DE3000660A1 - NON-FLOWING FLAME RETARDANT THERMOPLASTIC COMPOSITION - Google Patents

Description

Non-blooming flame retardant thermoplastic composition

The invention relates to new flame retardant thermoplastic compositions and it is particularly directed to non-blooming compositions of high molecular weight polyesters in combination with flame retardant amounts of brominated diphenyl ethers with 5 to 8 bromine atoms.

The use of high molecular weight polyesters in thermoplastic molding dimensions <3i is generally known to the person skilled in the art. Such polyester provide masses with excellent malleability and the objects molded from them have smooth and shiny surfaces, high strength, rigidity, temperature resistancekext and other desirable properties.

A major disadvantage of using such polyesters in molding compositions however, is their usually high flammability. The flammability of the polyester is already through use of halogen, phosphorus or nitrogen-containing additives

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and such compositions are in numerous Patents and publications. Flame retardant thermoplastic polyester compositions are used Desired for numerous areas of application, such as in the home, in the manufacture of automobiles and Aircraft, as packaging, as electrical devices and the like.

Particularly in the case of polyesters from the poly (alkylene

Co-

dicarboxylate) group and the related / polyesters are difficult have been shown to render such materials flame retardant without impairing their superior toughness properties will. In particular, the use of the conventional flame retardant additives in conventional amounts causes a reduction in toughness, for example impact resistance, ductility and dimensional stability in the Heat under load, especially in the glass-filled designs.

useful

It is already of an extraordinarily / class of flame retardant Agents have been reported containing polybrominated diphenyl ether compounds of the formula

wherein the total of χ and y ranges from 2 to 10 lies. Such flame retardants are described in US patents

3 624 024, 3 751 396, 3 873 491, 3 971 752, 4 010 219 and

4,070,332 - the disclosure of these US patents is incorporated into the present application in its entirety by this reference. Although diphenyl ethers

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30006C0

with 2 to 10 bromine atoms, for example in US Pat. _{No. 4,219, have been identified as being useful and preferably Brr., Br fi} "and Br ₁ " analogs (in combination with decabromodiphenyl) are used, dripping during firing Furthermore, the decabromodiphenyl ether analog, which is the economically used flame retardant of the polybrominated diphenyl ether family in poly (1,4-butylene terephthalate) resin compositions, exhibits the undesirable property of migrating to the surface of articles molded from the compositions. This property, known as "blooming" or "wandering", is not only unacceptable for aesthetic reasons, but also causes a breakdown in the electrical surface properties of the parts molded from these compositions which contain decabromodiphenyl ether as a flame retardant.

It has now been found that when polybrominated diphenyl ethers in the range from pentabromodiphenyl ether to octabromodiphenyl ether are used, flame-retardant compositions are obtained which show no tendency to bloom when they are exposed to high temperatures for a certain period of time. Furthermore, such compositions can be created, without adversely affecting the other desirable characteristics, such as toughness, of the known polyester resin compositions will.

For example, by adding a Br ₁ - to Br "-diphenyl ether additive, compositions are created which are in the

Flame-retardant in a way that they meet the requirements

nit of Underwriter Laboratories with respect / fulfill self-extinguishing compositions and the same time does not bloom or migrate to the surface of the molded parts when the same aged for 1 hour, 24 hours and 168 hours at oven temperatures of from 100 ⁰ C 140 ⁰ C and 170 ⁰ C. will.

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In contrast, decabromodiphenyl ether forms by blooming on the surface under the same conditions Powder that endangers the electrical properties.

It is accordingly a primary object of the present invention to provide a class of flame retardant polyester compositions to create that are resistant to blooming.

Another object of the invention is to provide flame retardant To provide polyester compositions which have excellent moldability and which are post oven-aged smooth and shiny surfaces, their high flexural strength and their superior electrical surface properties maintained.

Other objects and advantages of the present invention will become apparent from the detailed description below.

According to the present invention, non-blooming, flame retardant thremoplastic compositions containing:

(a) a normally flammable high molecular weight polyester;

(b) a flame retardant amount of a polybrominated diphenyl ether compound the formula

wherein χ + y is 2 to 10 and

(c) an effective amount of an organic or inorganic one

flame retardant synergistic compound, the improvement being that as a component

(b) a compound or mixture of compounds is used

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in which the sum of χ and y for each compound is neither less than 5 nor greater than 8, being a composition is obtained from which the polybrominated flame retardant does not bloom or migrate after molding.

