DE2162489A1 - Polymer mass - Google Patents

Description

PATENT LAWYERS! - | U {D Δ. H ö V?

DR. O. DlTTMANN KL SCHIFF DR. A. ν. FÜNI5R DIPL. ING. P. STREHL 8MONOIfBNOO MAHiAHILPPLATZ 2 Sc S

DA-4600

Description of the company's patent application

BERK ltd.
Gateford Hill, Worksap Nottinghamshire, England

concerning

Polynermr? ss e

Priority: 12/16/1970 No. 596SO / 7O, Great Britain

The invention relates to polymer outlines that end up as flaramhoj'ü.iende Kittel determined certain helical aromatic compounds

Eh v.urüo found that broken terphenyls are valuable flame-heating elements Ei ^^ oiiüchaf th on v / iron and are capable of this KiiVKjnoh.'iftoii polymer ruffles to which they are added v; ord ': n.

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The invention is therefore a Polyraerinasse that an organic polymer and, as a flame retardant it means -, - "" - · contains at least one brominated trphenyl

It can be any brominated o-, m- or p-5erphenyl uses v / earth; however, in order to achieve maximum flame protection, the terphenyl preferably contains 7 to 13, advantageously 11 up to 13 bromine atoms per molecule. It is not required as Part of the polymer mass is a single brominated terphenyl to use and it may be more convenient to add a mixture of compounds c-i? iz that through. Bromine! he en a commercially available Mixture of o-, m- and p-Ierphenyl is obtained. The mixture can also contain terphenyls with different degrees of brorination so that the average number of bromine atoms per terphenyl molecule in the mixture is not necessarily must be an integer.

The brominated terphenyls can be represented by several different Process are produced. Soi a suitable procedure the bromination of the terplienyl is by direct action of bromine in the presence of a Hrilo ^ enierungskatalysators, such as Iron, aluminum or their halides, in an inert solvent, like Dibronn.thpn.

If o-Terphcriyl is bronzed beyond the tetra-bromine stage, two V, ';: si: eisl.ol'f /' tonon hub drn Γ'ο-Ifilrül Ri W ^ s oh luft can intervene , whereby Biuiiitiiphonylcno formed

P09828 / 096 /. BATH ORIGINAL

^ r ^ ßj). ßöjcann. äi.e BrSmier-ung- yon / i, 4 ?, f ?? Λ «etrakrpra- £ u 3 _? 5, 1Ω, il-f / etarcteomtKipheja ^ lfii itß ^ fo§.gen # en

lead pn:.-..-.-

Br

The term "brominated Brplienyl ^11" is intended to include - for the purposes of the invention saleliB. Irlphenyiene _- the at least yier Broinetome per .Molecule.

To P, Qlyiae3? En, which can be obtained by adding tor-oiuated fl <? Ipmfes1,. ^, Explained v; erd.ep, gelioren urrrfciiariß, polyester, polyamides _? Pplyiiaiäe, Pplyätliep "Polyformaldehyc ⁵ e, Ppiyvlriylacjetale, E ^ rtc -rrniri-rornialdehyd resins substituted or Aerylpolyirmre, Harnßtpl'ir-pQrifialdeliyd-HRrEe, silicones, Celluloseester, PoD.yvinylchlo.x-id, Äcrylnitril-butadiene-styrene QppplyFLe-j'iRate, synthetiBchp Gppplymerkchuke, synthetic acrylonitrile-StyiOl-GopQlyraerkuke and natural rubber.

The amount of the award-winning phenyl added depends on the type of polymer (some polymers, for example polyvinyl chloride, have inherent floating properties)

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Total halogen content of the flame retardant used and. the level of flame retardant properties desired for the polymer composition.

In general it is necessary to use the brominated terphenyl to be added in an amount sufficient to give a total bromine content of at least 3 percent by weight, based on the Polymers, lead. Usually, a higher bromine content in the range of 5 to 10 percent by weight, based on 'the poly-' mers, preferred. It is generally uneconomical to have a bromine content greater than 20 percent by weight of the polymer.

