RU2773354C2 - Polyurethane foam premixes containing purge agents based on halogenated olefin, and foams produced from them - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a premixed polyol composition for the formation of foam, in particular for the production of polyurethane or polyisocyanurate foams with closed cells. At the same time, the premixed polyol composition contains: a) a purge agent based on hydrohaloolefin selected from a group consisting of trans-1,3,3,3-tetrafluorpropen (trans-1234ze) and trans-1-chlor-3,3,3-trifluorpropen (trans-1233zd) and combinations thereof, b) one or several polyols, c) one or several silicone surfactants, and d) a catalytic system including precipitation-resistant catalyst based on bismuth carboxylate. In this case, the purge agent is present in the amount from 1 wt. % to about 30 wt. % of the composition, and catalyst is present in the premixed polyol composition in the amount from about 0.001 wt. % to about 5.0 wt. % by weight of the premixed polyol composition, while the composition contains water in the amount of at least 1.5 pphp by weight.

EFFECT: ensuring the stability of the premixed polyol composition during long-term storage in the presence of water in the polyol composition in the amount of at least 1.5 pphp by weight.

14 cl, 4 dwg, 21 tbl, 9 ex

Description

LINKS TO RELATED APPLICATIONS

The present invention claims priority from US Patent Application 61/445027, filed Feb. 21, 2011, and US Patent Application 61/445,022, filed Feb. 21, 2011, each of which is hereby incorporated by reference in its entirety. Also included for reference herein is parallel filed application number H0030269.

FIELD OF TECHNOLOGY

The present invention relates to polyurethane and polyisocyanurate foams,

purge agents and catalytic systems, and methods for their preparation.

BACKGROUND OF THE INVENTION

Rigid and semi-rigid polyurethane and low density polyisocyanurate foams are widely used in insulation products and structures, including roofing systems, wall panels, building envelope insulation, spray foams, one and two component foams, refrigerator insulation and freezers, and so-called integral foams for use in the manufacture of automobile steering wheels and other parts of automobile and aerospace cabins, shoe soles and dampers in amusement parks. The ability of rigid polyurethane foams to provide a good balance of properties is important for large scale industrial applications. For example, many rigid polyurethane and polyisocyanurate foams are known to provide outstanding thermal insulation, excellent refractory properties, and excellent structural properties at reasonably low density levels. In general, integral foams are known to provide a rigid, durable outer surface and a porous resilient core.

It is known in the art to prepare rigid or semi-rigid polyurethane and polyisocyanurate foams by reacting a polyisocyanate with one or more polyols in the presence of one or more blowing agents, one or more catalysts, one or more surfactants and optionally other ingredients. Purge agents that have been used in the past include certain compounds within the group of compounds including hydrocarbons, fluorocarbons, chlorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, halogenated hydrocarbons, ethers, esters, aldehydes, alcohols, ketones, and organic acid or gas producing materials, most often -CO ₂ . When the polyisocyanate reacts with the polyol, heat is generated. This heat vaporizes the blowing agent contained in the liquid mixture, thereby forming bubbles therein. In the case of gas-forming materials, gaseous substances are generated by thermal decomposition or reaction with one or more ingredients used to form polyurethane and polyisocyanurate foams. During the polymerization reaction, the liquid mixture becomes porous-solid, capturing the blowing agent into the foam cells. In the event that no surfactant is used in the foam composition, in many cases the bubbles simply pass through the liquid mixture without foaming, or form a foam with large, uneven cells, making it unusable.

Foams have historically used liquid blowing agents that include certain fluorocarbons due to their ease of application and ability to form foams with excellent mechanical and thermal insulating properties. These certain fluorocarbons not only act as scavenging agents due to their volatility, but are also incorporated or immersed in the rigid foam's closed cell structure and contribute significantly to the low thermal conductivity properties of rigid urethane foams. These fluorocarbon blowing agents also produce foam with a favorable K-factor. The K-factor is the rate of thermal energy transfer by conduction through a one-square-foot, one-inch-thick homogeneous material in one hour, with a one degree Fahrenheit difference between the two surfaces of the material. Since the use of closed cell polyurethane foams is based in part on their thermal insulating properties, the identification of low Cofactor foam forming materials will be highly beneficial.

Preferred blowing agents also have a low GWP. Among these materials, there are certain hydrohaloolefins, including certain hydrofluoroolefins, of which trans-1,3,3,3-tetrafluoropropene (1234ze(E)) and 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm (Z)) are of particular interest, as well as hydrochlorofluoroolefins, of which 1-chloro-3,3,3-trifluoropropene (1233zd) (including its cis and trans isomers and combinations) is of particular interest. Methods for the production of trans-1,3,3,3-tetrafluoropropene are described in US Pat.

In various applications, it is convenient to use the components of polyurethane and polyisocyanurate foams in pre-mixed formulations. Most often, foam formulations are pre-mixed from two components. The polyisocyanate- and optionally isocyanate-compatible feedstock, including (but not limited to) certain scavenging agents and non-reactive surfactants, constitute the first component, commonly referred to as the "A" component. A polyol or mixture of polyols, one or more surfactants, one or more catalysts, one or more blowing agents, and optional components including (but not limited to) flame retardants, dyes, compatibilizers, and solvents, typically form the second component, commonly referred to as the "B" component. Accordingly, polyurethane and polyisocyanurate foams are easily made by combining components A and B, either by hand mixing in the case of small volumes, or preferably by machine mixing methods to obtain blocks, slabs, sandwich structures, embedded panels and other products, spray foams , foam products and the like. Other ingredients such as flame retardants, colorants, purge aids, and other polyols may optionally be added to the mixer or reaction zone. The most convenient, however, is to include them in component B.

Applicants have found that a disadvantage of two-component systems, especially those using certain hydrohaloolefins, including 1234ze(E), 1336(Z) and 1233zd(E), is the shelf life of the composition of component B. Usually when foam is formed by combining components A and B, a good foam is obtained. However, Applicants have found that if a polyol premix composition containing halogenated olefin-based purge agents, including but not limited to 1234ze(E), 1336(Z), and/or 1233zd(E), as well as conventional amine containing catalyst is old, undesirable effects may occur in the step prior to treatment with the polyisocyanate. For example, Applicants have found that these formulations can result in a foaming composition with an undesirable increase in reaction time and/or subsequent cell coalescence. The foams thus obtained are of poor quality and/or may even fall off during the foaming process.

Applicants have found that significant improvements in foam formation and/or foam efficiency can be achieved by reducing the amount of amine catalyst in the system, to the point of completely eliminating the amine catalyst in certain embodiments and using certain metal catalysts or catalyst mixtures instead. (s) based on metals and amines. While the use of this metal based catalyst has been found to be particularly effective in many formulations and applications, Applicants have found that there may be a difficulty/disadvantage with certain foam premix formulations. More specifically, Applicants have found that relatively high water concentration foam premix formulations, as described below, do not provide acceptable results in terms of storage stability, in the resulting foam and/or in the foaming process when using certain catalysts based on metals. Applicants have found that this unexpected problem can be solved by careful selection of metal catalyst(s), including complexes and/or mixtures of metal catalyst(s) and amines, with highly beneficial and unexpected results, as described below.

SUMMARY OF THE INVENTION

It has been found that one source of the problem observed by Applicants is the undesired reaction/reaction of certain amine-based catalysts with certain hydrohaloolefins, in particular during storage of the component and/or during the foaming reaction. Although applicants do not wish to be limited to any particular theoretical concept, it is believed that these reactions/interactions have direct and indirect negative effects. For example, the decomposition reaction between the amine catalyst and the blowing agent impairs the availability of the amine catalyst and/or the blowing agent and thus adversely affects reaction time and/or foam quality. In addition, the decomposition reaction produces fluoride ions, which can adversely affect other components of the premixed and/or foaming composition and/or foam, including the surfactant included in these materials.

As a result of intensive research, Applicants have found that it is possible to avoid the observed negative effects by careful and balanced selection of the catalyst system used. More specifically, Applicants have found that, in certain embodiments of the invention, significant benefit can be achieved by selecting a catalyst system with a relatively small and preferably zero amount of amine catalyst(s) and a relatively high proportion, preferably full metal catalyst (for example, inorganic metal catalysts, organometallic catalysts) and/or one or more optional quaternary ammonium carboxylate catalysts.

