EP4688937A1 - Composition de polymère ignifuge sans halogène et son utilisation - Google Patents

Composition de polymère ignifuge sans halogène et son utilisation

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Publication number
EP4688937A1
EP4688937A1 EP24716346.2A EP24716346A EP4688937A1 EP 4688937 A1 EP4688937 A1 EP 4688937A1 EP 24716346 A EP24716346 A EP 24716346A EP 4688937 A1 EP4688937 A1 EP 4688937A1
Authority
EP
European Patent Office
Prior art keywords
halogen
polymer composition
free flame
retardant
flame
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24716346.2A
Other languages
German (de)
English (en)
Inventor
Shuyu Liang
Herbert Ackermann
Robert Roskamp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP4688937A1 publication Critical patent/EP4688937A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen

Definitions

  • the invention relates to polymer compositions comprising a halogen-free flame-retardant system.
  • the invention also relates to shaped articles obtained using such polymer compositions.
  • Polymer materials are widely used in the construction materials. Typical applications of polymers in construction industry include areas such as flooring, windows, cladding, rainwater, pipes, membranes, seals, glazing, insulation, and signage. Membranes are used to protect underground and above ground constructions, such as basements, tunnels, facades, and roofs against penetration of water.
  • Waterproofing membranes are applied, for example, to prevent ingress of water through cracks that develop in the concrete structure due to building settlement, load deflection or concrete shrinkage.
  • roofing membranes are commonly used for waterproofing of flat and low-sloped roof structures.
  • Waterproofing tapes comprising a polymeric carrier layer are also used for sealing and waterproofing of construction gaps in building facades, for example gaps between a building structure and window or curtain wall components.
  • plastic materials for membranes and tapes include thermoplastics, such as plasticized polyvinylchloride (p-PVC), thermoplastic polyolefin elastomers (TPO, TPE- O), and elastomers such as ethylene-propylene diene monomer (EPDM) rubber.
  • thermoplastics such as plasticized polyvinylchloride (p-PVC), thermoplastic polyolefin elastomers (TPO, TPE- O), and elastomers such as ethylene-propylene diene monomer (EPDM) rubber.
  • p-PVC plasticized polyvinylchloride
  • TPO thermoplastic polyolefin elastomers
  • EPDM ethylene-propylene diene monomer
  • Thermoplastic polyolefin elastomers are heterophasic polymer systems comprising a high crystallinity base polyolefin and a low-crystallinity or amorphous polyolefin modifier.
  • Membranes based on crosslinked EPDM are very flexible and resistant to weathering, but joints formed between overlapped portions of adjacent membranes cannot be sealed by heat-welding due to the chemically crosslinked polymer structure.
  • Membranes composed of TPO materials are heat-weldable and less expensive than EPDM-membranes, but they are also more rigid, which can be a disadvantage in some applications.
  • Membranes based on plasticized PVC are more flexible than membranes based on TPO materials, but they also contain environmentally harmful plasticizers and heavy metal additives such as flame retardants that may restrict their use in some applications.
  • a common disadvantage of the polymeric materials is their inherently low fire resistance properties.
  • the limiting oxygen index (LOI) of most polymeric materials is less than 25%, which make them flammable or combustible.
  • construction products composed of polymeric materials must fulfill certain fire resistance requirements, i.e. , to achieve a specific “fire rating classification”. The required classification depends on the type of the product. For example, polymeric sheets used in the external fagade, such as breather membranes and vapor control layers, have a different fire rating requirement than roofing membranes used for covering a flat roof structure. In Europe, the requirements for fire safety in buildings have been increased after the Grenfell Tower disaster in 2017.
  • European fire standards for flat roofs are defined in EN 13501-5 standard.
  • the standard defines four tests for roof covering systems and “European Class ratings”, which are given to a roof system based on the results from testing.
  • the European Class ratings indicated the external fire performance of roofs, i.e., the response of the roof to fire from outside of the building.
  • Another standard EN 13501-1 sets the guidelines for testing fire performance of individual components of a building. This standard is concerned with behavior of roofs when subjected to effects of fire from the underside, i.e., from within the building.
  • the EN 13501-1 standard assigns construction materials a fire classification based on their capacity to spread fire. Classifications range from A1 , which is given to materials that offer no contribution to fire, through to F for materials with no tested performance. There are different classifications for surface covering materials, insulation materials, floor coverings, pipe insulation materials, and cables. In addition, the system contains additional classes for smoke development (s1-s3) and for burning droplets (d0-d2). For example, in UK the breather membranes installed behind the cladding and vapor barriers installed on the inside of the fagade are required by law to have a minimum Euroclass rating of B, s3- dO.
  • test t1 is used in Germany, test t2 in Scandinavia, test t3 in France, and test t4 in the UK (and in Republic of Ireland).
  • the fire rating classification for roof systems does not depend only on the product itself but also on its application.
  • a fire classification for a roofing membrane depends on whether the roofing membrane is used for providing an insulated roof system or a non-insulated roof system. Therefore, some roofing membranes are Broof(t1) classified for use with polyisocyanurate (cover) boards but when used with expanded polystyrene (insulation) boards.
  • Flame retardant additives are typically added to polymer blends to improve their fire resisting/retarding properties to enable their use in various applications.
  • Commonly used flame retardants for polymeric membranes include metal hydroxides, particularly alumina trihydrate (ATH), precipitated aluminum hydroxides, and magnesium hydroxide, and brominated flame retardants (BRF).
  • Commonly used halogen-free flame retardants for thermoplastic polymers include ammonium polyphosphate and 1 ,3,5-triazine compounds, such as melamine and melamine salts and adducts, and oligomeric and polymeric 1 ,3,5- triazine compounds.
  • Halogenated flame retardants, particularly brominated retardants are highly effective in achieving the requirements for fire classification, but their use is not preferred for environmental and safety issues. In fact, the use of brominated flame retardants has already been banned in some applications.
  • halogen-free flame retardants are their inferior efficiency compared to other flame retardants. Consequently, the amount of flame retardants added to a polymer blend to achieve a desired fire rating is very high, which typically has a significant adverse effect on their mechanical properties.
  • single-ply polyolefin-based roofing membranes typically contain up to 60 wt.-% of ATH to comply with the fire rating requirements.
  • the currently available roofing membranes do not fulfill the requirements for highest fire rating.
  • halogen-free polymer composition having improved flame retardancy properties and excellent mechanical properties.
  • Such halogen-free polymer compositions are especially suitable for use in the construction industry, for example, for providing sealing elements, such as membranes, for above and below ground applications.
  • the object of the present invention is to provide a halogen-free flame-retardant polymer composition having improved flame retardancy properties.
  • Such polymer compositions are especially suitable for providing shaped articles, particularly sealing elements for above and below ground applications.
  • a halogen-free flame-retardant polymer composition comprising: a) An organic polymer component comprising: a1) At least one thermoplastic polymer TP and/or a2) At least one elastomer E, and b) A flame-retardant system comprising: b1) At least one first nitrogen-containing organophosphorus compound and optionally at least one metal borate, b2) At least one organometallic salt, and b3) At least one second nitrogen-containing organophosphorus compound.
  • the inventive polymer composition exhibits improved flame retardancy properties, whereas the presence of the flame-retardant system in the polymer blend does not cause a significant negative effect on the mechanical properties of the polymer blend. It was also surprisingly found out that the addition of the flame-retardant system does not significantly increase the water absorption of the polymer blend.
  • a first aspect of the present invention is directed to a halogen-free flame-retardant polymer composition
  • a halogen-free flame-retardant polymer composition comprising: a) An organic polymer component comprising: a1) At least one thermoplastic polymer TP and/or a2) At least one elastomer E, and b) A flame-retardant system comprising: b1) At least one first nitrogen-containing organophosphorus compound and optionally at least one metal borate, b2) At least one organometallic salt, and b3) At least one second nitrogen-containing organophosphorus compound.
