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    • 专利摘要:
    The invention relates to a flame-retardant, vulcanized polymeric composition containing as the polymeric component at least one halogen-free olefinic elastomer of the saturated main-chain M group, with a content of more than 50 phr relative to the polymeric constituents. The invention is characterized in that at least one or a combination of different halogen-free dehydrating flame retardants is contained in a proportion of a total of 30 to 130 phr 10, and that the proportion of mineral oil plasticizers in the composition is less than or equal to 50 phr.
    公开号:AT517060A1
    申请号:T50240/2015
    申请日:2015-03-25
    公开日:2016-10-15
    发明作者:
    申请人:Bategu Gummitechnologie Gmbh & Co Kg；
    IPC主号:
    专利说明:

    Flame-retardant polymeric composition
    The invention relates to a flame-retardant polymeric composition according to the preamble of claim 1.
    Elastic elements, for example made of rubber or rubber, by themselves have no flame retardant or fire retardant properties, as required in some applications partly based on standards or statutory provisions. So far, for example, natural rubber or chloroprene rubber (CR) are used as base polymers for dynamic applications. Although they have the best mechanical properties and wear characteristics, they do not have flame-retardant or fire-retardant properties which can fulfill the requirements of EN 45 545-2. This relates in particular to problems regarding the smoke density (NR, CR) and the toxicity (CR).
    Achieving the low flammability, in particular according to the standard EN 45545-2, with the associated high requirements in terms of flame propagation, optical smoke density, smoke gas toxicity and heat release rate, first requires a special attention in the selection of polymers. The stringent requirements for smoke density and toxicity include, for example, the use of halogen-containing polymers, e.g. chloroprene rubber (CR) or R-group elastomers with unsaturated backbone, e.g. Nitrile rubbers, e.g. HNBR, a priori off. Olefinic polymers of the M group with low resistance to cracking and growth under static and dynamic stress and poor resistance to lubricating oils and greases and vinyl acetate-containing thermoplastic polymers are preferably used to meet the requirements of flue gas density and toxicity.
    It is also known to put elastomers with flame retardants or fire retardants in large quantities, but with the addition of such additives, the material properties are usually severely impaired, making such an existing rubber or rubber element, the required for use static and dynamic properties can no longer meet.
    In a dynamic use e.g. on the other hand, with known elastic elements based on NR and CR, the required fire protection provisions can not be satisfactorily fulfilled as a spring element or damping element or a similar, usually highly dynamically loaded element, for example in vehicles.
    Currently, for example, for elastomeric products in the rail vehicle sector, the problem arises that both the EN 45545-2 HL3 (eg R9, R22 / 23) and the requirements of DIN 5514 (profile) and BN 918043 (elastomers for technical purposes) not a single material to meet equally.
    In order to solve this, attempts were made in part to provide material combinations and thus to keep the protected elastic core free from flame retardants. Such composite elements are described for example in DE 38 31 894 A1 or WO 2010/069842.
    Polymeric, flame retardant-containing mixtures of ethylene vinyl acetate with ethylene-propylene-diene monomer rubber are also known from the prior art. In most cases, crosslinking is peroxidic or by irradiation. Such mixtures are mainly used in the sheathing of cables or electrical lines. For example, EP 2 343 334 A2 describes flame-retardant compositions of EVA, EPDM and LLDPE which have a peroxidic crosslinking system formed by di-cumyl peroxide. Most of these materials are based on EVA with low additions of EPDM / EPM or PE.
    Furthermore, numerous polymer blends with dynamically crosslinked thermoplastic elastomers (TPV or TPE-V) are known. These are two-phase systems in which finely dispersed crosslinked rubber particles are embedded in a continuous thermoplastic matrix. Thermoplastic elastomers behave at room temperature comparable to conventional elastomers, but are plastically deformable under heat and have a thermoplastic behavior at elevated temperature. This is precisely for use as a damping component, e.g. for rail vehicles, but not desired, because there is the maintenance of elastic properties necessary even at higher temperatures. Accordingly, thermoplastic elastomers are not suitable for this purpose.
    In WO 2014/019008 sulfur-crosslinked mixtures of EPDM and EVA are further described, which can be filled with very high amounts of flame retardants and therefore have good flame resistance, but still retain their advantageous mechanical properties due to a special sulfur crosslinking system.
    Often attempts are also made to correct the deterioration of mechanical properties caused by the high levels of flame retardants, in particular with regard to hardness and rigidity, by using plasticizers. Usually, such elastomer blends include e.g. based on EPDM or EPM high levels of mineral oil plasticizers, in particular to improve the processing properties (flowability) and mechanical characteristics such. Hardness to adjust module. Usual amounts can be from 50 to 200 phr (parts per hundred rubber) based on the polymer.
    Mineral oils are petroleum products and complex hydrocarbon mixtures and have paraffinic, naphthenic and aromatic components. For non-polar or weakly polar olefinic elastomers mineral oils are used for reasons of polarity and compatibility, the proportion of aromatically bound carbon atoms (caromatic) should not be greater than 50% by weight based on 100% by weight of mineral oil. For reasons of polarity, therefore, only mineral oils with a predominantly paraffinic or naphthenic content can be used for such quantities.