The designation "normally flammable high molecular weight polyesters" generally includes linear saturated condensation products of diols and dicarboxylic acids or corresponding derivatives the same. They preferably contain the condensation products of aromatic dicarboxylic acids and aliphatic acids Diols. It is also possible to use polyesters, such as poly- (1,4-dimethylol-cyclohexane) -dicarboxylate, for example to use terephthalates. In addition to the phthalates, small amounts of others can also be used in preferred compositions aromatic dicarboxylic acids such as naphthalenedicarboxylic acid or aliphatic dicarboxylic acids such as adipic acid. The diol component can in the same way in the preferred embodiments by adding small amounts of cycloaliphatic Diols can be varied. In any case, the preferred polyesters are known as film and fiber formers and they will created by the methods set forth in U.S. Patents 2,465,319 (Whinfield) and 3,047,539 (Pengilly) and others Are described. The preferred polyesters contain a poly (alkylene terephthalate, isophthalate, or mixed) isophthalate / terephthalate, for example up to 30 mol% isophthalate), the alkylene groups being 2 to 10 carbon Have atoms, for example poly (ethylene terephthalate) or poly (1,4-butylene terephthalate). Because of their rapid crystallizability from the melt, it is preferred to use poly (1,4-butylene terephthalate) to be used as the normally flammable polyester resin of the present compositions.

The molecular weight of the polyester component should be sufficiently high to have an intrinsic viscosity of about 0.6 to 2.0 dl / g, preferably 0.7 to 1.6 dl / g, measured for example

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wisely as a 1% solution in a 60:40 mixture of phenol and Tetrachloroethane at 25 ° C to give.

In preferred embodiments, the polyester component (a) Poly (1,4-butylene terephthalate), either straight chain or branched and it is alone or in combination with polyethylene terephthalate) or in the form of a block copolyester with an aromatic / aliphatic or aliphatic / aliphatic Polyester or in the form of a mixed composition with such a copolyester, or in the form of a mixed composition with a resin selected from an aromatic polycarbonate, a polyacrylate, one with a vinyl aromatic Compound modified polyacrylate, a copolymer of a vinyl aromatic compound and a diene, a polyolefin or copolymer of a polyolefin with a vinyl ester or a mixture of any of the aforementioned substances. Such Combinations and processes for their preparation are known to the person skilled in the art.

As previously mentioned, a conventional flame retardant synergist is used in the flame retardant compositions of the present invention. Component (c), such as an organic or inorganic antimony compound, aluminum or molybdenum compound, or mixtures thereof, are used. Such compounds are widely available or can be prepared by known methods. In preferred embodiments the synergist comprises an organic or inorganic antimony compound and the nature of the antimony compound is not critical and its selection is made only on the basis of economic considerations. For example, antimony oxide (Sb ₃ O.,); Antimony phosphate; KSb (OH) ,; NH ₄ SbF ₆ ; SbS ₀ and the like can be used. A wide variety of organic antimony compounds can also be used, such as antimony esters with organic acids, cyclic alkyl antimonites, aryl antimonic acids, and the like.

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Examples of the organic antimony compounds include inorganic salts of such compounds as KSb tartrate; Sb caproate; Sb (OCH ₂ CH ₃ ) ₃ ; Sb (OCH (CH ₃₎ CH ₂ CH _{3) 3;} Sb polymethylene glycolate; Triphenylantimony and the like. Antimony oxide is particularly preferred.

The flame retardant component (b) can either be prepared in a known manner and / or it is commercially available. If there are less than 5 bromine atoms per molecule, then the high level of flame retardant required affects the physical properties of the product, such as flexural modulus and heat distortion temperature under load. When there are more than 8 bromine atoms per molecule, "blooming" and loss of surface electrical properties becomes a problem. A mixture containing mainly Oktabromdxphenyläther has a melting range from 70 to 140 ⁰ C, a theoretical bromine content of 79.8% and is commercially available from the company. Great Lakes Chemical Corporation, West Lafayette, Indiana 47906, USA under under the trade name DE-79. This product contains small amounts of decabromodiphenyl ether and nonabromodiphenyl ether and causes slight blooming on aged parts. More suitable is a brominated diphenyl ether with slightly lower theoretical bromine content of 77.4% and a melting range from 58 to 129 ⁰ C. This product is from the Great Lakes Chemical Corporation under the trade designation DE-77 available and has a bromine content due to the distribution dampfphasenchromatografischen which is at Br _g . As explained in detail below, DE-77 does not produce any blooming of the polyester composition on oven aging at elevated temperature, in contrast to the Br ₁₀ analogs. Rather, the Br ₁ "analog must be completely absent from the flame retardant component (b) in order to achieve the advantageous results of the present invention.

