Cross-Reference to Related Application^) This is a continuation-in-part of U.S. Serial No. 07/771,442, filed October 4, 1991, incorporated hereinby reference. Technical Field

This invention relates to a blowing agent, an emulsion containing a hydrochlorofluorocarbon blowing agent, a perfluorocarbon blowing agent, and surfactant; a foamed plastic containing blowing agents; a process of preparing foamed plastic; and a method of using such foamed plastic, for example, to insulate articles of manufacture, such as appliances with such foams.

Background of the Invention According to "Cellular Materials," Encyclopedia of Polymer Science and Engineering, vol. 3, pages 1-59, (2d ed. John Wiley & Sons, 1985), foamed plastic is defined as a plastic in which the apparent density decreases substantially with the presence of numerous cells disposed through its mass. The gas phase in a foamed plastic is generally distributed in cells. Blowing agents produce gas used to generate cells in foamable polymeric materials, for example, to make foamed insulation. Physical blowing agents form cells by a phase change, for example, a liquid may be volatilized or a gas dissolved in a polymer under high pressure.

Commercially important liquid blowing agents are aliphatic hydrocarbons and their chloro- and fluoro-derivatives. For example, isomers of pentane, hexane, and heptane are used mainly in the production of very low density polystyrene foam. These liquids tend to be inexpensive and low in toxicity. However, they are highly flammable. See Encyclopedia, vol. 2, page 437, supra.

Methylene chloride is the most widely used chlorohydrocarbon blowing agent, it is nonflammable, and since the compound contains chlorine, methylene chloride may be subjected to the same restrictions as c orofluorocarbons and it is, in addition, a toxic, carcinogenic compound. As discussed in Chemical and Engineering News, July 16, 1991, pages 5-6, physical blowing agents, such as low boiling liquids, particularly cMorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), are used throughout the world on a large scale to produce foamed plastics, for example to produce polyurethane and polyisocyanurate foams. However, CFCs are linked to the destruction of the earth's protective ozone layer. See

Encyclopedia, vol 2, page 434, supra. Depletion of the ozone layer is likely to result in increased cases of skin cancer and ecosystem damage. Consequently, the major culprits are to be phased out by the year 2000, under the U.S. Clean Air Act and the Montreal Protocol. However, many environmental groups are calling for faster phaseout. Some European countries, in particular Germany, are requiring that all CFCs be replaced in polyurethane foams and polyisocyanurate foams by 1995.

Production of cellular plastic products, such as cellular polyurethane elastomers and flexible, semi-rigid or rigid polyurethane foams in the presence of catalysts, blowing agents, processing aids or additives is described in numerous patents and publications in the literature.

A survey of methods of producing cellular polyurethane elastomers, polyurethane foams and polyisocyanurate foams, their mechanical properties and their use can be found, for example, High Polymers, Vol. 14, "Polyurethanes," Parts I and π by J.H. Saunders and K.C. Frisch (Interscience Publishers, New York 1962 and 1964), Plastics Handbook. Volume VH, "Polyurethanes," 1st ed. 1966, published by R. Vieweg and A. Hochtlen and 2d ed. 1983, published by G. Oertel (Carl Hanser Verlag, Munich), and "Integral Foams," published by H. Piechota and H. Rohr (Carl Hanser Verlag, Munich, 1975).

A recent patent, U.S. Patent No. 4,972,002 (Volkert), describes producing cellular plastics by the polyisocyanate polyaddition process by

reaction of (a) organic and/or modified organic polyisocyanates with (b) at least one high molecular compound with at least two reactive hydrogen atoms and, optionally, (c) low molecular weight chain extenders and/or cross-linking agents in the presence of (d) blowing agents, (e) catalysts, (f) additives and/or processing aids, wherein the blowing agents are low boiling fluorinated aliphatic and/or cycloaliphatic hydrocarbons that have 3 to 8 carbons. For example, perfluorocyclopentane is used as a preferred blowing agent.

Another recent patent, U.S. Patent No. 4,981,879 (Snider), describes a process for preparing cellular polymers having urethane groups, isocyanurate groups, or both. The cellular polymers are prepared by reacting an organic polyisocyanate with a polyol in the presence of a blowing agent, typically a hydrocarbon, hydrochlorofluorocarbon, or chlorofluorocarbon, a catalyst and a perfluorinated hydrocarbon or a mixture of perfluorinated hydrocarbons, such that the lower boiling perfluorinated hydrocarbons can function as a co-blowing agent.

U.S. Patent No. 4,997,706 (Smits et al.) describes a process for preparing rigid, closed-cell, polymer foams having urethane groups, isocyanurate groups, or both, and uses C ^ polyfluorocarbon compounds containing no chlorine or bromine atoms as a physical blowing agent.

Summary. of the Invention Briefly, in one aspect of the present invention, a blowing agent (or foaming agent) emulsion is provided comprising: as a blowing agent, a mixture comprising, (a) one or more low boiling, hydrochlorofluorocarbon (hereinafter referred to as HCFC) and/or one or more low boiling, hydrofluorocarbon (hereinafter referred to as HFC) and/or one or more low boiling hydrochlorocarbons (hereinafter referred to as HCC) and (b) one or more low boiling, chlorine-free, perfluorinated compound (herein referred to as PFC); a fluorochemical surfactant; and

a continuous organic phase, for example, a polyol. "Perfluorinated" as used in this application means that essentially all hydrogen atoms have been replaced with fluorine atoms.

The blowing agent mixture is useful for producing foamed plastics by producing gas to generate cells (gas pockets) in foamable polymeric materials. The foamed plastics are fine-celled, such that the microcellular nature of the foam yields improved thermal insulation and exhibits decreased thermal conductivity (lambda values). In a recent paper presented to the Polyurethanes World Congress 1991 (September 24-26, 1991), "New Surfactant Technology for HCFC-123 and HCFC-141b Blown Rigid Foam Systems," (pgs 191-196) the author indicated thermal conductivity values decreased as little as 0.28 mW/mK and were considered to be significant improvements.

