CN111434710A

CN111434710A - High fire resistance foamed polymer materials

Info

Publication number: CN111434710A
Application number: CN201911255961.6A
Authority: CN
Inventors: J·博德里; D·波利托; K·帕特尔
Original assignee: Alos Enterprises Ltd And Joint Venture
Current assignee: Alos Enterprises Ltd And Joint Venture
Priority date: 2019-01-14
Filing date: 2019-12-10
Publication date: 2020-07-21
Anticipated expiration: 2039-12-10
Also published as: CN111434710B

Abstract

The present invention relates to a foamed polymeric material with high fire resistance, which is heat, sound and/or fire resistant, comprising: rubber; expandable graphite; at least one alkaline earth metal component selected from the group consisting of alkaline earth metal carbonates, alkaline earth metal hydroxides, hydrates of any thereof, and combinations thereof; and a silica or silicate containing component. The foamed polymeric material is preferably produced by a process comprising decomposition by a chemical blowing agent.

Description

High fire resistance foamed polymer materials

Technical Field

The present invention relates to a foamed polymeric material having high fire resistance, a process for producing such a material, and the use of such a material.

Background

Foamed polymeric insulation materials mainly include two types of materials, namely flexible resilient foam (FEF) and polyethylene foam (PEF).

Flexible resilient foams (FEFs) are flexible insulating materials with a high filler loading, which are obtained by a chemical expansion (foaming) process. This material is almost entirely based on a narrow selection of polymer binders. Most of these foam materials are based on NBR or NBR/PVC (for example under the name NH @bythe Applicant)

K-

ST、

KK), and EPDM (e.g., sold by the applicant under the trade name HT @)

A product for sale). Foamed EPDM is primarily used to insulate higher temperatures, such as solar applications, while NBR is a polymer matrix that is widely used in standard FEF, such as in heating and measuring (plumbig) and ventilation and cooling applications.

NBR dominates for a variety of reasons: it can be blended with various fillers, polymers, plasticizers and additives. NBR can be exemplifiedSuch as blending with PVC, which has a positive effect on the foaming process by melting and therefore allows the production of low-density materials in a chemical foaming process despite a high filler loading: (<50kg/m³). Furthermore, this material shows good mechanical properties and physical and chemical stability at a very economically feasible cost. In addition, NBR and NBR/PVC can be blended with high levels of fillers and flame retardants to achieve a high level of flame resistance.

A second type of insulation, known as polyethylene foam (PEF), is prepared by physical expansion (foaming) using a physical blowing agent. This material contains a very low content of filler, since filler leads to excessive nucleation, which in turn leads to material collapse. The possibilities of improving the properties of such materials are greatly limited due to the limited possibilities of filling them with fillers, plasticizers, etc. Therefore, compared to FEF, PEF has poor flexibility, e.g. due to a significantly higher amount of cutting stock during installation, which is a disadvantage in terms of installation time and cost. In addition, adhesion of PE (polyethylene) is often difficult, which again leads to some disadvantages compared to FEF.

Recently, expandable graphite has received increasing attention as a durable material for imparting flame resistance to polymer materials (see, for example, international patent publications WO 2017/083345, WO 2017/117013, and WO 2017/218547). Other fillers for foamed Polymer materials are described, for example, in "Polymer Degradation and stability" (96 (8) ", pages 1462-1469 (2011), and in european patent publications EP 1883664, EP 1831012 and EP 1400547.

Disclosure of Invention

The present invention has been made in view of the problems of the prior art. It is therefore an object of the present invention to provide a versatile, highly flame-retardant, low-smoke-producing material which can be modified in a wide range with fillers, additives, plasticizers and the like. Another object is to have low thermal conductivity and low water vapor transmission values, as well as high temperature resistance and ease of application. In addition, the material should have excellent UV resistance, aging resistance, weather resistance and chemical resistance. Furthermore, the material should be processable using standard methods of the rubber industry.

The inventors have surprisingly found that this object can be achieved by a foamed polymeric material consisting of at least 300phr, but less than 1200phr, of ingredients in total by mass, said foamed polymeric material comprising 100phr of rubber, expandable graphite, at least one alkaline earth metal carbonate, alkaline earth metal hydroxide, hydrate of either thereof or combination thereof (sometimes referred to herein simply as "at least one alkaline earth metal component"), and a silica or silicate containing component.

Brief Description of Drawings

The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there is shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:

fig. 1A to 1E are photographs of the foams of examples (a) - (E) in which flame spread resistance, flame penetration resistance, and char integrity were evaluated, as described below in the examples section of the present application.

Fig. 2 is a photograph showing an experiment with a MAPP gas torch at a temperature of 2000 ℃ at a distance of 10cm, as described below in the examples section of the present application.

Detailed Description

The unit of amount used herein "phr" means an amount based on 100 parts by mass of rubber. The term "elastomer" may be used in place of the term "rubber". Rubbers are predominantly amorphous polymers having a glass transition temperature below room temperature. As defined by IUPAC, the term "elastomer" means any polymer that exhibits rubber-like elasticity. The rubber is generally a polymer which can be crosslinked by any crosslinking system known in the art, in particular by a sulfur-based crosslinking system or a peroxide-based crosslinking system. Specific examples of the rubber include: natural Rubber (NR), acrylonitrile butadiene rubber (NBR), Chloroprene Rubber (CR), ethylene propylene diene monomer rubber (EPDM), Butadiene Rubber (BR), chlorosulfonated polyethylene rubber (CSM), and silicone rubber (MQ), or any combination thereof. Preferably, the unit "phr" is based on the total amount of Natural Rubber (NR), acrylonitrile butadiene rubber (NBR), Chloroprene Rubber (CR), ethylene propylene diene monomer rubber (EPDM), Butadiene Rubber (BR), chlorosulfonated polyethylene rubber (CSM), and silicone rubber (MQ) in the foamed polymeric material.

Commercial sources of acrylonitrile butadiene rubber include L G Chemicals, Zeon Elastomers, KumhoPetroleum Chemicals, Nantex and Dynasol, while polychloroprene rubber is available, for example, from Dupont/DOW, Arlanxeo, Denka and Tosoh.

Expandable graphite

Expandable graphite may also be referred to as expandable graphite flakes, expanded graphite flakes, or expandable flakes; for the purposes of the present invention, these terms may be used interchangeably. The process for preparing expandable graphite may be found in WO 2017/218547, which is incorporated herein by reference, in particular in paragraphs [0081] - [0094 ].

