DE1544834A1 - Process for rendering artificial or natural plastic masses incombustible - Google Patents

Description

plastic masses

The invention relates to the incombustibility of artificial or natural plastic masses with the help of bromine derivatives Triehlorbenzols, namely the mono-, di- or iribromo-Triehlorbenzo-Ie, which are used individually or in combination.

The invention also relates to the industrial production of the new combustion inhibitors from Bromtriehlorbenzenes by bromination of trichlorobenzene, which is obtained during the dehydrochlorination of the so-called "inactive ^M hexachlorocyclohexanes, ie the compounds that are obtained after separating the ^ - isomer of hexachlorocyclohexane.

The invention has found that the mono-, di- or tribromo-trichlorobenzenes, individually or in the form of their binary or ternary

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Mixtures in all proportions, valuable tools for To represent incombustibility, if one si · in plastic masses of artificial or natural origin of the most diverse Incorporated, especially in products of polymerization or copolymerization such as polystyrenes, polyolefins, polyesters or elastomers such as synthetic or natural rubber.

In general, an inventive addition of the above-mentioned substances in quantities below 40 satisfies öew.-SG of the offset with them plastic mass vat this remarkable combustion retardant properties to grant. But you can also use the additives in higher proportions, which can go up to 100 $ of the basic mass. The preferred additional amounts of the combustion-inhibiting additive are between 2 and 20% of the plastic mass added with it. However, this area need not be viewed as critical, since the amount of combustion-inhibiting substance incorporated depends on the type of base material. In addition, the substances used can be used together with additives of very different Dräger substances, be it with mineral or organic powdery or fibrous substances, with reinforcing agents, with colored or non-colored pigments, with plasticizers, lubricants, other burns.

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tension-inhibiting substances than those according to the invention, with vulcanizing agents, with polymerization or polycondensation capacitors, with antioxidants, stabilizers, blowing agents or other auxiliary materials. The application can be used according to the customary methods take place, such as incorporation under pressure, with physical contact, by extrusion, vulcanization or like that. It can therefore be seen that the raw materials or the finished products made from them render irreversible after they have been used various compositions according to the invention can have. The invention is accordingly not restricted to the exemplary embodiments given below.

The invention is illustrated with reference to the combustion-inhibiting bromotrichlorbeneols, the properties of which are obviously not depend on the origin of these products derived from the bromination of trichlorobenzene. In particular, you know that you 1, 2 or 3 Bromatoae in place of the corresponding number of hydrogen atoms in trichlorobenzene can be put according to the classical bromination processes as described in the literature. A method of obtaining these products, which proceeds directly and is of particular interest for practical use consists in the bromination of trichlorobenzene, as it is available as a mixture of its isomers

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is an intermediate product in the manufacture of hexachlorocyclohexane.

In fact, the existing industrial quantities consist of mixtures of the three isomers 1, 2, 3 or 1, 2, 4 or 1, 3, 5 of trichlorobenzene. This mixture of isomers is obtained from

DehydroChlorierung (thermal, alkaline, etc.) of the so-called "inactive ^w hexachlorocyclohexanes, which are separated from the insecticidal / insecticidal isomer, during whose production they unfortunately arise in large amounts (over 80 #) when chlorinating the benzene.

The mutual ratio of the three isomers of trichlorobenzene varies depending on the dehydration method used of hexachlorocyclohexanes, but isomer 1, 2, 4 generally predominates, whereupon isomer 1, 2, 3 and finally the isomers 1, 3, 5 follows.

The applicant has now found that when brominating the technical (xemize these three isomers as derived from dehydrochlorination of the hexachlorocyclohexane are obtained without prior separation being necessary, the recovery of mono-, Di- or tribromo-trichlorobenzenes or binary or ternary

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Mixtures in all proportions of the components mentioned is possible.

The mixture is used to prepare such bromothelobenzenes the trichlorobenzene isomer is brominated, for example by gradually adding the bromine to the trichlorobenzene, either without a diluent or in the presence of a diluent, which is insensitive to bromine or to the forming hydrogen bromide, and mostly also in the presence a catalyst, which can consist of iron bromide.