In another aspect of the present invention, a blowing agent emulsion for making polyurethane foam is provided comprising: (a) at least one high molecular weight compound with at least two reactive hydrogen atoms, such as a polyol, typically used in making foamed polyurethane,

(b) a blowing agent mixture wherein the mixture comprises

(1) one or more low boiling HCFC and/or one or more low boiling HFC and/or one or more low boiling HCC, and

(2) one or more low boiling, chlorine-free perfluorinated compound, and

(c) a fluorochemical surfactant.

Additionally, a silicone surfactant may be added to the blowing agent emulsion. Furthermore, the second component of a polyurethane, that is, an organic and/or modified organic polyisocyanate may be added to the emulsion in the absence of a polymerizing catalyst, which is added just prior to foaming the emulsion. Alternatively, a polymerizing catalyst may be added to the emulsion, and then the emulsion is added to an organic or modified organic polyisocyanate.

Description of the Preferred Embodiment(s) The HCFC, HFC, HCC, and PFC blowing agents used in the mixtures of the present invention are odorless, nontoxic, noncorrosive, and have a low flammability, preferably the blowing agents or mixture of blowing agents are nonflammable. The blowing agents are low boiling, typically boiling in the range of -50° to 175° C, preferably in the range of -50° to 125 °C, and more preferably in the range of -50° to 100°C. The blowing agent mixture is present in the emulsion in an amount effective to produce a rigid closed-cell foamed plastic, and typically is in the range of 1 to 100 parts by weight per 100 parts of total reaction mixture. The blowing agent mixture is a mixture of (1) HCFC and/or HFC and/or HCC, and (2) PFC, wherein the ratio of HCFC and/or HFC to PFC is typically in the range of 0.1 to 99 % by weight of PFC, preferably, in the range of 1 to 75 % by weight of PFC. Often, HCFCs and many HFCs are soluble in the polyurethane precursor. Despite the solubility of HCFCs and many HFCs, it has been found using the blowing agent mixture of this invention, fine-celled foams may be produced with improved thermal conductivity values.

The HCFC blowing agents have the general formula C _a Cl _b H _c F _d wherein a = 1 to 4, b = 1 to 8, c = 1 to 8, d = 1 to 8. Specific examples of suitable HCFC blowing agents useful in practicing the present invention include, among others, trifluorochloropropane, 1,1-dichloro-l-fluoroethane, 2,2-dichloro-l , 1 , 1-trifluoroethane, 1-chloro-l , 1-difluoroethane, 2-chloro- 1,1,1,2-tetrafluoroethane, l,l-dichloro-2,2,3,3,3-pentafluoropropane, 1 ,3-dichloro-l ,2,2,3,3-pentafluoropropane, and monochlorodifluoromethane. The HFC blowing agents have the general formula C _a H _b F _c O _d wherein a = 1 to 8, b = 1 to 17, c = 1 to 17, d = 0 to 4. Specific examples of suitable HFC blowing agents useful in practicing the present invention include, among others, trifluoromethane, pentafluoroethane, 1,1,1 ,2-tetrafluoroethane, 1 , 1 -difluoroethane, 1,1,1 ,4 ,4 ,4-hexafluorobutane, 1,1,2,2-tetrafluorocyclobutane, l-methyl-2,2,3,3,-tetrafluorocyclobutane, l-trifluoromethyl-l,2,2-trifluorocyclobutane, 1 trifluoro-l,2,2-trifluoro- methylcyclobutane, 1 -hydro-pentadecafluoroheptane,

2-hydro-3-oxa-perfluoroheptane, see, for example EP 431542 A (Behme et al.) for the description of additional hydrofluorocarbon ethers.

The HCC blowing agents have the general formula C _a H _b Cl _c wherein a = 1 to 4, b = 1 to 9, and c = 1 or 2. Specific examples of suitable HCC blowing agents useful in practicing the present invention include, among others, chloromethane, dichloromethane, trichloromethane, chloroethane, l,l-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2,2-trichloropropane, 1,1,1-trichloropropane, chlorobutane, 1,2-dichlorobutane, and chlorocyclobutane.

The PFC blowing agents are perfluoroaliphatic or perfluorocycloaliphatic, and have 4 to 12 carbons atoms, preferably 4 to 8 carbon atoms, and may contain heteroatoms, such as divalent oxygen, trivalent nitrogen, or polyvalent sulfur. Specific examples of suitable PFC blowing agents useful in practicing the present invention include, among others, perfluoroalkanes, such as perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane; perfluorocycloalkanes, such as perfluorocyclobutane, perfluorodimethylcyclobutane, perfluoromethylcyclopentane; perfluoroethers, such as perfluoro-2-butyl-tetrahydrofuran, formals, such as perfluoro-3,5-dioxaheptane; perfluoroamines, such as perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, perfluoro-N-methyl pyrrolidine; perfluoroaminoethers, such as perfluoro-N-methyl morpholine; and perfluorinated sulfiir compounds. The mixture can further include other conventional physical blowing agents, such as hydrocarbons, for example, pentane and hexane; or chlorofluorocarbons, for example, fluorotrichloromethane, dichlorodifluoromethane. The additional conventional physical blowing agents when used, may be mixed in an amount in the range of 0.5% to 99.5% by weight of the total amount of the mixture, preferably in the range of 40.0% to 95.0% by weight, and more preferably in the range of 75.0% to 90.0% by weight. Although chlorofluorocarbons may be used in the blowing agent mixture of the present invention, it is preferred that the mixture contains no

more than 5% by weight of chlorofluorocarbons. It is also within the scope of the present invention to add chemical compounds to the emulsion that form gaseous blowing agents by means of a reaction or thermal decomposition, such as, isocyanate groups reacted with water to produce CO ₂ . The blowing agents 5 are thermally stable in the gaseous form, that is, under conditions of use, and do not have deleterious effects on the physical or chemical properties of the foamed plastic.