The term "expandable graphite" generally includes intercalated graphite, wherein an intercalant of material is included between the graphite layers of graphite crystals or particles. Examples of intercalation materials include halogens, alkali metals, sulfates, nitrates, various organic acids, aluminum chloride, ferric chloride, other metal halides, arsenic sulfide, and thallium sulfide. The expandable graphite preferably comprises a non-halogenated intercalated material. In certain embodiments, the expandable graphite includes a sulfate intercalant, also known as graphite bisulfate. As is known in the art, bisulphate intercalation is achieved by treating highly crystalline natural graphite flakes with a mixture of sulphuric acid and other oxidising agents capable of catalysing sulphate insertion.

Examples of commercially available expandable graphite include HPMS expandable graphite (HP Materials Solutions, Inc., Woodland Hills, CA), expandable graphite grades 1721 (distribution Carbons, distribution, NJ), and Grafguard 180-60N, 200-.

The expandable graphite may be characterized as having a chemical formula represented by D₅₀Mean size or mean particle ofThe diameter is from about 30 μm to about 1.5mm, in other embodiments from about 50 μm to about 1.0mm, and in other embodiments from about 180 μm to about 850 μm. In certain embodiments, the expandable graphite may be characterized as having an average size or average particle diameter of at least 30 μm, in other embodiments at least 44 μm, in other embodiments at least 180 μm, and in other embodiments at least 300 μm. In one or more embodiments, the expandable graphite may be characterized as having an average size or average particle diameter of at most 1.5mm, in other embodiments at most 1.0mm, in other embodiments at most 850 μm, in other embodiments at most 600 μm, in other embodiments at most 500 μm, and in other embodiments at most 400 μm. Useful expandable graphite includes graphite grade #1721 (archive Carbons) which has a conventional size greater than 300 μm.

In one or more embodiments, the expandable graphite may be characterized as having a carbon content of about 70% to about 99%. In certain embodiments, the expandable graphite may be characterized as having a carbon content of at least 80%, in other embodiments at least 85%, in other embodiments at least 90%, in other embodiments at least 95%, in other embodiments at least 98%, and in other embodiments at least 99%. In one or more embodiments, the expandable graphite may be characterized as having a sulfur content of from about 0% to about 8%, in other embodiments from about 0.01% to about 8%, in other embodiments from about 2.6% to about 5.0%, and in other embodiments from about 3.0% to about 3.5%. In certain embodiments, the expandable graphite may be characterized as having a sulfur content of at least 0%, in other embodiments at least 0.01%, in other embodiments at least 2.6%, in other embodiments at least 2.9%, in other embodiments at least 3.2%, and in other embodiments 3.5%. In certain embodiments, the expandable graphite may be characterized as having a sulfur content of up to 8%, in other embodiments up to 5%, and in other embodiments up to 3.5%.

In one or more embodiments, the expandable graphite may be characterized as having an expansion ratio (cc/g) of from about 10:1 to about 500:1, in other embodiments from at least 20:1 to about 450:1, in other embodiments from at least 30:1 to about 400:1, and in other embodiments from about 50:1 to about 350: 1. In certain embodiments, the expandable graphite may be characterized as having an expansion ratio (cc/g) of at least 10:1, in other embodiments at least 20:1, in other embodiments at least 30:1, in other embodiments at least 40:1, in other embodiments at least 50:1, in other embodiments at least 60:1, in other embodiments at least 90:1, in other embodiments at least 160:1, in other embodiments at least 210:1, in other embodiments at least 220:1, in other embodiments at least 230:1, in other embodiments at least 270:1, in other embodiments at least 290:1, and in other embodiments at least 300: 1. In certain embodiments, the expandable graphite may be characterized as having an expansion ratio (cc/g) of up to 350:1, and in other embodiments up to 300: 1.

In one or more embodiments, the expandable graphite may be characterized as having a pH of from about 1 to about 10; from 1 to about 6 in other embodiments; and in other embodiments from about 5 to about 10. In certain embodiments, the expandable graphite may be characterized as having a pH of about 4 to about 8. In one or more embodiments, the expandable graphite may be characterized as having a pH of at least 1, in other embodiments at least 4, and in other embodiments at least 5. In certain embodiments, the expandable graphite may be characterized as having a pH of up to 10, in other embodiments up to 8, in other embodiments up to 6.5, in other embodiments up to 6, and in other embodiments up to 5.

The expandable graphite preferably has an activation temperature in the range of 180 ℃ to 300 ℃, preferably in the range of 190 ℃ to 260 ℃, more preferably in the range of 200 ℃ to 220 ℃. The activation temperature may be referred to interchangeably as the onset temperature or expansion temperature, and generally refers to the temperature at which the graphite begins to expand.

Inorganic filler

The foamed polymeric material of the present invention contains an inorganic filler comprising at least one alkaline earth metal component selected from the group consisting of alkaline earth metal carbonates, alkaline earth metal hydroxides, hydrates of any of them, and combinations thereof, and a silica or silicate containing component. Other inorganic fillers may be included in the foamed polymeric material of the present invention and are not limited.

There is no particular limitation on the at least one alkaline earth metal carbonate, alkaline earth metal hydroxide and/or hydrate of any thereof, and may represent any compound or mixture thereof containing at least one alkaline earth metal ion, at least one bicarbonate ion or carbonate ion and at least one hydroxyl group or water molecule.

The at least one alkaline earth metal carbonate, alkaline earth metal hydroxide, and/or hydrate of any of them, or combination thereof, is generally capable of releasing water and carbon dioxide at different temperatures. The release of water typically occurs at a temperature of from 170 ℃ to 270 ℃, preferably from 200 ℃ to 250 ℃, more preferably from 210 ℃ to 230 ℃ (preferably representing the temperature at which the rate of water removal from the material is highest when the temperature is increased at a rate of 10 ℃/min from 100 ℃). The release of carbon dioxide typically occurs at a temperature of 280 ℃ to 380 ℃, preferably 310 ℃ to 360 ℃, more preferably 320 ℃ to 340 ℃ (preferably representing the temperature at which the rate of carbon dioxide expulsion from this material is highest when the temperature is increased at a rate of 10 ℃/min from 200 ℃).

At a temperature of about 560 ℃, the at least one alkaline earth metal carbonate, alkaline earth metal hydroxide, and/or hydrates of any of them, or combinations thereof, is generally capable of forming a stable cement-like material that retards further decomposition of the underlying polymeric material and inhibits the spread of a flame by burning droplets of the polymeric material.

