DE2402260A1 - FLAME RESISTANT OR SELF-EXTINGUISHING PLASTIC OR PLASTIC-ELASTIC MASSES - Google Patents

Description

Flame retardant or self-extinguishing plastic or plastic-elastic masses

(Addition to patent application P 23 13 334.8)

Subject of the patent (patent application P 23 13 334.8)

are flame-retardant or self-extinguishing plastic or plastic-elastic masses based on polymeric olefins consisting of 7 to 50 percent by weight of a largely amorphous one Polyolefin or a mixture of up to 2 parts by weight of one Elastomers to 1 part by weight of the largely amorphous polyolefin, 10 to 40 percent by weight of a polybutene oil optionally containing up to 30 percent by weight of a drying oil, 3 to 30 percent by weight of a chlorinated paraffin, 30 to 70 percent by weight of a filler and optionally 0.5 to 5 percent by weight Antimony trioxide.

A largely atactic polybutene-1 and its copolymers are preferably used as the largely amorphous polyolefin up to 20 percent by weight ethane and / or propene or hexene-1 as well as mixtures of all kinds of these substances are used.

In a further development of these compositions it has now been found that it is also advantageous / as a largely amorphous polyolefin, polypropylene with a proportion of over 80 % soluble in boiling heptane, polyhexene-1 or a copolymer of propylene and up to 20 percent by weight of ethylene and / or butene 1 and / or hexene-1 and mixtures of these polymers with polybutene-1 to be used. The RSV values of these polyolefins are in the range from 0.2 to 2.5 dl / g, preferably from 0.3 to 1.2 dl / g. 73/73

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Surprisingly, the polypropylene that can be used is well compatible with the polybutene oil, the drying oil and also with the chlorinated paraffin, despite the partially incomplete solubility in boiling heptane. However, it is expedient to add a polypropylene with a proportion of up to 20 % insoluble in boiling heptane to the compositions according to the invention only up to 20 percent by weight, preferably up to 10 percent by weight, that is, if the polypropylene content is greater than 20 percent by weight, it should be completely soluble in boiling heptane Product to be used.

The polypropylene to be used according to the invention is obtained, for example, as a by-product in the production of isotactic polypropylene. It is dissolved in the diluents used or in the monomer and is converted from this solution by distilling off the diluent or the monomer. These largely amorphous polyolefins can also be obtained by targeted polymerization, for example by adding propylene, preferably with up to 20 % Athens, 1-butene or 1-hexene, with contacts made of TiCl., TiCl ₃ or preferably TiCl- · nAlCl_ on the one hand and AlR ₃ on the other hand at temperatures of 70 to 140 ⁰ C, in particular 80 to 120 ⁰ C, polymerized.

The amorphous polyhexene-1 can also be obtained at lower polymerization temperatures. Aluminum triisobutyl is preferably used _{as AlR 3.}

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

Compositions based on polypropylenes produced in this way stand out by a higher softening point compared to those compositions which, as a largely amorphous polyolefin, are exclusively polybutene-1 contain. Masses of a mixture with approximately equal proportions

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of polypropylene and polybutene-1 also have a very good rating Elongation behavior. This property also distinguishes the masses based on polyhexene-1.

To produce the compositions according to the invention, the largely amorphous polyolefins mentioned can also be used again in mixtures be used with elastomers, with 1 part by weight of the 'largely amorphous polyolefin up to 2 parts by weight of one Elastomers can come.

#As elastomers, both natural rubber and synthetic rubbers, s.B. Butadiene-styrene rubber, butadiene-acrylonitrile rubber, Butyl rubber, polybutadiene, polyisoprene and, above all, saturated and unsaturated polyolefin rubbers are used will. Of the polyolefin rubbers, those obtained by polymerizing ethylene and propylene are preferably used and / or butene-1 and optionally a diene, such as dicyclo- ' Pentadiene, methylene, ethylidene or propenyl norbornene and 1,4-hexadiene according to the known processes of the prior art (DT-OSS 1 595 447, 1 720 450, 1 570 352). In the case of the mixtures of largely amorphous polyolefin and elastomer one sets in general up to 2 parts by weight, preferably 0.4 to 2 parts by weight of the estomer to 1 part by weight of the largely amorphous polyolefin.

