NL8220052A - Non-dripping flame retardant polyester-carbonate compsn. - Google Patents

Abstract

Compsn. comprises (a) an aromatic polyester-carbonate resin, (b) at least one organic alkali(ne earth) metal salt of sulphobic acid and (c) a fluorinated polyolefin. Component (b) is pref. derived from unsubstd. monomeric or polymeric sulphonic acids, monomeric or polymeric aromatic sulphonesulphonic acids, sulphonic acids or aromatic ketones, heterocyclic sulphonic acids, sulphonic acids of aromatic sulphides, monomeric or polymeric aromatic ether sulphonic acids, olefinic sulphonic acids, monomeric or polymeric phenol ester sulphonic acids, sulphonic acids or monomeric and polymeric aromatic carboxylic acids and esters,halocycloaliphatic aromatic sulphonic acids, monomeric or polymeric aromatic amide sulphonic acids, monomeric or polymeric aromatic sulphonic acids and mixts. of these. (c) is pref. PTFE used in an amt. effective to retard dripping of the compsn. esp. 0.05-0.5 wt.% w.r.t. (a). (b) is present in a flame-retarding amt. esp. 0.2-2 wt.% w.r.t. (a). Specifically, claimed cpd. (b) is Na 2,4,5-trichlorobenzenesulphonate (I). The compsn.may also contain glass fibre. Prods. have good flame retardant and non-dripping properties.

Description

S 2348-1202 pct

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Flame retardant polyester carbonate containing compositions.

The invention relates to an improved flame retardant polyester carbonate material of an aromatic polyester carbonate which is mixed with an organic alkali metal salt of a sulfonic acid or an organic alkaline earth metal salt of a sulfonic acid or a mixture thereof, in which composition also a fluorinated polyolefin is included. in sufficient quantity to render the polyester carbonate material non-dripping.

It is known to make polycarbonate resins flame retardant and non-dripping by mixing an organic alkali metal salt or an organic sulfonic acid alkaline earth metal salt and a fluorinated polyolefin (U.S. Patent Application 949,964, filed October 10, 1978, and in the name of the same applicant as the present application). Polyester carbonate resins, however, are very different from polycarbonate resins. For example, polyester carbonates have a higher deformation temperature under load (generally about 28 ° C to about 33 ° C higher) than polycarbonates, and are usually more difficult to process (due to their higher intrinsic viscosity) than polycarbonates.

It is this difference in properties, especially the deformation temperature, that provides one of the main reasons for using polyester-carbonates instead of polycarbonates in certain applications. This is especially true in the case of a high temperature environment. Despite the disadvantage of the more difficult processability of the polyester-carbonate resin, it is still preferred in these applications over the polycarbonate resin because of its higher deformation temperature. However, this main advantage of polyester carbonates makes it particularly important that they be made flame retardant and non-dripping as they are used in high temperature environments where the chances of flaming and burning are increased.

It is known to those skilled in the art that modifying the physical properties of a polymer, for example imparting flame retardancy, by adding certain additive thereto, is largely an empirical technique and not scientifically predictable, ie the effects that a particular additive has on a particular polymer system will have little or no predictability. Thus, while a particular additive may have a particular effect on a particular polymer system, the same additive may give very different results when used in a different and different polymer system. Likewise, two fairly closely related additives can give completely different results when mixed with the same polymer.

8220052 - 2 -

The present situation is even more complicated since two completely dissimilar additives are used, namely (i) an organic alkali metal salt of a sulfonic acid or an organic alkaline earth metal salt of a sulfonic acid, and (ii) fluorinated polyolefin.

Therefore, there is a need for flame retardant and non-dripping aromatic polyester carbonate resins.

Description of the invention.

Surprisingly, it has been found that an aromatic polyester carbonate can be made both flame retardant and non-dripping by incorporating in the aromatic polyester carbonate (i) an organic alkali metal salt of a sulfonic acid, an organic alkaline earth metal salt of a sulfonic acid, or a mixture thereof, and (ii) a fluorinated polyolefin.