The catalyst can be washed out with water or alcohol at the end of the reaction if it is iron bromide, or the separation from the catalyst can also be carried out by subliming off the bromine chloride, in which case the catalyst then remains as a heavy residue.

If necessary, the bromotrichlorobenzene can be made from carbon tetrachloride be recrystallized. In all cases, and even if no subsequent recrystallization is carried out, is obtained one solid white powdery product, the melting point of which depends on the composition of the mixture used Trichlorobenzene isomers and their degree of bromination changes.

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The invention is therefore not restricted to the use of certain particular bromotrichlorobenzenes, as are given in the following examples, but rather encompasses very generally di
Use of these compounds or mixtures obtained
are brominated in the above technical mixtures of trichlorobenzene isomers.

The following examples 1 to 3 illustrate the position of trichlorobenzene and of bromotrichlorobenzenes, as used according to the invention, while Examples 4- to 12 the use of these bromotriochlorobenzenes as combustion-inhibiting additives for certain plastic materials and natural rubber describe.

example 1

For the preparation of trichlorobenzene by dehydrochlorination
of hexachlorocyclohexane, a 5 liter flask is used
Pyrex glass with external heating, for example an electric heating envelope, above which a vertical furnace, lined with pumice stone , is attached. 1 kg of so-called "inactive ^H isomers of hexachlorocyclohexane" are introduced into the flask and have the following composition

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83 H W isomer 14 Ji / J isomer 3 Ji TerscJiied other isomers.

The oven is heated to 500 ° C. and the temperature is gradually increased Temperature inside the flask up to 300 ° C, from 200 ° C one notices a decomposition of the hexachlorocyclohexane in hydrochloric acid and trichlorobenzene.

Bas trichlorobenzene, the boiling range between 200 and 200 C lies, has a certain amount of τοη hexachlorocyclohexane, its Vapor tension is already considerable at this temperature, ejected from the flask. When passing through the subsequent furnace, which is heated to 500 ° C and lined with pumice stone a substantial decomposition of the driven hexachlorocyclohexane in trichlorobenzene and hydrochloric acid has already taken place, so that one at the exit of the flask and then Oven existing unit only trichlorobenzene vapors and Catches hydrochloric acid without hexachlorocyclohexane. The vapors emerging from the furnace are condensed together and the trichlorobenzene is washed with water to remove the hydrochloric acid.

The trichlorobenzene obtained in the form of a mixture of the

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Isomers has the following composition:

24 i » 1, 2, 3 isomer
74 1 ° 1, 2, »4 isomer
2 $> 1, 3, 5-isomer.

This isomer mixture is a pale straw yellow clear liquid with a density of 1.5, the melting point of which is close to + 3 ° C, while the boiling range at atmospheric pressure is between 200 and 220 ° C.

Example 2

For the preparation of dibromotrichlorobenzene by brominating ! Trichlorobenzene uses a cylindrical pan made of Pyrex glass of 1 1 fitting space, which is to be heated on the sand bath and with a tight cover, as well as a stirrer and reflux condenser is equipped.

300 g of bromoform are introduced into this pan, as well as 250 g of trichlorobenzene from Example 1, 450 g of bromine and 40 g of iron bromide. It is carefully heated while stirring and the temperature regulated according to the evolution of hydrogen bromide and so that

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an escape of bromine is prevented. The reaction is brought to an end by heating to HO ⁰ G. The end of the reaction is assumed when all the bromine has been absorbed and when there is no further evolution of hydrogen bromide.

The bromoform is now distilled off under reduced pressure and a solid mass is obtained from which the dibromotrichlorobenzene is added in good purity by sublimation in a stream of air 250 ° 0 can be aborted and recovered., In this way 450 g of dibromotrichlorobenzene are obtained in the form of white needle-shaped crystals with a melting point of 245 ° 0.