The at least one alkaline earth metal carbonate, alkaline earth metal hydroxide and/or hydrate of any thereof preferably comprises at least a carbonate and a hydrate or hydroxide. It is to be understood that the carbonate may be present in the same or different compounds as a hydrate or hydroxide. Further, it is to be understood that the hydrate may be a monohydrate, or contain more than one mole of water per mole, such as a dihydrate, trihydrate, tetrahydrate, pentahydrate, hexahydrate, heptahydrate, octahydrate, nonahydrate, decahydrate, and the like. It will also be understood that when referring to carbonates of alkaline earth metals, this does not exclude the possibility that the alkaline earth metal carbonate may be hydrated and/or contain one or more hydroxyl groups.

The at least one alkaline earth carbonate, alkaline earth hydroxide and/or hydrate of any of them preferably contains at least one component that can release water at elevated temperature and at least one component that can release CO at elevated temperature₂The component (c).

More preferably, the at least one alkaline earth carbonate, alkaline earth hydroxide and/or hydrate of any thereof comprises:

a) at least one alkaline earth metal compound which is both a carbonate and one of a hydroxide or a hydrate,

b) at least one alkaline earth metal carbonate and at least one alkaline earth metal hydroxide or hydrate, or

c) Any combination thereof.

In other words, the at least one alkaline earth carbonate, alkaline earth hydroxide and/or hydrate of any thereof preferably comprises CO together with CO₃ ^2-And water (or CO)₃ ^2-And hydroxide) of an alkaline earth metal compound. An example of such a compound is brucite. Alternatively, the at least one alkaline earth metal carbonate, alkaline earth metal hydroxide and/or hydrate of any thereof preferably comprises a compound that is CO-containing₃ ^2-(and optionally water and/or hydroxide); and another compound which is water (and optionally CO)₃ ^2-And/or hydroxides) of alkaline earth metal compounds. One example is magnesium carbonate in combination with magnesium sulfate hydrate. The water is preferably present in the form of water of crystallization.

Examples of at least one alkaline earth metal carbonate, alkaline earth metal hydroxide, and/or hydrates of any thereof include, but are not limited to:

carbonate saltFor example magnesium carbonate (MgCO)₃) Calcium carbonate (CaCO)₃) Strontium carbonate (SrCO)₃) And barium carbonate (BaCO)₃)；

Hydroxides, e.g. magnesium hydroxide (Mg (OH)₂) Calcium hydroxide (Ca (OH)₂) Strontium hydroxide (Sr (OH))₂) And barium hydroxide (Ba (OH)₂)；

Any mixture of these carbonates and hydroxides, and any hydrates of these carbonates, hydroxides, and/or mixtures of carbonates and hydroxides.

Specific examples of the at least one alkaline earth metal carbonate, alkaline earth metal hydroxide and/or hydrate of any thereof include: hydrated magnesium carbonate, such as magnesium carbonate monohydrate (CAS No.13717-00-5), magnesium carbonate dihydrate (CASNO.5145-48-2), magnesium carbonate trihydrate (CAS No.14457-83-1), magnesium carbonate pentahydrate (CAS No.61042-72-6), or any combination thereof. The dihydrate, trihydrate and pentahydrate of naturally occurring magnesium carbonate are respectively referred to as brucite (MgCO)₃*2H₂O), magnesium hydrogen carbonate (MgCO)₃*3H₂O) and MgCO (MgCO) and₃ ^*5H₂o). The mixed form of magnesium carbonate and magnesium hydroxide comprises Celite (MgCO)₃·Mg(OH)₂·3H₂O), brucite (4 MgCO)₃·Mg(OH)₂·4H₂O) and cyclotopaz (4 MgCO)₃·Mg(OH)₂·5H₂O)。

Specific examples of the at least one alkaline earth metal carbonate, alkaline earth metal hydroxide, and/or hydrate of any of them include calcium carbonate (CAS No.471-34-1) and hydrates thereof. Naturally occurring forms of calcium carbonate are known as aragonite, calcite, chalk and limestone. Naturally occurring calcium carbonate hydrates include calcite monohydrate (CaCO)₃·H₂O) and hydrocarbonite (CaCO)₃·6H₂O)。

The mixed form containing both magnesium and calcium includes magnesium calcium carbonate, such as dolomite (usually of the formula CaMg (CO)₃)₂) And huntite (usually Mg)₃Ca(CO₃)₄)。

Preferred examples of at least one alkaline earth metal carbonate, alkaline earth metal hydroxide and/or hydrates of either include mixtures of huntite and brucite, such as available under the trade names Ultracarb (L K Minerals), C-TEC MC9(RJ Marshall), or Secure (Sibelco Specialty Minerals.) Ultracarb is preferably used in the present invention.

Basic magnesium carbonate based flame retardants can also be found in Polymer Engineering and Science (Polymer Engineering & Science), 32(5), page 327-.

Any mixture of at least one alkaline earth metal carbonate, alkaline earth metal hydroxide and/or hydrate may be used.

Silica or silicate containing component

The silica-or silicate-containing component is not particularly limited and represents any compound containing (or consisting of) silica and/or silicate. It should be understood that the "silica or silicate containing component" may contain one or more silica containing compounds or one or more silicate containing compounds or any combination thereof. Preferably, the "silica or silicate containing component" consists essentially of silica or silicate or a combination thereof. It is particularly preferred that the "silica or silicate containing component" contains 25 to 100% by weight of SiO as measured by elemental analysis using Atomic Absorption Spectroscopy (AAS)₂. Another method suitable for elemental analysis is proton-excited X-ray emission analysis (PIXIE).

The silicon dioxide can be used, for example, in the form of quartz, quartz phosphide, cristobalite, chrysolite, stibnite, clinoptite, chalcedony, precipitated silica or fumed silica.

Silicates can be classified according to their structure as: nesosilicates (e.g. olivine), sorosilicates (e.g. celosite and melilite), cyclic silicates (e.g. tourmaline), inosilicates (e.g. pyroxene and amphibole), phyllosilicates (e.g. mica and clay), tectosilicates (e.g. quartz, feldspar and zeolites). In the present invention, preferred are phyllosilicates (generally sheet-like structures) and tectosilicates (generally 3D-framework type structures). More preferred is phyllosilicate.