The polyester carbonates used in the present invention and the methods of their preparation are well known in the art, such as those described in U.S. Pat. Nos. 3,303,331, 3,169,121, 4,194,038 and 4,156,069, as well as in U.S. Patent Application 33,389 filed April 26, 1979 and in the name of the same applicant as the present application, all of which are incorporated herein by reference.

The polyester carbonates can generally be referred to as co-polyesters / containing carbonate groups, carboxylate groups and aromatic carbocyclic groups in the polymer chain, at least some of the carboxylate groups and at least some of the carbonate groups being directly bonded to ring carbon atoms of the aromatic carbocyclic groups. These polyester carbonates are generally prepared by reacting a bifunctional carboxylic acid or a reactive derivative of the acid, such as the acid dihalide, a divalent phenol, and a carbonate precursor.

The divalent phenols suitable for preparing the polyester carbonates useful in the present invention are generally represented by the general formula (1) of the formula sheet wherein A is an aromatic group such as phenylene, biphenylene , naphthylene, etc. E can be an alkylene or alkylidene group, such as methylene, ethylene, propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene, pentylene, isopentylene, pentylidene, isopentylidene, etc. When E is an alkylene or alkylidene group, it can also consisting of two or more alkylene or alkylidene groups joined by a non-alkylene or non-alkylidene group, such as an aromatic bridge group, a tertiary amino bridge group, an ether bridge group, a carbonyl 8220052-3 - bridge group, a silicon-containing bridge group, or a sulfur-containing bridge group such as sulfide, sulfoxide, sulfone, etc. Furthermore, E may be a cycloaliphatic group (e.g. cyclopentyl, cyclohexyl, etc.), a sulfur-containing bridge group, such as sulfide, sulfoxide or sulfone; an ether-5 bridge group; a carbonyl group; a tertiary nitrogen-containing group; or a silicon-containing bridge group such as silane or siloxy. R represents hydrogen or a monovalent hydrocarbon group, such as an alkyl group (methyl, ethyl, propyl, etc.), aryl group (phenyl, naphthyl, etc.), an aralkyl group (benzyl, ethylphenyl, etc.), an alkaryl group, or a cycloaliphatic group ( cyclo-10 pentyl, cyclohexyl, etc.) for. Y may be an inorganic atom, such as halogen (fluorine, bromine, chlorine, iodine), an inorganic group, such as the nitro group, an organic group such as the above-mentioned group R, or an oxy group, such as OR, only requiring that Y is inert with respect to and is not affected by the reaction components and reaction conditions. The letter m represents any integer ranging from and including 0 to the number of positions of A available for substitution; p represents an integer ranging from and including 0 to the number of positions of E available for substitution; t represents an integer with a value of at least 1; s is 0 or 1; and 20 u represents any integer, including 0.

When more than one substituent Y is present in the divalent phenol compound represented by formula (1), these substituents may be the same or different. The same applies to the substituent R. When s in formula (1) is 0 and u is not 0, the aromatic rings are directly bonded together without an alkylene group or other bridge group in between. The positions of the hydroxyl groups and of Y on the aromatic core groups A may be varied at the ortho, meta or para sites and the groups may be in vicinal, asymmetric or symmetrical relationship when two or more ring- carbon-30 atoms of the hydrocarbon group are substituted by Y and hydroxyl.

Some non-limiting examples of divalent phenols covered by formula (1) are: 2,2-bis (4-hydroxyphenyl) propane (bisphenol A); 2,41-dihydroxydiphenylmethane; 35 bis (2-hydroxyphenyl) methane; b is (4-hydroxyphenyl) methane; bis (4-hydroxy-5-nitrophenyl) methane; bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 8220052

I I

- 4 - 1.1-bis (4-hydroxy-2-chlorophenyl) ethane; 2.2-bis (3-phenyl-4-hydroxyphenyl) propane; bis (4-hydroxyphenyl) cyclohexylmethane; and 2.2-bis (4-hydroxyphenyl) -1-phenylpropane.

