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||||||||IHIII US005 130345A United States Patent (19) 11) Patent Number: 5,130,345 Li Et Al ||||||||IHIII US005 130345A United States Patent (19) 11) Patent Number: 5,130,345 Li et al. 45) Date of Patent: Jul. 14, 1992 (54) METHOD OF PREPARING FOAM USINGA 4,529,744 7/1985 Wood .................................. 521/1.31 PARTIALLY FLUORINATED ALKANE 4,624,970 1 1/1986 Dwyer et al. ....................... 521/13 HAVING ATERTARY STRUCTURE ASA OTHER PUBLICATIONS BLOWENGAGENT "The Perfluoro-ta-butyl Anion in the Synthesis of 75) Inventors: Chien C. Li, East Aurora, NY; Organofluorine Compounds"-Dyatkin et al. pard Sukornick, Cooper City, "How to Fix the CFC Mix', Chemicalweek/Oct. 18, 1989. 73) Assignee: AlliedSignal Inc. Morris Township, Pina Examiner-John Kight, III Morris County, N.J. Assistant Examiner-John M. Cooney, Jr. (21) Appl. No.: 546,173 Attorney, Agent, or Firm-Melanie L. Brown; Jay P. (22 Filed: Jun. 29, 1990 Friedenson CT 51 int.C.' ........................ co8J 9/14; cosGC08G 18/00,18/06 A method for ABSTRApreparing polyurethane and 52 U.S.C. ...................................... 521/131; 521/98; polyisocyanurate foams which comprises reacting and 521/155; 52 1/163.521/170 foaming a mixture of ingredients which will react to (58) Field of Search ................. 521/131,98, 155, 163, form the polyurethane or polyisocyanurate foams in the 52/170 presence of a blowing agent comprising a partially fluo 5 C rinated alkane having four or five carbon atoms and a (56) References Cited tertiary structure. The method is advantageous because U.S. PATENT DOCUMENTS partially fluorinated alkanes having a tertiary structure 3,183,92 5/1965 Bauer .................................. sy have zero ozone depletion potentials, are nonflamma 4,076,644 2/1978 Burnt et al. .... 521/1.31 ble, and have higher solvency toward polyols. 4,177,332 12/1979 Mitschke et al. .. m 521/13 4,417,00 1 1/1983 Suoboda et al. .................... 521/13 10 Clains, No Drawings 5,130,345 1. 2 earth's protective ozone layer. CFC-11 and CFC-12 are METHOD OF PREPARING FOAM USINGA controlled substances under the Montreal Protocol on PARTIALLY FLUORINATED ALKANE HAVING A Substances that Deplete the Ozone Layer. Mathemati TERTARY STRUCTURE ASA BLOWINGAGENT cal models have substantiated that hydrochlorofluoro carbons are negligible contributors to ozone depletion FIELD OF THE INVENTION and to green-house global warming in comparison to This invention relates to a method of preparing foam the fully halogenated species. using a partially fluorinated alkane having four or five As discussed in "How to Fix the CFC Mix', CHEM carbon atoms and a tertiary structure as the blowing ICAL WEEK 64 (Oct. 18, 1989), alternative blowing agent. O agents for currently used CFC blowing agents include chlorodifluoromethane (known in the art as HCFC-22 CROSS-REFERENCE TO RELATED and which has a boiling point of -40.8 C.), 1,1- APPLICATION dichloro-2,2,2-trifluoroethane (known in the art as Commonly assigned, U.S. Pat. No. 5,059,728 claims HCFC-123 and which has a boiling point of 27.8' C.), partially fluorinated alkanes having a tertiary structure 15 1-chloro-1,2,2,2-tetrafluoroethane (known in the art as and 4 to 9 carbon atoms. HCFC-124 and which has a boiling point of -12 C.), 1,1-dichloro-1-fluoroethane (known in the art as BACKGROUND OF THE INVENTION HCFC-141b and which has a boiling point of 32 C.), The art is continually seeking new fluorocarbons and 1-chloro-1,1-difluoroethane (known in the art as which are useful as blowing agents. Fluorocarbons such 20 HCFC-142b and which has a boiling point of -9.2 C.). as trichlorofluoromethane (known in the art as CFC-11 The use of HCFC-123 as a blowing agent is disadvan and which has a boiling point of 23.7 C.) have been tageous because HCFC-123 has a high molecular used commercially as auxiliary blowing agents for flexi weight; as a result, HCFC-123 is an inefficient blowing ble foams and as primary blowing agents for rigid agent. The use of HCFC-141b or HCFC-142b as a foams. Polyurethane foams are manufactured by react 25 ing and foaming a mixture of ingredients comprising in blowing agent is disadvantageous because the vapors of general an organic isocyanate, such as pure or crude HCFC-141b and HCFC-142b are flammable; as a result, toluene diisocyanate or a polymeric diisocyanate, with the shipping, handling, and use of HCFC-141b and an appropriate amount of polyol or mixture of polyols, HCFC-142b have to be carefully controlled due to the in the presence of a volatile liquid blowing agent, which 30 potential flammability. The use of HCFC-22 and vaporizes during the reaction, causing the polymerizing HCFC-124 as blowing agents is disadvantageous be mixture to foam. The reactivity of these ingredients is cause they have such low boiling points. enhanced through the use of various additives such as U.S. Pat. No. 