Phyllosilicates include any mineral listed as 09.E in the Nickel-Strunz classification. These are preferably selected from the group consisting of serpentine (e.g. antigorite, antigorite and antigorite), clay (e.g. halloysite, kaolinite, illite, montmorillonite, vermiculite, talc, sepiolite, palygorskite and pyrophyllite), mica (e.g. biotite, chromium mica, muscovite, phlogopite, lepidolite, margarite and glauconite) and chlorite.

Tectosilicates include any of the minerals listed as 09.F, 09.G, and 04.DA in the Nickel-Strunz classification. These are preferably selected from feldspars (including alkaline feldspar and plagioclase feldspar) (e.g. microcline feldspar, orthoclase feldspar, wail feldspar, diaclase feldspar, albite, anorthite), plagioclase feldspars (e.g. tetrahedrite, cancrinite, leucite, nepheline, sodalite, bluestone and chrysolite), petalite, andalusite (e.g. sodalite and calcilite), analcite, and zeolites (e.g. natrolite, erionite, chabazite, heulandite, stilbite, scolecite and mordenite).

Specific examples of preferred silica or silicate containing components are selected from silica, fly ash, feldspar, diatomaceous earth, mica, vermiculite, clay, zeolite, talc, kaolin, palygorskite, hectorite (cheto), montmorillonite, smectite (barasym), beryl, smectite, illite, nontronite, chrysolite, saponite, sepiolite and beidellite.

It should be understood that the silica or silicate containing component is not limited to the above examples, but may also include any compounds derived from these minerals.

More preferably, the silica or silicate containing component comprises or consists of clay. Clay generally means hydrous aluminum phyllosilicate. A preferred class of clays is kaolin. Typical kaolins include the minerals kaolinite, dickite, halloysite and nacrite, which are Al₂Si₂O₅(OH)₄The polymorph of (1). Other types of clays include smectite clays, illite clays, and chlorite clays.

In the present invention, the presence of a silica or silicate containing component, such as clay, is beneficial because it provides a coking treatment to the silica and is itself refractory. Thus, any type of silica or silicate-containing component, or any combination of these types, such as clay, may be used and result in a beneficial interaction between the silica or silicate-containing component and the at least one alkaline earth metal component.

Preferably, the silica or silicate containing component contains at least 50 wt% kaolin, more preferably 70 wt% kaolin, even more preferably 90 wt% kaolin, based on the total weight of the clay.

Rubber composition

As mentioned above, the rubber may be selected from a wide range of rubbers known to those skilled in the art. Preferably 80 wt.%, more preferably 90 wt.% or even 100 wt.% of the rubber component consists of Natural Rubber (NR), acrylonitrile butadiene rubber (NBR), Chloroprene Rubber (CR), ethylene propylene diene monomer rubber (EPDM), Butadiene Rubber (BR), chlorosulfonated polyethylene rubber (CSM), silicone rubber (MQ), or any combination thereof. More preferably 80 wt.%, more preferably 90 wt.% or even 100 wt.% of the rubber component consists of acrylonitrile butadiene rubber (NBR) and/or Chloroprene Rubber (CR).

In order to achieve the effect of the present invention, it is preferable that the foamed polymer material contains acrylonitrile butadiene rubber and/or polychloroprene rubber. More preferably, 100phr of rubber comprises 10 to 95phr of acrylonitrile butadiene rubber, 0 to 60phr of polychloroprene rubber, and 0 to 90phr of other rubber. Even more preferably, 100phr of rubber comprises 30 to 80phr of acrylonitrile butadiene rubber, 20 to 50phr of polychloroprene rubber, and 0 to 25phr of other rubber. Even more preferably, 100phr of rubber comprises 60 to 70phr of acrylonitrile butadiene rubber, 30 to 40phr of polychloroprene rubber, and 0 to 10phr of other rubbers. The other rubber is preferably selected from Natural Rubber (NR), ethylene propylene diene monomer rubber (EPDM), Butadiene Rubber (BR), chlorosulfonated polyethylene rubber (CSM), silicone rubber (MQ), or any combination thereof.

Polymers other than rubber

The foamed polymeric material of the present invention may further comprise a polymer other than rubber. The polymer different from rubber may for example be selected from: epoxy resins, acrylic resins, polyurethane resins, silicone resins, polysiloxanes, cyanate ester resins, phenol resins, bismaleimide resins, polycarbonate resins, polyolefin resins, olefin-maleimide resins, cycloolefin resins, polyester resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyether resins, polyoxyethylene benzyl polyphenylene resins, polyphenylene ether resins, polyether ether sulfone resins, polyether ketone resins, polyetherimide resins, polyamide resins, polyimide amide resins, polyacrylate resins, polyvinyl acetal resins, polyvinyl chloride resins, polystyrene resins, fluorine resins, or any combination of two or more thereof.

As the polyolefin resin, for example, Polyethylene (PE), Chlorinated Polyethylene (CPE), High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), low density polyethylene (L DPE), linear low density polyethylene (LL DPE), very low density polyethylene (V L DPE), ultrahigh molecular weight polyethylene (UHMWPE), polypropylene (PP), poly (4-methyl-1-pentene) may be used, and in the preparation of polyolefin, one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene are generally used as monomers.

The cycloolefin resin may be, for example, a ring-opened polymer of a monomer having a norbornene structure, a ring-opened polymer of one monomer with another monomer having a norbornene structure, an addition polymer of a monomer having a norbornene structure, an addition polymer of one monomer with another monomer having a norbornene structure, and a hydride of these ring-opened polymer or addition polymer.

Examples of the polyamide resin include: polyamide 6, polyamide 66, polyamide 46, polyamide 4T, polyamide 6I, polyamide 9T, polyamide 10T and polyamide M5T.

Examples of polyesters include: polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), polybutylene naphthalate (PBN).

Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, phenol novolac type epoxy resin, cresol-novolac type epoxy resin, epoxidized polybutadiene, glycidyl ester epoxy resin, glycidyl amine type epoxy resin, salicylaldehyde type epoxy resin, and bisphenol type epoxy resin.

For example, the foamed polymeric material may further comprise from 5 to 120phr of polyvinyl chloride, preferably from 10 to 100phr, more preferably from 20 to 80phr, even more preferably from 25 to 70phr, still more preferably from 30 to 55phr, still more preferably from 30 to 50phr, still more preferably from 35 to 45 phr.

