EP3145988A1 - Mélanges ignifuges sans halogène destinés à des mousses polyoléfines - Google Patents

Mélanges ignifuges sans halogène destinés à des mousses polyoléfines

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Publication number
EP3145988A1
EP3145988A1 EP15724633.1A EP15724633A EP3145988A1 EP 3145988 A1 EP3145988 A1 EP 3145988A1 EP 15724633 A EP15724633 A EP 15724633A EP 3145988 A1 EP3145988 A1 EP 3145988A1
Authority
EP
European Patent Office
Prior art keywords
weight
flame retardant
molding composition
polyolefin
composition according
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.)
Withdrawn
Application number
EP15724633.1A
Other languages
German (de)
English (en)
Inventor
Sabine Fuchs
Uwe Keppeler
Tim ALBERT
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP3145988A1 publication Critical patent/EP3145988A1/fr
Withdrawn legal-status Critical Current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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds

Definitions

  • the present invention relates to a molding composition containing
  • the sum of the components a) to d) being 100% by weight and the content of the flame retardant synergist S being more than 5% by weight if the proportion of the flameproofing agent FR is less than 1% by weight, and their use for Production of molded parts, foils and foams.
  • Expanded polyolefin foam particles are the starting material for a variety of products in the automotive, packaging, technical parts, sports & leisure etc. In these applications, in particular the special properties of such foam particles or the foam molded parts produced therefrom such as good resilience after static or dynamic stress and largely invariable energy absorption after multiple impact load to wear, the other particle foams such as expanded polystyrene (EPS) do not equally possess.
  • EPS expanded polystyrene
  • the polyolefin foams must also have significantly flame-retardant properties.
  • flame-retardant finishing of the polyolefin foam particles come here u. a. halogenated flame retardants, often in combination with antimony trioxide synergist (eg: JP-A-7-309967 or JP-A-10-147661).
  • US 5,393,812 and EP 1 239 005 A1 describe polyolefin compositions containing a brominated phosphate, e.g. B Tris (tribromoneopentyl) phosphate or phosphonate esters as flame retardants and sterically hindered amines as light stabilizers.
  • EP 2 420 533 A1 describes the use of sterically hindered amine ethers alone and in combination with condensed organic phosphoric acid esters for use as flame retardants in pre-expanded polyolefin particles and polyolefin foams.
  • the high levels of sterically hindered amine ethers used in the examples generally result in degraded product or processing properties.
  • WO2010 / 026230 A1 describes synergistic flame retardant mixtures of two or more phosphonate compounds or phosphonic acid derivatives and sterically hindered amines for polymers, in particular polyethylene films, for preventing dripping in the event of fire.
  • Flame retardants are primarily used to meet fire safety requirements in construction and transportation as well as in the electrical / electronics sector. Their addition should as far as possible not adversely affect the remaining properties of a material (for example processing, mechanics, migration of substances, recycling, environmental compatibility). This can be achieved all the easier the lower the content of flame retardants used.
  • Normally flame retardant systems are therefore very specific for thermoplastic polymers for the respective plastic and have to be selected in terms of. Thermostability, compatibility, processability and interaction with the polymer matrix very targeted for this and optimized in their composition and use.
  • Polystyrene and polypropylene differ, for example, not only by their chemical structure, but in particular by the partial crystallinity of the polypropylene, which causes a very different physicochemical behavior compared to polystyrene.
  • polypropylene compared to polystyrene when flame retardants are used which are suitable for both polymers, a significantly higher flame retardancy level is always required for the same fire classification.
  • the object of the present invention was therefore to provide a halogen-free molding composition for polyolefin foams, which ensures adequate flame retardancy in small amounts, is self-extinguishing in the event of fire and, in particular, does not substantially change the mechanical properties.
  • the molding composition according to the invention preferably contains a) 77 to 98% by weight of at least one polyolefin P,
  • Flame retardant FR also in polyolefin foams a significant flame retardant effect.
  • the flameproofing can be carried out even if the proportion of organic phosphorus compound is less than 1% by weight. , preferably less than 0.5% by weight, more preferably 0% by weight.
