DE2653327A1 - FLAME RETARDANT POLYCARBONATE COMPOSITION - Google Patents

Description

Flame retardant polycarbonate composition

The invention relates to a non-opaque, flame-retardant polycarbonate composition, the mixture special aliphatic Contains sulfonic acids, the aromatic polycarbonate and the additive having a refractive index in the range of 1.54 to 1.65. The invention also relates to articles made from this non-opaque, flame-retardant polycarbonate composition have been manufactured.

The present invention represents a further development of the earlier patent application P 24 60 787.2 of December 21 1974 described invention.

With the increased security requirements, there is a Trend also for use in public and in the Budget to create safe materials. A special concern

709822/0937

May consists in creating flame retardant or flame retardant Products or flame retardant, non-opaque products for use by the end consumer. Because of This requirement many products are required, which meet certain flame retardant criteria, both by the local as well as the state administrative bodies as well as by the manufacturers of such products.

A special set of conditions used as the standard measure for the flame retardant properties used can be found in Underwriter's Laboratories, Inc. Bulletin 94. This bulletin specifies certain conditions under which materials regarding the self-extinguishing properties.

Many flame retardant additives are described in the literature, which are mixed with products to make them self-extinguishing or Γ lamb-roughening. As is well known these flame retardant additives are used in amounts from 5 to 20 Gew. ^ Used, u'.i such flammable products self-extinguishing close. T-Is has also been found to have this Could a disadvantageous effect on the flame retardant <\ raw material can result in a loss valuable physical properties of the raw material makes noticeable, sneeze; Especially if you are acquainted flammhen'.mende With "'" cl -ait polycarbonate resin base materials used. Many of these hekannfon additives have a deteriorating effect Effect on the polymer.

In many cases it is desirable that those made from the fire retardant Articles made from polycarbonate resins retain their non-opaque properties.

"tberrasc forming ^Vv \ veise nun.rehr was found that a non-opaque aromatic Polycarbonai by incorporating 0.001 to about '1.0 wt." certain additives can be made flame-retardant while retaining the "non-opaque properties", whereby the additive has the formula:

709322/0937

BATH ORIGINAL

-Jr-

(. Λ rl) II ₁ A it) (, uU _M iu) 1.

m s <- η> —I ρ

wherein X is an electron withdrawing radical, M is a metal selected from the group consisting of alkali metals and alkaline earth metals, R ^{1 is} an aryl radical having 1 to 2 aromatic rings, R is an aliphatic radical having 1 to 10 carbon atoms, η and m are integers from 0 to 11, s is an integer from 0 to 5 and ρ is an integer from 1 to 4, or mixtures thereof, with the proviso that when s is 0, R is an aliphatic radical Is 2 to 10 carbon atoms and X is chlorine or bromine or mixtures thereof, wherein the polycarbonate and said additive have an index of refraction in the range 1.154 to 1.65. Such compositions can easily be formed into non-opaque articles. Particularly preferred molded articles are in the form of a sheet (plate) and a pellet.

The refractive indices of the materials described herein were determined by the immersion method which Arnold Weissberger in "Physical Methods of Organic Chemistry", Interscience Publishers, Volume II, IGSO (page 1433) is.

When the index of refraction of the present additives is in the range of the index of refraction of the aromatic carbonate polymer is 1.54 to 1.65 then the polycarbonate composition is and the molded article made therefrom is not opaque. That means that he is able to light let through and it is translucent to transparent. Depending on how close the index of refraction of the additive at the index of refraction of the polycarbonate is determined by the composition obtained, whether it is transparent or translucent. If the additive is in the concentration used partially or completely soluble in the polycarbonate polymer

709822 / 0S37

is borrowed, then the composition and that obtained from it Object all the more transparent.

The metal used in practicing the present Metal salt used in the invention is selected from Sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium.

The aliphatic sulfonic acids that are used in the practice of the present invention may be substituted with an electron withdrawing group. in the Any electron withdrawing group can be used in the practice of the present invention will. However, it is preferred if the electron withdrawing The remainder is halogen, nitro, trihalomethyl and cyano electrons withdrawing remainder is.

