Compositions – Fire retarding – For solid synthetic polymer and reactants thereof
Reexamination Certificate
2001-06-27
2003-06-10
Toomer, Cephia D. (Department: 1714)
Compositions
Fire retarding
For solid synthetic polymer and reactants thereof
C523S209000
Reexamination Certificate
active
06576160
ABSTRACT:
This is a 371 national stage application of PCT/EP99/06809, filed on Sep. 14, 1999, which has benefit of European Patent Application 98117342.0, filed on Sep. 14, 1998.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a surface-modified filler composition, its use for fireproof finishing of thermoplastic, duroplastic or elastomeric plastics, and the fireproof plastics produced therefrom.
2. Background Art
Flame-retardant fillers, such as, e.g., magnesium hydroxide or aluminum hydroxide, are often surface-modified for the purpose of improving the characteristics profile of the plastic mixtures that are produced with these fillers. This could be done with, e.g., salts of fatty acids according to DE-A-26 59 933, with polymers containing acid groups according to EP-A-292 233, with ethylene-propylene-copolymers EPDM or ethylene-propylene-terpolymers and other additives according to EP-B-0 426 196 or with special fatty acid derivatives according to WO-A-96/26240.
A drawback of the coatings of the prior art is the lack of universality. Thus, e.g., in coatings according to WO-A-96/26240, the effect with respect to the improvement of mechanical properties and/or the burning properties is very clearly pronounced in some plastics, such as, e.g., in EVA, but virtually does not occur in other systems, such as, e.g., in aliphatic polyketones, either only conditionally or in plastics such as, e.g., polyamides.
BROAD DESCRIPTION OF THE INVENTION
The object was consequently to develop surface-modified filler compositions that do not contain the drawbacks of the prior art, and thus can be used universally in the case of improved polymer compatibility and show improved mechanical and rheological properties and/or improved burning properties in comparison to the uncoated filler. In particular, the object was to develop surface-modified filler compositions that are especially suitable for the production of compounds for cable insulation.
The object can be achieved with the surface-modified filler compositions according to the invention.
According to the invention, the surface-modification of the halogen-free flame-retardant filler consists of one or more organotitanates and/or organozirconates and a siloxane derivative.
As halogen-free flame-retardant fillers, hydroxides of aluminum and/or hydroxides of magnesium, optionally mixed with oxides of aluminum, magnesium, titanium, silicon or zirconium or with other filler materials, such as, e.g, calcium carbonate, talc or calcined or non-calcined clays, are used.
Suitable hydroxides of aluminum are, e.g., natural Al(OH)
3
-containing materials, such as, e.g., hydrargillite or gibbsite, (AlO(OH)
x
)-containing materials, such as, e.g., boehmite or synthetic aluminum hydroxides, as they are marketed, e.g., under the trademark MARTIFIN® or MARTINAL® of the Alusuisse Martinswerk GmbH in Bergheim (Germany).
Suitable hydroxides of the magnesium are, e.g., natural Mg(OH)
2
types, such as, e.g., the brucite or sea water types, natural magnesium hydroxycarbonates, such as, e.g., dawsonite, huntite or hydromagnesite, or synthetic magnesium hydroxides, as are marketed, e.g., under the trademarks MAGNIFIN® of the Magnifin GmbH in Breitenau (Austria). As oxides of aluminum, magnesium, titanium or zirconium, the commercial oxides can be used. Depending on the required characteristics profile in the plastic, a hydroxide of aluminum and/or a hydroxide of magnesium by itself or in any mixture ratio is used with the above-mentioned oxides.
According to an embodiment of the invention, the filler composition in addition can contain a melamine derivative and/or a guanamine derivative. These additives can contribute to a further improvement of the flameproofing.
Suitable derivatives of the melamine are, e.g., melamine cyanurate/melaminisocyanurate or melaminediborate. A suitable derivative of guanamine is, e.g., acetoguanamine cyanurate.
For the purpose of better application, the melamine derivative and/or guanamine derivative can be taken up in a suitable vehicle. Such vehicles can be selected from polymers whose melting points are as much as possible below 150° C., from a suitable highly volatile organic solvent, which can be removed in further processing by evaporation, or from the organotitanates and/or organozirconates and a siloxane derivative that are used according to the invention.
The melamine derivative and/or guanamine derivative is suitably used in an amount of 0.01 to 25 parts, preferably 0.5 to 15 parts per 100 parts of halogen-free flame-retardant filler.
Suitable organotitanates and/or organozirconates are, e.g., those as described in the company publication “Ken-React Reference Manual,” Bulletin KR-1084-2 of the Kenrich Petrochemicals Inc; or as the are marketed by, e.g., the DuPont Company under the trade name TYZOR®.
