DE2402260C3 - Flame-retardant or self-extinguishing plastic or plastic-elastic masses - Google Patents

Description

The invention relates to flame-retardant or self-extinguishing plastic or plastic-elastic Polymeric olefin based masses.

For many areas of application, e.g. B. in the construction sector, in Equipment and vehicle construction require plastic or plastic-elastic compounds that are flame-retardant or are self-extinguishing and resistant to flying sparks and radiant heat are. For the production of roof coverings or roof waterproofing, the masses used must meet the requirements of DIN 4102. Inexpensive Masses, e.g. B. sealants containing fillers with phthalic acid esters and linseed oil are highly flammable. Filler-containing compositions made from largely amorphous polyolefins and polybutenols behave in this Respect much cheaper. However, these materials meet the requirements of DIN standard 4102 only if the proportion of solids is at least 5 (1% But masses have the disadvantage that they are more difficult to process, especially with simple ones Spray guns Ivw. with brush or tassel.

Flame-resistant b / w have this disadvantage. self-extinguishing plastic b / w. plastic-elastic Bulking compounds made from largely amorphous polybutene-1 b / w. a mixture of largely amorphous polybutene-1 with a rubber. PnIybutenol. (chlorinated paraffin and, if necessary, antimony trioxide not / to pay for state of the art, not (I) K-PS 2 313 334).

It was the task of the invention. other such compositions based on polymeric olefins develop a higher softening point,

This task is performed accordingly solved the details of the claim.

The RSy values of the polyolefins used (A) are in the range from 0.2 to 2.5 dl / g, preferably from 0.3 to 1.2 dl / g.

Surprisingly, the polypropylene that can be used is in spite of the partially incomplete solubility in boiling heptane well with the polybutene oil, the drying oil and also with the chlorinated paraffin compatible. However, it is useful to use a polypropylene with one that is insoluble in boiling heptane Share up to 20% of the compositions according to the invention only up to 20% by weight, preferably up to 10% by weight, to add, d. H. with larger polypropylene contents

A product that is completely soluble in boiling heptane should be used as 20% by weight. The polypropylene to be used according to the invention is obtained, for. B. as a by-product in the production of isotactic polypropylene. It is dissolved in the diluents used or in the monomer and is obtained from this solution by distilling off the diluent or the monomer. These largely amorphous polyolefins can also be obtained by targeted polymerization by, for example, adding propylene, preferably with up to 20% Athens, 1-butene or 1-hexene, with contacts made of TiCl., TiCl-, or preferably TiCl ₁ -IiAlCl , on the one hand and AIR, on the other hand at temperatures of 70 to 140 ° C, in particular 80

> ■> up to 120 ° C, polymerized.

The amorphous polyhexene-1 can also be obtained at lower polymerization temperatures. as AlR, aluminum triisobutyl is preferably used.

in The Al / Ti molar ratio is preferably 2 to 3. The polymerization can be carried out batchwise or continuously, in solution or in substance. The monomers themselves or a liquid gas are preferably used as the solvent.

j-, compositions based on polypropylenes thus produced are characterized by a higher softening point compared to those masses that are largely amorphous polyolefin containing only polybutene-1. Masses of a mix with

4π approximately equal proportions of polypropylene and polybutene-1 also show very good elongation behavior. This property also distinguishes the masses based on polyhexene-l.

For the production of the compositions according to the invention

4-, the above-mentioned largely amorphous polyolefins can also be used in mixtures with elastomers being largely to I weight percent amorphous polyolefin up to / u 2 (ieweilc of an elastomer can come.

Vi Both natural rubber like synthetic rubbers. /. H. riutadien-Sty ml rubber. Butadiene-acrylonitrile rubber. Butyl rubber. Polybutadiene. Polyisoprene and, above all, saturated and unsaturated polyolefin

v, chukc can be used. From the Polyolefinkau-Ischukcn preference is given to those produced by the polymerization of ethylene and propylene and mler butene-1 and optionally a diene, like / B dicydopcntadien. Methylene. Athyliden

_{h (} ) or Propcnyl-nnrborncn and tlc-xailicn-1.4 according to the known processes of the state of the art (Ub-USen IS ¹ JS 447, 1720451), 1570352) Alles-

generally up to 2 parts by weight, preferably 0.4 to 2 parts by weight of the elastomer per part by weight the largely amorphous polyolefin.

