DE1803645C - Pentabromophenoxysilanes their use as flame retardants - Google Patents

Description

The invention relates to pentabromophenoxy ! -. ilane's formula

wherein R 'en is methyl or the penlabromophenoxy radical.

The connection also affects the use Pentabrüiiiphcnoxysilane as Flamimer / ögerungsmitiel for Polynierenma ^ .en made of polyolefins. Polyesters and polyurethanes, optionally 0.5 to 1.5 parts by weight of monoxide per part by weight Contains silane in e. of such men. that the mixture is 5 to! 0 percent by weight prom, based on the polymer mass.

The inventive. brominated silver derivatives are in a known manner by reacting pentabromophenol with silicon tetrachloride or »Lyltrichlorosilane produced. This condensation becomes in the presence of a base as an acid acceptor and an inert organic solvent using st och 10 never Irish ei 'quantitative ratios-carried out.

When using a base that has a replaceable-., An has a nitrogen atom bonded Wasserstuffatoni, it is appropriate to carry out the procedure in two stages. Those in the first stage of this Yerfa'.rens The preferred base is diethylamine. Both stages of the procedure are preferably used at elevated temperature up to the boiling point of the reaction mixture ^ carried out. Suitable inert Examples of solvents are uenzene and toluene.

Fin particular preference is given to those used according to the invention as anti-scaling additives for polymer compounds Compounds is their property, in contrast to numerous common flam, .ihemmenden Additives for plastics to be stable at elevated temperatures up to 300 C Compounds are therefore advantageously left as flame-retardant additives to polymers used, which is worked out at high temperatures and / or during her: r application exposed to high temperatures. Λ5

For example , the tetrakivphenylabromophenoxysilane according to the invention has a melting point of 1 HO C and a decomposition temperature of 3X0 C, while known anti-inflammatory agents such as pentabroniphenyl allyl ether or pentabromophenol decompose at 260 C. Because of the higher melting points of the compounds according to the invention, they can be used at significantly higher temperatures than the known flame retardants and can therefore be incorporated into high-melting thermoplastic materials, which was previously not possible in practice. Nevertheless, their flame-inhibiting effect is in the range of the known flame retardant media specified.

The amount of flame retardants added to a polymer composition. according to the invention; ii. '; n connection is of the special one. Polymer depends and also depends on the total bromine content or the flame-retardant compound used and the desired degree of flame-retardant properties of the polymer composition. depending on whether you want to achieve a self-extinguishing or a non-combustible mass.

The effectiveness of the compounds of formula 1 as flame retardants can thereby increase: be, -laf! one of the polymer mixture as well in a manner known per se arsenic trioxide, arsenic sulfide, Antimo.iuxid, Antimonsiillid or organic antimonates incorporated. We prefer antimony oxide in an amount of 0.5 to 1.5: 1 parts by weight of the according to the invention Silane.

The flame retardant compound (and optionally the antimony or arsenic compounds mentioned above) can be added at any stage during the preparation of the polymer composition. So can flamrrhcmmendc compound before polymerization added to a monomer or, which may be more favorable, to an already formed polymer will. Other common components of polishing compounds, like Füü.-aoffe, plasticizer. Pigments and stabilizers can also be incorporated will.

Production of methyl-tris-penlabromophenoxysilane

2.98 g; 0.02 mol) methyltrichlorosilane were added to 29.2 g (0.06 mol! Pentabromophenol in 200 ml of toluene. Then 1 ml of dimethylformamide was added and the mixture was refluxed for 6 hours. Then the reaction was'.'7 ¹ V ₁ , expired (determined by HCl titration). A white solid was isolated and identified as methyl-tris-peniabromphenoxysiliin. (26.0 g. 80%) mp 256 C. Found: Br. 78.5%, for C ₁₀ H;, Br ,, O;, Si theoretical Br. 7'λ9%.