  • melting temperature refers to a melting point determined as a maximum of the curve determined by means of differential scanning calorimetry (DSC) using the measurement method as defined in ISO 11357 standard using a heating rate of 2°C/min.
  • DSC differential scanning calorimetry
  • the measurements can be performed with a Mettler Toledo DSC 3+ device and the Tm values can be determined from the measured DSC-curve with the help of the DSC- software. In case the measured DSC-curve shows several peak temperatures, the first peak temperature coming from the lower temperature side in the thermogram is taken as the melting temperature (T m ).
  • glass transition temperature (T g ) refers to the temperature above which temperature a polymer component becomes soft and pliable, and below which it becomes hard and glassy.
  • the glass transition temperature (T g ) is preferably determined by dynamical mechanical analysis (DMA) as the peak of the measured loss modulus (G”) curve using an applied frequency of 1 Hz and a strain level of 0.1 %.
  • DMA dynamical mechanical
  • elastomer designates a polymer or a polymer blend, which can cover from large deformations, and which can be, or already is, modified to a state in which it is essentially insoluble (but can swell) in a boiling solvent, in particular xylene.
  • Typical elastomers are capable of being elongated or deformed to at least 200% of their original dimension under an externally applied force, and will substantially resume the original dimensions, sustaining only small permanent set (typically no more than about 20%), after the external force is released.
  • the term “elastomer” may be used interchangeably with the term “rubber.”
  • crosslinked refers to a polymer matrix, in which the polymer chains are interconnected by a plurality of covalent bonds that are stable mechanically and thermally.
  • Other possible forms of crosslinked polymers such as physically crosslinked polymers are not regarded as “crosslinked” in the context of the present disclosure.
  • the terms “cured” and “vulcanized” may be used interchangeably with the term “crosslinked”.
  • crosslinking degree refers to a proportion of the component, which is insoluble in boiling xylene.
  • the percentage of insoluble proportion can be determined by refluxing a test specimen in boiling xylene, weighting the dried residue, and making suitable corrections for other soluble and insoluble components present in the tested composition.
  • the crosslinking degree is measured by using a method as defined in ISO 10147 standard.
  • the “amount or content of at least one component X” in a composition refers to the sum of the individual amounts of all thermoplastic polymers TP contained in the composition. Furthermore, in case the composition comprises 20 wt.-% of at least one thermoplastic polymer TP, the sum of the amounts of all thermoplastic polymers contained in the composition equals 20 wt.-%.
  • the halogen-free polymer composition comprises as the first compulsory constituent an organic polymer component a).
  • organic polymer encompasses in the present disclosure a collective of macromolecules that are chemically homogeneous but differ in relation to degree of polymerization, molar mass, and chain length, which has been prepared by a poly reaction (polymerization, polyaddition, polycondensation) and has a majority of carbon atoms in the polymer backbone, and reaction products of such a collective of macromolecules.
  • Polymers having a polyorganosiloxane backbone that are commonly referred to as “silicones” or “siloxane polymers” are not organic polymers in the context of the present disclosure.
  • the first component of the flame-retardant system b) comprises at least one nitrogencontaining organophosphorus compound and optionally at least one metal borate.
  • organophosphorus compound refers in the present disclosure to organic compounds containing phosphorus, whereas “nitrogen-containing” implies that the organophosphorus compound contains at least one nitrogen atom.
  • the at least one first nitrogen-containing organophosphorus compound is selected from piperazine pyrophosphate, piperazine orthophosphate, piperazine polyphosphate, piperazine bis(dimethyl) phosphoramidate, piperazine DOPO, and EDA-DOPO, preferably from piperazine pyrophosphate, piperazine bis(dimethyl) phosphoramidate, piperazine DOPO, and EDA-DOPO, more preferably piperazine pyrophosphate.
  • DOPO refers here to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and “EDA-DOPO” to 6,6'-(ethane-1 ,2-diylbis(azanediyl))bis(6H- dibenzo[c,e][1 ,2]oxaphosphinine-6-oxide.
  • EDA-DOPO 6,6'-(ethane-1 ,2-diylbis(azanediyl))bis(6H- dibenzo[c,e][1 ,2]oxaphosphinine-6-oxide.
  • Suitable methods for preparing EDA-DOPO are disclosed, for example, in EP 3 421 479 A1 .
  • Suitable piperazine group containing organophosphorus compounds are commercially available, for example, under the trade name of Mflam® (from Hangzhou Mei Wang Chemical Co., Ltd) and Aflammit® TLP, such as Aflammit® TLP 1715 (from Thor GmbH).
  • the at least one metal borate can be present in the flame-retardant system in addition to the at least one first nitrogen-containing organophosphorus compound.
  • Suitable metal borates include, for example, alkali metal borates, alkaline earth metal borates, and zinc borate.
  • the at least one metal borate is selected from zinc borate and calcium borate.
  • Zinc borates are a group of compounds based on Zn:B:O in their various molar ratios. Both hydrated and anhydrous zinc borates are suitable for use as the at least one metal borate.
  • the at least one metal borate is zinc borate, preferably having a median particle size dso of not more than 20 pm, more preferably not more than 10 pm, such as in the range of 1 - 10 pm.
  • a particle size distribution can be measured by laser diffraction according to the method as described in standard ISO 13320:2009 using a wet or dry dispersion method and for example, a Mastersizer 2000 device (trademark of Malvern Instruments Ltd, GB).
  • the second component of the flame-retardant system b) comprises at least one organometallic salt.
  • Suitable organometallic salts for use in the flame-retardant system include, particularly, aluminum salts, such as aluminum diethyl phosphinate, aluminum salts of 1- hydroxydihydrophosphole oxide and 1 -hydroxyphospholane oxide, and aluminum diisobutyl phosphinate.
  • aluminum salts are commercially available, for example, under the trade name of Exolit® OP, such as Exolit® OP 1230 (from Clariant plastics & Coatings GmbH).
  • the third component of the flame-retardant system b) comprises at least one second nitrogen-containing organophosphorus compound different from the at least one first nitrogen-containing organophosphorus compound.
  • Suitable compounds for use as the second nitrogen-containing organophosphorus compound include, for example, phosphoric acid triazine salts, especially phosphoric acid melamine salts, for example, melamine phosphate, melamine pyrophosphate, and melamine polyphosphate. These are commercially available, for example, under the trade name of Aflammit® PMN 200 (from Thor GmbH) and under the trade name of Melapur®, such as Melapur® 200 and Melapur® MC (from BASF).
  • the at least organometallic salt is an organic phosphinate metal salt, preferably an organic phosphinate aluminum salt and/or the at least one second nitrogen-containing organophosphorus compound is a phosphoric acid melamine salt, preferably selected from melamine polyphosphate, melamine phosphate, and melamine pyrophosphate.
  • the at least one organometallic salt is aluminium diethyl phosphinate and/or the at least one second nitrogen-containing organophosphorus compound is melamine polyphosphate.
  • the flame-retardant system b) preferably makes up at least 5 wt.-%, more preferably at least 15 wt.-%, even more preferably at least 25 wt.-%, still more preferably at least 35 wt.- %, of the total weight of the halogen-free polymer composition.
  • the flameretardant system b) makes up not more than 95 wt.-%, more preferably not more than 85 wt.-%, even more preferably not more than 80 wt.-%, still more preferably not more than 75 wt.-%, of the total weight of the halogen-free polymer composition.
  • the flame-retardant system b) makes up 35 - 75 wt.-%, preferably 40 - 70 wt.-%, more preferably 45 - 65 wt.-%, of the total weight of the halogen-free polymer composition.
