DE2758681A1 - POLYMERIC COMPOSITIONS BASED ON OLEFINE POLYMERS - Google Patents

Description

The invention relates to non-corrosive, flame-resistant polymers Compositions based on olefin polymers.

It is known that both natural and synthetic textile fibers generally show poor resistance to this exposure to flame.

On the other hand, it is necessary in numerous applications that the textile articles of manufacture and the plastic articles Withstand tests under various working conditions that involve direct exposure to flames and exposed to thermal radiation.

To improve the flame resistance of textile fibers Methods developed that allow the introduction of flame-retardant organic and inorganic nitrogen, phosphorus and / or halogen-containing compounds of antimony, boron and the like in the fibers.

These compounds can be added to the fiber-forming polymer before spinning and by impregnation or coating formation can be applied to the textile objects.

However, the applicant has found that the addition of halogen-containing compounds, especially bromine-containing Compounds, to the olefin polymers, as well as the addition of mixtures of antimony oxide and bromine-containing compounds, the flame resistance of the fibers obtained is improved, but the other characteristics are generally disadvantageous, in particular, the resistance of the fibers to light and thermo-oxidizing degradation reactions is impaired. White

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thereafter, the halogen-containing compounds "contribute the decomposition during the technological operations that the fibers, in the course of their conversion into textile objects, are subjected to hydrohalic acids, which the The metal equipment used will corrode and act on the stabilizers and pigments present in the Paser.

It is therefore an object of the invention to provide a polymeric composition based on olefin polymers which, besides that it is flame-resistant, non-corrosive and resistant to light and thermo-oxidizing degradation reactions and it is im generally allows the fiber to retain its chemical and physical properties.

In particular, it is the aim of the invention to produce an additive that is resistant to flames and to light and heat degradation is stable and does not decompose with the development of hydrohalic acids.

It has now been found that the present invention achieves these objectives by introducing into the polyolefin:

a) 0.01 to 15 percent by weight, based on the polyolefin, of an aliphatic-aromatic bromine-containing ether the general formula

(D

wherein R ^ and R ^, which can be the same or different, can be a partially or fully brominated alkyl radical having 1 to 20 carbon atoms, and R ₂ and R ,, the

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can be identical or different, hydrogen, an alkyl radical with 1 to 6 carbon atoms or a phenyl radical, each of which can optionally be brominated,

"b) Ο, ΟΟΊ to 15 percent by weight, based on the polyolefin, an antimony trioxide, and

c) 0.01 to 15 percent by weight, based on the polyolefin, of a phosphorus-containing organic compound of the general formula

O = P-A-P = O (II)

I I

E ^ -O ORo

Ό Ο

where R, -, Rg, R ₇ and Ro, which can be the same or different, can be hydrogen or an alkyl radical having 1 to 18 carbon atoms, and A is an alkylene, arylene or alkarylene radical, which may optionally be a heteroatom, such as O, S, N and P contains means.

The presence of the phosphorus-containing organic compound gives the flame-retardant fiber high durability against thermo-oxidizing degradation, light and gas development, without changing the mechanical properties of the fibers and without harmful interactions with the dyes and / or pigments, if any.

The polymeric compositions and textile fibers obtained in this way show oxygen index values (L.O.I.%), measured according to ASTM standard D-286J-70, of greater than 21%, while the polyolefins and the fibers derived from them, which do not contain any additive according to the invention, are markedly lower Have L.O.I. values.

In fact, the LOI values are 17.4 to 17.5 % for

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Polyethylene and 17.4 to 18.6% for polypropylene.

Starting from the polymeric compositions according to the invention manufactured fibers withstand flame resistance tests, which are measured according to the following standards:

- DIN-54332 (short flame test)

- BS-4790-1972 (ash test)

- ASTM-D-2859/1970 T (pill test)

- Swedish test BR-6 (tunnel test)

The corrosion resistance tests, which were carried out by placing the fibers or the polymer between ^{steel and iron plates kept at 240 °} C. for 30 minutes, show that the presence of the phosphorus derivatives according to the invention prevents corrosion of the metal equipment. Conversely, when common anti-corrosive and anti-acid agents are used together with flame retardant additives, undesirable side effects occur. In particular, the use of organotin compounds leads to a reduction in the molecular weight of the polymer used.

Isotactic polypropylene produced by stereospecific polymerization is preferably used to a large extent as the polyolefin obtained from propylene, and crystalline ethylene-propylene copolymers, which contain predominantly propylene, is used.

Further polyolefins suitable for the use according to the invention are those which are derived from monomers of the formula

E - CH = CH ₂

derive where B is an alkyl or aryl group or a hydrogen atom means, such as polyethylene, polybutene-1, polypentene-1,

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Poly-4-methylpentene-1, polystyrene and the like.