CH ₃ SiCl _n - 3C ₁₁ Bo ₁ OH -VClL ₁ Si (OC ₁₁ Br ₅ H 3Η'.ΓΙ

Manufacture of Tctrakis-pentabromophenoxysilane

\. 17.0 g (0.1 mol) of silicon tetrachloride were added at room temperature to 198.4 g (0.4 mol) of pentabromophenol in 500 ml of toluene and the mixture was heated under direct pressure in the presence of dimethylformamide (5 ml) for 12 hours second portion of dimethylformamide (5 nil) added. A white solid was isolated which was insoluble in toluene, stable to water, dilute acids and strong alcohols. Fr was identified as I etrakis-pentabroiii,) heno, <v-silan. r'p. 365 C (dec.). Found: B. 7'v, 9 "", for C ₂₁ Br ₂₀ O ₁ Si theoretical: Hr 80, .ΐ%. Yield 1 Sf) g | 95 "<_;.>. By titration

- ciitsi. '. ii.Ions of hydrogen chloride could be fe ^ tge-JIi. that a ¹ ) SS "" i ^ e reaction emueirelen

SiCl ₁ · _4C; Hr -, () H - SiM> C _i; Br. !, 4HCl.

i) i ·· Sublimation speed inditrkcit des 1 ■ _lraV is-penta- -.> ir: plien.i \\ -> jlan (.4 (5MPiSi) was created by hrlm / en r check from

or compound in a crucible

g g

a constant temperature \ on 25 () C uo-

dtetu-n furnace determined. The Cicw iditv.erk ^ i and d.i.- »in ι -, rather, animal test winds after 1.3 and Zt) hours

■ nnmil. The following results have been obtained:

. 'icwchN · .o

S /

K-1 2 ^: u ι p.ich

iiicil 1 2 \> SiU'.V.icrt

S /

S /

weak zerd / u

B. 100 g Pentahroniphoiiol ίΟ, Ι'ϋ. ^ \ | Nl | were 'hours with ^ι ·> .3 ΰ (0.0 ⁵ Mr ,!) Silici ii niieir-.ich' · .nd

■ u! 25 ml DrU ', \ Holm imid in toluene under Piiekiluss. ■■! ■ .'l / l. The white product has been purified. dried ι:.: ali Teirakis pentahrompheno. \\ -. i! .m iJentili / iert. • '• ■■! ■■ .heue: .U: t'4 "" i I p. Vi3 C ((.found: l! R.' -.X "": calculated for ('.., O ₁ U _{/ ü} Si. Br. SO ",,).

C. K) O g Pentahremplunnl (0.20.5 mol) were -nil '! .3 μ (0.Or, - minor Si'iciiimietrach> rid tiiid 25 ml Me-;'i>! Phen \ liorm.imid (N -Meth \ lfoimanihd) Hi Sum.! En πι.?! «) Ml Tokyo! reflux x-hook. The resulting blue-colored product was named lelrakisl'j'Viabroiiniiienoxy-Mlan uleriiüi / icr; l-'p. J55 l.iis 3Mi C. Ausbciile 5Ki: (5 '! "., I ((ief.:nden. Ii ;. ΤΗ". ,,, ι *, l ^ rethnet for C _2, ι' ( ' Dr ₁₁₁ Si. Lir. SO "_(; ».

I). 100 g (0.205 MÜ'.i l'enlabroirpiiemil were nut '), 3 w (0.05 MnI) Siliciumietr.ichlork! and 10g IM-pl eiijlfoimamid in 300 ml Γ'ΊηοΙ and treated for 20 hours at ':! 2 held under Rikkilull. The product obtained was isolated aK dunkehiruniT I est'-toff, which was ideniili / ierl a's \ erimiemigte- I elrakis penlabromphetioxy-silane, '' uisheuto: 26 g (. "! F>" · '"). The product proved to be difficult to clean, after several successes it retained its color and lilily a si hniel / punl-.i \ ou 34: "» until JS5 C. (fell: Hr. 7n .3 ".V lier.-i.hnel TUrCj ₁ Hr ₂₁₁ O ₁ Si. Hr. HO ₁ O ¹ V ₀ ).