  • the flame-retardant system b) comprises: b1) 0.5 - 25 wt.-%, preferably 1 .5 - 20 wt.-%, more preferably 1 .5 - 15 wt.-%, even more preferably 2.5 - 10 wt.-%, of the at least one first nitrogen-containing organophosphorus compound or of a mixture of the at least one metal borate and the at least one first nitrogen-containing organophosphorus compound, b2) 5 - 55 wt.-%, preferably 10 - 50 wt.-%, more preferably 20 - 50 wt.-%, even more preferably 25 - 50 wt.-%, of the at least one organometallic salt, and b3) 5 - 55 wt.-%, preferably 10 - 50 wt.-%, more preferably 20 - 50 wt.-%, even more preferably 25 - 50 wt.-%, of the at least one organometallic salt, and
  • the flame-retardant system b) comprises: b1) 0.5 - 15 wt.-%, preferably 1.5 - 12.5 wt.-%, more preferably 1 .5 - 10 wt.-%, even more preferably 2.5 - 10 wt.-%, of the at least one first nitrogen-containing organophosphorus compound or of a mixture of the at least one metal borate and the at least one first nitrogen-containing organophosphorus compound, b2) 5 - 55 wt.-%, preferably 10 - 50 wt.-%, more preferably 20 - 50 wt.-%, even more preferably 25 - 50 wt.-%, of the at least one organometallic salt, and b3) 5 - 55 wt.-%, preferably 10 - 50 wt.-%, more preferably 20 - 50 wt.-%, even more preferably 25 - 50 wt.-%, of the at least one second
  • the weight ratio of the at least one organometallic salt to the at least one second nitrogen-containing organophosphorus compound in the halogen-free flame-retardant polymer composition is not more than 3:1 , more preferably not more than 2:1 and at least 1 :3, more preferably at least 1 :2.
  • the weight ratio of the at least one organometallic salt to the at least one second nitrogen-containing organophosphorus compound in the halogen-free flame-retardant polymer composition is in the range of from 1 .5:1 to 1 :1.5, preferably from 1.3:1 to 1 :1.3, more preferably from 1.2:1 to 1 :1.2.
  • the flame retardancy properties of the polymer composition may further be improved if the flame-retardant system b) comprises an additional char source/blowing agent, such as expandable graphite or cellulose containing material, especially wood particles.
  • an additional char source/blowing agent such as expandable graphite or cellulose containing material, especially wood particles.
  • the flame-retardant system b) further comprises: b4) Expandable graphite and/or wood particles.
  • expandable graphite refers in the present disclosure to an intercalating graphite compound obtained by treatment of crystalline graphite with intercalants, such as nitric acid, sulfuric acid, and potassium permanganate, which are incorporated between the parallel layers of carbon atoms.
  • intercalants such as nitric acid, sulfuric acid, and potassium permanganate
  • the intercalant is transformed from a liquid or a solid phase to gas phase.
  • the adjacent graphite layers are forced apart by the released gases, which results in expansion of the graphite material.
  • the expandable graphite has an initiation expansion temperature determined by using the method as described below of at least 150 °C, more preferably at least 175 °C, even more preferably at least 185 °C.
  • the thermally expandable graphite has an initiation expansion temperature determined by using the method as described below in the range of 165- 300 °C, preferably 175 - 275 °C, more preferably 185 - 250 °C.
  • a sample of thermally expandable graphite having a volume of 2 cm 3 is placed in an oven in a test tube.
  • the temperature of the oven is increased at a constant rate until the volume of the sample has increased to a value corresponding to 1 .1 times the initial volume of the sample.
  • the temperature at which the 10 % increase in volume is reached is recorded as the “initiation expansion temperature”.
  • wood particle refers in the present disclosure to particles composed of wood fibers.
  • the length dimension of a wood particle is typically orientated parallel to the grain structure of the wood particle, i.e., parallel to the orientation of the long axis of the dominant fibers in the wood particle.
  • Suitable wood particles for use in the flame-retardant system b) include all types of soft wood and hard wood particles.
  • the wood particles have a Doo particle length of not more than 10 mm, preferably not more than 5 mm, more preferably not more than 2.5 mm, even more preferably not more than 1 .5 mm and/or at least 100 pm, preferably at least 250 pm, more preferably at least 500 pm.
  • the term D90 particle length refers in the present disclosure to a particle length below which 90 % of all particles by volume have a smaller length than the D90 value.
  • the “length of a particle” refers in the present disclosure to the maximum Feret diameter (XFe.max), i.e. the longest Feret diameter out of the measured set of Feret diameters.
  • the term “Feret diameter” refers in the present disclosure to the distance between two tangents on opposite sides of the particle, parallel to some fixed direction and perpendicular to the measurement direction.
  • the length the particle can be determined using any suitable measurement technique, preferably by using dynamic image analysis method conducted according to ISO 13322-2:2006 standard.
  • the dimensions of particles can be measured with a dry dispersion method, where the particles are dispersed in air, preferably by using air pressure dispersion method.
  • the measurements can be conducted using any type of dynamic image analysis apparatus, such as a Camsizer XT device (trademark of Retsch Technology GmbH).
  • the expandable graphite or wood particles or mixture thereof makes up 5 - 45 wt.-%, preferably 10 - 40 wt.-%, more preferably 15 - 40 wt.-%, of the total weight of the flame-retardant system b).
  • the flame-retardant polymer composition of the present invention comprises an organic polymer component a) comprising at least one thermoplastic polymer TP and/or at least one elastomer E.
  • thermoplastic polymer refers in the present disclosure to polymers which can be melted and re-solidified with little or no change in physical properties. It goes without saying that the thermoplastic polymer TP is different from the elastomer E.
  • the at least one thermoplastic polymer TP is selected from polyolefins, thermoplastic polyurethane (TPU), polyvinylchloride (PVC), and ketone ethylene esters (KEE).
  • polyolefin refers in the present disclosure to homopolymers and copolymers obtained by polymerization of olefin monomers optionally with other types of comonomers.
  • Suitable polyolefins for use as the at least one thermoplastic polymer TP include, for example, propylene-ethylene copolymers, a-olefin copolymers of propylene and one or more C4-C20 a-olefin monomers, ethylene-a-olefin copolymers of ethylene and one or more C3-C20 a-olefin monomers, and ethylene vinyl acetate copolymers.
  • thermoplastic polyolefin elastomers TPO-E
  • heterophasic propylene copolymers TPO-E
  • TPO-E thermoplastic polyolefin elastomers
  • These are polymer systems comprising a high crystallinity base polyolefin and a low-crystallinity or amorphous polyolefin modifier.
  • the heterophasic phase morphology consists of a matrix phase composed primarily of the base polyolefin and a dispersed phase composed primarily of the polyolefin modifier.
  • Thermoplastic polyurethanes are polyurethane-based thermoplastic elastomers (TPE) that are linear segmented block copolymers composed of alternating hard and soft segments or domains formed by the reaction of (1) diisocyanates with short-chain diols (so-called chain extenders) and (2) diisocyanates with long-chain diols.
  • thermoplastic polyurethanes are commercially available, for example, under the trade name of Pearlbond®, such as Pearlbond® TPU and Pearlbond® 700-series (all from Lubrizol) and under the trade name of Elastollan® (from BASF).
  • Pearlbond® such as Pearlbond® TPU and Pearlbond® 700-series (all from Lubrizol)
  • Elastollan® from BASF
  • Suitable PVC resins for use as the at least one thermoplastic polymer TP include ones having a K-value determined by using the method as described in ISO 1628-2-1998 standard in the range of 50 - 85, preferably 65 - 75.
