DE2110219A1 - Fire retardant polymer blend - Google Patents

Description

Priority: 3rd March 1970, England, No. 10105/70

The present invention is concerned with improvements to polyols, which refer to polymer compositions, and more particularly to certain specific thermoplastic and thermoset compositions having fire retardant properties. Brominated aromatic compounds have been used as fire retardants in polymer mixtures. For example, British patent application 1,100,605 describes the use of various brominated aromatic hydrocarbons, phenols and xethers as fire retardants in polyesters and British patent application 1,158,163 describes the use of similar fire retardants in a number of other types of polymers. British patent application 1,121,736 describes a preferred series of brominated hydrocarbons, phenols and ethers for use as fire retardants in mixtures containing homopolymers and copolymers of o ^ -olefins.
It has now been found that decabromodiphenyl is a much better one

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fire retardant for very different polymer mixtures is considered to be any of the specific compounds mentioned in the three above mentioned applications are mentioned. Although decabromodiphenyl is within the formulas used to define the brominated aromatic hydrocarbons are used in these three applications, decabromodiphenyl is not particularly in one of the applications mentioned and there is no evidence that decabromodiphenyl or compounds similar to it are better have fire retardant properties than the particularly mentioned compounds.

Decabromodiphenyl is an undesirable and advantageous combination of a better fire-retardant effect and a lower volatility _; compared to fire retardant compounds specifically mentioned in the three above mentioned applications. In other words, decabromodiphenyl provides better fire-retardant properties than the previously known compounds at a certain concentration and is also "less volatile, so that it is better retained by the polymer when the latter is heated to elevated temperatures. The comparison between decabromodiphenyl and certain compounds described in the above applications is given below with reference to the accompanying drawings.

According to the present invention, therefore, a polymer device is obtained created with fire-retardant properties, which consists of at least one polymer selected from polyolefins, polyesters, poly-

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urethanes. Polyamides, epoxy resins, acrylonitrile-butadiene-styrene copolymers, Ethylene-vinyl acetate copolymers, Polyvinyl chloride, polystyrene, polyvinyl acetate, silicone rubbers, natural and synthetic rubbers as well as - as fire retardant - decabromodiphenyl consists.

In general it is necessary to use the fire retardant decabromodiphenyl in an amount sufficient to provide a total bromine content of at least 3% by weight based on the polymer, although normally preferred is one higher erom content in the range of 5-10% by weight, based on the JPolvmere, _ to have ^ .. ^ s ^ is generally pneconomic, a bromine content of more than 20% by weight, based on the polymer, to have.

The effectiveness of the fire retardant decabromodiphenyl can be increased by also adding antimony oxide to the polymer. preferably in the range of 0.5-1.5: 1, based on weight of decabromodiphenyl, is incorporated.

The decabromodiphenyl (and the antimony oxides, if used ) can be incorporated at any suitable stage in the preparation of the polymer. It can be added to a monomer before polymerization or - as it can often be more suitable - added to the polymer that has already formed. Other conventional ingredients of the above-mentioned polymer blend such as fillers, plasticizers, pigments and stabilizers can also be incorporated. The following examples illustrate the invention. All parts

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are parts by weight.
example 1

50 parts of polyester DSR 19395 (a cold press resin sold by Bakelite Ltd.), 2.8 parts of Lucidol B 50 (50% benzoyl peroxide in phthalate plasticizers sold by the Pa. llovadel Ltd.), 6 parts of decabromodiphenyl and 6 parts of antimony oxide were mixed together mixed and stirred with an electric stirrer until the mixture was homogeneous, and then 50 parts of DSR 19378/1 (a fast-curing cold-press resin, sold by Bakelite Ltd.) was added and mixed with the mixture. A 3.17 mm thick picture frame mold with a Melinex film was surrounded, was placed on a 1.58 mm thick Feich steel plate and a piece of glass fiber was placed in the mold. The required Amount of dye mixture was spread on the glass and another piece of glass fiber was placed over it. Fine another layer of Felinex film and a 1.58 mm thick mild steel plate was placed on top of the glass to complete the sandwich shape.

The sandwich shape was then pressed at 50 ° C. under a heated steam pressure of 50 ° C. for 5 minutes at 14.06 kcr / cm ² and then cured for 5 hours at 80 ° C. before testing.