The electron withdrawing phenomenon, also called electronegativity was referred to by Roberts and Caserio in "Basic Principles of Organic Chemistry" 1964, pages 185-186 and by Jack Hine in "Physical Organic Chemistry" McGraw-Hill Book Company, Inc. 1962, pages 5, 32 and 85-93. Preferred connections are:

Potassium 3,4-dichlorotoluene- <Λ -sulfonate Sodium-2-bromoethane-1-sulfonate
Potassium 2-chlorithane-1-sulfonate.

The compositions of the present invention can contain fillers, Pigments, dyes, antioxidants, stabilizers, ultraviolet light absorbers, mold release agents, etc. Furthermore, the molded object can be coated with, for example, damage-resistant or scratch-resistant coatings be.

In the following examples, all parts and percentages are based on weight, unless otherwise stated is.

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Example I. H

100 parts of an aromatic polycarbonate, which was produced by reacting 2,2-bis (4-hydroxyphenyl) propane and phosgene in the presence of an acid acceptor and a molecular weight regulator and which had an intrinsic viscosity of 0, 57 was mixed with 0.20 parts of a finely ground dehydrated additive listed in Table 1 by mixing the ingredients together in a laboratory paddle mixer. The resulting mixture was then fed to an extruder which was operated at about 265 ° C. b
was crushed into pellets.

out, which was operated at about 265 C and the extrudate

The pellets were then injection molded at about 315 ° C into test sticks measuring about 127 mm by 12.7 mm by about 1.587 mm to 3.175 mm (5 inch by 1'2 inch by 1'16 to 1/8 inch) and formed into test squares measuring about 50, W mm 50, H mm χ about .3,175 mm (2 inches 2 inches χ about 1'8 inches). The test sticks (5 sticks for each additive as listed in the table) were subjected to the test procedure as described in the Underwriter's Laboratories, Inc. Bulletin UL-94 Combustion Test for Classification of Materials. According to this test procedure, the tested materials were classified into VO, VI or V-II based on the results of five samples. The criteria for each V value (V stands for vertical) according to UL-94 are briefly as follows:

"V-O" Average flame and / or glow after Removal of the pilot flame should not exceed 5 seconds and none of the samples should be flaming Drip particles that ignite absorbent cotton.

"V-I" Average post-flare and / or glow The pilot flame should not be removed for 25 seconds

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and the annealing should be in the vertical direction migrate no further than 0.318 cm (1'8 inch) in the sample after the flame has gone out, and the glow is said to be incapable of igniting absorbent cotton.

"V-II" Average flashing and / or glowing after removing the pilot flame should not be for 25 seconds and the samples drip off burning particles that ignite absorbent cotton.

In addition, it should be said that a test stick that after removal the pilot flame burns longer than 25 seconds, is not classified according to UL-i> 4 eir-classified, but according to the standards of the present invention is referred to as "burns". Furthermore, UL-94 requires that all test sticks in each test group the V-rating must meet the special classification to achieve. Otherwise, the five test sticks are given the rating of the worst individual stick. For example, if one staff is classified as V-II and the other four rods are classified as V-O, then the rating for all five bars V-II.

The test plates were based on a Gardner X / 10-CDM machine the light transmission tested. The data shows the amount of the incident light that passes through the test plates, with air as the medium with 100% permeability was taken as the basis.

The results with the various additives in the frame of the present invention are listed below, with a control experiment using the aromatic polycarbonate was carried out using no additive from the \ rt mentioned above.

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Table 1

Additive (0.20 parts light revenue number UL-94 Bepro one hundred) through- drop rating

lazy time per 5 keitC?) (sec. ) . Test rods

Control experiment B6

Potassium 3,4-dichlorotoluene-c / s-sulfonate SO

Sodium 2-fluoro-4-bromotoluene-o ^ -sulfonate 75

Potassium 2- (4-chlorophenyl)
-athane-1-sulfonate 70

Lithium 2,2-diphenylethane-1-sulfonate 66

38.9 4.2, 3.9 5, 2 6.2

14th

burns

V-O

V-O

V-I

V-I

Example II

This example was done to demonstrate the effect of the additive of the present invention at ranges of 0.10 parts per hundred parts of the polycarbonate.