In another aspect of the present invention, a blowing agent emulsion for making polyurethane foam is provided comprising: 0 (a) at least one high molecular weight compound with at least two reactive hydrogen atoms, such as a polyol, typically used in making foamed polyurethane,

(b) a blowing agent mixture wherein the mixture comprises

(1) one or more low boiling HCFC and/or one or more low boiling HFC and/or one or more low boiling HCC, and

(2) one or more low boiling, chlorine-free perfluorinated compound, and

(c) a fluorochemical surfactant.

Additionally, a silicone surfactant may be added to the blowing agent emulsion. Furthermore, the second component of a polyurethane, that is, an organic and/or modified organic polyisocyanate may be added to the emulsion in the absence of a polymerizing catalyst, which is added just prior to foaming the emulsion. Alternatively, a polymerizing catalyst may be added to the emulsion, and then the emulsion is added to an organic or modified organic polyisocyanate.

The blowing agent emulsion should remain sufficiently stable, ' that is, not phase-separate, long enough to prepare a foamed plastic. However, it is preferred that the emulsion is stable for at least one day at room temperature, and more preferably for at least one week at room temperature. In another aspect of the present invention, a foamed plastic, such as foamed polyurethane, is provided prepared from an emulsion comprising

(a) a foamable polymerizable precursor mixture wherein the polymerizable precursor comprises

(1) at least one high molecular weight compound with at least two reactive hydrogen atoms, and (2) an organic and/or modified organic polyisocyanate,

(b) a blowing agent mixture comprising

(1) one or more low boiling HCFC and/or one or more low boiling HFC and/or one or more low boiling HCC, and

(2) one or more chlorine-free perfluorinated compound, (3) optionally, one or more hydrocarbon compound

(c) a fluorochemical surfactant,

(d) a catalyst,

(e) optionally, a silicone surfactant, and

(f) optionally, one or more other conventional components of foam formulation such as, fillers, flame retardants, or colorants.

A class of fluorochemical surfactants suitable for use in the present invention are fluoroaliphatic oligomers, such as those represented by the following general formulae:

(R ⁴ _f ) _ra Q R ⁴ QΑ _n

(I)

(TI) wherein R ^ is a fluoroaliphatic group, R ⁴ is a water solubilizing divalent organic group free of functional groups containing active hydrogen atoms, such as poly(oxyal__ylene) or alkylene, Q is a linkage through which R ⁴ _f and R ⁴ radicals are covalentiy bonded together, A is a monovalent terminal organic group, A' is A or a valence bond, with the proviso that at least one A' is a valence bond connecting a Q-bonded R ⁴ group to another Q, Q' is a linkage through which A, or A', and R ⁴ are covalentiy bonded together, m is an integer of at least 2, and can be high as 25 or higher, n is an integer of at least 2, and

can be as high as 60 or higher, and z is an integer of 2 or higher, and can be as high as 30 or higher. Specific examples of fluorochemical surfactants are described in U.S. Patent Nos. 3,787,351 and 4,668,406, which descriptions are incorporated herein by reference. Fluoroaliphatic oligomers are commercially available from Minnesota Mining and Manufacturing Company, St. Paul, MN.

A class of silicone surfactants suitable for use in the present invention are those represented by the following formula described in Zaske et al., Journal of Cellular Plastics, Nov-Dec, pg. 38-45 (1981):

R ² — R2

(III) wherein R ¹ and R ² are a lower alkyl group, for example, containing 1 to 8 carbon atoms, M is a divalent linking group, such as alkylene (CH ₂ ) _q where q is 0 to 10, POA is (C _n H2 _n O) _m R ¹ consisting of polyoxyethylene and polyoxypropylene units, for example, in weight ratio of 50:50 to 80:20, n is an integer 1 to 4, m is an integer such that the molecular weight of the POA is in the range of 1400 to 3000. The average molecular weight of the surfactant is generally from about 2000 to 20,000, and preferably between 5000 and 50,000.

Silicone surfactants suitable for use in the present invention are also described, for example, in U.S. Patent Nos. 3,404,105, 3,519,579, 3,518,288, and 3,594,334 and U.K. Patent Nos. 1 114 428, 1 130 824, 1 130 824, and 1 151 960. Silicone surfactants are commercially available for example from Dow Corning, Union Carbide, Goldschmidt AG and Air Products.

Foamable polymerizable reaction mixtures that can be used in the practice of this invention to produce foamed plastic include polymerizable reaction mixtures of styrene or substituted styrene homopolymers or co- polymers with butadiene and acrylonitrile; vinyl chloride homopolymers or co- polymers with other vinyls; ethylene homopolymers and co-polymers with varying percentages of the materials, for example, 2-butene or acrylic acid, propylene, or butadiene; isocyanate-derived polymers, such as, polyurethanes and polyisocyanurates; and phenolic homopolymers (for example, resoles and novolacs). Preferably, the foamed plastics of the present invention are polyurethane foams and polyisocyanurate foams that can be used where conventional polyurethane and polyisocyanurate foams can be used.

The organic polyisocyanate component of the polyurethane precursor reaction mixture that can be cured or polymerized with the perfluorinated blowing agent emulsion of the present invention may be any aliphatic, cycloaliphatic, arylaliphatic, aromatic, or heterocyclic polyisocyanate, or any combination of such polyisocyanates.