The foamed polymeric material may also comprise from 5 to 120phr of chlorinated polyethylene, preferably from 5 to 100phr, more preferably from 10 to 80phr, even more preferably from 10 to 60phr, still more preferably from 15 to 50phr, still more preferably from 15 to 40phr, still more preferably from 20 to 30 phr. The chlorinated polyethylene preferably has a degree of chlorination of from 34 to 44% by weight.

Preferably, the total amount of polymer different from the rubber is between 5 and 240phr, preferably between 10 and 200phr, more preferably between 20 and 160phr, even more preferably between 25 and 120phr, still more preferably between 30 and 105phr, still more preferably between 40 and 90phr, still more preferably between 55 and 75 phr.

Other Components

The foamed polymeric material may further comprise one or more plasticizers in a total amount of 5-100phr, preferably 5-80phr, more preferably 10-60phr, even more preferably 15-30phr, still more preferably 15-25phr, the plasticizer should have a positive effect on the flame retardancy, so preferred plasticizers are phosphate plasticizers or halogen-containing plasticizers or any mixtures thereof, the halogen-containing plasticizers are preferably chlorinated paraffins and/or chlorinated fatty acid substituted glycerol and/or chlorinated α -olefins (especially preferred long chain chlorinated plasticizers of C > 17) having a chlorine content of at least 20 wt%, preferably at least 40 wt%, especially preferred at least 60 wt%, according to DIN 53474, such highly chlorinated long chain Materials have the greatest flame retardant effect and are not persistent, bioaccumulative or toxic compared to short or medium chain chlorinated plasticizers, furthermore, such plasticizers have a minor impact on the development of smoke compared to short chain or medium chain chlorinated plasticizers, the plasticizers may be aliphatic, chlorinated aliphatic or aromatic phosphates or any combination thereof, the preferred phosphates are phosphate esters having a high phosphorus content and the low smoke development viscosity, especially the low smoke development viscosity of sanbucin phosphate esters (e) as santochytrium phosphate esters, santochael phosphate esters, santo phosphate esters and pbioc phosphate esters, preferably low temperature smoke development of santo phosphate esters, santochytric flame retardants, santochytric acid phosphate esters, and tpichb.

The material may comprise at least one synergist for halogenated flame retardants and/or halogen containing plasticizers/polymers, such as antimony trioxide, zinc stannate, zinc hydroxystannate, 2, 3-dimethyl-2, 3-diphenylbutane, bismuth oxychloride and the like. Preference is given to materials based on bismuth (Bi) and/or zinc (Zn), particular preference to zinc stannate and bismuth oxychloride. The synergist increases the effectiveness of the flame retardant in smoke suppression and/or heat release in an ignition reaction. Depending on the desired level of flame retardancy, only the combination of synergist and conventional flame retardant can achieve the desired effect.

Furthermore, the material may comprise a thermal and/or deterioration stabilizer system. The stabilizer may be selected from carbon black (which is typically different from expandable graphite), metal oxides (e.g., iron oxide) and hydroxides (different from alkaline earth metal hydroxides of alkaline earth metal components), metal organic complexes, radical scavengers (e.g., tocopherol derivatives), and combinations thereof.

The material may also comprise any kind of flame retardant (preferably polymeric flame retardant) and synergist, biocide, plasticizer, stabilizer (e.g. against UV, ozone, spoilage, etc.), colorant, etc. in any ratio, including additives for improving its production, application, appearance and performance, such as inhibitors, retarders, accelerators, etc.; and/or additives selected to suit their application requirements, such as char forming and/or expanding additives, so that the material is self-expanding in the case of a flame, e.g. for conventional protection purposes, and/or to close and protect, e.g. wall and bulkhead penetrations; and/or substances which in case of fire lead to a self-ceramifying effect of the penetration of pipes, walls, etc., such as boron compounds, silicon-containing compounds, etc.; and/or internal adhesion promoters to ensure self-adhesion properties in coextrusion and co-lamination applications, such as silicates, functional silanes, polyols, and the like.

Preferably, the foamed polymeric material contains less than 100phr of aluminum hydroxide, more preferably less than 50phr of aluminum hydroxide, even more preferably less than 20phr of aluminum hydroxide, still more preferably less than 10phr of aluminum hydroxide, still more preferably less than 5phr of aluminum hydroxide.

Components used in the preparation of the foamed polymeric material:

in the preparation of foamed polymeric materials, additional components, such as crosslinking agents and chemical blowing agents, may be used. The crosslinking agent and chemical blowing agent are typically at least partially consumed during expansion of the polymeric material. They are no longer present in the foamed polymeric material or are present only in limited amounts. As a result, crosslinking agents and chemical blowing agents are not specifically listed as components of the foamed polymeric material of the present invention. However, it is to be understood that these components and their reaction products may be present in the foamed polymeric material of the present invention. Furthermore, because a cross-linking agent may be used in the preparation of the foamed polymeric material, it is to be understood that the above-described components of the foamed polymeric material may be at least partially cross-linked. The cross-linking may be between the same type of material, for example between rubber molecules; or between different types of materials, such as between rubber molecules and polymers different from rubber.

At least one crosslinking system, such as peroxides, triallyl cyanurate, triallyl isocyanurate, phenyl maleimide, thiadiazoles, fatty acid amides, hydrosilation agents, radiation activators (for radiation or UV curing), sulfur systems, bisphenols, metal oxides, and the like, may be used to crosslink the foamed polymeric material. Preferred are substances which decompose thermally to release free radicals, particularly preferred are peroxides (including TAC/TAIC), thiadiazoles (including fatty acid amides), metal oxides, and, in the case of polymer blends comprising unsaturated polymers, sulfur systems. The choice of curing system is influenced by the presence and/or amount of unsaturated bonds in the backbone of the polymer blend. Polymer blends with saturated polymer backbones can only be cured with peroxides and, in the case of halogenated polymers such as CPE or CSM, with thiadiazole systems. Materials cured with peroxide and thiadiazole are also preferred because they exhibit higher temperature and UV stability than materials cured with sulfur. The C-C and C-O bonds generated during the peroxide and/or thiadiazole cure are more resistant to high temperatures and UV radiation than the C-S bonds in the sulfur cure.

Furthermore, in the preparation of foamed polymeric materials, at least one chemical blowing agent selected from organic blowing agents and/or inorganic blowing agents (e.g. releasing carbon dioxide, nitrogen, oxygen or water) may be used.

All of the above ingredients show easy mixing and have good dispersibility over a wide dosage range.