Example 3

For the preparation of tribromotrichlorobenzene by brominating Trichlorobenzene, a cylindrical pan made of Pyrex-G-las is used of 1 1 capacity, which can be heated on the sand bath and with a tightly fitting lid, further with a stirrer and a reflux condenser kept at 0 ° C is equipped.

500 g of trichlorobenzene from Example 1 are introduced into the vat, and 1000 g of bromine , in which 25 g of iron powder are dissolved, are added. The mixture is stirred

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gradually heated from 30 ° C to 100 ° C, so that a uniform Hydrogen bromide evolution takes place and the escape substantial amounts of bromine is prevented. Starts at 30 ° C the evolution of hydrogen bromide, accompanied by the process of bromination of trichlorobenzene. After a certain time the reaction mixture has become thick and crystals of bromotrichlorobenzene appear, which are suspended by stirring must be kept. The trichlorobenzene originally used is completely brominated if there is no hydrogen bromide development takes place more.

The excess bromine is now distilled off and the tribromotrichlorobenzene obtained is washed with water to remove the greatest amount Remove part of the iron bromide. 1150 g of a solid powder are obtained which are colored slightly pink due to iron bromide residues is. If you want to remove all of the iron bromide, you can recrystallize the tribromotrichlorobenzene from carbon tetrachloride. In this way, fine white odorless crystals are obtained in the form of a mixture of different isomers, which correspond to the three isomers of the starting trichlorobenzene. The melting point is 265 ° C.

Example 4

In a Banburry mixer heated to 170 - 180 ° C ^:

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95 parts of polystyrene, 5 parts of dibromotrichlorobenzene from Example 2, or 5 parts of tribromotrichlorobenzene from Example 3 were introduced.

Before that, you have the anti-burn agent (dibromotrichlorobenzene or tribromotrichlorobenzene), if necessary also with customary additives such as lubricants, plasticizers agents, stabilizers, etc. in a part or the Total amount of polystyrene distributed. This first mix can take place at normal temperature or at elevated temperature, but always below a softening range Mixture. All devices suitable for mixing powders, such as drum mixers, ribbon mixers and the like, are suitable for this.

Have the products received at the exit of the Banburry machine remarkable resistance to scorching as summarized in Table I below Shows results obtained by applying the test according to ASTM D 635-56 T to the incombustible Polystyrene.

In the test method according to the test mentioned, an attempt is made to use a Bunsen burner for 30 seconds and two

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consecutive try 1 and 2, a sample of the product to inflame "

»Table L

Test material attempt 1
Number of samples flammable Attempt 2
Number of samples flammable Pure polystyrene self-extinguishing 20/20 self-extinguishing Polystyrene + 5 #
Tribromothrichloro
benzene 0/20 0/20 4/20 Polystyrene + 5 #
Dibromothrichloro
benzene 20/20 0/20 16/20 3/20 20/20 17/20

The mechanical properties and transparency of the
so unbrennbargemachten polystyrene were comparable to those of serving as a base material polystyrene _o

Example 5

In a Banburry mixer heated to 170-180 ° 0
incorporated 95 parts of granular polystyrene and 5 parts of tribromotrichlorobenzene from Example 3. The procedure and the conditions observed were the same as in Example 4. "

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A product is obtained which has good burning resistance, as shown in Table II below.

Table II

Test material Attempt 1
Number of samples flammable Attempt 2
Number of samples flammable Polystyrene grain
tion
Polystyrene grain
+ $ 5 tri-
bromtri chlorobenzene
zol self-extinguishing 20/20
3/20 self-extinguishing 2/17 0/20
17/20 15/17

Color, transparency and mechanical properties of the incombustible Polystyrene are in turn quite comparable to the polystyrene grains chosen as the starting material.

Example 6

82 parts of granular polystyrene mass, 11 parts of tribromotrichlorobenzene from Example 3 and 7 parts of antimony oxide are introduced into a mixer with two cylinders, which is heated to 170-180 ° C. This gives a remarkably feuerferfces product that goes 635-56 T when using the self-extinction test ASTM D as soon as the flame of the Bunsen burner "

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removed, as can be seen in Table III below.