I. K) Og (11.205 Moli l'enlahrnmpheno! Were treated with '.', ■■. I; (0.2 mol) Sibuuni urothloride and 30 ml \) i inelinlaeet.imid in 100 ml toluene and the 1 ic mix! Fi ■ t occurs at UO C under reflux challs. The solid product obtained was identified as a tetra'kis-penuhromphenoxy-siUin and isolated as a white ester with a melting point of 355 to 360.degree. Yield. Xi g! W ¹ · ',,). ((jefunde:.: Hr. 79,4 "/ ,,, lierechiiel for C ,, HrJ ₁₁ O ₁ Si. Hr. SO ⁰ ',,).

Il> - ■ i s ρ 1 c I I

100 parts of eitvs low-density polyethylene (Man- fi <> ddsname -.Alkatriene "XIKi 33, a product of the I. Cl. 1 ul.'i in coarse-grained lorm were plasticized on a / wci-W ^ / ui chair at 155C Telrakis-peiHiibromophynoxy-silane was slowly added and mixing continued for 5 minutes after the last addition from 'V'fornit, another 2 minutes at 70.31 kg-cm ² and 155 C \ erpreHi and then 2 minutes at a pressure of 35.15 kg cm- cooled.

The serformte material was in 5 samples of 12.7 cm length. '.27 cm wide and 0.317 cm thick. The test bars were annealed at 23 ° C. for 24 levels for their test for new properties. The testing of the samples for lamming properties was carried out according to the STM test method D 635-56, with the modification that the number of tested samples was 5. not 10 as seen in the test. The classification of the flammability takes place in the Λ. S. iMTest D 635-56T specified. The Rcs'.ilute obtained are shown in Table 1.

Example 2

The procedure according to Example 1 was repeated, with the modification that 5 parts of 1 eirakis-pentabromophenoxy-silane and use 5 files of antimony instead of 10 parts of tetrakis-pentabromophcuoxy-silane became. Test bars were made as in Example 1 and checked. The obtained b.ig results / ei «! Table 1.

B e 1. Γ · ι e 1 3

The procedure of Example 1 was repeated where in addition / u the 10 parts of Telrakis-pcntabromophenoxy silane 10 Ί parts antiinonoxide were used. The lamb-retardant properties achieved e-i are listed in dragonfly I.

B e 1 s ρ i e 1 4

The procedure of Example 1 was followed with the modification repeated. · Κι! 5 20 (i "-weight parts letrakispeniabromphenoxy-silane instead of the 10 used in Example 1 (each part of the view, "escin. The he / ial flame-suppressing effect is given in Table I. approved.

Comparative example I

There was a request for a review according to the procedure of Example 1 carried out, but no lamb-inhibiting compound / ugcset / t was. the Testing for lamb-retardant properties was carried out canceled after 3 samples were tested and classified as flammable. The received Events are listed in Table I.

V'ei equal, for example i I

Ιλ became a control according to the procedure carried out according to Example 1, the 10 parts by weight Telrakis-peulabromphenoKy-silane omitted, however, 20 (. icwiehlsieilc Anlimonoxid were added. The l-rgebmsse with regard to the llammhemnienden Properties are listed in Table I.

Example 5

/ u IO parts of a liquid polyester resin (trade name “Stypolc 40-2417, distributed by Freeman Chemicals Ltd.) were H parts of tetrakis-pentabromophenoxy-silane a sieve size of I 52 μ (corresponding to a BS test sieve of Maschen / ahl KX)). 2 parts Benzoyl peroxide and 50 parts of potassium carbonate were added as fillers. These additives were used in the The order listed follows' a / a by stirring with the polyester resin. mixed up until there. Mixture homogeneous was

¹ part ι ί fiberglass in the form of a size of 15.2 · 10.2 cm and the homogeneous mixture were placed as alternating layers of glass fibers and polymer mixture in an oven preheated to 120 ° C. and heated for 2 minutes under slight pressure. The material in the mold was then heated to a temperature of 120 ° C. for 1 Vimule. 40 seconds, under a pressure of at least 140 kg cm- pressed. The material was pressurized for a total of 2 minutes. The hot molding was removed from the mold and conditioned for 24 hours at room temperature.

