A method of reducing the allocation of phosphine from red phosphorus and fire protective polymer composition

 

(57) Abstract:

Use: in the manufacture of fire-protected polymeric materials and products from them. The inventive fire-protected polymer composition comprises a flame retardant 20-80 wt.% the product of the interaction of red phosphorus with cinnamon transliterator, taken in an amount of 0.1-100% by weight of red phosphorus. The relative content of phosphine 14 days in a sealed flask containing 1 g of red phosphorus and 1 g cinnamon translitered, when the moisture content of 70% to 0.22%. 2C. and 5 C.p. f-crystals, 4 PL.

The invention relates to a technology for fire protective polymer materials and products and related method of reducing the allocation of phosphine from red phosphorus and polymer compositions containing as a flame retardant, red phosphorus, either in the form of pre-treated red phosphorus, or in conjunction with uterine mixtures, or by adding a process connection that meets the present invention.

Red phosphorus, in itself, is a well-known inhibitor of ignition of polymeric materials. However, even at ambient temperatures it tends to medlen, phosphine is released in greater quantities. At atmospheric oxidation of the red phosphorus tends to allocation of phosphorous acid, hydrogen and phosphine, acting as the decomposition products of which the most dangerous is phosphine.

Masterbatches containing red phosphorus and a polymer that is widely used, for example, in the electrical industry, including as a cable cover. It's delivered in large quantities and stored until use. For this reason it is important, both from an economic and environmental point of view, to the selection of phosphine from red phosphorus contained in the fallopian mixtures were minimal.

There is a method of reducing the allocation of phosphine from red phosphorus treatment of carbonyl-containing compounds, as well as fire protective polymer composition comprising a thermoplastic thermosetting polymer, 1-20 wt. red phosphorus as a flame retardant and 0.01-3.00 wt. aliphatic or aromatic aldehyde or beta-ketone carbonyl-containing as an inhibitor of the formation of phosphine [1, 2] it is Noted that the aldehyde or ketone interact with formed by the decomposition of the red phosphor is FINA from red phosphorus treatment acyclic aliphatic compounds, containing an unsaturated double carbon-carbon bond and an electron-withdrawing group located in the alpha position relative to the double bond, when the mass ratio of the red phosphor and unsaturated acyclic aliphatic compounds, respectively, 5-95 5-50.

For example, red phosphorus treated with oligomers or polymers based on maleic, fumaric, crotonic and methacrylic acids or their anhydrides, including their esters, for example methyl methacrylate.

In the application described is also fire-protected polymer composition comprising a thermoplastic or thermosetting polymer and 0.2-20 wt. red phosphorus treated with the above unsaturated acyclic aliphatic compound containing in the alpha position electroencephalo group, taken in the mass ratio of the red phosphor, respectively, 5-50 50-95.

According to the formula of the invention, the red phosphor is mixed with a polymer-based unsaturated maleic and fumaric acids. However, the examples include only one specific compound of this type, namely: imido-4,4-diphenyl-methane-bis-maleic acid (BMEM).

In addition, given n red phosphorus in the composition should include oxides of metals.

Due to the high toxicity of phosphine even a relatively small quantity allocated in examples 1, 2 and 5, are too high. Therefore, in accordance with the data only with the addition of copper oxide can be eliminated selection of phosphine.

According to the present invention, a method for reducing the allocation of phosphine in which there is no need to add metal oxides.

It was found that acyclic aliphatic compounds containing at least one double carbon-carbon bond, which is in the alpha position relative to at least one group, dilatory electrons are effective in minimizing allocation of phosphine from red phosphorus.

Accordingly, the technical problem to be solved by the present invention is directed, is a decrease in the allocation of phosphine from red phosphorus.

The mentioned technical problem is solved by a method of reducing the allocation of phosphine from red phosphorus interaction with acyclic aliphatic compound containing ethylene unsaturated bond in the alpha position relative to electroanatomic the secure link in the alpha position relative to the electron-withdrawing group, use cinnamon translegal in the amount of from 0.1 to 100% by weight of red phosphorus, preferably in an amount of 5% by weight of red phosphorus.

The mentioned technical problem is solved also fire protective polymer composition containing as a flame retardant product of the interaction of red phosphorus with acyclic aliphatic compound containing ethylene unsaturated bond in the alpha position relative to the electron-withdrawing group, and according to the invention contains as a named product of the interaction of red phosphorus with cinnamon transliterator, taken in an amount from 0.1 to 100% by weight of red phosphorus, the content in the composition of the polymer 20-80 wt. named flame retardant 20-80 wt.

