DE2535263A1 - FLAME RETARDANT POLYCARBONATE COMPOSITION - Google Patents

Description

Flame retardant polycarbonate composition

The invention relates to an improved flame retardant polycarbonate composition of an aromatic carbonate polymer mixed with an organic alkali metal salt or an organic Alkaline earth metal salt or mixtures of the two. The improvement is that the polycarbonate has fibrous glass is admixed in an amount sufficient to make the polycarbonate compositions to make non-dripping.

There are already many flame retardant additives known to be used with blended with the polycarbonate to make such materials self-extinguishing or flame retardant. Such flame retardant additives are used in varying amounts to extinguish the burning of such products, which are inherently flammable.

609808/0951

However, even if the E ^j olycarbonat no longer burns with a flame so it drips but from still-hot particles underlying material can ignite.

It has now surprisingly been found that an aromatic Polycarbonate obtained by incorporating organic alkali metal salts or organic alkaline earth metal salts or Mixtures thereof have been made flame retardant by admixing glass fibers to the flame retardant polycarbonate non-dripping can be made.

The term glass fibers refers to glass silk and all glass fiber materials, derived therefrom includes, including fiberglass fabrics, strands, staple fibers, and fiberglass batt. The length of the glass threads and whether they are bundled into fibers and the fibers in turn into yarns, strands or rovings combined, or woven into mats, is also not critical to the present invention. However, if fibrous glass threads When used, they can first be formed and united into a bundle, also known as a strand. To the To tie threads together into a strand so that the strand can be handled, a binder or a binding agent is applied to the Glass threads applied. Then the strand can be made to the desired various lengths can be chopped briefly. It is convenient to have these strands in lengths from about 3.2 mm (1/8 inch) up about 2.54 cm (1 inch), preferably less than 6.4 mm (1/4 inch). These are called short-chopped strands. Some these binders are polymers such as polyvinyl acetate, especially polyester resins, Polycarbonate, starch, acrylic acid melamine, polyvinyl chloride, polyethylene oxide or polyvinyl alcohol. Preferably the composition contains from about 1 to about 50 weight percent glass fibers.

The composition according to the invention can also be fluorinated Contain polyolefin, as described in our own application 3669-8CH-1915, filed at the same time.

6,9808 / 0951

The composition according to the invention can furthermore also contain siloxanes as described in our own patent application 3671-8CH-2O14, filed at the same time.

The disclosure content of these two aforementioned applications is incorporated into the present application by this reference.

The present composition can also contain fluorinated polyolefin and siloxanes. The organic alkali metal and organic used herein Alkaline earth metal salts are described in detail in the following applications.

P 24 61 146.9 of December 23, 1974. This application discloses a flame retardant polycarbonate composition (s) in admixture aromatic carbonate polymer and a flame retardant additive which is the metal salt of monomeric or polymeric aromatic Sulfonic acids or mixtures thereof.

P 24 61 077.3 of December 23, 1974. This application discloses one flame retardant polycarbonate composition which blends an aromatic carbonate polymer and a flame retardant additive contains, which can be the metal salt of monomeric or polymeric aromatic sulfonic sulfonic acids or mixtures thereof.

P 24 61 145.8 of December 23, 1974. This application discloses one flame retardant polycarbonate composition which blends an aromatic carbonate polymer and a flame retardant additive contains, which is made from the metal salts of sulfonic acids more aromatic

P. Π Q, 9 Γι R / η Q r;

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- 4 ketones or mixtures thereof can exist.

P 24 60 937.8 of December 21, 1974. This application discloses a flame retardant polycarbonate composition (s) in admixture contains aromatic carbonate polymer and a flame retardant additive derived from the metal salts of heterocyclic sulfonic acids or mixtures thereof.

P 24 60 944.7 of December 21, 1974. This application discloses a flame retardant polycarbonate composition which in admixture aromatic carbonate polymer and a flame retardant additive derived from the alkali metal salts of halogenated methanesulfonic acids or mixtures thereof or mixtures of the alkali metal salts and the alkaline earth metal salts.

P 24 60 946.9 of December 21, 1974. This application discloses a flame retardant polycarbonate composition which in admixture contains aromatic carbonate polymer and a flame retardant additive derived from the metal salts of a halogenated non-aromatic May consist of carboxylic acid or mixtures thereof.

P 24 60 786.1 of December 21, 1974. This application discloses a flame retardant polycarbonate composition which in admixture aromatic carbonate polymer and a flame retardant additive derived from the metal salts of sulfonic acids of aromatic sulfides or mixtures thereof.