    A typical formulation of a known polymeric composition has the following composition: • EPDM 100 phr • carbon black 20 phr • aluminum trihydrate (ATH) 180 phr • zinc borate 50 phr • plasticizer 45 phr • Crosslinking chemicals: 12 phr • Processing aids: 5 phr
    The content of dehydrating flame retardants here is 230 phr. Such mixtures can meet the fire protection requirements of EN 45545-2 (R22 / 23, R9), but prove to be disadvantageous here, due to the high content of flame retardants, deficient mechanical properties:
    • Hardness: 64 Shore A • Density: 1,47g / cm3 • Elasticity: 31% • Tensile strength: 4,2 MPa • Elongation at break 560% • Abrasion:> 600 cm3
    It is therefore an object of the invention to overcome these disadvantages and to provide a flame-retardant polymeric material which has exceptional fire protection properties, in particular the fulfillment of the standard EN 45545-2 HL3, in combination with improved mechanical and dynamic characteristics.
    This object is achieved in a composition of the type mentioned by the characterizing features of claim 1.
    According to the invention, it is provided that at least one halogen-free dehydrating flame retardant or a combination of different halogen-free dehydrating flame retardants is contained in a proportion of 30 to 130 phr in total, and that the proportion of mineral oil plasticizers in the composition is less than or equal to 50 phr.
    As described above, it is usually the case that the content of flame retardants is set as high as possible in such elastomers in order to meet the fire protection standards can. However, as this often worsens the mechanical properties below the tolerable values, an attempt is made to counteract this by using larger amounts of mineral oil plasticizers and thereby to improve the mechanical properties.
    However, it has now surprisingly been found that precisely this procedure, that is to say the careless use of mineral oil plasticizers, is counterproductive and can entail considerable disadvantages in the reaction to fire.
    Accordingly, it was unexpected that the composition according to the invention despite the counterintuitive and considerable reduction of the proportion of dehydrating flame retardants to below 130 phr, contrary to expectations, did not deteriorate the fire protection properties, but both the fire protection standard EN 45545-2 and the required mechanical properties DIN 5514 (Profile, eg tensile strength> 8.5 MPa, abrasion <300 mm3) or the BN 918043 (elastomers for technical purposes, tensile strength> 8 MPa Gl and abrasion maximum 300mm3 for N II) could be met.
    In this context, the proportion of additives in mineral oil plasticizers has proven to be a relevant feature. This is to be kept as low as possible in the mixture or even excluded. Exceeding the value of 50 phr of the mineral oil plasticizer content leads to a marked deterioration of the fire protection properties, in particular to a deterioration of the self-extinguishing flame retardance properties, and the standard can no longer be met. Accordingly, the underlying finding is that in the present case not only the amount of flame retardants determines the fire behavior, but the fire behavior is achieved primarily by the reduction or the waiver of mineral oil additives.
    At the same time, the reduction of the flame retardants achieves an improvement in the mechanical properties, which is accompanied by improved dynamic properties.
    The proportion of the saturated main chain olefinic elastomer of greater than 50 phr is also advantageous for good dynamic properties.
    Further advantageous embodiments and further developments of the composition result from the features of the dependent claims:
    Advantageous dynamic properties are achieved when the olefinic elastomer is contained at a level of greater than or equal to 70 phr, or is contained at a level of 100 phr as the sole polymeric component.
    In order to further increase the properties of the composition and above all the fire resistance, it is advantageous if, as a single plasticizer, at least one mineral oil plasticizer with a maximum fraction of less than or equal to 20 phr, preferably less than or equal to 10 phr, is contained. Very beneficial flame retardant properties are achieved when the composition is completely free of mineral oil plasticizer.
    In order to achieve good fire protection properties with the least possible influence on the material properties, it has proved to be advantageous to add magnesium hydroxide (MDH), aluminum hydroxide (ATH), antimony trioxide, nanoclays and / or zinc borate as flame retardants, preferably a synergistic mixture of two or more thereof are. In particular, the flame retardant (s) is / are solid and pulverulent or crystalline.
    In order to produce a good flameproofing effect (self extinguishing) with simultaneously improved mechanical properties, it may be provided that solid dehydrating flame retardants (for example ATH, MDH, zinc borate) are used in an amount of 50 to 110 phr, preferably 60 to 100 phr the polymer is / are included, provided that the mineral oil content is less than 50 phr. The reduction of the flame retardant content improves the mechanical parameters, especially the dynamic and elastic properties of the composition. Self extinguishing in case of fire is achieved.
    The olefinic elastomer is advantageously a homopolymer or a copolymer or a terpolymer of or with diene monomer units, in particular a terpolymer consisting of ethylene, propylene and a diene-containing termonomer, preferably having a termonomer content of at least 0 wt .-% to 12 wt .-% based on the olefinic elastomer (according to ASTM D 6047). In this way, the double bonds necessary for sulfur crosslinking can also be provided.
    In this context, it is advantageous if the olefinic elastomer is selected from the group consisting of ethylene-propylene-diene rubber (EPDM) and ethylene-propylene rubber (EPM) and / or that the composition of ethylene-propylene-diene Rubber (EPDM) and / or ethylene-propylene rubber (EPM) as the only polymeric components. Ethylene-propylene-diene monomer rubbers (EPDM) have great advantages in case of fire in terms of their low smoke density and toxicity. EPDM rubbers can also be adjusted in a wide range of hardness and mechanical properties. Furthermore, EPDM rubbers offer advantages in terms of weathering, UV, ozone and heat resistance and are able as a protective layer, the aging of the dynamically loaded components to be protected, eg. B. natural rubber, to minimize.
    The halogen-free, olefinic rubbers of the M group, e.g. In addition, particularly high molecular weight EPM or EPDM may be drawn with mineral oils from manufacturers to improve processing performance. Preferably, they contain non-conjugated diene monomer units selected from the group of 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3 Pentadiene, 1,3-cyclopentadiene, dicyclopentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,4-cyclohexadiene, tetrahydroindene, methyl tetrahydroindene, ethylidenenorbornene and 5-ethylidene, respectively -2-norbornene (ENB), 5-methylene-2-norbornene (MNB), 1.6 octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5-iso Propylidene-2-norbornene, 5-vinyl-2-norbornene (VNB).