Furthermore, while Applicants believe that all halogenated olefin purge agents will have the above negative effects to some extent, Applicants have surprisingly found that certain halogenated olefins, in particular monochlorotrifluoropropenes and in particular trans-1 -chloro-3,3,3-trifluoropropene (1233zd(E)), have a relatively low level of negative effect, especially when used in combination with a catalyst that contains a relatively low level and preferably does not contain a significant amount of amine-containing catalyst.

Thus, in accordance with one aspect of the invention, Applicants have found that blowing agents, foam compositions, premixes and foams using metal catalysts (and/or optionally carboxylate-based catalysts) alone or in combination with an amine-based catalyst, preferably in a minor proportion relative to the total weight of the active catalyst, can extend the shelf life of hydrohaloolefin-containing polyol premixes and can improve the quality of foams made therefrom. This benefit is believed to be associated generally with hydrohaloolefins, more preferably (but not exclusively) 1234ze(E) and/or 1233zd(E) and/or 1336mzzm(Z) and more preferably 1233zd(E). Applicants have found that good quality foams can be obtained according to the present invention even if the polyol mixture has been stored for several weeks or months.

One aspect of the invention thus relates to foam-forming catalysts comprising one or more metal-based catalysts and optionally an amine-based catalyst, preferably in a small proportion, of the type and present in an amount effective to provide preferably little or no loss of reactive capacity and/or cell structure (i.e. shelf life) over time (preferably at least about two (2) months) when combined with a hydrohaloolefin purge agent, preferably 1234ze(E), 1233zd(E) , and/or 1336mzzm(Z), preferably achieving a reactivity profile similar to conventional amine catalyst system purge agents, as well as to purge agent compositions, premix compositions, foam forming compositions and foams containing or made using a catalyst.

Another aspect of the present invention relates to an advantageous choice of metal catalyst for use in conjunction with high water foaming systems and/or foam premix compositions. As used herein, the term "high water content" refers to systems and compositions containing more than about 0.5 parts of water (by weight) per hundred parts of polyol (hereinafter referred to as "pphp" or "php") in system/composition. In preferred embodiments, high water systems contain water in an amount of at least about 0.75 and more preferably at least about 1.0 and more preferably at least about 1.5 pphp. As will be appreciated by those skilled in the art, certain formulations are known to provide benefit when relatively high levels of water are used and/or present in the system, particularly in a premixed foam component containing a polyol component. While Applicants have found that certain zinc-based catalysts are generally effective in systems with HFO and HFCO purge agents, in particular systems with a purge agent comprising or consisting primarily of HFCO-1233zd, some of these catalysts report to a significant degradation in efficiency when used in systems with a high water content.

Applicants have found that significant benefits in terms of foam properties and/or foam generation efficiency can be achieved by using precipitation-resistant metal-based catalyst(s), and more preferably precipitation-resistant organometallic catalysts, and more preferably catalysts selected from the catalyst(s) ) based on organozinc, catalyst(s) based on organomolybdenum and combinations thereof. The terms "organometallic catalysts", "organozinc catalysts", "organomolybdenum catalysts" and the like mean and broadly cover pre-formed organometallic complexes and compositions (including physical combinations, formulations and/or mixtures) comprising metal carboxylates, preferably zinc and/or bismuth carboxylates and amidines. Applicants have found that these metal-based catalyst(s), and in particular combinations of zinc-based catalyst(s) and bismuth-based catalysts, largely avoid precipitation, either when present in a polyol-based formulation at elevated temperature for a certain period of time, and/or when stored at room temperature for an extended period of time.

As used herein, the term "settling resistant" means substantially no settling upon visual inspection of the polyol composition, and preferably the polyol preblended composition, under test conditions comprising at least. High Temperature and/or Low Temperature as described here. A precipitate-resistant material satisfies the High Temperature conditions if it does not form any visually noticeable precipitate when stored in a pressure reaction vessel at about 54° C. for 7 days. A deposit resistant material satisfies the Low Temperature conditions if it does not form any visually noticeable deposit when stored at about room temperature for a period of at least about one month, more preferably about two months, and even more preferably about three months. Applicants have also found that a manufacturer's designation of a metal catalyst as water soluble is not indicative of the ability of the metal catalyst, and preferably the zinc or bismuth catalyst, to be a precipitation resistant metal catalyst of the present invention. Applicants have found that outstanding and unexpected results can be achieved using a precipitation-resistant metal-based catalyst, and preferably a precipitation-resistant zinc-based catalyst, bismuth-based catalysts, and combinations thereof in high water systems/premix compositions and, even more preferably in high water systems/premix compositions with at least about 1 pphp of water in accordance with the present invention.

Preferred catalysts for use as the precipitation resistant metal catalyst of the present invention include a zinc (preferably zinc(II)) catalyst, a bismuth catalyst, and preferably a combination thereof comprising metal complexes and/or compositions, preferably in the form carboxylate with substituted amidines. In preferred embodiments, the precipitation resistant catalyst of the present invention comprises: (a) a metal selected from the group consisting of zinc, lithium, sodium, magnesium, barium, potassium, calcium, bismuth, cadmium, aluminium, zirconium, tin, or hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, cesium, preferably zinc and/or bismuth; (b) in complex and/or composition with an amidine compound; and (c) in complex and/or composition with an aliphatic, aromatic or polymeric carboxylate, preferably with an equivalent weight of from about 45 to about 465.

Although it is contemplated that the metal content (at the elemental level) in the precipitation-resistant metal-based catalyst can vary widely, in certain embodiments of the invention, a catalyst content of from about 5 wt. % to about 20 wt. %, more preferably from about 5 wt. % to about 15 wt. % metal and more preferably zinc and/or bismuth. Preferred amidine compounds for certain embodiments of the invention are compounds containing catalytic amidine groups, in particular groups with a heterocyclic ring (preferably with a -N=CN- bond), for example a ring based on imidazoline, imidazole, tetrahydropyrimidine, dihydropyrimidine or pyrimidine. Acyclic amidines and guanidines can also be used. One preferred catalyst complex/composition includes zinc(II), methyl, ethyl or propyl hexanoate and imidazole (preferably (lower alkyl)imidazole such as methylimidazole). The preferred catalyst includes Zn(1-methylimidazole) ₂ (2-ethylhexanoate) ₂ along with diethylene glycol, preferably as a solvent for the catalyst; a preferred form of this preferred catalyst is sold under the trade name K-Kat XK-614 from King Industries, Norwalk, Connecticut. A preferred form of this bismuth-based catalyst is a catalyst in solution comprising from about 25% to about 50% metal carboxylate and more preferably from about 35% to about 40% metal carboxylate with a metal content of from about 5% to about 20% and , more preferably from about 10% to about 15%. This preferred catalyst has a specific gravity of 1.12 g/ml at 25°C. Preferred precipitation-resistant catalysts of the present invention may generally be prepared in accordance with US Pat. No. 7,485,729, incorporated herein by reference in its entirety. Another preferred catalyst according to the present invention comprises a bismuth carboxylate, preferably a chelated bismuth carboxylate, and is preferably a precipitation resistant catalyst. A preferred form of this bismuth-based catalyst is a catalyst in solution comprising from about 25% to about 50% metal carboxylate and more preferably from about 35% to about 40% metal carboxylate with a metal content of from about 5% to about 20% and , more preferably from about 10% to about 15%. This preferred catalyst has a specific gravity of 1.12 g/ml at 25°C and is sold under the trade name K-Kat XC-227 from King Industries, Norwalk, Connecticut.

In certain preferred embodiments of the invention, the catalyst used in accordance with the present invention includes a zinc-based catalyst and a bismuth-based catalyst. Although it is contemplated that many of these combinations can be used in accordance with the present invention, in general, a zinc-based catalyst to bismuth-based catalyst weight ratio of about 4:1 to about 1:1 is preferred, and more preferably , from about 4:1 to about 2:1, and more preferably from about 2.5:1 to about 3.5:1.