In making the test samples of this example, 100.00 parts of the polycarbonate of Example I were mixed with 0.10 parts of the additives listed in Table 2 are mixed using the same procedure. The test samples were then described using the same as described in Example I. Process shaped. The test samples were then subjected to the test procedure according to Bulletin UL-94 according to Example I, the following results were obtained:

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_ f. _
Table 2 \ nnumber
drops
per 5
Test sticks UL-S4
valuation Additive (0.10 parts
per hundred) Extinction
Time
(Seconds) 18th
0
3 burns
VO
V-II Control attempt
Disodium-1,2-ethansul-
fonat
Sodium 1-decanesulfonate 11.6
• 4.2
R, 2 Example III

This example was done to demonstrate the effect of the additive of the present invention at ranges of 0.20 parts per hundred parts of the polycarbonate.

In making the test samples of this example,
100.00 parts of the polycarbonate according to Example I with 0.20 parts of the additives listed in Table 1 using
mixed using the same procedure. The test samples were
then molded using the same procedure described in Example I. The test samples were then subjected to the Bulletin UL-94 test procedure of Example I, with the
the following results were obtained:

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-S-
Table 3 Additive (0.20 parts
per hundred) Extinction
Time
(Seconds) number
drops
per 5
Test sticks UL-e4
valuation Control attempt 26th 13th burns Sodium 2,4 dichlorotoluene
oC sulfonate • 3.7 1 V-II Sodium-2-bromoethane-l-sul-
fonat 2.8 2 V-II Potassium-2-chlorothane-l-sul-
f onat 4.8 0 V-O Lithium-2,3,4-trichloro-l-
methylnaphthalene-x-sulfonate 4.6 2 V-II Sodium triphenylmethanesul-
fonat 6.6 0 V-I

Example IV

This example was done to demonstrate the effect of the additive of the present invention at ranges of 0.50 parts per hundred parts of the polycarbonate to demonstrate.

In making the test samples of this example,
100.00 parts of the polycarbonate according to Example I with 0.50 parts of the additives listed in Table 4 using
mixed using the same procedure. The test samples were
then molded using the same procedure described in Example I. The test samples were then also the
Subjected Bulletin UL-94 to the test procedure of Example I with the following results:

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- ie -

Table \

Additive (0.50 parts per hundred ")

Extinction

time fseconds)

\ nnumber
drops
per 5
Test sticks

U L-94 rating

Control attempt 26

Potassium 2,5-dichloro-p-xylene sulfonate "5.1

Dipotassium-2,1, H ₇ c £ ^ft -tetrachloromesitylene- <*., O <. ' -disul-

sonat! 3

13th

burns V-I

V-O

Example V

The effect of the additive to demonstrate the present invention in ranges from 1.0 parts per hundred parts of ^o olycarbonats This example was carried out.

In making the test samples of this example, 100.00 parts of the polycarbonate ".jach Example I" was 1.0 part using the additives listed in Table F. mixed using the same procedure. The test samples were then molded using the same procedure used in Example I. The test samples were then sent to the bulletin Subjected to UL-04 test method according to Example I, the the following results were obtained:

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Table 5

Additive (1.0 part
per hundred ")

Extinction

time (seconds)

■ '.number
drops
per 5
Tests tribe

U L-St rating

Control attempt Ί1, Γ>

Sodium-2,4-dichlorotoluene
^ -sulfonate "3.7

Disodium-2,1,5, R-tetrachlor-

m-xylene - ^ ,, - ^ '- disulfonate 1,6

Calcium pentabromotoluene; ^ -

sulfonate 2, f;

18th

burns

V-II

V-O

V-O

Example VI

This example was carried out to demonstrate the effect of a well-known, commercially available flame retardant additive to demonstrate.

Example I was repeated with the exception that only a part of decabromodiphenyl ether was used instead of the additives used therein. After ^A iuswertung five Teststfiben results obtained were the same as those obtained in the control experiment shown in Table 1.

Example VII

This example was done to the effect of well-known , commercially available flame retardant additives too demonstrate.

Example V was repeated with the exception that instead of the additive used therein, only a part 1,2,5,6,9,10-

Hexabromocyclododecane was used. After evaluating The results obtained from five test bars were the same as those obtained in the control experiment listed in Table ο became.

B.

Experiment A above was repeated using 5% by weight of decabromodiphenyl ether. The results obtained were the same as obtained in Experiment A above.

