NL7900452A - Flame retardant thermoplastics - comprising arylene carbonate! aryl sulphone or aryl ether sulphone polymers and organic sulphonate salt - Google Patents

Abstract

Polyaryl sulphone, polyarylether sulphone or polyphenyl sulphide compsns., or blends of >=2 of these with polyarylene carbonate and/or ABS contg. an organic sulphonate as flame-retardant additive. Small amts. of 0.01-10% additive are required to meet UL-94 requirements.

Description

S 2348-916 Ned. * '* * * S'

P&C

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General Electric Company of Schenectady, New York, USA.

Flame retardant thermoplastic materials.

The invention relates to a flame-retardant thermoplastic material; more particularly, the invention relates to a material containing an organic sulfonate as a flame retardant additive in combination with one or more of the following materials: polyaryl sulfones, polyareyl ether sulfones, polyphenyl sulfides, mixtures of a polyaryl ether sulfone and a polyaryl sulfone, and mixtures of a polyaryl ether sulfone and a polyphenyl sulfide, mixtures of a polyarylsulfone and a polyphenyl sulfide, mixtures of a polyarylene carbonate and an acrylonitrile-butadiene-styrene copolymer (ABS), mixtures of a polyarylene carbonate, acrylonitrile-butadiene-styrene copolymer (ABS) and a polyarylsulfone , acrylonitrile-butadiene-styrene copolymer (ABS) and a polyaryl ether sulfone, mixtures of a polyarylene carbonate, acrylonitrile-butadiene-styrene copolymer (ABS) and a polyphenyl sulfide, mixtures of a poly-15-acrylene carbonate, acrylonitrile-butolene-styrene copolymer and bought two or more connections polyaryl sulfone, polyaryl ether sulfone and polyphenyl sulfide / 1 compositions The composition may further contain an organic halogen-containing compound as a flame retardant additive.

Due to the increasing concern for safety, more and more materials are provided that are safe for general and household use. In particular, there is a need for flame-resistant or flame-retardant products to be used by the ultimate user; this requires many products that must meet certain requirements set by the government and manufacturers of these products with regard to flame retardancy. A particular set of conditions used as a standard for flame retardancy is described in "Subject 94" of Underwriters Laboratories, Inc.;

This publication describes certain circumstances for the valuation of materials.

Many flame retardant additives are known which are used by mixing them with certain materials to make these materials flame retardant. These flame retardant additives P and mixtures of a polycarbonate and one or more compounds selected from polyaryl sulfones, polyaryl ether sulfones and polyphenyl sulfides.

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. / 2 are used in amounts of about 5-20% by weight to impart flame retardant properties to flammable products.

Aromatic carbonate polymers (polyarylene carbonates), polyaryl sulfones and polyaryl ether sulfones mixed with one another or with acrylonitrile-butadiene-styrene copolymer (ABS) exhibit a suitable flame retardancy that meets the requirements for certain thicknesses in "Subject 94" of Underwriters' Laboratories. Several flame retardant additives are known which render these materials flame retardant and are effective in various sizes.

10 While the above aromatic carbonate polymers (polyarylene carbonates), polyaryl sulfones and polyaryl ether sulfones sometimes meet the broad standard of Underwriters' Laboratories Subject 94 when used alone, they nevertheless exhibit longer quenching times than when used in combination with the present compounds .

Surprisingly, it has now been found that polyaryl sulfones, polyaryl ether sulfones, and mixtures of two or more of the following compounds: polyarylene carbonates, acrylonitrile-butadiene-styrene copolymers, polyaryl sulfones, and polyaryl ether sulfones, can be made flame retardant in these compositions as a small amount of an organic sulfonate. to include flame retardant additive.

The organic sulfonates suitable as flame-retardant additives according to the invention have the general formulas RSO-m "1" and 25 (RSO ^), in which M + represents an alkali metal ion and M '^ + an alkaline earth metal ion and R represents a group of the formula (1 ) or (2), in which formulas each of the symbols X is fluorine, bromine, iodine, a -MO ^ group or a group of the formula (3) of the formula sheet, X 'has the same meanings as X, n = 0-5 and m = 0-4.

The preferred flame-retardant additives are compounds of the formulas (4), (5), (6) and (7) of the formula sheet, in which the last formula X is Cl or Br and n a number with a value of 0-5 and mixtures thereof.