The flammability of the molded panels was tested by 26.67 χ 12.7 cm specimens were cut from the center of a j The sample to be tested was horizontally across clamped onto a bunsen burner and set the temperature of the flame

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■ adjusted so that a piece of copper wire with a diameter of 0.73 mm, the 5.08 cm above the glowing Bunsen flame was held, melted within 6 seconds. The flame was about 5 inches high. With the sample, the gas was as above The set Bunsen burner is turned on and ignited. After 30 seconds the gas was turned off. Then the for the sample determines the time required for extinction (extinction time). 10 samples were tested. The results are shown in Table I.

Comparison attempt "L '"'

50 parts of each of DSR 19395 and 19378/1 were combined with 2.8 parts of Lucidol B 50 in a sandwich form in the same Molded manner as in Example 1; but without the addition of decabromodiphenyl or anti-ironoxide.

The flammability of the molded material was determined using the same procedure as described in Example 1 with the exception that on the samples to be tested two Lines 7.62 and 10.16 cm were drawn from one end in the right fin to the longitudinal axis. When the flame - after the Bunsen flame was extinguished - the sample continued to burn the burning rate is determined by the time required for the lower end of the flame to pass the first dash (Tl) and subsequently to reach the second stroke (T2) was recorded. The burning speed in cm / minutes was after Formula calculated

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"* 52 4 burning speed = cm / minutes,

Only one sample was tested. The result is shown in Table I.

Example 2

100 parts of Kralastic 2997 (an acrylonitrile-butadiene-styrene copolymer, that from the company üniroyal Ltd. sold v / ird) was placed in an electrically heated two-roll mill and at Ground at 160 ° C. When the polymer had melted and became too— '^ "aruhenHangende ^^ and ^ nr cTie" Väl'zeh "around bildVte," would 14 "Tel— Ie decabromodiphenyl and 6 parts of antimony oxide were added. That Mixing was done 5 minutes after adding these ingredients continued.

A sandwich mold was made as described in Example 1 except that no glass was used. she was placed in an electrically heated press maintained at 160 ° C. and the pressure applied was slowly increased to

2
70.30 kg / cm and kept on this foie for 2 minutes.

The mold was then removed from the hot press and Cooled for 2 minutes under a pressure of 35.15 kg / cm.

The flammability of the molded plate was determined using of ASTM Test D-635-56T except * that one 12.7 mm bunsen flame instead of the specific 25.4 ram bunsen flame was used as an ignition source.

10 samples were tested. The results are shown in Table I.

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guided.

Example 3

A molded plate was prepared in the same manner as in Example 2 except that 18 parts of decabromodiphenyl and 2 parts of antimony oxide in the acrylonitrile-butadiene-styrene polymer were incorporated.

10 samples were tested as described in Example 1. The results are listed in Table I.

Figure 4 "-" * ------ · "-" · - 'A molded plate was made in the same manner as in Example 2 except that 10 parts of decahrondiphenyl and 10 parts of antimony oxide were incorporated into the acrylonitrile Butadiene-styrene polymers were incorporated. 10 samples were tested as described in Example 2. The results are shown in Table I.

Comparative experiment 2

Eire molded plate of Fralastic 2997 was made on the same Prepared as in Example 2 without adding antimony trioxide or decabron diphenyl. The flammability of the Plate was tested using the procedure described in Comparative Experiment 1 and the burn rate was determined. Only one sample was tested. The result is shown in Table I.

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Example 5

A molded sheet containing 100 parts of Alkathene XDG 33 (a low density polyethylene, that from Imperial Chemical Industries Ltd. is sold), containing 25 parts of decabromodiphenyl and 15 parts of antimony oxide, and was prepared in the same way tested as indicated in Example 2. The results are shown in Table I.

Comparison attempt 3

A molded sheet of Alkathene XDG 33 was made in the same manner as specified in Example 5 without the addition of decabromodi ¹ -phenyl and antimony oxide. The flammability of the panel was determined using the test procedure described in comparison experiment 1. The results are shown in Table I.

Example 6

An extruded rod containing 100 parts of TPX (a methylpentene polymer, that from Imperial Chemical Industries Ltd. is sold), contains 20 parts of decabromodiphenyl and 20 parts of antimony oxide, was made and tested using the procedure described in Example 2. 2 samples were tested. the Results are shown in Table I.