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The amount of the polybrominated used as the flame retardant component (b) Diphenyl ether is not critical to the present invention so long as it is compositionally is present in a small proportion. Larger proportions are uneconomical and can affect the moldability, the gloss and affect the like. However, there should be at least an amount sufficient to make the thermoplastic Polyester resin flame retardant, non-burning or self-extinguishing close. Those skilled in the art will readily recognize that the amount of ingredient (b) depends on the nature of the combustible Resin (s) and the relative effectiveness of the additive will vary. In general, the amount of additive is in Range from 0.5 to 50 parts by weight per 100 parts by weight of the resinous ingredients. A preferred range includes about 5 to about 25 parts of ingredient (b) per 100 parts of the resinous ingredients in the composition. The amount of synergistic ^ component (c) can be used in the same way within vary over a wide range, but generally about 0.5 to about 20 parts by weight per 100 parts of combined resinous components are used in the composition, and preferably about 1 to about 12 parts by weight.

The present invention relates in particular to compositions which also comprise an effective amount (d) of a conventional filler and / or reinforcing agent. Under the Fillers and / or reinforcing agents that are suitable for this purpose are glass, talc, mica, clay or a mixture of any of the foregoing. The amounts used are the usual and generally range in a range of from about 1 to about 80 parts by weight per 100 parts by weight of the total composition. Particularly preferred comprises the filler and / or the reinforcing agent (d) glass fibers. Preferably the amount of glass fibers used is about 5.0 to about 40 parts by weight per 100 parts by weight of the total composition.

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It is also within the scope of the features of the present invention if the compositions contain other ingredients such as mold release agents, pigments, stabilizers, nucleating agents and the like can be added in conventional amounts for their usual purposes.

The way in which the flame retardant additives are added to the thermoplastic Polyester resin is not critical. It takes place in the usual way and is readily known to the person skilled in the art. Preferably however, each ingredient is added as part of a premix and the latter is added by, for example, passing through by an extruder or by plasticizing on a roll, depending on the specific requirements of each Composition-dependent temperature admixed. The mixed composition can then be cooled and converted into any Shape to be cut. Typical processing and shaping techniques are explained below.

The compositions according to the invention can be used for the production various forms can be used. They can be made into three-dimensional objects using conventional processing techniques or they can be formed into films or extruded into rods, tubes, etc., or formed into fibers.

The following examples illustrate the preparation of certain compositions within the scope of the present invention. You should however, do not limit the invention in any way.

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30006G0

example 1

In a Prodex extruder, which was operated at a temperature of 282 ⁰ C (540 ⁰ F), poly (1.4-butylene terephthalate), Oktabromdiphenyläther (Great Lakes Chemical Corporation DE-79), antimony oxide and small amounts of a stabilizer combination mixed together. The mixed composition was molded in a Van Dorn injection molding machine at 260 ⁰ C into test pieces, the physical measurements, aging at elevated oven temperature and the Flaminbeständigkeitsmessungen subjected wurden.Für comparative purposes, a composition was mixed, molded and tested, that of a bromäquivalente amount Decabroindiphenyläthers contained. The compositions and the results obtained are shown in Table 1 below.

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Table 1 - Composition, the polyester, brominated diphenyl ether and contains antimony oxide

example

Composition (%)

Poly (1,4-butylene terephthalate) Octabromdiphenyl ether

Decabromodiphenyl ether

Antimony oxide

Stabilizer (filled up to 100)

properties

Heat distortion temperature under load (4.62 kg / cm ² - 66 psi) ⁰ C

⁰ F

Heat distortion temperature under load (18.48 kg / cm ² - 264 psi) ⁰ C

⁰ F

Oven aging at 100 ⁰ C, 140 ⁰ C, 170 ⁰ C (168 hours)

Notched Izod Impact Strength ft.lbs./in.

Unnotched Izod Impact Strength ft.lbs./in.

Flexural Strength, psi
Flexural modulus, psi
Tensile strength, psi
% Strain
spec. weight

Flammability, U.L. Standard 94, 0.762mm (30 mils)

ASTM D-495 Arc Resistance As Molded In Sec.

ASTM D-495 arc resistance after 24 hours at 170 ^° C., sec.