As examples of polyisocyanates there may be mentioned any of the polyisocyanates proposed in the literature for use in the production of foams. Of particular importance are aromatic diisocyanates, such as tolylene and diphenylmethane diisocyanate in pure, modified or crude forms. Special mention may be made of MDI variants or modified organic polyisocyanate (diphenylmethane diisocyanate modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine, or isocyanurate residues) and the mixture of diphenyl dϋsocyanate(s) and oligomers thereof known in the art as "crude" or "polymeric" MDI (polymethylene polyphenylene polyisocyanates).

Examples of polyisocyanates that can be used in this invention are as follows: ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6- hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 1,12- dodecane diisocyanate, cyclobutane-l,3-diisocyanate, cyclohexane-1,3- and - 1,4-diisocyanate, and mixtures of these isomers, diisocyanato-3,3,5-trimethyl-5- isocyanatomethyl cyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate,

and mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, and mixtures of these isomers, diphenylmethane-2,4'- and/or -4,4'-diisocyanate, naphthalene- 1,5-diisocyanate, and the reaction products of four equivalents of the aforementioned isocyanate-containing compounds with compounds containing two isocyanate-reactive groups. See U.S. Patent 4,972,002 (Volkert) describing the various polyisocyanates and polyols useful in practicing the present invention, and such description is incorporated herein by reference. According to the present invention, it is also possible, for example, to use triphenyl methane-4,4',4"-triisocyanate, polyphenyl polymethylene polyisocyanates, m- and p-isocyanatophenyl suphonyl isocyanates, perchlorinated aryl polyisocyanates, polyisocyanates containing carbodiimide groups, norbornane diisocyanates, polyisocyanates containing allophanate groups, polyisocyanates containing isocyanurate groups, polyisocyanates containing urethane groups, polyisocyanates containing acrylated urea groups, polyisocyanates containing biuret groups, polyisocyanates produced by telomerization reactions, polyisocyanates containing ester groups, reaction products of the above-mentioned diisocyanates with acetals and polyisocyanates containing polymeric fatty acid esters.

It is within the scope of this invention to use distillation residues having isocyanate groups obtained in the commercial production of isocyanates, optionally in solution in one or more of the above-mentioned polyisocyanates. It is within the scope of this invention to use any mixtures of the above- mentioned polyisocyanates.

Suitable compounds which can be reacted with the polyisocyanates in the practice of this invention are those containing at least 2 isocyanate-reactive hydrogen atoms. Such compounds can be high or low molecular weight compounds, having a weight average molecular weight, generally from about 50 to 50,000. In addition to compounds containing amino groups, thiol groups, or carboxyl groups, are preferably, compounds containing hydroxyl groups, particularly compounds containing from about 2 to 50

hydroxyl groups and above all, compounds having a weight average molecular weight of from about 500 to 25,000, for example, polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polymethacrylates, polyols, and polyester amides, containing at least 2, generally from about 2 to 8, but preferably from about 2 to 4 hydroxyl groups, or even hydroxyl-containing prepolymers of these compounds and a less than equivalent quantity of polyisocyanates, of the type known for the production of polyurethanes.

Representatives of the above-mentioned compounds used in accordance with the present invention are described, for example, in Saunders and Frisch, supra. Kuntstoff-Handbunch, supra. It is, of course, possible to use mixtures of the above-mentioned compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of from about 50 to 50,000 for example, mixtures of polyethers and polyesters.

In some cases, it is particularly advantageous to combine low- melting and high-melting polyhydroxyl containing compounds with one another, as described in German Offenlegungsschrift No. 2,706,297.

Low molecular weight compounds containing at least two isocyanate-reactive hydrogen atoms (molecular weight from about 50 to 400) suitable for use in accordance with the present invention are compounds preferably containing hydroxyl groups and generally containing from about 2 to 8, preferably from about 2 to 4 isocyanate-reactive hydrogen atoms. It is within the scope of this invention to use mixtures of different compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight in the range of from about 50 to 400. Examples of such compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3- butylene glycol, 1,5-pentane diol, 1,6-hexane diol, 1-8-octane diol, neopentyl glycol, 1,4-bis-hydroxymethyl cyclohexane, 2-methyl-l,3-propane diol, dibromobutene diol (U.S. Patent No. 3,723,392), glycerol, trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, higher polyethylene glycols, dipropylene glycol, higher polypropylene glycols,

dibutylene glycol, higher polybutylene glycols, 4,4'-dihydroxyl diphenyl propane and dihydroxy methyl hydroquinone.

Other polyols suitable for the purposes of the present invention are the mixtures of hydroxy aldehydes and hydroxy ketones ("formose") or the polyhydric alcohols obtained therefrom by reduction ("formito ) that are formed in the autocondensation of formaldehyde hydrate in the present of metal compounds as catalysts and compounds capable of enediol formation as co- catalysts (German Offenlegungsschrift Nos. 2,639,084, 2,714,084, 2,714,104, 2,721,186,2,738,154, and 2,738,512). Solutions of polyisocyanate polyaddition products, particularly solutions of polyurethane ureas containing ionic groups and/or solutions of polyhydrazodicarbonamides, in low molecular weight polyhydric alcohols may also be used as the polyol component in accordance with the present invention (German Offenlegungsschrift No. 2,638,759).

Many other compounds containing isocyanate-reactive hydrogen atoms and polyisocyanates are useful in the present invention, and will be apparent to those skilled in the art of polyurethane science and technology, in light of this specification.