The effectiveness of the brominated terphenyl can be increased if antimony oxide is also added to the polymer composition. It has been found that at least 1 part by weight of antimony oxide is required to 8 Gewichtsteilebromicrtes terphenyl to discuss the increase in measurable Weise.die flame retardant properties of the polymer f Pale Polymeriiiasse the same, only the flame retardant was added. Preferably, antimony oxide is added in an amount ranging from 0.3 to 1.5: 1 percent by weight of the brominated terphenyl. A greater increase in flame retardancy can be achieved with a weight ratio of antimony oxide to brominated terphenyl of 2 or more to 1.

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The broinated terphenyl (and, if used, antimony oxide) can be mixed in at any suitable stage during the preparation of the polymer composition. For example, the "broinated terphenyl" can be added to a monomer before the polymerization or, which is often more convenient, can be added to a polymer that has already been formed. In the production of polymeric fiber materials, for example polyethylene terephthalate, the brominated terphenyl is advantageously mixed into the molten polymer before it is shaped into fibers. Other conventional components of the said polymer compositions, such as fillers, ■. \ ^R eichma.cher, pigments and stabilizers may also be incorporated.

It was; found the brominated terphenyls to be particularly beneficial for use as flame retardants for polyolefins. Used in polyolefins, especially polyethylene conventional flame retardants tend to migrate to the surface of the polymeric material, a phenomenon known as "bloom". It was found, that brominated terphenyls have other flame retardants in this regard are generally superior. It is believed that these superior properties are due to the fact are that the increased molecular size of the brominated terphenyls allows the compound to pass through the polymer chains of the polyolefin.

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For a better understanding of the invention, the following, examples illustrative of the invention are given. In. In these examples all parts are parts by weight if nothing other is indicated. Examples 1 and 2 are intended to illustrate typical manufacturing processes for being flame retardant Means to indicate used denominated terphenyls. the Examples 3 to 17 relate to a brominated terphenyl which was prepared according to Example 1.

A brominated terphenyl is made of a Terpheayl-gernisches by bromination, the 12.3 ° f ortho-terphenyl, contains 57.7% meta-terphenyl and 30.0 # para-terphenyl. 30 parts of terphenyl, 6 parts of iron powder and 500 parts of dibronethane were placed in a reactor and stirred for one hour. 325 parts of bromine were added over a period of 2 1/2 hours, the mixture being heated to 50 ° C. at the beginning of the addition of the bronze. The mixture was heated under reflux for 14 hours, cooled and the solid product obtained was filtered and washed with dibromate until the washing liquid was colorless. The product was recrystallized from trichlorobenzene, wherein 120 g of brominated terphenyl, corresponding to a yield of 15.5 fi> ouf the relative used as starting material terphenyl. This process was repeated to obtain a second batch of broadened terphenyl. The two

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End products were put together. The combined product, which was contaminated with residues of the iron halogenation catalyst, was then used in the following \ ^,; ice cleaned:

212 parts of the crude brominated terphenyl, 272 parts of water, 88 parts of concentrated hydrochloric acid and 284 parts of toluene were placed in a reaction vessel and allowed to take 3 hours stirred under reflux. The device was then converted to carry out the distillation and the toluene was distilled off, The residue was filtered, washed with water until neutral and then with acetone and the product was added for 5 hours 80 ° C dried. It became a light brown crystalline plague obtained with a melting point of 375-379 ° C. The product was found by analysis to have 11.5 bromine atoms per Molecule contained.

The volatility of this brominated terphenyl was in one electrically heated oven with air circulation using a 5 g sample in a porcelain dish with a diameter of 1.5 cm

knife checked. The results are shown in the table below.

Temperature ° C 200 240 260 280 Weight Loss # 0.06 0.10 0.23 0.35

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Example 2

The "procedure described in Example 1" was carried out using
the amendment repeats that the starting material is pure
para-terphenyl was used. The brominated terphenyl was found as a light brown powder with a melting point greater than ice
400 ° C obtained. The analysis showed that there were 11.0 bromine atoms
contained per molecule.

