HALOBENZOATE ESTERS, FLAME RETARDANT COMPOSITION CONTAINING SAME AND, POLYURETHANE FOAM MADE THEREWITH
There is provided herein a hydroxyl group-terminated halobenzoate ester of the general formula (1), wherein each X independently is bromine, chlorine, or hydrogen, provided that at least one X is bromine or chlorine, and R is a divalent organic group of from 1 to about 20 carbon atoms, wherein R can optionally contain at least one additional hydroxyl group. There is also provided herein a flame-retardant composition, which comprises a first flame-retardant which is at least one of the aforementioned ester and further comprises a second flame-retardant which is at least one phosphate ester. There is provided flame-retardant polyurethane foams comprising said ester or said composition. There is still also provided herein, process(es) of making the hydroxyl group-terminated halobenzoate ester of the general formula (1) wherein R is a divalent organic group of from 2 to about 20 carbon atoms, wherein R can optionally contain at least one additional hydroxyl group, and polyurethane foams made using the same.
1 . A hydroxyl group-terminated halobenzoate ester of the general formula (1):
wherein each X independently is bromine, chlorine or hydrogen, provided that at least one X is bromine or chlorine, and R is an organic group of up to about 20 carbon atoms, wherein R can optionally contain at least one additional hydroxyl group.
2 . The ester of claim 1 wherein in formula (1), each X is bromine.
3 . The ester of claim 1 wherein in formula (1), R is a divalent hydrocarbon group of from 1 to about 12 carbon atoms, optionally containing at least one heteroatom in said hydrocarbon group.
4 . The ester of claim 1 wherein in formula (1), R is a linear, branched or cyclic divalent hydrocarbon group of up to about 8 carbon atoms, optionally containing at least one heteroatom in said hydrocarbon group.
5 . The ester of claim 1 wherein in formula (1), each X is bromine and R is a linear, branched or cyclic divalent hydrocarbon group of up to about 8 carbon atoms, optionally containing at least one heteroatom in said hydrocarbon group.
6 . The ester of claim 1 wherein in formula (1), R is selected from the group consisting of methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, isohexylene, 2-ethylhexylene, cyclohexylene, methyl cyclohexylene, butoxyethylene and combinations thereof.
7 . The ester of claim 1 wherein the hydroxyl group-terminated halobenzoate ester is selected from the group consisting of hydroxyethyl, hydroxypropyl, hydroxybutyl, cyclohexylmethanol, and combinations thereof.
8 . A polyol blend comprising the ester of claim 1 ; and, at least one other polyol.
9 . A polyol blend comprising the ester of claim 1 wherein said ester contains at least two hydroxyl groups therein; and, at least one other polyol.
10 . A flame-retardant composition comprising:
a) a first flame-retardant which is at least one hydroxyl group-terminated halobenzoate ester of the general formula (1):
wherein each X independently is bromine, chlorine, or hydrogen, provided that at least one X is bromine or chlorine, and R is an organic group of up to about 20 carbon atoms, wherein R can optionally contain at least one additional hydroxyl group; and,
b) a second flame-retardant which is at least one phosphate ester.
11 . The composition of claim 10 wherein phosphate ester (b) is of the general formula (3):
wherein n is 0, or an integer of 1 to 10, wherein, R 1 , R 2 , R 3 , and R 4 each independently is a non-halogenated or halogenated unsubstituted alkyl group of from 1 to about 10 carbon atoms, a non-halogenated or halogenated substituted alkyl group of from 4 to about 10 carbon atoms, a non-halogenated or halogenated aryl group of from 6 to about 20 carbon atoms, or a non-halogenated or halogenated substituted aryl group of from 7 to about 20 carbon atoms, R 5 is a non-halogenated or halogenated, substituted or unsubstituted alkylene or arylene group, provided, that when n is 1 to about 10, at least one of R 1 , R 2 , R 3 , R 4 and R 5 is substituted with at least one halogen atom.
12 . The composition of claim 10 wherein each X is bromine.