These divalent phenols can be used alone or as mixtures of two or more different divalent phenols.

In general, any bifunctional carboxylic acid or reactive derivative thereof, such as the acid dihalide, which is customary for the preparation of polyesters, can be used to prepare the polyester carbonates suitable for preparing the flame retardant, non-dripping compositions of the present invention. Generally, the cabonic acids that can be used are aliphatic carboxylic acids, aliphatic-aromatic carboxylic acids or aromatic carboxylic acids. The aromatic dicarboxylic acids or their reactive derivatives, such as the aromatic acid dihalides, are preferred as they give the aromatic polyester carbonates which are most suitable according to the present invention.

These carboxylic acids can be represented by the general formula (2) of the formula sheet, wherein R represents: an alkylene group, an alkylidene-20 group or a cycloaliphatic group, analogous to those mentioned above for E in formula (1); an alkylene group, alkylidene group or cycloaliphatic group with olefinic unsaturation; an aromatic group such as phenylene, naphthylene, biphenylene, substituted phenylene, etc .; two or more aromatic groups joined by non-aromatic bridging groups such as those defined by E in formula (1); or an aralkyl-2 group, such as tolylene, xylene, etc. R is a carboxyl or hydroxy group.

2

The letter q has the value 1 when R is a hydroxy group and the value 2 0 or 1 when R is a carboxyl group. Thus, the bifunctional acid is a monohydroxy-monocarboxylic acid or a dicarboxylic acid. For the purposes of the present invention, preference is given to the bicarboxylic acids or their reactive derivatives, such as the acid dihalides, with the aromatic dicarboxylic acids or their dihalides being even more preferred.

2

Thus, in these more preferred acids, R is a carboxyl group 1 and R is a divalent aromatic group such as phenylene, naphthylene, bi-phenylene, substituted biphenylene, etc .; two or more aromatic groups bonded by non-aromatic bridging groups; or a divalent aralkyl group. Some non-limiting examples of suitable preferred aromatic and aliphatic-aromatic dicarboxylic acids which can be used in preparing the polyester carbonates 82-2 00 5 2

• I

Suitable according to the present invention are phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, ο-, m- and p-phenylene diacetic acid; the multinucleated aromatic acids such as 2,2'-diphenyldicerboxylic acid and 1,4-naphthalenedicarboxylic acid. These acids can be used individually or as a mixture of two or more different acids.

The carbonate precursor can be a carbonyl halide, a carbonate ester or a haloformate. The carbonyl halides that can be used here are carbonyl chloride, carbonyl bromide and mixtures thereof. Examples of carbonate esters that can be used here are diphenyl carbonate, di (halophenyl) carbonates such as di (chlorophenyl) carbonate, di (bromophenyl) carbonate, di (trichlorophenyl) carbonate, di (tri-bromophenyl) carbonate, etc. ; di (alkylphenyl) carbonates such as di (tolyl) carbonate, etc., di (ndftyl) carbonate, di (chloronaphthyl) carbonate, phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof. The halogen formates suitable for use herein include bishalogen formates of divalent phenols (bischloroformates of hydroquinone, etc.), or glycols (bishalogen formates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). Carbonyl chloride, also known as phosgene, is preferred.

During the co-reaction between the divalent phenol, the carbonate precursor and the dicarboxylic acid or reactive derivative thereof, catalysts, molecular weight regulators and acid acceptors are also present. Examples of suitable molecular weight regulators are phenol, p-ter-butylphenol, etc. Examples of suitable catalysts are tertiary amines, quaternary ammonium compounds, quaternary phosphonium compounds, etc. Examples of suitable acid acceptors are tertiary amines, alkali metals. and alkaline earth metal hydroxides, etc.