The foams of this invention containing urethane groups or urethane and isocyanurate groups can be produced with or without the use of chain extenders and/or crosslinking agents. To modify the mechanical properties, for example, hardness, however, it is known to be advantageous to add chain extenders, crosslinking agents or a mixture thereof. Suitable chain extenders and/or crosslinking agents include diols, and triols with a molecular weight of less than 400. Examples include aliphatic, cycloaliphatic, arylaliphatic diols with 2 to 14 carbon atoms. Specific examples of diols include but are not limited to ethylene glycol, 1,3-propanediol, 1,10-decandiol, o-, m-, and p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, and bis(2-hydroxyethyl)hydroquinone. Some examples of triols include but are not limited to 1,2,4- and 1,3,5- tiihydroxycyclohexane, glycerol, trimethylolpropane and low molecular weight hydroxyl group containing polyalkylene oxides based on ethylene oxide and 1,2- propylene oxide.

In addition to the aforementioned diols and triols, it is also within the scope of this invention to use secondary aromatic diamines, primary aromatic diamines, 3,3'-di- or 3,3',5,5'-tetraal- yl-substi_uted diaminodiphenylme thanes . Examples of secondary aromatic diamines include N,N'-d_alkyl- substituted aromatic diamines, which may optionally be substituted on the aromatic ring by alkyl groups, where there are 1 to 20 carbon atoms in the N- alkyl group, such as N,N'-diethyl, N,N'-di-sec-pentyl, N,N'-di-sec-hexyl, N,N'-di-sec-decyl, N,N'-dicyclohexyl-p- and -m-phenylenediamine, N,N'- dimethyl, NjN'-dicyclohexyM^'-diaminodiphenylmethane, and N,N'-di-sec- butylbenzidine.

The chain extenders or crosslinking agents may be used individually or as mixtures of the same of different types of compounds.

If chain extenders, crosslinking agents or mixtures thereof are used, they are generally used in the amounts of 2 to 60 wt%, based on the weight of the components.

The blowing agent mixture used to practice this invention, may be emulsified in either one of the polyurethane precursor components or in mixtures of the second component and cross-linking agents to form emulsions. In a preferred embodiment, the emulsion containing a blowing agent mixture according to this invention comprises:

(1) 0.1 to 150 parts by weight of a blowing agent mixture, wherein the mixture comprises (a) one or more low boiling HCFC and/or one or more low boiling HFC, (b) one or more low boiling chlorine-free perfluorinated compound, and (c) optionally, one or more conventional physical blowing agent such as, for example, hydrocarbons, or chlorofluorocarbons,

(2) 80 to 300 parts by weight of at least one higher molecular weight compound with at least two reactive hydrogen atoms, or mixtures thereof, (3) 80 to 300 parts by weight of at least one organic and/or modified organic polyisocyanate, and low molecular chain extenders and/or crosslinking agents,

(4) 0.01 to 10.0 parts by weight of at least one fluorochemical surfactant,

(5) 0 to 10 parts by weight of at least one silicone surfactant, and (6) 0 to 50 parts by weight of water.

To produce emulsions containing a blowing agent, polyurethane precursor components or the high molecular weight compound with at least two reactive hydrogens or mixtures thereof and low molecular chain extenders and/or crosslinking agents, and blowing agent are mixed thoroughly together in the presence of the fluorinated surfactant or a mixture thereof with a silicone surfactant at temperatures in the range of 0°C to 70 °C, preferably in the range of 20 °C to 50° C. If the perfluorinated blowing agents are gaseous at room temperature, they are liquified before or during preparation of the emulsion by applying a pressure of up to 5 Megapascal (MPa) to the reaction mixture. The preferred blowing agent mixture to produce a foamed polyisocyanate and foamed polyisocyanurate depends on the density that is desired and the amount of water, optionally to be added to the reaction mixture. In general, amounts of 1 to 50 parts by weight blowing agent mixture, based on 100 parts by weight precursor components or high molecular compound with at least two reactive hydrogens and low molecular chain extenders and/or crosslinking agents yield satisfactory results.

Suitable polymerization catalysts for producing the foamed plastics of this invention include especially compounds that greatly accelerate the reaction of the hydroxyl group-containing compounds and optionally, the chain extenders and/or crosslinking agents with the organic polyisocyanates. Catalysts are present in catalytically effective amounts and suitable catalysts are described in U.S. Patent No. 4,972,002 and EPO 0 364 074 Al, and such descriptions are incorporated herein by reference.

Optionally, other additives and/or processing aids may be incorporated into the reaction mixture to produce the foamed plastics.

Examples include surface active substances, foam stabilizers, cell regulators, fillers, colorants, flame retardants, hydrolysis preventing agents, fungicides,

actericides, and other additives and/or processing aids as known to those skilled in the art can be added to the reaction mixture. These additives and/or processing aids can be added in an amount effective for their intended purpose. Generally, the amount of such additives and/or processing aids is in the range of 0.001 to 99.9 parts by weight, per 100 parts by weight of the reaction mixture.

The soft elastic, semirigid, and rigid foams of this invention can be produced with a density of 0.02 to 0.75 g-cm ^"3 . The foams can be used, for example, in the automobile industry, aircraft industry, shipbuilding industry, furniture and athletic equipment industry and upholstery materials, housing parts, sM shoes, and sM cores. They are especially suitable as insulation materials in the construction and refrigeration industry.

