1,1,4,4,4-hexafluorobuta-2-ene.

18. The method according to claim 16, wherein the stable and substantially homogeneous composition remains a substantially homogeneous mixture when stored under ambient conditions for a period of four months.

19. A foaming composition comprising a mixture of an organic polyisocyanate and the polyol premix composition described in claim 8.

20. The foaming composition according to claim 19, wherein the organic polyisocyanate comprises polymethylene polyphenyl isocyanate, methylene bis(phenyl isocyanate), toluene diisocyanate, or a combination thereof.

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