The polyester carbonates suitable according to the present invention are the aromatic polyester carbonates obtained from divalent phenols, aromatic dicarboxylic acids or their reactive derivatives, such as the aromatic acid dihalides, eg dichlorides and phosgene. A very suitable group of aromatic polyester carbonates are those obtained from bisphenol-A; terephthalic acid, isophthalic acid or a mixture thereof or terephthaloyl dichloride, isophthaloyl dichloride or a mixture thereof; and phosgene. When a mixture of terephthaloyl dichloride nisophthaloyl dichloride is used, the weight ratio between terephthaloyl dichloride and isophthaloyl dichloride is about 5:95 - 95: 5.

The present invention relates to novel flame retardant 8220052 i <- 6 - and non-dripping compositions containing a mixture of: (a) an aromatic polyester carbonate resin, - (b) at least one compound selected from organic alkali metal salts of sulfonic acids and organic alkaline earth metal salts of sulfonic acids; and (c) a fluorinated polyolefin.

The fluorinated polyolefins used in the present invention as anti-drip agents are commercially available or can be prepared by known methods. They are white solids, which are obtained by polymerization of tetrafluoroethylene, for example in aqueous media with free-radical forming catalysts, such as sodium, potassium or ammonium peroxide disulfate, at about 690-6895 kPa and 0-200 ° C and preferably 20-100 ° C. See U.S. Patent 2,393,967 (Brubaker), which is incorporated herein by reference. Although this is not essential, it is preferred to use the fluorinated polyolefins in the form of relatively large particles, for example, with an average size of 0.3-0.7 mm, largely 0.5 mm. These are better than conventional polytetrafluoroethylene powders, the particles of which have a diameter of 0.05-0.5 millimicron. It is particularly preferred to use the relatively large particle size material because it tends to be easily dispersed in polymers and to bind them together into fibrous materials. These preferred polytetrafluoroethylenes are referred to as Type 3 by ASTM, and are commercially available from E.I. DuPont de Nemour 25 and Company under the trade name Teflon.

The amount of the fluorinated polyolefins used in the compositions of the present invention is an amount that prevents dripping. This is understood to mean an amount of a fluorinated polyolefin which is effective in controlling the dripping of flaming particles from a product formed of aromatic polyester-carbonate. Generally, this amount is about 0.01-3% by weight, based on the weight of the aromatic polyester carbonate resin. Preferably, the composition contains about 0.02-2% by weight of the polyolefin, based on the weight of the polyester carbonate, and even more preferably about 0.05-0.50% by weight. % polyolefin.

The organic alkali metal salts of sulfonic acids and organic alkaline earth metal salts of sulfonic acids used herein are fully described in the following applications and patents: (A) U.S. Patent 3,933,734 (Victor Mark and Thomas J. Hoogeboom).

8220052 i ι - 7 -

This patent describes a flame-retardant polycarbonate material, containing a mixture of an aromatic carbonate polymer and a flame-retardant additive, which may be a metal salt of a monomer or polymeric aromatic sulfonic acid or a mixture of these salts.

5 (B) U.S. Patent 3,948,851 (Victor Mark). This patent describes a flame-retardant polycarbonate material, containing a mixture of an aromatic carbonate polymer and a flame-retardant additive, which may be a metal salt of a monomer or polymer aromatic sulfonic sulfonic acid or a mixture of these salts.

10 (C) U.S. Patent 3,928,908 (Victor Mark). This patent describes a flame-retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame-retardant additive, which may be a metal salt of a sulfonic acid of an aromatic ketone, or a mixture of these salts.

15 (D) U.S. Patent 3,919,167 (Victor Mark). This patent describes a flame retardant polycarbonate material containing a mixture of aromatic carbonate polymer and a flame retardant additive, which may be a metal salt of a heterocyclic sulfonic acid or a mixture of these salts.

20 (E) United States Patent Application 429,125, filed December 28, 1973, entitled "A Flame Retardant Pcbly Carbonate Material", in the name of the same applicant as the present application. This application describes a flame-retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame-retardant additive, which may be an alkali metal salt of halogenated methanesulfonic acid or a mixture of alkali metal salt and alkaline earth metal salt.

(F) U.S. Patent 3,909,490 (Victor Mark). This patent describes a flame-retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame-retardant additive, which may be a metal salt of a sulfonic acid of an aromatic sulfide or a mixture of these salts.