The amount of additive used is preferably about 0.01-10 parts by weight per 100 parts by weight of the composition. In a preferred embodiment, the amount of additive included in the composition is 0.5 parts by weight per 100 parts by weight of aromatic polycarbonate.

7900452 \ 3

In a second preferred embodiment, the amount of additive is 1.0 part by weight per 100 parts by weight. The compositions of the invention may also contain other flame retardant additives, pigments, dyes, fillers, stabilizers and the like.

It is also possible to further comprise in the composition agents which prevent the dripping of burning particles, for example fluorinated polyolefins, glass fibers, siloxanes and mixtures thereof. The compositions can be processed by conventional methods for thermoplastic materials, for example, injection molding, foaming molding, extrusion, blow molding and the like.

Preferred Embodiments

The invention is further illustrated by the following non-limiting examples.

EXAMPLE I

- from Union Carbide) 15 100 parts of polyacrylsulfone ("UDEL P-1700" / and 1 part of a compound of formula (4) were mixed by subjecting these materials to a dry tumbling operation. The resulting mixture was then passed into an extruder operating at about 265 ° C. The extrudate was comminuted into granules, which were then injection molded at approximately 300 ° C into test bars of approximately 12.7 cmx 1.27 cm x 0.16 cm. Five test rods were subjected to the test method described in "Subject UL-94" of Underwriters' Laboratories, "Burning Test for Classifying Materials." According to this test method, these materials are rated 25 VO, Vl, or V-2 at based on the results of five samples.

The ratings according to UL-94 are briefly described below: "94 V-0": Burning after removal of the ignition flame lasts no longer than 10 sec. and none of the samples drip off, wetting cotton wool which is about 12 inches below the sample. The total quenching time for all five samples (10 ignitions) is no more than 50 sec.

"94 V-1": Burning after removing the ignition flame does not last _ burning longer than 30 sec. and none of the samples drip particles that light cotton wool which is about 30.5 cm below the sample. The total quenching time for all five samples (10 ignitions) does not exceed 250 sec.

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Λ 4 "94 V-2": Burning after removing the ignition flame lasts no longer than 30 sec. Burning particles drip from the samples and burn only briefly; some of these particles light cotton wool about 30.5 cm below the sample. 5 The total quenching time for all five samples (10 stitches) does not exceed 250 sec.

A test state that lasts longer than 30 sec. remains lit after removal of the ignition flame, is classified as "burning"

(not according to UL-94 but according to the standards applied according to the invention). Furthermore, UL-94 requires that all test bars in each group must meet the V-type rating for this rating to be assigned to the group. Otherwise, the five bars receive the worst bar rating. For example, if one bar is classified as 94 V-2 and the other four are classified as 94 V-0, then the rating for all five bars is 94 V-2. Control test I

Control test bars were prepared as described above, but without the flame-retardant additive. The results of the control test bars are listed below: 20 Total quench time (sec.): 158.1

Extinction time range (sec.): 2.6 - 47.7

Number of dripping burning particles 2 per test state:

Evaluation: Burning In contrast, the results of test bars containing as a flame retardant additive 1 part by weight of a compound of the formula (4) per 100 parts by weight of "UDEL P-1700" (polyarylsulfone) are as follows: EXAMPLE I - With additive

Total extinguishing time (sec.): 30.0 30 Extinguishing period (sec.): 0.8-6.2

Number of dripping burning particles per test state: 0

Rating: 94 V-0

EXAMPLE II

A composition of 100 parts by weight of polyaryl ether sulfone ("PES 35 200 P" from ICI) and 0.5 parts by weight of a compound of formula (4) as a flame retardant additive was prepared in the same manner as in Example 1 and formed into test bars . Below are the results given ^ 0 ft Π i s 5 6 J ------ i 5 of flame tests with these rods, compared to control rods of the same material, but without additive:

Control test II

Total extinguishing time (sec.): 27.3 5 Extinction time range (sec.): 1.3-4.3

Number of dripping burning particles per test bar: 0

Rating: 94 V-0 EXAMPLE II - With additive

Total extinguishing time (sec.) 12.8 10 Extinction time range (sec.): 0.9-2.3

Number of dripping burning particles per test rod: 0

Rating: 94 V-0

EXAMPLE III

A composition of 100 parts by weight of a mixture of 90% by weight of poly (BFA) carbonate and 10% by weight of "RYTON P4" (a polyphenyl sulfide of

