FR2604179A1 - HALOGEN-FREE, FLAME-RESISTANT FRAME FOR LONG-TERM MATERIALS - Google Patents

Abstract

A. HALOGEN-FREE, HIGHLY FLAMMABLE REINFORCEMENT FOR LONG-TERM MATERIALS. B. CHARACTERIZED IN THAT THE BASE OF THE PLASTIC MATERIAL IS A MIXTURE BASED ON RUBBER-PROPYLENE-ETHYLENE AS WELL AS ETHYLENE COPOLYMERS WITH A CO-MONOMER FRACTION OF UP TO 35 BY WEIGHT OR ALSO A POLYETHYLENE DENSITY OF LESS THAN 0.915 GCM ALONE OR IN MIXTURE WITH COPOLYMERS, FOR WHICH THE POLYMER MIXTURE IS FILLED WITH A FILLING SUBSTANCE WHICH MAKES COMBATIVE TO FIRE AND BY GRAFTING OF INSATURE ORGANOSILANES IS REPUBLICABLE BY ACTION OF HUMIDITY. C. THE INVENTION RELATES TO A HALOGEN-FREE AND HARDLY FLAMMABLE REINFORCEMENT FOR LONG-TERM MATERIALS.

Description

"Halogen-free and flame retardant frame

for long-distance materials ".

A frame without halogen and different

  highly flammable for electric cables and

  similar products consists of a rubber-based mixture

  ethylene-propylene rubber and ethylene copolymers

  with a fraction of a comonomer up to 35% by weight or also based on polyethylene having a density

  less than 0.915 g / cm3, alone or in combination with the co-

  polymer, for which the mixture is lined with

  filler that fights the fire and is

  culminated by unsaturated organosilane grafting under

the action of moisture.

Description:

  The invention relates to a halogen-free and flame-resistant frame with suitable packing materials, for long-distance materials such as electrical cables,

  pipe bundle and tubular pipes based on

  extruded and cross-linked plastics material.

Mixtures that are difficult to ignite

  mables, to obtain the most varied products

  are required in many technical fields.

  For example, insulation of electrical cables

  and pipes based on polyvinyl chloride.

  must be noncombustible, when such cables or pipes find use in mines on

  vessels or other facilities easily

  flammable or at risk of fire.

  Plasticizer-free polyvinyl chloride is certainly incombustible, but

  inappropriate for the manufacture of electrical cables.

  and conduct. For this purpose, it is up to

  conventional use of polyvinylchloride

  a plasticizer which can be defined as

fighting the fire.

  This property is obtained by the hydrochloric gas released by the heating during the combustion which occurs during the decomposition of the insulation based on polyvinyl chloride and which

  causes extinction of the formed flame.

  Nevertheless, the subsequent known damages are perishable, which result from this

  that the hydrochloric gas released by heating is combined

  with water or water vapor to form acid

  hydrochloric acid that corrodes or destroys metals,

concrete or other objects.

  In the effort to stop this ensuing damage, it has already been planned to add to the polymeric materials, an acid-bonded packing material, very finely pulverized with an average particle size of less than 250 μm, for

  fix the volatile acids detached by the action of the

  their (German patent application DE-OS published under No. 1,769,343). This known process could not prevail in

convenient.

  In the meantime, this has led to halogen-free base materials which are difficult to ignite by fire-fighting additives which are halogen-free. From this angle, a mixture of halogen-free polymers, which fights the fire is known (German patent application DE-OS published

  2 809 294) which contains a specific quantity of

  hydrate of aluminum oxide. As material

  basis, rubber products are used here.

  rubber-type products, which afterwards

  transformation into final product by action of the

  are chemically cross-linked. Such a crosslinking

  has been practiced for years in the

  plants so called vulcanization plants

  continuous operation (CV installations). To this end, the

  material to be crosslinked is transformed, for example into a mold of a chain line - into a corresponding tube

  filled with steam or protective gas -. With the increase

  cross-section, for example of an electric cable, and the rigidity of such a product which will

  by increasing, this way of crosslinking is, however,

  more and more problematic. Damage to the frame of the insulation or the casing of a cable

  by contact with the product through the installation

  CV with the wall of the pipe of the tube, do not

are not always excluded.

  It is furthermore known that a series of polymers which are basically suitable, on the basis of which the mixtures for the reinforcement of cables and pipes to be obtained, can be crosslinked with organic silanes. In this respect the variants of

  different processes may come into consideration

  all of which are actually used in practice.