Certain preferred catalysts in accordance with the present invention include catalysts Nos. 9, 12, 15, 21, 24, and 27 of Table 2 of US Pat. No. 7,485,729. Annex A to the above provisional application and incorporated herein by reference, and a copy of the provisional certificate for this catalyst is incorporated as Annex B in the above provisional application and incorporated herein by reference.

According to one aspect, the present invention relates to rigid or semi-rigid polyurethane and polyisocyanurate foams and methods for making the same, wherein the foams are characterized by excellent uniform cell structure and little or no foam drop. These foams are preferably produced with an organic polyisocyanate and a polyol premix composition that includes a combination of a blowing agent, which is preferably a hydrohaloolefin, a polyol, a silicone surfactant, and a catalyst comprising one or more non-amine catalysts, preferably an organometallic or organometallic compound and/or a catalyst based on carboxylates, preferably based on quaternary ammonium, and may also include one or more amine based catalysts, preferably in a small proportion of all catalysts in the system. Although it is contemplated that the amount of metal catalyst and amine catalyst may vary according to the broad scope of the present invention, in certain embodiments of the invention, the weight ratio of amine catalyst to metal catalyst is preferred, and more preferably , a zinc or bismuth catalyst, or a combination of catalysts based on these metals, equal to from about 1:1 to about 1:4, and more preferably from about 1:1 to about 1:3, and more preferably from about 1: 1 to about 1:1.5.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a graphical representation of the results as described in

Table B.

Fig. 2 is a graphical representation of test results with respect to

reaction rates as described in the description.

Fig. 3 is a graphical representation of the results as described in

Example 1A.

Fig. 4 is a graphical representation of the results as described in

Example 3B.

DETAILED DESCRIPTION OF THE INVENTION

While Applicants do not wish to be limited to any particular theoretical concept, it is believed that these adverse effects observed by Applicants may result from a reaction between a hydrohaloolefin-based purge agent and amine-based catalysts; one exemplary scheme of this possible reaction is given below:

It is believed that the reaction according to this scheme or reactions according to similar schemes produce a halogen ion, such as a fluorine ion or a chlorine ion, which leads to a decrease in the reactivity of the purge agent. In addition, applicants believe that negative effects can also be caused, alone or in addition to the above reasons, by a halogen ion such as fluoride produced by the above reaction and reacting in turn with the silicone surfactant present in these purge agents and related systems to produce a lower molecular weight surfactant that reduces efficiency. It is believed that this depletion/degradation of the surfactant leads to a reduction in the integrity of the cell surface and thus results in foams with higher levels of cell failure than desired levels of cell failure.

In another aspect, this invention provides a high water content polyol premix composition that includes a blowing agent, one or more polyols, one or more surfactants, and a catalyst comprising a precipitation resistant metal-based catalyst, more preferably a precipitation resistant catalyst. a zinc-based, precipitation-resistant bismuth-based catalyst, and more preferably a combination of a precipitation-resistant zinc-based catalyst and a precipitation-resistant bismuth-based catalyst, including the particularly preferred zinc and bismuth-based carboxylic catalysts described above. In certain preferred embodiments of the invention, the catalyst comprises components (a) to (c) described above (preferably obtained as described in US Pat. No. 7,485,729), wherein the purge agent comprises one or more hydrohaloolefins and optionally a hydrocarbon, a halogenated hydrocarbon, an ether, an ester, an alcohol, an aldehyde, a ketone, an organic acid, a gas producing material, water, or a combination thereof. One preferred catalyst comprises an amine-based catalyst and a precipitation-resistant metal-based catalyst comprising a combination of a zinc-based carboxylic catalyst, such as the catalyst sold under the tradename K-Kat XK-614 by King Industries, Norwalk, Connecticut, and a carboxylic catalyst. based on bismuth, such as the catalyst sold under the tradename K-Kat XC-227 by King Industries, Norwalk, Connecticut. The invention provides a polyol premix composition comprising a combination of a blowing agent, one or more polyols, one or more silicone surfactants and a catalyst, said catalyst comprising a large proportion and, more preferably, essentially consisting of a non-amine catalyst such as an organometallic or organometallic compound or ammonium carboxylate based material. In certain preferred embodiments, a non-amine catalyst may be used alone or in combination with amine catalysts, wherein the purge agent comprises one or more hydrohaloolefins and optionally a hydrocarbon, fluorocarbon, chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon, ether, ester , an alcohol, an aldehyde, a ketone, an organic acid, a gas producing material, water, or a combination thereof.

The invention also provides a process for the production of polyurethane and polyisocyanurate foams, comprising the reaction of an organic polyisocyanate with a polyol premix composition.

BLOWING AGENT BASED ON HYDROHALOOLEFIN

The purge agent component comprises a hydrohaloolefin, preferably comprising at least one or a combination of 1234ze(E), 1233zd(E) and isomeric mixtures thereof, and/or 1336mzzm(Z) and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether, ester, alcohol, aldehyde, ketone, organic acid, gas producing material, water, or combinations thereof.

The hydrohaloolefin preferably comprises at least one haloalkene, such as a fluoroalkene or chlorofluoroalkene, having 3 to 4 carbon atoms and at least one carbon-carbon double bond. Preferred hydrohaloolefins do not exclusively include trifluoropropenes; tetrafluoropropenes such as (1234); pentafluoropropenes such as (1225); chlorodifluoropropenes; chlorotrifluoropropenes; chlorotetrafluoropropenes; hexafluorobutenes (1336) and combinations thereof. More preferred compounds of the present invention are tetrafluoropropene, pentafluoropropene and chlorotrifluoropropene compounds in which the unsaturated terminal carbon has no more than one F or Cl substituent. Also included are 1,3,3,3-tetrafluoropropene (1234ze); 1,1,3,3-tetrafluoropropene; 1,2,3,3,3-pentafluoropropene (1225ue), 1,1,1-trifluoropropene; 1,2,3,3,3-pentafluoropropene, 1,1,1,3,3-pentafluoropropene (1225zc) and 1,1,2,3,3-pentafluoropropene (1225ye); (Z)-1,1,1,2,3-pentafluoropropene (1225yez); 1-chloro-3,3,3-trifluoropropene (1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm) and combinations thereof, and any and all stereoisomers of each.

Preferred hydrohaloolefins have a Global Warming Potential (GWP) value of no more than 150, more preferably no more than 100, and more preferably no more than 75. As used herein, "GWP" is measured relative to the value of this carbon dioxide factor over a time span of 100 lay down 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. Preferred hydrohaloolefins also preferably have an Ozone Depletion Potential (ODP) value of at most 0.05, preferably at most 0.02, and more preferably around zero. The term "ODP" is used here in accordance with the definition 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.

ASSOCIATED BLOWING AGENTS

Preferred optional co-purging agents non-exclusively include water; organic acids producing CO ₂ and/or CO; hydrocarbons; ethers; halogenated ethers; esters; alcohols; aldehydes; ketones; pentafluorobutane; pentafluoropropane; hexafluoropropane; heptafluoropropane; trans-1,2-dichloroethylene; methylal; methyl formate; 1-chloro-1,2,2,2-tetrafluoroethane (124); 1,1-dichloro-1-fluoroethane (141b); 1,1,1,2-tetrafluoroethane (134a); 1,1,2,2-tetrafluoroethane (134); 1-chloro-1,1-difluoroethane (142b); 1,1,1,3,3-pentafluorobutane (365mfc); 1,1,1,2,3,3,3-heptafluoropropane (227ea); trichlorofluoromethane (11); dichlorodifluoromethane (12); dichlorofluoromethane (22); 1,1,1,3,3,3-hexafluoropropane (236fa); 1,1,1,2,3,3-hexafluoropropane (236ea); 1,1,1,2,3,3,3-heptafluoropropane (227ea); difluoromethane (32); 1,1-difluoroethane (152a); 1,1,1,3,3-pentafluoropropane (245fa); butane; isobutane; normal pentane; isopentane; cyclopentane or combinations thereof. In certain embodiments, the co-purge agent(s) comprises water and/or normal pentane, isopentane, or cyclopentane alone or in combination, which may be present in one hydrohaloolefin purge agent described herein or in a combination of hydrohaloolefin purge agents described herein. The blowing agent component is preferably present in the polyol premix composition in an amount of from about 1 wt. % to about 30 wt. %, preferably from about 3 wt. % to about 25 wt. %, and more preferably from about 5 wt. % to about 25 wt. % weight of the polyol premix composition. In the presence of a hydrohaloolefin and an optional blowing agent, the hydrohaloolefin component is preferably present in the blowing agent component in an amount of from about 5 wt. % to about 90 wt. %, preferably from about 7 wt. % to about 80 wt. %, and more preferably from about 10 wt. % to about 70 wt. % weight of the components with a purge agent; and the optional purge agent is preferably present in the purge agent component in an amount of from about 95 wt. % to about 10 wt. %, preferably from about 93 wt. % to about 20 wt. %, and more preferably from about 90 wt. % to about 30 wt. % weight of the components with a purge agent.