Preparation of foamed polymeric materials:

the preparation of the foamed polymer material can be carried out according to conventional preparation methods, provided that the above-mentioned materials are used.

The following is an example of a specific production method. However, it should be understood that the present invention is not limited to this method.

In the first step, all other materials except the crosslinking agent are passed through the rubber industry as is knownStandard methods of mixing, e.g. in

In a mixer, on a mill, in an extruder, etc., and heated to an elevated temperature, e.g., 149-. The masterbatch is then placed back in the mixer and the cross-linking agent and any blowing activator are added and mixed to the final batch temperature, e.g., 82-93 ℃. The final batch is then cooled to room temperature (25 ℃) and passed through the extruder, for example at a temperature of 63-93 ℃. The extruded material is placed in a hot air oven and pre-cured, for example at 93-105 ℃ for 10-20 minutes, and then exposed to higher temperatures, for example 143-.

The shaping of the material may be carried out in an extruder, press, calender or the like. An extruder is preferred because it can easily form sheets and tubes and pass them directly and continuously from a hot air oven, salt bath, or the like. A hot air oven is preferred because an additional cleaning step is required in the case of a salt bath.

Technical effects achieved by the invention

The inventors have surprisingly found that the combination of a) expandable graphite, b) at least one alkaline earth metal component, and c) a silica-or silicate-containing component surprisingly improves the resistance to flame propagation, flame penetration and char integrity, which is believed to be a synergistic effect from the combination of these three components. It can be seen from the experiments of the present application that flame spread resistance, flame penetration resistance and char integrity are at the highest level only when these three components are all present (5). If even one of these three components is not present, neither flame spread resistance, flame penetration resistance, nor char integrity reach a level greater than 3. This synergistic effect is therefore quite surprising and cannot be foreseen on the basis of the prior art.

Furthermore, it was found that the combination of expandable graphite, Ultracarb (combination of brucite and huntite) and phosphate ester plasticizer resulted in rapid and very stable coking. This coking has an extremely high heat resistance over a long period of time, far exceeding that of conventional systems based on ATH (aluminum trihydrate). In particular, it can withstand direct flames up to 10,000 ° F for periods of minutes, even hours.

The material used to prepare the foamed polymeric material forms the basis of a hybrid material that can be foamed into a lightweight foamed polymeric material that exhibits extremely high fire resistance while producing very little smoke at the same time the foamed material can have a density as low as about 50-75 g/L at which a sample of foamed material having a thickness of 2.5cm can withstand treatment with a direct flame at 2000 ℃ for up to 2 hours and cannot be burned through at a thickness of 3.2cm the same material can withstand a temperature of 5500 ℃ generated by a direct flame from an oxyacetylene burner for up to 5 minutes before the first signal of burning through is observed.

The combination of expandable graphite with at least one alkaline earth metal component (e.g., Ultracarb) in a foamed polymeric material containing NBR and chloroprene (and optionally PVC and/or chlorinated PE) results in a flexible cellular foamed material of low density.

Without wishing to be bound by any theory, it is believed that the addition of the silica or silicate containing component to the foamed polymeric material results in lower flame spread and improved scorch stability, further improving the flame resistance of the foamed polymeric material.

The flame resistance of foamed polymeric materials can be further improved by the addition of chlorinated polymers, such as PVC and/or chlorinated polyethylene. It is believed that the effectiveness of the smoke generation can be further improved by dilution with higher levels of chlorine. A similar effect can be achieved by using chloroprene rubber and chlorinated paraffin. Furthermore, it is believed that the density of the foamed polymeric material can be reduced by the addition of chlorinated polymers, which can result in less material matrix being consumed by the flame, and thus less smoke being produced. By using as much of the solid chlorine-containing material as possible (at 25 ℃) in the structure of the foamed polymeric material, it is not necessary to use liquids that are volatile and generate fumes, it is possible to obtain formulations with a low plasticizer content, which are still processable and achieve a low density.

Another advantage of the material is its versatility of properties due to the multiple possibilities of using various amounts of fillers, plasticizers, flame retardants, additives, cross-linking agents, etc. and various combinations thereof. The above ingredients exhibit ease of mixing and excellent dispersibility over a wide dosage range.

Another advantage of the material is its versatility in terms of production facilities. This material can be produced in an economically viable manner in a continuous process, for example by extrusion, extrusion and co-lamination, or direct co-extrusion. The materials can also be directly laminated, molded, co-molded, over-molded, etc., as a single layer system or a multi-layer system, and thus can be formed without limitation to a variety of surfaces in automotive, transportation, aerospace, building and construction, marine, furniture, mechanical engineering, and many other industries, and even by thermoforming or other forming processes. The material can be produced in a continuous process in various wall thicknesses and internal diameters, in particular in the form of tubes and sheets; the most suitable wall thickness is 3-50 mm.

As can be seen from the experimental data provided below, the foamed polymeric materials of the present invention are particularly advantageous because they exhibit improved resistance to flame propagation, heat and flame penetration, and char integrity.

It is to be understood that the present invention is specifically directed to the individual features and embodiments described herein and various combinations thereof, including combinations of general and/or preferred features/embodiments.

In this specification, a number of documents are cited. Including patent applications and scientific literature, which, although not pertinent to the patentability of the invention, are incorporated herein by reference. More specifically, all references are to the same extent if an individual document is specifically and individually indicated to be incorporated by reference.

The invention will be better understood by reference to the following examples. These examples represent specific embodiments of the present invention, but do not limit the scope of the present invention.

The present invention can be summarized as the following items 1 to 29:

1. a foamed polymeric material consisting of a total amount by mass of at least 300phr but less than 1200phr of ingredients, the foamed polymeric material comprising:

100phr of rubber, based on the total weight of the composition,

the amount of expandable graphite is such that,

at least one alkaline earth metal component selected from the group consisting of: alkaline earth metal carbonates, alkaline earth metal hydroxides, hydrates of any of them, and combinations thereof, and

a silica or silicate containing component.

2. The foamed polymeric material of item 1, wherein the foamed polymeric material consists of ingredients in a total amount by mass of at least 400phr, at least 500phr, at least 600phr, or more preferably at least 700 phr.

3. The foamed polymeric material of item 1 or 2, wherein the foamed polymeric material is comprised of ingredients having a total amount by mass of 1100phr or less, 1000phr or less, 900phr or less, or 800phr or less.

