Flame retardant additives and flame retardant polymer...

Compositions – Fire retarding – For solid synthetic polymer and reactants thereof

Reexamination Certificate

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C524S371000, C524S373000

Reexamination Certificate

active

06780348

ABSTRACT:

TECHNICAL FIELD
This invention relates to additive compositions that serve as flame retardants and that have the capability, when blended with suitable thermoplastic polymers, of providing thermally-stable flame-retardant thermoplastic polymer compositions. This invention also relates to the resultant flame retarded polymer compositions.
BACKGROUND
Over the years much effort has been devoted to the discovery and development of effective flame retardants for use in thermoplastic polymers.
Japan Kokai 08-208939 A2, laid open Aug. 13, 1996, describes flame retarded compositions composed of (A) HIPS containing (B) 4-8 parts of tetrabromobisphenol-A and polyhalogenated aliphatic ether derivatives, (C) polyhalogenated diphenylalkanes in an amount of 20-50% of the amount of (B), (D) Sb
2
O
3
, and (E) 0.0005-0.05% (as Si) of organic polysiloxane. According to this prior disclosure, the amount by weight of the polyhalogenated diphenylalkanes to be used is at most one-half of the amount of tetrabromobisphenol-A and polyhalogenated aliphatic ether derivatives used. It has been found that such compositions possess poor thermal stability.
Thus, while in many cases effective flame retardancy can be achieved by various flame retardant additives, one or more other properties of the resultant polymer compositions, such as thermal stability, may be sacrificed. In particular, a need exists for a new, effective flame retardant having high thermal stability for use in thermoplastic polymers and little, if any, tendency to bloom when used in polyolefin polymers.
Thus a welcome contribution to the art of would be the provision of new additive compositions of enhanced thermal stability that have the capability, when blended with suitable thermoplastic polymers, of providing thermoplastic polymer compositions having enhanced thermal stability, especially if this could be accomplished on an economically-attractive basis. It would also be very welcome contribution to provide an effective thermally-stable flame retardant additive composition which has little, if any, blooming tendency when used in blends with polyolefins. This invention is deemed to constitute such a contribution.
BRIEF SUMMARY OF THE INVENTION
Provided by this invention in one of its embodiments is a flame retardant additive composition which comprises a mixture of:
a) (i) at least one polybromodiphenylalkane in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule and in which the alkane portion of the molecule contains 1 to 3 carbon atoms, preferably 2 carbon atoms or (ii) at least one polybromodiphenyl oxide in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule, or (iii) a mixture of (i) and (ii); and
b) at least one tetrabromobisphenol-A-bis(bromoalkyl ether);
wherein a) and b) are in proportions such that per each 100 parts by weight of a) and b), 50 to 80 parts by weight are a) and 50 to 20 parts by weight are b). Thus contrary to the teachings of the above Japanese Kokai, in this embodiment of the invention the amount by weight of component a) used is at least the same as, or more than, the amount of component b).
A preferred embodiment is a flame retardant additive composition which comprises a mixture of:
a) (i) at least one polybromodiphenylalkane in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule and in which the alkane portion of the molecule contains 1 to 3 carbon atoms, preferably 2 carbon atoms or (ii) at least one polybromodiphenyl oxide in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule, or (iii) a mixture of (i) and (ii);
b) at least one tetrabromobisphenol-A-bis(bromoalkyl ether); and
c) at least one synthetic zeolite or at least one hydrotalcite, or both;
wherein a) and b) are in proportions such that per each 100 parts by weight of a) and b), 20 to 80 parts by weight are a) and 80 to 20 parts by weight are b), and wherein c) is in an amount such that there is one part by weight thereof per each 4 to 6 parts by weight of b) in the composition. As between the zeolite(s) and the hydrotalcite(s), use of the synthetic zeolite as c) is more preferred. As will be seen hereinafter, the presence of component c) greatly enhances the thermal stability of the compositions and thus makes possible, inter alia, use of proportions described in the above Japanese Kokai with satisfactory results.
In another preferred embodiment there is provided a flame retardant additive composition which comprises a mixture of:
a) at least one polybromodiphenylalkane in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule and in which the alkane portion of the molecule contains 1 to 3 carbon atoms, preferably 2 carbon atoms; and
b) at least one tetrabromobisphenol-A-bis(bromoalkyl ether);
wherein a) and b) are in proportions such that per each 100 parts by weight of a) and b), 50 to 80 parts by weight are a) and 50 to 20 parts by weight are b).
Still another preferred embodiment is a flame retardant additive composition which comprises a mixture of:
a) at least one polybromodiphenylalkane in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule and in which the alkane portion of the molecule contains 1 to 3 carbon atoms, preferably 2 carbon atoms;
b) at least one tetrabromobisphenol-A-bis(bromoalkyl ether);
c) at least one synthetic zeolite or at least one hydrotalcite, or both;
wherein a) and b) are in proportions such that per each 100 parts by weight of a) and b), 20 to 80 parts by weight are a) and 80 to 20 parts by weight are b), and wherein c) is in an amount such that there is one part by weight thereof per each 4 to 6 parts by weight of b) in the composition. As between the zeolite(s) and the hydrotalcite(s), use of the synthetic zeolite as c) is more preferred.
Yet another embodiment of this invention is a flame retardant additive composition which comprises a mixture of:
a) at least one polybromodiphenyl oxide in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule; and
b) at least one tetrabromobisphenol-A-bis(bromoalkyl ether);
wherein a) and b) are in proportions such that per each 100 parts by weight of a) and b), 50 to 80 parts by weight are a) and 50 to 20 parts by weight are b).
A further embodiment of this invention is a flame retardant additive composition which comprises a mixture of:
a) at least one polybromodiphenyl oxide in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule;
b) at least one tetrabromobisphenol-A-bis(bromoalkyl ether); and
c) at least one synthetic zeolite or at least one hydrotalcite, or both;
wherein a) and b) are in proportions such that per each 100 parts by weight of a) and b), 20 to 80 parts by weight are a) and 80 to 20 parts by weight are b), and wherein c) is in an amount such that there is one part by weight thereof per each 4 to 6 parts by weight of b) in the composition. As between the zeolite(s) and the hydrotalcite(s), use of the synthetic zeolite as c) is more preferred.
Further embodiments of this invention include a flame retardant polymer composition comprised of at least one thermoplastic polymer with which has been blended, separately or in combination, a flame-retardant amount of:
a) (i) at least one polybromodiphenylalkane in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule and in which the alkane portion of the molecule contains 1 to 3 carbon atoms, preferably 2 carbon atoms or (ii) at least one polybromodiphenyl oxide in which the phenyl groups are substituted by a total of at least 6 bromine atoms per molecule, or (iii) a mixture of (i) and (ii); and
b) at least one tetrabromobisphenol-A-bis(bromoalkyl ether);
in proportions such that per each 100 parts by weight of a) and b), 50 to 80 parts by weight are a) and 50 to 20 parts by weight are b). Preferably such polymer composition further contains as component c) at least on

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