For example, flexible polyurethane foam of this invention can be used in transportation, principally for passenger car seating, as underlay for carpeting, laminate textile products, engineering packaging, filters, sponges, scrubbers, fabric softener carriers, squeegees, and paint applicators. Rigid polyurethane can be used for insulation. Foam laminates of rigid polyurethane foam are useful for residential sheathing (with aluminum skins) and roofing board (with roofing-paper skins). Metal doors and appliance insulation can be insulated by a foam-in-place process. For example, in refrigeration, the polyurethane foam of the present invention can replace fiberglass insulation. Rigid polyurethane of this invention also used as insulation for refrigerated truck trailers, bodies, and rail cars. Packaging can also be foamed-in-place to protect equipment such as pumps or motors. Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All materials are commercially available or known in the literature except where otherwise stated or apparent. The fluorochemical surfactant used in the Examples and Comparative Examples are as described in Example 1 of U.S. Patent No. 3,787,351 and the fluorochemical surfactant designated with a (*) is as described in Example 2 of

U.S. Patent No. 3,787,351. The lambda values were measured on a Hesto Lambda Control A50-A thermal conductivity analyzer with a reproducibility of + _. 0.1. The comparative cell sizes described in the examples are as follows:

Examples

Example 1 This example illustrates the making of a polyurethane-based foam containing a blowing agent mixture of an HCFC and a chlorine-free perfluorinated compound; and a fluorochemical surfactant. Component A contained:

187.5 parts by weight of a mixture of polymeric methylene diphenyldiisocyanate, having an isocyanate equivalent of 132 (commercially available from Dow Chemical as PAPI 135).

Component B contained:

(1) 150 parts by weight of a mixture of polymeric polyetherpolyol having an average molecular weight of 630 prepared by the reaction of sorbitol with propylene oxide (commercially available from ICI America);

(2) 3.0 parts by weight of water;

(3) 4.5 parts by weight of an oligomeric fluorochemical surfactant, as described in Example 1 of U.S. Patent No. 3,787,351; (4) 3.75 parts by weight of N,N-dimethylcyclohexylamine catalyst (commercially available from Aldrich Chemical); (5) 20.1 parts by weight of l,l,l-trifluoro-2,2-dichloroethane (commercially available as HCFC-123); and

(6) 9.5 parts by weight of perfluoropentane (commercially available from 3M Co.). Components A and B were admixed in a container at room temperature and vigorously stirred for 15 seconds at about 2000-3000 rpms with an electric stirrer. The product was a rigid foam having a uniform distribution of fine closed cells. The percentage of closed cells was approximately 90%. The thermal conductivity (lambda factor) was measured in a section of the rigid foam and was 21.7 mW'(nvK) . The same section of foam was measured a total of four (4) times, the four measurements were 21.7, 21.7, 21.6 and 21.6. Two different sections of the rigid foam were measured for thermal conductivity and the results were 21.7 and 21.6.

Examples 2-10 In Examples 2-10, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated in Tables 2 and 3. The results are summarized in Table 6. Examples 2-6 illustrated foamed plastic prepared using various perfluorinated compounds combined with HCFC-123 and a fluorochemical surfactant. Examples 7-10 illustrated foamed plastic prepared using perfluorohexane in combination with an HCC, hydrocarbon, or water, and a fluorosurfactant.

Comparative Examples C1-C9 In Comparative Examples C1-C9, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated in Tables 4 and 5. The results are summarized in Table 6.

Examples 11-17 In Examples 11-17, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated below:

Component Amount (Examples 11-17) Parts by Weight

Polyisocyanate: PAPI 27 109.6

Polyol: Voranol 360 (Dow Chemical) 100 Fluorochemical surfactant 3

Water 1.6

Perfluorohexane 7.2

Catalyst: N,N-dimethylcyclohexylamine 1.5

The HFC component of the blowing agent mixture was as follows:

Amount Example HFC Component Parts by

Weight 11 l-methyl-2,2,3,3-tetrafluorocyclobutane 9.6

1-trifluoromethyl-l ,2,2-trifluoro cyclobutane

12 14.4

13 2-hydro-3-oxa-perfluoroheptane 21.2

14 2-methyl-2-trifluoromethyl perfluoropentane 22.2 15 l-trifluoromethyl-l,2,2-trifluoro-cyclobutane 25.1 •

16 1,1,1,2,2,3,3-heptafluoroheptane 13.5

17 1-hydropentadecafluoroheptane 24.1

The results are summarized in Table 6 and illustrated that the foamed plastics prepared using perfluorohexane, a fluorochemical surfactant and a variety of HFCs had cell sizes ranging from medium to very fine.

Example 18

Component Amount (Example 18) Parts by Weight

Polyisocyanate: PAPI 135 125

Polyol: ICI-C 100 Fluorochemical surfactant 3

Water 2

Perfluorotripropylamine 11.4

1-Hydropentadecafluoroheptane 36.8

Catalyst: N,N-dimethylcyclohexylamine 2

A foamed plastic was prepared according to the procedure of Example 1 using the ingredients as listed in the above table. The resulting rigid, closed-cell foamed plastic had a fine cell size and an initial lambda value of 21.6 mW/mX. This example illustrated a foamed plastic prepared using a perfluorinated compound combined with an HFC and a fluorochemical surfactant.

Examples 19-23 and CIO In Examples 19-23, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated in Table 7. These examples illustrate foamed plastics prepared with various perfluorinated compounds combined with trifluorodichloroethane and a fluorochemical surfactant. The results are summarized in Table 12. In Comparative Example CIO, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated in Table 7. This example illustrates a foamed plastic prepared without a perfluorinated compound, that is, only trifluorodichloroethane and a fluorochemical surfactant were used. The results are summarized in Table 12.

Examples 24 and C11-C12

In Example 24, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated in Table 8. These examples illustrate foamed plastics prepared with a perfluoro N-isopropylmorpholine combined with trifluorodichloroethane and a fluorochemical surfactant. The results are summarized in Table 12.

In Comparative Examples Cll-12, foamed plastics were made according to the procedure of Example 1, using the components and amounts as indicated in Table 8. These examples illustrate foamed plastics prepared (Cll) without a fluorochemical surfactant, that is, only trifluorodichloroethane, perfluoro N-isopropylmorpholine, and a silicone surfactant; and (C12) without a

hydrochlorofluorocarbon, that is, only a perfluorinated compound and a fluorochemical surfactant were used. The results are summarized in Table 12.