  • the K-value is a measure of the polymerization grade of the PVC-resin, and it is determined from the viscosity values of the PVC homopolymer as virgin resin, dissolved in cyclohexanone at 30° C.
  • the at least one thermoplastic polymer TP comprises at least one propylene copolymer TP1 and/or at least one ethylene copolymer TP2
  • the expression “the at least one component X comprises at least one component XN”, such as “the at least one thermoplastic polymer TP comprises at least one propylene copolymer TP1” is understood to mean in the context of the present disclosure that the polymer composition comprises one or more propylene copolymers as representatives of the at least one thermoplastic polymer TP.
  • the at least one propylene copolymer TP1 has a propylene content of at least 60 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 75 wt.-%, based on the weight of the propylene copolymer and/or at least one ethylene copolymer TP2 has an ethylene content of at least 50 wt.-%, more preferably at least 55 wt.-%, even more based on the weight of the ethylene copolymer.
  • “Monomer/comonomer content of a copolymer” refers to the total amount of monomers/comonomers in the copolymer given in wt.-% or mol-%.
  • the monomer/comonomer content can be determined by IR spectroscopy or by quantitative nuclear-magnetic resonance (NMR) measurements.
  • the at least one propylene copolymer TP1 is a propylene-ethylene copolymer, preferably a propylene-ethylene random copolymer, preferably having an ethylene content of 5 - 20 wt.-%, more preferably 9 - 18 wt.-%, even more preferably 12 - 18 wt.-%, even more preferably 12 - 16 wt.-%, based on the weight of the propylene-ethylene copolymer.
  • the at least one propylene copolymer TP1 has:
  • melt flow rate (230°C/2.16 kg) determined according to ISO 1133 standard of not more than 50 g/10 min, preferably not more than 35 g/10 min, more preferably not more than 25 g/10 min, even more preferably not more than 20 g/10 min and/or - a density at 23°C determined according to ASTM D-792 standard of 0.850 - 0.900 g/cm 3 , preferably 0.855 - 0.890 g/cm 3 .
  • propylene-ethylene copolymers for use as the at least one propylene copolymer TP1 include the propylene-ethylene copolymers, which are commonly characterized as “propylene-based elastomers”. These are commercially available, for example, under the trade name of Versify® (from Dow Chemicals) and under the trade name of Vistamaxx® (from Exxon Mobil).
  • Suitable polymers for use as the at least one ethylene copolymer TP2 include ethylene-a- olefin copolymers, particularly copolymers of ethylene and one or more C3-C20 a-olefin monomers, preferably one or more of propylene, 1 -butene, 1 -pentene, 1 -hexene, 1- heptene, 1 -octene, 1 -decene, 1 -dodecene, and 1 -hexadodecene.
  • Suitable ethylene-a-olefin copolymers include, for example, ethylene-based plastomers, which are commercially available, for example, under the trade name of Affinity®, such as Affinity® EG 8100G, Affinity® EG 8200G, Affinity® SL 8110G, Affinity® KC 8852G, Affinity® VP 8770G, and Affinity® PF 1140G (all from Dow Chemical Company); under the trade name of Exact®, such as Exact® 3024, Exact® 3027, Exact® 3128, Exact® 3131 , Exact® 4049, Exact® 4053, Exact® 5371 , and Exact® 8203 (all from Exxon Mobil); and under the trade name of Queo® (from Borealis AG).
  • Affinity® such as Affinity® EG 8100G, Affinity® EG 8200G, Affinity® SL 8110G, Affinity® KC 8852G, A
  • ethylene-a-olefin copolymers include, for example, ethylene-based polyolefin elastomers (POE), which are commercially available, for example, under the trade name of Engage®, such as Engage® 7256, Engage® 7467, Engage® 7447, Engage® 8003, Engage® 8100, Engage® 8480, Engage® 8540, Engage® 8440, Engage® 8450, Engage® 8452, Engage® 8200, and Engage® 8414 (all from Dow Chemical Company).
  • Engage® such as Engage® 7256, Engage® 7467, Engage® 7447, Engage® 8003, Engage® 8100, Engage® 8480, Engage® 8540, Engage® 8440, Engage® 8450, Engage® 8452, Engage® 8200, and Engage® 8414 (all from Dow Chemical Company).
  • ethylene-a-olefin copolymers include ethylene-a-olefin block copolymers, such as ethylene-based olefin block copolymers (OBC), which are commercially available, for example, under the trade name of Infuse®, such as Infuse® 9100, Infuse® 9107, Infuse® 9500, Infuse® 9507, and Infuse® 9530 (all from Dow Chemical Company).
  • OBC ethylene-based olefin block copolymers
  • the least one ethylene copolymer TP2 has: - a flexural modulus at 23°C determined according to ISO 178:2019 standard of not more than 150 MPa, preferably not more than 125 MPa, more preferably not more than 100 MPa, even more preferably not more than 85 MPa and/or
  • melt flow rate (190°C/2.16 kg) determined according to ISO 1133 standard of not more than 50 g/10 min, preferably not more than 35 g/10 min, more preferably not more than 25 g/10 min, even more preferably not more than 15 g/10 min and/or
  • the at least one ethylene copolymer TP2 is an ethylene-butene copolymer or an ethylene-octene copolymer, preferably an ethylenebutene random copolymer or an ethylene-octene random copolymer, preferably having a comonomer (butene or octene) content of 5 - 50 wt.-%, more preferably 10 - 45 wt.-%, even more preferably 15 - 40 wt.-%, based on the weight of the ethylene copolymer.
  • the at least one ethylene copolymer TP2 is an ethylene-octene copolymer, preferably an ethylene-octene random copolymer, preferably having an octene content of 5 - 45 wt.-%, more preferably 10 - 40 wt.-%, even more preferably 15 - 35 wt.-%, still more preferably 15 - 30 wt.-%, such as 15 - 25 wt.-%, based on the weight of the ethylene-octene copolymer.
  • the proportion of butene or octene in an ethylene-butene copolymer or in an ethylene- octene copolymer can be determined directly by 1 H-NMR spectroscopy method known to a person skilled in the art.
  • I CH2 corresponds to the integral of the peak at 1 .3 ppm which is assigned to the H atoms of the CH2 groups of the base structure and of the 1 -octene side chains
  • x corresponds to the content of octene in mol.-%.
  • the content of octene in wt.-% can be calculated from the content of octene in mol.-% by using the following formula: 100 %
  • the measured peak positions correspond to the data presented in the literature.
  • Particularly suitable ethylene-octene copolymers for use as the at least one ethylene copolymer TP2 include the ethylene-octene copolymers, which are commercially available, for example, under the trade name of Engage® (from Dow Chemicals), under the trade name of Exact® (from Exxon Mobil), and under the trade name of Queo® (from Borealis AG).
  • the at least one thermoplastic polymer TP further comprises at least one thermoplastic polyolefin elastomer TP3 different from the at least one propylene copolymer TP1 and from the at least one ethylene copolymer TP2.
  • TPOs include reactor blends of the base polyolefin and the polyolefin modifier, also known as “in-situ TPOs” or “reactor TPOs or “impact copolymers (ICP)”, as well as physical blends of the components.
  • ICP impact copolymers
  • the components are typically produced in a sequential polymerization process, wherein the components of the matrix phase are produced in a first reactor and transferred to a second reactor, where the components of the dispersed phase are produced and incorporated as domains in the matrix phase.
  • a physical-blend type of TPO is produced by melt-mixing the base polyolefin with the polyolefin modifier each of which was separately formed prior to blending of the components.
  • Reactor-blend type TPOs comprising polypropylene homopolymer as the base polymer are often referred to as “heterophasic propylene copolymers (HECO)” whereas reactorblend type TPOs comprising polypropylene random copolymer as the base polymer are often referred to as “heterophasic propylene random copolymers (RAHECO)”.
