DE1669938C3 - Process for reducing the flammability of organic high polymers - Google Patents

Description

Cl

/ \ RR

Ci ₁₁ "j y.-x - y ICl-C-CI

Cl

IC "

CVl

Cl

/ H, H-, \! Cl

Cl

in an amount of 1 to 40 percent by weight (based on the high polymer without further Supplements) incorporated, where R is hydrogen or an alkyl group and X is sulfur. oxygen or means one of the following bifunctional radicals:

-SO - -SO ₂

-CH; O CH ₂ -

-CH ₂ S -CH ₂ -
-CH ₂ SO CH ₂

CH ₂ SO ₂ CH ₂ -

CO-O- CH ₂ -

2. The method according to claim 1, characterized in that that one of the compounds or the mixtures of compounds of the general formula given in claim I partially through replaces known fire retardants containing halogens.

3. The method according to claim 1 and 2, characterized in that additionally antimony compounds, especially antimony trioxide. in an amount from 1 to 20 percent by weight, in particular 3 to 13 percent by weight, incorporated.

Flammability is important for a number of purposes of most organic high-polymer materials. Areas of application in which fire safety must be guaranteed. are z. B. construction, mining and electrical engineering. Hs are therefore several attempts have been made to make flammable plastics flame-resistant.

For example, chlorinated hydrocarbons along with salts of metals were the fifth Group of the periodic table used as fire retardant additives. Such mixtures tend to be however, at the mostly usual elevated processing temperatures to thermal breakdown. which affects the mechanical properties of the fittings. This disadvantage is also due to the Use of esters of halophenols with organic "acids" does not fix, since these too Ve'rhinduniien already with the for a deformation or hardening of various plastics necessary higher temperatures hydrogen chloride or hydrogen bromide form which, depending on the duration of the 1 cm peruturous stress, the mechanical and optical Damage properties of the plastic.

Other flame retardants such as kernchloiierie or -brominated aromatic or aromatic-aliphaiisdie? * Vther or kernbromierle aniline, which in combination with antimony trioxide. especially Polvolefinen were mixed, show the camps emigration to form \ on efflorescence on the thus produced self-extinguishing molding materials.

For the purpose of "reducing the flammability of homo- and copolymers! Of styrene. Butadiene", or acrylonitrile has also been omitted that m- or ρ - bis - (1.4.5.6.7.7 - hexachlorbicyclo - (2.2.1) -5-hcpicn-2-yl) -ben / ol to use. These products do not cause any disruptions in the processing process due to decomposition reactions at the increased temperatures. They are against it poorly compatible with the polymers.

Additions of antimony compounds play a special role in flame-retardant plastic mixtures, especially of antimony trioxide. However, these antimony compounds are not alone effective, but only in combination with halogen-containing substances. The anti-lamb effect of antimony trioxide is based on its reaction with that contained in the thermal decomposition of the halogen Product released hydrohalic acid. Different reactions play out away. which lead to the suffocation of the flame.

The present invention now relates to a method for reducing the flammability of organic high polymers, characterized that one compounds or mixtures of compounds of the general formula

Cl

Cl

R R

Y- x-V: ηί

Cl-CCl I I Cl C-C

ί Ή, ΙΐΛ

Cl

Cl

Cl

in an amount of 1 to 40 percent by weight. \ preferably 10 to 30 percent by weight, where R is hydrogen or an alkyl group. in particular is a methyl group, and X is sulfur. Oxygen or one of the following bifunctional Leftovers means:

SO SO ₂

ClI ₂ ■ O · CII,
(II. SO ■ ClI ₂
CO ■ O ■ CH.

CH ₂ ■ S CIl,
■ CII, ■ SO, -C

The amount stated is calculated on the high polymer without any further surcharges.

These substances are of the chemical formula above Suitable for reducing the flammability of most high polymer!) materials. Especially "\ vhsk ^ ungs \ oll is the use in materials which through the polymerization of unsaturated compounds, originated in particular from olefins, such as /. B. polyethylene. Polypropylene. Polystyrene, opposing Copolymers, also combined with acrylonitrile and diolelines and crosslinkable butadiene-styrene polymers. Also, calcium bodies based on natural and synthetic rubber are on this basis effective flame retardant ·. / u do. So also the well-known diolelin-based polymers iHomou. Copolymers) including the siereo-specific types are to be mentioned here.