    It is particularly advantageous if the ethylene-propylene-diene monomer rubber (EPDM) is a terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene (ENB) or
    Dicyclopentadiene (DCPD) is, preferably with a Termonomer portion of at least 2 to 12 wt .-% based on the terpolymer (according to ASTM D 6047). Due to the comparatively low double bond content of EPDM compared to other diene rubbers, a higher amount of accelerator must be used in order to achieve an economically expedient vulcanization rate. The solubility of EPDM for sulfur and the mostly polar accelerator or accelerator residues is low. Therefore, this is usually a combination of several accelerators used to prevent blooming.
    Crosslinking with sulfur and sulfur donors requires the presence of double bonds of the ter component. The ratio of sulfur, sulfur donors and accelerators and the type of accelerators determine the length of the sulfur network bridges and the network density. Frequently used accelerators are e.g. Sulfenamides, e.g. N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), thiazoles, e.g. 2-mercaptobenzothiazole (MBT),
    Dithiocarbamates, e.g. Zinc dibenzyldithiocarbamate (ZBEC), guanidines, e.g. Diphenylguanidine (DPG) or thiophosphates. As sulfur donors, e.g. Thiuram, Caprolactamdisulfid or Phosphorylpolysulfid used.
    Olefinic elastomeric copolymers such as EPM are usually crosslinked with peroxides. Typical peroxides are, for example, dicumyl peroxide, di (2-tert-butyl-peroxyisopropyl) benzene and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1,1-di (tert-butyl) butylperoxy) -3,3,5-trimethylcyclohexanes and n-butyl-4,4-di (t-butylperoxy) valerates.
    According to an advantageous embodiment, it is provided that a vinyl acetate-containing thermoplastic polymer is contained as further polymeric component, in particular a homopolymer, copolymer or terpolymer of vinyl acetate and preferably selected from the group of polyvinyl acetate (PVAc) or ethylene vinyl acetate (EVA).
    A particularly low flue gas density combined with good chemical properties is obtained if the vinyl acetate-containing polymer has a vinyl acetate content of 40 to 75% by weight (LP Testing instruction No. 015, Lanxess).
    Ethylene vinyl acetate is mostly used in the cable sector. The polar vinyl acetate group improves the flame retardance and at the same time the oil resistance. The smoke density is low and the flue gas has no toxicity. Ethylene vinyl acetate has at the same time excellent weathering, UV, ozone and heat resistance.
    In this context, it is advantageous if the vinyl acetate-containing polymer has a melting temperature or a start of the melting range of less than 150 ° C, preferably less than 100 ° C, and optionally one in typical
    Rubber processing temperatures low viscosity. In this way, a good mixture can be achieved while avoiding the vulcanization completely.
    An advantageous composition is characterized in that EPM or EPDM having 50 to 100 phr, in particular 70 to 100 phr, preferably 80 to 100 phr, that the vinyl acetate-containing polymer in an amount of 0 to 50 phr, in particular 0 to 30 phr, preferably 0 to 20 phr, based in each case on the total weight of the polymers, wherein the data in phr in each case on the ratio of the pure polymeric components to each other or to the amount of polymers EVA + EPDM (= 100 phr) without fillers, additives , Flame retardant refer. In this way, an intimate mixture of the polymeric constituents and a nearly single-phase system is obtained.
    Vinyl acetate-containing polymers without double bonds in the main chain and without double bond-containing monomers are predominantly crosslinked with peroxides.
    If vinyl acetate-containing polymers are used together with EPDM, it may also be desirable for sulfur crosslinking to form only the EPDM a continuous network and for the vinyl acetate-containing polymer to be uncrosslinked.
    For plasticizing vinyl acetate-containing polymers are often used paraffinic plasticizers. Synthetic plasticizers such as adiapates or sebacates are used for improved low temperature flexibility, and phosphoric acid esters are used, for example, to improve flame retardancy.
    Finally, particularly advantageous compositions with regard to their mechanical and fire-retarding properties consist of the following polymeric components:
    Ethylene-propylene-diene rubber (EPDM) or ethylene-propylene rubber (EPM) or
    Ethylene-propylene-diene rubber (EPDM) and ethylene vinyl acetate (EVA) as a homogeneous polymer mixture, or
    Ethylene-propylene rubber (EPM) and ethylene-vinyl acetate (EVA) as a homogeneous polymer blend, or
    Ethylene-propylene-diene rubber (EPDM) and polyvinyl acetate (PVAc) as a homogeneous polymer mixture, or
    Ethylene-propylene rubber (EPM) and polyvinyl acetate (PVAc) as a homogeneous polymer mixture.
    To achieve further desired or required properties of the flame-retardant polymeric composition is also proposed that the material further additives such as fillers or dyes, carbon black, processing aids, anti-aging agents or the like. And crosslinking agents are added. When using flame retardant plasticizers find their application in phosphoric acid, which are only compatible with nonpolar rubbers due to their polarity to a limited extent. A particularly advantageous qualitative and quantitative composition is as follows:
    Ethylene-propylene-diene rubber (EPDM) or ethylene-propylene rubber (EPM): 70 - 100 phr, - vinyl acetate-containing polymer, in particular ethylene vinyl acetate (EVA): 0 - 30 phr, - mineral oil plasticizer: 0-10 phr,
    Flame retardant, in particular aluminum hydroxide (ATH): 60 to 100 phr,
    Carbon black variable depending on the hardness: 0 - 80 phr, - Remainder auxiliaries, additives etc.