POLYOL COMPONENT

The polyol component, which includes mixtures of polyols, can be any polyol or mixture of polyols that reacts in a known manner with an isocyanate to form a polyurethane or polyisocyanurate foam. Possible polyols include one or more sucrose-containing polyols, phenols, phenol-formaldehyde-containing polyols, glucose-containing polyols, sorbitol-containing polyols, methyl glucoside-containing polyols, aromatic polyester polyols, glycerols, ethylene glycols, diethylene glycols, propylene glycols, graft copolymers of polyester polyols with a vinyl polymer, copolymers of polyester polyols with polyurea; one or more (a) fused with one or more (b), where (a) is selected from glycerol, ethylene glycol, diethylene glycol, trimethylolpropane, ethylenediamine, pentaerythritol, soybean oil, lecithin, tall oil, palm oil and castor oil; and (b) is selected from ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide, and combinations thereof. The polyol component is typically present in the polyol premix composition in an amount of from about 60 wt. % to about 95 wt. %, preferably from about 65 wt. % to about 95 wt. % and, more preferably, from about 70 wt. % to about 90 wt. % weight of the polyol premix composition.

SURFACE-ACTIVE SUBSTANCE

The polyol premix composition preferably also contains a silicone surfactant. The silicone surfactant is preferably used to form the foam of the mixture as well as to control the size of the bubbles of the foam to obtain a foam with the desired cell structure. Preferably, a foam with small bubbles or uniformly sized cells is desirable because it has the most desirable physical properties such as compressive strength and thermal conductivity. In addition, it is important to obtain a foam with stable cells that do not collapse before the formation or during the rise of the foam.

Silicone surfactants for use in the production of polyurethane or polyisocyanurate foams are available under a number of trade names known to those skilled in the art. These materials are applicable in a wide range of formulations to provide uniform cells and maximize gas entrainment for a very low density foam structure. A preferred silicone surfactant includes a polyoxyalkylene-polysiloxane block copolymer. Some suitable silicone surfactants for use in this invention are L-5130, L-5180, L-5340, L-5440, L-6100, L-6900, L-6980 and L-6988 from Momentive; Air Products DC-193, DC-197, DC-5582 and DC-5598; B-8404, B-8407, B-8409 and B-8462 from Evonik Industries AG, Essen, Germany. Others are described in US Pat. Nos. 2,834,748; 2,917,480; % to about 5.0 wt. %, preferably from about 1.0 wt. % to about 4.0 wt. % and, more preferably, from about 1.5 wt. % to about 3.0 wt. % weight of the polyol premix composition.

The polyol premix composition may optionally contain a non-silicone surfactant, such as a non-silicone nonionic surfactant. These surface agents may include ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, sulfonated castor oil, peanut oil, paraffins, and fatty alcohols. The preferred non-silicone nonionic surfactant is LK-443, which is commercially available from Air Products Corporation. When used, a non-silicone nonionic surfactant is typically present in the polyol premix composition in an amount of from about 0.25 wt. % to about 3.0 wt. %, preferably from about 0.5 wt. % to about 2.5 wt. % and, more preferably, from about 0.75 wt. % to about 2.0 wt. % weight of the polyol premix composition.

CATALYTIC SYSTEM

Applicants have generally found that identifying amine-based catalysts that produce relatively low levels of halogen ions when contacted with hydrohaloolefins such as fluoride and chloride is difficult, while they have sufficient activity characteristics to be used by themselves in the preparation Pen. In other words, Applicants have found that a large number of relatively stable amine-based catalysts can be detected in the presence of hydrohaloolefins, however, these catalysts are generally not active enough to provide the required foam reactivity. On the other hand, applicants have also found that a relatively large number of amine-based catalysts can be identified that are active enough to provide acceptable foam reactivity, however, these catalysts are generally not stable enough for use in combination with hydrohaloolefins based on the level of fluoride production. .

Applicants have investigated a large number of amine-based catalysts to determine the physical and chemical interaction with certain hydrohaloolefins, and to determine and study their stability. Some of the investigated catalysts are listed in Table A below:

* - wt. % of the specified molecule in the catalyst with the remainder being a carrier such as water, glycol and the like.

Applicants investigated the compatibility of the catalyst with gaseous and/or liquid purge agent using a pressure reaction vessel. Three grams of catalyst was added to the tarred vessel and sealed. After closing through the gas port, 3 grams of a purge agent such as 1234ze(E) was added to the vessel. The contents were mixed and the final weight was recorded. The vapor pressure of the feed solution was recorded and photographs were taken to document the color and consistency of the solution and catalyst. Then the vessel was placed in an oven with a temperature of 54°C for 24 hours. The vapor pressure of the solution was measured twice within 24 hours at elevated temperature. The solution was removed from the oven and left to cool. The vapor pressure was measured and the solution photographed. The pressure of the pressure reaction vessel was reduced. The remaining solution was dissolved with deionized water to a total volume of 100 ml. The concentration of fluorides and chlorides was measured using ion chromatography.

Applicants measured the degree of formation of fluorides when processing each catalyst 1234ze(E) for 24 hours at 54°C. The results are shown in Table B below:

TABLE B

Applicants present the results of this study in FIG. 1 Applicants also tested the compatibility of the catalyst with a gaseous purge agent using a pressure reaction vessel as described above containing a 50/50 solution of purge agent such as 1234ze(E) and catalyst. The vessel was then placed in an oven at 54° C. for an extended period of time, and the fluoride concentration was determined by ion chromatography after extended periods of time in accordance with the procedure described above. Shown in FIG. The results in Figure 2 show that tertiary amine catalysts react with hydrohaloolefin scavengers at different rates, the rate generally being inversely related to the degree of steric effect around the amine nitrogen.

Based on the experimental results above, Applicants have found that the stability of a particular amine based catalyst is partly related to the steric hindrance of the amine group as well as the pKa of the amine. In particular, Applicants have found that it is highly desirable to select an amine-based catalyst, if one is to be used, with a pKa of at least about 10. Applicants have also analyzed the relationship between the degree of fluoride ion production and the vapor pressure of the solution containing the purge agent and the catalyst, after certain time. These results are shown in Table C below:

Based on the results shown in Table C, Applicants have determined that there is a strong relationship between a reduction in vapor pressure (indicative of reduced purge efficiency) and an increase in F- formation in hydrohalogen catalyst/purge agent solutions (such as 1234ze(E)) at room temperature. At fluoride concentrations >4000 ppm, there is a significant reduction in vapor pressure. However, Applicants have found unexpected results regarding the interaction between Jeffamine D 230 and 1234ze(E) catalysts, in particular that this combination leads to an increase in vapor pressure over time even though the levels of fluoride formation are significant and reach the level approximately 4000 ppm.

Based on the study carried out by the applicants, it was found that fluorides are formed in the presence of 1234ze(E) in the case of the following catalysts.