Example 3

50 parts of an unsaturated polyester resin for the cold press process (DSR 19395 from Bakelite Ltd.), 2.8 parts of a mixture of 50 $ benzoyl peroxide in phthalate plasticizer
(Lucidol B 50 from Novadel Ltd.), 8 parts of the brominated terphenyl and 8 parts of antimony oxide were mixed with one another and stirred with an electrically operated stirrer until the mixture was homogeneous. Then 50 parts of an accelerated unsaturated polyester resin for the KoIt-. pressing process (polyester DSR 19378/1 from Bakelite Ltd.) was added and stirred into the mixture.

A 3.18 Bim thick Bilderrahiaeniorm lined with Kelinex film was placed on a 1.5 mm thick mild steel plate and a piece of fiberglass mat cut to the shape and size of the mold was placed in the mold. The required amount of the Horz mixture was distributed over the gypsum fiber mat and another identical piece, fiberglass mat placed on top.

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209828/0964

On the top of the fiberglass mat were another strip of the Kelinex film and a 1.6 mm thick mild steel plate to complete the sandwich arrangement to be formed.

The sandwich was then placed in a steam "heated press" placed at 50 ° C, pressed for 5 minutes at 14 kg / cm and finally cured for 5 hours at 50 ° C before being tested became.

The flammability of the molded panels was tested by. 26.7 x 12.7 cm samples from the central area of each laminate were cut out. The samples to be tested were clamped in a horizontal position above a Bunsen burner and the temperature of the flame adjusted so that a piece of copper wire 0.73 mm in diameter, 5> 1 cm above Holding the tip of the lit Bunsen burner, melted within 6 seconds, the flame being 12.7 cm high was. When the sample and bunsen burner were at the above setting, the Sas was fed and ignited. Compartment 30 seconds, the gas supply was turned off and then measured the time that elapsed until the sample went out (extinction time). Ten samples were tested and the one The results achieved are shown in a table.

Fading pre-1

A mixture of the same composition as in the example 3 used, but not brominated terphenyl and

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contained no antiinone oxide, was manufactured and in the in Example 3 deformed manner as a sandwich structure described.

The flammability of the molded material was tested according to the procedure described in Example 3, with the Modification that the samples to be tested were marked by two lines spaced 7.6 cm and 10.2 cm from one end at right angles to the longitudinal axis. If the flame on the sample continued to burn after the Bunsen burner was extinguished, the burning rate was measured by recording the time in seconds that Elapsed until the lower edge of the flame reached the first line (T1) and then the second line (T2). The burning rate in 2.54 cm / min is calculated using the following formula:

Burn rate = 2.54 cm / min

T2-T1

Only one sample was tested; the result obtained is shown in Table 1.

Example 4

100 parts of an acrylonitrile-butadiene-styrene copolymer (Kralastic 2997 from Üniroyal Ltd.) were electrically applied

given a heated two-roll mill and kneaded at 160 ° C. The polymer became fluid and formed an endless melt

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Tape that encircled the reels. 15 parts of the brominated terphenyl and 5 parts of antimony oxide were added and mixing continued for 5 minutes after the addition of these ingredients.

A sandwich structure is similar to that described in Example 3 Made in iron, with the modification that no fiberglass mat inserted vmrde. The laminate was kept in a 160C placed electrically heated press and the pressure vmrde slowly increased to 70.3 kg / cm and 2 minutes at this Fourth. Then the mold was removed from the hot press and cooled under a pressure of 35.1 kg / cm for 2 minutes.

The molded panel was flammable by the ASTM test method D 635-63 tested.

Five probes were tested; the results achieved are shown in Table 1.