P 24 60 788.3 of December 21, 1974. This application discloses one flame retardant polycarbonate composition, the blend of an aromatic carbonate polymer and a flame retardant additive contains, which consist of the metal salts of monomeric or polymeric aromatic ether sulfonic acids or mixtures thereof can.

P 24 60 787.2 of December 21, 1974. This application discloses a flame-retardant polycarbonate composition which in admixture aromatic carbonate polymer and a flame retardant additive

Contains, which can consist of the metal salts of aliphatic and olefinic sulfonic acids and mixtures thereof.

P 24 58 968.2 of December 13, 1974. This application discloses one flame retardant polycarbonate composition which blends an aromatic carbonate polymer and a flame retardant additive contains, which can consist of the metal salts of monomeric or polymeric phenol ester sulfonic acids or mixtures thereof.

P 24 60 945.8 of December 21, 1974. This application discloses a flame retardant polycarbonate composition which in admixture contains aromatic carbonate polymer and a flame retardant additive which is unsubstituted or halogenated from the metal salts Oxocarboxylic acids or mixtures thereof can exist.

P 24 58 527.1 of December 11, 1974. This application discloses one flame-retardant polycarbonate composition in a blend contains aromatic carbonate polymer and a flame retardant additive, which is monomeric and from the metal salts of sulfonic acids polymeric aromatic carboxylic acids and esters and mixtures thereof can exist.

P 24 60 935.6 of December 21, 1974. This application discloses a flame retardant polycarbonate composition which in admixture contains aromatic carbonate polymer and a flame retardant additive derived from the metal salts of halogencycloaliphatic aromatic sulfonic acids can exist.

P 24 61 144.7 of December 23, 1974. This application discloses a flame retardant polycarbonate composition which in admixture contains aromatic carbonate polymer and a flame retardant additive derived from the metal salts of monomeric or polymeric aromatic Amidesulfonic acids or mixtures thereof can exist.

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P 24 61 063.7 of December 23, 1974. This application discloses a flame retardant polycarbonate composition which in admixture aromatic carbonate polymer and a flame retardant additive contains that of the metal salts of monomeric or polymeric aromatic Sulphonic acids or mixtures thereof can exist.

The disclosure content of this above-mentioned own older Patent applications are incorporated into the present application by this reference.

The metal salts mentioned in these applications as well as mixtures of any of these metal salts described in the aforementioned applications can be used in accordance with the present invention will.

Preferred balances include sodium 2,4,5-trichlorobenzene sulfonate; Sodium benzene sulfonate; Disodium naphthalene-2,6-disulfonate, sodium p-iodobenzene sulfonate; Sodium 4,4'-dibromobiphenyl-3-sulfonate; Sodium 2,3,4,5,6-pentachloro-betastyrene-sulfonate; Sodium 4,4'-dichlorodiphenyl sulfide-3-sulfonate; Disodium tetrachlorodiphenyl ether disulfonate; Disodium 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 calcium salt of 2,4,5-trichlorobenzenesulfonanilide-4'-sulfonate; Sodium 4 · - {i, 4,5,6,7,7-hexachlorobicyclo- (2.2.1 I -hept-5-en-endo-2-ylI-benzo] sulfonate; disodium hexafluoroglutarate; disodium chloranilate; and mixtures thereof. these salts are used in amounts of from 0.01 to about 10 wt .-% _/ by weight of the aromatic carbonate polymer.

Those used in practicing the present invention Aromatic carbonate polymers used are homopolymers and copolymers obtained by reacting a dihydric phenol with a carbonate precursor. The usable bivalent ones Phenols are bisphenols such as: bis (4-hydroxyphenyl) methane,

603808/0951

2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol-A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) ) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, etc .; dihydric phenol ethers such as: bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, etc .; Dihydroxydiphenyls such as: p, p ¹ -dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, etc .; Dihydroxyarylsulfones such as: bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, etc .; Dihydroxybenzenes, resorcinol, hydroquinone, halogen- and alkyl-substituted dihydroxybenzenes such as: 1,4-dihydroxy-2,5-dichlorobenzene, 1 ^ -dihydroxy-S-methylbenzene etc., and dihydroxydiphenyl sulfoxides such as: bis (4-hydroxyphenyl) sulfoxide, Bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, etc.. A variety of other dihydric phenols are also available to provide carbonate polymers and are described in the U.S.

. Described patents 2 999 835, 3 028 365 and 3 153 008 ¹ I are also suitable for the production of aromatic carbonate polymers are copolymers which are obtained from any of the aforementioned substances by copolymerization with halogen-containing dihydric phenols such as 2,2-bis- (3, 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, etc. have been prepared. It is of course possible to use two or more different dihydric phenols or a copolymer of a dihydric phenol and a glycol or a hydroxy- or acid-terminated polyester or a dibasic acid in the case that a carbonate copolymer or interpolymer instead of a homopolymer is used for the Making the aromatic carbonate polymers of the present invention is desired.