In addition to the above, Applicants investigated the reactivity of some of the above catalysts based on the gel time in seconds of a conventional wallboard formulation with a purge agent consisting of 1234ze(E). The results are shown in Table 2A and Table 2B below:

Based on the applicants' research, it has been found that purge agents comprising and preferably consisting for the most part of 1234ze(E), i.e. catalysts Nos. 1-9 in Table 1 above are generally not preferred due to problems with stability, as evidenced by the high level of fluoride concentration. On the other hand, applicants have found that Catalysts Nos. 12-15 are generally not preferred due to the fact that they are not considered to have sufficient activity to produce an acceptable level of foam reactivity despite a high level of stability. Applicants have surprisingly found that Catalysts #10 and #11, specifically p-methyldicyclohexylamine and methyl(p-methylamine b-sodium acetate nonylphenol) 2-, are preferred in accordance with the present invention because they provide a desirable but difficult to achieve combination of stability and activity when used in combination with hydrohaloolefins.

Applicants have also surprisingly found that, among hydrohaloolefins, 1233zd(E) is significantly less reactive with amine catalysts than other hydrohaloolefins, in particular hydrohalogenated propenes. More specifically, as a result of the study, the applicants found that the following catalysts have a relative level of production of fluorides in the presence of 1233zd(E), as indicated in Table 3 below.

As can be seen from the above results, applicants have found that 1233zd(E) is much more stable in the presence of amine-based catalysts than other halogenated olefins, in particular tetrafluoropropenes such as 1234ze, as evidenced by the level of production of fluoride ions. Furthermore, even more surprisingly, Applicants have found that 1-methylimidazole has an extremely high level of stability while maintaining a relatively high level of foam reactivity when used in combination with 1233zd(E). Similarly, Applicants have surprisingly found that p-methyldicyclohexylamine has an extremely high level of stability while maintaining a relatively high level of foam reactivity when used in combination with 1233zd(E).

Contrary to the unexpected and useful results described above regarding combinations of halogenated olefins and certain amine catalysts, Applicants have found that even the best of these combinations are not entirely satisfactory in many ways of carrying out the invention, and that a subsequent and unexpected improvement can be achieved by replacing all or a substantial portion of the amine catalyst(s) with one or more metal catalysts, and more preferably two or more catalysts, at least the first and second of said catalysts being a different metal catalyst. In general, Applicants have found that metal-based catalysts are relatively unreactive with halogenated olefins that can be used as purge agents and thus produce a relatively stable system, and that due to the balanced selection of at least the first and second catalysts on metal-based compositions, systems and methods that are surprisingly effective and stable can be obtained.

Applicants have found that the use of a single metal catalyst system is not capable of producing satisfactory and desired foam composition and/or process reactivity profiles in many embodiments of the invention. Applicants have found that, in many embodiments of the invention, surprising and extremely beneficial results can be achieved by selecting catalyst systems comprising a first metal-based catalyst, said first metal being selected from catalytic metals with relatively high activity at low temperatures, and a second catalyst based on metal-based, wherein said second metal-based catalyst is selected from catalytic metals with relatively high activity at high temperatures. In certain preferred embodiments of the invention, the metal of the first metal-based catalyst is selected from the group consisting of tin, zinc, cobalt, lead, and combinations thereof, wherein the catalyst comprises or, more preferably, consists predominantly of zinc-based catalysts (and, more preferably organozinc catalysts), which is particularly preferred. In certain preferred embodiments, the metal of the second metal-based catalyst is selected from the group consisting of bismuth, sodium, calcium, and combinations thereof, wherein the catalyst comprises or, more preferably, consists predominantly of bismuth-based catalysts (and more preferably , organo-bismuth catalysts), which is particularly preferred. In the most preferred embodiments of the present invention, the catalyst system includes a first metal-based catalyst and a second metal-based catalyst in accordance with the broad and preferred aspects of the present invention, however, contains less than 50 wt. % amine based catalyst relative to the total weight of the catalyst, and certain preferred embodiments of the invention substantially do not include amine based catalyst.

In addition, Applicants have found that blowing agents and foaming systems, which are highly desirable in certain embodiments of the invention, can be obtained by using one or more preferred amine-based catalysts of the present invention in combination with at least one, and preferably, at least two metal catalysts according to the invention as described above.

In certain embodiments, the non-amine catalysts are inorganic or organometallic compounds. Possible inorganic or organometallic compounds include (but are not limited to) organic salts, Lewis acid halides, or the like of any metal, including (but not limited to) transition metals, post-transition (poor) metals, rare earth metals (e.g., lanthanides), metalloids, alkali metals, alkaline earth metals and the like. In accordance with certain broad aspects of the present invention, these metals may include, but are not limited to, bismuth, lead, tin, zinc, chromium, cobalt, copper, iron, manganese, magnesium, potassium, sodium, titanium, mercury, zinc, antimony, uranium , cadmium, thorium, aluminum, nickel, cerium, molybdenum, vanadium, zirconium, or combinations thereof. Non-exclusive examples of these inorganic and organometallic catalysts include, but are not limited to, bismuth nitrate, lead 2-ethylhexoate, lead benzoate, lead naphthanate, ferric chloride, antimony trichloride, antimony glycolate, tin salts of carboxylic acids, dialkyl tin salts of carboxylic acids, potassium acetate, octoate potassium, potassium 2-ethylhexoatom, potassium salts of carboxylic acids, zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts, alkaline salts of carboxylic acids, N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate sodium, 2- tin (II) ethylhexanoate, dibutyl dilaurate, or a combination thereof. In certain preferred embodiments of the invention, these catalysts are present in the polyol premix composition in an amount of from about 0.001 wt. % to about 5.0 wt. %, from about 0.01 wt. % to about 3.0 wt. %, preferably from about 0.3 wt. % to about 2.5 wt. % and, more preferably, from about 0.35 wt. % to about 2.0 wt. % weight of the polyol premix composition. While these amounts are common, the amount of the above catalyst can vary widely, and the appropriate amount can be readily determined by those skilled in the art.

In addition, as noted above, Applicants have found that it is desirable to use certain metal-based catalysts in blowing and foaming systems with relatively high water levels, in particular in polyol premix compositions with high water content. More specifically, Applicants have found that certain zinc, iron, bismuth and potassium based catalysts are preferred in these systems due to their ability to maintain reactivity and avoid stability problems in these high water systems. In addition, Applicants have found that zinc and bismuth based catalysts generally provide acceptable performance in systems with relatively low water content, however, not all of these catalysts are capable of providing the most desirable results in systems and compositions with high water content. Applicants have found that the class of metal based catalysts described above, and preferably zinc and bismuth based catalysts, and more preferably certain amine/zinc/bismuth based catalyst blends, are capable of providing high performance in high water systems and compositions, wherein the metal-based catalyst includes precipitation-resistant metal-based catalyst(s) as defined herein. In other or additional embodiments of the invention, the applicants have found that in certain systems it is preferable if the metal-based catalysts include at least a first catalyst based on tin and/or zinc and a second catalyst based on potassium and/or bismuth, while the first and second metal-based catalysts comprise and preferably consist for the most part of precipitation-resistant metal-based catalyst(s).

In another embodiment, the non-amine catalyst is a quaternary ammonium carboxylate. Possible quaternary ammonium carboxylates include, but are not limited to: (2-hydroxypropyl)trimethylammonium 2-ethylhexanoate (TMR-2®, sold by Air Products and Chemicals) and (2-hydroxypropyl)trimethylammonium formate (TMR-2®, sold by Air Products). and Chemicals). These quaternary ammonium carboxylate catalysts are typically present in the polyol premix composition in an amount of from about 0.25 wt. % to about 3.0 wt. %, preferably from about 0.3 wt. % to about 2.5 wt. %, more preferably from about 0.35 wt. % to about 2.0 wt. % weight of the polyol premix composition. While these amounts are common, the amount of catalyst can vary widely, and the appropriate amount can be readily determined by those skilled in the art.

