US 2003/0149143 A1 · Flame retardant compositions

Abstract

Polyolefins, especially polypropylene, can be made flame retardant by the incorporation therein of a synergistic mixture of a selected hindered amine substituted by an alkoxy, cycloalkoxy or hydroxyalkoxy moiety and a selected organic or inorganic brominated and/or phosphorus containing flame retardant, such as ammonium polyphosphate or decabromodiphenyl oxide wherein the amount of organic or inorganic flame retardant required to achieve an acceptable level of flame retardancy is significantly reduced compared to that needed when the hindered amine is not present.

A flame retardant composition which comprises

(a) a polymer substrate, and
(b) an effective flame retarding amount of a synergistic mixture of
(i) a hindered amine of formula A
16
wherein
E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or aralkoxy of 7 to 15 carbon atoms, or E is —O—T—(OH)b,
T is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 carbon atoms;
b is 1, 2 or 3 with the proviso that b cannot exceed the number of carbon atoms in T, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atoms of T;
R is hydrogen or methyl,
m is 1 to 4,
when m is 1,
R2 is hydrogen, C1-C18alkyl or said alkyl optionally interrupted by one or more oxygen atoms, C2-C12alkenyl, C6-C10aryl, C7-C18aralkyl, glycidyl, a monovalent acyl radical of an aliphatic, cycloaliphatic or aromatic carboxylic acid, or a carbamic acid, preferably an acyl radical of an aliphatic carboxylic acid having 2-18 C atoms, of a cycloaliphatic carboxylic acid having 5-12 C atoms or of an aromatic carboxylic acid having 7-15 C atoms, or
17
wherein x is 0 or 1,
18
wherein y is 2-4;
when m is 2,
R2 is C1-C12alkylene, C4-C12alkenylene, xylylene, a divalent acyl radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid or of a dicarbamic acid, preferably an acyl radical of an aliphatic dicarboxylic acid having 2-18 C atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C atoms;
19
wherein D1 and D2 are independently hydrogen, an alkyl radical containing up to 8 carbon atoms, an aryl or aralkyl radical including 3,5-di-t-butyl-4-hydroxybenzyl radical, D3 is hydrogen, or an alkyl or alkenyl radical containing up to 18 carbon atoms, and d is 0-20;
when m is 3, R2 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic tricarboxylic acid;
when m is 4, R2 is a tetravalent acyl radical of a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid including 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-enetetracarboxylic, and 1,2,3,5- and 1,2,4,5-pentanetetracarboxylic acid;
or
wherein the hindered amine compound is a mixture of N,N′,N′″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;
N,N′,N″-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine, and bridged derivatives as described by formulas I, II, IIA and III
R1NH—CH2CH2CH2NR2CH2CH2NR3CH2CH2CH2NHR4 (I)T—E1—T1 (II)T—E1 (IIA)G—E1—G1—E1—G2 (III)
where in the tetraamine of formula I
R1 and R2 are the s-triazine moiety E;
and one of R3 and R4 is the s-triazine moiety E with the other of R3 or R4 being hydrogen,
E is
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R is methyl, propyl, cyclohexyl or octyl, preferably cyclohexyl,
R5 is alkyl of 1 to 12 carbon atoms, preferably n-butyl,
where in the compound of formula II or IIA when R is propyl, cyclohexyl or octyl,
T and T1 are each a substituted by R1-R4 as is defined for formula I, where
(1) one of the s-triazine moieties E in each tetraamine is replaced by the group E1 which forms a bridge between two tetraamines T and T1,
E1 is
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(2) the group E1 can have both termini in the same tetraamine T as in formula IIA where two of the E moieties of the tetraamine are replaced by one E1 group, or
(3) all three s-triazine substituents of tetraamine T can be E1 such that one E1 links T and T1 and a second E1 has both termini in tetraamine T,
L is propanediyl, cyclohexanediyl or octanediyl;
where in the compound of formula III
G, G1 and G2 are each tetraamines substituted by R1-R4 as defined for formula I, except that G and G2 each have one of the s-triazine moieties E replaced by E1, and G1 has two of the triazine moieties E replaced by E1, so that there is a bridge between G and G1 and a second bridge between G1 and G2;
which mixture is prepared by reacting two to four equivalents of 2,4-bis[(1-hydrocarbyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine with one equivalent of N,N′-bis(3-aminopropyl)ethylenediamine;
or the hindered amine is a compound of the formula IIIb
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in which the index n ranges from 1 to 15;
R12 is C2-C12alkylene, C4-C12alkenylene, C5-C7cycloalkylene, C5-C7cycloalkylenedi(C1-C4alkylene), C1-C4alkylenedi(C5-C7cycloalkylene), phenylenedi(C1-C4alkylene) or C4-C12alkylene interrupted by 1,4-piperazinediyl, —O— or >N—X1 with X1 being C1-C12acyl or (C1-C12alkoxy)carbonyl or having one of the definitions of R14 given below except hydrogen;
or
R12 is a group of the formula (Ib′) or (Ic′);
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with m being 2 or 3,
X2 being C1-C18alkyl, C5-C12cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl;
phenyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl or C1-C4alkoxy;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl;
and
the radicals X3 being independently of one another C2-C12alkylene;
R13, R14 and R15, which are identical or different, are hydrogen, C1-C18alkyl, C5-C12cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl;
C3-C18alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl or C1-C4alkoxy;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl;
tetrahydrofurfuryl or C2-C4alkyl which is substituted in the 2, 3 or 4 position by —OH, C1-C8alkoxy, di(C1-C4alkyl)amino or a group of the formula (Ie′);
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with Y being —O—, —CH2—, —CH2CH2— or >N—CH3, or —N(R14)(R15) is additionally a group of the formula (Ie′);
the radicals A are independently of one another —OR13, —N(R14)(R15) or a group of the formula (IIId);
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X is —O— or >N—R16;
R16 is hydrogen, C1-C18alkyl, C3-C18alkenyl, C5-C12cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl;
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl;
tetrahydrofurfuryl, a group of the formula (IIIf),
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or C2-C4alkyl which is substituted in the 2, 3 or 4 position by —OH, C1-C8alkoxy, di(C1-C4alkyl)amino or a group of the formula (Ie′);
R11 has one of the definitions given for R16;
and
the radicals B have independently of one another one of the definitions given for A;
(ii) a brominated and/or phosphorus containing flame retardant with the proviso that when the polymeric substrate is polypropylene, the flame retardant is not a halogenated hydrocarbyl phosphate or phosphonate.

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Flame retardant compositions

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Flame retardant compositions

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Abstract

Claims17