DLe plate was tested to determine the strength of the Emigration of the brominated terphenyl to the surface of the Determine plate. The following test method is used: · - ■ ■

Remove a 7.6 cm 1.3 cm 0.5 cm sample of the plate using a band saw provided with a metal saw blade cut out ^ and the entire, from the sawing process any loose dust is carefully removed. Carefully wipe the sample with a black cloth cleaned, with the black cloth folded in between to expose an unused area. This ver

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Driving was carried out until there was no deposit or dirt on a fresh area of the cloth more was recorded. Then the sample was placed in a tray and the tray in a storage chamber in one temperature constant room transferred. The shell was made with covered with a sheet of Melinex film to seal it off against dust.

After 24 hours, one side of the sample was covered with a fresh Piece of black cotton cloth wiped off with finger pressure and the debris left on the cloth was examined and compared to a standard debris table.

The standard deposit tables show 5 classes of "blooming" on, that is, (1) none, (2) easy, (5) strong. The blooming of the brominated terphenyl on the plate Kralastic 2997 was classified as "no bloom".

Deterioration attempt 2

A compression-molded plate made of Kralastic 2997 "was produced in the manner described in Example A , but the antimony oxide and brominated terphenyl were omitted. The flammability of the plate v.airde was tested according to the method described in Comparative Experiment 1 and the burning rate was measured. It v / Only one sample was tested; the result obtained is shown in Table 1.

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Example 5

A molded plate was made from 100 parts of polyethylene with low density (Alkathene XDG- 33 from Imperial Chemical Industries Ltd.), 20 parts of the brominated terphenyl and 20 parts of antimony oxide prepared in the manner used in Example 4. The flammability of 5 samples was determined in the in Example 4 described manner tested {the thereby achieved Results are shown in Table 1 *

¥ match search 3

A molded plaque was made from 100 parts of Alkathene XDG 33 in the manner described in Example 5, but without addition of brominated terphenyl and antioxidant. the Flammability of a single sample of the plate was determined using of the test method described in Comparative Experiment 1 measured. The result obtained is shown in Table 1,

Example 6

A molded plate was made from 100 parts of a polypropylene resin (Propathene GY 702ΙΊ from Imperial Chemical Industries Ltd.), 25 parts of the brominated terphenyl and 15 parts of antimony oxide produced in the manner indicated in example 4 * The flammability of 5 Broben was that described in Example 4 Way tested; the results obtained are given in Table 1,

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Comparative experiment 4

A molded plaque was made from 100 parts of Propathene GY.702M prepared in the manner described in Example 6, but without adding the brominated terphenyl and the antimony oxide » The flammability of a single sample of the plate was tested according to the test method described in Comparative Experiment 1; the result obtained is shown in Table 1.

Example 7

An extruded rod containing 100 parts of a methylpentene polymer (TPX by Imperial Chemical Industries Ltd.), 20 parts of the brominated terphenyl and 20 parts of antimony oxide was prepared and tested according to ASTM test method D 655-68 checked. Two samples were tested; the results achieved are shown in Table 1.

Comparative experiment 5

* The flammability of an extruded rod made of TPX that is not a

brominated terphenyl and contained no antimony oxide

tested using the ASTK test method D 635-68. That included The result obtained is shown in Table 1.

Example 8

A pleasure made from 100 parts of a nylon 6 polymer. (Karaiiyl F 124 from Imperial Chemical Industries Ltd.) ». 6 parts of the broniexHen TerpheByls and 4 parts of AntimanQxyd were extruded into rods and the cooled rods were in a

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Mold pressed into sheets. The plate was cut into strips and their flammability tested according to ASTM test method D 635-68. 4 samples were tested; the achieved Results are shown in Table 1.

Example 9

A nylon plate was made in the same manner as in Example 8 produced, with the modification that 12 parts of the brominated terphenyl and 8 parts of antimony oxide are mixed into the polymer became.

3 samples were subjected to ASTM Test Procedure D 635-68; the results obtained are shown in Table 1.

Example 10

A nylon plate was made in the manner described in Example 8 except that 20 parts of the bromj terphenyls were mixed into the polymer and that no antimony oxide was used.

3 samples were tested in the manner described in Example 8; the results are shown in Table 1.

