MXPA00000742A - Flame resistant rigid polyurethane foams blown with hydrofluorocarbons - Google Patents

Abstract

Rigid polyurethane foams having improved flame resistance are disclosed. The foams are prepared from a composition containing (a) an isocyanate, (b) an isocyanate reactive composition containing an aromatic polyester polyol, (c) an organo phosphorus compound and (d) a C1 to C4 hydrofluorocarbon.

Description

FIRE-RESISTANT RIGID POLYURETHANE FOAMS EXPANDED WITH HYDROFLUOROCARBURS.

FIELD OF THE INVENTION The present invention relates to foams with improved fire resistance. In particular, the foams of the invention are rigid with closed cells of polyurethane or of urethane-modified polyisocyanurate.

Background of the invention A crucial factor for the commercial acceptance on a large scale of rigid polyurethane foams in the insulation industry of buildings has been their ability to provide a good balance of properties. Rigid polyurethane foams are known to provide it is outstanding, excellent fireproof performance and superior structural properties, all at a reasonably low density. Such rigid foams are prepared (in general) by reacting the appropriate reactive isocyanate polyisocyanurate compound in the presence of a pneumogenic agent. Pneumogenous chlorofluorocarbon (CFC) agents such as CFC-11 (CCF3F) and CFC-12 (CCI2F2) have been commercially the most important pneumogenic agents mainly due to their good thermal properties and little or no inflammability. The use of such pneumatic agents has been the key reason for the good balance of the properties of rigid polyurethane foams. In recent times, CFCs were related to 1 a. of the concentration of ozone in the Earth's atmosphere and its use has been severely restricted. Hydrochlorine fluorides or carbides, especially HCFC-141b (CCI2FCH3) and HCFC-22 (CHCIF2) have become the temporary solution in many applications, once again due to their good properties. 1 year and low or no flammability. HCFCs also have some potential for ozone depletion and their use is constantly being monitored. The production and use of HCFC-1412b is scheduled to end in 2003 in the United States. Such environmental concerns have led to "the need to develop reaction systems that use agent (s) ne urna t or ge (s) with potential ozone decline celexa and that, at the same time, retains the good balance of properties that made famous rigid polyurethane foams. A class of materials that has been investigated as pneumogenic agents are hydrofluorine or carbides (HFC), for example: 1,1,1,3,3-pentafluoropropane (HFC-45fa); 1, 1,1,3 , 3-penta-fluorobutane (HFC-365mfc), 1,1,1,2-tetrafluoroethane (HiFC-134a), 1,1-di fluoride (HFC-152a) There are numerous patents and literary references on the use of HFCs as pneumogenous agents of rigid polyurethane foam.The use of such mater is disclosed, for example, in US Patent Nos. Nos. 5,496,866 (Bayer); . 461,084 (Bayer); 4,997,706 (Dow); 5,430,071 (BASF); 5,444,101 (ICI). Although HFCs are more environmentally acceptable than CFCs and HCFCs, they are inferior even in terms of their flame retardant properties. Polyurethane foams prepared with pneumogenous agent should have good fireproof properties and at the same time retain good thermal and structural properties, all at densities comparable to those that are possible using the pneumogenic agents CFC and HCFC. Fireproof properties are especially important for rigid polyurethane foams used in the construction industry as they meet strict fire resistance codes. Currently, hydrocarbons and hydrocarbons are the two main classes of materials that are being evaluated in the rigid foam industry as pneumogenous agents with zero ozone depletion potential (ODP). Neither of these two materials has all the attributes of an "ideal" pneumogenic agent. For example, the global warming potentials of HECs are high (lower than those of CFCs but still high in certain ways), but the VOC content is low. Hydrocarbons have an extremely low global warming potential, but are considered VOC. So, there are still unmet needs in terms of developing reaction systems in which the pneumogenic agents have the potential for zero ozone depletion and which produce foams with the good balance of properties that made rigid polyurethane foams famous.

SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to provide rigid foams with closed cells of polyurethane or urethane-modified polyisocyanurate having, even when expanded with the use of one or more materials, strength properties. to fire equivalent or improved ared to foams expanded with CFC or HCFC. It is another object of the present invention to provide rigid foams with closed cells of polyurethane or urethane-modified polyisocyanurate expanded with hydrofluorinated hydrocarbons having good thermal and structural properties together with the improved fire-retardant properties. It has now been unexpectedly discovered that the use of more than 40% polyeste rpo 1 i ol is aromatics of average functionality of less than 3.0 as the reactive isocyanate polifonate 1 osition, together with organophosphorus ounds in the formulation of the foam improves the fireproofing properties of the polyurethane foam prepared in the presence of HFC pneumogenic agents. Such foams expanded with HFC also surprisingly have good thermal insulating and structural properties together with the improved fireproofing properties. The ositions of the present invention advantageously make it possible to obtain the right balance of properties to satisfy both the ercial and environmental demands of our times. It has now been surprisingly discovered that rigid polyurethane foam with a density between 1.2 and 4.2 pounds / cubic feet can be obtained with excellent fireproofing properties and good thermal insulating and structural properties using the formulation: (1) organic polyisocyanates, (2) a pneumogenic agent rising a) C i -C C hydrofluorocarbons which are vaporizable under foam generating conditions such as the naumatógeno agent; and (b) water (3) reactive isocyanate polyfunctional ositions containing more than 40% aromatic polymers 1 or 1 s of average functionality less than 3.0; (4) organophosphorus ounds; and (5) One or more other conventional additives or auxiliaries to the formulations for the purpose of producing rigid urethane-modified polyurethane or polyisocyanurate foams. Such optional additives include but are not limited to: cross-linking agents, foam stabilizing agents or surfactants, catalysts, infrared opacifiers, cell size reducing ounds, viscosity reducers, atibility agents, mold release agents, fillers, pigments and antioxidants, wherein the amount of said organophosphorus ounds used is such that the amount of phosphorus is between 0-01 and 2.5% by weight, based on the total weight of the foam forming the reaction mixture. In summary, the surprising technical advantages of this invention are the discovery of rigid expanded polyurethane foams formulations using pyridogenous (1-ODP zero) pneumatic agents that give foams whose fireproof performance in laboratory tests is equal to or greater than expanded foams with CFC or HCFC; structural performance, such as ressive strength and long-term dimensional stability, is arable or superior to that of expanded foams with CFC or HCFC; and the initial and long-term initial performance is arable to that of expanded foams with CFCs or HCFCs. The foams of the present invention are suitable for use in continuous lamination wood foams for the insulation of ercial roofs and residential walls, as well as in metal recirculation panels, injection foams and fireproof doors. .

DETAILED DESCRIPTION OF THE INVENTION Each of the materials mentioned above used in the foams of the present invention are described hereinafter: (1) Isocyanate: Any organic polyisocyanate can be used to practice the invention. A preferred isocyanate is the polyisocyanate of po 1 i f eni 1 enpo 1 ime t i 1 ene (PMDI). A more preferred isocyanate is PMDI with a diisocyanate content of about 15 to 42% by weight on the basis of 100% by weight of the isocyanate. The amount of isocyanate is usually between about 30 and 75%, more preferably between 40 and 70% and more preferably still between 45 and 4165% by weight based on 100% of the total foam formulation. (2a) HFC Pneumogenic Agent: Any of the C 1 -C 4 or C 1 -C 4 or C 1 -C 4 mixtures which are vaporizable under foam generation conditions can be used alone or in mixtures. • Suitable HFCs include difluoromethane (HFC-32); trifluoromethane (HFC-23); 1,1-difluoroethane (HFC-152a): 1,1,1-trifluoroethane (HFC-143a); 1,1,1,2-tetrafluoroethane (HFC-134a): pentafluoroethane (HFC-125); all isomers of pentafluoropropane (HFC-245fa, ca, eb, EAO-, etc.): all isomers of heptafluoro propane (HFC-236ca, cb, ea, eb); the isomers of pentafluorobutane (HFC-365); 1, 1, 1, 4,, 4-hexaf luorobutane (H FC - 356mf f). Preferred HFCs include 1, 1, 1, 3, 3 -p e n t a f 1 u o r op r op a n o (HFC-245fa); 1, 1, 1.3, 3 -p e n t a f 1 u o r ob u t a n (HFC-365mfc). The most preferred is HFC-245f a. Other pneumogenic agents, especially air, nitrogen, carbon dioxide, alkanes, alkenes, ethers, may be used as the minimum physical pneumogenic agent. Representative alkanes include n-butane, n-pentane, isopentane. Cyclopentane and mixtures thereof.

Representative alkanes include 1-pentene. Representative ethers include dimethyl ether. (2b) Water; The water reacts with the isocyanate under foam generating conditions to release C02. Water could be used with any of the physical pneumogenic agents specified in (2a) The pneumogenic agents are used in an amount sufficient to give the resulting foam the desired density between 1.2 and 4.2 Pounds / cubic feet, preferably between 1.4 and 4.0 Pounds / cubic feet and more preferably between 1 , 6 and 3.8 pounds / cubic feet. Also, the amount of the HFC used is such that the gaseous mixture in the closed cell is the rigid foam, when initially prepared, is between about 99 and 20%, preferably between about 97 and 30%, more preferably between about 95 and 40% molar percentage of HFC. (3) Polyfunctional reactive polyisocyanate compositions: They generally contain more than about 40% aromatic polymers of average functionality of less than 3, the remainder being other types of the reactive isocyanate compound.

