Mixtures containing 1,1,1,4,4,4-hexafluorobutene and 1-chloro-3,3,3-trifluoropropene

Abstract

To provide blowing agents that exhibit low k-factor values, low global warming potential, low molecular weight, cost effectiveness, and optimal performance over a wide temperature range.SOLUTION: A blowing agent composition comprises: 1,1,1,4,4,4-hexafluorobutene (1336mzzm); 1-chloro-3,3,3-trifluoropropene (1233zd); and optionally at least one adjuvant selected from the group consisting of co-blowing agent(s), polyol(s), surfactant(s), polymer modifier(s), colorant(s), dye(s), solubility enhancer(s), flammability suppressant(s), flame retardants(s), antibacterial agent(s), viscosity reduction modifier(s), filler(s), vapor pressure modifier(s), nucleating agent(s), catalyst(s) and combination of any two or more of these.SELECTED DRAWING: None

Description

Technical Field

[0001]

[0001] This application is related to and claims the benefit of priority of U.S. Provisional Application No. 61 / 407,708, filed on October 28, 2010, the content of which is incorporated herein by reference.

[0002] The present invention relates to a mixture of 1,1,1,4,4,4 - hexafluorobutene (1336mzzm) and 1 - chloro - 3,3,3 - trifluoropropene (1233zd). More particularly, the present invention relates to a blowing agent composition comprising 1,1,1,4,4,4 - hexafluorobutene and 1 - chloro - 3,3,3 - trifluoropropene.

Background Art

[0002]

[0003] Foams of the type known as low - density rigid polyurethane or polyisocyanurate foams have utility in a wide range of insulation applications such as roofing systems, building panels, refrigerators, and freezers. An important factor in the large - scale commercial acceptance of rigid polyurethane foams in the building insulation industry has been their ability to provide a good balance of properties. Rigid polyurethane and polyisocyanurate foams are known to provide excellent insulation properties, good combustion characteristics, and excellent structural properties at moderately low densities.

[0003]

[0004] Methods for producing polyurethane and polyisocyanurate foams are known and generally consist of reacting an organic polyisocyanurate (such as a diisocyanate) and a polyol or a mixture of polyols in the presence of a volatile blowing agent that vaporizes due to the heat released during the reaction of the isocyanate and the polyol. This reaction can be facilitated by using amines and / or other catalysts as well as surfactants. The catalyst ensures proper curing of the foam, while the surfactant adjusts and controls the cell size. Flame retardants have traditionally been added to rigid polyurethane or polyisocyanurate foams to reduce their flammability.

[0004]

[0005]

[0005] In the foam material industry, liquid fluorocarbon blowing agents such as trichlorofluoromethane (CFC-11) and 1,1-dichloro-1-fluoroethane (HCFC-141b) have historically been used for ease of use under processing conditions. Fluorocarbons function as blowing agents due to their volatility and are encapsulated or incorporated within the closed-cell structure of rigid foams, becoming a major factor contributing to the low thermal conductivity characteristics of rigid urethane foams.

[0005]

[0006]

[0006] The use of fluorocarbons as preferred commercial blowing agents or foaming agents in thermal insulation foam applications is based in part on the k-factor obtained in relation to the foam produced. The k-factor is defined as the rate of heat energy transfer by conduction that gives a 1°F difference across two perpendicular faces of a 1 square foot uniform material 1 inch thick in 1 hour. Since the usefulness of closed-cell polyurethane-type foams is based in part on their insulation properties, it would be advantageous to identify materials that form foams with a lower k-factor than those described above.

[0006]

[0007]

[0007] Many of these blowing agents currently used for thermosetting foams (PUR / PIR / phenol) also have environmental or performance drawbacks. Concerns about potential damage to the Earth's atmosphere and climate have increased in recent years, and several chlorine-based compounds have been identified as particularly problematic in this regard. The use of chlorine-containing compositions (e.g., chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), etc.) Many of these compounds have generally fallen out of favor due to their ozone - depleting properties. Therefore, there is an increasing need for novel fluorocarbon and hydrofluorocarbon compounds that provide alternatives for foaming applications, as well as blends of existing compositions. Blowing agents having boiling points higher than atmospheric temperature are characterized by poor low - temperature thermal performance. Thus, an ideal blowing agent or blowing agent blend must be an LGWP material having optimal performance over a wide temperature range.