Suitable polybutene oils that are up to 10 to 40 weight percent, preferably added to the compositions of the invention to 20 to 30 weight percent are those having molecular weights of 500 to lOOÖ and viscosities above 500 cP / 20 ⁰ C, preferably 1000 to 20 000c P / 20 ⁰ C in particular from 2000 to 10,000 cP / 20 ⁰ C. These polybutene oils should not contain any low-boiling components that ^{boil below 100 °} C. to 15 mm Hg. Polybutene oils of this type are obtained, for example, by polymerizing 1-butene, 2-butene and optionally isobutylene and / or 1,3-butadiene-containing C ₄ cuts with Friedel-Crafts catalysts, preferably AlCl ₃ , at temperatures from 0 to 100 ⁰ C. By adding services and /

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or acetylenes, the viscosity of the polybutene oils can be greatly increased (DT-OS 2 005 207). After the polymerization and, if appropriate, after a wash, the low boilers are ^{removed by simply heating the polybutene oils to 100 to 150 °} C. at a pressure of about 15 mm Hg.

Up to 30 percent by weight of the polybutene oil used is replaced with a drying oil, plastic or plastic-elastic masses are obtained, which are attached to the surface when air is admitted Harden. Suitable drying oils are e.g. polybutadiene oils and drying triglycerides such as linseed oil. As polybutadiene oils are preferably those with molecular weights from 1500 to 3000, viscosities from 750 to 3000 cP / 20 ° C and iodine numbers between 400 and 500, as they can be produced by the process of DT-PS 1,186,631.

To accelerate the hardening process, siccatives can be added to the masses, preferably cobalt octoate and cobalt naphthenate in amounts of up to 0.5 percent by weight, in particular 0.1 to 0.2 percent by weight, based on the drying oil.

Suitable chlorinated paraffins are those with a chlorine content of 45 to 58 percent by weight, in particular 50 to 55 %. Chlorinated paraffins with a low chlorine content have less of an effect on making the compounds flame-retardant and self-extinguishing. Chlorinated paraffins with higher chlorine contents are well suited to make the compounds flame-retardant and self-extinguishing, but they worsen the properties of the plastic or plastic-elastic compounds, in particular they make the compounds according to the invention brittle. The chlorinated paraffins are stabilized with ethylene oxide derivatives or with PVC stabilizers.

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The chlorinated paraffin content is in the compositions according to the invention 3 to 30 percent by weight, preferably 6 to 20 percent by weight, in particular 8 to 12 percent by weight.

However, if the claimed masses are exposed to mixtures a largely amorphous polyolefin and an elastomer, the preferred range is 15 to 25 percent by weight.

The compositions according to the invention contain powdery substances as fillers, preferably silica, silicates, sulfates and phosphates such as talc, barite and kaolin, and optionally 1 to 5 %, preferably 1.5 to 3 %, iron oxide Fe ₅ O ₃ or carbon black for UV stabilization «

The use of antimony trioxide makes it flame retardant the compositions according to the invention are still improved. Simultaneously This additive enables the chlorinated paraffin content to be greatly reduced. In the presence of 3 percent by weight of antimony trioxide, for example, the chlorinated paraffin content can be from 14 to 24 percent by weight to 4 to 12 percent by weight, preferably 6 to 10 percent by weight to be humiliated.

These compositions according to the invention are suitable for many areas of application, e.g. for the production of roof coverings or roof seals, as sealing compounds, joint tapes or adhesive tapes, im Building construction, in particular in precast concrete construction, for pipe laying, in automobile construction, for repairs, for connecting parts Plastic, etc. They have excellent adhesiveness and extensibility. The adhesion of the masses is so good that no primer is required is required.