82.3 11.5

6.0

IA * 83.8

10.0 6.0

161
322 139
283 , 4 , 68 ,1 40
104 50
122 , 2 , 5 no
bloom ** bloom 0.67 0 8.3 10 15,000 13 400 411 000 414 000 , 43 8 900 9 000 V-2 27 57 10 1.41 1 2 V-2 14.6 2h
14.3

* Control attempt
** only at the corners.

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30006Π0

It can be readily seen that there is a substantial improvement in resistance to blooming and in relation on the retention of the electrical properties was achieved.

Example 2

The general procedure of Example 1 was repeated, but in this case glass fibers were used to make a added to the reinforced molded composition. The formulations used and the results obtained are listed in Table 2 below.

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Table 2 - Reinforced compositions of polyester, brominated Diphenyl ether, antimony oxide and glass fibers

Example 2 ^ 2A *

Composition (%)

Poly (1,4-butylene terephthalate) Octabromodiphenyl ether

Decabromodiphenyl ether

Antimony oxide

Glass fiber reinforcement stabilizers (made up to 100)

Polytetrafluoroethylene ^a 0.2 0.2

properties

Heat distortion temperature below

54 , 4 55 , 4 8th , 0 - - 7th , 0 7th , 2 7th , 2 30th 30th

Load (4.62 kg / cm ² - 66 psx) ⁰ C
⁰ F 1, 205
401 210
410 Heat distortion temperature below
Load (18.48 kg / cm ² - 264 psi) ⁰ C
⁰ F 194.4
382 195.5
384 Oven aging at 100 ⁰ C, 140 ⁰ C, 170
for a period of 168 hours ⁰ C no
Blooming Blooming Notched Izod Impact Strength ft.lbs./in. 1.8 1.9 Izod unnotched ~ impact strength
ft. lbs./in. " 10.9 11.7 Flexural Strength, psi 27 300 26 200 Flexural modulus, psi 160 000 1, 1 20,000 Tensile strength, psi 17 300 17 600 % Strain 10 11 spec. weight 1, 66 1, 66 Flammability UL standard 94,
0.762 mm (30 mils) V-2 V-2 ASTM D-495 Arc Resistance
as formed / in sec. 8.7 16.5 ASTM D-495 Arc Resistance
after 24 hours at 170 ^° C., sec. 50.6 12.5

* Control attempt
a Dupont, Teflon 6

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Again, it is readily apparent that in the case of the objects formed from the compositions according to the invention surprisingly, no blooming occurred.

Example 3

The procedure of Example 1 was repeated using a polybrominated diphenyl ether having a melting range 58-129 ⁰ C and 18.0 _g% instead of the 12.5% Oktabromdiphenyläthers <Br, Br 50.0% ₆ 27.0% Br_, 4.8% Br ₈ and 0.3% Br _{9 were} used. The color was 73 (% T), the acid content 0.12 mg KOH / g and the theoretical bromine content was 77.4%. The product was free from decabromodiphenyl ether and was supplied by Great Lakes Chemical Corporation under the designation DE-77. After extrusion, molding and oven aging at 100, 140 and 170 ⁰ C for 1 hr., 24 hrs. And 168 hrs. Occurred no blooming. The compositions used and the properties obtained are shown in Table 3 below.

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Table 3 - Composition of polyester and polybrominated diphenyl ether

Example _3 Composition (%)

Poly (1,4-butylene terephthalate) 81.35

DE-77 (polybrominated diphenyl ether) 12.5 antimony oxide 6.0

Stabilizers (filled up to 100)

properties

Heat distortion temperature below

Load (4.62 kg / cm ² - 66 psi) ⁰ C
op 14th 145.5
294 Heat distortion temperature below
Load (18.48 kg / cm ² - 264 psi) ° C
op 408 51.1
124 Oven aging at 100, 140 and 170 ⁰ C.
for a period of 168 hours 7th »No blooming Notched Izod Impact Strength ft.lbs./in. 0.52 Izod unnotched impact strength
ft.lbs./in. 9.5 Flexural Strength, psi 600 Flexural modulus, psi 000 Tensile strength, psi 700 % Strain 242 spec. weight 1.47 Flammability UL standard 9 4
0.762 mm (30 mils) V-O

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Examples 4 to 8

DE-77, antimony oxide, stabilizers, Fillers and resins as listed in Table 4 are mixed together. These examples illustrate the use of DE-77 in formulations which contained copolymers, polymer blends and various fillers. In all cases there was no blooming and the materials scored 94 by Underwriters Laboratories Standard Test Rate V-O. The properties obtained are shown in Table 4 below.