    If or by the fact that it is provided that the polymeric components together form a substantially, in particular both macroscopic and light microscopic, single-phase and homogeneous mixture, in particular without visible with the naked eye and / or visible light phase separation, particularly advantageous mechanical properties of Polymer, in particular with regard to the elastic-dynamic character. This is understood here to mean that the mixture is advantageously so single-phase that in the mixture and / or in the final composition no elastomer particles having an average particle diameter of more than 0.5 .mu.m, in particular more than 0.1 .mu.m, preferably more than 0.01 pm, and / or no rubber domains with an average diameter of more than 0.5 pm, in particular more than 0.1 pm, preferably more than 0.01 pm. In particular, there are no identifiable or detectable polymer particles or rubber domains.
    In this context, it is particularly advantageous if or that the vulcanized polymer mixture has exclusively elastomeric and no thermoplastic properties or if or that the vulcanized polymer mixture or the composition both in the temperature range of application and up to elevated temperatures, in the short term from 150 to 200 ° C, in particular predominantly, has elastomeric properties. This is also a significant difference to thermoplastic elastomers and crosslinked thermoplastic elastomers (TPE-V):
    Crosslinked thermoplastic elastomers (TPE-V) prepared by dynamic vulcanization are within the range of application at lower temperatures, e.g. at room temperature, largely elastomeric properties and behave in this area comparable to traditional elastomers. In the processing range at elevated temperature, however, they have predominantly thermoplastic properties, are accordingly flowable and plastically deformable or hot-formable and have a characteristic melting point or melting range or softening range. Their properties are determined here by the thermoplastic, uncrosslinked, for example polypropylene or vinyl acetate, polymer matrix. The intrinsically crosslinked elastomer particles embedded therein have certain elastic properties, but have no significant influence on hot workability and flowability.
    By contrast, the compositions according to the invention after vulcanization have almost exclusively elastomeric or rubber-elastic properties over the entire relevant temperature spectrum, both in the field of application and in the elevated temperature range. When the temperature increases, the body softens, but never becomes fluid, so has no melting point or range. The vulcanized polymer mixture or the composition accordingly has a melting peak, measured by differential scanning calorimetry, in the temperature range up to 200 ° C. Also, after vulcanization no hot forming and no second shaping step is possible.
    Thermoplastic elastomers are therefore also much less thermally and dynamically resilient than the advantageous compositions according to the invention and tend to creep at elevated temperatures.
    An advantageous vulcanized polymer mixture or the composition further has a loss factor (ratio of loss to storage modulus with dynamic shear stress) of tan <0.3, measured according to ISO 4664 "elastomers or thermoplastic elastomers in a temperature range from room temperature to about 200 ° C - Determination of dynamic properties ", on. This shows that in a temperature range in which TPE-Vs are typically processed, the elastic properties of the composition according to the invention outweigh the viscous properties and thus no further shaping is possible.
    In any case, it is thus advantageous that the composition is not formed as a thermoplastic elastomer (TPE), in particular not as an olefin-based thermoplastic elastomer (TPE-O) or as a crosslinked thermoplastic elastomer based on olefin (TPE-V).
    A particularly advantageous composition according to the invention is prepared or obtainable by mixing the polymeric component or components into a homogeneous blend and in particular subsequent incorporation of the crosslinking agents, flame retardants and optionally further additives and / or auxiliaries while strictly avoiding any crosslinking or Vulcanization, preferably at a maximum temperature of 110 ° C. Only then is a shaping step and the vulcanization, in particular at elevated temperature and optionally under pressure. The vulcanization does not take place under shear stress, that is not during the intensive mixing, as in the case of dynamic vulcanization.
    The vulcanization temperature is advantageously, in particular in EPDM / EVA, at a temperature of less than 240 ° C, preferably in a temperature range of 130 to 190 ° C. Thereby, there is a further difference to crosslinked thermoplastic elastomers in which the crosslinking by means of dynamic vulcanization already takes place during mixing at a higher temperature and under high shear stress. In contrast, in the composition according to the invention, vulcanization is already avoided during the mixing and the crosslinking takes place only at the end, in particular after the shaping, at elevated temperature, but not under shear stress. In this way, the rubber-typical properties of the composition are positively influenced even at high flame retardant content.
    The resulting so advantageous composition is thus obtainable by "static" vulcanization, especially after shaping. The term static vulcanization in the present case is understood to mean vulcanization while avoiding any shear stress or avoiding dynamic vulcanization.
    The composition according to the invention advantageously has the following characteristics, namely a hardness of 40 to 90 Shore A, preferably 55 to 85, Shore A (DIN ISO 7619-1) and / or a tensile strength> 5 MPa, preferably> 7 MPa (DIN 53504 ) and / or a tear propagation resistance of> 7 N / mm, preferably> 10 N / mm (DIN ISO 34-1 B) and / or abrasion <400 mm 3, preferably <300 mm 3 (DIN ISO 4669) and / or a density <1.4 g / cm3, preferably <1.3 g / cm3 (DIN ISO 1183-1) and / or - a MARHE value (ISO 5660-1) <90 kW / m2, in particular <60 kW / m2 and / or - complies with standards EN 45545-2 HL 3 R9 / R22 / 23.
    From this it can be seen that the characteristic values which are essential for the dynamic-elastic properties are maintained and fulfilled, and that the mechanical characteristics are significantly higher than for today's standard flame-retardant mixtures according to EN 45545-2.
