SELF-EXTINGUISHING POLYOLEFINIC COMPOSITIONS HAVING IMPROVED FLAME RESISTANT CHARACTERISTICS AND A HIGH THERMAL STABILITY

Abstract: Self-extinguishing compositions comprising: 1) from 35.5 to 87% by weight of at least a polyolefin 2) from 5 to 20% by weight of an ammonium polyphos­ phate 3) from 2 to 20% by weight of polycarbonylpiperazine 4) from 2 to 20% by weight of melamine phosphate 5) from 0.5 to 3% by weight of titanium dioxide 6) from 0 to 1.5% by weight of a compound of formula R-SH wherein R is a radical of imidazole or of uracyl.

Description: This invention relates to self-extinguishing polyolefinic compositions. Several methods of imparting self-extinguishing properties to the olefinic polymers are known in the art. The less recent methods include those based on the addition of the polymers with metal compounds, particularly antimony and bismuth in combination with thermally unstable halogen compounds such as, for example, the chlorinated paraffinic waxes. Such combinations are affected, however, by serious drawbacks, such as corrosion of the equipment utilized for processing the polymeric compositions,and the emission of obscuring smokes and of corrosive and toxic gases. ore recently the research has been directed to the use of combinations free from halogen compounds and based on ammonium polyphosphates in admixture with particular nitrogenous organic compounds. They give rise, in case of combustion, to a consistent foamed carbonaceous structure, which acts as a thermal shield between flame and polymer. such systems exhibit, however, the drawback of possessing a limited resistance to heat and to thermo-oxidation. A certain improvement in the performances has been obtained, according to French patent application No. 2,352,857 in the name of the Applicant, with systems based on the combination of an ammonium polyphosphate with carbonylpiperazine. There are an object of the present invention particular polyolefinic compositions characterized by the combinatinn of high levels of self-extinguishing properties with an excellent resistance to heat and to thermo-oxidation. Shch compositions comprise 1) from 35.D to 87.0 bg weight of an olefinic polymer or copolymer, 2) from 5 to 20 % by weight, preferably 8 to 18% by weight, of an ammonium polyphosphate, 3) from 2 to 20 % by weight, preferably 3 to 8% by weight, of polycarbonylpiperazine, 4) from 2 to 20 % by weight, preferably 3 to 8% by weight, of melamine phosphate, 5) from 0.5 to 3 % by weight, preferably 1 to 1.5% by weight, of titanium dioxide, 6) from 0 to 1.5 % by weight, preferably 0.5 to 1.5% by weight, of a compound comprised in one of the following general (tautotneric) formulas: (I) (R -S- Hi (II) R2=S in which: : S = a sulphur atom R1 R2 = radicals selected from the groups of (a) imidazole, where R and R2 have respectively the formula EMI2.1 (b) uracyl, with R1 and R2 having repsectively the formula EMI2.2 where R4 = an alkyl radical containing from 1 to 4 carbon atoms, or hydrogen. oo.me examples of olefinic polymers and copolymers which can form the compositions of the present invention are : polypropylene, ethylene-modified polypropylene, the mixes of polypropylene with up to 20% by weight of ethylene-propylene elastomeric copolymers, containing up to 50% by weight of copolymerized ethylene and said ethylene-propylene vulcanized elastomers. Ammonium polyphosphates of general formula (NH4) n+2 Pn 3n+1 wherein n is an integer 2 are employable; n may be as high as 100; preferably, they have a molecular weight Which is sufficiently high to guarantee a low ater-solubility. Eesples of polyphosphates are the commercial products "Exolit 263" and "Exolit 422" (manufactured by Benckise Knapsack G.m.b.H.) where n is greater than 50. Examples of compounds as per point 6) hereinbefore are mercaptobenzoimidazole, 4-methylthio uracyl, thiouracyl. The melamine phosphate according to point 3) is a salt which can be prepared by reacting melamine and phosphoric acid (e.g. sold by SKW firm). The compounds according to point 6) impart prevailingly antiageing properties to the compositions forming the object of the present invention, and are therefore suited to improve their resistance to heat and to Thermo-oxidation. Preferably they are used in amounts