In another embodiment of the invention, a non-amine catalyst is used in combination with an amine-based catalyst as described above. These amine-based catalysts may include any compound containing an amine group and having the catalytic activity described here. These compounds may be straight chain or cyclic non-aromatic or aromatic compounds. Possible amines include, without limitation, primary amines, secondary or tertiary amines. Possible tertiary amine catalysts include non-exclusively N,N,N',N'',N''-pentamethyldiethyltriamine, N,N-dicyclohexylmethylamine, N,N-ethyldiisopropylamine, N,N-dimethylcyclohexylamine, N,N-dimethylisopropylamine, N -methyl-N-isopropylbenzylamine, N-methyl-N-cyclopentylbenzylamine, N-isopropyl-N-sec-butyl-trifluoroethylamine, N,N-diethyl-(α-phenylethyl)amine, N,N,N-tri-n- propylamine or combinations thereof. Possible secondary amine catalysts include non-exclusively dicyclohexylamine, t-butylisopropylamine, di-t-butylamine, cyclohexyl-t-butylamine, di-sec-butylamine, dicyclopentylamine, di-(α-trifluoromethylethyl)amine, di-(α-phenylethyl) amine; or combinations thereof. Possible primary amine catalysts include non-exclusively: triphenylmethylamine and 1,1-diethyl-n-propylamine.

Other possible amines include morpholines; imidazoles; compounds containing ethers, and the like. These include:

dimorpholinodiethyl ether

N-ethylmorpholine

N-methylmorpholine

bis(dimethylaminoethyl)ether

imidazole

n-methylimidazole

1,2-dimethylimidazole

dimorpholinodimethyl ether

N,N,N',N',N'',N''-pentamethyldiethylenetriamine

N,N,N',N',N'',N''-pentaethyldiethylenetriamine

N,N,N',N',N''N''-pentamethyldipropylenetriamine

bis(diethylaminoethyl)ether

bis(dimethylaminopropyl)ether.

In embodiments of the invention in which an amine-based catalyst is provided, this catalyst may be provided in any amount to achieve the function of the invention without affecting foam formation or composition stability during storage, as defined here. To this end, the amine-based catalyst may be provided in a smaller or larger amount relative to the amount of the non-amine catalyst.

The preparation of polyurethane and polyisocyanurate foams using the compositions described herein can be carried out according to any of the methods known in the art, see Saunders and Frisch, vol. I and II Polyurethanes Chemistry and technology, 1962, John Wiley and Sons, New York, N.Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, N.Y. or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, ON. In general, polyurethane and polyisocyanurate foams are made by combining an isocyanate, a polyol premix composition, and other materials such as optional flame retardants, colorants, and other additives. These foams may be rigid, flexible, or semi-rigid, and may have a closed cell structure, an open cell structure, or a combination of open and closed cells.

In various fields of application, it is convenient to use components of polyurethane and polyisocyanurate foams in pre-mixed solutions. Most often, foam solutions are pre-mixed from two components. Isocyanate and optionally other isocyanate-compatible feedstocks, including but not limited to purge agents and certain silicone surfactants, constitute the first component, commonly referred to as the "A" component. The polyol premix composition, including surfactant, catalysts, scavengers, and optionally other ingredients, constitutes the second component, commonly referred to as the "B" component. In any use case, component "B" cannot contain all of the above components, for example, some formulations do not include flame retardants if fire protection is not a desired property of the foam. Accordingly, polyurethane and polyisocyanurate foams are easily made by combining components A and B, either by hand mixing in the case of small volumes, or preferably by machine mixing methods to obtain blocks, slabs, sandwich structures, embedded panels and other products, spray foams , foam products and the like. Other ingredients such as flame retardants, dyes, purge aids, water, and even other polyols may optionally be added as a jet to the mixer or reaction center. Most convenient, however, is their inclusion in component B, as described above.

A foam composition suitable for forming a polyurethane or polyisocyanurate foam can be prepared by reacting an organic polyisocyanate and the above-described polyol premix composition. Any organic polyisocyanate can participate in the synthesis of polyurethane or polyisocyanurate foam, with the exception of aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic isocyanates, which are well known in the art of polyurethane chemistry. These isocyanates are described, for example, in US Pat.

Suitable organic polyisocyanates correspond to the formula:

R(NCO)z

where R is a polyvalent organic radical representing an aliphatic, aralkyl, aromatic radical or a mixture thereof, and z is an integer corresponding to the valency of R and equal to at least two. Suitable organic polyisocyanates contemplated 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, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate, and the like; aromatic triisocyanates such as 4,4',4''-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates; aromatic tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'5,5-'tetraisocyanate and the like; aralkyl polyisocyanates such as xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene-1,6-diisocyanate, lysine diisocyanate methyl ether and the like; and their mixtures. Other organic polyisocyanates include polymethylene polyphenylisocyanate, hydrogenated methylene diphenylisocyanate, t-phenylene diisocyanate, 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; conventional aliphatic polyisocyanates are alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, isophorene diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate) and the like; common aromatic polyisocyanates include t- and p-phenylene diisocyanate, polymethylene polyphenylisocyanate, 2,4- and 2,6-toluene diisocyanate, dianisidine diisocyanate, bitoluene isocyanate, naphthylene 1,4-diisocyanate, bis(4-isocyanate-phenyl)methene, bis(2-methyl-4 -isocyanatephenyl)methane and the like. Preferred polyisocyanates are polymethylene polyphenylisocyanates, in particular mixtures containing from about 30 to about 85 wt. % methylenebis(phenylisocyanate) with the remainder of the mixture comprising polymethylene polyphenyl polyisocyanates with a functionality greater than 2. These polyisocyanates are prepared according to conventional methods known in the art. In the present invention, the polyisocyanate and polyol are used in amounts that produce an NCO/OH stoichiometric value in the range of about 0.9 to about 5.0. In the present invention, the NCO/OH equivalent ratio is preferably about 1.0 or more and about 3.0 or less, with the ideal range being about 1.1 to about 2.5. A particularly suitable organic polyisocyanate includes polymethylene polyphenylisocyanate, methylene bis(phenylisocyanate), toluene diisocyanates, or combinations thereof.

In the preparation of polyisocyanate foams, trimerization catalysts are used to convert mixtures together with excess A component to polyisocyanurate-polyurethane foams. The trimerization catalysts used can be any catalyst known to the person skilled in the art, including, but not limited to, glycine salts, tertiary amine-based trimerization catalysts , carboxylates of quaternary amines, alkaline salts of carboxylic acids and mixtures of various types of catalysts. Preferred compounds within these classes are potassium acetate, potassium octoate, and sodium N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

May also include known flame retardants, preferably in an amount of not more than 20 wt. % reactants. Optional flame retardants include tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tris(1,3-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-bis-2 (chloroethyl)ethylene diphosphate, triethyl phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, melamine, and the like. Other optional ingredients may include about 0 to about 7 percent water to chemically react with the isocyanate to form carbon dioxide. The carbon dioxide acts as an auxiliary scavenging agent. Formic acid is also used to produce carbon dioxide by reaction with isocyanate and optionally added to component "B".

In addition to the ingredients described above, other ingredients such as colorants, fillers, pigments, and the like may be included in the foams. Dispersing agents and cell stabilizers can be added to existing mixtures. Standard fillers for use here include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fiber, carbon black and quartz. When used, the filler is typically present in an amount of from about 5 parts to 100 parts per 100 parts by weight of the polyol. The pigment that can be used here can be any conventional pigment such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, sienna blue, molybdate yellow and organic pigments such as Para Red, benzidine yellow, toluidine red, toners and phthalocyanine dyes.

The density of the resulting polyurethane and polyisocyanurate foams can be from about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably from about 1.0 to about 20.0 pounds per cubic foot, and most preferably from about 1.5 up to about 6.0 pounds per cubic foot. The density obtained is a function of the amount of blowing agent or mixture of blowing agents described in this invention, as well as the amount of auxiliary blowing agent, such as water or other co-blowing agents, present in components A and/or B, or added during foam production. These foams may be rigid, flexible, or semi-rigid, and may have a closed cell structure, an open cell structure, or a combination of open and closed cells. These foams are widely used, including but not limited to the following fields: thermal insulation, damping, flotation, packaging materials, adhesives, void filling, craft and decorative production, and cushioning. The following non-limiting examples serve to illustrate the present invention.

EXAMPLE 1A - SPRAY FOAM

In accordance with Table E1A below, two formulations of a standard spray foam based on polyols were prepared.