Polymers 1 to 1 are suitable aromatics include those prepared by the reaction of a carboxylic acid and / or a derivative thereof or an anhydride with a polyhydric alcohol, where at least one of those reactants be aromatic. The hydrophobic acids can be any of the known aliphatic, cycloaliphatic, aromatic and / or heterocyclic acids and can be substituted (for example, with halogen atoms). ) and / or not saturated. Examples of suitable polyhydric acids and anhydrides include oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid anhydride, pi-ionic dianhydride, phthalic anhydride, acid anhydride , the anhydride of acid, the anhydride of endometallic acid, the anhydride of glutaric acid, the maleic acid, the anhydride of maleic acid, the fumaric acid and the dimeric and trimeric fatty acids, such as those of oleic acid which may be mixed with monomeric fatty acids. The simple esters of the po 1 and ca-box acids can also be used, such as terephthalic acid dimethyl ester, terephthalic acid big glycol and extracts thereof. Examples of suitable aromatic polyhydric acids are: phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid. Suitable aromatic acid derivatives are: dimethyl to diethyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid. the examples of aromatic anhydrides. Suitable for phthalic anhydride, the anhydride, and the pyromellilic anhydride. Although the po 1 iesterpo 1 io 1 es can be prepared from substantially pure reactive materials such as those enumerated above, more complex ingredients, such as waste from side streams, waste or debris from the manufacture of acid, can be advantageously used. phthalic, phthalic anhydride, terephthalic acid, dimethyl terephthalate, terephthalate, polyethylene terephthalate and the like.The polyhydric alcohols suitable for the preparation of the polymers can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic. The polyhydric alcohols may optionally include substituents which are inert in the reaction for example 'substituents' of chlorine and bromine, and / or may be unsaturated. Amino acids can also be used as suitable alcohols, such as monoethanolamine, diethanolamine or the like. Examples of suitable polyhydric alcohols include ethylene glycol, propylene glycol, po 1 i ox i 1 i i 1 in g 1 i co 1 (such as diethylene glycol, polyethylene glycol, dip r op i 1 eng 1 ico 1 and polypropylene glycol), glycerol and trimethylolpropane. Examples of suitable aromatic polyhydric alcohols are 1, 4-b e n c endi or 1, hydroquinone di- (2-hydroxy t i 1) e t er bi (hydr ox ime t i 1) t er e f t a 1 a and resorcinoi. The polymer 1 used in the present invention is aromatic and has an average functionality of less than 3. Thus, the polymeric acid (and / or a derivative thereof or a anhydride component) or the polyhydric alcohol or both are aromatic and the average functionality of the reaction product is less than 3.0.

There are a number of such polyols available in the market. STEPANPOL © PS-2352, PS-3152 are such polyols manufactured by the Stepan Company. TERATE® 2541.254, 403, 203 are some of those polyols, manufactured by Hoe chs t -Ce 1 ane Corporation, TEROL® 235, 235N, 250 are some such polyols manufactured by Oxid, Inc. Polyfunctional compositions of the reactive isocyanate can contain up to 60% of other suitable reactive isocyanate compounds. Examples of such compositions include polyethylene glycol, polyethylene and aliphatics and mixtures thereof, which have equivalent weights of between about 40 and 4000, preferably between about 50 and 3000 and an average density. of hydroxyl of about 2 and 8 and preferably between about 2 and 6. Additional examples of suitable reactive isocyanate polyfunctional compositions include polyether-terminated active polyether polymers, polyamides, po 1 -ester amides, polycarbonates, polyacetate, polyolefins and po 1 isi loxane s. Useful additional reactive isocyanate materials include primary and secondary diamines (Unilink 4200), enamines, cyclic ureas, cyclic carbonate, and polyhydric acid. Some of these compounds react with isocyanate to develop carbon dioxide and contribute to the expansion of the foam. (4) Compounds or o rganized f o s: Various organic compounds containing phosphorus can be used. Suitable compounds include phosphates, phosphites, phosphonates, polyphosphates, polyphosphites, phosphonates, ammonium polyphosphate, etc. The phosphate compounds are of the following formula; I I R1-0-P-0-R2 OR where R1 to R3 means alkyl groups, substituted halogen alkyl, aryl, substituted halogen aryl and cycloalkyl. Preferred phosphates are those in which R 1 to R are C 1 -C 12 alkyl groups, substituted C 1 -C 12 halogen alkyl, phenyl, cresyl, substituted halogen phenyl and C 5 -C 10 cycloalkyl. The most preferred phosphates are those in those which R 1 to R 3 mean C 1 -C 4 alkyl groups substituted halogen C C ~C and phenyl. "Some especially suitable phosphates are triethyl phosphate, (Eastman's TEP), tri bu ti 1 phosphate, tri (2-c 1 or op r op i 1) - phosphate (Antiblaze 80 from Albright &Wilson) and c 1 or op r opi 1 - (bi (br op op op i 1) - phosphate (Firemaster FM836 from Great Lakes.) Suitable phosphite compounds are of the following formula; F ^ -O-P-O-R2 I OR3 where R a R means H, substituted alkyl, halogen alkyl, aryl, substituted aryl * halogen and cycloalkyl groups. Preferred phosphites are those in which R a R means C C 2 alkyl groups, substituted C 1 -C 12 halogen alkyl, cresyl phenyl, substituted halogen phenyl and C 5 -C 10 cycloalkyl. The most preferred phosphites are those in which R.sub.1 to R.sub.3 is C? -C8 alkyl, substituted C? ~8 halogen alkyl and phenyl. The most preferred phosphite compounds are those in which R 1 to R 3 means C 1 -C 4 alkyl groups, substituted C 1 -C 4 halogen alkyl and phenyl. Some especially suitable phosphites with triethylphosphite (Albrite TEP from Albright &; ilson), t r i (2 -al or r o and i 1) f o s fi t and triphenyl phosphite (Albrite PP).