Comparative experiment 4

The flammability of an extruded rod made from TPX was determined

1 0 9 8 4 o / 1 5-3 6

ORfQiNAL INSPECTED

tested using the test procedure described in Example 2. The results are shown in Table I.

Example 7

A mixture of 100 parts of Maranyl F124 (a nylon 6 polymer, that from Imperial Chemical Industries Ltd. is sold), 6 parts of decabromodiphenyl and 4 parts of antimony oxide were ben extruded and the cold rods pressed in a mold to form a plate. The plate was cut into strips and their flammability using the ■ ^ SChrtetyenefi ^ FfiTZedar ^^ gete-st ^ t "described in Example 2. *> 3 '"Pröbe'n ~ was * n-tested-; · D ±" e-Er- * " Results are given in Table I.

Example 8

A nylon plate was prepared in the same manner as in Example 7 except that 12 parts of decabron diphenyl and 8 parts of antimony oxide incorporated into the polymer. 4 samples were tested as described in Example 2. The results are shown in Table I.

Example 9

A nylon plate was prepared in the same manner as in Example 7 except that 20 parts of decabromodiphenyl was incorporated into the polymer and no antimony oxide was used.
4 samples were tested as described in Example 2. Which he-

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Results are given in Table I.

Comparative experiment 5

A nylon plate was prepared in the same manner as in Example 7 except that no decabromodiphenyl or antimony oxide was used. The flammability the panel was tested using the procedure described in Comparative Experiment 1 and the burn rate certainly.

Only one sample was tested. The result is in Table I.

Example 10

A molded sheet containing 100 parts of Alkathene A9839 (an ethylene-vinyl acetate copolymer, that from Imperial Chemical Industries Ltd. is sold), 2O parts decabromodiphenyl and containing 20 parts of antimony oxide was prepared and tested as described in example 2.

4 samples were tested. The results are shown in Table I.

Comparative experiment 6

A molded plate made from Alkathene A9 839 that does not contain decabromodiphenyl or antimony oxide was prepared and its flammability using that in Comparative Experiment 1 described test procedure. '

OFMGfNAL INSPECTED

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Example 11

A mixture of 100 parts Epikote 828, 20 parts Epicure T (both Epoxy resins available from Shell Chemical Ltd. are sold), 8 parts of diallylphanol phthalate, 15 parts of decabromodiphenyl and 15 parts of antimony oxide are poured into a plate and examined in the same manner as indicated in Example 2. 5 samples were examined. The "results are in Table I. listed.

Comparative experiment 7

^ Tne ^ ßpbxyH'är ^ zpTrktCe ** liiurde vi'e ⁵ "fn * ~ Beisp" ie "l ^r 11"BescKrieb'e'n * "manufactures with the exception that the decabromodiphenyl and antimony oxide The flammability of the panel was tested using the procedure described in Comparative Experiment 1. The result is shown in Table I.

Example 12

Fine aeformte plate, the 100 parts Styrene 491 (a tough polystyrene, that from Dow Chemical Company Ltd. is sold), contains 8.5 parts of decabromodinhenyl and 8.5 parts of anti-iron oxide, was prepared and tested in the same manner as indicated in Example 2.

5 samples were tested. The results are shown in Table I. .

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Comparative experiment 8

The flammability of a molded sheet of tough polystyrene, which does not contain decabromodiphenyl or antimony oxide, was carried out using the procedure described in Comparative Experiment 1 tested. The results are shown in Table I.

Example 13

The flammability of a rigid polyurethane foam, the decabromodiphenyl contains alone and in combination with antimony oxide has been tested in the following ways:

- • ♦ ■ A masterbatch ^ K ^ telysfat cruder * folwend ^ n "Fo-rinirH-erung- was - produced:

Atpol G2571 (a polyether manufactured by Fa.