The above experiment Λ was repeated using 10 wt. ^R i 1, 2, 5, 6, 9, 10-hexabromocyclododecane. At this addition level, the test bars were rated "V-II" in accordance with UL-94. The polycarbonate was severely degraded, which was visible through very dark stripes on the molded test rods. Such degradation does not occur when the additives of the present invention are used.

Example VIII

Example VII was repeated with the exception that the additive used therein consisted of a combination of antimony oxide and a material which was a mixture of polychlorinated Diphenyl (\ roclor from Monsanto Company) was. The proportions of the constituents of this additive that are in this Example used were based on 3 parts of chlorine per 1 part of antimony. The results obtained with 1 wt.% And with 5 wt% amounts obtained were the same as in Example III.

For larger amounts, at 10 wt.%, A flame-retardant effect was found which was, however, in turn, associated with severe degradation of the polycarbonate, which by a

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There was a significant reduction in the intrinsic molar viscosity of the molded test rods, and when molded, the intrinsic molar viscosity of the test rods with 1% by weight of the aforementioned additive was about 0.50. The intrinsic viscosity of the molded test bars containing 10 wt.% Of the flame retardant additive according to this example contain, was 0.253. This clearly shows the severe degradation of the polycarbonate when this type of known flame retardant is used.

As mentioned above, the additive of the present invention contains the alkali or alkaline earth metal salts of substituted and unsubstituted aliphatic sulfonic acids and mixtures thereof. The term aliphatic indicates that the carbon atoms are ₍₃ M SO) group bound directly to, and even if these carbon atoms or an aromatic ^ö

carry several / residues, then they will be chemical and for the purpose of the present classification as aliphatic designated. Albeit a large number of aliphatic sulfonic acid salts η are listed in the tables of the examples of the present invention, they are only representative Examples of the additives of the present invention.

Any aromatic polycarbonate having an index of refraction from 1.54 to 1.65 can be used in the practice of the present invention. They are homopolymers and copolymers, and mixtures thereof, made by reacting a dihydric phenol with a carbonate precursor. Typical examples of some of these dihydric phenols which can be used in the practice of the present invention are: bisphenol-A, (2,2-bis (4-hydroxyphenyl) propane), bis (4-hydroxyphenyl) methane, 2 , 2-bis (4-hydroxyphenyl-3-methylphenyl) -propane, 4,4-bis (4-hydroxyphenyl) -heptane, 2,2- (3,5,3 *, 5 * -tetrachloro-4,4 ' -dihydroxydiphenyl) -propane, 2,2- (3,5,3 ', 5 ^f -tetrabromo-4, 4' dihydroxydiphenyl) -propane, (3,3'-dichloro-4,4 * -dihydroxyphenyl) -

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methane, other dihydric phenols are of the bisphenol type also available and they are described in U.S. Patents 2,999,835, 3,028,365 and 3,334,154.

It is of course possible to have two or more different ones dihydric phenols or a copolymer of a dihydric phenol with a glycol or hydroxy or acid terminated Polyester or with a dibasic acid to be used in the case of a carbonate copolymer or interpolymer rather than a homopolymer for use in making the aromatic carbonate polymers of the present invention it is asked for. Mixtures of any one can also be used in practicing the present invention of the foregoing materials can be used to create the aromatic carbonate polymer.

The carbonate precursor iaui deweaer a carbony halide, be a carbonate ester or a haloformate. The carbonyl halides, which can be used according to the invention, are carbonyibromide, carbonyl chloride, and mixtures thereof. Typical examples of the carbonate esters which can be used herein are diphenyl carbonate, di (halophenyl) carbonates such as di (chlorophenyl) carbonate, di (bromophenyl) carbonate, di (trichlorophenyl) carbonate, di (tribromophenyl) carbonate etc., di (alkylphenyl) carbonates such as di (tolyl) carbonate etc., di (naphthyl) carbonate, di-chloronaphthy-D carbonate, Phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, etc. or mixtures thereof. The halogen formates that are used for the Suitable uses in the present invention include bis-haloformates of dihydric phenols (bischloroformates of hydroquinone etc.) or of glycols (bishalogen forms of ^ 'ethylene glycol, neopenty! glycol, polyethylene glycol etc.). Although other carbonate precursors are readily known to those skilled in the art, carbonyl chloride is also known as phosgene, the preferred carbonate precursor.