In practicing the present invention, you may Mixtures of any of the foregoing materials can also be used to provide the aromatic carbonate polymer.

The carbonate precursor can be either a carbonyl halide Be carbonate ester or a halogen formate. The carbonyl halides which can be used in the present invention are Carbonyl bromide, carbonyl chloride and mixtures thereof. Typical

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Representatives of the carbonate esters used in the present invention Can be used are diphenyl carbonate, di (halophenyl) carbonates such as di (chlorophenyl) carbonate, di (bromophenyl) carbonate, Di (trichlorophenyl) carbonate, di (tribromophenyl) carbonate etc., di (alkylphenyl) carbonate such as di (tolyl) carbonate etc., di (naphthyl) carbonate, Di- (chloronaphthyl) carbonate, phenyl tolyl carbonate, Chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof. The haloformates suitable for use include Bis-haloformates of dihydric phenols (bischloroformates des Hydroquinones, etc.) or of glycols (bishalogen formates of ethylene glycol, neopenyl glycol, polyethylene glycol, etc.). Although those skilled in the art are familiar with other carbonate precursors, but carbonyl chloride / also known as phosgene is the preferred one Carbonate precursors.

Also included are the polymeric materials made of bivalent Phenol, a dicarboxylic acid and carbonic acid. The same are disclosed in U.S. Patent 3,169,121 and the disclosure of that patent is incorporated herein by reference Registration recorded.

The aromatic carbonate polymers of the present invention are using a molecular weight regulator, an acid acceptor and a catalyst. The molecular weight regulators, which can be used in carrying out the method according to the invention include phenol, cyclohexanol, Methanol, para-tertiary-batylphenol, para-bromophenol, etc. Phenol is preferably used as a molecular weight regulator.

A suitable acid acceptor can be either an organic or an inorganic acid acceptor. A suitable organic one Acid acceptor is a tertiary amine and it includes such materials as pyridine, triethylamine, dimethylaniline, tributylamine, etc. The inorganic acid acceptor can, for example, be a hydroxide, a carbonate, a bicarbonate or a phosphate of an alkali or Be alkaline earth metal.

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It is obvious that other materials are also related can be used with the aromatic carbonate polymer of the present invention and include such materials as antistatic Agents, pigments, mold release agents, thermal stabilizers, ultraviolet light stabilizers, reinforcing fillers and the same.

The composition of the invention is made by mixing the aromatic Carbonate polymers made with the organic alkali metal or alkaline earth metal salts and the fibrous glass.

The following examples serve to further explain the principle and the practical implementation of the present invention. Unless expressly stated otherwise, the parts or percentages are parts or percentages by weight.

Example I.

A polycarbonate composition was prepared by extruding a homopolymer of 2,2-bis- (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol-A) which is obtained by reacting substantially equimolar amounts of bisphenol-A and phosgene in an organic medium with Triethylamine, sodium hydroxide and phenol had been prepared under standard conditions. The polymer obtained was then fed to an extruder operated at about 265.degree
nert.

265 ° C was operated and the extrudate was comminuted to pellets

The pellets were then injection-molded at about 315 ° C. into test rods with the dimensions of about 127 mm by 12.7 mm by about 1.6-3.2 mm thick. The test sticks (5 pieces for each additive listed in the table) were subjected to the test method according to Underwriters ¹ Laboratories, Inc. Bulletin 94, Combustion Test for Classification of Materials (hereinafter referred to as UL-94

609808/0951

7 5 3 5 ? B.

designated). According to this test procedure, the materials tested in this way were rated either with UL-94 V-O, UL-94 V-I and UL-94 V-II classified based on the results obtained with the five samples. The criteria for each of these V-classifications according to UL-94 are briefly as follows:

UL-94 V-O The average flaming and / or glowing

after removal of the pilot flame should not exceed 5 seconds and none of the samples should Drip particles that ignite absorbent cotton.

UL-94 V-I The average flame and / or glow

after removal of the pilot flame should not exceed 25 seconds and none of the samples should Drip particles that ignite absorbent cotton.

UL-94 V-II The average flaming and / or glowing

after removal of the pilot flame should not exceed 25 seconds and the samples drip flaming Particles which ignite absorbent cotton.