Preferred bromine-containing aliphatic-aromatic ethers are those whose bromine content is between 30 and 35 % and preferably between 50 and 80 % , such as, for example: 2,2'-bis- [4- (2,3-dibromopropoxy) -3, 5-dibromophenyl] propane, 2,2'-bis- [4- (2,3-dibromopropoxy) -3,5-dibromophenyl] -butane, 2,2'-bis- [ ² } - (2,3-dibromopropoxy ) -3,5-dibromophenyl! Methane, 2,2 'bis [4- (2,3-dibromopropoxy) -3,5-dibromophenyl] neopentane, 2,2' bis [4 - (2, 3-dibromobutoxy) -3,5-dibromophenyl] propane and the like.

Preferred phosphorus-containing compounds of the general formula (II) are those in which Rc, R ^, Rr ₇ and Rq, which may be the same or different, denote an alkyl radical having 1 to 4 carbon atoms, and A is an alkylene group having 1 to 6 represents carbon atoms, optionally containing 0, S, N or P. Some examples of such phosphorus compounds are: di- (ethylphosphono) methane, 2,2'-bis (diethylphosphono) ethylene, 2,2'-bis (diethylphosphono) -di- * ethyl ether, 2,2'-bis - (diethylphosphono) dimethyl ether, 2,2'-bis (methylphosphono) ethylene and the like,

The admixing of the formulation components according to the invention to the polyolefin is generally brought about with stirring. However, it is also possible to add it by other methods, such as mixing the polyolefins with a solution the additives in a suitable solvent, what this is followed by evaporation of such a solvent, or the addition of the additives to the polyolefin on To bring about the end of the polymerization.

It is also possible to use the flame retardant effect Applying the compound to the article of manufacture, for example by immersing it in a solution or dispersion of the mixture of additives and subsequent evaporation

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to effect the solvent.

The additives according to the invention show good compatibility with polyolefins in the molten state and lead to no staining effect.

The mixtures are granulated and then with devices, which are suitable for melt spinning, preferably through a spinneret with a length / diameter ratio of extruded higher than 1. Granulating and spinning is carried out in the absence of oxygen, preferably in an inert gas atmosphere, such as nitrogen.

During the mixing it is possible, in addition to the additives according to the invention, to add organic matting agents to the polyolefin or inorganic color pigments and compounds that neutralize possible acid residues of the polymerization catalyst are suitable, such as zinc stearate or calcium stearate, to be added.

The filaments produced by extrusion are subjected to a stretching process at stretching ratios in the range from 2 to 10 at a temperature of 80 to 150 ^° C. in stretching devices heated by warm air, steam or a similar fluid or equipped with a hot plate.

The stretched filaments are then subjected to dimensional thermal fixation treatment with free or hindered shrinkage at a temperature of 80 to 160 ⁰ C.

Those obtained by extrusion from the mixtures according to the invention Threads can be mono- or multifilaments and are used to produce continuous filaments or Staple fibers or used to make textured or bulky yarns.

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In addition to the production of yarns, the invention Compositions for making films, raffia, fibrils from solutions, chips and the like molded products are used.

In practicing the invention, there can be wide variations and changes in terms Details can be made without, however, departing from the scope of the invention.

The following examples illustrate the invention.

example 1

The following were mixed in a 10 liter Henschell mixer Components:

- 10 kg of polypropylene with a melt index = 15 »a heptane extraction residue = 97> 8% and an ash content = 160 ppm;

- 0.2 kg of an aliphatic-aromatic containing bromine Ether of the general formula (I) of the type indicated in Table I;

- 0.1 kg of antimony oxide;

- 0.05 kg of zinc stearate and

- 0.04 kg of 2,2'-bis (diethylphosphono) diethyl ether.

The mixture was then granulated ^{at 200 °} C. in an extruder in an oxygen-free atmosphere.

The granules were used to make small plates and fibers. The small plates were placed in a Carver press

under a pressure of 20 kg / cm and with a residence time in the press made of 15 minutes.

The fibers were produced under the following working conditions:

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Sennecke temperature: 220 ⁰ C head temperature: 220 ⁰ C spinneret temperature: 22O ⁰ C

using a spinneret with 40 orifices, each opening a diameter of 0.8 mm and a length of 16 millimeters. The maximum pressure used was

100 kg / cm and the speed for releasing the thread 400 m / minute. The stretching was carried out in water vapor at 100 ^° C. in accordance with a stretching ratio of 3 »4.

After stretching, the fibers were curled. The cut stacks were then transferred into a needle felt.

The properties of small plates of fibers and needle felt are given in Table I below.

The needle felts not treated with resin survive the following Flammability Tests:

- DIN-54332

- British Standard 4790/1972 (ash test)

- ASTM D 2859/1970 T

- Swedish test BE-6

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Tatelle I.