Phillips Chemical Co.) and 0.5 parts by weight of a compound of the formula as

(4) As a flame retardant additive, it was prepared in the same manner described in Example I and formed into test bars. Below are the results of flame tests with these rods, compared to 20 control rods of the same material, but without additives: CHECK TEST III

Total extinction time (sec.): 60 1)

Extinction time range (sec.): 3.3 - 15.8

Number of dripping burning particles per test bar: 3 25 Rating: 94 V-2 1) Only three bars were tested, the average quenching time per ignition (2 per bar) was 10 sec.

EXAMPLE III- With additive

Total extinction time (sec.): 26.9 30 Extinction time range (sec.): 0.8 - 5.5

Number of dripping burning particles per test bar: 0-1

Rating: 94 V-2

EXAMPLE IV

A composition of 100 parts by weight of a mixture of 90 wt.% Poly (BFA) carbonate and 10 wt.% Polyethersulfone ("PES 200S"

of I.C.I.) and 0.5 parts by weight of a compound of formula (4) as a flame retardant additive was prepared in the same manner as in Example I

7900452 • s 6 prepared and formed into test bars. Below are the results of flame tests with these rods, compared to control rods of the same material, but without additives:

AUDIT TEST IV

5 Total extinction time (sec.): 42 1)

Extinction time range (sec.): 0.9-11.2

Number of dripping burning particles per test rod: 2-3

Rating: 94 V-2 1) Only three bars were examined: the average quenching time 10 per ignition (2 per bar) was 7 sec.

EXAMPLE IV - With additive

Total extinction time (sec.): 31.4

Extinction time range (sec.): 1.7 - 5.4

Number of dripping burning particles per test bar: 0-1 15 Rating: 94 V-2

EXAMPLE V

A composition of 100 parts by weight of a mixture of 90% by weight poly (BFA) carbonate and 10% by weight polyether sulfone ("PES 300S" from ICI) and 0.5 part by weight of a compound of the formula (4) as a flame-retardant additive, it was prepared in the same manner as in Example 1 and formed into test bars. Below are the results of flame tests with these rods, compared to control rods of the same material, but without additives:

AUDIT TEST V

25 Total extinction time (sec.): 60 1)

Extinction time range (sec.): 6.6 - 13.8

Number of dripping burning particles per test rod: 2-3

Rating: 94 V-2 1) Only three bars were examined; the average quench time 30 per ignition (2 per bar) was 10 sec.

EXAMPLE V - With additive

Total extinction time (sec.) 29.4

Extinction time range (sec.): 1.1 - 5.5

Number of dripping burning particles per test bar: 0-1 35 Rating: 94 V-2

Any aromatic polycarbonate (polyarylene carbonate) can be used according to the invention, namely homopolymers and copolymers "9 0 0 -v 5 2 7 and mixtures thereof, which are prepared by reacting a divalent phenol with a carbonate precursor. bivalent phenols to be used: bisphenol-A (2,2-bis (4-hydrophyphenyl) propane), bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 5 4, 4-bis (4-hydroxyphenyl) heptane, 2,2- (3,5,31,5'-tetrachloro-4,4'-dihydroxydiphenyl) propane, 2,2- (3,5,31,5'-tetrabromo -4,41-dihydroxydi-phenyl) propane, (3,5, -dichloro-4,4'-dihydroxyphenyl) methane Other available bisphenol type bivalent phenols are described in U.S. Patents 2,999,835, 3,028,365 and 3,334,154.

It is, of course, possible to use two or more different bivalent phenols or a copolymer of a bivalent phenol with a glycol or with a polyester with terminal hydroxy or acid groups or with a dibasic acid when a carbonate copolymer instead of a homopolymer it is desirable for the preparation of the aromatic carbonate polymers to be used according to the invention. Mixtures of the above materials can also be used to provide the aromatic carbonate polymer.