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Table 4 - Compositions of polyesters and polybrominated diphenyl ether

Example A 5_ 6_ ] _ Q_

Poly (1,4-butylene tere-

phthalate) - 60.85 43.0 20.35 48.15

Poly (ethylene tere-

phthalate) - - - 20 20

Bisphenol-A-poly-

carbonate - 10 11

Ethylene vinyl acetate
copolymer - - 7th - Acrylate / methacrylate
copolymer 10 - - - Polyethylene - - 2 - Copolyester 81.85 - - - - DE-77 12 13th 9 9 9 Antimony oxide 6 6th 6.6 - 7.2 Thermogard CPA - - 5 - Fiberglass - 30th 11 15th mica - - 25th - Stabilizers (except
100 filled) Polytetrafluoroethylene - 0.1 0.5 0.5 Properties Heat distortion temperature
under pressure
(18.48 kg / cm ² - 264 psi)
⁰ C 49
° F120 57
134 189
372 182
360 185
365

Oven aging at 100 ⁰ C,

140 ⁰ C, 170 ⁰ C for the no no no no no

Duration of 168 hours. Blooming Blooming Blooming Blooming Blooming

Notched Izod Impact Strength ft.lbs./in. 0.6 2.3 1.5 0.9 1.0

Izod unnotched

Impact resistance

ft. lbs./in. / 16> 16 10 5 9

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3003660

Table 4 continued

Example " £ 1 Ü 1 Q.

Flexural Strength, psi 7 100 12 500 28 100 16 700 24 000

Flexural modulus, psi 169,000 342,000 1,240,000 1,140,000 833,000

Tensile strength, psi 4,900 7,200 17 500 9 600 15 300

% Elongation "460 137

spec. ^ Weight 1.43 1.41 1.69 1.75 1.61

Flammability according to
ü. L-. -Standard test 94
0.762 mm 130 mils) VO VO VO VO VO

All obvious variations on the above compositions are within the scope of the following claims.

$ 3 00- ^ 97 $ 8 61

Claims (12)

Claims 1) Flame retardant thermoplastic composition (a) a normally flammable high molecular weight Polyester; (b) a flame retardant amount of a polybrominated diphenyl ether compound the formula wherein χ + y is from 2 to 10 and (c) an effective amount of an organic or inorganic one flame retardant synergistic compound, characterized in that a compound or a mixture of such compounds is used as component (b) becomes, in which the sum of χ + y for each connection is not less than 5 and not more than 8, whereby a composition is obtained from which the polybrominated flame retardant does not bloom after molding. 030029/0863 BATH ORIGINAL -000660 2) Composition according to claim 1, characterized in that the amount of component (b) 3 to 25 parts by weight and the amount of component (c) 1 to 12 parts by weight per 100 Parts of the composition is. 3) Composition according to claim 1, characterized in that the polyester component (a) is either straight chain or branched chain poly (1,4-butylene terephthalate) and alone or in further combination with poly (ethylene terephthalate) or in the form of a block copolyester with an aromatic / aliphatic or aliphatic / aliphatic polyester, or in the form of a mixed composition with such a copolyester or in the form of a blended composition with a resin selected from an aromatic one Polycarbonate, a polyacrylate, a polyacrylate modified with a vinyl aromatic compound, a copolymer of a vinyl aromatic compound and a diene, a polyolefin or a copolymer of an olefin with a vinyl ester or a mixture of any of the foregoing. 4) Composition according to claim 1, characterized in that in component (b) the total amount of χ + y = 8. 5) Composition according to claim 4, characterized in that in component (b) the total amount of χ + y mainly ranges from 5 to 7 with about 50% of component (b) with a total of χ + y = 6. 6) Composition according to claim 1, characterized in that component (c) is an organic or inorganic antimony, Aluminum or molybdenum compound includes. O30Ö29 / Ö883 BATH ORIGINAL 7) Composition according to claim 6, characterized in that component (c) is an organic or inorganic antimony-containing compound. 8) composition according to claim 1, characterized in that it further contains 0.01 to 1.0% Polytetrafluoräthyleη. 9) Composition according to claim 1, characterized in that it contains an effective amount of a filler and / or reinforcing agent contains. 10) Composition according to claim 9, characterized in that the filler and / or the reinforcing agent (d) glass, talc, Contains mica, clay or a mixture of these substances. 11) Composition according to claim 10, characterized in that the filler and / or reinforcing agent component (d) Includes glass fibers. 12) Composition according to claim 11, characterized in that the glass fibers are about 5 to 40 parts by weight per 100 parts by weight of the composition include. 030029/0863 BATH ORIGINAL