  • Suitable polyolefin P are, for example
  • Preferred comonomers are ethylene, styrene, dienes such as butadiene or a C4-10 alpha-olefin or mixtures thereof.
  • Particularly preferred random copolymers are copolymers of propylene with 0.5 to 6 wt .-% of ethylene or 0.5 to 15 wt .-% 1-butene, or a terpolymer of propylene, 0.5 to 6 wt .-% of ethylene and From 0.5 to 6% by weight of 1-butene, or copolymers of ethylene, propylene and a diene,
  • Polyethylenes for example LD (low density), LLD (linear low density), MD (medium density) or HD (high density), HMW (high molecular weight) or UHMW (ultra high molecular weight), or
  • polystyrene resin which can be used according to the invention are mentioned, for example, in EP 1 514 896 B1.
  • the at least one polyolefin P is a propylene-ethylene random copolymer, wherein the content of ethylene is more preferably 1 to 5 wt .-%, based on the total copolymer.
  • Suitable polyolefins prepared with both Ziegler and metallocene catalysts.
  • the crystallite melting point (DSC maximum) of the polyolefins which can be used according to the invention is generally between 90 and 170.degree. Their heat of fusion, determined according to the DSC
  • melt index MFI 230 ° C, 2.16 kg for propylene polymers and 190 ° C, 2.16 kg for ethylene polymers
  • DIN 53 735 is preferably from 0.1 to 100 g / 10 min.
  • the polyolefins may be blended with up to 50% by weight of another type of thermoplastic having a glass transition temperature (DSC inflection point) below 180 ° C.
  • the invention is preferably carried out without admixing a heterogeneous thermoplastic. This is preferred insofar as the recyclability of the polyolefin or of the foam produced therefrom suffers due to a foreign thermoplastic. Rubbery ethylene / propylene copolymers which can be added for elastification are not alien in this sense.
  • polyolefins P which are synthesized as homopolymers or copolymers from the monomers ethylene, propylene, butene-1 or isobutene, as well as polyolefin derivatives and copolymers.
  • Polyolefins which are suitable are, polypropylene homopolymers (PP), polyethylene homopolymers, such as low-density polyethylene (LLDPE), low-density polyethylene (LLD), high-density polyethylene (PE-MD), high-density polyethylene (PE).
  • the molding composition may contain 0 to 10 wt .-%, preferably 1 to 8 wt .-%, particularly preferably 1, 5 to 5 wt .-% of at least one organic phosphorus compound as a flame retardant FR.
  • the organic phosphorus compounds used according to the invention as flame retardants FR contain no sulfur atoms. Compounds containing sulfur and phosphorus are considered as flame retardant synergists S in the context of the invention. Suitable organic phosphorus compounds are, for example, phosphates, phosphonates, phosphinates, phosphine oxides, phosphines or phosphites.
  • Suitable phosphates are, for example, resorcinol bis (diphenyl phosphate) (FYROLFLEX® RDP), bisphenol A bis (diphenyl phosphate) (FYROLFLEX® BDP), hydroquinone bis (diphenyl phosphate), triphenyl phosphates, hydroxyalkyl esters based on phosphoric acid, ammonium polyphosphate (APP), resorcinol bis (diphenyl phosphate) as oligomer (RDP), phosphazene based compounds, ethylene diamine diphosphate (EDAP).
  • resorcinol bis diphenyl phosphate
  • FYROLFLEX® RDP bisphenol A bis (diphenyl phosphate)
  • FYROLFLEX® BDP bisphenol A bis (diphenyl phosphate)
  • hydroquinone bis diphenyl phosphate
  • triphenyl phosphates triphenyl phosphates
  • Suitable phosphonates are, for example, alkyl esters of methanephosphonic acid, monomethyl methanephosphonate aluminum salt, diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonates, melamine phenylphosphonate.
  • a suitable one Phosphinate is, for example, melamine phenylphosphinate.