  By using these techniques concerning

  usual mixing positions with these substances of

  filling, however,

  insurmountable because the amounts of moisture supplied with the fillers induce the crosslinking reactions too early and in a manner

not controlled.

  From this state of the art

  that the invention lies in the fact, therefore, that a halogen-free and flame-resistant framework is created which can be produced without problem also for larger sections of coating, which

  while also suffices for mechanical requirements and,

  that it is necessary, at the same time electrical for the corresponding field of play and whose manufacturing and processing technology excludes

  the disadvantages mentioned above.

  This problem is solved according to the

  in that the base of the plastics is a mixture of rubber-propylene-ethylene, EPDM and the like, as well as copolymers of ethylene with a comonomer, such as acrylate or vinyl acetate

  in which the percentage of comonomers rises to

  than 35% by weight, or also based on polyethylene having a density of less than 0.915 g / cm 3, alone or as a mixture with the copolymers mentioned, where the mixture

  of polymers is crosslinkable by grafting organosilane

  unsaturated by action of moisture and garnished with

  a filler that fights the fire.

  Thanks to the crosslinking of the silane

  without pressure, products of larger section

  can be isolated without problems or can be

  coated without having to use

tinu (CV) expensive.

The planned mix combination

  allows a fraction of the filling substance

  health and who fights the fire without losing the

  particularity - in particular neither electrical nor mechanical. Although copolymers based on acetate or acrylate have been found to be

  be particularly appropriate mixture compounds

  5. For the purpose of the invention, however, also extremely low density polyethylenes (VLDPE)

  as for example from 0.890 to 0.915 g / cm3. If the copoly-

  mother of ethylene is an acetate, a fraction of

  monomer of 5 to 35% by weight has been found to be the most

  appropriate, if the copolymer is an acrylate, the fraction

  The comonomer content is preferably 5 to 20%

in weight.

The ratio of the mixture of

  basic materials, that is to say the rubber-pro-

  pylene-ethylene / ethylene copolymer or VLDPE, is located

  preferably between 40: 60 and 60:40.

  In order to achieve the necessary fire antagonism, the corresponding fillers of the basic mixture are added in quantities of 80 to 180 parts.

  preferably from 90 to 120 parts referred to 100 parts

mixing.

The requirement for insulation of

  halogen-free and hardly inflammable cables

  the simultaneous requirement of good electrical properties

  cudgels. This problem is solved by the invention to help

  simultaneous implementation of several poly-

  mothers. Thus, electrical properties are

  particularly good components of the propylene-ethylene rubber (EPR) mixture with the high mechanical values of the copolymer or VLDPE, as well as the good filling qualities of all the components. It may be further appropriate

  to mix with this material other polymers, ad-

  as stabilizers for aging.

  thermal effect, against the influence of radiation

  energy additives or the like, as well as processing aids such as lubricants, dispersants, plasticisers and optionally

coloring additives.

  The realization of such an appropriate mixture can, according to the invention, proceed in such a way that the cutting of the components, the introduction of fillers and other additives,

  auxiliary substances of manufacture, catalytic

  condensation and the grafting of silane to the

  of the mixture, are carried out separately in a suitable manner, according to the process. In an other

  step of the process after a corresponding

  In the case of a manufactured granulate, the transformation is carried out as a final product which is finally exposed for the purpose

  from cross-linking to water placement or simple-

  the installation of moist air.

  A variant of the process, advantageously

  In the embodiment of the invention, when the components of the grafting mixture are first grafted with the organosilanes, each for itself alone, or together, but without the presence of the products.

  filling and then the graft material is

  the material fights the flames, as well as with the additional additives and usual processing aids, melted and shaped into the same

  operation or in an operation put in place

  quently. Such a process has the advantage that

  filling products that make the product combat-

  both flames, can also be used, which at high temperatures, about the grafting temperature above 180 C, decompose or form fission products which on their side, again,

  uncontrollably hamper the process of grafting

  fage or the subsequent crosslinking process.

The following mixing examples

  serve a more complete explanation of the invention.

  tion. Example I represents a suitable blending composition.

Example I:

  Rubber-propylene-ethylene (EPR) 50 p. 50% ethylene-vinyl acetate copolymer (% monomer 20% by weight) Fillers as fire protector (aluminum hydrate oxide) 100 p. Silane (vinyltrimethoxysilane) 2 p. Peroxide 0.05 p. Dibutylzinc dilaurate condensation catalyst 0.05 p. Plasticizer (Naptenic oil) 10 p. Processing auxiliary lubricant (wax) 5 p.