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

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The following examples serve to illustrate the present Invention.

example 1

In 17 parts by weight of a polybutene oil with a viscosity of 4100 cP / 20 C and a molecular weight of 680, produced by polymerizing a (^ cut from 43 % isobutylene, 24 % butene-1, 24 % butene-2 and 9 % butane at 30 ⁰ C in the presence of 1 % butadiene with the help of 0.4 % A1C1_ as a catalyst, 17 parts by weight of a largely amorphous polypropylene, inevitable in the production of isotactic polypropylene, with an RSV value of O _# 5 dl / g and one largely amorphous polybutene-1 with an RSV value of 0.5 dl / g and an ether-soluble fraction of 76 %, obtained by polymerizing butene-1 with a contact from

0.35 AlCl- and Aifi C..H _Q ), (molar ratio Al: Ti = 3) at 95 ⁰ C and at a hydrogen partial pressure of 2.0 at, dissolved at 200 C. Then 35 parts by weight of talc, 3 parts by weight of antimony trioxide and 1 part by weight of Printex 60 carbon black (Degussa, Frankfurt) are added and the mass is stirred well until uniform mixing is achieved. After cooling to 170 ° C, 10 parts by weight of a chlorinated paraffin, the

Contains 52 % chlorine, added. After uniform mixing has been achieved, the mass is poured in a hot liquid state onto a roof surface to be sealed at this temperature and distributed with slides or applied with brushes. When it has cooled down, a dense, homogeneous, plastic roof covering is obtained; it adheres well to concrete, stone, masonry, wood, metal, bitumen and plastics and can be used on dry substrates without a primer. The mass is resistant to flying sparks and radiant heat. It fulfills the requirements • of DIN 4102. It is largely resistant to UV radiation. If, instead of the largely amorphous polypropylene, a largely amorphous propylene-ethylene copolymer, which contains about 5 % ethylene, and has an RSV value of 0.5 dl / g, as well as full

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is constantly soluble in boiling heptane, one also obtains A mass that is easy to process and also meets the requirements of DIN 4102.

Example 2

In 17 parts by weight of a polybutene oil with a viscosity of 10 400 cP / 20 ⁰ C ₁ with a molecular weight of 760, which does not contain any low-boiling components that ^{boil below 150 0} C at 15 mm Hg, obtained by polymerizing a (!!, - Cut from 52 % butene-1, 40 % butene-2 and 8 % butane in the presence of 5 % butadiene with 0.4% AlCl ₃ at 30 ⁰ 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 ⁰ C with a contact of TiCl ₃ * 0.5 AlCl ₃ and Al (C ₃ H c) ₃ (molar ratio Al / Ti = 2.5) at a pressure of 2.6 Wasserstoffpartial-7 at dissolved at 180 ⁰ C. Subsequently, 35 parts by weight of talc, 3 parts by weight of antimony trioxide, and 2 parts by weight of iron oxide FSPO ₃ (type AK / F, Ziegler & Co., Stuttgart) are added and the mass is stirred well. After cooling to 160 ^° C., 8 parts by weight of a chlorinated paraffin containing 55 % chlorine are added with stirring holds, admittedly. 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.

The same amount is used instead of the 35 parts by weight of talc Barite, you get a comparable mass. If you replace the talc with kaolin, you get a mass that at a temperature of 160 to 170 ° C can be applied as a melt by filling with steel trowels on dry roof surfaces. At room temperature, these compounds are suitable as sealants that can be troweled.