As the carbonate precursor, a carbonyl halide, a carbonate ester or a haloformate can be used. As carbonyl-20 halides, carbonyl bromide, carbonyl chloride or a mixture thereof can be used. Representative carbonate esters that 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) carbonates such as di (tolyl) carbonate, etc., di (naphthyl) carbonate, di (chloronaphthyl) carbonate, phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof. Suitable halogen formates 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 called phosgene) is the preferred carbonate precursor.

Polymeric materials obtained from a divalent phenol, a dicarboxylic acid and carbonic acid can also be used. These materials are described in U.S. Patent No. 3,169,121.

The aromatic carbonate polymers (polyarylene carbonates) used according to the invention can be prepared using - - λ, Λ Λ »*

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One of a molecular weight regulator, an acid acceptor and a catalyst. Molecular weight regulators include monovalent phenols such as phenol, chroman-I, para-tert-butylphenyl, para-bromophenol, primary and secondary amines, etc.

Preferably, phenol is used as the molecular weight regulator.

Both an organic and an inorganic acid acceptor can be used. Examples of suitable organic acid acceptors are tertiary amines such as pyridine, triethylamine, dimethylaniline, tributyl-10 amine, etc. As an inorganic acid acceptor, one can use, for example, a hydroxide, a carbonate, a bicarbonate or a phosphate of an alkali metal or alkaline earth metal.

Any suitable catalyst which promotes the polymerization of bisphenol-A with phosgene can be used. Examples of suitable catalysts are a) tertiary amines such as triethylamine, tripropylamine and Ν, Ν-dimethylaniline; b) quaternary ammonium compounds such as tetraethylammonium bromide, cetyltriethylammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propylammonium bromide, tetramethyl ammonium chloride, tetramethylammonium hydroxide, tetra-n-butylammonium; and c) quaternary phosphonium compounds such as n-butyltriphenylphosphonium bromide and methyltriphenylphosphonium bromide.

Branched polycarbonates can also be used according to the invention; these branched polycarbonates can be prepared by reacting a polyfunctional aromatic compound with a divalent phenol and a carbonate precursor to yield a thermoplastic polycarbonate with random branching.

These polyfunctional aromatic compounds contain at least three functional groups, namely carboxyl, carboxylic anhydride, haloformyl or mixtures thereof. Examples of these polyfunctional aromatic compounds are: trimellitic anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesienic acid, benzophenophenetracetric carboxylic acid, benzarenophetracetric carboxylic acid. The preferred polyfunctional aromatic compounds are trimellitic anhydride, trimellitic acid and haloformyl derivatives thereof.

According to the invention, a mixture of a linear Λ Λ l * 0 can also be used

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9 use polycarbonate and a branched polycarbonate.

The polyaryl sulfones and polyaryl ether sulfones that can be used according to the invention are strong, stable plastics primarily used in heavy load applications. These materials are commercially available from various sources; for example, Union Carbide markets a product under the name "UDEL Polysulfone"; I.C.I. markets polyether sulfones of various qualities with different properties. The chemical structure and preparation of these materials are known and are discussed in detail in "Encyclopedia of Polymer Science and Technology", John Wiley & Sons, New York, 1969, Volume II, p. 747 ff.

The polyphenyl sulfides that can be used according to the invention are compounds such as "RYTON P4", a polyphenyl sulfide from Philips Chemical Company.

Likewise, the acrylonitrile-butadiene-styrene copolymers which can be used according to the invention are known commercially available products; these materials are thermoplastic polymeric materials which can be prepared from the three monomers or blends of copolymers or graft polymers such as, for example, polybutane diene to which graft styrene and acrylonitrile have been added. The chemical structure and preparation of these copolymers are known and are discussed in detail in "Encyclopedia of Polymer Science and Technology", Volume 1, page 436 et seq.

Of course, other materials may also be included in the compositions of the invention, for example, anti-static agents, pigments, mold release agents, thermal stabilizers, ultraviolet stabilizers, reinforcing fillers, and the like.