Furthermore, a test stick was used more than 25 seconds after removal the pilot flame burned, not classified according to UL-94, but the same was according to the standard conditions of the present Invention referred to as "burns". The UL-94 regulation also requires that all test sticks in an experiment must comply with the respective Must meet the V-rating, otherwise the five test rods are given the rating of the worst individual rod. For example, if 1 stick is rated UL-94 V-II and the other 4 test sticks are rated UL-94 V-O, then get all 5 bars the rating UL-94 V-II.

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The results are shown in the table below. Example II

0.5% by weight of sodium 2,4,5-trichlorobenzene sulfonate was added to the polycarbonate according to Example I admitted. The mixture was extruded, molded and prepared in the same manner as in Example I. described tested.

Example III

To the polycarbonate according to Example I were O ₁ 5 wt .-% of sodium 2,4,5-trichlorobenzenesulfonate, and optionally 6.0 wt .-% glass fibers. The mixture was extruded, molded and tested in the same manner as described in Example I.

The remaining compositions were made according to the procedures of Examples I through III.

The percentages by weight given in Examples II and III relate to the total composition.

Tabel Example of adding salt

II sodium-2,4,5-trichloro-

benzene sulfonate

III Sodium 2,4,5-trichlorobenzene sulfonate

IV sodium benzene sulfonate

V disodium naphthalene-2,6-disulfonate

VI ■ disodium tetrachloride

phenyl ether disulfonate

VII disodium tetrachlorodiphenyl ether disulfonate

VIII Sodium 2,3,4,5,6-pentachloro-betastyrene sulfonate

IX Sodium 4,4'-dichlorodiphenyl sulfide-3-sulfonate

X disodium 4,4'-dichlorobenzophenone-3,3'-disulfonate

XI Sodium 2,5-dichlorothiophene-3-sulfonate

XII Sodium Diphenylsulfone-3-sulfonate

XIII sodium dimethyl 2,4,6-trichloro-5-sulfoisophthalate

Revenue number
Glass in shear of the drops
Wt% wt% time (0) per 5 bars

13.4

3.4

10

0.5 6th _f o 4th ,8th 1.0 8th 5 , 0 1.0 6th , 0 4th , 6 0.5 - , 0 4th , 4 0.5 8th / 0 4th ,1 0.5 4th 3 , 6 0.5 ' 10 4th , 6

0.5 6.0 4.6

0.3 8.0 3.2
0.4 8.0 3.3

1.0 6.0 4.0

0
0

0
2

0
0

0
0
0

Evaluation burns

UL-94 V-II

UL-94 V-O UL-94 V-O

UL-94 V-O UL-94 V-II UL-94 V-O UL-94 V-O UL-94 V-O

UL-94 V-O UL-94 V-O UL-94 V-O

UL-94 V-O

in ■ v)

Tabel Example of adding salt

XIV

XV

XVI

XVII XVIII

Potassium salt of the sulfonic acid of dichlorophenyl-2,4,5-trichlorobenzenesulfonate

Calcium 2,4,5-trichlorobenzenesulfonanilide-4'-sulfonate

Sodium 4 '- (1,4,5,6,7,7-hexachlorbicyclo- (2.2.1 ^ - hept-5-en-endo-2-yi | - benzoisulfonate

Disodium hexafluorglutarate disodium chloranilate% by weight

Revenue

Glass in shing weight% time (01

number

the drop

per 5 bars

valuation

6.0

7.0

5.0

4.9

1 , 0 3 , 0 3 ,8th 0 1 , 0 - 2 , 0 5 , 6 0 0 , 2 6th , 0 4th , 3 0

UL-94 V-O

UL-94 V-O

UL-94 V-O UL-94 V-I UL-94 V-O

As can be seen from the data in the table, the polycarbonate composition drips then, if it contains fiberglass in addition to the flame retardant additives, it does not and will either rated with UL-94 V-O or UL-94 V-I.

Other flame retardant additives can produce similar results can be used instead of the substances listed in the table.

98 08/0351

Claims (4)

- 15 claims 1. Improved, flame-retardant polycarbonate composition of an aromatic carbonate polymer in admixture with a organic alkali metal salt or an organic alkaline earth metal salt or mixtures thereof, thereby characterized in that the flame-retardant polycarbonate contains glass fibers mixed in in sufficient quantities, to make the polycarbonate composition non-drip. 2. Composition according to claim 1, characterized in that that the glass fibers in an amount of 1.0 to about 50.0 wt .-%, based on the total weight of the polycarbonate. 3. Composition according to claim 1, characterized in that the organic alkali metal salt Is sodium 2,4,5-trichlorobenzene sulfonate. 4. Composition according to claim 1, characterized that the organic alkali metal salt is sodium benzene sulfonate. 609803/0951