Suitable phosphonate compounds are of the following formula: I I R1-OP-0-R2 0RJ where Ri to R3 means alkyl groups, substituted halogen alkyl, aryl, substituted halogen aryl and cycloalkyl. Preferred phosphonates are those in which Ri to R means C? -C? 2 alkyl groups, Ci-Cn substituted halogen alkyl, phenyl, cresyl, substituted halogen phenyl and C5-C10 cycloalkyl. The most preferred phosphonates are those in which Ri to R3 means C?-C8 alkyl groups, substituted C 1 -C 8 halogen alkyl and phenyl. The most preferred phosphonate compounds are those in which R ± a R 3 is C 1 -C 4 alkyl, substituted C 1 -C 4 halogen alkyl and phenyl. Some particularly suitable phosphonates are di eti 1 et il phosphonate, (Amgard V 490 from Albright &Wilson), tell me the useable fungi (Amgard DMMP), bi (2-chloroethyl) and 2-cl or oe ti 1 phosphona Illustrative examples of the polyphosphate compounds are Amgard V-6, a chlorinated diphosphate ester of A & W. Illustrative examples of ammonium polyphosphate [(NH4P03) n ?; n = approximately 1000) is Hostaflam AP 422 from Hoechst AG. The organophosphorus compounds used in the invention may have one or more reactive isocyanate hydrogens comprising a hydroxyl group, amino group, thio group, or mixture thereof. Suitable compounds include monomeric or oligogenic phosphates, phosphites and phosphonates. Suitable compounds of reactive isocyanate phosphates are those prepared by: (1) the reaction of polyalkylene oxides with (a) phosphoric acids (b) partial esters of phosphoric acids; (2) the reaction of aliphatic alcohols with (a) phosphoric acids (b) partial esters of phosphoric acids, (3) by means of t i n i f i ca t ion of the products of (1) and (2). Preferred compounds include t r i bu t ox i e t i 1 f or s (Phosflex T-BEP from Akzo); oligomeric organophosphate diol Hostatian- TP OP 550 of Hoechst AG); esters of ethoxylated phosphate (Unithox X-5126 from Petrolite); and mono and diesters of phosphoric acid and alcohols (Unithox X-1070 from Petrolite).

