FR2485027A1 - FLAME RETARDANT MIXTURE OF TRIARYLPHOSPHATES AND FLAME RETARDANT COMPOSITIONS - Google Patents

Abstract

MIXTURE ENSURING AN INCREASED IGNITION. IT INCLUDES A MIXTURE OF AROMATIC PHOSPHATES RESPONDING TO THE FOLLOWING AVERAGE FORMULA: (CF DRAWING IN BOPI) IN WHICH X REPRESENTS A WHOLE OR FRACTIONARY NUMBER INCLUDED BETWEEN SLIGHTLY MORE THAN 0 AND SLIGHTLY LESS THAN 3 AND REPRESENTS A WHOLE NUMBER OR INCLUDING THEREIN 1 AND 2. APPLICATION TO IGNITION OF A COMPOSITION OF POLY (OXYPHENYLENE) AND A STYRENE RESIN.

Description

The invention relates to a flame retardant mixture comprising

  a mixture of triaryl phosphates and a resi-

  consisting of normally flammable resinous material

and the flame retardant mixture.

  U.S. Patent No. 3,639,506 discloses a blend of poly (oxyphenylene) and styrene resin to which is added a flame retardant combination comprising a

  aromatic phosphate and a halogenated aromatic compound. This letter

  describes a wide variety of phosphates which can be used for the aromatic phosphate component of the mixture,

  a preference for triaryl phosphates, and recom-

  especially triphenyl phosphate. The breed

  United States of America No. 3 883 613 indicates that phosphorus

  trimesityl phate behaves itself as a very effective flame retardant in compositions of a poly (oxyphenylene) and

of a styrene resin.

  It has now been discovered that a new mixture of phos-

  triaryl phates, which contains at least one phosphate of which at least 1 or 2 of the three aryl groups are mesityl groups, and whose remaining group or groups are independently selected from the group consisting of the phenyl radical or the radicals

  xylyles was an effective flame retardant. We have again discovered

  green that, in resinous compositions containing a material

  normally inflammable resinous and mixing, the action igni-

  fugency of the mixture per unit weight of phosphorus is higher than

  than triphenyl phosphate (TPP) alone or phosphorus

  trimesityle phage (TMP) alone. Advantageously, this increase in flame retardancy is obtained when the resin is composed of poly (oxyphenylenes) and styrene resins, which are known in the art and described in US Pat. Nos. 3,639,506 and 3,883. 613, quoted above and in

  U.S. Patent 3,383,435.

  In general, the present invention provides

  point, in one of his creations, a flame retardant com-

  taking a mixture of aromatic phosphates having the following average formula:

CH3) 3 -X

  y where x represents an integer or fractional number between slightly more than 0 and slightly less than 3, and y represents an integer or fractional number between

1 and 2.

  In another embodiment, the invention develops a

  resinous composition comprising (A) a resinous resin material

  malin flammable and (B) an effective amount of the mixture

flame retardant indicated above.

  The invention will be better understood by reading the

detailed description which follows:

  Among the aromatic phosphates which may be

  part of the aromatic phosphate mixture, for example

  For example, triphenyl phosphate (TPP), diphenyl phosphate

  nity and mesityl (DPMP), dimesityl phenyl phosphate (DMPP), trimesityl phosphate (TMP), trixylyl phosphate (TXP), dixylyl phosphate and mesityl phosphate

  (DXMP) and dimesityl and xylyl phosphate (DMXP).

  In a preferred embodiment, y is 2, and the flame retardant mixture comprises at least 2 compounds selected from the group consisting of (a) triphenyl phosphate (TPP), (b) diphenyl phosphate and mesityl (DPMP), ( c) dimesityl phenyl phosphate (DMPP) and (d) trimesityl phosphate (RMP), provided that at least one of these two compounds is selected from the group consisting of DPMP and

  DMPP. The mixture preferably comprises at least 3 of these compounds.

  posed, and better still these four compounds.

  In another preferred embodiment, y represents 1, and the flame retardant mixture comprises at least 2 compounds selected from the group consisting of (a) trixylyl phosphate (TXP), (b) dixylyl phosphate and mesityl (DXMP), (c) dimesityl and xylyl phosphate (bMXP) and (d) phosphate

  trimesityle (TMP), provided that at least one of these 2

  posed is selected from the group consisting of DXMP and DMXP. The mixture preferably comprises at least 3 of these compounds, and more preferably these 4 compounds. - The flame retardant mixture can still include, in addition

  of the mixture corresponding to the previous average formula, phos-

  (isopropylphenyl) phates and for example tri (isopropylphenyl) phosphate, such as Kronitex K-50, which is found

in the trade.