The lamb-resistant according to the invention made 1 01mmass In addition, other additives commonly used in polymer chemistry, such as. B. Plasticizers. Lubricants and fillers. Hel / .e- and light stabilizers etc. included. The fire-retardant to be used according to the invention can optionally be used Agents also with other fire retardants /. B. C'hlorparaffinen can be combined.

The substances with a high chlorine content used in accordance with the invention are known per se, but not here claimed by the Diels-Alder theory of hexachlorocyclopentadiene and divinyl ether. Diallyl ether or thioether. Diallylsulfone. Allyl acrylate or methacrylal etc. are easy to manufacture. With regard to to the simple production of particularly advisable anti-lamb additives within the meaning of the invention are those where X is given in the above Shape! Is oxygen or one of the following bifunctional radicals;

CM ₂ ■ O CH,
(O ■ O CH,

(H, SO, (H,

The Au:, gang substances containing two double bonds for these flame-retardant substances are iiämlieh chemicals very suitable for the Diels-Alder reaction and fall into chemical factories significant amounts as waste products.

The additives used according to the invention have compared to chlorinated hydrocarbons. Esters of halophenols with organic acids and similar substances have the advantage of improved temperature stability against elimination of HCl. It is therefore when the substances used according to the invention are used no more related disruptions during processing, even at higher temperatures expected.

Because of this special behavior of the fire retardants according to the invention with respect to With temperature changes, additional heat stabilization is generally superfluous. High polymers, where very high temperatures are required for processing, the customary heat stabilizers and antioxidants are added. In principle, you can also also the usual stabilizers and high polymer additivesc. like sunscreens. lubricant and the like.

On the other hand, these additives also advantageously differ in terms of temperature resistance of the already mentioned m- and p-bis- (1.4,5.6,7,7 - hexachlorbicyclo - (2.2.1) - 5 - hepten - 2 - y 11-hrri7nl While the latter isomers in bezuü aul Substances that are very stable under high temperature stress, decompose those used according to the invention Body at lower temperatures. On the one hand, they are stable enough so that disturbances such. B. due to IK '! Splitting-offs during processing can be avoided, on the other hand they are sufficiently unstable to Heat to just in the temperature range that occurs when the high polymers burn decompose and release the chlorine that is effective during extinguishing.

Another advantage of the fire-retardant additives to be used according to the invention should be emphasized that the amount required to achieve a certain fire-retardant effect is less is than in the case of using the last-mentioned known flame retardant.

In contrast to the last-mentioned known additives, the additives according to the invention also the advantage of good compatibility with high polymers, especially with the polyolefins in a broader sense.

The incorporation of the flame retardant additives. optionally together with further additives, can according to methods known per se. /. B. in the kneader, on the roll and by mixing and granulating on extruders.

To test for flame-retardant wedges, the mixtures were plasticized on the roller and pressed to form sheets 2 mm in diameter. From these pia! Th film strips of H) O>10> 2 mm were cut, which were subjected to a burning test. For this purpose, the film strips were attached to a tripod and 10 seconds! .Mg with a non-luminous one. 4 cm high gas flame at the lower end in this way. that the lower linden tree of the test specimen protruded 1.5 cm into the flame cone. After the flame was removed, the afterburning time of the Pi ₁ 'be measured until it went out. The flame retardant wedge was also confirmed by testing according to the VDE regulations (VDE 0472) ". · ■

example 1

70 parts of polypropylene. 25 parts of the flame retardant ether of the chemical formula given above, in the X the bifunctional residue

-CH ₂ O CH,

means, and 5 parts of antimony trioxide were ^{plasticized at about 170 to 180 1} C on the mixing roll and the rolled sheet obtained was pressed under pressure to form a sheet 2 mm thick. 10 strips of film 200 10 χ 2 mm were punched out of the plate and subjected to the burning test described above. Out of 10 samples, 4 extinguished within one second. 2 within 3 seconds and 4 within 5 to 7 seconds. According to VDE 0472, the afterburning time for door 2 samples was less than 1 second and for 1 sample 4 seconds.

The flame-retardant ether used in Example 1 was made in a manner known per se such as lolgi produced: 546g hexachlorocyclopentadiene and ^ Sg Dialiyl ethers were left with stirring for 12 hours heated to 150 to 160 C. The crude product was dissolved in 500 ml of acetone. After that, as much as a mixture of acetone and water in the volume ratio Sieve 1: 1. until the solution looks easy

clouded. After 16 hours the product which had crystallized out was filtered off. The yield was 92 "u of theory. A melting point of 170 to 172 ° C. was determined.