[0007]

[0008] Hydrohaloolefins such as 1,1,1,4,4,4 - hexafluorobutene (1336mzzm) and 1 - chloro - 3,3,3 - trifluoropropene (1233zd) have been developed independently as unparalleled agents that meet these requirements. However, one problem associated with 1336mzzm is that it has a high boiling point and contains six fluorine atoms in its structure. Thus, this exhibits some of the above - mentioned drawbacks on its own, making it of little value as an agent and very costly.

Summary of the Invention

Problems to be Solved by the Invention

[0008]

[0009] Therefore, a blowing agent that exhibits a low k - factor value, a low global warming potential, a low molecular weight, cost - effectiveness, and optimal performance over a wide temperature range is desirable in the art. The present invention addresses each of the above in the aspects and examples provided herein.

Means for Solving the Problems

[0009]

[0010] The present invention relates to a mixture comprising 1,1,1,4,4,4 - hexafluorobutene (1336mzzm) and 1 - chloro - 3,3,3 - trifluoropropene (1233zd), consisting essentially of these, or composed of these. In some forms, the composition comprises from about 5 to about 70 mol% of 1,1,1,4,4,4 - hexafluorobutene and from about 30 to about 95 mol% of 1 - chloro - 3,3,3 - trifluoropropene. The composition may also comprise from about 30 to about 70 mol% of 1,1,1,4,4,4 - hexafluorobutene and from about 30 to about 70 mol% of 1 - chloro - 3,3,3 - trifluoropropene. In a further aspect, the composition comprises from about 40 to about 60 mol% of 1,1,1,4,4,4 - hexafluorobutene and from about 40 to about 60 mol% of 1 - chloro - 3,3,3 - trifluoropropene. In a further aspect, the composition comprises about 50 mol% of 1,1,1,4,4,4 - hexafluorobutene and about 50 mol% of 1 - chloro - 3,3,3 - trifluoropropene.

[0010]

[0011] Accordingly, in one aspect, the present invention relates to a blowing agent composition comprising 1,1,1,4,4,4 - hexafluorobutene (1336mzzm); 1 - chloro - 3,3,3 - trifluoropropene (1233zd); and optionally at least one auxiliary selected from the group consisting of one or more co - blowing agents, one or more polyols, one or more surfactants, one or more polymer modifiers, one or more colorants, one or more dyes, one or more solubility improvers, one or more flammability inhibitors, one or more flame retardants, one or more antibacterial agents, one or more viscosity - reducing regulators, one or more fillers, one or more vapor pressure regulators, one or more nucleating agents, one or more catalysts, and any combination of two or more thereof.

[0011]

[0012] 1,1,1,4,4,4 - Hexafluorobutene can be provided in any effective amount that achieves the desired effects discussed herein. In one embodiment, such an effective amount is from about 5 to about 70 mol%. In a further embodiment, such an effective amount is from about 30 to about 70 mol%; from about 40 to about 60 mol%; or about 50 mol%. 1,1,1,4,4,4 - Hexafluorobutene can be provided as any isomer or a mixture of multiple isomers, but as defined herein, in one embodiment, the composition comprises at least 1336 m / z of the cis isomer, which can be provided alone or as a mixture with the trans isomer. Thus, 1336 m / z can comprise from about 50 wt% to about 100 wt% cis isomer and from about 0 wt% to about 50 wt% trans isomer; from about 75 wt% to about 100 wt% cis isomer and from about 0 wt% to about 25 wt% trans isomer; or from about 90 wt% to about 100 wt% cis isomer and from about 0 wt% to about 10 wt% trans isomer.

[0013] 1 - Chloro - 3,3,3 - trifluoropropene can likewise be provided in any effective amount that achieves the desired effects discussed herein. In one embodiment, such an effective amount is from about 30 to about 95 mol%. In a further embodiment, such an effective amount is from about 30 to about 70 mol%; from about 40 to about 60 mol%; or about 50 mol%. 1 - Chloro - 3,3,3 - trifluoropropene can be provided as any isomer or a mixture of multiple isomers, but as defined herein, in one embodiment, the composition comprises at least 1233zd of the trans isomer, which can be provided alone or as a mixture with the cis isomer. Thus, 1233zd can comprise from about 50 wt% to about 100 wt% trans isomer and from about 0 wt% to about 50 wt% cis isomer; from about 75 wt% to about 100 wt% trans isomer and from about 0 wt% to about 25 wt% cis isomer; or from about 90 wt% to about 100 wt% trans isomer and from about 0 wt% to about 10 wt% cis isomer.