Examples 25-28 and C13 In Examples 25-28, foamed plastics were made according to the procedure of Example 1, using the components and amounts as indicated in Table 9. These examples illustrate foamed plastics prepared with a perfluorinated compound combined with 1,1,2,2-tetrafluorocyclobutane, and a fluorochemical surfactant. Examples 25 and 27, also included a silicone surfactant. The results are summarized in Table 12.

In Comparative Example C13, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated in Table 9. This example illustrates a foamed plastic prepared without a fluorochemical surfactant, or a perfluorinated compound, that is, only 1,1,2,2-tetrafluorocyclobutane and a silicone surfactant. The results are summarized in Table 12.

Examples 29-32 and C14-C15 In Examples 29-32, foamed plastics were made according to the procedure of Example 1, using the components and amounts as indicated in Table 10. These examples illustrate foamed plastics prepared using varying amounts of perfluorinated compound with a hydrochlorofluorocarbon, and a fluorochemical surfactant. The results are summarized in Table 12.

In Comparative Examples C14-15, foamed plastics were made according to the procedure of Example 1, using the components and amounts as indicated in Table 10. These examples illustrate foamed plastics prepared (C16) without a hydrochlorofluorocarbon, that is, only a perfluorinated compound, and a fluorochemical surfactant; and (C17) without a perfluorinated compound that is, only a hydrochlorofluorocarbon, and a fluorochemical surfactant were used. The results are summarized in Table 12. These examples illustrated the effect of varying the concentration of perfluorinated compound while keeping the other components constant.

Examples 33-36 and C16 In Example 33-36, foamed plastics were made according to the procedure of Example 1, using the components and amounts as indicated in Table 11. These examples illustrate foamed plastics prepared with varying ratios of fluorochemical surfactant with silicone surfactant. The results are summarized in Table 12.

In Comparative Example 16, a foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated in Table 11. These examples illustrate foamed plastics prepared without a fluorochemical surfactant, that is, only trifluorodichloroethane, perfluoro N-methylmorpholine, and a silicone surfactant. The results are summarized in Table 12.

Examples 37-43 and P1-P7 In the following Examples, a series of fluorinated surfactants corresponding to Formulas I and II were prepared as indicated below. In these examples, foamed plastic was made according to the procedure of Example 1, using the components and amounts as indicated below, varying only the fluorochemical surfactant component, and the amount of silicone surfactant. The foamed plastics were tested as described in Example 1 and the results are summarized in Table 13. The fluorochemical surfactants used in the preparation of the foamed plastics of Examples 37-43 were prepared as described in Examples P1-P7.

Components Amount (.Examples 37-43) Parts by Weight

Polyisocyanate: PAPI-135 270

Polyol: ICI-C 150

Water 3.5

Perfluoro-N-methyl morpholine 4 Trichlorodichloroethane 29

Catalyst: N,N-dimethylcyclohexylamine 3.6

Example PI In a 500 ml 3-necked flask was placed 20 grams of C ₈ F ₁₇ SO ₂ N(C2H5)CH2CH2θ2CCH=CH2, 10 grams of tridecyl acrylate, 50 grams of acrylated Carbowax 750™ (methoxypolyethylene glycol, avg. M.W 750, available from Union Carbide), 20 grams of acrylic acid, 100 grams of ethyl acetate (solvent), 2 grams of n-octyl mercaptan (a chain transfer agent) and 0.75 gram of azobisisobutyronitrile (AIBN) (available as VASO-64™ from DuPont). The flask was fitted with a condenser, thermometer, stirring bar, and a gas inlet. The flask was purged three times with a vacuum aspirator followed by nitrogen. The mixture was warmed to 65°C and allowed to react for 16 hours under nitrogen. The solvent was removed under vacuum yielding a clear yellow liquid. The resulting product was used in the preparation of foamed plastic as the fluorochemical surfactant.

Example P2

A fluorochemical surfactant was prepared as described in Example PI using 15 grams of C ₈ F ₁₇ SO ₂ N(C2H ₅ )CH ₂ CH ₂ O2CCH=CH2, 15 grams of tridecyl acrylate, and 70 grams of acrylated Carbowax 750™ (methoxypolyethylene glycol, avg. M.W 750, available from Union Carbide).

Example P3 A 1000 ml 3-necked flask was fitted with a reflux condenser, a gas inlet, a stirrer and a thermometer, and charged with 57.1 grams of C ₈ F ₁₇ SO ₂ N(C ₂ H ₅ )CH ₂ CH ₂ OH, 39.6 grams of PAPI-135 and 300 grams of dry ethyl acetate. The reaction mixture was heated to 75 °C and 2 drops of dibutyltindilaurate catalyst was added. The temperature was maintained for 5 hours, then cooled to 50 °C under a continuous flow of nitrogen. 200 grams of Jeffamine M-1000 (available from Texaco) was added, and the reaction continued for 2 hours at 50°C. An infrared spectrum of the reaction mixture indicated the isocyanate groups initially present to be completely reacted. The solvent was removed under vacuum. The resulting product was used in the preparation of foamed plastic as the fluorochemical surfactant.

Example P4 A fluorochemical surfactant was prepared as described in Example P3 using C ₈ F ₁₇ SO ₂ N(C2H5)CH2CH(OH)CH ₂ OH, 2,4-toluenediisocy__nate, and Pluronic™ L-44 in a 1/2/3 molar ratio.

Example P5 A fluorochemical surfactant was prepared as described in Example PI using 30 grams of C ₈ F ₁₇ SO ₂ N(C ₂ H ₅ )CH ₂ CH ₂ O ₂ CCH=CH ₂ , 65 grams of acrylated Carbowax 750™ and 5 grams of dimethylaminoethylacrylate. The resulting product was quaternized with diethyl sulfate.