7 0 9 8 2 2/0937

- / If.

Also included are the polymeric derivatives of a divalent one Phenol, a dicarboxylic acid and carbonic acid. The same are disclosed in U.S. Patent 3,169,121, whose Disclosure content through this reference in the present Registration is recorded.

The aromatic carbonate polymers of the present invention can be prepared using a molecular weight regulator, an acid acceptor and a catalyst. When carrying out the method according to the invention Molecular weight regulators used include monohydric phenols such as phenol, chroman-I, paratertiary butylphenol, parabromophenol, primary and secondary mines, 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 one organic S-Mur acceptor is a tertiary amine and includes Materials like pyridine, triethylamine, dimethylaniline, tributylamine etc. The inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate or a phosphate an alkali or alkaline earth metal.

The catalysts that can be used in the present application are any suitable catalysts, which support the polymerization of bisphenol-A with phosgene. Suitable catalysts include tertiary amines such as for example triethylamine, tripropylamine, N, N-dimethylaniline, quaternary ammonium compounds such as tetraethylammonium bromide, Cetyl-triethylammonium bromide, tetra-n-heptylammonium iodide, Tetra-n-propylammonium bromide, tetramethylammonium chloride, tetramethylammonium hydroxide, tetra-n-butylammonium iodide, Benzyltrimethylammonium chloride and quaternary phosphonium compounds such as n-butyltriphenylphosphonium bromide and methyl triphenyl phosphonium bromide.

70 9 822/0937

-w-

Also included are branched polycarbonates in which a polyfunctional aromatic compound with the divalent Phenol and the carbonate precursor has been reacted to make an arbitrarily branched thermoplastic To yield polycarbonate.

These polyfunctional aromatic compounds contain at least three functional groups that are the carboxyl group, the carboxylic acid anhydride group, the halogenform group or mixtures thereof. Examples of these polyfunctional aromatic compounds that may be used in the practice of the present invention include: trimellitic anhydride, Trimellitic acid, trimellityl trichloride, 4-chloroformyphthalic anhydride, Pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenone tetracarboxylic acid, Benzophenone tetracarboxylic anhydride and the like. The preferred polyfunctional aromatic Compounds are trimellitic anhydride or trimellitic acid or their halogenoform derivatives.

Blends of a linear polycarbonate are also included and a branched polycarbonate.

7 '

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Claims (8)

Claims 1. Non-opaque ΐ lamb-retardant polycarbonate composition, characterized in that it contains in a mixture an aromatic carbonate ^{polymer and 0.001 to 2.0 wt. "7} -, based on the polymer of an additive with the following formula: (X * ϊΜ where X is an electron withdrawing group, M is an alkali or alkaline earth metal, R ^{1 is} an aryl group consisting of 1 to 2 aromatic rings, R is an aliphatic group with 1 to 10 carbon atoms, η and m are integers from 0 to 11, s is an integer is from 0 to 5 and ρ is an integer from 1 to 4; or mixtures thereof, with the proviso that when s is 0, R is an aliphatic radical of 2 to 10 carbon atoms and X is chlorine or bromine, the aromatic carbonate polymer and the additive having a refractive index in the range from 1.54 to 1.65 exhibit. 2. Composition according to claim 1, characterized that the electron withdrawing residue is a halogen, nitro, trihalomethyl or cyano radical or a mixture thereof. 3. Composition according to claim 1, characterized that the additive sodium 2-bromoethane-l-sulfonate is. 4. Composition according to claim 1, characterized that the additive potassium 2-chloroethane-l-sulfonate is. 709822/0937 ORIGINAL INSPECTED - In the- - 5. Composition according to claim 2, characterized that the additive potassium 3,4-dichlorotoluene-oC-sulfonate is. 6. Shaped article, characterized in that it has a refractive index in the area from 1.51 to 1.65 and formed from a composition according to any one of the preceding claims is. 7. Shaped article according to claim 6, characterized marked that he has the shape of a Has foil. 8. Shaped article according to claim 6, characterized in that it has the shape of a Has pellets (tablet). 709822/0937