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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 in a kneader at 120 ^{° C.} obtained by polymerization of propylene with 20 weight percent hexene-1 at 120 ⁰ C by means of a contact from TiCl ₃ · 0.5 AlCl- and Al (1C ₄ H) "(molar ratio Al / Ti = 3), a hydrogen partial pressure of 1 5 at, and 17 parts by weight of an ethylene-propylene rubber with a Mooney viscosity ML-I, 4 of 70, measured according to DIN 53 523, and a double bond content of 8 DB / 1000 C, produced by copolymerization of ethylene with propylene and small amounts of dicyclopentadiene with the help of a contact of vanadium oxychloride and ethylaluminum sesquichloride at 0 C, mixed. 15 parts by weight of a polybutene oil with a viscosity of 5300 cP / 20 ^° C., which does not contain any low-boiling components which ^{boil below 150 °} C. at 15 mm Hg, are added _{to the mixture, obtained by polymerizing a C 4 cut} from 52 % butene-1 , 40 % butene-2 and 8 % butane in the presence of 50 % butadiene with 0.3 56AlCl ₃ at 50 ⁰ C, 33.5 parts by weight talc, 4 parts by weight antimony trioxide and 1.5 parts by weight carbon black Printex 60 (Degussa, Frankfurt) admitted. After uniform mixing has been achieved, 12 parts by weight of a chlorinated paraffin containing 52 % chlorine are added. An elastic-plastic mass is obtained that is resistant to flying sparks and radiant heat. The mass does not continue to burn when the ignition source is removed. It is largely resistant to UV radiation.

If, instead of the 17 parts by weight of the ethylene-propylene rubber, 17 parts by weight of a butadiene-styrene rubber with a composition of 76% butadiene and 24 % styrene with a Mooney viscosity ML-1.4 of 50, measured according to DIN 53 523, are produced by emulsion polymerization of 1,3-butadiene with styrene at 5 C with redox activators, a comparable mass is obtained.

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If, instead of the largely amorphous propene-hexene-1 copolymer, a largely amorphous propene-butene-1 copolymer is used which contains about 20 % butene-1, has an RSV value of 0.4 dl / g and is completely boiling Heptane is soluble, a comparable mass is also obtained.

Example 4

In a kneader at 120 ° C., 10 parts by weight of a largely amorphous polypropylene, an inevitable result related to the production of isotactic polypropylene, with an RSV value of 0.5 dl / g and a heptane-soluble content of 100 %. 10 parts by weight of a largely amorphous polybutene-1 with an RSV value of 0.5 dl / g and an ether-soluble content of 76 %, prepared according to the information in Example 1, and 16 parts by weight of an ethylene-propylene rubber with a Mooney viscosity ML -I, 4 out of 70, measured according to DIN 53 523, and a double bond content of 8 DB / 1000 C, prepared according to the information in Example 3, mixed. To the mixture are added 12.5 parts by weight of a polybutene oil with a viscosity of 5300 cP / 20 ° C., prepared as described in Example 3, 1.5 parts by weight of linseed oil to which 0.0015 parts by weight of cobalt octoate has been added, 33 parts by weight of talc, 4 parts by weight Antimony trioxide and 1 part by weight of Printex 60 carbon black (Degussa, Sankfurt). After uniform mixing has been 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 plug fire and radiant heat. The mass does not continue to burn when the ignition source is removed.

If one uses the same instead of the ethylene-propylene rubber Amount of a butyl rubber, a comparable mass is obtained.

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Claims (1)

- 10 - OZ 2766 January 16, 1974 Claim Further development of the flame-retardant or self-extinguishing plastic or plastic-elastic masses on the basis polymeric olefins consisting of 7 to 50 percent by weight of a largely amorphous polyolefin or a mixture of up to 2 parts by weight of an elastomer to 1 part by weight of the largely amorphous polyolefin, IO to 40 weight percent of one optionally up to 30 percent by weight of a drying oil containing polybutene oil, 3 to 30 percent by weight of a chlorinated paraffin, 30 to 70 percent by weight of a filler and optionally 0.5 to 5 percent by weight of antimony trioxide, according to the patent (Patent application P 23 13 334.8), characterized in that as a largely amorphous polyolefin polypropylene with a proportion of over 80 % soluble in boiling heptane, polyhexene-1 or a copolymer of propylene and up to 20 percent by weight of ethylene and / or butene-1 and / or hexene-1 and mixtures of these polymers with polybutene -1 used. 509830/0796