Suitable compounds of reactive isocyanate phosphites are those prepared by: (1) the reaction of polyalkylene oxides with (a) phosphorous acids (b) partial esters of phosphorous acids; (2) the reaction of aliphatic alcohols with (a) phosphorous acids (b) partial esters of phosphorous acids; (3) by transesterification of the products of (1) and (2). Suitable compounds of reactive isocyanate phosphonates are those prepared by: (1) the reaction of polyalkylene oxides with phosphonic acids; (2) the reaction of f o s f i t opol i o 1 e s with alkylhaiurans; (3) by the condensation of di a 1 qui 1 f or s t on s, die anolamine and formaldehyde: (4) by transesterification of products (1), (2) and (3); and (5) by the reaction of di a 1 qui 1 to the quil f os f ona t o with phosphorous pentaoxide and alkylene oxide. Preferred compounds include diethyl-N-bi (2-hydroxyethyl) -aminoethyl-phosphonate (Fyrol 6 from Akzo); hydroxyl containing oligomeric phosphonate (Fyrol 51 from Akzo). The amount of said organeous compound used is such that the amount of phosphorus is between about 0.01 and 2.5% by weight, based on the total weight of the foam that forms the reaction mixture. The preferred amount of phosphorus is between about 0.025% and 1.5% and more preferred between about 0.05 and 1.0% by weight, based on the total weight of the foam that forms the reaction of the mixture. (5) Additives: The resin side may also contain various auxiliary agents and additives as necessary for a particular purpose. Auxiliary agents and additives include cross-linking agents, such as triethanolamine and glycerol; foam stabilizing agents or surfactants, such as copolymers of s i 1 ox ano -ox i a 1 qu i 1 e not; oxyethylene-oxyalkylene copolymer; catalysts, such as tertiary amines (for example, dimethylcyclohexylamine, pentamethyl diethylenetriamine, 2, 6-tri (dimethylaminomethyl) phenol-triethylenediamine, organometallic compounds (for example, potassium octoate, potassium acetate, dirate of styrene 1 this year), quaternary ammonium salts (e.g., 2 -hi dr op r op i 11 r ime ti 1 ammonia format) and n-substituted triazines (N, N ', N "- dime ti 1 ami nop r op i 1 - hexahydrotriazine); viscosity reducers such as propylene carbonate, 1-methyl-pyrrolidinone; infrared opacifiers such as black carbon, titanium dioxide, metal flakes; cell-size reducing compounds, such as inert and insoluble fluorinated compounds, composite compounds, reinforcing agents, such as glass fibers, ground foam debris; mold releasing agents, such as zinc stearate; antioxidants, such as butylated hydroxytoluene; and pigments such as azo / diazo dyes, phthalocyamines. The amount of such additives is generally between about 0.1-20%, preferably between about 0.3-15% and more preferably between about 0.5-10% by weight based on 100% of the total foam formulation. In order to carry out the manufacturing process of rigid foams in accordance with this invention, the known techniques of prepolymers or semi-polymers of single application can be used together with the mixing methods including impact mixing. The rigid foam can be produced in the form of sheets, moldings, cavity fill material, sprayed foam, bubble foam or laminates, with other materials such as paper, metal, plastic or wooden plates. The various aspects of this invention are illustrated, without being limited thereto, by the following examples. Unless otherwise indicated, all temperatures are expressed in degrees Celsius and all components of the formulation, in parts by weight.

In the examples, reference should be made to the following materials: STEPANDOL®PS-2352: A po 1 ieste rp or 1 io 1 aromatic of 240 mg KOH / g of hydroxyl value, average functionality of approximately 2 and viscosity of 3,000 cPs @ 25 ° C from the company Stepan. The aromatic polyester polyol content of this polyol is greater than 80% by weight. VORANOL® 240-800: A p or 1 i s t p r 1 1 or 1 whose hydroxyl value is 800 mg KOH / g, average functionality of 3 and viscosity of 3,000 centistokes @ 100 ° F from Dow Chemical Company. ALKAPOL® A-630: A p or 1 i e t p r 1 1 or 1 based on aliphatic amine of 630 mg KOH / g hydroxyl value, average functionality of 3 and viscosity of 450 cPs @ 25 ° C from Dow Chemical Company. RUBINOL® R159: A polymeric 1-amine based on 500 mg of KOH / mg of hydroxyl value,. { Average functionality of 3.2 and viscosity of 18000 cPs @ 25 ° C from ICI Americas Inc. RUBINOL R124: 1 pore rp or 1 io 1 based on amine of 395 mg of KOH / mg of hydroxyl value, average functionality of 3.9 and viscosity of 18000 cPs @ 25 ° C from ICI Americas Inc. TCCP: Tri (be ta-chloropropy 1) fos fa to (% P 9.5) available from Akzo Nobel Chemical Inc. TEP: Trie tilf os f ato (% P = 17) acquirable to Eastman Cha ical Corporation. PELRON® 9540A: Potassium octoate in diethylene glycol available from Pelron Corp. PELRON® 9650A: Diethylene glycol potassium acetate available from Pelron Corp. POLYCAT® 5: P in t ame t i 1 di e t i 11 e n t r i am i nailable to Air Products. DABCO® 33LV: T r i e t i 1 endi ami na in dip r op i 1 engl i col acquirable to Air Products. DABCO® 125: Organotin polyurethane catalyst available from Air Products.