  • Suitable phosphites are, for example, aluminum phosphite with and without water of crystallization, metal salts of hypophosphorous acid, in particular aluminum hypophosphite, and melamine salts of organic phosphorus-based acids of different oxidation states.
  • the novel molding composition preferably contains as flame retardant FR an organic phosphate, phosphonate, phosphinate, phosphine oxide, phosphine or phosphite.
  • a flame retardant FR is a solid having a melting point o-, if the flame retardant FR does not melt undecomposed, with a decomposition point of at least 150 ° C, more preferably of at least 200 ° C.
  • Such flame retardants FR are e.g. sold by Thor GmbH under the trade name Aflammit® PCO. Suitable types are, for example, the PCO 900, the PCO 800 or the PCO 700.
  • the melting point can be determined with the usual methods, for example in a Thiele, DAB, Linström, Kofier or Tolotti apparatus with sufficient accuracy. In practical laboratory operation mostly automatic melting point measuring devices are used.
  • the melting or decomposition points are particularly preferably determined by thermographimetry (TG) or differential scanning calorimetry (DSC).
  • the molding composition contains 0.5 to 15 wt .-%, preferably 1 to 5 wt .-%, in particular preferably 1, 5 to 2.5 wt .-% of at least one sulfur-containing flame retardant synergist S, if Proportion of the flame retardant FR at least 1 wt .-% is.
  • Sulfur-containing flame retardant synergists S are elementally sulfur or organic sulfur compounds.
  • the elemental sulfur can also be used in the form of starting compounds which are decomposed under the process conditions to elemental sulfur.
  • elemental sulfur in encapsulated form. Suitable materials for encapsulating are, for example, melamine resins and urea-formaldehyde resins.
  • the flame-retardant synergist is preferably largely homogeneously distributed in the molding composition, which can be achieved, for example, by admixture during extrusion or by static or dynamic mixers (eg kneaders).
  • Suitable sulfur compounds are furthermore those of the formula (I)
  • R is identical or different, preferably identical, C 6 -C 2 aryl, a 5-10 membered
  • X is the same or different, preferably the same, OR 2 , SR 2 , NR 2 R 3 , COOR 2 , CONR 2 ,
  • Y 1 is O, S or NR '"
  • Y 2 is O or S
  • p is 0 or 1;
  • R 1 is identical or different, preferably identical, C 1 -C 6 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18
  • R 2 , R 3 are identical or different, preferably identical, H, C 1 -C 6 -alkyl, C 2 -C -alkenyl,
  • n is an integer from 1 to 8 and
  • m is a number from 0 to 1000
  • the flame retardant synergist S is selected from elemental sulfur or an organic disulfide.
  • Suitable disulfides are dimeric, oligomeric or polymeric disulfides.
  • R is phenyl in which the groups X and R 1 are in the para position.
  • X is preferably OH or a group 0-P (0) (O-phenyl) 2 .
  • R 1 is preferably tC 4 Hg or t-CsHu.
  • n is preferably 2.
  • m is preferably a number from 3 to 100.
  • the sulfur content of the sulfur compounds (I) is preferably 5 to 80% by weight, more preferably 10 to 60% by weight, most preferably 12 to 40% by weight, based on the sulfur compound (I).
  • the molecular weight of the sulfur compounds (I) is preferably at least 200 g / mol, more preferably at least 500 g / mol.
  • 2-aminophenyl disulfide poly (ferric butylphenol disulfide), poly (fe / t-amylphenol disulfide) and poly (ferric butylphenol disulfide) phosphated with diphenyl phosphate groups.
  • Poly (ferric butylphenol disulfide) and poly (ferric amylphenol disulfide) are from the company
  • the weight ratio of flame retardant FR to synergist S in the novel molding composition is preferably in the range from 1:10 to 10: 1 and particularly preferably in the range from 2:10 to 10: 2.
  • the optimum of the weight ratios may be different for the individual combinations of flame retardant FR and synergist S and is usually in an even narrower range.
  • Further additives A are customary additives, such as antioxidants, stabilizers, waxes, fillers, pigments and dyes, halogenated flame retardants, UV and heat stabilizers, carbon black or graphite, processing aids in customary amounts (for example: Plastics Additives Handbook , Ed., By H. Zweifel, 5th Ed., Hanser Publ., Kunststoff 2001, pp. 681-698).
