Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
1998-08-04
2001-03-27
Hoke, Veronica P. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S133000, C524S416000, C524S417000
Reexamination Certificate
active
06207736
ABSTRACT:
The invention relates to a synergistic flameproofing combination which contains calcium, aluminum or zinc phosphinates and nitrogen-containing phosphates.
BECKGROUND OF THE INVENTION
Polymers are frequently rendered flame-retardant by adding to them phosphorus-containing or halogen-containing compounds or mixtures thereof. Mixtures of phosphorus- and nitrogen-containing compounds are also often used as flame retardants.
Alkali metal salts of phosphinic acid have already been proposed as flame-retardant additives for polyesters (DE-A-2 252 258). They must be introduced in amounts of up to 30% by weight and some of them have a disadvantageous, corrosion-promoting effect on the processing machines.
Furthermore, the salts of phosphinic acids with an alkali metal or with a metal from the second or third main group of subgroup of the Periodic Table have been used for the preparation of flame-retardant polyamide molding materials, in particular the zinc salts (DE-A-2 447 727).
Calcium and aluminium phosphinates have proven particularly effective in polyesters (EP-A-699 708). However, the preparation of these phosphinates on an industrial scale is relatively complicated and expensive, which very greatly limits the potential uses of the products as flame retardants for plastics.
The application PCT/EP97/01664 describes synergistic combinations of different phosphinates with heat-stable organic nitrogen compounds which are not very volatile and have a particularly good and also economical flameproofing effect in polymers.
Aluminum hydroxide or phosphate, too, can be used in mixtures with said phosphinic acid salts as a flame-retardant additive (German Patent Application No. 19708726.4), even if the synergistic action is not so pronounced as in the case of the organic nitrogen compounds.
It was found, surprisingly, that nitrogen-containing, purely inorganic phosphates mixed with the phosphinates have an action which is similarly good but in some cases even better. In addition, compared with commercial flame-retardant molding materials, molding materials treated according to the invention have high light stability if light stabilizers of the type comprising sterically hindered amines and/or UV absorbers are used together with the flameproofing mixtures.
SUMMARY OF THE INVENTION
The invention thus relates to a synergistic flameproofing combination for polymers which contains, as component A, a phosphinic acid salt of the formula (I) and/or a diphosphinic acid salt of the formula (II) and/or polymers thereof
in which
R
1
and R
2
are linear or branched C
1
-C
6
-alkyl, preferably C
1
-C
4
-alkyl, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or n-pentyl, or phenyl;
R
3
is linear or branched C
1
-C
10
-alkylene, preferably C
1
-C
6
-alkylene, e.g. methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene;
C
6
-C
10
-arylene, e.g. phenylene or naphthylene, preferably phenylene;
alkylarylene, e.g. methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene;
arylalkylene, e.g. phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene;
M is a calcium, aluminum or zinc ion, preferably an aluminum ion;
m is 2 or 3;
n is 1 or 3;
x is 1 or 2,
and which contains, as component B, a nitrogen-containing phosphate of the formulae (NH
4
)
y
H
3−y
PO
4
or (NH
4
PO
3
)
z
, in which y may assume numerical values from 1 to 3 and z is any desired number, typically also the average value of a chain length distribution.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Below, the term “phosphinic acid salt” denotes salts of phosphinic and diphosphinic acids and polymers thereof.
The phosphinic acid salts, which are prepared in aqueous medium, are essentially monomeric compounds. Depending on the reaction conditions, polymeric phosphinic acid salts can also form under certain circumstances.
Suitable phosphinic acids as a component of the phosphinic acid salts are, for example: dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylenephosphinic acid, methanedi(methylphosphinic acid), benzene-1,4-(dimethylphosphinic acid), methylphenylphosphinic acid and diphenylphosphinic acid.
The salts of the phosphinic acids according to the invention can be prepared by known methods which are described in more detail in EP-A-699 708. The phosphinic acids are reacted in aqueous solution with metal carbonates, metal hydroxides or metal oxides.
Polymers in the context of the invention are also described on pages 6 to 9 of the Application PCT/EP97/01664, which is hereby expressly incorporated by reference.
The amount of the phosphinic acid salt of the general formula I which is to be added to the polymers, or of the diphosphinic acid salt of the formula II, may vary within wide limits. In general, from 1 to 30% by weight, based on the prepared polymer compound, are used. The optimum amount depends on the nature of the polymer, on the type of component B and on the type of the phosphinic acid salt itself which is used and can be readily determined by experiments. From 3 to 20, in particular from 5 to 15, % by weight are preferred.
The phosphinic acid salts according to the invention can be used in different physical forms, depending on the polymer used and on the desired properties. Thus, the phosphinic acid salts may be milled to give a finely divided form, for example for achieving better dispersion in the polymer. If desired, mixtures of different phosphinic acid salts may also be used.
The phosphinic acid salts according to the invention are thermally stable and neither decompose the polymers during processing nor influence the preparation process of the plastics molding material. The phosphinic acid salts are nonvolatile under preparation and processing conditions for polymers.
The polymer molding material contains, as component B, a nitrogen-containing phosphate of the formulae (NH
4
)
y
H
3−y
PO
4
(monophosphates) or (NH
4
PO
3
)
z
(polyphosphates), in which y may assume numerical values from 1 to 3 and z is any desired number, typically also the average value of a chain length distribution. There may be a smooth transition between the monophosphates and the polyphosphates, for example with diphosphates, triphosphates, etc. (NH
4
PO
3
)
z
typically denotes commercial ammonium polyphosphates having different chain lengths, which can be prepared by various processes. Both short-chain and long-chain polyphosphates may be used, so that z may assume, for example, values from 5 to 10,000. Poorly water-soluble, relatively long-chain ammonium polyphosphates having chain lengths>100 are preferred.
The amount of the phosphates (component B) to be added to the polymers may vary within wide limits. In general, from 1 to 30% by weight, based on the prepared polymer compound, are used. The optimum amount depends on the nature of the polymer, on the type of phosphinate (component A) used and on the type of the phosphate itself and can be readily determined by experiments. From 3 to 20, in particular from 5 to 15, % by weight are preferred.
Preferred thermoplastic polymers are industrial plastics, such as, for example, HI polystyrene (having a high impact strength), polyphenylene ethers, polyamides, polyesters, polycarbonates and blends or polyblends, such as ABS or PC/ABS.
ABS polymers are particularly preferred.
The flame-retardant components A and B can be incorporated into plastics molding materials by, for example, premixing all components as powder and/or granules in a mixer and then homogenizing them in the polymer melt in a compounding apparatus (e.g. a twin-screw extruder). The melt is usually extruded, cooled and granulated. The components A and B may also be introduced directly and separately into the compounding apparatus via a metering unit.
It is also possible to mix the flame-retardant additives A and B with prepared polymer granules or polymer powder and to process the mixture directly on an injection molding machine to give shaped articles
Nass Bernd
Wanzke Wolfgang
Clariant GmbH
Hanf Scott E.
Hoke Veronica P.
Jackson Susan S.
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