Tribromotri
chlorobenzene Sb ₂ O ₃ Tabel III ν er suct burning
bar attempt 2 burning
bar 0
11 0
7th L 1 20/20
0/20 Number of samples 0/20 Number of samples self
going out self
seeing eril 20/20 composition of the mixture 0/20
20/20 Self-extinguishing test olystyrene
örnung 100
82

The incombustible granular polystyrene produced in this way is white, translucent and has good impact resistance.

Example 7 ·>

84 parts of low-pressure polyethylene, 11 parts of dibromotrichlorobenzene from. Example 2 and 5 parts of antimony oxide are introduced into an internal mixer of the Banburry type, which is heated to 150> -170 ° C. The samples prepared from the product obtained are again subjected to the ASTM D 635-56 T self-extinguishing test

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subject. Your burning goes out immediately when the bunsen flame Will get removed.

They show mixtures made incombustible according to the invention the appearance of translucent white bodies with mechanical Properties that come close to those of the original polyethylene.

Example 8

The same procedure was used as in Example 7 "and the same results were obtained, only with the difference that that the raw material used was polypropylene instead of the polyethylene previously used.

Example 9

They were placed in a two-cylinder mixer heated to 150 ° C 85 parts of low-pressure or high-pressure polyethylene, 15 parts of dibromotrichlorobenzene from Example 2 or tribromotrichlorobenzene from Example 3. The resistance to burning of these mixtures was again determined using the ASiEM D 635-56 T test tested, with good results according to the following Table IV were obtained.

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Table IV

Test material Attempt 1
Number of samples flammable Attempt 2
Number of samples flammable Polyethylene
Polyethylene +
1556 tribrom tri-
chlorobenzene
Polyethylene +
15 # dibromtri-
chlorobenzene self-extinguishing 20/20
0/20
0/20 self-extinguishing 2/20
3/20 0/20
20/20
20/20 18/20
17/20

The mechanical properties of the products obtained were close to those of the polyethylene base materials.

Example 10

A mixture was made from the following components:

100 parts of a polyester resin with a viscosity of 110 cP. at 25 ° 0 and a grade of $ 42 styrene and $ 58 one Condensation product of 1 mol of steel anhydride and 1 mol Maleic anhydride with 2 moles of propylene glycol.

40 parts of the mixture of tribromotrichlorobenzene from Example

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1.5 parts, a 50 ^ solution of peroxide of methyl ethyl ketone in a plasticizer such as diethyl phthalate

0.2 parts cobalt naphtenate with a metal content of $ 6.

A glass fiber mat of 900 g / m 2 was obtained with this mixture. soaked in such a way that the product was about $ 40 glass wool. It was left for 48 hours and then polymerized for 15 hours at 80 ° C to give a translucent To obtain laminated bodies, a sample of this was made 400 χ 100 mm cut off, which were hung vertically at a distance of 20 mm from the floor in a housing 20 mm in diameter. 2 com of absolute ethyl alcohol was poured into the vessel and lit. The following resulted:

Burn time of alcohol 165 seconds

Burning time of the layered mat sample 620 seconds burned surface '87 com.

In contrast, a corresponding layer mat sample burned, which did not contain any tribromotrichlorobenzene, completely under the same conditions.

Example 11

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The following mixture was produced:

100 parts of a polyester resin with a viscosity of 110 oP. at 25 ° C and a content of 42? 6 styrene and 585 t of a condensation product from 1 mole of steel anhydride and 1 mole of maleic anhydride with 2 moles of propylene glycol.

100 parts of the mixture of iribromotrichlorobenzene according to the example 3.

2 parts of a 50 ^ solution of peroxide of methyl ethyl ketone in a plasticizer such as diethyl phthalate.

0.5 part cobalt phtenate with 636 metal content.