Suitable polybutene oils that can be used

Corresponding masses of up to 10 and 4% by weight, preferably 20 to 30% by weight, are those with molecular weights of 50 to 100% and viscosities above 500 cP / 20 ° C, preferably 1000 to 20,000 cP / 20 ° C , in particular from 2000 to 10000 cP / 20 ° C. These polybutene oils should not contain any low-boiling fractions that boil below 100 ° C. to 15 mm Hg. Such polybutene oils are obtained, for example, by polymerizing butene-1, butene-2 and optionally iso- Carbon cuts containing butylene and / or 1,3-butadiene with Friedel-Crafts catalysts, preferably AlCl ₃ , at temperatures from 0 to 100 ° C. The viscosity of the polybutene oils can be greatly increased by adding dienes and / or acetylenes (DE-OS 2005 207) After the polymerization and, if necessary, after washing, the low boilers are removed by simply heating the polybutene oils to 100 to 150 ° C. at a pressure of about 15 mm Hg.

Replacing bisiu 30 wt.% Of the used Po Iybutcnölcs by a drying oil, one obtains plastic or plastic-elastic compositions that cure at the surface of contact with air. Suitable drying oils are e.g. B. polybutadiene oils and drying triglycerides, such as. B. linseed oil. Preferred polybutadiene oils are those with molecular weights from 1500 to 3000, viscosities from 750 to 3000 cP / 2 ° C. and iodine numbers between 400 and 500, as can be prepared by the process of DE-PS I 186631.

To accelerate the hardening process, siccatives, preferably cobalt tooate, can be added to the masses and cobalt naphthenate in amounts up to 0.5 wt. Of, in particular 0.} to U ,? Weight · f. Related on the oil to be dried.

Suitable chlorine paraffins are those with a Chlorine content of 45 to 58% by weight. especially from 50 to 55%. Chlorinated paraffins with a low Chlorine contents have less of an effect on making the compounds flame-retardant and self-extinguishing. Oilor paraffins with higher chlorine contents are well suited to make the masses flame-retardant and self-extinguishing, they worsen but the property values of the plastic b / w. plastic-elastic masses, in particular, make them the compositions according to the invention brittle. The chlorinated paraffins are b / w with ethylene oxide derivatives. with PVC stabilizers stabilized.

The chlorinated paruffin content in the compositions according to the invention is 3 to 30% by weight. preferably (S to 20% by weight, especially S to 12% by weight.

Set / t one with the claimed masses, however Mixtures of a largely amorphous polyolefin and an illastomer. so is the preferred area at 15 to 25% by weight.

The fillers according to the invention are used Masses of powdery substances, preferably silica. Silicates. Sulfates and phosphates such as talc. Barite and kaolin, and optionally 1 to 5 '/. preferably 1.5 to V ,. Iron oxide Fe, O, or Kiss for UV stabilization.

Through the use of antimony trioxide, the flame retardancy is de? according to the invention Masses still improved. At the same time, this additive enables the chlorinated paraffin content to be greatly reduced, In the presence of 3% by weight of antimony trioxide, for example, the chlorinated paraffin content of L4 up to 24% by weight to 4 to 12% by weight, preferably ο to 10% by weight.

These compositions according to the invention are suitable for many areas of use, e.g. B. for the production of Roof coverings or roof seals, as sealing compounds, Joint tapes or adhesive tapes, in building construction, especially in precast concrete construction Pipe laying, in automobile construction, for repairs, for connecting parts made of plastic, etc. ίο They have excellent adhesion and elasticity. The adhesion of the masses is so good that no primer is required.

Due to the limited thermal resistance of the chlorinated paraffins, however, the masses should be possible not be heated to temperatures above 170 "C for a long period of time.

The following examples serve to illustrate the present invention.