[0012]

[0014] In a further aspect of the blowing agent composition, at least one type of auxiliary agent includes a co-blowing agent, examples of which include hydrofluorocarbons (HFCs) or hydrocarbon co-blowing agents. Regarding the former, examples of HFC co-blowing agents include difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), all isomers of all of these, and one or more combinations of two or more of these (but not limited to these), etc. One or more C 1 ~C 4 HFCs can be mentioned. Regarding the latter, examples of such agents include isopentane, n-pentane, cyclopentane, butane, and isobutane, and one or more combinations of two or more of these (but not limited to these), etc. One or more C 4 ~C 6 hydrocarbons can be mentioned.

[0013]

[0015] Additional or alternative co-blowing agents that can be provided as auxiliary agents include the following: water, CO 2 、CFC、HCC、HCFC、C 1 ~C 5 alcohols, C 1 ~C 4 aldehydes, C 1 ~C 4 ketones, C 1 ~C 4 ethers and diethers, organic acids such as formic acid (but not limited to this), and one or more combinations of two or more of these can be mentioned.

[0014]

[0016] In a further aspect, the present invention also relates to a foamable composition comprising a foaming agent and the foaming agent composition described herein. The foaming agent can be provided as a pre-blend in which one or more of the above components are first pre-blended and then supplied to the foamable composition. Alternatively, the respective components of the foaming agent composition can be supplied separately to the foamable composition to form the foaming agent composition therewith.

[0015]

[0017] The foamable composition exhibits an advantageous k-factor value. In one aspect, the foamable composition has an initial (measured within 24 hours of foam production) k-factor (BTU·inch / h·ft 2 ·°F) at 40°F of about 0.14 or less, and in some aspects 0.138 or less. In a further aspect, the foamable composition has an initial k-factor (BTU·inch / h·ft 2 ·°F) at 75°F of about 0.16 or less, and in some aspects 0.158 or less. In a further aspect, the foamable composition has an initial k-factor (BTU·inch / h·ft 2 ·°F) at 110°F of about 0.18 or less, and in some aspects 0.1772 or less.

[0016]

[0018] The present invention also relates to a foam premix composition comprising one or more polyols and the foaming agent composition described herein. Again, the foaming agent can be provided as a pre-blend in which one or more of the above components are first pre-blended and then supplied to the foam premix. Alternatively, the respective components of the foaming agent composition can be supplied separately to the foam premix to form the foaming agent composition therewith.

[0017]

[0019] In a further aspect, the present invention also relates to a method of forming a foam by reacting a foaming agent composition described herein, in addition to the foaming and / or foamed composition, under conditions effective to form a cell structure. Without limitation, the foaming composition can include isocyanate and one or more polyols. The foaming composition can also include at least one additional component selected from the group consisting of catalysts, surfactants, flame retardants, colorants, and combinations thereof.

[0018]

[0020] In a further aspect, the present invention relates to a foam comprising a plurality of polymer cells and a foaming agent composition described herein. This foam exhibits an advantageous k-factor value. In one aspect, this foam has an initial k-factor at 40°F of about 0.14 or less, and in some aspects 0.138 or less (BTU·inch / h·ft 2 ·°F). In a further aspect, this foam has an initial k-factor at 75°F of about 0.16 or less, and in some aspects 0.158 or less (BTU·inch / h·ft 2 ·°F). In a further aspect, this foam has an initial k-factor at 110°F of about 0.18 or less, and in some aspects 0.1772 or less (BTU·inch / h·ft 2 ·°F). Without limitation, such a foam can be a rigid foam, an open-cell foam, a closed-cell foam, a flexible foam, or a foam with a skin layer. It can also be a pre-expanded foam or an in-situ injection foam. It can also be included in an article such as a refrigerator or freezer (but not limited thereto), or in other forms within an article or device.

[0019]

[0021] Further aspects and advantages of the present invention will become readily apparent based on the disclosure provided herein.