    To improve the requirements in terms of smoke density and toxicity, it is advantageous if all the polymeric components, in particular the entire composition, is halogen-free / is.
    According to the invention, a method for producing an advantageous composition according to the invention is also proposed in this connection, in which first the polymeric components, the crosslinking agent (s), the flame retardant (s) and optionally other additives and auxiliaries are mixed to form a homogeneous blend while avoiding crosslinking and / or vulcanization and then at least one subsequent step of shaping takes place, for example by injection (IM). Only then, at the earliest during or at the end of shaping, in particular after completion of the molding, the vulcanization is carried out as a static, non-dynamic vulcanization while avoiding shear stress.
    In this context, it is particularly advantageous for avoiding premature vulcanization if the step of preparing the mixture before molding is below a critical temperature and within a critical time, in particular at a maximum temperature of 125 ° C., preferably in the range from 50 ° C. to maximum 110 ° C, is performed. The blend or the polymeric components are advantageously present in a softened state during the preparation of the mixture.
    A further advantageous procedure, likewise for avoiding too early crosslinking or vulcanization, provides that the shaping is also carried out below a critical temperature and within a critical time, in particular at a temperature of at most 130 ° C., in particular in the range of 70 ° C to 100 ° C, takes place.
    The actual vulcanization is then advantageously carried out at a temperature of at most 240 ° C, in particular in the range of 160 ° C to 180 ° C. Advantageously, the crosslinking takes place at a higher temperature in comparison to mixing and / or shaping, in particular also at a pressure of 100 to 200 bar, but optionally also without pressure.
    As a result of these method steps or method guidance, an advantageous composition is obtained which has the desired characteristics.
    Compared to processes according to the invention, in the case of the known "dynamic vulcanization", such a polymer mixture is mixed under high shear stress and at the same time vulcanized, that is to say even before the shaping. In this way, small droplets of the unsaturated elastomer are formed, in which the crosslinking takes place. The intensive processing under high shear stress leads to a permanent isolation of these droplets and causes no compounds or sulfur bridges build up between the individual elastomer droplets. For example, a uniform, thermoplastic matrix of vinyl acetate-containing polymer, e.g. EVA, into the isolated islets of the elastomer dispersed in this thermoplastic matrix, e.g. EPDM. There are no connections between the separate elastomer particles. Thus, there is also no network that penetrate through the entire matrix of the mixed body thus obtained and would fully enforce this body, on the contrary, the networking is limited exclusively to the respective elastomer particles.
    In contrast, formed by the advantageous process according to the invention no isolated, self-crosslinked elastomer particles, but there is an interpenetrating mixture of the chains of vinyl acetate-containing polymer and the elastomeric chains. The polymeric components are present as chemically weitmaschig networked spatial network molecules, the crosslinks without decomposition of the material can not be solved. The polymer mixture is free of vulcanized elastomer particles dispersed therein, in particular free of elastomer particles or rubber domains having an average (particle) diameter of more than 0.5 gm, in particular more than 0.1 pm, preferably more than 0.01 pm.
    The invention further relates to a flame-retardant article. This article can either consist exclusively of the composition according to the invention, for example as a molded part. Alternatively, such an article may also only partially comprise this composition, for example in the form of a coating on a base body, for example on a fabric.
    Also, the invention relates to an elastic composite element, suitable for vibration and vibration damping and suspension, with a base body which is provided at least partially or in sections, on its outer surface, optionally on its entire outer surface, with at least one coating of the composition according to the invention. In the case of a combination of materials is advantageously provided that the body for the greater part
    Rubber or rubber, for example of polybutadiene rubber, styrene-butadiene rubber, acrylonitrile rubber, ethylene-propylene-diene rubber, sponge rubber or mixtures thereof, preferably of natural rubber, is formed. The required elastic or dynamic properties of the main body of the elastic element are also preferably reinforced or supported by additionally adding fillers or reinforcing materials, plasticizers, vulcanization accelerators, crosslinking agents, aging inhibitors or the like in a manner known per se. According to a preferred development, it is provided that the coating is firmly and inseparably connected to the main body, wherein the coating is applied to the main body, preferably by fabrication, extrusion, pressing, spraying and subsequent co-extrusion. By means of said methods, the elastic composite element consisting of the base body and of the flame-retardant or fire-retarding coating can be provided in a simple and reliable manner to produce a correspondingly secure bond between the base body and the coating. According to the invention, it can further be provided that the base body is provided with a reinforcement, for example fibers, in particular glass fibers, synthetic fibers, CFRP fibers, GFRP fibers, a fabric or the like or the like.
    The invention further relates to the advantageous use of the material, the article or the elastic composite element as a spring element, damping element, seal, hose, mat, molded part, protective clothing, etc., or as a component thereof. The article may advantageously also be used as an elastomer profile, in particular as an endless profile, in particular for windows or as a seal between the frame and the glass.
    Examples of the Composition According to the Invention: Example 1: EPDM Mixture Without Vinyl Acetate-Containing Polymer Crosslinking: Sulfur
    Hardness: approx. 50 - 80 Shore A
    Recipe information in phr
    It can be seen here, among other things, that only at less than 50 phr Mineralö, the standards for fire protection are met and at the same time the mechanical and dynamic values are advantageous.
    Example 2:
    EPDM blend without vinyl acetate-containing polymer Hardness: 80 Shore A
    Crosslinking: Peroxide
    Reference: Mixture 2.1 not flame retarded Recipe information in phr
    Example 3: EPDM mixture with vinyl acetate-containing polymer Crosslinking: peroxide
    Hardness: 75-80 Shore A
    Recipe information in phr
    Examples 2 and 3 show the effects of mineral oil and flame retardant contents. The burner test was realized with the following structure:
    The distance from Bunsen burner to sample is 140 mm. The test piece has a diameter of 42 mm at a thickness of 6 mm. It is flamed for 45 seconds. Thereafter, the flame treatment is stopped, the afterburning behavior is observed and the time to self extinguishment is measured.
