United States Patent (19) 11 Patent Number: 4,666,967 Richardson, Deceased Et Al
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United States Patent (19) 11 Patent Number: 4,666,967 Richardson, deceased et al. 45 Date of Patent: May 19, 1987 54 FLAME RETARDANTS FOR 10947.17 12/1967 United Kingdom. POLYURETHANES Primary Examiner-Veronica P. Hoke 75 Inventors: Norman Richardson, deceased, late of Attorney, Agent, or Firm-Luther A. R. Hall Middleton, England, by Joyce (57) ABSTRACT Richardson, legal heir; Brian G. The invention provides polyurethanes and Clubley, Wilmslow; Richard J. polyisocyanurate having incorporated therein a flame Dellar, Hale, both of England retardant amount of a salt formed by reaction between 73) Assignee: Ciba-Geigy Corporation, Ardsley, dimethyl methyl phosphonate, monomethyl methyl N.Y. phosphonate or methyl phosphonic acid, and a com (21) Appl. No.: 821,178 pound of the general formula (I). 22 Filed: Jan. 22, 1986 X Rl I (30) Foreign Application Priority Data R-C-N N Jan. 23, 1985 GB United Kingdom ................. 8501704 R2 51] Int. Cl4........................... CO7F 9/40; C07F 9/38; C08K 5/53; C08H 9/18 in which X is O, S or NH, R1 is H, alkyl with 1 to 4 52) U.S. C. ............................... 524/130; 260/501.14; carbon atoms, alkenyl of up to 4 carbon atoms, CN, 260/501.17; 260/501.19; 260/502.52; 521/85; CONH2 or NH2, R2 is H, alkyl with 1 to 4 carbon atoms 521/107; 524/131; 524/132; 528/71; 528/72; or alkenyl of up to 4 carbon atoms or R1 and R2 together 544/82; 544/85; 544/87; 544/106; 54.6/164; with the nitrogen atom to which they are attached form 546/189: 546/243; 546/244; 546/245; 558/131; a heterocyclic ring of up to 6 carbon atoms which may 558/154 optionally contain another hetero atom and R is H, an 58) Field of Search ...................... 260/501.14, 501.17, alkyl group with 1 to 8 carbon atoms, an aryl group 260/501.19,502.5 E; 546/243, 244, 245, 189, with 6 to 10 carbon atoms, a cycloalkyl group with 5 to 164; 524/130, 131, 132; 521/85, 107; 528/71, 12 carbon atoms or a heterocyclic group with up to 9 72; 544/82, 85, 87, 106,468, 491; 558/131, 154 ring carbon atoms, or, together with R forms an alkyl ene chain of 3 to 10 carbon atoms, or R is a group (56) References Cited NHR3 wherein R3 is H, alkyl with 1 to 4 carbon atoms, U.S. PATENT DOCUMENTS alkenyl of up to 4 carbon atoms, CN, CONH2 or NH2 or 3,134,742 5/1964 Wismer et al. ...... ... 521/107 together with R1 forms an alkylene chain of 2 or 3 car 3,400,085 9/1968 Kujawa et al. ..... ... 524/130 bon atoms, or R is a group 3,963,437 6/1976 Le Blanc et al. ....... ... 524/130 4,025,470 5/1977 Andres et al. ...................... 521/107 R1 4,165,411 8/1979 Marans et al. / 4,308,197 12/1981 Byrd et al. R-C-N 4,341,694 7/1982 Halpern ................................. 521/85 N 4,403,075 9/1983 Byrd et al. X R2 4,407,981 10/1983 Aaronson ............................ 524/130 4,452,849 6/1984 Nachbur et al. where R1 and R2 are as defined above and R is a direct 4,487,800 12/1984 Nachbur et al. bond or an alkylene group having up to 8 carbon atoms FOREIGN PATENT DOCUMENTS or is an arylene group having 6 to 10 carbon atoms. 919067 2/1963 United Kingdom. 999588 7/1965 United Kingdom . 19 Claims, No Drawings 4,666,967 1. FLAME RETARDANTS FOR POLYURETHANES The present invention relates to the use of organic I salts of phosphonic acids in rendering polyurethanes X R2 and polyisocyanurates more flame retardant, and also to novel organic salts of phosphonic acids. wherein R, R2 and X are as defined above and R is a Polyurethanes and polyisocyanurates are usually direct bond or an alkylene group having up to 8 carbon atoms or is an arylene group having 6 to 10 carbon made more flame retardant by adding a phosphorus 10 containing compound, a halogen-containing compound atOmS. or a mixture thereof. One commonly used phosphorus Various compounds of formula (I) may be used. One containing compound is dimethyl methyl phosphonate suitable and preferred class of compounds has the gen (DMMP)-see, for instance, British patent specifica eral formula (II) tions Nos. 1094717, 999588 and 919067, and U.S. Pat. 15 No. 4,165,411. However, there are certain problems R1 II N associated with the use of DMMP. First it is a relatively N-C-NHR3 volatile liquid (boiling point 181 C) which means that / material may be lost