Brief Description of the Drawings

[0020]

Figure 1

[0022] Figure 1 shows a comparison of the initial k-factor for 1,1,1,4,4,4-hexafluorobutene (1336mzzm), E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and a blend of 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and E-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

Figure 2

[0023] Figure 2 shows a comparison of the percentage increase in the k-factor after a 14-day aging period for 1,1,1,4,4,4-hexafluorobutene (1336mzzm), E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and a blend of 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and E-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

Figure 3

[0024] Figure 3 shows a comparison of the k-factor on the 14th day for 1,1,1,4,4,4-hexafluorobutene (1336mzzm), E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and a blend of 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and E-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

Figure 4

[0025] Figure 4 shows a comparison of the k-factor on the 8th day for 1,1,1,4,4,4-hexafluorobutene (1336mzzm), E-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and a blend of 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and E-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

Mode for Carrying Out the Invention

[0021]

[0026] The present invention relates to a mixture comprising 1,1,1,4,4,4-hexafluorobutene (1336mzzm) and 1-chloro-3,3,3-trifluoropropene (1233zd), consisting essentially of these, or composed of these. As described above, the use of 1336mzzm does not meet all the ideal requirements of a blowing agent, most notably due to its boiling point, high molecular weight, and very high manufacturing cost. The present invention has surprisingly and unexpectedly found that adding 1233zd, particularly the trans isomer, as a co-blowing agent reduces the cost of the blowing agent, and more importantly, gives an unexpectedly large improvement in the thermal performance of the foam produced using this blend.

[0022]

[0027] As used herein, the term "1,1,1,4,4,4-hexafluorobutene" or "1336mzzm" generally refers to either or both the cis or trans forms. The terms "cis HFO-1336mzzm" and "trans HFO-1336mzzm" are used herein to describe the cis and trans forms of 1,1,1,4,4,4-hexafluorobutene, respectively. Thus, the term "1,1,1,4,4,4-hexafluorobutene" or "1336mzzm" encompasses within its scope cis HFO-1336mzzm, trans HFO-1336mzzm, as well as all combinations and mixtures thereof. In a preferred embodiment, 1336mzzm refers to the cis isomer. However, the present invention is not limited thereto and can include only trans 1336mzzm, or a mixture of cis and trans isomers. In a further embodiment, 1336mzzm can contain from about 50 wt% to about 100 wt% cis isomer and from about 0 wt% to about 50 wt% trans isomer; from about 75 wt% to about 100 wt% cis isomer and from about 0 wt% to about 25 wt% trans isomer; or from about 90 wt% to about 100 wt% cis isomer and from about 0 wt% to about 10 wt% trans isomer. Such ranges regarding the composition of 1336mzzm do not necessarily limit the present invention and can be provided in any effective amount that achieves the advantages provided by the present invention.

[0023]

[0028] As used herein, the term "1-chloro-3,3,3-trifluoropropene" or "1233zd" generally refers to either or both of the cis or trans forms. The terms "cis HCFO-1233zd" and "trans HCFO-1233zd" are used herein to describe the cis and trans forms of 1,1,1-trifluoro,3-chloropropene, respectively. Thus, the term "1-chloro-3,3,3-trifluoropropene" or "1233zd" encompasses within its scope cis HCFO-1233zd, trans HCFO-1233zd only, as well as all combinations and mixtures thereof. In a preferred embodiment, 1233zd refers to the trans isomer. However, the present invention is not limited thereto and can include cis 1233zd, or a mixture of cis and trans isomers. In a further embodiment, 1233zd may comprise from about 50 wt% to about 100 wt% of the trans isomer and from about 0 wt% to about 50 wt% of the cis isomer; from about 75 wt% to about 100 wt% of the trans isomer and from about 0 wt% to about 25 wt% of the cis isomer; or from about 90 wt% to about 100 wt% of the trans isomer and from about 0 wt% to about 10 wt% of the cis isomer. Such ranges regarding the composition of 1233zd do not necessarily limit the present invention and can be provided in any effective amount that achieves the advantages provided by the present invention.