The compositions of the invention may further contain a minor amount of a halogen-containing flame retardant additive, preferably in an amount of about 0.01-5 parts by weight per 100 parts by weight of aromatic polycarbonate. Representative, non-limiting examples of halogen-containing flame retardant additives are hexabromobenzene, hexabromodiphenyl, hexachlorodiphenyl, decabromodiphenyl, decachlorodiphenyl, decabromodiphenyl ether, decachlorodiphenyl ether, 2,2- (3,3 ^ 5,51-tetrahydroxy-4,4'-4,4'-hydroxy) propane, 2,2- (3,31,5,5'-tetrachloro-4,4'-dihydroxydiphenyl) propane, an adduct of cyclohexane and 7900452

Claims (13)

A flame retardant thermoplastic material, containing an organic sulfonate as a flame retardant additive in combination with one or more of the following materials: polyaryl sulfones, polyaryl ether sulfones, polyphenyl sulfides, mixtures of a polyaryl ether sulfone and a polyaryl sulfone, mixtures of a polyphenyl sulfone and a polyphenyl of a polyarylsulfone and a polyphenylsulfide, mixtures of a polyarylene carbonate and acrylonitrile-butadiene-styrene copolymer (ABS), mixtures of a polyarylene carbonate, acrylonitrile-butadiene-styrene copolymer (ABS) and a polyarylsulfone, mixtures of a polyarylene-styrene-butyrene-polycarbonate-acrylonitrile-acrylate ) and a polyaryl ether sulfone, mixtures of a polyarylene carbonate, acrylonitrile-butadiene-styrene copolymer (ABS) and a polyphenyl sulfide, mixtures of a polyarylene carbonate, acrylonitrile-butadiene-styrene copolymer (ABS), and 2 or more compounds selected from polyaryl sulfones, polyaryl sulfones sulfones and polyphenyl sulfides, and mixtures of polycarbonate and one or more compounds selected from polyaryl sulfones, polyaryl ether sulfones and polyphenyl sulfides; and optionally an organic halogen-containing flame retardant additive. Flame retardant thermoplastic material according to claim 1, wherein the organic sulfonate is a compound of the general formula + 2+ + 2+ RSO ^ -M or (RSO ^^ M ', where M represents an alkali metal ion and M' an alkaline earth metal ion and R is a group of the formula (1) or (2), wherein each of the symbols X is a fluorine atom, a bromine atom, an iodine atom, a -NC 2 group or a group of the formula (3), X 'has the same meanings as X, n = 0-5 and m = 0-4. Flame retardant thermoplastic material according to claim 1 or 2, wherein the organic sulfonate is a compound of the formula (7), in particular a compound of the formula (4) or (6), or a compound 7900452 Flame retardant thermoplastic material according to claims 1-3, wherein the organic sulfonate is present in an amount of from about 0.01-10 parts by weight per 100 parts by weight of the composition. The flame retardant thermoplastic material of claim 4, wherein the organic sulfonate is present in an amount of about 0.5-1.0 parts by weight per 100 parts by weight of the composition. 6. Flame-retardant thermoplastic material according to claims 1-5, 10 also containing a sufficient amount of an agent that prevents the dripping of burning particles from occurring, namely a fluorinated polyolefin, glass fibers, a siloxane or a mixture thereof. Flame retardant thermoplastic material according to claims 1-6, also containing a halogen-containing flame retardant additive. Flame retardant thermoplastic material according to claims 1-7, containing an organic sulfonate as flame retardant additive in combination with one or more compounds selected from polyarylene carbonates, acrylonitrile-butadiene-styrene copolymer (ABS), polyarylsulfones, polyaryl ether sulfones and polyphenyl sulfides. The flame retardant material of claim 8, wherein the acrylonitrile-butadiene-styrene copolymer is present in an amount up to about 50% by weight of the composition. Flame retardant thermoplastic material according to claim 8 or 9, containing an organic aryl sulfonate as a flame retardant additive in combination with a mixture of a polyarylene carbonate and acrylonitrile-butadiene-styrene copolymer (ABS). A flame retardant thermoplastic material according to claim 8, containing an organic sulfonate as a flame retardant additive in combination with a polyaryl ether sulfone. 11 is A of formula (5), wherein in formula (7) X represents Cl or Br and n represents a number having a value of 0-5, or a mixture thereof. Flame retardant thermoplastic material according to claim 8, containing an organic sulfonate as a flame retardant additive in combination with a polyarylsulfone. A flame retardant thermoplastic material according to claim 8, containing an organic sulfonate as a flame retardant additive in combination with a polyphenyl sulfide. 7 η, λ * \ /,? n J <J l v i.