  • HECO heteroophasic propylene copolymers
  • RAHECO heterophasic propylene copolymers
  • typical ICPs tend to have a lower xylene cold soluble (XCS) content determined according to ISO 16152 2005 standard as well as higher flexural modulus determined according to ISO 178:2019 standard compared to reactor-TPOs and soft- TPOs.
  • XCS xylene cold soluble
  • a xylene cold soluble content determined according to ISO 16152-2005 standard of at least 10 wt.-%, preferably at least 25 wt.-%, more preferably at least 35 wt.-%, even more preferably at least 45 wt.-%, still more preferably at least 55 wt.-%, such as in the range of 15 - 95 wt.-%, preferably 25 - 90 wt.-%, more preferably 35 - 85 wt.-%, even more preferably 45 - 80 wt.-%, still more preferably 50 - 70 wt.-%.
  • the at least one thermoplastic polyolefin elastomer TP3 is a heterophasic propylene copolymer, preferably comprising:
  • T g glass transition temperature
  • EPR ethylene-propylene rubber
  • the heterophasic propylene copolymer is a reactor blend of A) and B), wherein the reactor blend has preferably been obtained by using a sequential polymerization process, wherein constituents of the matrix phase are produced in a first reactor and transferred to a second reactor where constituents of the dispersed phase are produced and incorporated as domains into the matrix phase.
  • heterophasic propylene copolymers of use as the at least one thermoplastic polyolefin elastomer TP3 include, for example, “reactor TPOs” and “soft TPOs” produced with LyondellBasell's Catalloy process technology, which are available under the trade names of Adflex®, Adsyl®, Clyrell®, Hifax®, Hiflex®, and Softell®, such as Hifax® CA 10A, Hifax® CA 12A, and Hifax® CA 60 A, and Hifax® CA 212 A.
  • Further suitable heterophasic propylene copolymers are commercially available under the trade name of Borsoft® (from Borealis Polymers), such as Borsoft® SD233 CF.
  • Suitable compounds for use as the at least one elastomer E include, for example, butyl rubber, halogenated butyl rubber, ethylene-propylene diene rubber, natural rubber, chloroprene rubber, synthetic 1 ,4-cis-polyisoprene, polybutadiene, ethylene-propylene rubber, styrene-butadiene copolymer, isoprene-butadiene copolymer, styrene-isoprene- butadiene rubber, methyl methacrylate-butadiene copolymer, methyl methacrylateisoprene copolymer, acrylonitrile-isoprene copolymer, and acrylonitrile-butadiene copolymer.
  • the term “degree of unsaturation” refers in the present disclosure to the ratio of the number of unsaturated carbon-to-carbon bonds to the number of atoms in the linear chain of the average theoretical linear elastomer molecule.
  • the low degree of unsaturation is essential in applications, where shaped articles such as membrane sheets obtained by using the thermoplastic composition must be able to withstand permanent exposure to various environmental factors, particularly UV-radiation.
  • some degree of unsaturation may also be preferred to enable the chain extension and/or crosslinking/ and/or coupling reactions to occur during processing of the halogen-free flame-retardant polymer composition to shaped articles.
  • the at least one elastomer E has a mole percent unsaturation of not more than 15, preferably not more than 10, more preferably not more than 5, even more preferably not more than 2.5.
  • the at least one elastomer E has a Mooney Viscosity (ML 1+8 at 125°C) of not more than 150 MU, preferably not more than 100 MU, more preferably not more than 85 MU, even more preferably not more than 70 MU, still more preferably not more than 55 MU, such as in the range of 10 - 125 MU, preferably 15 - 100 MU, more preferably 15 - 75 MU, even more preferably 20 - 65 MU.
  • Mooney viscosity refers in the present disclosure to the viscosity measure of rubbers. It is defined as the shearing torque resisting rotation of a cylindrical metal disk (or rotor) embedded in rubber within a cylindrical cavity. The dimensions of the shearing disk viscometer, test temperatures, and procedures for determining Mooney viscosity are defined in ASTM D1646 -19a standard.
  • the at least one elastomer E comprises at least one butyl rubber E1 and/or at least one ethylene propylene diene monomer (EPDM) rubber E2.
  • butyl rubber designates in the present disclosure a polymer derived from a monomer mixture containing a major portion of a C4 to Ci monoolefin monomer, preferably an isoolefin monomer and a minor portion, such as not more than 30 wt.-%, of a C4 to C14 multiolefin monomer, preferably a conjugated diolefin.
  • the preferred C4 to C? monoolefin monomer may be selected from the group consisting of isobutylene, 2-methyl-1 -butene, 3-methyl-1 -butene, 2-methyl-2-butene, 4-methyl-1- pentene, and mixtures thereof.
  • the preferred C4 to C14 multiolefin comprises a C4 to C10 conjugated diolefin.
  • the preferred C4 to C10 conjugated diolefin may be selected from the group comprising isoprene, butadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl-1 ,3-pentadiene, 2,4- hexadiene, 2-neopentyl-1 ,3-butadiene, 2-methyl-1 ,5-hexadiene, 2,5-dimethyl-2,4- hexadiene, 2-methyl-1 ,4-pentadiene, 2-methyl-1 ,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene and mixtures thereof.
  • the at least one butyl rubber E1 is derived from a monomer mixture containing from about 80 wt.-% to about 99 wt.-% of a C4 to C7 monoolefin monomer and from about 1 .0 wt.-% to about 20 wt.-% of a C4 to C14 multiolefin monomer. More preferably, the monomer mixture contains from about 85 wt.-% to about 99 wt.-% of a C4 to C7 monoolefin monomer and from about 1 .0 wt.-% to about 10 wt.-% of a C4 to C14 multiolefin monomer.
  • the monomer mixture contains from about 95 wt.-% to about 99 wt.-% of a C4to C7 monoolefin monomer and from about 1 .0 wt.-% to about 5.0 wt.-%of a C4 to C14 multiolefin monomer.
  • the most preferred at least one butyl rubber E1 is derived from a monomer mixture comprising from about 97 wt.-% to about 99.5 wt.-% of isobutylene and from about 0.5 wt.- % to about 3 wt.-% of isoprene. It is furthermore possible to include an optional third monomer to produce a butyl terpolymer. For example, it is possible to include a styrenic monomer in the monomer mixture, preferably in an amount up to about 15 wt.-% of the monomer mixture.
  • the preferred styrenic monomer may be selected from the group comprising p-methylstyrene, styrene, a-methylstyrene, p-chlorostyrene, p-methoxystyrene, indene, indene derivatives and mixtures thereof.
  • the most preferred styrenic monomer may be selected from the group comprising styrene, p-methylstyrene and mixtures thereof.
  • Other suitable copolymerizable termonomers will be apparent to those of skill in the art.
  • the at least one butyl rubber E1 is a halogenated butyl rubber.
  • halogenated rubber refers in the present disclosure to a rubber having a halogen content of at least 0.1 mol.-%, wherein the halogen is preferably selected from the group consisting of bromine, chlorine and iodine.
  • Preferred halogenated butyl rubbers to be used as the at least one butyl rubber E1 have a halogen content of 0.1 - 10 wt.-%, preferably 0.5 - 8 wt.-%, more preferably 0.5 - 5.0 wt.-%, based on the weight of the halogenated butyl rubber.
  • the at least one butyl rubber E1 is a bromobutyl rubber or a chlorobutyl rubber, preferably having a halogen content in the range of 0.1 - 10 wt.-%, more preferably 0.5 - 8 wt.-%, even more preferably 0.5 - 5.0 wt.-%, based on the weight of the halogenated butyl rubber.
  • EPDM rubber refers in the present disclosure to terpolymer of ethylene, propylene and a non-conjugated diene.