Suitable organotitaniums or oragnozirconates are, for example:
Titanium tetra-2-ethylhexanoate, titanium tetrabutanolate, tetraisopropyl titanate, triethanolamine zirconate, tetra-n-propyl-zirconate, tetra-n-butyl-zirconate, diethylcitrate chelate-zirconate,
(triisosteary-isopropyl-titanate), tris-isooctadecanoato-O-titanium(IV)-2-propanolate,
iscoctadecancato-O-2-propanolato-titanium(IV) bis-2-methyl-2-propanolate,
tris(dodecyl)benzosulfonato-O-titanium(IV) 2-propanolate,
tris(dioctyl)phosphato-O-titanium(IV) 2-propanolate,
bis(dodecyl)benzosulfonato-O-2-propanolato-titanium(IV) (4-amino)benzenesulfonate,
methoxydiglycolato-O-titanium(IV) tris(2-methyl)-2-propenoate,
tris(dioctyl)pyrophosphato-O-titanium(IV) 2-propanolate,
methoxydiglycolato-O-titanium(IV) tris(2-propenoate),
tris(3,6-diaza)hexanolato-titanium(IV)-2-propanolate,
oxoethylenediolato-titanium(IV) bis[4-(2-phenyl)-2-propyl-2]phenolate,
titanium(IV) bis(dioctyl)pyrophosphato-O-oxcethylenediolate, adduct with (dioctyl-O-hydrogenphosphite),
tris-(2-methyl)-2-propenoato-O-titanium(IV) oxoethylenediolate,
titanium(IV) bis(butyl,methyl)pyrophosphato-O-oxoethylene-diolate, adduct with bis(dioctyl)-hydrogenphosphite,
ethylenediolato-O-titanium(IV) bis (dioctyl)phosphate,
ethylenediolato-O-titanium(IV) bis (dioctyl)pyrophosphate, adduct with bis(dioctyl)-hydrogenphosphite,
ethylenediolato-O-titanium(IV) bis(butyl,methyl)pyrophosphate, adduct with bis(dioctyl)-hydrogenphosphite,
oxoethylenediolato-titanium(IV) bis(dioctyl)pyrophosphate, adduct with 2 mol of 2-N,N-dimethylamino-2-methylpropanol,
methylpyrophosphato-O-titanium(IV) bis(butyl), adduct with 2 mol of 2-N,N-dimethylamino-2-methylpropanol, bis(dioctyl)pyrophosphato-O-titanium(IV) ethylenediolate-bis-(triethyl)amine salt,
bis(dioctyl)pyrophosphato-O-bis(dialkyl)aminoalkyl-2-methylpropenoate-titanium(IV) ethylenediolate,
ethylenediolato-O-titanium(IV) bis(dioctyl)pyrophosphate, adduct with 2 mol of acrylato-O-amine,
ethylenediolato-O-titanium(IV) bis(dioctyl)pyrophosphate, adduct with 2 mol of 2-methylpropenoamido-N-amine,
methylpyrophosphato-ethylenediolato-titanium(IV) bis(butyl)-bis(dialkyl)aminoalkylacrylate salt,
bis(dioctyl)pyrophosphato-O-titanium(IV) (bis-2-propenolatemethyl)-2-butanolate, adduct with 3 mol of N,N-dimethylaminoalkylpropenoamide,
bis(dioctyl)pyrophosphato-O-zirconium(IV) 2,2-dimethyl-1,3-propanediolate, adduct with 2 mol of N,N-dimethylaminoalkylpropenoamide,
cyclo-bis-2-dimethylaminopyrophosphato-O,O-zirconium(IV) (2-ethyl, 2-propenolatomethyl)1,3-propanediolate, adduct with 2 mol of methanesulfonic acid,
titanium(IV) tetrakis-2-propanolate, adduct with 2 mol of (dioctyl)hydrogen phosphate,
titanium(IV) tetrakis octanolate, adduct with 2 mol of (ditridecyl)hydrogen phosphite,
methylbutanolato-titanium(IV) tetrakis(bis-2-propenolate), adduct with 2 mol of (di-tridecyl)-hydrogen phosphite,
zirconium(IV) tetrakis-2,2-(bis-2-propenolatomethyl)butanolate, adduct with 2 mol of ditridecyl hydrogen phosphite,
tris-neodecanolato-O-titanium(IV) 2,2-(bis-3-propenolatomethyl)butanolate,
tris(dodecyl)benzenesulfonato-O-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(dioctyl)phosphato-O-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(dioctyl)pyrophosphato-
Eichler Hans-Jurgen
Herbiet Rene
Palmer Michael
Fisher Christen & Sabol
Toomer Cephia D.
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