ranging from 0.5 to 1.5 % by weight referred to the composition. The compositions of the invention may contain usual additives like common thermal stabilizers. The compositions of the present invention are preparable according to conventional methods: for example, the polyolefin and the anti-flame additives are mixed in a Banbury vane mixer at the polyolefin plasticization temperature, The resulting mix is then extruded in a DOLCI die (screw diameter = 20 mm; length/diameter ratio of the screw - 23; screw speed = 20 rpm) at the temperature which is best suited to obtain a granulated product. To determine the self-extinguishing properties of the polyolefinic compositions object of this invention it is operated as follows : plates having a 3 mm thickness are molded from the granulated product by means of a small CARVER-$ype press, by operating for 7 minutes at a pres 2 sure of 40 kg/cm and at a suitable temperature. The self-extinguishing level was determined on the plates so prepared both by measuring (according to standard ASTM D-2863) the oxygen index, which expresses the lowest 2 percentage in a 02/N2 mixture necessary for the specimen to continuously burn, and by following the UL-94 standards (published by Underwriters Laboratories" - USA) which provide an evaluation of the plastic materials' self -extinguishing degree. UL-94 standards contemplate various, more or less severe test conditions and permit to classify the specimen at different self-extinguishing levels In the tests reported on the Table, the Vertical Burning Test has been adopted, which permits to classify the material at the following decreasing levels: 94 V-O, 94 V-1 and 94 V-2. Each test is carried out on a group of 5 specimens which may have a thickness of 1/4, 1/8 or 1/16 inch. The specimen,raintained in a vertical position by a proper support, is fired with flame at the lower end, and 2 lighting attempts of 10 seconds each are made. The three above-mentioned levels of self-extinguishing power may be briefly defined as follows 94 V-0 No specimen burns for more than 10 seconds after each flame application, and no burning particles fall therefrom. Furthermore, the total combustion time does not exceed 50 seconds for the 10 at tempts made with the 5-specimen group. 94 V-l Combustion times up to 30 seconds for each in dividual specimen and up to 250 seconds for the 10 attempts made with the 5-specimen group are allowed. Also at this level no specimen lets burn ing particles drop. 94 V-2 The albwable combustion times are the same as for level 94 V-l, but the fall of burning particles is allowed. For the tests in oven at 1500C with induced air circulation, from the plates there are obtained, by punching, small bars of type I, as is described in ASTM D-638: the colour change evaluation is carried out visually, while the ageing test due to thermo-oxidation is effected by evaluating the embrittlement, which is coincident with the appearing of the first pulverization point. The following examples are given with a view to illustrating, but not to limiting, the present invention0 The compositions of each example were prepared as described hereinbefore, by using a DOLCI-type die having a screw diameter of 20 mm, a screw's length/diameter ratio = 23, and operating at a screw speed of 20 rpm, at a temperature of 200-240 DC. Example 1 This example relates to compositions A through M (compositions A through C being reference compositions), not containing imidazole compounds and uracyl compounds, the characteristics thereof being recorded on Table I. The amount of the components of such compositions indicat ed in the table are to be considered as amounts by weight. T A B L E I EMI7.1 A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> G <SEP> I <SEP> L <SEP> K <tb> Formulation <tb> 75,4 <SEP> 74,4 <SEP> 72,4 <SEP> 71,4 <SEP> 74,4 <SEP> 74,4 <SEP> 74,4 <SEP> 60 <SEP> 50 <SEP> 40 <tb> polypropylene <tb> (h.d.) <SEP> polyethylene <SEP> + <SEP> C2/C3 <SEP> (50/50) <SEP> copolymer <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 40 <SEP> 50 <SEP> 60 <tb> ammonium <SEP> polyphosphate <SEP> (Exolit <SEP> 422) <SEP> 18 <SEP> 18 <SEP> 18 <SEP> 18 <SEP> 15 <SEP> 13 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <tb> polycarbonylpiperazine <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 10 <SEP> 10 <SEP> 10 <tb> melamine <SEP> phosphate <SEP> - <SEP> - <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 5 <SEP> 8 <SEP> 10 <SEP> 10 <SEP> 10 <tb> titanium <SEP> dioxide <SEP> - <SEP> 1 <SEP> - <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 2 <SEP> 2 <SEP> 2 <tb> Irganox <SEP> 1010 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <tb> lauryl <SEP> thiopropionate <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <tb> Self-extinguishing <SEP> characteristics <SEP> determinen <SEP> on <SEP> a <SEP> 3-mm <SEP> thick <SEP> specimen <tb> Oxygen <SEP> index <SEP> 31,5 <SEP> 34,0 <SEP> 33,5 <SEP> 35,5 <SEP> 35,5 <SEP> 35 <SEP> 34,5 <SEP> 35 <SEP> 34,5 <SEP> 34 <tb> 1"10"B <SEP> 1" <SEP> 3" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 2" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 3" <tb> UL <SEP> - <SEP> 94 <SEP> * <tb> 1" <SEP> 3" <SEP> 2" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 2" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 1" <SEP> 2" <SEP> 1" <SEP> 3" <tb> * reference times for 4 consecutive light. ings B = it burns completely Example 2 This example illustrates compositions A through G (out of which the ones from A to D are reference compositions) containing compounds of imidazole and of uracyl, the characteristics of which are reported on Table II. T A B L E II EMI9.1 A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> G <tb> Formulation <tb> <SEP> Polypropylene <SEP> 75,4 <SEP> 74,4 <SEP> 75,4 <SEP> 74,4 <SEP> 73,4 <SEP> 73,4 <SEP> 72,4 <tb> Ammonium <SEP> polyphosphate <SEP> (Exolit <SEP> 422) <SEP> 18 <SEP> 18 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <tb> <SEP> Polycarbonylpiperazine <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 6 <tb> Melamine <SEP> phosphate <SEP> - <SEP> - <SEP> 8 <SEP> 8 <SEP> 8 <SEP> 8 <SEP> 8 <tb> Titanium <SEP> dioxide <SEP> - <SEP> 1 <SEP> - <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 2 <tb> Mercaptobenzoimidazole <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> - <SEP> 1 <tb> 4-methylthiuracyl <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 1 <SEP> Irganox <SEP> 1010 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <SEP> 0,2 <tb> Lauryl <SEP> thiopropionate <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <SEP> 0,4 <tb> Self-extinguishing <SEP> characteristics <SEP> on <SEP> a <tb> 3-mm <SEP> thick <SEP> specimen <tb> Oxygen <SEP> index <SEP> 31,5 <SEP> 34 <SEP> 33 <SEP> 34,5 <SEP> 32 <SEP> 31,5 <SEP> 31,5 <tb> UL-94 <SEP> 1"10" <SEP> B <SEP> 1"3"1"3" <SEP> 1"2"1"1" <SEP> 1"2"1"1" <SEP> 1"1"1"1" <SEP> 1"1"1"1" <SEP> 1"1"1"1" <tb> Specimen <SEP> colour <SEP> due <SEP> to <SEP> ageing <SEP> at <SEP> 150 C <tb> after <SEP> days <SEP> : <SEP> 0 <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> 3 <tb> +++++ <SEP> +++ <SEP> +++++ <SEP> +++ <SEP> ++ <SEP> ++ <SEP> ++ <tb> 7 <tb> +++++ <SEP> ++++ <SEP> +++++ <SEP> ++++ <SEP> +++ <SEP> +++ <SEP> +++ <tb> 14 <tb> ++++++ <SEP> +++++ <SEP> ++++++ <SEP> +++++ <SEP> +++ <SEP> ++++ <SEP> +++ <tb> 21 <tb> ++++++ <SEP> +++++ <SEP> ++++++ <SEP> +++++ <SEP> +++ <SEP> ++++ <SEP> +++ <tb> 30 <tb> ++++++ <SEP> +++++ <SEP> . <SEP> +++++ <SEP> ++++ <SEP> +++++ <SEP> +++ <tb> 45 <tb> . <SEP> . <SEP> . <SEP> ++++ <SEP> . <SEP> ++++ <tb> 60 <tb> . <SEP> . <tb> + white; ++ ivory; +++ light brown; ++++ brown; +++++ dark brown; ++++++ black; @ pulverization.

Claims: Claims 1. Polymeric compositions endowed with self-extinguish ing characteristics when exposed to the flame, com prising, by weight : 1) from 35.5 to 87 . of at least a polyolefin, 2) from 5 to 20 % of an ammonium polyphosphate; 3) from 2 to 20 ç of polycarbonylpiperazine; 4) from 2 to 20 % of melamine phosphate; 5) from 0.5 to 3 % of titanium dioxide; 6) from 0 to 1.5 ffi of a compound of formula R-SH wherein R is a radical of imidazole or of uracyl. 2. The compositions according to claim 1, in which compound 6) is in an amount ranging from 0.5 to 1.5 % by weight. 3. Use of the compositions according to claims 1 and 2 for the preparation of manufactured articles.

Inventors: BERTELLI, GUIDO, LOCATELLI, RENATO
Applicants: AUSIMONT S.R.L.
Application year: 1984
Main classification: C08L23
IPC codes: C08K5, C08K3, C08L23