TEGOS ® B84PI: Acquired silicone surfactant. to Goldschmidt Corporation. TEGOS ® B8404: Silicone surfactant available from Goldschmidt Corporation. LK-221®: Non-silicone surfactant available from Air Products. HCFC-141b: Pneumogenic fluorine diuretic agent available from Elf-Atochem North Ame rica. HFC-245fa (pressurized): Acquired from Allied Signal Chemicals RUBINATE® 1850: highly functional polymeric MDI available from INI Americas.

Example 1 A quantity of polyurethane foam was prepared using the formulations shown in Table 1. All the foams were made using the following general procedure. The polyol mixture was made by mixing all the ingredients listed in "Polyol side", except HFC-245fa, using a high speed mixer at room temperature. The polyol mixture was added to the "Polyol side" tank of a high pressure impact mixing machine Edge-Sweets. To the "Polyol side" tank was added an appropriate amount of HFC-245fa, based on the composition shown in Table 2, and mixed vigorously using an air mixture coupled to the tank. Isocyanate was added to the "Iso side" tank, coupled to the dispensing machine, and the parameters of the machine were set as follows: Parameter * of the Espumae machine No. 1, 2, and 3 £ puma No. 4 Temperature Tempura Side by side. " • F 70 ßo TßittpAralura -1 * 1"Polyol ledo *." F 60 70 maillion, stick, 2,000 2,000 Indo iao pump ", RPM? 0 70 QombH rlül" Polio side! ", RPM Adjusted for give the polyol of the Adjusted Side to give the side Pollol or the proportion of motilled weight in iso the proportion of breastplate shown in Table 1 Table 1 Download speed, Qint / iag 200 200 1 The foam generation ingredients were applied from the dispensing machine in a 5 liter vessel and the reactivity and density were measured in this free expansion foam. The density of the foam core was measured following the ASTM D 1622. Flame retardant performance was tested on the foam samples taken from the 4"x 15" x 15"blocks according to the Butler Chimney Test, ASTM D 3014. This test measures the weight retention and flame extinction time of the foam sample.The flame retardant performance was also measured by the Hot Pipe Test in the core samples taken from 7"x foams. 7"x 15" made by unloading the ingredients in a cardboard box. The hot place test is described in "Flammabi 1 ity Study of Hydrocarbon-Blown Isocyanurate Foams" (Study of flammability of isocyanurate foams expanded with hydrocarbons) Proceedings of the 35th Annual Meeting of the Ec c Polyurethane SPI, Page 561 (1994). The maximum smoke density under flame generation conditions of the NBS Smoke Test (NBS Smoke Test) was measured in accordance with ASTM E662. Structural properties were measured in the core samples taken from 7"x 7" x 15"foams made by pouring the foaming ingredients into a cardboard box.The low temperature dimensional stability was measured after 7 days of exposure to -25 ° C following the "Dimvac Method" described in "Techniques to Assess The Various Factors Affecting the Long Term Dimensional Stability of Rigid Poiyurethane Foam" (Techniques to evaluate the various factors that affect the long-term dimensional stability of rigid foam of Polyurethane), Proceedings of the Polyurethane Meeting 1995, Page 11 (1995) The compressive force was measured in a parallel direction and perpendicular to the direction of expansion of the foam, following ASTM 1621, Procedure A. The thermal properties of the Foams were measured according to the procedures set forth in ASTM C 518 on the core foam taken from the 4"x 15" x 15"foam blocks. the foams Nros. 1 and 2 represent the foams prepared using the formulations according to the invention. Foams Nros. 3 and 4 represent the comparative foams. Foams Nros. 1, 2 and 3 were expanded using an ODP pneumatic agent of HFC-245fa. The formulation used to make the foam No. 4 represents the current state of the art and is expanded using a pneumogenic agent that declines the ozone concentration, HCFC-14 Ib. In the Butler chimney test, the higher weight retention, the lower flame height and the shorter extinguishing time indicate higher fire resistance. As can be seen in Table 1, fire resistance performances (as per the Butler chimney test) of foam No. 1 and No. 2 foam are much better than foam no. 3 and equivalent or better than foam no. 4. In the hot place test, greater weight retention and superior thickness retention imply superior fire resistance. The properties of fire resistance (as measured by the hot spot test) of foam No. 1 and No. 2 foam are much better than those of No. 3 foam and equivalent to or better than those of No. 1 foam. 4. In the NBS smoke test, the lower the maximum smoke density, the better the fire resistance of the foam. Again, Foam No. 1 and Foam No. 2 produced much better fire resistance results than those of No. 3 foam and No. 4 foam. Thus, in all endurance tests the laboratory fire, foams No. 1 and 2 gave much better results than foam No. 3 and results equivalent to or better than those of foam No. 4. Although foams No. 1, 2 and 3 are expanded using a. HFC and employ) 50% aromatic polyester polyol, only foams Nos. 1 and 2 contain the f or f or f or f or f o ried compound or composition disclosed in this invention. Foam No. 4 representing the present state of the art also does not use the orga nized compound and is expanded using a pneumatic HCFC, HCFC-141b. In a dimensional stability test, the closer to zero is the% linear change, the better the dimensional performance of the foam. Foam No. 1 and Foam No. 2 produced better dimensional stability compared to No. 3 foam and No. 4 foam. In compressive strength measurements, the greater the amount, the better the structural performance of the foam.