Comparative experiment 6

A nylon burst was made in the same way as in Example 8 produced, with the modification that no brominated terphenyl or antimony oxide was used. The flammability of the plate

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was tested using the method described in Comparative Experiment 1 and the burning rate vmrde was measured. Only one sample was tested; the result obtained is
listed in Table 1.

Example 11

A mold plate was made containing 100 parts of a
Ethylene-vinyl acetate copolymers (Alkathene A9S39 from Imperial FC Chemical Industries Ltd.), 20 parts of the brominated texphenyl and 20 parts of antimony oxide. The panel was tested using ASTM test method D 635-68. 4 samples were tested; the results obtained are shown in Table 1
shown.

Comparison comparison 7

A molded plate of .Alkathene A9839 containing no brominated terphenyl or antimony oxyc was made. the
^ Flammability was measured using the test method described in Comparative Experiment I.

Example 12

A Genisch cup 100 parts of the epoxy resin Epikoto 828, 20 parts len des Ep oxyb.2 rises Epicure T (Shell Chemicals Ltd.), 8 Teileij

Dialphanol phthalate, Aiphanoi = commercial mixture of
C-7 to C-9 alcohols, 15 parts of the brominated terphonyl
and 15 parts of antimony oxide became one

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Plate potted and tested using ASTM test method D 635-68 checked. The results obtained by testing 5 samples are shown in labeile 1.

Comparative experiment 8

An epoxy resin sheet was made in that described in Example 12 Made dry, with the modification "that the broiaierte Terphenyl and the antimony oxide have been omitted for flammability the plate was borrowed using the 1 described "procedure; the result is shown in Table 1"

Example 15

100 part © polyethylene terephthalate (KYP Hostaäur 4022 Farbwerke Hoechst), 4 parts of Bror / iierten terphenyl and 2 parts Antiraonoxyd were mixed miteinsndei ¹ and extruded the mixture into rods having a diameter of 0.6 em. The polyethylene terephthalate rods were cut into 15.2 times long sections, the detachability of which was tested with the aid of ASTH test method D 635-68. The results obtained by testing 5 samples are shown in Table 1,

Example 14

II'lscim-retardant PolyUthylerite terephthalate sticks were in dex * in Example 13 described Veiae produced, with de * Abänüeiung,

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BAD OBlGiNAL 209828/096 /,

that 8 parts of the brominated terphenyl and 4 parts of antimony oxide were used. 5 samples were tested; the results obtained are shown in Table 1.

Comparison test 9

A polyethylene terephthalate rod containing no brominated terphenyl or antimony oxide was extruded in the manner described in Example 13. The flammability was determined using ψ of the DCFs test method D 635-68 measured. The result obtained is shown in Table 1.

Example 15

100 parts of silicone rubber (Silastomer 2454 Masterbatch der Midland Silicones Ltd.), 16 parts of the brominated terphenyl and 8 parts of antimony oxide were formed into a plate shape at 45 C, formed into a flat plate at 115 ° G and post-cured for 24 hours at 250 ° C,

The flammability of the material was determined using the example 3 tested procedure. A time to extinguish 8? Seconds found. A comparative experiment was carried out using a silicone rubber sheet performed »the no brominated torphenyl or antimony oxide. When testing according to the method described in Example 3, it was found that the material 19Q Se- • announce burned.

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Example 16

A flame retardant sheet made from flexible polyvinyl chloride was made manufactured according to the following recipe:

Polyvinyl chloride (Corvic P65 / O2 from Imperial

Chemical Industries Ltd.) 100 parts

Uialphanol phthelate 80 parts *

Epoxy Stabilizer "2 parts

bariuii- / cac! mium-containing stabilizer '2 parts

bronzed terphenyl 10 parts

Antimonoxyci 5 parts

The flammability of the material vmräe with the help of the British Standard test procedure ITr. 3119: checked in 1959. In this test a strip of the material to be tested is hung vertically and the lower end is ignited. The duration of the burn After removing the pilot flame is determined and a Spreading afterglow after the flame has been extinguished is observed. It was found that after the above formulation The catalytic converter produced was self-extinguishing, with the flame extinguishing after 3 seconds.