(G) U.S. Patent 3,953,396 (Victor Mark). This patent describes a flame retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame retardant additive, which may be a metal salt of a monomer or polymer aromatic ether sulfonic acid or a mixture of these salts.

(H) U.S. Patent 3,931,100 (Victor Mark). This patent describes a flame retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame retardant 8220052-8 additive, which can be selected from metal salts of aliphatic and olefinic sulfonic acids, and mixtures thereof.

(I) U.S. Patent 3,978,024 (Victor Mark). This patent describes a flame-retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame-retardant additive, which may be a metal salt of a monomer or polymer phenol ester sulfonic acid or a mixture thereof.

(J) U.S. Patent 3,953,399 (Victor Mark). This patent describes a flame retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame retardant additive, which may be a metal salt of a sulfonic acid of a monomer or polymer aromatic carboxylic acid or an ester thereof or a mixture of these salts.

(K) U.S. Patent 3,917,559 (Victor Mark). This patent describes flame-retardant polycarbonate materials containing a mixture of an aromatic carbonate polymer and a flame-retardant additive, which may be a metal salt of a halo-cyeloaliphatic aromatic sulfonic acid or a mixture of these salts.

(L) U.S. Patent 3,951,910 (Victor Mark). This patent describes flame retardant polycarbonate materials containing a mixture of an aromatic carbonate polymer and a flame retardant additive which may be a metal salt of a monomer or polymeric aromatic amide sulfonic acid or a mixture of these salts.

(M) U.S. Patent 3,940,366 (Victor Mark). This patent describes a flame retardant polycarbonate material containing a mixture of an aromatic carbonate polymer and a flame retardant additive, which may be a metal salt of a monomer or polymer aromatic sulfonic acid or a mixture of these salts.

The above references A to M are incorporated herein by reference. The alkali or alkaline earth metal salts can be used as well as mixtures of any of the alkali or alkaline earth metal salts of these references.

These salts are used in a flame retardant amount. This is understood to include an amount of the salt which imparts flame retardant properties to the aromatic polyester-carbonate material. Generally, this amount is about 0.01-10% by weight, based on the weight of the aromatic polyester-carbonate resin, and preferably about 0.1-5% by weight, based on the weight of the aromatic polyester. carbonate resin, and even more preferably about 0.2-2%.

8 2. 2. 0 0 5 2 - 9 -

Preferred salts include sodium 2,4,5-trichlorobenzenesulfonate; sodium benzene sulfonate; disodium naphthalene-2,6-disulphonate; sodium p-iodobenzene sulfonate; sodium 4,4'-dibromobiphenyl-3-sulfonate; sodium 2,3,4,5,6-pentachloro-betastrene-sulfonate; sodium 4,4'-5 dichlorodiphenyl sulfide-3 sulfonate; disodium tetrachlorodiphenyl ether disulfonate; sodium 4,4'-dichlorobenzophenone-3,3'-disulfonate; sodium 2,5-dichlorothiophene-3-sulfonate; the sodium salt of diphenylsulfone-3-sulfonic acid; sodium dimethyl 2,4,6-trichloro-5-sulfoisophthalate; the potassium salt of the sulfonic acid of dichlorophenyl 2,4,5-trichlorobenzene sulfonate; the m 10 calcium salt of 2,4,5-trichlorobenzene sulfonanilide-4 sulfonate; sodium 4 '- (1,4,5,6,7,7-hexachlorobicyclo- [2.2.1] hepta-5-en-endo-2-yl) benzenesulfonate. As mentioned previously, these sulfonic acid salts can be used alone or as mixtures of two or more different salts.

The flame retardant, non-dripping compositions of the present invention may optionally contain the well known and used additives such as antioxidants, anti-static agents, mold release agents, colorants, impact modifiers, ultraviolet stabilizers, plasticizers, fillers, glass fibers, color stabilizers and hydrolysis stabilizers.

Description of the preferred embodiment. .