Bromine contains ali-
phatic-aroma- properties of the plates Corro Properties of the -C CLOCXJLJ. Deh Sour Oxygen- tic ether sion b. Ice cream tion material index * Oxygen index * Melt index 240 ⁰ C Titer fes- in index Deim inSLu.ex—
felt in % at at during in tig- % in % 200 ⁰ C 240 ⁰ C 260 ⁰ C 200 ⁰ C 240 ⁰ C 260 ⁰ C 30riin. dtex speed in g /
dtex no 105 24.2 24.2 2,2'-bis [4 (2,3- 2.7 dibromopropoxy) -
3,5-dibromophe- 23.5 23.5 23.4 18 21 38 17th nyl] propane no 110 23.8 23.8 2,2'-bis [4 (2,3- 2.4 dibromopropoxy) -
3,5-dibromophe- 22.2 22.1 22.1 19 25 41 17th nyl] methane no 97 23.2 23.2 2,2'-bis [4 (2,3- 2.8 dibromopropoxy) -
3,5-dibromophe- 22.9 22.7 22.6 18 24 39 17th nyl3-butane no 101 23 23 2,2'-BisC4 (2,3- 2.5 dibromopropoxy) -
3,5-dibromophe- 22.8 22.6 22.5 19 22 35 17th nyl] neopentane

• The oxygen index was determined according to the standard ASTM D 2863-70

Example 2

Working according to Example 1, the following ingredients were mixed in a 10 liter Henschell mixer:

- 10 leg polypropylene with a melt index = »15» a heptane extraction residue = 97 »8% and an ash content = 160 ppm;

0.1 kg of 2,2'-bis [4- (2,3-dib: rompiOpoxy) -3,5-dibromophenyl] propane;

- 0.05 kg of antimony oxide;

- 0, OJy kg of zinc stearate and

- 0.04 kg of 2,2'-bis (diethylphosphono) diethyl ester.

The plates showed the following L.O.I. values {oxygen index in percent) and melt index values at the molding temperatures given below:

- Temperature: 200 ⁰ C LOI: 21.2% melt index: 20 -Temperature: 240 ° C LOI: 21.2% melt index: 21

- Temperature: 260 ⁰ C LOI: 21.1 % melt index: 40

In all tests, the panels showed no undesirable discoloration due to degradation. They showed no corrosion in a corrosion test at 240 ^° C. for 50 minutes.

The fibers produced under the same process conditions as in Example 1 showed the following properties: denier: 17 dtex; Tear strength: 2.6 g / dtex; Elongation: 98%; LOI: 22.5 %

They had a LOI of 22.3% and passed the following flammability tests:
SIN 5 ^ 352
British Standard 4790/1972 (ash test)

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ASTM-D-2859/1970 T (pill test) Swedish test BR-6 (tunnel test)

Examples 3 to 8

Operating as in Example 1, the following were mixed in a Henschell mixer having a capacity of 10 liters Components:

- 10 kg of polypropylene with a melt index = 15, a heptane extraction residue = 97.8% and an ash content = 160 ppm;

- 2,2'-Bis- [4- (2,3-dibromopropoxy) -3,5-dibromophenyl] propane in the amount given in Table II;

- Antimony oxide in the amount indicated in Table II;

- zinc stearate in the amount indicated in Table II;

- A phosphorus compound of the general formula (II) of the type indicated in Table II and in the type shown in Table (II) specified amount.

After grinding, the mixtures were in plates and in Fibers transferred by working according to the working conditions given in Example 1.

The properties of the boards, fibers and needle felts are given in Table II.

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Table II

Melting - corrosion Example 3 Example 4 Example 5 23.9 Example 6 ■ Example 7 Example 8 17.4 ■ jiteß & wss * ·· "· '' · '- . index at aoo «c EifceTchaften der Fibers 0.2 kg 0.2 kg 0.2 kg 23.9 0.2 kg 0.2 kg . - 17.4 - Antimony oxide: amount 24Q »C - titer in dtex 0.1 0.1 " 0.1 " 23 $ 0.1 " 24.2 _- 17.2 - Zinc tar: amount 260'C BeißfrctfiEiw **? ^ pg / ^ t ^e T 0.05 » 0.03 " 0.03 » 0.03 » 0.05 kg - Phosphorus ver
binding: type - stretch in 5 * Uhylpho *
phor ») * thyXtn Ulithylpho «- - 17th 2.2 '- <la {diethyl
ethyiiither 2.2'-Bl «(d! Ithyl
pnosphono) di- "* - 19th : Lot -UO.I, InX 0.04 kg 0.04 kg m ".- '20.5 -Ζ ■ ·':;. ' 0.04 kg 0.04 kg - 22nd Properties of the Properties of the 40 plates Felts , ti «for _r .. · ■■ i no -uo. ι. / at 2oo »c -UO.I. InX 23.4 23.5 23.5 21.7 240 * C 23.3 23.4 [ η.;. ■: /: .. '. 23.5 21.6 17th 260 * C 23.4 23.4 2.4 23.4 21.6 9 f 107 2.7
105 18th 18th 24.5 18th 19 ■ 18.6 - ■■ 2t ■ '''.^; 22nd 21st 22nd 37 39 37 37 no no 24.5 no no 18.8 .17 17 ■; ■ '■ 17th 17th 2.8 2.7 2.6 9 \ *. V
105 *. ·
112 98 110 24.1 24 24.2 22.2 24.0 ·. 24 ♦ 22.1