[0024]

[0029] The amounts of 1336mzzm and 1233zd included in the composition can vary widely depending on the particular application, and compositions containing more than trace amounts and less than 100% of the compounds falls within the broad scope of the present invention. Further, the compositions of the present invention may be azeotropic mixtures, azeotrope-like mixtures, or non-azeotropic mixtures. In some embodiments, the composition comprises from about 5 to about 70 mol% of 1336mzzm and from about 30 to about 95 mol% of 1233zd. In further non-limiting embodiments, the composition comprises from about 30 to about 70 mol% of 1336mzzm and from about 30 to about 70 mol% of 1233zd; from about 40 to about 60 mol% of 1336mzzm and from about 40 to about 60 mol% of 1233zd; or about 50 mol% of 1336mzzm and about 50 mol% of 1233zd;

[0025]

[0030] Compositions of 1336mzzm and 1233zd can be provided as blowing agent compositions, but additional components or aids can be provided, including one or more co-blowing agents, one or more polyols, one or more surfactants, one or more polymer modifiers, one or more colorants, one or more dyes, one or more solubility enhancers, one or more flammability inhibitors, one or more flame retardants, one or more antibacterial agents, one or more viscosity reducing regulators, one or more fillers, one or more vapor pressure regulators, one or more nucleating agents, one or more catalysts, and any combination of two or more of these, but are not limited thereto. Also, another co-blowing agent can be provided.

[0026]

[0031] In one embodiment, such co-blowing agents include one or more hydrocarbons or hydrofluorocarbons (HFCs), particularly C 4 ~C 6 hydrocarbons or C 1 ~C 4HFCs can be mentioned. Examples of such HFC co-blowing agents include difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and all isomers of all such HFCs, but are not limited thereto. Regarding hydrocarbons, in some preferred embodiments, the blowing agent composition may also include, for example, iso, n-, and / or cyclopentane for thermosetting foams, and butane or isobutane for thermoplastic foams. Water, CO 2 , CFCs (e.g., trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such as dichloroethylene (preferably trans-dichloroethylene), ethyl chloride, and chloropropane), HCFCs, C 1 ~C 5 alcohols (e.g., ethanol and / or propanol and / or butanol), C 1 ~C 4 aldehydes, C 1 ~C 4 ketones, C 1 ~C 4 ethers (ethers (e.g., dimethyl ether and diethyl ether), diethers (e.g., dimethoxymethane and diethoxymethane), etc.), and methyl formate, organic acids (e.g., formic acid (but not limited thereto)), and other materials such as any combination of these can also be included, but such components are not necessarily preferred in many embodiments due to their negative environmental impacts. The relative amounts of any of the above additional co-blowing agents and any additional components that can be included in the composition can be varied widely within the general broad scope of the present invention according to the specific use of the composition, and all such relative amounts are considered to be within that range.

[0027]

[0032] One aspect of the present invention provides a foaming composition. As is known to those skilled in the art, a foaming composition generally contains one or more components capable of forming bubbles. As used herein, the term "foaming agent" is used to refer to a component or combination of components capable of forming a foam structure, preferably generally a bubble-like foam structure. The foaming composition of the present invention contains one or more such components and a blowing agent blend, for example, a blend containing at least 1336mzzm and 1233zd.

[0028]

[0033] The foams and foaming compositions of the present invention generally refer to all foams (closed-cell foams, open-cell foams, rigid foams, flexible foams, with skin layers, etc. (but not limited thereto)) produced from a foam formulation containing the blowing agent composition of the present invention. The applicant has found that one advantage of the foam is its ability to achieve very excellent thermal performance under low temperature conditions as shown by the k-factor data provided herein. Although the foam is intended to be used in a wide range of applications, in some preferred embodiments, the present invention includes foams for refrigerators, foams for freezers, foams for refrigerators / freezers, panel foams, and foams for devices according to the present invention such as other low temperature or cryogenic manufacturing applications.

[0029]

[0034] In some embodiments, the one or more components capable of forming bubbles include a thermosetting composition capable of forming a foam and / or a foaming composition. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and phenolic foam compositions. This reaction and foaming process can be facilitated by using various additives such as catalysts and surfactant materials that act to control and regulate the bubble size and stabilize the foam structure during formation. Further, it is contemplated that any one or more of the additional components described above with respect to the foaming agent composition of the present invention can be included in the foaming composition of the present invention. In such embodiments of the thermosetting foam, one or more of the present compositions are included as, or as part of, a foaming agent in a foaming composition comprising one or more components capable of reacting and / or foaming, preferably under suitable conditions, to form a foam or a cellular structure, or as part of a portion of two or more foaming compositions.

[0030]

[0035] Regarding the production of rigid or flexible polyurethane or polyisocyanurate foams using the above as a foaming agent, any method well-known in the art can be used. See Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and Technology (1962). Generally, polyurethane or polyisocyanurate foams are produced by mixing an isocyanate, a polyol or a mixture of polyols, a foaming agent or a mixture of foaming agents, and other materials such as catalysts, surfactants, and optionally flame retardants, colorants, or other additives.