Example 2

In the same way as in Example 1, 72.5 parts of high-pressure polyethylene were obtained. 20 parts of the ilamnihemmep.den ether of the chemical formula given above, in which X is the bifunctional radical

- CH ₂ O CH ₂ -

means, and 7.5 parts of antimony trioxide at 130.degree processed. Of 10 test strips, 5 extinguished within 2 seconds and 5 after 5 to 7 seconds. To VDl; afterburn times of 2.3 seconds and less than 1 second resulted.

Example 3

In the same way as in Example 1, 72.5 parts of low-pressure polyethylene were obtained. 20 parts of the flame retardant ether of the chemical formula given above, in which X is the bifunctional radical

25th

-CH, ■ O CH, -

\\ ot> percent made of acrylonitrile, up to 2 percent by weight from butadiene and / u 74 percent by weight from styrene components composed. 15 parts of the flame retardant ether of the general above Formula in which X is the bifunctional radical

CH, ■ O-Cll,

mean! (systematic name bis- (1.4.5.6.7.7-he \ achlorhicyclo- [2.2.1] - 5-hepten-2 (methyl) ethene. and 5 parts of antimony trioxide processed at 160.degree.

Out of 10 samples, 7 extinguished within one second and 3 within. 3 seconds. According to N ^- I) Ii 0472, the afterburning time for all 3 samples was less than 1 second.

Example ⁷

Example 6 was carried out on the same copolymer with 15 parts 2.2'.3.3'.4.4'.5.5'.7.7.7'.7-lWekachloro - 1.1 \ 2.2'.5.5'.6.6 '- octahydro - 2.2.5.5 - inethanodiphenyl (Melting point at 232 to 235 (1 in place of the inventive compound worked.

None of 10 samples extinguished within 10 seconds. At the VDE-Tesl all samples burned with a slightly sooty flame.

means, and 7.5 parts of ammonium dioxide at 160.degree processed. Of 10 test strips, 4 extinguished after 2 seconds. 4 after 5 seconds and 2 after 7 seconds.

e i s ρ i c 1 4

In the same way as in Example 1, 67.5 parts of polypropylene were made. 25 parts of the flame-retardant ether of the chemical formula given above, in which X is the bifunctional radical -CH ₂ -S-CH, --- and 7.5 parts of antimony trioxide are processed. Of 10 test strips, 2 extinguished within 2 seconds and X within 4 to 6 seconds.

Example 5

Analogously to Example 1, 72.5 parts of styrene-butadiene copolymer were used. which was composed of 75% styrene and 25 "ο of butadiene. 5 parts of the Hammhemmend'.n ether of the chemical formula given above, in which X is the bifunctional radical --CH ₂ -O-CH, -. 5 Parts of the ether according to the formula given above, in which X is the bifunctional radical

CH ₂ SCH ₂

means, and 7.5 parts of antimony trioxide
processed. Out of 10 samples, 7 extinguished
and 3 within 2 seconds.

160 C immediately

Example K

ίο Analot: Example 6 was the same copolymer with 1 ^ς parts of m from about 55 weight percent and 45 weight percent ρ isomers existing Cjemisches of bis (1.4.5.6.7.7-he \ achlorbicyclo- [2.2.1] -5- hepten-2-yl) -benzene (softening ¹ Y ngs-

or melting range between 159 and 1S6 (. ge measure under the Kofler microscope) in place of the flame protection device according to the invention.

N'on 10 samples extinguished 2 after 5 seconds. 4 after 10 seconds and 4 did not go out. At the VDE test burned all samples very slowly, however without going out, with a very sooty flame ah.

Example 6

Analogously to Example 1, 50 parts of acrylonitrile-butadiene-styrene copolymer were used. that itself / u 24 (ic-

table

.,. Comparison of physical properties on xorrik sticks from samples from Examples 6 to S with the untreated acrylonitrile-butadiene-styrene copolymer as nullprohe

ArI of the exam

Flexural strength
after
DIN 53 452

ss impact strength
after
DIN 53 453

O-l'roK-

1340 13S0
(kp curl

without
fracture

I 300

<200

without j 3

Fractionj (kpcm cnr

Claims (1)

Patent claims: 1. Process for reducing the flammability of organic odor polymers. through this characterized by having connections or mixtures of compounds of the general formula