4. The foamed polymeric material of any one of items 1-3, wherein the foamed polymeric material is comprised of ingredients having a total amount by mass of 400phr or more and 1100phr or less, preferably 400phr or more and 1000phr or less, more preferably 500phr or more and 900phr or less, even more preferably 600phr or more and 800phr or less, still more preferably 650phr or more and 800phr or less.

5. The foamed polymeric material of any one of claims 1-4, wherein the foamed polymeric material comprises from 5 to 200phr, preferably from 5 to 100, more preferably from 10 to 70phr, even more preferably from 20 to 50phr, and still more preferably from 20 to 40phr, expandable graphite.

6. The foamed polymeric material according to any one of items 1-5, wherein the foamed polymeric material comprises at least one alkaline earth metal component in a total amount of 50-500phr, preferably 150-400, more preferably 220-380phr, even more preferably 250-350phr, still more preferably 280-320 phr.

7. The foamed polymeric material of any one of claims 1-6, wherein the foamed polymeric material comprises 5-200phr, preferably 5-100, more preferably 10-90phr, even more preferably 20-80phr, still more preferably 40-60phr of the silica or silicate containing component.

8. The foamed polymeric material of any of claims 1-7, wherein the expandable graphite has an activation temperature in the range of 180 ℃ to 300 ℃, preferably 190 ℃ to 260 ℃, more preferably 200 ℃ to 260 ℃.

9. The foamed polymeric material of any of claims 1-8, wherein expandable graphite has a chemical formula of D₅₀The average size represented is 20 μm or more to 1410 μm or less, preferably 30 μm or more to 1000 μm or less, more preferably 50 μm or more to 600 μm or less, even more preferably 70 μm or more and 400 μm or less, still more preferably 80 μm or more and 250 μm or less, still more preferably 90 μm or more and 200 μm or less, still more preferably 100 μm or more and 150 μm or less.

10. The foamed polymeric material of any of claims 1-9, wherein the expanded volume of expandable graphite at 600 ℃ is in the range of 25-450cm³In the range of 50 to 350cm, preferably³In the range of/gram.

11. The foamed polymeric material of any of claims 1-10, wherein the at least one alkaline earth metal component contains a total of greater than 60 wt% hydrated magnesium carbonate and magnesium calcium carbonate.

12. The foamed polymeric material of any of claims 1-11, wherein the at least one alkaline earth metal component comprises a mixture of 60 wt% hydrated magnesium carbonate and 40 wt% calcium magnesium carbonate to 40 wt% hydrated magnesium carbonate and 60 wt% calcium magnesium carbonate, based on the total amount of the at least one alkaline earth metal component.

13. The foamed polymeric material of any of claims 1-12, wherein the at least one alkaline earth metal component comprises 25-50 wt.% MgO and 2-15 wt.% CaO, calculated as oxides.

14. The foamed polymeric material of any of claims 1-13, wherein the at least one alkaline earth metal component comprises 36-39 wt.% MgO and 6-9 wt.% CaO, calculated as oxides.

15. The foamed polymeric material of any of claims 1-14, wherein the at least one alkaline earth metal component exhibits an ignition loss at 1000 ℃ of 45-60 wt%, preferably 50-55 wt%.

16. The foamed polymeric material of any of claims 1-15, wherein the silica or silicate-containing component is selected from the group consisting of phyllosilicates and tectosilicates.

17. The foamed polymeric material of any one of claims 1-15, wherein the silica or silicate containing component is selected from the group consisting of silica, fly ash, feldspar, diatomaceous earth, mica, vermiculite, clay, zeolite, talc, kaolin, palygorskite, montmorillonite, hectorite, montmorillonite, smectite, amesite, smectite, illite, nontronite, chrysolite, saponite, sepiolite, and beidellite.

18. The foamed polymeric material of any of claims 1-17, wherein the silica or silicate containing component is a clay.

19. The foamed polymeric material of item 18, wherein the clay comprises kaolin, wherein the clay preferably contains at least 50% by weight kaolin, based on the total weight of the clay.

20. The foamed polymeric material of any of claims 1-19, wherein the rubber is selected from Natural Rubber (NR), acrylonitrile butadiene rubber (NBR), Chloroprene Rubber (CR), ethylene propylene diene monomer rubber (EPDM), Butadiene Rubber (BR), chlorosulfonated polyethylene rubber (CSM), silicone rubber (MQ), or any combination thereof.

21. The foamed polymeric material of any of claims 1-20, wherein 100phr of rubber comprises 10-95phr of acrylonitrile butadiene rubber, 0-60phr of polychloroprene rubber, and 5-90phr of other rubbers.

22. The foamed polymeric material of any of claims 1-21, wherein the rubber comprises acrylonitrile butadiene rubber and/or polychloroprene rubber.

23. The foamed polymeric material of any of claims 1-22, wherein the foamed polymeric material further comprises 5-120phr, preferably 10-100phr, more preferably 20-80phr, even more preferably 25-70phr, still more preferably 30-55phr, still more preferably 30-50phr, still more preferably 35-45phr of polyvinyl chloride.

24. The foamed polymeric material of any of claims 1-23, wherein the foamed polymeric material further comprises 5-120phr, preferably 5-100phr, more preferably 10-80phr, even more preferably 10-60phr, still more preferably 15-50phr, still more preferably 15-40phr, still more preferably 20-30phr of chlorinated polyethylene.

25. The foamed polymeric material of any of claims 1-24, wherein the foamed polymeric material further comprises 5-120phr, preferably 20-100phr, more preferably 40-90phr, even more preferably 60-90phr, still more preferably 70-90phr, still more preferably 75-85phr of chlorinated paraffin.

26. The foamed polymeric material of any one of claims 1-25, wherein the foamed polymeric material further comprises at least one phosphate plasticizer in a total amount of 5-100phr, preferably 5-80phr, more preferably 10-60phr, even more preferably 15-30phr, still more preferably 15-25 phr.

27. The foamed polymeric material of any of claims 1-26, wherein the foamed polymeric material further comprises 1-50phr, preferably 1-30phr, more preferably 2-20phr, even more preferably 5-15phr, of the hydrocarbon wax.

28. A process for producing a foamed polymeric material according to any one of items 1 to 27, which process comprises foaming a polymeric material by decomposition of a chemical blowing agent, preferably of the nitroso type, azo type and/or aromatic hydrazide type, particularly preferably azodicarbonamide.

29. Use of a material according to any of claims 1-27 for thermal insulation, sound insulation and/or fire protection.

Examples

Material

Preparation method

(1) DecrosslinkingAll other materials than the agents are

The mixture was mixed in the mixer and heated to 149-155 deg.C to obtain a master batch, which was then cooled to room temperature.