Preferably fire-protected polymer composition comprises 50 wt. polymer and 50 wt. these flame retardant.

As fire protective polymer polymer composition may contain a thermoplastic polymer selected from the group comprising polyethylene, polypropylene, polystyrene, high impact polystyrene, copolymer of Acrylonitrile-butadiene-styrene copolymer is a styrene-butadiene-styrene and a copolymer of styrene with butadiene.

For example, fire is amide, polyester, polyacrylate or a vinyl polymer.

The composition according to the invention may contain, in addition, thermosetting polymer is selected from the group comprising polyepoxide resin, polyurethane, phenolic resin, urea resin and polyurea.

Preferred implementations of the present invention are illustrated by the following examples.

Example 1. A method of reducing the allocation of phosphine from red phosphorus.

1 g of red phosphorus powder is mixed with 1 g of the inhibitor. The mixture is placed in a sealed conical flask of 250 ml, equipped with a gasket, which allows the selection of gas. The humidity in the flask is maintained at the level of about 70% for what it is connected to a tube containing saturated mixed salt solution of ammonium chloride and potassium nitrate. The amount of phosphine in the flask was measured after 14 days, which produce gas analysis in the throat space on a gas chromatograph equipped with flame photometric detector. The calibration is performed relative to the cylinder with a known concentration of phosphine in nitrogen (see table.1).

Example 2. A decrease in the allocation of phosphine from masterbatches containing red phosphor is Elena low density (LDPE) (melt flow index, equal to 7). The mixture is stirred and ekstragiruyut through 25/25-odnochastny extruder, equipped with a mixer, remove voids. Royal blend tabletirujut, and the content of phosphine control by placing 1 g of masterbatches in the flask, 250 ml, as described in example 1 (see tab.2).

Example 3. A decrease in the allocation of phosphine from fire protective polymeric composition.

Uterine mixture in an amount of 160 g, prepared as described in example 2, is added to 850 g of low density polyethylene (LDPE) (melt flow index equal to 7) and molded by injection molding, receiving the samples in the form of rods, each of which weighs 8,4, the Rod is cut in half and placed in a flask of 250 ml to control the content of phosphine as described in example 1 (see tab.3).

Example 4. A decrease in the allocation of phosphine when using media inhibitor.

Cinnamon translegal in the amount of 2.5 g dissolved in 10 g of acetone and impregnated with carbon black, taken in an amount of 5 g Acetone is evaporated. The treated carbon black is then injected into the low-density polyethylene (melt flow index equal to seven) for the preparation of masterbatches containing the inhibitor with the media, and determined the, the manual shrink selection of phosphine from red phosphorus according to the invention and of fire protective polymer composition according to the invention are characterized by greater efficiency of inhibition allocation of phosphine than previously known technical solutions.

1. A method of reducing the allocation of phosphine from red phosphorus interaction with acyclic aliphatic compound containing Ethylenediamine bond in the alpha position relative to electroanatomic group, characterized in that as an acyclic aliphatic compounds containing Ethylenediamine bond in the alpha position relative to the electron-withdrawing group, use cinnamon translegal in an amount of 0.1 to 100.0% by weight of red phosphorus.

2. The method according to p. 1, characterized in that the cinnamon translegal used in an amount of 5% by weight of red phosphorus.

3. Fire protective polymer composition containing as a flame retardant product of the interaction of red phosphorus with acyclic aliphatic compound containing Ethylenediamine bond in the alpha position relative to the electron-withdrawing group, characterized in that it contains as the named product pogo phosphorus, when the content in the composition of the polymer is 20 to 80 wt. named flame retardant 20 to 80 wt.

4. The composition according to p. 3, characterized in that it contains 50 wt. polymer and 50 wt. these flame retardant.

5. The composition according to PP.3 and 4, characterized in that it contains a polymer selected from the group comprising polyethylene, polypropylene, polystyrene, high impact polystyrene, copolymer of Acrylonitrile-butadienestyrene, a styrene-butadienestyrene and a copolymer of styrene with butadiene.

6. The composition according to PP.3 and 4, characterized in that it contains a polymer selected from the group comprising polyamide, polyester, polyacrylate or a vinyl polymer.

7. The composition according to PP.3 and 4, characterized in that it contains a polymer selected from the group comprising polyepoxide resin, polyurethane, phenolic resin, urea resin and polyurea.

 

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1 tbl, 1 ex

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2 tbl, 6 ex

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