Example P6 A fluorochemical surfactant was prepared as described in Example PI using 30 grams of C ₈ F ₁₇ SO ₂ N(C ₂ H ₅ )CH ₂ CH ₂ O ₂ CCH=CH ₂ , 65 grams of acrylated Carbowax 750™, and 5 grams of dimethylaminoethylacrylate. The resulting product was quaternized with propanesultone.

Example P7 A fluorochemical surfactant was prepared as described in

Example PI using 20 grams of C ₈ F ₁₇ SO ₂ N(C2H5)CH2CH ₂ O ₂ CCH=CH ₂ , 70 grams of acrylated Carbowax 750™, and 10 grams of a silicone macromer methacrylate having the structure (CH ₃ ) ₂ Si-O-

(Si(CH ₃ ) ₂ 0) _n Si(CH ₃ ) ₂ (CH ₂ ) ₃ OCO-C(CH3)=CH ₂ (avg.M.W. 2200, available from Shin-Etsu, Japan).

Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and principles of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth hereinabove.

Table 2 Examples (All amounts are parts by weight)

Component 3 4 5

Polyol: ICI-C

Isocyanate: PAPI 135

Fluorochemical surfactant

Silicone surfactant: Dow Corning DC- 193

Water

Trifluorodichloroethane: HCFC- 123

Perfluoro N-methylmorpholine

Perfluoropentane

Perfluorotripropylamine

Perfluoropolyether: Galden LS-217

Catalyst: N,N-Dimethylcyclohexylamine

Table 3 Examples (All amounts are parts by weight)

Component 7 8 9 10

Polyol: Bayer PU 1732

Isocyanate: PAPI 135

Fluorochemical surfactant

Silicone surfactant: Dow Corning DC-193

Water

Cyclopentane

Isopropylchloride

Perfluorohexane

Catalyst: N,N-Dimethylcyclohexylamine

Table 4 Comparative Examples (AH amounts are parts by weight)

Component Cl C2 C3 C4 CS

Polyol: ICI-C 150 150 150

Polyol: Bayer PU 1732

Isocyanate: PAPI 135

Fluorochemical surfactant

Silicone surfactant: Dow Corning DC- 193

Water

Trifluorodichloroethane: HCFC- 123

Cyclopentane

Perfluorohexane

Perfluoropentane

Catalyst: N,N-Dimethylcyclohexylamine

Table 5 Comparative Examples (All amounts are parts by weight)

Component C6 C7 C8 C9

Polyol: ICI-C

Polyol: Bayer PU 1732

Isocyanate: PAPI 135

Fluorochemical surfactant

Silicone surfactant: Dow Corning DC-193

Water

Trifluorodichloroethane: HCFC- 123 t

Cyclopentane

Perfluorohexane

Catalyst: N,N-Dimethylcyclohexylamine

Example Cell Size

1 fine

2 medium

3 fine

4 fine

5 fine

6 medium

7 fine

8 medium

9 fine

10 medium

11 very fine

12 very fine

13 fine

14 medium

15 very fine

16 medium 17 medium Cl medium 24.8 25.3 C2 very fine 22.4 23.4 C3 medium 22.4 23.2 C4 large 28.2 30.2 C5 medium 23.6 24.0 C6 fine 23.6 23.7 C7 large 25.2 C8 medium 22.3 C9 medium 24.1

The data indicates that the insulation properties of the present invention are improved, both as indicated by the initial lambda and by the aged lambda. Silicone surfactant tends to produce foams with larger cells and reduced thermal insulation.

Table 7 Examples (All amounts are parts by weight)

Component CIO 19 20 21 22 23

Polyol: X-6018

Isocyanate: PAPI 135

Fluorochemical surfactant

Water

Trifluorodichloroethane

Perfluoro[2-butyl tetrahydrofuran]

Perfluorotributyl amine

Perfluoro N-methylmorpholine

Perfluoro N-isopropylmorpholine

Perfluorophenanthrene 4

Catalyst: N,N-Dimethylcyclohexylamine 3

Table 8

Component

Polyol: ICI-C

Isocyanate: PAPI 135

Fluorochemical surfactant

Silicone surfactant: Goldschmidt B-8423

Water

1 , 1 -Dichloro- 1 -fluoroethane

Perfluoropentane

Perfluoro N-methylmorpholine

Catalyst: N,N-Dimethylcyclohexylamine

Table 9 Examples (All amounts are parts by weight)

Component C13 25 26 27 28

Polyol: ICI-C

Isocyanate: PAPI 135

Fluorochemical surfactant

Silicone surfactant: Goldschmidt B-8423

Water

1 , 1 ,2,2-tetrafluorocyclobutane Perfluoro N-methylmorpholine

1 -Hydropentadecoheptane

Perfluorotripropylamine

Perfluoropentane

Catalyst: N,N-Dimethylcyclohexylamine

Table 10 Examples (All amounts are parts by weight)

Component C14 29 30 31 32 C15

Polyol: ICI-C

Isocyanate: PAPI 135

Fluorochemical surfactant

Water

Trifluorodichloroethane: HCFC-141b

Perfluoro N-methylmorpholine

Catalyst: N,N-Dimethylcyclohexylamine

Table 11 Examples (All amounts are parts by weight)

Component 33 34 35 36 C16

Polyol: 1CI-C

Isocyanate: PAPI 135

Fluorochemical surfactant

Silicone surfactant: Goldschmidt B-8423

Water

Trifluorodichloroethane: HCFC- 14 lb

Perfluoro N-methylmorpholine

Catalyst: N , N-Dimethylcyclohexylamine

Table 13

Examples (All amounts are parts by weight)