The examples below are given to further illustrate the present invention and do not limit the invention. Unless otherwise indicated, the parts or percentages reported are parts by weight or percentages by weight.

EXAMPLE I (control)

6 l of deionized water, 10 l of dichloromethane, 1910 g (8.36 mol) of bisphenol-A, 24 ml of trimethylamine, 3.4 g of sodium gluconate and 65 g (0.43 mol) of p are placed in a reactor equipped with a mechanical stirrer. tert-30 butylphenol. This reaction mixture is stirred and a mixture of 890 g of terephthaloyl dichloride and 160 g of isophthaloyl dichloride as a solution in dichloromethane with 25% by weight solid is added to the mixture with stirring over a period of 15 minutes. During the acid chloride addition, the pH is maintained in the range of 8.5-11.5 by addition of 25% aqueous sodium hydroxide. The resulting reaction mixture is then phosgenated by introducing phosgene at a rate of 36 g / minute for 15 minutes, the pH being adjusted to a value of 9.5-12 by addition of the aqueous sodium hydroxide. After the phosgenation has ended, 6 L of dichloromethane is added, the layer of salt solution is separated by centrifugation and the resin solution is washed with aqueous acid and with water. The resin is precipitated with steam and dried in a nitrogen bed drier with fluidized bed at about 116 ° C.

To this resin obtained as a product, small amounts (about 0.1 part by weight per 100 parts by weight of resin) of a phosphite as a color stabilizer are mixed with an epoxy resin as a stabilizer. This stabilized resin product is then fed to an extruder operating at a temperature of about 316 ° C to extrude the resin into strands, and the extruded strands are chopped,

10 to grains. The granules are then injection molded at about 327 ° C

formed into test specimens measuring approximately 6.35 cm x 1.27 cm x 0.32 cm.

Examples II-VII illustrate compositions that are outside the scope of the present invention since these compositions do contain an alkali metal or alkaline earth metal salt of a sulfonic acid but not a fluorinated polyolefin.

EXAMPLE II

To the aromatic polyester carbonate prepared according to the method of Example 1, 0.25 part by weight of sodium 2,4,5-trichlorobenzene sulfonate per 100 parts by weight. polyester carbonate resin added. The mixture 20 is extruded in the same manner as described in Example I and formed into test samples.

EXAMPLE III

To the aromatic polyester carbonate prepared according to the method of Example 1, 0.5 part by weight of sodium 2,4,5-trichlorobenzene sulfonate per 100 parts by weight. polyester carbonate resin added. The mixture is extruded in the same manner as described in Example I and formed into test samples.

EXAMPLE IV

To the aromatic polyester carbonate prepared according to the method of Example 1, 0.75 part by weight of sodium 2,4,5-trichlorobenzene sulfonate per 100 parts by weight. polyester carbonate resin added. The mixture is extruded in the same manner as described in Example I and formed into test bars.

EXAMPLE V

To the aromatic polyester carbonate prepared according to the method of Example I, 0.5 part by weight of a mixture of (i) the potassium salt of diphenyl sulfone-3-sulfonic acid and (ii) the dipotassium salt of diphenyl sulfone-3 .3'-disulfonic acid per 100 parts by weight. polyester carbonate resin added. The mixture is extruded in the same manner as described in Example 1 - 8220052

«I

- 11 - thirds and formed into test bars.

EXAMPLE VI

To the aromatic polyester carbonate prepared according to the method of Example I, 0.5 part by weight of a mixture of (i) the potassium-5 salt of diphenylsulfone-3-sulfonic acid and (ii) the dipotassium salt of diphenylsulfone-3 , 3'-disulfonic acid and 1.5 parts by weight. glass fibers per 100 parts by weight. of the polyester-carbonate resin. The mixture is extruded in the same manner as described in Example I and formed into test samples.