, ₀ bis ρ ic 1 1

In 17 parts by weight of a polybutene oil with a viscosity of 4100 lP / 20 ⁰ C and a molecular weight of 680, produced by polymerizing a C _{4 cut} from 43% isobutylene, 24% butene-1, 24% butene-2 and 9% Butane at 30 ° C. in the presence of 14 butadiene with the aid of 0.4% AlCl, 17 parts by weight of a largely amorphous polypropylene are used as a catalyst. Obsession in the production of isotactic polypropylene, with a

jo RSV value of 0.5 dl / g and a largely amorphous polybutene-1 with an RSV value of 0.5 dl g and an ether-soluble content of 76%. obtained by polymerizing butene-1 with a contact of _{TiCl 1} 0.35 AlCl, and Al (iC ₄ H _g ), (molar ratio

j-, Al: Ti = 3) at ¹ J5 'C and at a hydrogen partial pressure of 2.0 at. at 200' C. Then 35 parts by weight of talc, 3 parts by weight of antimony trioxide and 1 part by weight of carbon black are added and the mass is stirred well until it is uniform

4 (i mixing is achieved. After cooling down to I 7 (1 C are K while stirring) parts by weight of one Chlorinated paraffins containing 52% chlorine were added. After an even mixing has been achieved. is the mass at this temperature in hot-liquid

4-, sigem condition on a roof surface to be sealed poured on and spread with sliders or applied with brushes. When cooled down, you get a dense, homogeneous, plastic roof covering; it adheres well to concrete. Stone. Masonry.

-, ii wood. Metal. Bitumen and plastics and can on can be used on dry substrates without a primer. The crowd is against flying fire and shining Heat resistant. It meets the requirements of DIN 4102. It is widely protected against UV radiation.

-, -, persistent. Is used in place of the largely amorphous polypropylene is a largely amorphous propylene-ethylene-C opolymer. that about Vr Contains ethylene, and has an RSV value of 0.5 dl g and is completely soluble in boiling heptane.

_{h ()} this also results in a mass that is easy to process, which also meets the requirements of DIN 4102

Example 2

In 17 parts by weight of a polybutene oil with a viscosity of 1040 cP / 20 ° C. and a molecular weight of 760, which does not contain any low-boiling components that boil below 150 ° C at 15 mm FIg, obtained by polymerizing a C-cut from

52% butene-1,4UOi butene-2 and 8% butane in the presence of 5% butadiene with 0.4% AICI, at 30 ° C, 35 parts by weight of an amorphous polyhexene-1, which has an RSV value of 0.7 dl / g and completely soluble in heptane, obtained by polymerization of hexene-1 at 50 ° C with a contact of TiCl ₃ -U ₁ S AlCl ₃ and Al (C ₂ Hj), (molar ratio Al / Ti = 2.5) at a hydrogen partial pressure of 2.6 at, dissolved at 180 ° C. Then 35 parts by weight of talc, 3 parts by weight of antimony trioxide and 2 parts by weight of iron oxide Fe ₂ O _{3 are} added and the mixture is stirred well. After cooling to 160 ° C while stirring 8 parts by weight of a chlorinated paraffin containing 55% of chlorine aas added. After uniform mixing has been achieved, the mass is used according to the information in Example 1 at 160 ° C. to produce a seamless roof covering. The roof covering meets the requirements of DIN 4102. The mass is largely resistant to UV radiation.

Instead of 35 parts by weight of talc the same amount of barite. this gives a comparable mass. Replace the talc with Kaolin, one obtains a mass that is at one temperature from 160 to 170 ° C as a melt using a spatula can be applied to dry roof surfaces with steel trowels. At room temperature are suitable these compounds as sealants that can be troweled.