[0031]

[0036] Although not exclusive, in many applications it is convenient to provide a foam formulation in which the components for polyurethane or polyisocyanurate foams are pre-blended. Most typically, the foam formulation is pre-blended into two components. The isocyanate or polyisocyanate composition constitutes the first component, usually referred to as the "A" component. The polyol or polyol mixture, surfactant, catalyst, blowing agent, flame retardant, and other isocyanate-reactive components constitute the second component, usually referred to as the "B" component. The surfactant, one or more catalysts, and the blowing agent composition are usually placed on the polyol side, but these can be placed on either side, or part on one side and part on the other side. Thus, polyurethane or polyisocyanurate foams can be easily manufactured for small-scale production by hand mixing, or preferably by any of the mechanical mixing techniques for forming blocks, slabs, laminates, on-site injection panels and other members, spray-applied foams, bubbles, etc., by blending the components on the A side and the B side. In some cases, flame retardants, colorants, auxiliary blowing agents, water, and even other components such as other polyols can be added as a third stream to the mixing head or reaction site. However, most conveniently, all of these are included in one B component.

[0032]

[0037] In the synthesis of polyurethane or polyisocyanurate foams, any organic polyisocyanate containing aliphatic and aromatic polyisocyanates can be used. As one type, aromatic polyisocyanates are preferred. Preferred polyisocyanates for the synthesis of rigid polyurethane or polyisocyanurate foams are polymethylene polyp enyl isocyanate, especially a mixture containing about 30 to about 85% by weight of methylene bis(phenyl isocyanate) and the balance containing polymethylene polyphenyl polyisocyanate with a functionality greater than 2. Preferred polyisocyanates for the synthesis of flexible polyurethane foams are toluene diisocyanates including 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and mixtures thereof, but are not limited thereto.

[0033]

[0038] Typical polyols used in the production of rigid polyurethane foams include, but are not limited to, aromatic amino-based polyether polyols such as those based on a mixture of 2,4- and 2,6-toluenediamine condensed with ethylene oxide and / or propylene oxide. These polyols have been found to be useful in in-situ injection molded foams. Another example is aromatic alkylamino-based polyether polyols such as those based on ethoxylated and / or propoxylated aminoethylated nonylphenol derivatives. These polyols have generally been found to be useful in spray applied polyurethane foams, but such uses are not considered limitations to the present invention and can be adapted as other forms understood in the art or as provided herein. Another example is sucrose-based polyols such as those based on a mixture of sucrose derivatives and / or a mixture of sucrose and glycerin derivatives condensed with ethylene oxide and / or propylene oxide. These polyols generally have been found to be useful in in-situ injection molded foams, but similarly such uses are not considered limitations to the present invention and may be configured as other forms understood in the art or as provided herein.

[0034]

[0039] Typical polyols used in the production of flexible polyurethane foams include, but are not limited to, those based on glycerol, ethylene glycol, trimethylolpropane, ethylenediamine, pentaerythritol, etc. condensed with ethylene oxide, propylene oxide, butylene oxide, etc. These are generally referred to as "polyether polyols". Another example is graft copolymer polyols such as normal polyether polyols with vinyl polymers grafted onto the polyether polyol chain (but not limited thereto). Yet another example is polyurea-modified polyols composed of normal polyether polyols with polyurea particles dispersed therein.

[0035]

[0040] Examples of polyols used in polyurethane-modified polyisocyanurate foams include, but are not limited to, aromatic polyester polyols such as those based on complex mixtures of phthalate-type or terephthalate-type esters formed from polyols such as ethylene glycol, diethylene glycol, or propylene glycol. These polyols are used in rigid laminate materials and can be blended with other types of polyols, such as sucrose-based polyols, for use in polyurethane foam applications.

[0036]

[0041] Catalysts used in the production of polyurethane foams are typically tertiary amines such as N-alkylmorpholines, N-alkylalkanolamines, N,N-dialkylcyclohexylamines, and alkylamines (where the alkyl groups are methyl, ethyl, propyl, butyl, etc.), and isomers thereof (but not limited thereto); and heterocyclic amines. Representative examples (but not limiting) are triethylenediamine, tetramethylethylenediamine, bis(2-dimethylaminoethyl) ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N,N-dimethylcyclohexylamine, N-ethylmorpholine, 2-methylpiperazine, N,N-dimethylethanolamine, te tramethylpropanediamine, methyltriethylenediamine, and mixtures thereof.