EXAMPLE VII

To the aromatic polyester carbonate prepared according to the method of Example I, 0.5 part by weight of a mixture of (i) the potassium salt of diphenylsulfone-3-sulfonic acid and (ii) the dipotassium salt of diphenylsulfone-3,3 disulfonic acid, and 3.0 parts by weight. glass fibers per 100 parts by weight. polyesterΛ carbonate resin added. The mixture is extruded in the same manner as described in Example I and formed into test samples.

Examples VIII-X illustrate the flame retardant, non-dripping compositions of the present invention.

EXAMPLE VIII

To the aromatic polyester carbonate prepared according to the method of Example I, 0.75 parts by weight of sodium 2,4,5-trichlorobenzenesulfonate and 0.12 parts by weight of polytetrafluoroethylene per 100 parts by weight. polyester carbonate resin added. The mixture is extruded in the same manner as described in Example I and formed into test samples.

EXAMPLE IX

0.5 parts by weight of sodium 2,4,5-trichlorobenzene sulfonate and 0.24 parts by weight of polytetrafluoroethylene per 100 parts by weight of the aromatic polyester carbonate prepared according to the method of Example 1. polyester carbonate resin added. The mixture is extruded in the same manner as described in Example I and formed into test samples.

EXAMPLE X

To the aromatic polyester carbonate prepared according to the method of Example 1, 0.75 parts by weight of sodium 2,4,5-trichlorobenzene sulfonate and 0.24 parts by weight of polytetrafluoroethylene per 100 parts by weight. polyester carbonate resin added. The mixture is extruded in the same manner as described in Example I and formed into test samples.

The examples below illustrate a composition of the present invention which also optionally contains glass fibers.

EXAMPLE XI

0.5 parts by weight of a mixture of (i) the potassium salt of diphenylsulfone sulfonic acid and (ii) the dipotassium salt of diphenyl- are prepared to the aromatic 8220052-12-polyester-carbonate prepared according to the method of Example I. sulfone-3,3'-disulfonic acid, 0.24 part by weight of polytetrafluoroethylene and 1.5 wt. din. glass fibers per 100 parts by weight. polyester carbonate resin added.

The mixture is extruded in the same manner as described in Example I and formed into test bars.

The test samples obtained in Examples I - XI were subjected to a test method to determine the flammability and dripping properties of these samples. This test method is a modification of ASTM D-3713. The modification consists in examining only 5 samples of each material, keeping a flame on the sample for only 60 seconds. According to this modified test method, the materials thus tested are rated as satisfactory and unsatisfactory, based on the results obtained from the examination of 5 samples. In short, the criteria for satisfying or not satisfying are the following: "Fulfills": If a sample extinguishes within 30 seconds after removal of the ignition flame and none of the samples drip burning particles that are approx. 30.5 cm below absorbent cotton will ignite 20.

"Does not pass": (i) any sample that does not go out within 30 seconds of the flame being removed; and / or (ii) any sample that - during the period of contact with the flame or after removal of the flame - forms 25 flaming droplets which ignite absorbent cotton placed about 30.5 cm below.

Furthermore, all 5 samples must be sufficient for the "satisfactory" rating to be awarded. If one of the 5 samples fails, all 5 sample bars are considered to be non-satisfactory.

The results of this test are given in Table A.

The samples obtained in Examples VIII - XI are also subjected to the following test method:

The deformation temperature under load (VTOL) of the formed samples was determined according to ASTM D-648, modified using 35 bars of the type of Example I;

The notched Izod impact strength (I-K) of the formed samples was determined according to ASTM D-256.

The results of these tests are given in Table B.

From the data in Table A, it is clear that to obtain 8220052-13 - the rating "satisfies" by the method of ASTM D-3713, the polyester carbonate material is both the fluorinated polyolefin and the alkali or alkaline earth metal salt of a sulfonic acid. should contain. However, this material need not also contain glass fibers. This is in sharp contrast to polycarbonate materials which, in order to be rated as satisfying according to ASTM D-3713, must contain (i) a fluorinated polyolefin, (ii) an alkali or alkaline earth metal salt of a sulfonic acid, and (iii) glass fibers. This is only another indication of the aforementioned difference between polyester carbonates and polycarbonates.