A comparative experiment was carried out with the aid of a polyvinyl chloride material carried out according to the recipe given above, but which did not contain any brominated terphenyl or antimony oxide. This hangover burned steadily and the 31.7 cm line wnr jr'.oh reached 62 seconds.

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Example 17

100 parts polycarbonate (Kakralon 3000 L NAT from the paint factories Bayer) -were with 10 parts of the brominated terphenyl and 5 parts of antimony oxide mixed in a tumble mixer and then in Extruded shape of rods with a diameter of 0.6 cm.

Polycarbonates are without the addition of flame retardants self-extinguishing and it is therefore difficult to explain the effect of adding a flame retardant to the polymer. Although the polycarbonate is self-extinguishing, it is desirable to add a flame retardant to it, because in a fire the polycarbonate can come into contact with flammable material ^^ and cause the fire to spread can.

In this example the effectiveness of the brominated terphenyl as a flame retardant in a polycarbonate Use of laboratory oratory test UL 94 proven by applicant. A 15 j 2 cm rod of the extruded polycarbonate that Containing brominated terphenyl and antimony oxide became vertical hung so that the lower end is 0.95 a above the Sp.it>. · ο of a bunsen burner.

The burner was removed from under the sample and adjusted so that he trained a ο 1.19 cm high blr-ue llr-mipie '. lic Test flame was placed under the sample for 10 seconds and there in

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removed. A layer of cotton wool was placed under and from the sample at a distance of 30.5 cm from the end of the sample Particles falling from the sample which ignited the cotton wool were considered to be flammable. During the test, no ignition of the cotton was observed by particles falling from the polycarbonate rod with the Brominated terphenyl and antimony oxide levels fell. When a comparative rod was tested, that of polycarbonate without a content of brominated terphenyl or antimony oxide the falling particles ignited the cotton wool.

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209828/0964

Tabel

Example number of average burning speed

Samples lent extinction

duration (seconds) 2.54 cm / min.

Comparative experiment 1

Comparative experiment 2

Comparative experiment 3

Comparative experiment 4

Comparison attempt 5

10

Comparison document 6

11

Comparative experiment 7

12th

Comparative experiment 8-

13th

Comparative experiment 9

10

5 1

5 1 2 1

4 3 3

5 1

5 1 1.6
1.5
3.1
6.0
47

1.9

1.3
5.0

1.5
10.0

15.7

0.50

1.60

0.70

0.90

0.76

0.60

0.60

0.95

0.60

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209828/0964

Claims (7)

Claims 1. Polymer composition, characterized in that it is an organic polymer and as a flame retardant Contains at least one bronated terphenyl. 2. Polymer composition according to claim 1, characterized in that it has a brominated terphenyl 7 "to 13 bromine atoms, preferably 11 to 13 brometomaipro Molecule, contains. 3. Polymer composition according to claim 1 or 2, characterized in that it is a mixture as brominated terphenyl from broiaierten o-, m- and p-terphenyl contains. 4. Polymer composition according to claims 1 to 3, characterized g e k e η η draws that it contains the brominated terphenyl in such an amount that a total bromine content of at least 3 percent by weight, preferably from 5 to 10 percent by weight, of the polymer is achieved. 5 · Polymer composition according to claims 1 to 4, characterized in that g e k e η η draws that they additionally antiinonoxide in an amount of at least 1 part by weight to 8 parts by weight of the brominated terphenyl, preferably in a small amount BATH ORIGINAL 209828 / 096A from 0.3 to 1, 5 parts by weight of antiinone oxide per part by weight of brominated terphenyl. 6. Polymer composition according to Claims 1 to 5> characterized in that it is a polyolefin as the polymer contains. 7. Polymer composition according to claim 6, characterized in that sic contains polyethylene as the polymer. ORIGINAL BATHROOM 209828 / 098Λ