  • suitable non-conjugated dienes to be used in EPDM rubber include, for example, 5-ethylidene-2-norbornene (ENB); 1 ,4-hexadiene; 5-methylene-2-norbornene (MNB); 1 ,6-octadiene; 5-methyl-1 ,4-hexadiene; 3,7-dimethyl-1 ,6-octadiene; 1 ,4-cyclohexadiene; tetrahydroindene; methyltetrahydroindene; dicyclopentadiene; 5-isopropylidene-2-norbornene; and 5-vinyl- norbornene.
  • Suitable EPDM rubbers for use as the at least one EPDM rubber E2 have an ethylene content of at least 20 wt.-%, preferably at least 25 wt.-%, based on the weight of the EPDM rubber and a non-conjugated diene content of not more than 20 wt.-%, preferably not more than 15 wt.-%, based on the weight of the EPDM rubber, with the remaining content being essentially composed of polypropylene.
  • the at least one EPDM rubber E2 has
  • non-conjugated diene content of 1 - 20 wt.-%, preferably 1 - 15 wt.-%, more preferably 2 - 15 wt.-%, even more preferably 2 - 10 wt.-%, based on the weight of the EPDM rubber and/or
  • Mooney Viscosity (ML 1+4 at 125°C) of not more than 125 MU, preferably not more than 100 MU, more preferably not more than 75 MU, even more preferably not more than 65 MU, still more preferably not more than 55 MU, such as in the range of 5 - 100 MU, preferably 10 - 85 MU, more preferably 15 - 75 MU, even more preferably 20 - 65 MU.
  • Suitable EPMD rubbers are commercially available, for example, under the trade name of Nordel® (from Dow Chemical Company), under the trade name of Buna EP® (from Lanxess), and under the trade name of Vistaion® (from Exxon Mobil).
  • the at least one elastomer E is composed of the at least one butyl rubber E1 and/or the at least one EPDM rubber E2.
  • the organic polymer component a) comprises: a1) 35 - 90 wt.-%, preferably 40 - 85 wt.-%, of the at least one thermoplastic polymer TP and/or a2) 5 - 60 wt.-%, preferably 10 - 55 wt.-%, of the at least one elastomer E, all proportions based on the total weight of the organic polymer component.
  • the sum of a) and b) makes up at least 55 wt.-%, preferably at least 65 wt.-%, more preferably at least 75 wt.-%, of the total weight of the halogen-free flame-retardant polymer composition.
  • the halogen-free flame-retardant polymer composition may further comprise at least one catalyst.
  • the catalyst may be added to the halogen-free flame-retardant polymer composition, for example, to catalyze chain extension and/or crosslinking and/or coupling reactions of the polymeric constituents, such as the at least one elastomer E, during meltprocessing and/or shaping of the polymer composition.
  • the at least one catalyst is preferably selected from the group consisting of metal oxides, metal salts of fatty acids and metal salts of boric acid, sulfur catalysts, phenol resin catalysts, fatty acids, and mixtures thereof.
  • Suitable metal oxide catalysts and metal salts of fatty acids include, for example, ZnO, CaO, MgO, AI2O3, CrO3, FeO, Fe2O3, and NiO and zinc salts of fatty acids having at least 6 carbon atoms.
  • Suitable sulfur catalysts include powdered sulfur, precipitated sulfur, high dispersion sulfur, surface-treated sulfur, insoluble sulfur, dimorpholinedisulfide, alkylphenoldisulfide, and mixtures thereof.
  • Suitable phenol resin catalysts include bromide of an alkylphenol resin or mixed catalysts containing stannous chloride, chloroprene, or another halogen donor and an alkylphenol resin, and mixtures thereof.
  • the at least one catalyst is selected from the group consisting of ZnO, CaO, MgO, AI2O3, CrO3, FeO, Fe2O3, and NiO, zinc salts of fatty acids having at least 6 carbon atoms, preferably at least 13 carbon atoms, zinc borate, and mixtures thereof.
  • the at least one catalyst may also be used in combination with at least one accelerator selected from the group consisting of guanidine compounds, aldehyde amine compounds, aldehyde ammonium compounds, thiazole compounds, sulfonamide compounds, thiourea compounds, thiuram compounds, xanthane compounds, and dithiocarbamate compounds.
  • accelerators may be present in the halogen-free flame-retardant polymer composition in an amount of 0.1 - 5.0 phr (parts by weight per 100 parts by weight of the at least one elastomer E).
  • the at least one catalyst, if used, is preferably present in the halogen-free flame-retardant polymer composition in an amount of not more than 10 wt.-%, more preferably not more than 7.5 wt.-%, even more preferably not more than 5 wt.-%, based on the total weight of the halogen-free flame-retardant polymer composition.
  • the at least one catalyst makes up 0.01 - 5 % wt.-%, more preferably 0.05 - 2.5 wt.-%, even more preferably 0.1 - 1.5 wt.-%, most preferably 0.25 - 1 wt.-%, of the total weight of the halogen-free flame-retardant polymer composition.
  • the at least one catalyst is zinc oxide and the halogen-free flame-retardant polymer composition further comprises at least 0.05 wt.-%, preferably 0.1 - 0.5 wt.-%, based on the total weight of the polymer composition, of at least one zinc salt of a fatty acid, preferably zinc stearate and/or at least 0.05 wt.-%, preferably 0.1 - 0.5 wt.-%, based on the total weight of the polymer composition, of at least one saturated fatty acid having at least 6 carbon atoms, preferably at least 13 carbon atoms.
  • the at least one catalyst is zinc oxide and the halogen-free flame-retardant polymer composition further comprises at least 0.05 wt.-%, preferably 0.1 - 0.5 wt.-%, based on the total weight of the polymer composition, of zinc stearate and/or at least 0.05 wt.-%, preferably 0.1 - 0.5 wt.-%, based on the total weight of the polymer composition, of a fatty acid selected from the group consisting of stearic acid and montanic acid.
  • the at least one thermoplastic polymer TP comprises or is composed of a polyvinylchloride resin TP4 or a thermoplastic polyurethane TP5.
  • the organic polymer component does not comprise the at least one elastomer E.
  • thermoplastic polymer TP comprises or is composed of a polyvinylchloride resin TP4
  • the halogen-free flame-retardant polymer composition may further contain a plasticizer for the PVC resin.
  • Suitable plasticizers for the PVC resin include, for example, linear or branched phthalates such as di-isononyl phthalate (DINP), di-nonyl phthalate (L9P), diallyl phthalate (DAP), di- 2-ethylhexyl-phthalate (DEHP), dioctyl phthalate (DOP), diisodecyl phthalate (DI DP), and mixed linear phthalates (911 P).
  • Other suitable plasticizers include phthalate-free plasticizers, such as trimellitate plasticizers, adipic polyesters, and biochemical plasticizers.
  • biochemical plasticizers include epoxidized vegetable oils, for example, epoxidized soybean oil and epoxidized linseed oil and acetylated waxes and oils derived from plants, for example, acetylated castor wax and acetylated castor oil.
  • the halogen-free flame-retardant polymer composition may further comprise various additives, such as fillers, UV- and heat stabilizers, antioxidants, plasticizers, dyes, pigments, matting agents, antistatic agents, impact modifiers, biocides, and processing aids such as lubricants, slip agents, antiblock agents, and denest aids.
  • the total amount of these types of additives is preferably not more than 15 wt.-%, more preferably not more than 10 wt.-%, even more preferably not more than 5 wt.-%, based on the total weight of the polymer composition.