13 . The composition of claim 10 wherein R is a divalent hydrocarbon group of from 1 to about 12 carbon atoms, optionally containing at least one heteroatom in said hydrocarbon group.
14 . The composition of claim 10 wherein R is a linear, branched or cyclic divalent hydrocarbon group of up to about 8 carbon atoms, optionally containing at least one heteroatom in said hydrocarbon group.
15 . The composition of claim 10 wherein each X is bromine and R is a linear, branched or cyclic divalent hydrocarbon group of up to about 8 carbon atoms, optionally containing at least one heteroatom in said hydrocarbon group.
16 . The composition of claim 10 wherein R is selected from the group consisting of methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, isohexylene, 2-ethylhexylene cyclohexylene, methyl cyclohexylene, butoxyethylene and combinations thereof.
17 . The composition of claim 10 wherein the hydroxyl group-terminated halobenzoate ester is selected from the group consisting of hydroxyethyl, hydroxypropyl, hydroxybutyl, cyclohexylmethanol, and combinations thereof.
18 . A blend comprising the ester of claim 1 .
19 . A blend comprising the flame-retardant composition of claim 10 , wherein the at least one hydroxyl group-terminated halobenzoate ester is blended in a minor amount of the at least one phosphate ester (b) which is present in a major amount.
20 . A polyol blend comprising the flame-retardant composition of claim 10 ; and at least one other polyol.
21 . A flame-retardant polyurethane foam made using the hydroxyl-group terminated halobenzoate ester of claim 1 .
22 . A flame-retardant polyurethane foam made using the flame-retardant composition of claim 10 .
23 . A flame-retardant polyurethane foam made using the flame-retardant composition of claim 15 .
24 . A flame-retardant polyurethane foam made using the blend of claim 18 .
25 . A flame-retardant polyurethane foam made using the blend of claim 19 .
26 . A flame-retardant polyurethane foam made using the blend of claim 20 .
27 . A process of producing the hydroxyl group-terminated halobenzoate ester of the general formula (1):
wherein each X independently is bromine, chlorine or hydrogen, provided that at least one X is bromine or chlorine, and R is a divalent organic group of from 2 to about 20 carbon atoms, wherein R can optionally contain at least one additional hydroxyl group; which comprises:
a) reacting halophthalic anhydride of the general formula (2):
wherein each X independently is bromine, chlorine or hydrogen, provided that at least one X is bromine or chlorine, with at least one alkanol possessing at least two carbon atoms and having at least two hydroxyl groups; and,
b) decarboxylating substantially any carboxylic acid moieties present in the reaction product of (a) to produce the hydroxyl group-terminated halobenzoate ester of formula (1).
28 . The process of claim 27 wherein the alkanol is a diol.
29 . The process of claim 27 wherein the alkanol is of the general formula (5):
R(OH) a (5)
wherein R is an organic group of from 2 to about 20 carbon atoms and a is an integer of at least two.
30 . The process of claim 29 wherein R is a divalent hydrocarbon group of from 2 to about 12 carbon atoms.
31 . The process of claim 29 wherein R is a divalent linear, branched or cyclic hydrocarbon group of up to about 8 carbon atoms.
32 . The process of claim 29 wherein X is bromine and R is a divalent linear, branched or cyclic hydrocarbon group of up to about 8 carbon atoms.
33 . The process of claim 27 wherein the alkanol is selected from the group consisting of 1,2-ethane diol; glycerin; 1,2-propane diol; ethylene glycol; 1,3-propane diol; 1,2-butanediol; 1,3-butanediol; 1,5-pentanediol; neopentylglycol; alkoxydiols such as diethylene glycol; triethylene glycol; trimethylolethane; trimethylolpropane; and, mixtures thereof.
34 . The process of claim 27 wherein each X is bromine.
35 . A flame-retardant polyurethane foam made using the hydroxyl-group terminated halobenzoate ester made by the process of claim 27 .
36 . A flame-retardant polyurethane foam made using the hydroxyl-group terminated halobenzoate ester made by the process of claim 32 .