by volatilisation under certain R2 circumstances. Secondly, DMMP is usually formulated 20 with polyols used to manufacture polyurethanes and where R, R2, R3 and X are as defined above. polyisocyanurates together with catalysts, blowing Another suitable class of compounds has the general agents and other ingredients before the isocyanate is formula (III) added. There is a tendency for the formulation to be 25 somewhat unstable if it is stored for a long period before R6 III use. The viscosity of such formulations may increase on standing and variable forming characteristics may be R7 observed when mixed with the isocyanate co-reactant. Some salts of, inter alia, DMMP with amino com 30 where R is H, alkyl with 1 to 8 carbon atoms, an aryl, pounds are known and are described in EP No. 0057668 cycloalkyl or heterocyclic group; and R6 and R7 are the and U.S. Pat. No. 4,308,197. However, the use of such same or different and are H or an alkyl group with 1 to salts as flame retardant additives for polyols or polyure 4 carbon atoms, or R6 and R7 together with the nitrogen thanes is not mentioned. atom to which they are attached form a heterocyclic It is an object of the present invention to provide 35 ring of up to 6 carbon atoms which may optionally phosphorus-containing flame retardants of low volatil contain another hetero atom, and X is as defined above. ity and which give polyol formulations which are stable Another suitable class of compounds has the general on storage. formula Accordingly the present invention provides a poly urethane or polyisocyanurate having incorporated 40 therein a flame retardant amount of a salt formed by X X reaction between dimethyl methyl phosphonate, mono methyl methyl phosphonate or methyl phosphonic acid, and a compound of the general formula (I) 45 where R', R6 and R7 are as defined above. X R I Another suitable class of compounds has the general formula (V) 50 CEX / in which X is O, S or NH, R1 is H, alkyl with 1 to 4 (CH2) carbon atoms, alkenyl of up to 4 carbon atoms, CN, CONH2 or NH2, R2 is H, alkyl with 1 to 4 carbon atoms or alkenyl of up to 4 carbon atoms or Rand R2 together 55 where R8 is H or alkyl having 1 to 4 carbon atoms and with the nitrogen atom to which they are attached form n is an integer from 3 to 10, and X is as defined above. a heterocyclic ring of up to 6 carbon atoms which may When R or R5 is a C1-C8 alkyl group it may be, for optionally contain another hetero atom and R is H, an example, methyl, ethyl, isopropyl, n-butyl, sec-butyl, alkyl group with 1 to 8 carbon atoms, an aryl group 60 hexyl or octyl, with 6 to 10 carbon atoms, a cycloalkyl group with 5 to When R, R2, R3, R6, R7 or R8 is a C1-C4 alkyl group 12 carbon atoms or a heterocyclic group with up to 9 it may be, for instance, methyl, ethyl, isopropyl, n-butyl ring carbon atoms, or, together with R1 forms an alkyl or sec-butyl. ene chain of 3 to 10 carbon atoms, or R is a group When R, R2 or R3 is alkenyl with up to 4 carbon NHR3 wherein R3 is H, alkyl with 1 to 4 carbon atoms, 65 atoms it may be, for instance, allyl, propenyl or butenyl. alkenyl of up to 4 carbon atoms, CN, CONH2 or NH2 or When R1 and R2 or R6 and R7 form a heterocyclic together with R1 forms an alkylene chain of 2 or 3 car ring, it may be, for instance, a pyridine, morpholine, bon atoms, or R is a group piperidine, or piperazine ring. 4,666,967 3 4. When R is a heterocyclic ring with up to 9 carbon . The salts used in the invention may be used alone or atoms it may be, for instance, a pyridine, morpholine, together with other flame retardants such as those given piperidine, indole or quinoline ring. below for imparting flame retardance to rigid or flexible When R is an aryl ring with 6-10 carbon atoms it may polyurethanes or polyisocyanurates. Polyurethanes and be, for instance a benzene or naphthalene ring. 5 polyisocyanurates are prepared by reacting a polyol When R is a cycloalkyl ring with 5-12 carbon atoms with a polyisocyanate, in the presence of a blowing it may be, for instance a cyclopentyl, cyclohexyl, cy agent if a foam is desired and a catalyst. The amount of clooctyl or cyclododecyl ring. polyisocyanate is varied to produce the desired prod When R is an aryl, cycloalkyl or heterocyclic group, uct. The present invention is applicable to the whole it may be a radical such as those described above for R.