♦ The Uadelfelts not treated with resin "are subjected to the following flammability tests subjected: DHT-54332; British Standard 4790/1972; ASTM-D-2859/1970 T and Swedish Test BR-6

Claims (8)

Dr. F. Zumstein Sr. - Cr. Ξ. Assmenn - Dr. R. Koenigsberger Dipl.-Phys. R. Holzbauer - Oipi.-ing. F. KUngs-Eisen - Dr. F. Zumstein jun. PATENT LAWYERS? 7 R R R 8 1 BOOO Munich 2 - BrachausstraOe 4 - Tatefon SammeINr. 225341 ■ Telegrams Zumpat - Telex 529979 Case MF.2554 14/90 / Si Polymeric compositions based on olefin polymers Patent claims 1. Flame-resistant and non-corrosive polymeric compositions based on olefin polymers, thereby marked that they contain: a) a polyolefin, t>) 0.1 "to 15 percent by weight, based on the polyolefin _{} of} a bromine-containing aliphatic-aromatic ether general formula wherein H ^ and E ₇ ,, which can be the same or different, an alkyl radical which is partially or completely brominated 809828/0716 ORIGlNfAL INSPECTED is, with 1 to 20 carbon atoms, and Rp and E ,, which can be the same or different, hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group, each of which is optionally brominated is, mean c) 0.001 to 15 percent by weight, based on the weight of the polyolefin, of antimony trioxide, d) 0.01 to 15 percent by weight, based on the weight of the polyolefin, on a phosphorus-containing organic compound of the general formula R ₁ -O OR ₉
O = PAP = O (II) R ₆ O OR ₈ wherein Rt, R ^ »R ₉ and Rg, which can be the same or different, denote hydrogen or an alkyl radical having 1 to 18 carbon atoms, and A denotes an alkylene, arylene or alkarylene group, which may optionally be a heteroatom, such as 0, S , Contains N or P, means. 2. Polymeric compositions according to claim 1, characterized in that the bromine content of the aliphatic-aromatic Ether of the general formula (I) between 30 and 85 percent by weight amounts to. 3 · Polymeric compositions according to claim 2, characterized characterized in that the bromine content is between 50 and 80 percent by weight amounts to. 4. Polymeric compositions according to one of the foregoing Claims, characterized in that the bromine-containing aliphatic-aromatic ether of the general formula (I) is selected from the class consisting of: 809828/0716 2,2'-bis- [4- (2,5-di "bromopropoxy) -3i5-di'bromophenyl] propane, 2,2 'bis- [4- (2,3-dibromopropoxy) -3,5-dibromophenyl] -butane, 2,2'-bis- [4- (2,3-dibromopropoxy) -3, 5-dibromophenyl] methane, 2,2 * -bis- [4- (2,3-dibromopropoxy) -3,5-aibromophenyl] neopentane and 2,2 '-Bis- [4- (2,3-dibromobutoxy) -3, ^ - dibromophenyl propane. 5. Polish compositions according to one of the preceding claims, characterized in that the phosphorus-containing compound of the general formula (II) is selected from those in which Er, Eg, Er ₇ and Eq, which can be the same or different, represent an alkyl radical with 1 to 4 carbon atoms and A is an alkylene radical having 1 to 6 carbon atoms, which optionally contains 0, S, N or P is. 6. Polymeric compositions according to any one of the preceding claims, characterized in that the phosphorus containing organic compound is selected from the class consisting of di- (ethylphosphono) methane, 2,2'-bis (diethylphosphono) ethylene, 2,2'-bis (diethylphosphono) diethyl ether, 2,2'-bis (diethylphosphono) dimethyl ether and 2,2'-bis (methylphosphono) ethylene. 7 · Polymeric compositions according to any one of the preceding Claims characterized in that the polyolefin is a highly isotactic polypropylene. 8. Flame-resistant, non-corrosive polymeric compositions according to any one of the preceding claims in the form of Fibers, films, eaffia, fibrils, chips or similarly shaped products. 809828/0716