    The fire tests according to EN 45545-2 were carried out according to the stored standards.
    The preparation of the exemplary example formulations was alternatively carried out on a rolling mill or in an internal mixer:
    If you work on rolling mills, the process is carried out in the following order: EPM / EPDM and possibly EVA are mixed together until a smooth rolled skin is formed. It works without roller cooling. To ensure homogeneity, the mixture is alternately cut three times from left and right to about 3/4 of the roll width at an angle of about 45 ° before addition of the aggregates and the mixture thus removed again on the other side abandoned, in the following 3x left and called right incision. Before starting the mixing process of the other mixture components, the water cooling of the rollers is turned on. The addition of the solid and liquid additives takes place continuously in small quantities and permanent gap adjustment. Once the rubber has absorbed all substances, it is again homogenized by cutting three times to the left and right. The rolled sheet is removed from the roll and stored at room temperature for 10 minutes to achieve cooling of the mix and rolls. The addition of the accelerator takes place together with the sulfur. Once the mixture has absorbed the accelerator and sulfur, the mixture is cut in three times left and right again. Then the mixture is completely removed from the roll and toppled six times. Alternately, the roll is fed in and across the rolling direction. Thereafter, the removal of the rolled skin takes place in the desired coat thickness.
    If you work with an internal mixer, the process takes place in the following order:
    The mixing chamber is tempered to 50 ° C +/- 5 ° C before the start of the mixing process. First, EPM / EPDM and optionally EVA are filled in and kneaded for 120 seconds with the punch down. This is followed by the addition of the solid and liquid additives. The punch is lowered and it is kneaded again for 120 seconds. The stamp is then cleaned and the mixture is mixed again for a maximum of 60 seconds or until a melt temperature of 100 ° C. has been reached in the mixing chamber and then ejected. The mixture cooling and homogenization takes place at the downstream rolling mill by means of stockblender. The cooling water temperature at the inlet is max. 30 ° C. If the mixture has reached a temperature of about 80 ° C +/- 5 ° C, the accelerator is added. After further homogenization by means of stock blender (5 cycles), the mixture fur is removed from the roll and stored on transport vehicles until further processing.
    The example formulations were made in an internal mixer of the type LH 50 A (built in 1961) according to the above method with a speed of the tangential blades of 30 rev / min. After ejecting the mixture at 100 ° C, the mixture was cooled on a rolling mill (Berstorff 1500 mm) as described above, and the accelerators were mixed. Mixture skins with a thickness of 4 mm were removed from the roll and stored on a trolley until further processing.
    The vulcanization of the mixtures of Example 1 was carried out in an electric press at 160 ° C, 30 min and a pressure of 200 bar, but in any case after shaping and avoiding any shear stress, the vulcanization of the mixtures of Examples 2 and 3 was carried out at 180 ° C, 10 min under otherwise identical conditions. Alternatively, the vulcanization can also be carried out without pressure or at normal pressure, but in any case at elevated temperature, e.g. with continuous vulcanization in salt bath for profiles.
    The composition thus obtained can thus be subjected to shaping and then vulcanized, and be used directly in this form without further processing step as a flame-retardant article, for example as a profile. Alternatively, however, the composition thus obtained can also be further processed into a composite element and then vulcanized to the finished end product.
    权利要求:
    Claims (31)
    [1]
    claims:
    1. A flame-retardant, vulcanized polymeric composition comprising as a polymeric component at least one halogen-free olefinic elastomer of the saturated main-chain M group with a content of more than 50 phr relative to the polymeric constituents, characterized in that at least one or a combination of different halogen-free dehydrating Flame retardant is contained in a proportion of 30 to 130 phr in total, and that the proportion of mineral oil plasticizers in the composition is less than 50 phr.
    [2]
    2. The composition according to claim 1, characterized in that mineral oil plasticizer with a maximum proportion of less than or equal to 20 phr, preferably less than or equal to 10 phr, and / or that the composition is free of mineral oil plasticizer.
    [3]
    3. Composition according to one of the preceding claims, characterized in that the halogen-free olefinic elastomer is contained in a proportion of greater than or equal to 70 phr or is contained in a proportion of 100 phr as the sole polymeric component.
    [4]
    4. The composition according to any one of the preceding claims, characterized in that the proportion of dehydrating flame retardants in the range of 50 to 110 phr, preferably from 60 to 100 phr, is located.
    [5]
    5. Composition according to one of the preceding claims, characterized in that as flame retardants dehydrating metal hydrates, preferably magnesium hydroxide (MDH), aluminum hydroxide (ATH) and / or zinc borate, preferably a mixture thereof, are included and / or that the flame retardants solid and powdery or are crystalline.
    [6]
    6. Composition according to one of the preceding claims, characterized in that the olefinic elastomer is a homopolymer or a copolymer or a terpolymer of or with diene monomer units, in particular a terpolymer consisting of ethylene, propylene and a diene-containing termonomer, preferably with a termonomer Content of at least 0 wt .-% to 12 wt .-% based on the olefinic elastomer.
    [7]
    Composition according to any one of the preceding claims, characterized in that the olefinic elastomer is selected from the group consisting of ethylene-propylene-diene rubber (EPDM) and ethylene-propylene rubber (EPM) and / or the composition of ethylene Propylene-diene rubber (EPDM) and / or ethylene-propylene rubber (EPM) as the sole polymeric components.