Honeywell Stein Ltd. sold), 100 pieces

Propamine A (an amine catalyst used by the

LpnVro Chemicals Ltd. sold) 22 parts

DC 113 (a silicone surfactant, that from Midland Silicones Ltd. sold) 22 parts

Dabco 33 (an alfine catalyst manufactured by Jacobson Van Den Berg & Co. Ltd. sold) 5.5 parts

100 parts Atpol G2571, 45 parts decabiroradiphenyl and 15 parts Antimony oxide were first mixed together and the masterbatch catalyst and 27.5 parts of Arcton 11 (trichlorofluoromethane, that from Imperial Chemical Industries Ltd. is then added. The temperature was on set about 21 ° C and 102 parts of Hylene TRC (crude toluene diiso-

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cyanate available from E.I. du Pont de Nemours & Co.) is added while the temperature is maintained at about 21 ° C became. The mixture was then stirred mechanically until just before creaming, which was followed by a color change from dark brown is recognized after pale brown, and then poured into a mold. The foam was then cut before cutting conditioned at 23 ° C for 24 hours. The flammability of this foam was determined using those described in Example 2 Procedure tested. 10 samples were tested. The results are shown in Table I.

Example 14

A rigid polyurethane foam was prepared in the same manner as described in Example 13 except that the antimony oxide was omitted and 60 parts decabromodiphenyl were used. The flammability of this foam was tested using the procedure described in Example 2. The results are given in Table I -

Comparative experiment 9

A polyurethane foam was produced in the same manner as described in Example 14 except that the Decabromodiphenyl and antimony oxide were omitted. The flammability of this plate was determined using that in the comparative test 1 was tested. The results are shown in Table I. '

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Example 15

100 parts of Revinex XF5218 (a liquid synthetic rubber latex, manufactured by Revertex Ltd.), 5 parts of Decabrom Diphenyl and 3 parts of antimony oxide were mixed together and then stirred into the air mechanically 'Mixture converted into a foam. The foam turned into sheets poured and cured at 140 ° C for 20 minutes.

The flammability of the foam was tested using the procedure described in Example 2. The results are listed in Table I.

Comparison test OK

A latex foam that does not contain decabromodiphenyl or antimony oxide contains, was prepared as described in Example 15 and the flammability of the foam using that in the comparative experiment 1 procedure described. The results are shown in Table I.

Example 16

5 parts of decabromodiphtenyl and 5 parts of antimony oxide were added 100 parts of polyvinyl acetate emulsion were added and the mixture was poured into a film and barrel evaporated by removing the film left to stand over power at room temperature. A 50.8 by 304.8 by 0.254 mm sample was cut from the foam and its flammability is determined by the 5O, 8 mn edge was held horizontally 25.4 mm above a small bunsen flame

153 8

de. After 10 seconds, the Bunsen flame was removed and the Sample stopped burning after 3 seconds.

A comparative experiment was carried out using a. Sample of the same size but containing no decabromodiphenyl or antimony oxide. After holding over the for 7 seconds Eunsenflamme was used up the whole sample.

Example 17

100 parts Silastomer 2454 Masterbatch (a silicone rubber, that of Midland Silicones Ltd. supplied), 16 parts

became * ztf'öiner "Pl-a-tte *"

molded at 45 ° C, deformed into a thin plate at 115 ° C and Post-cured for 24 hours at 25O ° C.

The flammability of the material was determined using the in Example 1 described procedure determined. The extinction time was 95 seconds.

A comparative experiment was carried out using a Silicone rubber sheet which does not contain decabromodiphenyl or antimony oxide, and - if it is made according to that described in Example 1 Procedure tested - the material burned 190 seconds.

Example 18

A flame retardant sheet made of flexible polyvinyl chloride was made from of the following formulation:

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Corvia D65 / O2 (a polyvinyl chloride used by the

Imperial Chemical Industries Ltd. sold

will) 100 parts

Dialphanol phthalate 80 parts

An epoxy stabilizer 2 parts

A barium / cadmium stabilizer 2 parts

Decabromdiphfenyl 10 parts

Antimony oxide 5 parts

The flammability of the material o / urde using the British Standard Test Procedure No. 3119: 1999 tested. In this ^ -e ^ irÄH-rd-eim-StiPed ^ etr- ^ es- ^ u nintersuchenöen "Mai: erial-es nied-" " drooped right down and the lower end inflamed. The burning time after removing the pilot flame is measured and any spread of afterglow after the flame was extinguished. The one made according to the above formulation Material went out by itself. The flame went out after 5 seconds.

A comparative test was carried out on a polyvinyl chloride material of the above formulation, but which does not contain decabromodiphenyl or antimony oxide. This material burned continuously and the 31.75 cm line was reached in 62 seconds.