After the stability study, the results shown in FIG. 3. The compositions were maintained for up to 168 hours at a temperature of about 52°C in accordance with the procedure described above. Three different foams were formed from each composition: one directly during the formation of the composition; one after about 62 hours; and one after 168 hours. The gelation time of each thus formed foam was recorded; these results are shown in FIG. 3. As can be seen from the above example and the data in FIG. 3, the gel time of a conventional foam formulation, in particular a spray foam formulation, increases significantly with aging of the foam forming composition using a conventional catalyst formulation, especially when compared to saturated materials with blowing agents such as HFC-245fa. Those skilled in the art will appreciate that this level of performance is generally not considered

acceptable in many commercial products.

EXAMPLE 1B-SPRAY FOAM

Formed two common commercial polyol spray foam formulations in

according to Table E1 BA below:

* - The Safety Data Sheet for this material is included in Appendix C and is included here for reference.

The above table indicates that while the zinc-based catalyst and bismuth-based catalyst used in this system do not produce precipitation in low water systems (Low Water Sample) when tested at High Temperature or Low Temperature, precipitation generated in tests where the composition is identical except that the system is a high water system (High Water Sample). For purposes of comparison, the zinc-based catalyst used in the High Water Sample was replaced by the precipitation-resistant zinc-based catalyst of the present invention, as shown in Table E1 BB below:

In the above formulation, K-Kat XK-614 was first mixed with a blend of polyols (resins) and then the water component was added, which Applicants have found to be the preferred order in which the components are added to the system. After stability testing using the same procedure as described in Example 1 above, the stability of the High Water Samples in BB Table E1 increased significantly, with no increase in gel time even when the solution was stored for 168 hours at 52°C.

EXAMPLE 2 - SPRAY FOAM WITHOUT CATALYST

Conventional commercial formulations were prepared according to Table E2A below.

spray foam based on polyols without a catalyst.

After the stability study, results were obtained corresponding to those in FIG. 1 indicating that 1233zd(E) is suitable for use as a blowing agent in combination with conventional commercially used polyol compounds, including in particular those used in conventional commercial spray foam formulations.

EXAMPLE 3 - SPRAY FOAM WITHOUT CATALYST

The spray foam polyol formulations of the present invention were formed using the preferred blowing agent 1233zd(E) and a less preferred catalyst system consisting of a single bismuth-based metal catalyst and a non-preferred amine-based catalyst according to Table E3A below:

The same composition was formed as in Table E3A, however, the catalyst was replaced with the more preferred catalyst system of the present invention, consisting of a first precipitation-resistant metal catalyst (zinc-based) and a second metal catalyst (bismet-based) and a preferred amine-based catalyst according to Table E3B below:

* The zinc-based catalyst was K-Kat XK-614 described here and the bismuth-based catalyst was MB-20 described here.

After the stability study, the results shown in FIG. 4, where the data indicated as a white column labeled "1233zd(E)" corresponds to the composition results in Table E3A, and the data indicated as a green column labeled "1233zd(E) + modified catalyst" corresponds to the composition results in Table E3B showing no increase in gel time after 62 hours and only an 8% increase in gel time after 168 hours. This formulation shows a negative result for resistance to precipitation under High Temperature conditions (significant precipitation was not observed after the High Temperature test) and a positive result for bismuth (precipitation of a bismuth salt was observed after three months under Low Temperature conditions).

The results presented in this example illustrate the surprising and highly beneficial benefits associated with the use of blowing agents, foam formulations, foams and foam processes with the preferred catalyst systems of the present invention.

EXAMPLE 3C - SPRAY FOAM WITH CATALYST

A polyol spray foam formulation identical to that of Example 3A was formed, except that the bismuth-based catalyst, which was not precipitation resistant according to the Low Temperature study, was replaced with a bismuth-based catalyst, which was precipitation resistant according to the Low Temperature study. By temperature and research with High Temperature.

* The zinc-based catalyst was K-Kat XK- described here and the bismuth-based catalyst was K-Kat XC-227 described here.

The gel time of this conventional foam formulation, in particular the spray foam formulation, did not increase after three months of storage at room temperature using a purge agent consisting of 1233zd and the preferred catalyst of the present invention in accordance with Table 3C. Those skilled in the art will appreciate that this level of performance is generally considered to be acceptable in many commercial products, and that this improvement in performance relative to gel time is significant, significant, and surprising.

In addition, this formulation showed a negative result for precipitation resistance under High Temperature conditions (no significant precipitation was observed after the High Temperature test) and a negative result for bismuth (no precipitation of bismuth salt after three months under Low Temperature conditions). Accordingly, both metal catalysts in this system are resistant to precipitation under High and Low Temperature conditions.

EXAMPLE 3D - SPRAY FOAM WITH CATALYST

A polyol spray foam formulation was formed using the preferred blowing agent 1233zd(E) and the preferred catalyst system from Example 3C as indicated in Table E3D below, different from the formulation of Example 3C:

As can be seen from the above table, the type and amounts of various catalysts were changed, however, a catalyst consisting of a first precipitation resistant metal (zinc) catalyst and a second precipitation resistant metal (bismuth) catalyst and a preferred metal catalyst was used. In addition, this formulation exhibits precipitation resistance under High Temperature conditions (significant precipitation was not observed after the High Temperature test) and precipitation resistance under Low Temperature conditions (bismuth salt precipitation after three months under Low Temperature conditions was not observed). Accordingly, both metal catalysts in this system are resistant to precipitation under High and Low Temperature conditions.

EXAMPLE 3E - SPRAY FOAM WITH CATALYST

A polyol spray foam formulation was formed using the preferred blowing agent 1233zd(E) and the preferred catalyst system from Example 3C as indicated in Table E3D below, different from the formulation of Example 3C:

This formulation showed a negative result for precipitation resistance under High Temperature conditions (no significant precipitation was observed after the High Temperature test) and resistance to precipitation under Low Temperature conditions (no significant precipitation was observed three months after the Low Temperature test). Accordingly, the metal catalysts in this system are resistant to precipitation under both High and Low Temperature conditions.

EXAMPLE 3F - SPRAY FOAM WITH CATALYST

A polyol spray foam formulation was formed using the preferred blowing agent 1233zd(E) and the preferred catalyst system as indicated in Table E3F below, different from the formulation of Example 3C:

This formulation showed a negative result for precipitation resistance under High Temperature conditions (no significant precipitation was observed after the High Temperature test) and resistance to precipitation under Low Temperature conditions (no significant precipitation was observed three months after the Low Temperature test). Accordingly, the metal catalysts in this system are resistant to precipitation under both High and Low Temperature conditions.

EXAMPLE 3G - SPRAY FOAM WITH CATALYST

A polyol spray foam formulation was formed using the preferred blowing agent 1233zd(E) and the preferred catalyst system as indicated in Table E3G below, different from the formulation of Example 3C:

This formulation showed a negative result for precipitation resistance under High Temperature conditions (no significant precipitation was observed after the High Temperature test) and resistance to precipitation under Low Temperature conditions (no significant precipitation was observed three months after the Low Temperature test). Accordingly, the metal catalysts in this system are resistant to precipitation under both High and Low Temperature conditions.

EXAMPLE 4 (COMPARATIVE EXAMPLE)

A polyol formulation (component B) was prepared in an amount of 100 parts by weight of a mixture of polyols, 1.5 parts by weight of a Niax L6900 surfactant, 1.5 parts by weight of water, 1.2 parts by weight of a pentamethyldiethylenetriamine catalyst (sold under trade name Polycat 5 by Air Products and Chemicals) and 8 parts by weight of trans-1,3,3,3-tetrafluoropropene purge agent. The total composition of component B produced a good quality foam with a fine and uniform cell structure when formulated and combined with 120.0 parts by weight of Lupranate M20S polymeric isocyanate. Foam reactivity was typical for locally prepared foam. The total composition of component B (112.2 parts) was kept at 130°F for 62 hours and then combined with 120.0 parts of M20S polymeric isocyanate to form a foam. The resulting foam was extremely weak with significant cell disruption. Significant yellowing of the polyol premix was noted during exposure.