Example 3

17 parts by weight of a largely amorphous propene-hexene-1 copolymer which contains about 20% hexene-1, has an RSV value of 0.4 dl / g and is completely soluble in boiling heptane is obtained in a kneader at 120 ^{° C.} Polymerization of propene with 20% by weight of hexene-1 at 120 ° C. with the aid of a contact composed of TiCl, -0.5 AlCl, and AKiC ₄ HJ, (molar ratio Al / Ti = 3) at a hydrogen partial pressure of 1.5 at, and 17 Parts by weight of an ethylene-propylene rubber with a Mooney viscosity ML-1.4 of 70, measured according to DIN 53 523. and a double bond content of 8 DB / 1000 ⁰ C. produced by copolymerization of ethylene with propylene and small amounts of dicyclopentadiene with the aid of a Contact of vanadium oxychloride and ethyl aluminum sesquichloride mixed at 0 ° C. 15 parts by weight of a polybutene oil with a viscosity of 5300 cP / 2 ° C., which does not contain any low-boiling components boiling below 150 ° C. at 15 mm Hg, are added to the mixture, obtained by polymerizing a C _{4 cut} of 52% rods -1.40% butene-2 and 8% butane in the presence of 50% butadiene with 0.3% AlCl, at 50 "C. 33.5 parts by weight talc. 4 parts by weight of antimony trioxide and 1.5 parts by weight of RuU were added. After uniform mixing has been achieved, 12 parts by weight of a chlorinated paraffin containing 53% chlorine are added. An elastic-plastic mass is obtained that can withstand flying sparks and

radiant heat is resistant. The mass does not continue to burn when the ignition source is removed.

It is largely resistant to UV radiation.

Instead of 17 parts by weight of ethylene-propylene rubber 17 parts by weight of a butadiene-styrene rubber of the composition 76% butadiene and 24% styrene with a Mooney viscosity ML-1.4 of 50, measured according to DIN 53 523, produced by emulsion polymerization

of 1,3-butadiene with styrene at 5 ° C with redox activators, this gives a comparable mass.

The largely amorphous propene-hexene-1 copolymer is substituted a largely amorphous propene-butene-1 copolymer, which is about

Jd contains 20% butene-1, an ^ SV value of 0.4 dig and is completely soluble in boiling heptane. this also gives a comparable mass.

Example 4

r> In a kneader at 120 ° C 10 parts by weight of a largely amorphous polypropylene. Inevitable occurrence in the production of isotactic polypropylene, with an RSV value of 0.5 di / g and a heptane-soluble proportion of 100%. 10 Gt-

! (I parts of a largely amorphous polybutene-1 with an RSV value of 0.5 dl / g and an ether-soluble content of 76%. manufactured according to the information of Example 1 and 16 parts by weight of an ethylene propylene rubber with a Mooney viscose

j-, did ML-1.4 of 70. measured according to DIN 53 523. and a double bond content of 8 DB / 1000 "C, prepared according to the instructions in Example 3, mixed. 12.5 parts by weight of a polybutene oil with a viscosity of 5300 are added to the mixture cP 20 C. prepared according to the information in Example 3. 1.5 parts by weight of linseed oil, the 0.0015 part by weight of c Carbon octoate are added. 33 cattle parts Talc, 4 parts by weight of antimony trioxide and 1 part by weight of carbon black. After an equal

4-, moderate mixing is achieved. 12 parts by weight of a chlorinated paraffin containing 50% chlorine are added. An elastic-plastic mass is obtained which hardens on the surface and which is resistant to flying sparks and radiant heat.

-, o The mass does not continue to burn if the ignition source away.

It is used in place of ethylene propylene rubber the same amount of a butyl rubber. . So you get a comparable mass.

Claims (1)

Claim: Flame-resistant or self-extinguishing plastic or plastic-elastic masses, consisting the end A) 7 to 50% by weight of largely amorphous polypropylene with a boiling heptane soluble content of more than S0%, polyhexene-1 or a copolymer of propylene and up to 2U% by weight of ethylene and / or 1-butene and / or 1-hexane and mixtures of these Polymers with polybutene-1, B) lü to 40% by weight of a Poiybutene oil with a Molecular weight from 500 to 1000 and a viscosity over 500 cP / 20 ° C, which is up to to 30% by weight of a drying oil and optionally up to 0.5% by weight of a siccative, in relation to the drying oil, may contain, C) 3 to 30 Gew.Or a chlorinated paraffin with a Chlorine content of 45 to 58% as well D) 30 to 70% by weight of a customary filler and optionally E) 0.5 to 5% by weight of antimony trioxide.