The test for lamb-inhibiting properties is based on a modified version of 11. S. 35/2 I ¹ HiI; uif as follows: "

Line cut sample of the glass fiber containing rOlyesicrmaierials a length of 12.7 cm. !. ■ Here width of 1.27 cm and a Diel- ⁿ before, was: 0.32 cm 111 an I ntfernung of 7.6cm from inside labeled end to be ignited. The sample was clamped in a rigid layer in such a way that its longitudinal axis was horizontal and its transverse axis 45 inclined to the horizontal.

A bunsen burner was zeniral under the free one Place the end of the test so that the burner is 5.1 cm located below the longitudinal axis of the sample. The examination of the lamb temperature showed that this was the in B. p. 3532: Dd. The flame was removed after 30 seconds and the / expressly determined. which had passed. his the sample stopped burn or glow.

The results are shown in Table II.

1! c ί s ρ ι e I (1

The explanation given in Example 5 was repeated. 11111 tier amendment that 4 parts 1 etrakis-pentahromphenoxy-silane and 4 parts of Anlimonoxyd instead of S parts 1 cli \ ikis-peniahroniphen '\\ V-silane used became. The Anlmiommd was after the addition by Benzoylpeiovvd and before the addition of the C alciiimearbonai-l-üllsioffs m das (stirred in. The results regarding the tiamr.ihenimcnd I ige :, are listed in Table II.

Example 7

The procedure according to Example 5 was repeated, with the modification that 4 parts of methyl-tris-penubromphenoxv-silane and 4 parts of anionic oxide were used instead of X parts of Telrakis-pentabromophenoxv-SiLin. Ls samples were prepared and; ·. S tlamni-inhibiting Ligeiisehafien checked. The crha! The best results are shown in fabeile 11!

Example X

i-method according to example 5 was again! ^ h.

Mh'i

mL of the change that you rush nromphenoxy-silane instead of 'mn S Share leti.iki-penlahrompheni' \ y-silaii \ erwui> iet. The Ir Results are shown in Table 11.

Comparative experiment St.

lim control request was made according to the procedure of Example 5 carried out, the flammhenimende Connection was omitted. Hold the egg. Material was tested as in Example 5. The Ir Results are listed in Table II.

Comparative experiment IV

A control experiment was carried out according to the procedure of Example 5. being the one used there H Gi'vichtsteile Telrakis-pentabn> mpheno \ y-si! An Put away and keep its S parts antimony oxide were added. The results obtained when testing the lamb-inhibiting properties are 11, Table II shown.

B ice pie1 ^{1 year}

S-in flexible pole al her- urethane foams off was made as follows:

Three proposals were made with the following composition hergesicMi:

Polyether polyol (Voranol Cl '3720'). . . .
/ innl i I) -ocloal-Katalv, salor (Nuoeure 2S)

Scliauiiistaliilisatoi (Sik'ocell 3N (V)

Amine catalyst (l'ropamme A I

Voranol (P 3720 "is tier I landelsiianie for a through diel inua Dow (henueal Co. (I '. K.) I Id Polvälherpolvol.

Nuoeure? * "Isl dei trade name Γ ί 11 a / in nil I) -Oelnalkaiai ^ saior of I Irina Lankioi iiuiuiwals Ltd,; i5

Silcocell 3S () ^K is tier I lamleUnaine for one by LC. I. Lid. awarded Se'iaunis stabilizer.

Propamme A 'lsi der I landelsiianie for one through I ankro Chemical-. I class displaced AininkataUsalcr.

z'11 255 I cιι> · ιι v'oranol Cl '372 (1 "were XO I eile fm I et 1 al. is-penlaL.i ■ 'iiplienow-sil.m and da 11 acIi 12 Ί hurry ties Aiisal / e-v 1. 20 UiIe des Ansal / cs 2 and IN 'parts tks approach 3 j'ei'ebeu. The (iemisch became after jeili.M / ugabe ι: · ιι .iiiiilui.

Nt I hurry Wa-Ci Aiiiden the mixture zin'eiui'l. fi ;, da-, then ^ e '111. Il Ό seconds ι'.ιίίΊΙιιΊ was, woiaiil I'll I rush 1 in Ic 1 > \ in I l.md' .- l .uamen II ν lone IM through ''"'l'ii'ii (.1 I |. | μ 111 n'lv'iieii I oluoldii ^ ocv anals

An-at / 100 Ί rush
6.x I hurry

Anvil / Z

100 parts

6.6 file

Allsill / 3

lOOleilc iK file

were quickly admitted. The Kühn.-n became like this lye forigc'-eizi. until the (. leiniscii thickened hall, and the mixture was sealed in a ue Eiguele Ii .111 go s, .- ii.