Comparative experiment 11

The improved fire retardant effect achieved with decabromodiphenyl in conjunction with antimony oxide (weight ratio 1: 1) was, with the use of two well-known fire

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inhibitory agents obtained, namely by 70% chlorinated paraffin and pentabromophenyl allyl ether, both in Combination with antimony oxide (weight ratio 1: 1). The polymer base was a glass fiber reinforced polyester resin.

The flame retardant material was tested using British Standard Test Procedure No. 3532 (described in Example 1) and ASTM Test Procedure D-635 (described in Example 2 except for flame size). Fig. 1 of the accompanying drawings is a graph showing the differences in the Ve-riföschZ & itTifi ^ '^ Sifei ettHe'TrrMen'geTi afi ^ fe-uerTTeminend'en "means ^r.

In the graph, the units on the X-axis represent the concentration of halogen-containing, fire-retardant Mean (in% by weight, based on the weight of the polymer) and the units on the Y-axis represent the extinguishing time in seconds. The curves in the graph are shown as follows:

A: Pentabromophenyl allyl ether 2.54 cm flame ASTM D-635

B: Pentabromophenyl allyl ether 12.7 cm flame BS 3532 C: Decabromodiphenyl 2.54 cm flame ASTM D-635

D: decabromodiphenyl. 12.7 cm flame BS 3532

E: 70% chlorinated paraffin 2.54 cm flame ASTM D-635 F: 70% chlorinated paraffin 12.7 cm flame BS 3532

Because certain polymers are compounded at relatively high temperatures

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are, for example, acrylonitrile-butadiene-styrene resins Manufactured by grinding at 150 - 160 ° C, the fire retardant additives must withstand the manufacturing process without volatilize or have adverse effects on the heat stability of the resins. The volatility measurements were made on decabromodiphenyl, Pentabromophenyl allyl ether and chlorinated paraffin carried out, each in a mixture with an equal weight Antimony oxide. Figure 2 of the drawings is a graph of percent weight loss plotted against temperature. ^ In Fig. 2, the units on the X-axis represent the temperature

_w in C and ^ the ^ J ^ inheiter ^ .on ^ jder. Y Achse..den PJR zentgewichtsyer- ^ _fc _ loss. Curve A is 70% chlorinated paraffin + antimony, curve B is Pentabromphenylallyläther + antimony oxide, and curve C is decabromodiphenyl + antimony. The volatility shown clearly shows the stability of the decabromodiphenyl.

The thermal stability of the flame retardant agent Decabrondiohenyl / Antimonoxvd is particularly useful in silicone rubber mixes (Example 17), where curing takes place at 250 ° C.

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Table I.

Example sample no. average Extinguishing burning speed

time (in sec.) (in mm / min.)

1 10 3.3 -

12.7 1.0 2.0 2.0

40.6 8.0

17.8 52.5

Comparison
attempt 1 1 2 10 3 10 4th 10 Comparison
attempt 2 1 S. 10 Viilr'gTr &'lehs ^ "*
attempt 3 1 6th 2 Comparison
attempt 4 1 7th 3 8th 4th 9 4th Comparison
attempt 5 1 10 4th Verrrleichs-
attempt 6 1 11 5 Comparison
attempt 7 1 12th 5 Comparison
attempt 8 1

6.9 2.4 10

15.24 9.5

15.24 10.0

24.9 12.0

22.86

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Table (continued )

13th 10 21.5 14th IO 19.9 Comparative
attempt 9 10 - 15th 4th 0.0 Comparison
attempt 10 1

23.62

101.6

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Claims (3)

Claims 1. Polymer mixture with fire-retardant properties, consisting of at least one polymer selected from polyolefins, Polyesters, polyurethanes, polyamides, epoxy resins, acrylonitrile-butadiene-styrene copolymers, Ethylene-vinyl acetate copolymers, Polyvinyl chloride, polystyrene, polyvinyl acetate, silicone rubbers, natural rubbers and / or synthetic rubbers and - as a fire retardant - a brominated diphenyl .mi ^d .-- £ 3ilf..aes: £ nsc & k-r ^ Fi-, to strengthen properties, characterized in that the brominated Diphenyl is decabromodiphenyl. 2. Mixture according to claim 1, characterized in that the incorporated The amount of decabromodiphenyl is so large that the total bromine content is at least 3% by weight, based on the polymer component, amounts to. 3. Mixture according to claim 2, characterized in that the Total bromine content is 5-10% by weight of the polymer component. 1Ü9840 / 1536