Also in this cave, the foams No. 1 and No. 2 had better performance than the foams No. 3 and 4. In the evaluations of the thermal properties, the lower the k factor, the better performance the foam has in terms of insulation In Table 1, we see that the foams No. 1, 2 and 3 have the same initial factor k, although slightly higher than that of the foam No. 4. The aged k factor of the foams No. 1 and No. 2 of the invention is inferior and therefore better than the current state of art, foam No. 4 EXAMPLE 2 For comparison, a rigid polyurethane foam No. 5 was prepared using the formulation shown in Table 2. The foam No. 5 was made using an organic polyisocyanate, a hydrocarbon carbide (HFC-245fa) as the agent pneumogen, po 1 Ite rpo 1 io 1 is like the reactive isocyanate polifunctional composition, a phosphorus organic compound and other additives. Foam No. 5 did not use an aromatic polymer as a reactive isocyanate composition and is therefore a comparative foam. As can be seen in Table 2, the fire resistance performance (as measured by the Buller chimney test, the hot place test and the HBS smoke test) of the No. 5 foam was much worse than that of the the foams No. 1 and 2. The properties of fire resistance of foam No. 5 were similar to those of foam no. 3 and deficient. Although the foams Nos. 1, 2 and 5 were expanded using an HFC and contained the forged metal, only foams Nos. 1 and 2 used aromatic polyester polyols in the manner disclosed in this invention. This suggested that both the oregano and the aromatic polyester were required to obtain good fire resistance when using an HFC pneumogenic agent.

The structural properties of 0.a Foam No. 5 were similar to those of foams No. 1 and No. 4 and were acceptable. The initial as well as aged factor k of the foam No. 5 was not as good as that of the foams Nos. 1 and 2 of the invention. The aged k-factor of the foam No. 5 is similar to the current state of the art, the foam No. 4. The results clearly showed that by expanding them with an environmentally acceptable HFC pneumogenous agent, the foams (Nros. 1 and 2) made using the formulations of the invention had a fire resistance performance superior and equivalent to or superior to the structural performance yte rmoa is 1 aci on, compared to the foams (No. 3 and 5) made using foreign formulations to this invention. The formulations of the present invention made it possible to produce foams whose flame retardancy, structural and heat insulating performance were equivalent or better than those made using the current HFCF pneumatic agent. The present invention has been described above in considerable detail. It will be understood that modifications that a skilled artisan can routinely make should be considered within the scope of the present invention.

Table 2

Claims (30)

1. A foam-forming composition, characterized in that it comprises: a) an organic isocyanate; b) a reactive isocyanate composition containing at least 40% by weight based on the total weight of the reactive composition of an aromatic polyether polyol having an average functionality of less than 3; c) a hydrofluorocarbon pneumatic agent C i to C; and d) an organic phosphorus compound.

2. The foam-forming composition of clause 1, characterized in that the organic isocyanate is polyphenylene polymethylene polyisocyanate.

3. The foam-forming composition of clause 2, characterized in that the isocyanate contains di-difcyanate di-difcyanate in an amount equal to between 15% and 42% by weight based on the total weight of the isocyanate.

4. The foam-forming composition of clause 1, characterized in that the amount of isocyanate is equal to between 30% and 75% by weight based on the total weight of the foam-forming composition.

5. The foam-forming composition of clause 1, characterized in that the aromatic polymer of the reactive isocyanate composition is prepared by the reaction of an aromatic carboxylic acid and a polyhydric alcohol.

6 The foam-forming composition of clause 1, characterized in that the reactive isocyanate composition, also contains a compound selected from the group consisting of po 1 tete rpol i ol es, pol ieste rpo 1 i ol is aromatic, po 1 itio e beings Finished in hydrogen, polyamides, polystyrene, polycarbonates. polyalefins and polysiloxanes.