The in tier Lorm '· (icmisc'.i --cliiinmie auf. And after becndigieni Sliäum CJd seconds) the foamed material became a reverberating l'oiin ISMinuien in an oven at 140 C with air circulation J ¹ C-UlIi. wrap around the foam / u. After 2 Miiiiilen Ycrueilzcii in the oven the I Οπή eiiilci ui.

After the foam had hardened, 10 samples were lent a length by 5.1 cm by a thickness of 1 Λ cm. The so ei Ιι: · .Ιΐι · ηι · η Pi'i'ieii wind again in the oils mil I ullzii'kul.ilinn gel; ι and Id hours Ki 140 C IuI /ei'c.illei I.

The l'iobcn w Mitleii! '' MIaIi the /\.S. IN THE.

) 16 ') ?. S ¹ ) T on Ihiniinhetnineiide l.iuensehaflen geiriift.

The so (.TlKtUcIK-Ii iTjiebnisse he / üglidi der Iknnm-Fcsi iiikcit are shown in Table III.

Hey play IO

The process according to Example 9 was repeated using 40 parts of tetrakis-pentabroin-phenoxysilane and 40 parts of antimony oxide in place of the 80 parts by weight of tetrakis-pentabroin-phenoxysilane. The raw materials were produced and tested as in Example 9. The results relating to flame resistance are shown in Table III.

Comparative example! V

The procedure of Example 9 was repeated, but without adding a flame-retardant compound. Test bars were placed in the same manner as in Example 9 on F ^; Lamb strength tested and the results obtained are recorded in Table 111.

Table I.

Weight percent Weight Weight number of flameproof percent percent examined iics means, Bromine, Sb ₅ O ,. rehearse related to based based the resin on the resin on the resin 3 10 8.0 3 5 4.0 5 3 10 8.03 10 3
3
3 20th 16.0 - Γ. 20th

Brandaus spread cm

border

fast-

kcit in

cm / min

Classification of flammability

example 1

Example 2 Example 3 Example 4

Comparative experiment I Comparative experiment II 1.475

1.37

0.685

0.965

1.93

1.81

flammable flammable flammable flammable flammable flammable

Table II Weight percent

flame retardant

dcs means,

related to

the resin

Weight percent bromine based on the resin

Weight percent Sb ₁ O ₁ , based on the resin number of

examined

rehearse

Brandaus spread

in cm / min

Spread of fire in cm

Until

Going out

consumed

time

Example 5 Example 6 Example 7 Example 8

Comparative experiment III. Comparative experiment IV.

8 4 4 8

6.4 3.2 3.2 6.4

4th
4th
4th
4th
4th
4th

1.27

3.56
2.29 3.3 3.8

4.06

122 34 52

115

118

Table III

Salary of Bromine content Sb, O, -G «stop fire Fire protection Classification finally of of the foam spread spreading the focal received Foam Weight percent cm fast- availability Foam on Weight
percent speed in
cm / min flame
inhibiting
Medium, flammable Weight percent 12.82 8th 9.65 4.06 self-assured Example 9 16 6.4 erasing BeisDiel 10 .... 8th - - flammable - 4.8 Comparison attempt V ... -

Claims (3)

Patent claims: 1. Pentahromphenoxysilane of the formula RSi (OQBr.,), ^S wherein R is the methyl or the pemabromophenoxyre > t means. 2. Use of the PentabromophenoxvMlane according to claim 1 as lammver / ögerungsniiitel for polymer masses made from polyolefins. Polyesters and polyurethanes, in such an amount that the mixture was 5 to 10 weight percent bromine based on the Polymeven mass. contains. 3. Use me claim 2. characterized / eidinet, that the polymer mass also 0.5 to 1.5 parts by weight of antimony oxide per part by weight Contain silane.