  • Suitable fillers for use in the halogen-free flame-retardant polymer composition include, for example, inorganic fillers, such as sand, granite, calcium carbonate, clay, expanded clay, diatomaceous earth, pumice, mica, kaolin, talc, dolomite, xonotlite, perlite, vermiculite, Wollastonite, barite, magnesium carbonate, calcium hydroxide, calcium aluminates, silica, fumed silica, fused silica, aerogels, glass beads, hollow glass spheres, ceramic spheres, bauxite, comminuted concrete, and zeolites.
  • inorganic fillers such as sand, granite, calcium carbonate, clay, expanded clay, diatomaceous earth, pumice, mica, kaolin, talc, dolomite, xonotlite, perlite, vermiculite, Wollastonite, barite, magnesium carbonate, calcium hydroxide, calcium aluminates,
  • the halogen-free flame-retardant polymer composition comprises at least one solid particulate filler, preferably selected from calcium carbonate, magnesium carbonate, clay, expanded clay, diatomaceous earth, pumice, mica, kaolin, talc, dolomite, xonotlite, perlite, vermiculite, Wollastonite, barite, calcium hydroxide, calcium aluminates, silica, fumed silica, and fused silica.
  • solid particulate filler preferably selected from calcium carbonate, magnesium carbonate, clay, expanded clay, diatomaceous earth, pumice, mica, kaolin, talc, dolomite, xonotlite, perlite, vermiculite, Wollastonite, barite, calcium hydroxide, calcium aluminates, silica, fumed silica, and fused silica.
  • the at least one solid particulate filler is preferably present in the thermoplastic composition in the form of finely divided particles.
  • finely divided particles refers here to particles, whose median particle size dso does not exceed 100 pm, preferably 50 pm, more preferably 25 pm.
  • median particle size dso“ refers in the present disclosure to a particle size below which 50% of all particles by volume are smaller than the dso value.
  • the particle size distribution can be determined by sieve analysis according to the method as described in ASTM C136/C136M -2014 standard (“Standard Test Method for Sieve Analysis of Fine and Coarse Aggregates).
  • Suitable UV-stabilizers include, particularly, the hindered amine light stabilizers (HALS). These types of compounds are typically added to polymer blends to prevent light-induced polymer degradation. Such UV-stabilizers are needed especially in case shaped articles prepared from the halogen-free flame-retardant polymer composition are used in outdoor applications, for example, in waterproofing of roof or fagade substrates.
  • HALS hindered amine light stabilizers
  • the halogen-free flame-retardant polymer composition further comprises: d) 0.05 - 10 wt.-%, preferably 0.1 - 5 wt-%, more preferably 0.25 - 2.5 wt.-%, even more preferably 0.25 - 1 .5 wt.-%, based on the total weight of the halogen-free flame-retardant polymer composition, of at least one hindered amine light stabilizer (HALS).
  • HALS hindered amine light stabilizer
  • the halogen-free flame-retardant polymer composition may further comprise at least one UV-absorber, preferably selected the group consisting of hydroxybenzophenones, hydroxybenzotriazoles, anilides, benzoates, cyanoacrylates, phenylformamidines, and mixtures thereof.
  • at least one UV-absorber preferably selected the group consisting of hydroxybenzophenones, hydroxybenzotriazoles, anilides, benzoates, cyanoacrylates, phenylformamidines, and mixtures thereof.
  • Suitable UV-absorbers are commercially available, for example, under the trade name of Tinuvin® (from Ciba Specialty Chemicals), such as Tinuvin ® 213, 234, 320, 326-329, 350, 360, 571.
  • Tinuvin® from Ciba Specialty Chemicals
  • Tinuvin ® 213, 234, 320, 326-329, 350, 360, 571 the trade name of Tinuvin ® 213, 234, 320, 326-329, 350, 360, 571.
  • the preferences given above for the halogen-free flame-retardant polymer composition apply equally apply equally to all other subjects of the present invention unless otherwise stated.
  • Another aspect of the present invention is a sealing element comprising a shaped article obtained by using the halogen-free flame-retardant polymer composition according to the present invention.
  • the shaped article can be, for example, in form of a layer, cube, or a tube and it can be obtained from the halogen-free flame-retardant polymer composition by using conventional manufacturing techniques, for example, extrusion, hot pressing, injection molding, or additive manufacturing techniques, such as 3D printing.
  • the shaped article is obtained by a process comprising melt-processing a starting composition comprising or composed of the constituents of the halogen-free flame-retardant polymer composition of the present invention.
  • melt-processing refers here to a process, in which at least one molten polymeric component is intimately mixed with at least one other component, which may be another molten polymeric component or a solid component, such as a flame retardant, filler or a catalyst, until a melt blend, i.e., a substantially homogeneously mixed mixture of the polymeric component(s) and the other constituents is obtained.
  • the melt processing of the starting composition can be conducted as a batch process using any conventional mixer, such as a Brabender, Banbury, or roll mixer or as continuous process using a continuous type of mixer, preferably an extruder, such as a single screw or a twin-screw extruder or a planetary roller extruder.
  • any conventional mixer such as a Brabender, Banbury, or roll mixer
  • an extruder such as a single screw or a twin-screw extruder or a planetary roller extruder.
  • the process for obtaining the shaped article preferably comprises a further step of meltshaping of the melt-processed starting composition into a form of a shaped article.
  • the melt-shaping step can be conducted by using various techniques known to those of skill in the art, such as, extruding, co-extruding, injection molding, thermoforming, film blowing, casting, calendaring, or 3D printing.
  • a skilled person is familiar with melt-shaping techniques and can select the suitable alternative based on the dimensions of the shaped article. For example, layers having a thickness of below 350 pm, such as of below 250 pm, may be preferably produced by a blown film extrusion or co-extrusion process.
  • a molten polymer composition obtained from an extruder is forced through an upwards facing opening of a blown film extruder die, typically an upright cylinder with an annular opening, like a pipe extrusion die.
  • substrate layers having a thickness of at least 0.5 mm, such as at least 0.75 may be preferably produced by a die extrusion, hot-pressing, or calendaring processes.
  • the sealing element comprises a further shaped article, wherein the shaped article and the further shaped article are directly or indirectly connected, preferably directly connected, to each other over at least a portion of their opposing major surfaces.
  • the further shaped article may also be obtained using the halogen-free polymer composition of the present invention.
  • the composition of the shaped article and the further shaped article may also differ from each other.
  • the sealing element is a membrane, preferably a fagade membrane, roofing membrane, waterproofing membrane, gas barrier membrane, volatile organic compound (VOC) barrier membrane, vapor barrier membrane, vapor retarder membrane, or a geomembrane.
  • a membrane preferably a fagade membrane, roofing membrane, waterproofing membrane, gas barrier membrane, volatile organic compound (VOC) barrier membrane, vapor barrier membrane, vapor retarder membrane, or a geomembrane.
  • Another aspect of the present invention is a method for producing a sealing element comprising a shaped article, the method comprising steps of melt-processing a starting composition comprising or composed of the constituents of the halogen-free flameretardant polymer composition of the present invention and melt-shaping the melt- processed starting composition into a form of a shaped article.
  • the melt processing of the starting composition can be conducted as a batch process using any conventional mixer, such as a Brabender, Banbury, or roll mixer or as continuous process using a continuous type of mixer, preferably an extruder, such as a single screw or a twin-screw extruder or a planetary roller extruder.
  • any conventional mixer such as a Brabender, Banbury, or roll mixer
  • an extruder such as a single screw or a twin-screw extruder or a planetary roller extruder.
  • the method for producing a sealing element preferably comprises a further step of meltshaping of the melt-processed starting composition into a form of a shaped article.
  • the melt-shaping step can be conducted by using various techniques known to those of skill in the art, such as, extruding, co-extruding, molding, thermoforming, film blowing, casting, or calendaring, or 3D printing, as already discussed above.