  The normally flammable resinous material of the com-

  resinous position comprises one or more normally flammable resins, the fire behavior of which can be improved by the addition of substituted triaryl phosphates or

  no. It is well known in the art that these resins can

  For example, polyvinyl chlorides, poly (oxyphenylenes), cellulosic resins, and many polyesters may be used. In a preferred embodiment, the normally flammable resinous material comprises: (i) a poly (oxyphenylene) having the formula:

Q, Q,

  0 n Qil QI in which the oxygen atom of a motif is connected to the nucleus

  benzene of the adjacent motif; Q represents a mono substituent

  are selected from the group consisting of hydrogen, a hydrocarbon radical, a halogenated hydrocarbon radical having at least two carbon atoms between the halogen atom and the

  phenol nucleus, an oxyhydrocarbon radical and an oxyhydro-

  halogenated carbon having at least two carbon atoms between

  the halogen atom and the phenol ring, Q 'and Q "I' can represent

  have the same radicals as Q, and in addition a halogen, provided that Q, Q 'and Q "are all free of tertiary carbon atoms, and n represents an integer of at least 50, and

(ii) a styrene resin.

  Poly (oxyphenylenes) having the formula of component (i) above and processes for their preparation in U.S. Patent No. 3,306874 can be found,

3,306,875, 3,257,357, and 3,257,358.

  The styrene resin (ii), as described in the aforementioned U.S. Patent No. 3,383,435, has at least% by weight of polymer units derived from the compound of the formula:

R1 -

  (Z) p wherein R1 is hydrogen, (lower) alkyl or halogen, Z is a member selected from the group consisting of vinyl, halogen and (lower) alkyl; and p represents an integer between 0 and the number of replaceable hydrogen atoms on the benzene ring. For example, among the

  styrene resins, homopolymers such as poly-

  styrene and polychlorostyrene, modified polystyrenes

  rubber-modified polystyrenes (styrene

  high impact strength), and copolymers containing styrene

  such as styrene-acrylonitrile copolymers (SAN), copolymers

  styrene-butadiene resins, styrene-acrylonitrile copolymers O-alkylstyrene, styrene-acrylonitrile-butadiene copolymers

  (ABS), poly (v-methylstyrene), copolymers of ethylvinyl-

  benzene and divinylbenzene, etc. The alkyl groups (lower

  up to 6 carbon atoms.

  A ratio of poly (oxyphenylene) to styrene resin such that the latter is from 20 to 80% by weight is recommended. The poly (oxyphenylene) is preferably poly (2,6-oxydimethylphenylene-1,4). The styrene resin is preferably a resistance-modified rubber polystyrene

  to high shocks, such as that described in the United States Patent

United States of America No. 3,383,435.

  The way the flame retardant blend is added to the

  Normally flammable resinous composition is not critical.

  than. Each of the components is preferably added as part of a premix, passing it through an extruder, maintaining the extrusion temperature between about 2320 and 3370C, depending on the composition. It is possible to cool the base wires coming out of the extruder, the

  cut into pellets, re-extrude them, cut them into pastil-

  and mold them to the desired shape.

  The concentration of flame retardant blend in the composition

  resin is not critical and depends largely on the degree of

  flammability of the normally flammable resinous composition

  mable. When this last composition comprises a poly

  (oxyphenylene) and a styrene resin, the degree of

  Much depends on the concentration of the styrene resin

  and the nature of the styrene resin used. Composites

  with a lower concentration of resin

  of styrene or containing styrene resins which are less

  may have a lower concentration of

  giant. It is recommended, in general, a small concentration of

  flame retardant, a concentration of 0.5 to 15 parts per 100

  polymer stocks being generally acceptable, and a concentration

  from 1 to 10 parts per 100 being recommended, when

the styrene content allows it.

  This invention is further illustrated by the following nonlimiting examples: Preparation of a mixture of mesityl phosphates and

  xylyl from a mixture of polymethylphenols.

  It was added to a 250 ml flask equipped with stirring.

  a reflux condenser, a thermometer and a heater, 386 g of a mixture of polymethylphenols. The mixture

  consists of 75% 2,4,6-trimethyl phenol, 23% dimethyl-

  2,4 and 2,6-phenols, and 2,3,6-trimethyl phenol and anisoles.