A glass fiber mat of 900 g / m 2 was made with this mixture soaked in such a way that about 40% of the product made of glass fibers duration. This mat was left to stand for 48 hours and then polymerized at 80 ° C. for 15 hours to produce a translucent layer mat

from this a sample of 400 100 mm was cut out vertically at a distance of 20 mm from the floor in a vessel of 20 mm in diameter was hung. 2 ecm of absolute ethyl alcohol was poured into the vessel and set on fire. It resulted the following:

Burn time of alcohol 180 seconds

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Burning time of the layered mat 120 seconds

ρ burned area. 10 centimeters.

example

Ee several mixtures were prepared, their composition for are given in Table 7 below.

Table Y

Mixtures A-B

Natural rubber (smoked leaves) natural carbonate of lime (chalk) Stearic acid zinc cyanide sulfur mercaptobenzothiazole Tribromotrichlorobenzene from Example 3

100 100 100 100 1 ■ 1 5 5 3 3 1 1

210 240

Of the raw mixes, the Mooney properties were; ten determined; vulcanization was then carried out for 20 or 30 minutes at 143 ° C., and the mechanical

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Properties of the vulcanizates thus obtained are determined. The results are summarized in Table VI:

Table VI

igensohaften (viscosity level in ⁰ M) tooney (fixation time t, - in min.)

at 120 ° C (vulcanization index in minutes) ulcanization: 20 minutes at 143 ° C

Module 300 £ Extension in kg / cm. Rebound elasticity i » Shore hardness

ulcanization »30 minutes at 143 ° C

Module 300? I Extension in kg / cm Rebound elasticity % Shore hardness

On test panels with a thickness of 2 mm, which are heated for 20 minutes at 143 ° C were vulcanized, plam-extinguishing agents were now in the following way search employed:

ichun S A Mixture B 39 25th 44 30th 30th 30th 29 30th 50 52 54 55 28 29 57 52 54 54

It was placed the plate on a tripod, at which

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a .Bunsen burner with burning ignition flame was attached. The burner was set up in such a way that the children laughed the plate was in the cone of flame. The contact of the flame and the plate was held for 30 seconds and the flame then withdrawn. The vulcanizate sample A ignited his son Ss formed a rather extensive one Flame. When the Bunsen burner was withdrawn, the flame remained until the plate was completely consumed. The plate of vulcanizate pattern B ignited - much more difficult, and the resulting flame was also much smaller.After removing the Bunsen burner, the flame went out after 3 Seconds «,:

As already stated at the outset, the invention is not based making incombustible as discussed in the previous examples plastic masses limited. Rather, it can be generally used in the most varied of types and ways plastic masses of artificial or natural origins, use.

Patent anaprüohey . - *

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Claims (1)

S.A. Etablissements KUHLMAMN, Paris (P-rankr.) Claims · Process to identify artificial or natural plastic mass, characterized in that the base mass at least one bromine derivative of tri chlorobenzene, ie a mono-, di- or tribromo-trihlobenzene individually or in Jonah of their binary or ternary mixtures in all proportions, is incorporated. 2 · The method according to claim 1, characterized in that the at least one bromotrichlorobenzene-containing combustion-related Substance in quantities up to 100 6ew .- # of those mixed with it plastic hatred is applied. -, 3. The method according to claim 1, characterized in that an amount of bromotrichlorobenzene of less than 40 weight percent, preferably between 2 and 20 weight percent, is added to the plastic compound to which it is added. 009811/1386 -2- 4. Procedure according to. Claims 1 - 3, characterized in that bromotrichlorobenzenes which inhibit combustion are used which are obtained by bromination of technical mixtures of triochlorobenzene isomers, such as those which are formed by dehydrochlorination of hexachlorocyolohexanes except for the t ¹ isomers of these compounds. 5. Process according to Claims 1-4, characterized in that the products of polymerization or copolymerization processes, such as polyolefins or polyesters, serve as the plastic masses to be made incombustible. 6. The method according to claims 1-4, characterized in that artificial or natural elastomers, such as rubber, are used as plastic masses to be made incombustible. 009811/1366