  • the molding composition according to the invention preferably contains from 0.001 to 10.0%, particularly preferably from 0.01 to 1.0%, very particularly preferably from 0.02 to 0.06%, for example from 0.04 to 0.06%, based on the granules, at least one nucleating agent. Suitable z.
  • talc paraffins and / or waxes and carbon black, graphite and fumed silicas, also natural or synthetic zeolites and, optionally modified, bentonites, particularly preferably talc. They cause a fine-celled foam arises, in some cases, they allow foaming in the first place.
  • the molding composition according to the invention particularly preferably contains from 0.1 to 5% by weight of carbon black and / or graphite as additive A.
  • Suitable halogenated flame retardants are, for example, organic bromine compound such as decabromodiphenyl oxide, tris (tribromoneopentyl) phosphate (FR-370), tris (2,3-dibromopropyl) phosphate, tetrabromophthalic acid, bis (2,3-dibromopropyl ether) of tetrabromobisphenol A ( FR-720), brominated epoxy resins, 1,2-ethylene-bis (tetrabromophthalimide) (BT-93), 1,2-bis (tribromophenoxy) ethane, decabromodiphenylethane (FR-1410), tetrabromobisphenol A, 1, 2- Ethylene bis (dibromorobornane dicarboximide), tris (2,3-dibromopropyl) isocyanurate,
  • organic bromine compound such as decabromodiphenyl oxide, tris (tribromoneopenty
  • the molding composition according to the invention preferably contains no or only small amounts of halogenated flame retardants.
  • the molding composition of the invention can be prepared by known methods by mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted.
  • the incorporation of the flame retardants FR, synergists S and additives A into the polyolefins P is preferably carried out by adding to a polymer melt and mixing in an extruder.
  • the flameproofing components can be mixed with a polymer, compounded and granulated. The granules obtained can then be used as a well-dosed concentrate (masterbatch)
  • the molding composition of the invention is characterized by a good flame retardancy and is suitable for the production of fibers, moldings, films or foams.
  • the films and multilayer film bodies of the molding composition of the invention preferably have layer thicknesses in the range from 1 to 250 ⁇ m, in particular in the range from 50 to 150 ⁇ m.
  • the molding composition according to the invention is prepared by the customary processes known to the person skilled in the art, preferably by extrusion.
  • the preparation of the polymer films with thicknesses below 150 ⁇ m can likewise be carried out by the customary methods known to the person skilled in the art, either by extrusion directly in one step after compounding or in a second step after preparation of the compound as granules (eg blow molding, calendering, pressing or To water).
  • the invention also provides the use of the molding composition for the production of fibers, films or foams and foams with cell walls or cell webs from the molding composition described above.
  • Expanded foam particles can be obtained for example by impregnation of granules with a blowing agent in aqueous suspension in a pressure vessel and subsequent expansion.
  • the bulk density of expanded particles obtainable in this manner is preferably from 10 to 300 kg / m 3 .
  • the foam particles can then be welded in a mold into foam moldings.
  • a preferred process for the preparation of polyolefin foam particles comprises the steps:
  • step (b) preparing a preferably aqueous suspension of the granules of step (a), (c) impregnating the granules with at least one volatile propellant in a vessel under pressure,
  • step (d) relaxing the granules impregnated in step (c) and isolating the polyolefin foam particles.
  • step (a) granules of the molding composition according to the invention are provided.
  • the molding composition can be prepared and granulated as described above. Cylindrical granules can be obtained by continuous granulation, and almost spherical granules by underwater pressure granulation (UWG).
  • UWG underwater pressure granulation
  • the compact, unfoamed granules are generally referred to as minigranules and impregnated in the subsequent stages and expanded to polyolefin foam particles.
  • This polyolefin granules preferably has average diameters of 0.2 to 10 mm, in particular of 0.5 to 5 mm.