EXAMPLE 5 (COMPARATIVE EXAMPLE)

A polyol formulation (component B) was prepared in an amount of 100 parts by weight of a mixture of polyols, 1.5 parts by weight of a Niax L6900 surfactant, 1.5 parts by weight of water, 1.2 parts by weight of a pentamethyldiethylenetriamine catalyst (sold under trade name Polycat 5 by Air Products and Chemicals) and 8 parts by weight of trans-1-chloro-3,3,3-trifluoropropene purge agent. The total composition of component B produced a good quality foam with a fine and uniform cell structure when formulated and combined with 120.0 parts by weight of Lupranate M20S polymeric isocyanate. Foam reactivity was typical for locally prepared foam. The total composition of component B (112.2 parts) was kept at 130°F for 168 hours and then combined with 120.0 parts of M20S polymeric isocyanate to form a foam. The resulting foam was extremely weak with significant cell disruption. Significant yellowing of the polyol premix was noted during exposure.

EXAMPLE 6 (FOAM TEST)

A polyol composition (component B) was prepared in the amount of 100 parts by weight of a mixture of polyols, 1.5 parts by weight of Niax L6900 surfactant, 1.5 parts by weight of water, 2.0 parts by weight of catalyst based on M, "M -decyclohexylmethylamine (sold under the trade name Polycat 12 by Air Products and Chemicals) (a different amine was used so that this foam and comparative had the same initial reactivity), 1.75 parts by weight of bismuth-based catalyst (sold under the trade name Dabco MB -20 by Air Products and Chemicals) and 8 parts by weight of a trans-1,3,3,3-tetrafluoropropene blowing agent.The total composition of component B produced a good quality foam with a fine and uniform cell structure when formulated and combined with 120, 0 parts by weight of Lupranate M20S polymeric isocyanate Foam reactivity was typical for a locally prepared foam. and B (114.75 parts) was held at 130°F for 336 hours and then combined with 120.0 parts of M20S polymeric isocyanate to form a foam. The foam had an excellent appearance with no signs of cell destruction. Yellowing of the polyol premix was not observed during exposure.

EXAMPLE 7 (FOAM TEST)

A polyol composition (component B) was prepared in the amount of 100 parts by weight of a mixture of polyols, 1.5 parts by weight of Niax L6900 surfactant, 0.5 parts by weight of water, 2.0 parts by weight of catalyst Based on "K, M -decyclohexylmethylamine (sold under the tradename Polycat 12 by Air Products and Chemicals) (a different amine was used so that this foam and the comparative example had the same initial reactivity), 1.75 parts by weight of zinc 2-ethylhexanoate catalyst (sold under the trade name 30-3038 by Strem Chemicals) and 8 parts by weight of a trans-1-Chloro-3,3,3-trifluoropropene blowing agent. 103.0 parts by weight of Lupranate M20S polymeric isocyanate Foam reactivity was typical for a locally prepared foam. Tape B (113.75 parts) was held at 130°F for 336 hours and then combined with 103.0 parts of M20S polymeric isocyanate to form a foam. The foam had an excellent appearance with no signs of cell destruction. Yellowing of the polyol premix was not observed during exposure.

EXAMPLE 8 (FOAM TEST)

A polyol formulation (component B) was prepared in an amount of 100 parts by weight of a mixture of polyols, 1.5 parts by weight of Niax L6900 surfactant, 1.0 parts by weight of water, 2.0 parts by weight of an N,N-based catalyst. decyclohexylmethylamine (sold under the trade name Polycat 12 by Air Products and Chemicals) (a different amine was used so that this foam and comparative had the same initial reactivity), 1.75 parts by weight of potassium-based catalyst (sold under the trade name Dabco K 15 Air Products and Chemicals) and 8 parts by weight of trans-1-chloro-3,3,3-trifluoropropene purge agent. The total composition of component B produced a good quality foam with a fine and uniform cell structure when formulated and combined with 112.0 parts by weight of Lupranate M20S polymeric isocyanate. Foam reactivity was typical for locally prepared foam. The total composition of component B (114.75 parts) was held at 130°F for 504 hours and then combined with 112.0 parts of M20S polymeric isocyanate to form a foam. The foam had a good appearance with little evidence of cell failure. Very slight yellowing of the polyol premix was noted during exposure.

EXAMPLE 9 - FOAM FOR BUILDING PANELS

In accordance with Table E9A below, two conventional commercial foam formulations for building panels based on polyols were prepared.

The above table indicates that the zinc-based catalyst does not produce precipitation in systems with low water content (Low Water Sample), however, precipitation forms with an identical composition in case the system is a high water content system (High Water Sample). water). The zinc-based catalyst used in the High Water Sample was replaced by the precipitation-resistant catalyst of the present invention, as shown in Table E9B below:

In the above formulation, K-Kat XK-614 was first mixed with a blend of polyols (resins) and then the water component was added, which Applicants have found to be the preferred order in which the components are added to the system. After the stability test, the High Water Sample exhibited a performance substantially inferior to that of the Settling Resistant High Water Sample within the gel time frame.

Claims (19)

1. A polyol premix composition for foaming, wherein the polyol premix composition contains: a) a hydrohaloolefin purge agent selected from the group consisting of trans-1,3,3,3-tetrafluoropropene (trans-1234ze) and trans-1-chloro-3,3,3-trifluoropropene (trans-1233zd) and their combinations b) one or more polyols, c) one or more silicone surfactants, and d) a catalyst system comprising a precipitation resistant bismuth carboxylate catalyst, while the purge agent is present in an amount of 1 wt. % to about 30 wt. % of the composition and the catalyst is present in the polyol premix composition in an amount of from about 0.001 wt. % to about 5.0 wt. % by weight of the polyol premix composition, wherein the composition contains water in an amount of at least 1.5 pphp by weight. 2. The polyol premix composition according to claim 1, characterized in that the catalyst system further comprises a precipitation-resistant zinc carboxylate catalyst. 3. A polyol premix composition according to any one of the preceding claims, characterized in that the hydrohaloolefin purge agent contains trans-1,3,3,3-tetrafluoropropene (trans-1234ze). 4. A polyol premix composition according to any of the preceding claims, characterized in that the hydrohaloolefin purge agent contains trans-1-chloro-3,3,3-trifluoropropene (trans-1233zd). 5. A polyol premix composition according to any of the preceding claims, further comprising one or more amine catalysts. 6. The polyol premix composition of claim 5 wherein the one or more amine catalysts have a pKa of at least about 10. 7. Polyol premix composition according to claim 5 or 6, characterized in that the weight ratio of amine-based catalyst to zinc carboxylate and bismuth carboxylate catalysts is from 1:1 to 1:4. 8. Polyol premix composition according to claim 5 or 6, characterized in that the weight ratio of amine based catalyst to zinc carboxylate and bismuth carboxylate based catalysts is from 1:1 to 1:3. 9. Polyol premix composition according to claim 5 or 6, characterized in that the weight ratio of amine catalyst to zinc carboxylate and bismuth carboxylate catalysts is from 1:1 to 1:1.5 by weight. 10. Polyol premix composition according to any one of the preceding paragraphs, characterized in that the catalysts are present in the polyol premix composition in an amount of from about 0.01 wt. % to about 3.0 wt. % by weight of the polyol premix composition. 11. Polyol premix composition according to any one of the preceding paragraphs, characterized in that the catalysts are present in the polyol premix composition in an amount of from about 0.3 wt. % to about 2.5 wt. % by weight of the polyol premix composition. 12. Polyol premix composition according to any one of the preceding paragraphs, characterized in that the catalysts are present in the polyol premix composition in an amount of from about 0.35 wt. % to about 2.0 wt. % by weight of the polyol premix composition. 13. Polyol premixed composition according to any one of the preceding paragraphs, characterized in that the purge agent is present in an amount of 3 wt. % to about 25 wt. % by weight of the composition. 14. Polyol premixed composition according to any one of the preceding paragraphs, characterized in that the purge agent is present in an amount of 5 wt. % to about 25 wt. % by weight of the composition.

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