The data in Table B illustrate that these flame retardancy and non-dripping properties are achieved without any significant adverse effect on the other beneficial physical properties of the aromatic polyester-carbonate resin (the VTOL of the resin of Example 1). carries approx. 162 ° C and the IK is 3.95 joules / cm).

As mentioned previously, the composition of the present invention may optionally contain glass fibers. Glass fibers are here understood to mean glass silk, as well as all glass fiber materials obtained therefrom, including glass fabric, wicks, stable fibers and glass fiber mats. The length of the glass filaments and whether or not they are bundled into fibers and the fibers in turn bundled into yarns, cords or slivers, or woven into mats and the like, is not critical to the invention. However, when using fibrous glass filaments, one can first form and join them into a bundle known as strand. In order to tie the filaments into a strand so that the strand can be handled, a binder is applied to the glass filaments. Then the strand can be chopped to different lengths as desired. It is suitable to use the strands with lengths from about 0.32 cm to about 2.54 cm, preferably with a length of less than 0.64 cm. Preferably, the composition contains about 1-50% by weight of glass fibers.

Thus, it appears that the objectives set forth in the foregoing description are effectively achieved, and since certain changes may be made to the above method and compositions within the scope of the invention, the content of this application is illustrative and not meant in a restrictive sense.

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Claims (14)

An improved flame retardant, non-dripping polyester-carbonate-containing composition containing a mixture of: (i) an aromatic polyester-carbonate resin; (Ii) at least one compound selected from the group consisting of organic alkali metal salts of sulfonic acids and organic alkaline earth metal salts of sulfonic acids; and (iii) a fluorinated polyolefin. The composition of claim 1, wherein the organic alkali metal salts of sulfonic acids and organic alkaline earth metal salts of sulfonic acids are derived from acids selected from the group consisting of: unsubstituted monomeric or polymeric sulfonic acids; monomeric or polymeric aromatic sulfone sulfonic acids; Sulfonic acids of aromatic ketones; heterocyclic sulfonic acids; sulfonic acids of aromatic sulfides; monomeric or polymeric aromatic ether sulfonic acids; olefinic sulfonic acids; Monomeric or polymeric phenol ester sulfonic acids; sulfonic acids of monomeric and polymeric aromatic carboxylic acids and their esters; halo-cycloaliphatic aromatic sulfonic acids; monomeric or polymeric aromatic amide sulfonic acids; Monomeric or polymeric aromatic sulfonic acids; and mixtures thereof. The composition of claim 2, wherein the fluorinated polyolefin is polytetrafluoroethylene. The composition of claim 3, wherein the polytetrafluoroethylene 30 is present in an amount effective to prevent dripping of the composition. The composition of claim 4, wherein the amount is about 0.05-0.5 wt% based on the weight of the polyester carbonate resin. The composition of claim 4, wherein the organic alkali metal metal salt of a sulfonic acid or organic alkaline earth metal salt of a sulfonic acid is present in a flame retardant amount. The composition of claim 6, wherein the flame retardant amount is about 0.2-2% by weight, based on the weight of the polyester-carbonate resin. 8220052 - 17 - The composition of claim 6, wherein the aromatic polyester carbonate is obtained from a divalent phenol, a carbonate precursor and at least one aromatic dicarboxylic acid or a reactive derivative thereof. The composition of claim 8, wherein the divalent phenol is 5 bisphenol-A. The composition of claim 9, wherein the carbonate precursor is phosgene. 11. A composition according to claim 10, wherein the reactive derivative of the aromatic dicarboxylic acid is selected from the group consisting of isophthaloyl dichloride, terephthaloyl dichloride and mixtures thereof. The composition of claim 11, wherein the reactive derivative of the aromatic dicarboxylic acid is a mixture of isophthaloyl dichloride and terephthaloyl dichloride. The composition of claim 12, wherein the organic alkali metal salt of a sulfonic acid is sodium 2,4,5-trichlorobenzene sulfonate. The composition of claim 2, which contains glass fibers. ¥ 8220052