  Stabilizer (TMQ = tetramethyldihydro-

  quinoline) 0.4 p. The exemplary embodiment illustrates

a possible path of the process.

Example II

  A. Rubber-propylene-ethylene (EPR) 45 p. Silane 2 p. EPR graft peroxide 0.05 p. B. Ethylene Vinyl Acetate (EVA) Copolymer (Mw% 20%) 100 p. Silane 2 p. Graft peroxide of the copolymer 0.04 p. C. Charging filler p. EPR and 5 p. EVA 10 p. Aluminum hydrate oxide 120 p. Plasticizer 10 p. & Processing aid 5 p. Stabilizer 0.8 p. The constituents of this charge are mixed. D. mixture A 60 p. mixture B 40 p. mixture C 150 p. Catalyst optionally as 0.05 p. Mixtures: This embodiment is in

  particular, in all cases, to be preferred in

  which fire-fighting fillers are used, such as for example oxide hydrate

  of aluminum, give up water at high temperatures.

  Here we proceed in such a way that the components of the mixture are grafted in the first place each to be with the silane, and then mixed

  components grafted together with the load of pro

  fillings (C) approximately in a process of

  cold mix, or already dosed it is brought to the

  funnel of a processing extruder.

  Fusion, homogenization and shaping can be carried out in this process

  in a work stage; the crosslinking of the envelope

  eg, shaping, isolation or the like is

  taken by subsequent placement of water or simply

  in that the product is exposed to atmospheric moisture

for a long time.

  Another improvement concerning the fight against fire is characterized in that the substance that makes incombustible is used magnesium hydroxide alone or in mixture

with aluminum oxide hydrate.

Claims (10)

R E V E N D I C A T I 0 N S 1) Armature hardly ignited   mable thanks to suitable halogen-free fillers, for long-distance material such as electrical cables, tube bundle cables   or pipe pipes made from a plastic material   as extruded and crosslinked, characterized in that the base of the plastics material is a rubber-propylene-ethylene mixture as well as copolymers of ethylene with a comonomer fraction of up to 35% by weight or also of polyethylene having a density of less than 0.915 g / cm3 alone or in admixture with the copolymers, for which the polymer blend   is stuffed with a filling substance that makes   fire and, by grafting unsaturated organosilanes,   is crosslinkable by action of moisture.   2) Reinforcement according to claim 1, characterized in that the ethylene copolymer is an acetate with a co-monomer percentage of 5 to 35% by weight.   3) Reinforcement according to claim 1, characterized in that the ethylene copolymer is an acrylate having a co-monomer percentage of 5 to % in weight.   4) Reinforcement according to claim 1, characterized in that the density of the polyethylene is 3. is about 0.890 to 0.915 g / cm3.  ) Armature according to one   any of claims 1 to 4, characterized   in that the proportions of the rubber mixture   propylene-ethylene compared to ethylene copolymers   lene or very low density polyethylene (VLDPE) represent 40: 60 to 60:40. 6) Reinforcement according to any one   Claims 1 to 5, characterized in that   plastic contains the filling substance which makes it fight the fire in a quantity of 80 to 180   parts - preferably from 90 to 120 parts -   100 parts of the base mixture.   - 7) Reinforcement according to any one   Claims 1 to 6, characterized in that the   lange contains additional polymers, additives   processing aids and processing aids and coloring additives.   8) Process for obtaining a   reinforcement according to one of claims 1 to 7,   characterized in that at least one of the components of the mixture in the first place is grafted with the organosilane for it and then the components are mixed with   filling products which make them incombustible   as well as with additional additives and usual processing aids, in which it is shaped in a subsequent step. 9) Method according to claim 8, characterized in that the filling substance   which makes it incombustible, is finally blended into   me of highly concentrated mixture (product load of   filling) of the components of the mixture.   10) Method according to claim 9, characterized in that the mixing of the components of the cutting with the highly concentrated mixture of components and   other additives as well as the shaping by the   mature are done in one operation.   11) Process according to any one of   Claims 1 to 10, characterized in that the catalyst   The condensing agent required for the moisture crosslinking is added as a load immediately   before the formatting operation.   12) Process according to any one of   claims i to 11, characterized in that   reads aluminum oxide hydrate as a substance of filling that makes it incombustible.   13) Process according to claim 8, characterized in that magnesium hydroxide, alone or in part, is used as the incompressible substance.   mixture with aluminum oxide hydrate.