  Phenolic compounds were combined with 153 g of phosphorus oxychloride and 8 g of magnesium chloride at 25 ° C.

  this mixture at 250 ° C. for six hours and hydrochloric acid

  that has been continually released. After purging the reaction mass with nitrogen, it was purified by distilling under

  empty the unreacted phenolic compounds.

  Gas chromatographic analysis showed

  that the flask contained 95% of a mixture of triazine phosphates

  After the phenolic compounds were removed, the yield of mixed mesityl and xylyl phosphates was 78%. The mixture of products is transparent and vitreous and has a freezing point of about 80 C. It is hereinafter referred to as "mixture of phosphates of mesityia and

of xylyl ".

EXAMPLE 1

  400 parts of poly (2,6-oxydimethylphenylene)

  1.4); 600 parts of resilient rubber modified polystyrene

  high shock rate Foster Grant 834; 5 parts of diphenyl and decyl phosphite; 15 parts of polyethylene; and 130 parts of the mixture of mesityl and xylyl phosphates in a Waring blender and extruded in a Werner extruder

  Pfleidererde 28 mm (rear 282 C, before 291 C, die 288 C).

  The extruded pellets are extruded again in the same conditions.

  then molded as standard test specimens in a 93.3g Newbury injection molding machine (nozzle, front, rear, all at 232 ° C., die: 77 ° C.). For comparative purposes, a second composition is prepared, exactly

  in the same way, except that half of the

  mixture of mesityl and xylyl phosphates with 65 g of phos-

  triphenyl phate and a third composition is prepared with a mixture of quality isopropylphenyl phosphates

commercial.

  Specimens of 1.587 mm thickness of all compositions are subjected to combustibility tests.

  igniting in a gas flame and measuring the time required

  prior to the extinction of the flame for each of the

  vettes according to the U.L. 94, modified. We also submit

  the molded parts to measurements of physical properties, the deflection temperature under load being measured

according to ASTM D.648.

  The results of the fire tests were reported on 5 test specimens and the physical properties in the

table 1:

TABLE 1

  Fire behavior and physical properties of poly (oxyphenylene) and polystyrene containing

  mesityl and xylyl phosphates. -

  Compositions compositions of the mixture of

A- B.- C

  Compositions (parts by weight) poly (2,6-oxymethyl-1,4-phenylene) high-impact polystyrene mixture of mesityl phosphates and xylyl triphenyl phosphate isopropylphenyl phosphite diphenyl and decylphenyl phosphite phosphate combustibility Mean time to extinction (s) 1st inflammation Mean time to extinction (s) 2nd inflammation

400 400

600,600 600

-

-

- 130

5

15

14 12 9

8 10 14

  Physical Properties: Deflection temperature under load C at 0, 182 daN / mm 2 96 91 84 Melting viscosity at 282 C -1 and 1500 s 1400 1200 1150 Impact strength Izod on notched specimen Joules / cm notch 1.76 1.76 1.39 Yellowing index 32 32 28 The composition according to the invention (composition A) has a significantly higher sag temperature under load and is, for its other properties, comparable to

other compositions.

EXAMPLE 2

  550.0 parts of poly (2,6-oxy-2,6-phenylphenyl)

  1,4-lene), 450.0 g of resistant rubber modified polystyrene

  high impact strength, 15 parts of polyethylene, 10 parts of diphenyl and decyl phosphite, 1.5 parts of zinc sulfide, 1.5 parts of zinc oxide, and 35 parts of the mixture of mesityl phosphates and xylyle and one molds them off

  same way as in Example 1. A second component is prepared

  the same way, except that one half of the mixture of mesityl and xylyl phosphates

  of triphenyl phosphate and a third

  using 35 parts of triphenyl phosphate.

  The average burn time (U.L.94 Test, 1st ignition) is measured on five test specimens with a thickness of 1.587 mm, as well as the physical properties, not to mention the bending temperature under load. The results have been reported in

Table 2.

TABLE 2

  Fire behavior and physical properties of poly (oxyphenylene) and poly (styrene) compositions containing the mixture

  of mesityl and xylyl phosphates.

compositions

D E F

  Compositions (parts by weight) poly (2,6-dimethyl-2,6-phenylene) polystyrene high impact strength mixture of mesityl phosphates and xylyl triphenyl phosphate polyethylene phosphite diphenyl and decyl zinc sulfide zinc oxide

550 550 550

450 450 450

18

- 17

15

  1.5 1.5 1.5 1.5 1.5 1.5 Combustibility test: Time to average extinction (s) of 5, 1st ignition

14 17 17

  Physical Properties: C depressed temperature under load C at 0, 182 daN / mm2 Melt viscosity at 282 C -1 and 1500 s1 Yellowness index Izod impact strength on notched specimen joules / cm notch 1.55

114 113

1.98 1.33

  The composition according to the invention (composition D) has a significantly higher sag temperature under load and is, for its other properties, comparable to

other compositions.