(2) The masterbatch was returned to the mixer and the crosslinker and any blowing activator were added and mixed to a final batch temperature of 82-93 ℃.

(3) The final batch was cooled to room temperature (25 ℃) and passed through the extruder at a temperature of 63-93 ℃.

(4) The extruded material was placed in a hot air oven and pre-cured at 93-105 ℃ for 10-20 minutes, then exposed to a temperature of 143-160 ℃ and allowed to reach full expansion.

Components

Flame evaluation results

The foams of five examples, examples (A) - (E), were tested for flame spread resistance, flame penetration resistance, and scorch integrity. Each of the foamed polymeric materials of examples (B) to (E) was heated at a distance of 10cm with a MAPP (methylacetylenepropanedial propane) torch, in which a flow valve was fully opened to reach a surface temperature of 2000 ℃ in a time of 10 minutes, as shown in fig. 2. Example (a) was treated in the same manner but only for a period of 3 minutes. The results are shown in the following tables and in FIGS. 1A-1E.

Resistance to flame propagation: 0 to 5, 0 is poor in fire resistance, and 5 is excellent in fire resistance

Flame penetration resistance: 0 to 5, 0 is poor in flame penetration resistance, and 5 is excellent in flame penetration resistance

Coking integrity: 0 to 5, 0 is poor in coking stability, and 5 is excellent in coking stability

From these experiments, it can be seen that the flame spread resistance, flame penetration resistance and char integrity are each at the highest level (5) only when all three of the above-mentioned desired components are present (see example (C)). If even one of these three components is not present, neither flame spread resistance, flame penetration resistance, nor char integrity can reach levels greater than 4. This synergy is therefore surprising and cannot be expected on the basis of the prior art.

It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

100phr of rubber, based on the total weight of the composition,

the amount of expandable graphite is such that,

a silica or silicate containing component.

2. The foamed polymeric material of claim 1, wherein the foamed polymeric material consists of ingredients having a total amount by mass of 400phr or more and 1100phr or less, preferably 400phr or more and 1000phr or less, more preferably 500phr or more and 900phr or less, even more preferably 600phr or more and 800phr or less, still more preferably 650phr or more and 800phr or less.

3. The foamed polymeric material according to claim 1 or 2, wherein the foamed polymeric material comprises from 5 to 200phr, preferably from 5 to 100phr, more preferably from 10 to 70phr, even more preferably from 20 to 50phr and still more preferably from 20 to 40phr of expandable graphite.

4. The foamed polymeric material according to any one of claims 1-3, wherein the foamed polymeric material comprises at least one alkaline earth metal component in a total amount of 50-500phr, preferably 150-400phr, more preferably 220-380phr, even more preferably 250-350phr and even more preferably 280-320 phr.

5. The foamed polymeric material of any one of claims 1-4, wherein the foamed polymeric material comprises 5-200phr, preferably 5-100phr, more preferably 10-90phr, even more preferably 20-80phr, and still more preferably 40-60phr of the silica or silicate containing component.

6. The foamed polymeric material of any of claims 1-5, wherein expandable graphite has an activation temperature in the range of 180 ℃ to 300 ℃, preferably in the range of 190 ℃ to 260 ℃, more preferably in the range of 200 ℃ to 260 ℃.

7. The foamed polymeric material of any of claims 1-6, wherein at least one alkaline earth metal component contains a total amount of hydrated magnesium carbonate and magnesium calcium carbonate greater than 60 wt%.

8. The foamed polymeric material of any of claims 1-7, wherein at least one alkaline earth component comprises a mixture of 60 wt.% hydrated magnesium carbonate and 40 wt.% magnesium calcium carbonate to 40 wt.% hydrated magnesium carbonate and 60 wt.% magnesium calcium carbonate, based on the total amount of the at least one alkaline earth component.

9. The foamed polymeric material of any of claims 1-8, wherein the at least one alkaline earth metal component comprises 25-50 wt.% MgO and 2-15 wt.% CaO, calculated as oxides.

10. The foamed polymeric material of any of claims 1-9, wherein the silica or silicate containing component is selected from the group consisting of phyllosilicates and tectosilicates, preferably wherein the silica or silicate containing component is clay, more preferably wherein the clay preferably contains at least 50 wt% kaolin clay, based on the total weight of the clay.

11. The foamed polymeric material of any one of claims 1-10, wherein the rubber is selected from Natural Rubber (NR), acrylonitrile butadiene rubber (NBR), Chloroprene Rubber (CR), ethylene propylene diene monomer rubber (EPDM), Butadiene Rubber (BR), chlorosulfonated polyethylene rubber (CSM), silicone rubber (MQ), or any combination thereof, and/or wherein 100phr of the rubber comprises 10-95phr of acrylonitrile butadiene rubber, 0-60phr of polychloroprene rubber, and 5-90phr of other rubbers, preferably wherein the rubber comprises acrylonitrile butadiene rubber and/or polychloroprene rubber.

12. The foamed polymeric material of any one of claims 1-11, wherein the foamed polymeric material further comprises 5-120phr, preferably 10-100phr, more preferably 20-80phr, even more preferably 25-70phr, still more preferably 30-55phr, still more preferably 30-50phr, still more preferably 35-45phr of polyvinyl chloride, and/or wherein the foamed polymeric material further comprises 5-120phr, preferably 5-100phr, more preferably 10-80phr, even more preferably 10-60phr, still more preferably 15-50phr, still more preferably 15-40phr, still more preferably 20-30phr of chlorinated polyethylene.

13. The foamed polymeric material according to any one of claims 1-12, wherein the foamed polymeric material further comprises at least one phosphate ester plasticizer in a total amount of 5-100phr, preferably 5-80phr, more preferably 10-60phr, even more preferably 15-30phr, still more preferably 15-25phr, or wherein the foamed polymeric material further comprises 1-30phr, preferably 2-20phr, more preferably 5-15phr, of a hydrocarbon wax.

14. A process for producing a foamed polymeric material according to any one of claims 1 to 13, which process comprises foaming the polymeric material by decomposition of a chemical blowing agent, preferably of the nitroso type, azo type and/or aromatic hydrazide type, particularly preferably azodicarbonamide.

15. Use of the foamed polymeric material of any one of claims 1-13 for thermal insulation, sound insulation and/or fire protection.