7. The foam-forming composition of clause 1, characterized in that the pneumogenic agent of hi dr o f luo r o c a rbur o C? -C4 is selected from the group consisting of di f ior one ome ta, trif luoromethane; 1, 1-fluorine oe grade; 1,1, 1-trifluoroethane; 1,1, 1,2-tetrafluoroethane; pentafluoroethane; any isomer of pentafluoropropane; any isomer of heptaf-luoro propane; .any isomer of pentafluorobutane; 1,1,1,4,4,4,4-hexafluorobutanol, 1, 1, 1, 3, 3 -pen t a f 1 or op opene and 1, 1, 1, 3, 3-pentafluorobutane.

8. The foam-forming composition of clause 7, characterized in that the pneumogenic agent of hydr or luor ocarbur or is 1,1, 1,3,3-p e n t a f l_u oropropane.

9. The foam-forming composition of clause 1, characterized in that the composition contains water as an additional pneumogenic agent.

10. The foam-forming composition of clause 1, characterized in that the organophosphorus compound is selected from the group consisting of phosphates, phosphites, phosphonates, polyfines, polyphosphites, phonates, ammonium polyphosphate.

11. The foam-forming composition of clause 1, characterized in that the orga nized organic compound is a phosphate compound having the following formula 27a **** where R, R 'and R are independently selected from alkyl groups, substituted halogen alkyl, aryl, substituted halogen aryl and cycloalkyl.

12. The foam-forming composition of clause 11, characterized in that R, R and R are independently selected from C ± -Cu alkyl groups, C hal-C? Substituted halogen alkyl, phenyl, cresyl, substituted halogen phenyl and C 5 cycloalkyl- C io -

13. The foam-forming composition of clause 11, characterized in that R1, R2 and R3 are Ci-Cß alkyl groups, substituted halogen alkyl C i-C g.

14. The foam-forming composition of clause 11, characterized in that R1, R2 and R3 are C?-C4 alkyl groups, substituted halogen alkyl C - C 4.

15. The foam-forming composition of clause 11, characterized in that R1, R2 and R3 are phenyl.

16. The foam-forming composition of clause 1, characterized in that the organophosphate compound is a phosphite compound having the following formula: 27 * * * * wherein R1, R2 and R3 are independently selected from H-, substituted alkyl, halogen alkyl groups, aryl, substituted halogen aryl and cycloalkyl.

17. The foam-forming composition of clause 16, characted in that R1, R2 and R3 are independently selected from Cj.-Cp alkyl groups, substituted C? -C? 2 halogen alkyl, cresyl phenyl, substituted halogen phenyl and C5-C cycloalkyl. or -

18. The foam-forming composition of clause 16, characted in that R1, R2 and R3 are independently selected from Cx-Cd alkyl groups, substituted halogen alkyl C? -C8

19. The foam-forming composition of clause 16, characted in that R1, R2 and R3 are independently selected from Ci-C4 alkyl groups, substituted C alquilo-C halogen alkyl.

20. The foam-forming composition of clause 1 to 16, characted in that R1, R2 and R3 are phenyl.

21. The foam-forming composition of clause 1, characted in that the organe-containing compound is a phosphonate compound having the following formula: 28a ***** wherein R1, R2 and R3 are independently selected from alkyl groups, substituted halogen alkyl, aryl, substituted halogen aryl and cycloalkyl.

22. The foam-forming composition of clause 21, characted in that R1, R2 and R3 are independently selected from C 1 -C 12 alkyl groups, C 1 -C 12 substituted halogen alkyl, phenyl, cresyl, substituted halogen phenyl and C 5 -C 12 cycloalkyl. .

23. The foam-forming composition of clause 21, characted in that R1, R2 and R3 are independently selected from C?-Cg alkyl groups, substituted C alquilo-Cg halogen alkyl.

24. The foam-forming composition of clause 21, characted in that R1, R2 and R3 are independently selected from C alquilo ~C alkyl groups, substituted C alquilo-C4 halogen alkyl.

25. The foam-forming composition of clause 21, characted in that R1, R2 and R3 are phenyl.

26. The foam-forming composition of clause 1, characted in that the organophosphorus compound contains at least one reactive hydrogen isocyanate group selected from hydroxyl, amino and thio.

27. The foam-forming composition of clause 1, characted in that the. The amount of organophosphorus compound used is such that the amount of phosphorus in the composition is equal to between about 0.01 and 2.5% by weight, based on the total weight of the composition.

28. The foam-forming composition of clause 27, characted in that the amount of organophosphorus compound used is such that the amount of phosphorus in the composition is between about 0.025 and 1.5% by weight, based on the total weight of the composition. composition.

29. The foam-forming composition of clause 27, characted in that the amount of organic compound used is such that the amount of phosphorus in the composition is between about 0.05 and 1.0% by weight, based on the weight total of the composition.

30. A rigid polyurethane foam, characted in that it has a density between 1.2 and 4.2 pounds / cubic feet and is prepared from the composition of clause 1.