  • the method for producing a sealing element comprises steps of: i) Melt-processing the starting composition in an extruder to provide a melt-blend of the starting composition and ii) Extruding or injecting said melt-blend through an extruder or injection die.
  • any conventional extruder may be used for conducting step i) of the method, such as, a ram extruder, single screw extruder, a twin-screw extruder, or a planetary roller extruder.
  • the extruder is a screw extruder, more preferably a twin-screw extruder comprising a barrel and a screw unit contained in the barrel.
  • the screw unit of a conventional screw extruder is typically considered to comprise feed, transition, and metering sections. In the feed section the thermoplastic composition enters the channels of the rotating screw and is conveyed towards the transition section, in which the composition is compressed and melted. The composition should be fully melted when it leaves the transition section.
  • the function of the metering section is to homogenize the melted composition and to allow it to be metered or pumped out at constant rate.
  • the extruder die used for conducting step ii) of the method is preferably a flat die, consisting of manifold, approach, and lip regions.
  • the extruder barrel comprises a feed port through which the material to be extruded is fed to the extruder and an outlet port through which the material leaves the barrel.
  • the outlet port is coupled with the die via a gate or adapter piece.
  • a mixing device may be interposed between the barrel and the die.
  • the feed port is generally connected with a hopper to which the material to be extruded is added. It is preferred that a screen pack and a breaker plate are positioned at the end of the barrel to avoid plugging in the nozzles.
  • the extruder further comprises heating elements, cooling elements, temperature sensors and temperature control elements to provide temperature-controlled zones along the barrel, also known as barrel zones.
  • the extruder may comprise, for example, from 3 to 8 barrel zones, preferably at least 5 barrel zones, by the use of which a temperature profile can be realized in the barrel.
  • the extrusion process may be conducted by using different temperature profiles, such as an increasing temperature profile where the temperature increases downstream the barrel, a decreasing temperature profile where the temperature decreases downstream the barrel, and a humped temperature profile where the temperature increases from the feed port toward a certain set point, for example toward the middle of the barrel.
  • the maximum temperature of the starting composition during melt processing in the screw section of the extruder i.e. , the temperature in at the end of the screw section, is preferably not less than 150°C, more preferably not less than 160°C, most preferably not less than 180°C.
  • the maximum temperature of the starting composition during melt processing in the screw section of the extruder can be in the range of 150 - 250°C, for example 160 - 220°C, such as 180 - 200°C.
  • the at least one thermoplastic polymer TP, the at least one elastomer E, the at least one siloxane polymer SP, if used, the flame-retardant system, and the at least one catalyst, if used, may be fed to the extruder as individual streams, as a pre-mix, dry blend, or as a master batch.
  • the at least one thermoplastic polymer TP and the at least one elastomer E may be fed into the extruder through the feed port and the at least one catalyst, if used, may fed into the extruder through another port located downstream from the feed port.
  • the term “downstream” designates in the present document the direction to the outlet port.
  • the at least one elastomer E can also be mixed with the at least one catalyst, if used, to obtain a premix, which is then fed into the extruder through the feed port.
  • the premixing can be carried out using a blending apparatus, which are known to a person skilled in the art.
  • the premixing of the at least one elastomer E and the at least one catalyst is preferably conducted at a temperature, which is above the melting point of the at least one elastomer E and below the activation temperature of the at least one catalyst, i.e. temperature at which the chain extension and/or crosslinking/ and/or coupling reactions of the at least one elastomer E are initiated.
  • the at least one thermoplastic polymer TP and the at least one elastomer E can be processed in a compounding extruder to pellets or granules, which are dry-blended with the at least one catalyst, if used, and the resulting dry-blend is then fed into extruder though the feed port.
  • Still another aspect of the present invention is use of the halogen-free flame-retardant polymer composition according to the present invention for providing a membrane, preferably a fagade membrane, roofing membrane, waterproofing membrane, gas barrier membrane, volatile organic compound (VOC) barrier membrane, vapor barrier membrane, vapor retarder membrane, or a geomembrane.
  • a membrane preferably a fagade membrane, roofing membrane, waterproofing membrane, gas barrier membrane, volatile organic compound (VOC) barrier membrane, vapor barrier membrane, vapor retarder membrane, or a geomembrane.
  • Table 1 The materials shown in Table 1 were used for preparing the samples of shaped articles. Table 1
  • inventive and reference shaped articles were prepared from the tested halogen-free flame-retardant compositions according to the procedure as described below and tested for their flame retardancy properties.
  • the shaped articles were produced from the starting compositions using a laboratory scale extrusion-calendering apparatus consisting of a twin-screw extruder (Berstorff GmbH), a flat die and set of water-cooled calender rolls.
  • a laboratory scale extrusion-calendering apparatus consisting of a twin-screw extruder (Berstorff GmbH), a flat die and set of water-cooled calender rolls.
  • thermoplastic polymers TP and the elastomers E were fed to the extruder hopper.
  • the polymer blend was melt-processed in the first of the four zones of the extruder and a pre-mix of flame retardants, catalyst (if used), hindered amine light stabilizer (if used), and the additive package (if used) was added to the partially melt-processed blend at beginning of the second zone of the extruder.
  • the melt-processed blend was then extruded through an extruder flat die into single ply sheets having a thickness of 0.3 - 0.6 mm.
  • the extrusion was conducted using an extrusion temperature of 200 - 210 °C and pressure of 156 - 166 bar.
  • Tensile stress and elongation at break The tensile stress and elongation at break were measured for samples cut from the membrane sheets in machine and cross machine direction. The measurements were conducted according to EN 12311-2:2013 standard at a temperature of 23°C using a cross head speed of 500 mm/min. The values for tensile stress and elongation at break obtained with the tested membrane sheets are presented in Table 5.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition polymère ignifuge sans halogène comprenant : a) un composant polymère organique comprenant : a1) au moins un polymère thermoplastique TP et/ou a2) au moins un élastomère E, et b) un système ignifuge comprenant : b1) au moins un premier composé organophosphoré contenant de l'azote et éventuellement au moins un borate métallique, b2) au moins un sel organométallique, et b3) au moins un deuxième composé organophosphoré contenant de l'azote. L'invention concerne également un élément d'étanchéité comprenant un article façonné obtenu par l'utilisation de la composition polymère ignifuge sans halogène.
EP24716346.2A 2023-03-31 2024-03-28 Composition de polymère ignifuge sans halogène et son utilisation Pending EP4688937A1 (fr)

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EP23166229 2023-03-31
PCT/EP2024/058668 WO2024200758A1 (fr) 2023-03-31 2024-03-28 Composition de polymère ignifuge sans halogène et son utilisation

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CN120399340A (zh) * 2025-04-29 2025-08-01 江苏东旭电缆有限公司 一种高强度阻燃防火电缆及其制备方法

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US7655714B2 (en) * 2007-09-27 2010-02-02 Sabic Innovative Plastics Ip B.V. Flame-retardant poly(arylene ether) composition and its use as a covering for coated wire
CN101835832B (zh) * 2007-10-11 2013-03-27 帝斯曼知识产权资产管理有限公司 用于电子设备的柔性阻燃绝缘线
JP5387016B2 (ja) * 2009-02-02 2014-01-15 三菱エンジニアリングプラスチックス株式会社 難燃性熱可塑性ポリエステル樹脂組成物
CN102666693A (zh) * 2009-10-27 2012-09-12 巴斯夫欧洲公司 具有阻燃性的耐热老化性聚酰胺
DE102010023770A1 (de) * 2010-06-15 2011-12-15 Basf Se Glühdrahtbeständige Formmassen
US8781278B2 (en) * 2011-03-02 2014-07-15 E I Du Pont De Nemours And Company Low smoke halogen free flame retardant thermoplastic elastomer compositions containing zeolites
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