[0037]

[0042] In some cases, a non-amine polyurethane catalyst is used. Representative examples of such catalysts are organometallic compounds of lead, tin, titanium, antimony, cobalt, aluminum, mercury, zinc, nickel, copper, manganese, zirconium, bismuth, and mixtures thereof. Representative catalysts include lead 2-ethylhexanoate, lead benzoate, ferric chloride, antimony trichloride, and antimony glycolate. Preferred organotin species include stannous salts of carboxylic acids such as stannous octanoate, stannous 2-ethylhexanoate, stannous laurate, and dialkyltin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin diacetate (however, it is not limited thereto).

[0038]

[0043] In the production of polyisocyanurate foams, a trimerization catalyst is used for the purpose of converting the blend together with an excess of component A into a polyisocyanurate-polyurethane foam. The trimerization catalyst used may be any catalyst known to those skilled in the art such as glycerin salts and tertiary amine trimerization catalysts, alkali metal carboxylates, and mixtures thereof (however, it is not limited thereto). Preferred species within this class are potassium acetate, potassium octanoate, and N-(2-hydroxy-5-nonylphenyl)methyl-N-methylglycinate.

[0039]

[0044] A dispersant, a foam stabilizer, and a surfactant can be included in the blowing agent mixture. The surfactant is well known as a silicone oil and is added to act as a foam stabilizer. Generally, some representative materials that are polysiloxane polyoxyalkylene block copolymers such as those disclosed in U.S. Patent Nos. 2,834,748, 2,917,480, and 2,846,458 are sold under the names DC-193, B-8404, and L-5340.

[0040]

[0045] Other optional additives for the blowing agent mixture include flame retardants such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, etc. Other optional components can include 0 to about 3% water, which chemically reacts with the isocyanate to produce carbon dioxide. This carbon dioxide functions as an auxiliary blowing agent.

[0041]

[0046] Generally speaking, the amount of the blowing agent composition to be present in the blended mixture is determined by the desired foam density of the final polyurethane product or the final polyisocyanurate foam product. The polyurethane foam produced can have a density of about 0.5 pounds / ft 3 ~ about 40 pounds / ft 3 、preferably about 1.0 to about 20.0 pounds / ft 3 、most preferably about 1.5 to about 6.0 pounds / ft for rigid polyurethane foams 3 、and about 1.0 to about 4.0 pounds / ft for flexible foams 3 and can be in the range. The resulting density is a function of how much blowing agent or blowing agent mixture is present in components A and / or B, or added at the time the foam is produced.

[0042]

[0047] In other embodiments, the mixtures and compositions of the present invention can be used as propellants in sprayable compositions, either alone or in combination with known propellants. The sprayable composition includes, consists essentially of, or consists of the material to be sprayed and the propellant, and the propellant includes, consists essentially of, or consists of the mixture or composition of the present invention. Inert components, solvents, and other The material can also be present in a sprayable mixture. Preferably, the sprayable composition is an aerosol. Suitable materials to be sprayed include, but are not limited to, deodorants, perfumes, hairsprays, facial cleansers, and cosmetic materials such as brightening agents, as well as pharmaceutical materials such as anti-asthma drugs, bad breath preventives, and metered-dose inhalers (MDIs).

[0043]

[0048] The composition of the present invention can also be used in a method for dissolving contaminants or removing contaminants from the surface of a substrate, where the method includes, consists essentially of, or consists of the step of contacting the substrate with the composition of the present invention.

[0044]

[0049] In some preferred embodiments, the foam according to the present invention, in addition to the low ozone depletion potential and low global warming potential associated with many of the preferred blowing agents of the present invention, provides one or more outstanding features, characteristics, and / or properties such as heat insulation efficiency (especially for thermosetting foams), dimensional stability, compressive strength, and the change over time of heat insulation properties. In some highly preferred embodiments, the present invention provides a thermosetting foam (including such a foam formed in a foam article) that exhibits improved thermal conductivity compared to a foam produced using the same amount of the same blowing agent (or HFC-245fa, a commonly used blowing agent) but without using the blowing agent composition of the present invention. In some highly preferred embodiments, the thermosetting foam of the present invention, preferably a polyurethane foam, exhibits an initial k-factor (BTU·inch / hour·ft 2 ·°F) at 40°F of about 0.14 or less, more preferably 0.138 or less. Further, in some embodiments, the thermosetting foam of the present invention, preferably a polyurethane foam, preferably exhibits an initial k-factor (BTU·inch / hour·ft 2 ·°F) at 75°F of about 0.16 or less, more preferably 0.158 or less. In a further embodiment, the thermosetting foam of the present invention, preferably a polyurethane foam, exhibits an initial k-factor (BTU·inch / hour·ft 2It is preferable to indicate (°F).