    [8]
    8. Composition according to one of the preceding claims, characterized in that the olefinic elastomer is a rubber having an unsaturated side group, in particular an ethylene-propylene-diene rubber (EPDM), which preferably comprises non-conjugated diene monomer units selected from the group of 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-cyclopentadiene, dicyclopentadiene, 2- Methyl 1,3-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,4-cyclohexadiene, tetrahydroindene, methyl tetrahydroindene, ethylidene norbornene and 5-ethylidene-2-norbornene (ENB), 5-methylene-2 norbornene (MNB), 1.6 octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5-iso-propylidene-2-norbornene, 5-vinyl-2-norbornene (VNB), wherein the ethylene-propylene-diene rubber (EPDM) is preferably a terpolymer of ethylene, propylene and 5-ethylidene-2-norbornene (ENB) or dicyclopentadiene (DCPD).
    [9]
    9. Composition according to one of the preceding claims, characterized in that a thermoplastic polymer is contained as a further polymeric component, wherein the polymeric components are present in particular as a homogeneous polymer mixture or blend.
    [10]
    10. The composition according to any one of the preceding claims, characterized in that the further polymeric component is a vinyl acetate-containing thermoplastic polymer, in particular a homopolymer, copolymer or terpolymer of vinyl acetate and preferably selected from the group of polyvinyl acetate (PVAc) or ethylene vinyl acetate (EVA ).
    [11]
    11. The composition according to any one of the preceding claims, characterized in that the vinyl acetate-containing polymer has a melting temperature or a start of the melting range of less than 150 ° C, preferably less than 100 ° C, and / or that the vinyl acetate-containing polymer a vinyl acetate content of 40 to 75 wt .-%, and / or that, optionally uncrosslinked, vinyl acetate-containing polymer is contained in a proportion of 0 to 50 phr.
    [12]
    Composition according to any one of the preceding claims, consisting of the following polymeric components: ethylene-propylene-diene rubber (EPDM) or ethylene-propylene rubber (EPM) or ethylene-propylene-diene rubber (EPDM) and ethylene-vinyl acetate (EVA ) as a homogeneous polymer mixture, or ethylene-propylene rubber (EPM) and ethylene-vinyl acetate (EVA) as a homogeneous polymer mixture, or ethylene-propylene-diene rubber (EPDM) and polyvinyl acetate (PVAc) as a homogeneous polymer mixture, or ethylene-propylene rubber ( EPM) and polyvinyl acetate (PVAc) as a homogeneous polymer mixture.
    [13]
    13. The composition according to any one of the preceding claims, characterized in that a by a, in particular peroxide or sulfur or sulfur-containing, crosslinking system vulcanized matrix or mixture matrix is formed, wherein the crosslinking system extends over the entire matrix and this passes completely.
    [14]
    14. The composition according to any one of the preceding claims, characterized in that the polymer mixture is formed as an interpenetrating mixture of the chains of the vinyl acetate-containing polymer and the, for example sulfur-crosslinked, elastomeric chains and / or that the polymeric components are present as chemically weitmaschig networked space network molecules.
    [15]
    15. The composition according to any one of the preceding claims, characterized in that the polymeric components together give a substantially single-phase mixture, in particular without macroscopic and visible light microscopic phase separation, and / or that the polymer mixture free of dispersed vulcanized elastomer particles, in particular free of elastomer Particles or rubber domains with an average diameter of more than 0.5 μm, in particular more than 0.1 μm, preferably more than 0.01 μm.
    [16]
    16. A composition according to any one of the preceding claims, characterized in that the composition both in the temperature range of use and in the range of elevated temperature, especially in the short term even at 150 to 200 ° C, has elastomeric properties or exclusively elastomeric and has no thermoplastic properties and the thermoplastic properties are in the background or not present at all or that the composition is not formed as a thermoplastic elastomer (TPE), in particular not as an olefin-based thermoplastic elastomer (TPE-O) or as a crosslinked thermoplastic elastomer based on olefin (TPE-V) is.
    [17]
    17. The composition according to any one of the preceding claims, characterized in that the composition in the temperature range up to 200 ° C has no melting peak, measured by differential scanning calorimetry.
    [18]
    18. The composition according to any one of the preceding claims, characterized in that the composition in a temperature range from room temperature to about 200 ° C has a loss factor (ratio of loss to storage modulus at dynamic shear stress) of tan <0.3.
    [19]
    19. A composition according to any one of the preceding claims, prepared or obtainable by presentation of the polymeric component or by mixing the polymeric components into a homogeneous blend and, in particular, subsequent incorporation of the crosslinking agents, flame retardants and other additives and / or auxiliaries while avoiding cross-linking and / or vulcanization, preferably at a maximum temperature of 110 ° C, then shaping and vulcanization, especially at elevated temperature and optionally under pressure, wherein the vulcanization is not under shear stress.
    [20]
    20. The composition according to any one of the preceding claims, obtainable by static vulcanization while avoiding shear stress or while avoiding dynamic vulcanization, in particular after shaping.
    [21]
    21. A composition according to any one of the preceding claims, characterized in that the polymeric components, in particular the entire composition, are / is halogen-free.
    [22]
    22. A composition according to any one of the preceding claims having the following composition: Ethylene-propylene-diene rubber (EPDM) or ethylene-propylene rubber (EPM): 70 - 100 phr, - vinyl acetate-containing polymer, in particular ethylene vinyl acetate (EVA): 0 - 30 phr, mineral oil softener: 0-10 phr, flame retardant, especially aluminum hydroxide (ATH): 60 to 100 phr, - carbon black: 0 - 80 phr, balance adjuvants, additives, etc.