  Of course we can make other modifications,

  in the light of the preceding examples. For example, we can

  place poly (2,6-oxydimethyl-1,4-phenylene) with poly

  (2,6-oxydiphenyl-1,4-phenylene). With regard to polys-

  rubber tyrene of high impact resistance, it can be replaced by a homopolystyrene or a copolymer

  : 20 styrene and methyl methacrylate.

  In addition, other additives can be incorporated into

  positions of this invention, for conventional purposes, and for example pigments, plasticizers, fillers,

  reinforcement, etc. In addition, resins can be added

  third component, such as polyethylene in addition

  small concentration without departing from the scope of the invention.

  The compositions are useful for forming films, fibers,

  molded articles, etc. according to usual practice.

. '11.

Claims (11)

  1. Flame retardant mixture, characterized in that   takes a mixture of aromatic phosphates corresponding to the following average formula: C10e 4C   (CH3) wherein x represents an integer or fractional number between slightly more than 0 and slightly less than 3 and y represents an integer or fractional number between 1 and 2.   2. Mixture according to claim 1. characterized in that   that it comprises at least 2 compounds selected from the group   by (a) triphenyl phosphate (TPP), (b) phosphate   diphenyl and mesityl (DPMP), (c) di-calcium phosphate   phenyl (DMPP) and (d) trimesityl phosphate   (TMP), at least one of these two compounds being DPMP or DMPP.   3. Mixture according to claim 1, characterized in that y = 1 and in that the mixture comprises at least 2 compounds   selected from the group consisting of (a) trixyphosphate   lyle (TXP), dixylyl phosphate and mesityl (DXMP), (c) dimesityl phosphate xylyl (DMXP), and (d) trimesityl phosphate (TMP), at least one of these two compounds being the DXMP or the DMXP.   4. Mixture according to one of claims 1, 2 and 3,   characterized in that it still comprises phosphate sorting (Isopropylphenyl).   5. resinous composition, characterized in that it comprises (a) a normally flammable resinous material and (b) an effective amount of the flame retardant mixture according to one of the following:   any of claims 1 to 4.   6. resinous composition according to claim 5, characterized in that the normally flammable resinous material comprises: (i) a poly (oxyphenylene) corresponding to the formula: Q "Q <-04 4   Qi, QI in which the oxygen atom of a motif is connected to the nucleus   benzene of the adjacent motif; Q represents a mono substituent   are chosen from the group consisting of hydrogen, a radical   hydrocarbon cal, a halogenated hydrocarbon radical having at least two carbon atoms between the halogen atom and the   phenyl ring, an oxyhydrocarbon radical, and an oxyhydroxy radical;   halogenated hydrocarbon having at least two carbon atoms between   the halogen atom and the phenyl ring; Q 'and Q "may represent   have the same radicals as Q and, in addition, a halogen, provided that Q 'and Q "are all tertiary carbon-free alpha, and n is an integer of not less than 50, and (ii) a styrene resin.   7. resinous composition according to one of the claims   and 6, characterized in that the styrene resin is present in an amount of from about 80 to about 20% by weight of the weight of the components (i) and (ii) of the composition and   less than 25% by weight of units derived from a vinylaromatic compound   wherein R 1 is hydrogen, lower alkyl, or halogen, Z is vinyl, halogen or lower alkyl, and p is equal to 0 or   to an integer equal to the number of hydrogen atoms replacing çable on the benzene nucleus.   8. resinous composition according to one of the claims   , 6 and 7, characterized in that the flame retardant mixture is present in an amount of 0.5 to 15 parts by weight per 100   parts by weight of normally flammable resinous material.   9. resinous composition according to claim 8, characterized in that the flame retardant composition is present in an amount of 1 to 10 parts by weight per 100 parts by weight.   weight of normally flammable resinous material.   10. A resinous composition according to any one of   Claims 6 to 9, characterized in that the poly (oxyphenylene)   is poly (2,6-oxydimethyl-1,4-phenylene).   11. Resinous compositions according to any one of   Claims 6 to 10, characterized in that the resin of   Styrene is a Resistance Rubber Modified Polystyrene to high shocks.