Example

[0045]

[0050] The following examples are given for the purpose of illustrating the present invention, but do not limit its scope.

[0051] As foaming agents, foams were prepared using 1336mzzm, 1233zd(E), a 30 / 70 mol% blend of 1233zd(E) / 1336mzzm, and a 70 / 30 mol% blend of 1233zd(E) / 1336mzzm. The composition of the polyol masterbatch is shown in Table 1, while a typical spray foam formulation using corresponding amounts of foaming agent is shown in Table 2. Foams were produced using an injection time of 3 seconds and a mixing time of 8 seconds. The temperature of the raw materials was 50°F for the polyol and 70°F for the MDI.

[0046]

Table 1

[0047]

Table 2

[0048]

[0052] Physical properties - Reactivity:

[0053] Predict the relationship between emulsification time, gelation time, and non-stick time. These are equivalent for all foams produced.

[0049]

Table 3

[0050]

[0054] The foams produced were well mixed and of equivalent quality. The block densities of the foams produced were equivalent, as were the ratios of block density to core density. This was expected since the foams were produced using equimolar amounts of foaming agent.

[0051]

Table 4

[0052]

[0055] Thermal conductivity:

[0056] Initially, the foam produced using 1336mzzm exhibits the non-linear curve shape commonly seen with high-boiling blowing agents. This is because the blowing agent is concentrated in the foam matrix at temperatures below its boiling point. Since the 30 / 70 mol% blend of 1336mzzm / 1233zd(E) and the 70 / 30 mol% blend of 1336mzzm / 1233zd(E) are not azeotropic compositions, it is not unexpected that they do not exhibit the same curve shape. Furthermore, the thermal conductivity of the foams produced using these blends is significantly improved compared to those produced using 1233zd(E). Not only are they improved, but the improvement is non-linear with respect to the amount of 1336mzzm added to the blowing agent blend. It is particularly interesting that the improvement is large at low average temperatures and does not depend on the concentration of 1233zd(E). Furthermore, it is noteworthy that the foams produced from these blends change over time more slowly than the 1233zd(E) and 1336mzzm foams.

[0053]

Table 5

Claims

1. 1,1,1,4,4,4-Hexafluorobutene (1336 mzzm); 1-chloro-3,3,3-trifluoropropene (1233zd); and optionally at least one auxiliary selected from the group consisting of one or more co-blowing agents, one or more polyols, one or more surfactants, one or more polymer modifiers, one or more colorants, one or more dyes, one or more solubility enhancers, one or more flammability suppressants, one or more flame retardants, one or more antimicrobial agents, one or more viscosity reduction modifiers, one or more fillers, one or more vapor pressure modifiers, one or more nucleating agents, one or more catalysts, and combinations of any two or more thereof; 1. A blowing agent composition comprising:

2. 2. The blowing agent of claim 1, wherein the 1-chloro-3,3,3-trifluoropropene (1233zd) comprises 50% to 100% by weight of trans-1-chloro-3,3,3-trifluoropropene and 0% to 50% by weight of cis-1-chloro-3,3,3-trifluoropropene.

3. 3. The blowing agent of claim 1 or 2, wherein the 1,1,1,4,4,4-hexafluorobutene (1336 mzzm) comprises 50% to 100% by weight of cis-1,1,1,4,4,4-hexafluorobutene and 0% to 50% by weight of trans-1,1,1,4,4,4-hexafluorobutene.

4. The blowing agent of any one of claims 1 to 3, wherein 1,1,1,4,4,4-hexafluorobutene is provided in an amount of 5 to 70 mol % and 1-chloro-3,3,3-trifluoropropene is provided in an amount of 30 to 95 mol %.

5. A foamable composition comprising a foam-forming agent and the foaming agent composition according to any one of claims 1 to 4.

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