    [23]
    23. A composition according to any one of the preceding claims, characterized in that it has a hardness of 40 to 90 Shore A, preferably 55 to 85, Shore A and / or a tensile strength> 5 MPa, preferably> 7 MPa, and / or abrasion 400 mm3, preferably <300 mm3, and / or a density <1.4 g / cm3, preferably <1.3 g / cm3, and / or a MARHE value (ISO 5660-1) <90 kW / m2, in particular <60 kW / m2, and complies with the EN 45545-2 standard.
    [24]
    24. A process for the preparation of a composition according to one of the preceding claims, by - first the polymeric component (s), the / the crosslinking agent, the / the flame retardants and optionally other additives and auxiliaries to avoid crosslinking and / or vulcanization to a homogeneous blend are then mixed, - then a step of shaping takes place, - and then, at the earliest during or at the end of molding, in particular after completion molding, the vulcanization is carried out as static, non-dynamic vulcanization while avoiding shear stress.
    [25]
    25. The method according to claim 24, characterized in that the preparation of the mixture before molding at a time critical for the premature vulcanization temperature and time, in particular at a temperature of at most 125 ° C, preferably in the range of 50 ° C to 110 ° C. , and / or that the blend or the polymeric component (s) are in a softened state during the mixing.
    [26]
    26. The method according to claim 24 or 25, characterized in that the shaping is carried out at an uncritical for the premature vulcanization temperature and time, in particular at a temperature of at most 130 ° C, in particular in the range of 70 ° C to 100 ° C, he follows.
    [27]
    27. The method according to any one of the preceding claims 24 to 26, characterized in that the vulcanization at a temperature of at most 240 ° C, in particular in the range of 160 ° C to 180 ° C, takes place, preferably at a compared to the mixture and / or shaping higher temperature, in particular at a pressure of 100 to 200 bar, takes place.
    [28]
    28. A composition, in particular according to one of claims 1 to 23, obtainable by a method according to one of claims 24 to 27.
    [29]
    29. A flame retardant article comprising or consisting of the composition of any of the preceding claims.
    [30]
    30. Elastic flame-retardant composite element, suitable for vibration damping and suspension, with a body, in particular made of rubber, at least partially or in sections, on its outer surface, optionally on its entire outer surface, with at least one coating, from the composition according to one of the preceding Claims is provided.
    [31]
    31. Use of the composition, of the article or of the composite element according to one of the preceding claims as a spring element, damping element, seal, hose, mat, molded part, protective clothing, as an elastomer profile, in particular for windows, etc., or as a component thereof.
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    同族专利:
    公开号 | 公开日
    EP3274402B1|2019-04-24|
    JP2018509521A|2018-04-05|
    CN107735447A|2018-02-23|
    US20200032030A1|2020-01-30|
    ES2737407T3|2020-01-14|
    SI3274402T1|2019-09-30|
    EP3524636A1|2019-08-14|
    AU2016236815B2|2019-12-19|
    CN109354781A|2019-02-19|
    RU2017135120A3|2019-04-08|
    EP3274402A1|2018-01-31|
    TR201910672T4|2019-08-21|
    WO2016149729A1|2016-09-29|
    AT517060B1|2017-03-15|
    PL3274402T3|2019-10-31|
    US10472489B2|2019-11-12|
    HUE044955T2|2019-12-30|
    HRP20191309T1|2019-10-18|
    AU2016236815A1|2017-10-12|
    RU2686903C2|2019-05-06|
    US20180051157A1|2018-02-22|
    RU2017135120A|2019-04-08|
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    法律状态:
    2017-08-15| PC| Change of the owner|Owner name: BATEGU GUMMITECHNOLOGIE GMBH, AT Effective date: 20170628 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50240/2015A|AT517060B1|2015-03-25|2015-03-25|Flame-retardant polymeric composition|ATA50240/2015A| AT517060B1|2015-03-25|2015-03-25|Flame-retardant polymeric composition|
    EP19158664.3A| EP3524636A1|2015-03-25|2016-03-24|Flame retardant polymer composition|
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    AU2016236815A| AU2016236815B2|2015-03-25|2016-03-24|Flame-proofed polymer composition|
    TR2019/10672T| TR201910672T4|2015-03-25|2016-03-24|Flame retardant polymer compound.|
    SI201630325T| SI3274402T1|2015-03-25|2016-03-24|Flame-proofed polymer composition|
    CN201811172127.6A| CN109354781A|2015-03-25|2016-03-24|Flame retardant compositions|
    US15/560,925| US10472489B2|2015-03-25|2016-03-24|Flame-proofed polymer composition|
    PCT/AT2016/050078| WO2016149729A1|2015-03-25|2016-03-24|Flame-proofed polymer composition|
    EP16719002.4A| EP3274402B1|2015-03-25|2016-03-24|Flame-proofed polymer composition|
    RU2017135120A| RU2686903C2|2015-03-25|2016-03-24|Fire-resistant polymer composition|
    CN201680018175.2A| CN107735447A|2015-03-25|2016-03-24|Flame retardant compositions|
    JP2018500824A| JP2018509521A|2015-03-25|2016-03-24|Flame retardant polymer composition|
    HUE16719002A| HUE044955T2|2015-03-25|2016-03-24|Flame-proofed polymer composition|
    HRP20191309TT| HRP20191309T1|2015-03-25|2019-07-19|Flame-proofed polymer composition|
    US16/589,577| US20200032030A1|2015-03-25|2019-10-01|Flame-proofed polymer composition|
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