Flame retardant composition and hydrolysis-susceptible resin containing same
A flame retardant composition is provided which contains at least one phosphate ester containing at least one acidic substance resulting from the process of its manufacture, at least one acidity-reducing hydrotalcite and, optionally, at least one acidity-reducing oxetane. The flame retardant composition is especially useful for addition to resins that are susceptible to hydrolytic degradation such as polyesters and polycarbonates, and to resin blends (alloys) containing one or more of such resins, e.g., a blend of polycarbonate and acrylonitrile butadiene-styrene terpolymer.
1. A resin composition comprising
(i) a normally solid resin which is susceptible to hydrolysis or normally solid resin blend containing at least one normally solid resin component which is susceptible to hydrolysis,
(ii) a flame retardant effective amount of at least one phosphate ester flame retardant containing at least one acidic substance,
(iii) an acidity-reducing amount of at least one hydrotalcite and,
(iv) at least one oxetane,
wherein the resin susceptible to hydrolysis is a polycarbonate, blended with an acrylonitrile-butadiene-styrene terpolymer.
2. The resin composition of claim 1 wherein:
the phosphate ester is represented by general formula:
wherein X is the residue of a C 2 -C 30 dihydroxy compound or a C 6 -C 30 -dihydroxy aryl compound, R 1 , R 2 , R 3 and R 4 each independently is C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl or C 6 -C 20 -aryl, j, k, l and m each independently is 0 or 1 and n is 0 to 5;
the hydrotalcite is a synthetic or natural mineral represented by the general formula:
M 2+ (1−x) M 3+ x (OH) 2 A n x/2 m H 2 O
wherein M 2+ is a divalent metal ion, M 3+ is a trivalent metal ion, A n is an n-valent anion, n is an integer greater than 0, and m≧0; and,
the oxetane is represented by the general formula:
wherein R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently is hydrogen, C 1 -C 18 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 15 -aryl, C 7 -C 15 -aralkyl or a radical —CH 2 O—R″, wherein R″ is hydrogen, C 1 -C 18 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 15 -aryl, C 7 -C 15 -aralkyl or an acyl radical of a monobasic or polybasic carboxylic acid or of an inorganic acid.
3. The resin composition of claim 1 wherein the phosphate ester is represented by the general formula:
wherein X is the residue of a C 2 -C 30 dihydroxy compound or a C 6 -C 30 -dihydroxy aryl compound, R 1 , R 2 , R 3 and R 4 each independently is C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl or C 6 -C 20 -aryl, j, k, l and m each independently is 0 or 1, and n is 0 to 5.
4. The resin composition of claim 3 wherein R 1 , R 2 , R 3 and R 4 each is phenyl and —O—X—O— is derived from bisphenol A, resorcinol or neopentyl glycol.
5. The resin composition of claim 4 wherein j, k, l and m each is 1 and n is 0 to 3.
6. The resin composition of claim 1 wherein the hydrotalcite is a synthetic or natural mineral represented by the general formula:
M 2+ (1−x) M 3+ x (OH) 2 A n x/2 m H 2 O
wherein M 2+ is a divalent metal ion, preferably Mg 2+ , M 3+ is a trivalent metal ion, preferably Al 3+ , A n is an n-valent anion, preferably CO 3 2− or SO 4 2− , n is an integer greater than 0, preferably 2, x is 0 to 0.5, preferably 0 to 0.33 and m≧0.
7. The resin composition of claim 1 wherein the hydrotalcite is a natural hydrotalcite of the formula Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, a synthetic hydrotalcite selected from the group consisting of Mg 0.7 Al 0.3 (OH) 2 (CO 3 ) 0.15 .0.54H 2 O, Mg 4.5 Al 2 (OH)13CO 3 .3.5H 2 O, Mg 4.2 Al 2 (OH) 12.4 CO 3 , Mg 4.3 Al 2 (OH) 12.6 CO 3 .4H 2 O, Zn 6 Al 2 (OH) 16 CO 3 .4H 2 O, Ca 6 Al 2 (OH) 16 CO 3 .4H 2 O, and Mg 14 Bi 2 (OH) 29.6 .4.2H 2 O or mixture thereof.
8. The resin composition of claim 1 wherein the oxetane is represented by the general formula:
wherein R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently is hydrogen, C 1 -C 18 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 15 -aryl, C 7 -C 15 -aralkyl or a radical —CH 2 O—R″, wherein R″ is hydrogen, C 1 -C 18 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 15 -aryl, C 7 -C 15 -aralkyl or an acyl radical of a monobasic or polybasic carboxylic acid or of an inorganic acid.
9. The resin composition of claim 1 wherein the oxetane is represented by the general formula:
wherein R 12 is hydrogen, C 1 -C 18 -alkyl, C 1 -C 18 -hydroxyalkyl, C 6 -C 15 -aryl, (C 6 -C 15 -aryl)-oxymethyl, C 7 -C 15 -aralkyl or (C 7 -C 15 -aralkyl)-oxymethyl, R 13 is hydrogen, C 1 -C 18 -alkyl, C 6 -C 15 -aryl, C 7 -C 15 -aralkyl or the acyl radical of a monobasic or polybasic carboxylic acid or inorganic acid, and p is an integer which has a value of 1 or is equal to the acid functionality of the acid from which the acid radical R 13 is derived.
10. The resin composition of claim 1 wherein the oxetane is at least one member of the group consisting of 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-amyloxetane, 3-hydroxymethyl-3-phenoxymethyloxetane, 3-hydroxymethyl-3-p-tert.-butyl-phenoxymethyloxetane, 3,3-bis-hydroxymethyloxetane, 3-hydroxymethyl-3-octyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-phenoxymethyl-3-ethyloxetane, 3-octadecyloxymethyl-3-ethyloxetane, 3-phenoxymethyl-3-amyloxetane, [3-ethyloxetanyl-(3)]-methyl benzoate, [3-methyl-oxetanyl-(3)]-methyl cinnamate, [3-ethyloxetanyl-(3)]-methyl stearate, [3-amyl-oxetanyl-(3)]-methyl acrylate and esters of polybasic carboxylic acids or inorganic acids.
11. The resin composition of claim 1 wherein the amount of oxetane is such that it will supplement or enhance the acidity-reducing effect of the hydrotalcite component.