4,624,970 discloses the use of mixtures amine and/or tin catalysts and surfactant materials of CFC-11 and dichlorotrifluoroethane to blow ure which serve to control and adjust cell size as well as to 35 thane type foams. Such blowing agent mixtures were stabilize the foam structure during its formation. found to permit greater amounts of low cost aromatic Flexible polyurethane foams are generally manufac polyester polyols to be used in rigid foam formulations tured using an excess of diisocyanate which reacts with without serious degradation in foam properties. the water also included as a raw material, producing Although hydrochlorofluorocarbon blowing agents gaseous carbon dioxide, causing foam expansion. Flexi have low ozone depletion potentials compared with the ble foams are widely used as cushioning materials in fully halogenated chlorofluorocarbons, a need exists in items such as furniture, bedding and automobiles. Auxil the art for a method of preparing foam with a blowing iary physical blowing agents such as methylene chlo agent which has a zero ozone depletion potential and is ride and/or CFC-11 are required in addition to the nonflammable. water/diisocyanate blowing mechanism in order to 45 It is an object of this invention to provide a method produce low density, soft grades of flexible polyure for the preparation of polyurethane and polyisocyanu thane foam. rate foams. Rigid polyurethane foams are almost exclusively A further object of the invention is to provide envi expanded using CFC-11 as the blowing agent. Some ronmentally acceptable blowing agents for the produc rigid foam formulations do incorporate small amounts tion of rigid and flexible polyurethane and of water in addition to the CFC-11, but the CFC-11 is the major blowing agent component. Other formula polyisocyanurate foams. tions sometimes use small amounts of the more volatile SUMMARY OF THE INVENTION dichlorodifluoromethane (known in the art as CFC-12 The present invention fills the need in the art by and which has a boiling point of -29.8' C.) in addition 55 providing a method of forming polyurethane and to CFC-11 for producing so-called froth-type foams. polyisocyanurate foams by reacting and foaming a mix Rigid foams are closed-cell foams in which the CFC-11 vapor is trapped in the matrix of cells. These foams offer ture of ingredients which will react to form polyure excellent thernal insulation characteristics, due in part thane and polyisocyanurate foams in the presence of a to the low vapor thermal conductivity of CFC-11, and 60 blowing agent comprising a partially fluorinated alkane are used widely in thermal insulation applications such having four or five carbon atoms and a tertiary struc as roofing systems, building panels, refrigerators and ture. The phrase "tertiary structure' as used herein freezers and the like. means a structure with one carbon having three alkyl Currently, fluorocarbons are of particular interest groups and one hydrogen thereon. This method is ad because they are considered to be stratospherically safe 65 vantageous because partially fluorinated alkanes having substitutes for the presently used fully halogenated this tertiary structure have higher solvency toward chlorofluorocarbons. The latter are suspected of caus polyols in addition to having zero ozone depletion po ing environmental problems in connection with the tentials and being nonflammable. 5,130,345 3 4. Other objects and advantages of the invention will may then be hydrogenated to form 2-fluoromethyl become apparent from the following description. 1, 1,4,4-tetrafluorobutane. Preferably, each R in the Formula above is the same. DETALED DESCRIPTION OF THE When each R is CHF2 and R' is CF3, the compound is PREFERRED EMBODIMENTS 2-difluoromethyl-1,1,1,3,3-pentafluoropropane. When Preferably, in the present method, the blowing agent each R is CHF2 and R' is CH2F, the compound is 2 comprising a partially fluorinated alkane having four or fluoromethyl-1,1,3,3-tetrafluoropropane. When each R five carbon atoms and a tertiary structure is of the For is CHF2 and R' is CH3, the compound is 2-methyl mula: 1,1,3,3-tetrafluoropropane. When each R is CH2F and R" is CHF2, the compound is 2-fluoromethyl-1,1,3-tri fluoropropane. The 2-difluoromethyl-1,1,1,3,3-pentafluoropropane may be prepared by fluorinating commercially available 1,1,1,3,3-pentachloro-2-propanone to form 1,1,1,3,3- 15 pentafluoro-2-propanone which may then be reacted wherein each R is the same or different and is selected with CF2 carbene to form 2-difluoromethyl-1,1,3,3,3- from the group consisting of CF3, CHF2, CH2F, and tetrafluoro-1-propene. The 2-difluoromethyl-1,1,3,3,3- CH3CF2-, and R' is selected from the group consisting tetrafluoro-1-propene may then be hydrogenated to of CF, CHF2, CH2F, CH3, CFCF2-, CF3CHF-, form 2-difluoromethyl-1,1,1,3,3-pentafluoropropane.
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