  • This preferably cylindrical or round granules can be prepared by all methods known to those skilled in the art, in particular by extruding the polyolefin, optionally together with the thermoplastic and other additives to be admixed, extruding from the extruder, optionally cooling and granulating.
  • Such granules preferably provided in step (a) are also called "minigranules.”
  • the individual particles of such granules generally have a weight of 0.5 to 10 mg / particle, preferably 0.6 to 1.4 mg / particle. A preferred process for producing this granulate is described, for example, in EP 1 182 225 B1.
  • Step (b) of the process according to the invention comprises preparing a suspension containing the granules of the molding composition according to the invention in a suspending medium.
  • the granules are suspended in step (b) of the process according to the invention in a suitable suspending medium.
  • suspending media which are known to the person skilled in the art and which ensure that the granules used do not dissolve therein can be used.
  • suspending media which are particularly suitable according to the invention are water, polar organic solvents, for example alcohols, such as methanol, ethanol, propanols, such as isopropanol, glycerol, ethylene glycol, or ketones, such as acetone, or mixtures thereof.
  • the amount of suspending medium, more preferably water, in the suspension is generally chosen so that the phase ratio of granules used in step (b) to suspending medium is> 0.2, preferably> 0.35.
  • the phase ratio of granules used in step (b) to suspension medium is generally ⁇ 0.90, preferably ⁇ 0.80, more preferably ⁇ 0.70.
  • the phase ratio relates to the ratio of granules, measured in kilograms, to suspending medium, which is preferably water, also in kilograms. It is known to the person skilled in the art how the ratio according to the invention can be adjusted, for example, for 500 kg of granules in 1000 kg of water, the phase ratio of granules to water is 0.5.
  • the amount of granules containing at least one polyolefin, which is introduced into the suspension according to step (b), results from the above-described phase ratio of granules to suspending medium.
  • the granules containing at least one polyolefin are suspended in water in a stirred reactor.
  • at least one suspending aid is added in order to ensure a uniform distribution of the granules in the suspending medium.
  • Suitable suspending aids are water-insoluble inorganic stabilizers, such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates, furthermore polyvinyl alcohol and surfactants, such as sodium dodecyl arylsulfonate.
  • These suspending aids, in particular the said water-insoluble inorganic stabilizers are usually used in amounts of from 0.005 to 10% by weight, based on the total suspension.
  • Surfactants for example the ionic surfactant sodium dodecyl arylsulfonate or nonionic surfactants, for example based on a saturated linear Ci6Ci8 fatty alcohol, are usually used in an amount of 2 to 2000 ppm, in particular 2 to 500 ppm, based on the total suspension.
  • Step (b) of the process according to the invention can be carried out at all suitable temperatures. These temperatures are known to the person skilled in the art, for example step (b) of the process according to the invention is generally carried out at a temperature at which the suspending medium used is liquid, for example at a temperature of 15 to 35 ° C., more preferably at ambient temperature.
  • Step (c) of the method according to the invention comprises impregnating the granules suspended in step (b) with at least one propellant in order to obtain a propellant-laden granules in suspension.
  • step (c) of the process according to the invention for example, batchwise operation is carried out in an impregnating vessel, for example in a stirred tank reactor.
  • an impregnating vessel for example in a stirred tank reactor.
  • the suspension from step (b) of the process according to the invention comprising the at least one polyolefin, preferably as minigranulose, in water as suspending medium, and optionally a suspending aid.
  • At least one propellant is now preferably added to this suspension.
  • blowing agents known to the person skilled in the art can be used.
  • the boiling point of the blowing agent is generally at normal pressure between -25 and 150 ° C, in particular between -10 and 125 ° C.
  • the propellant is preferably a linear or cyclic aliphatic hydrocarbon such as methane, ethane, propane, butane, iso-butane, pentanes, cyclopentane, hexanes and heptanes, halogenated hydrocarbons such as dichlorodifluoromethane, trichloromonofluoromethane, an alcohol such as methanol, ethanol, n Propanol, iso-propanol and n-butanol, a ketone, such as 3,3-
  • Propellant mixtures can also be used. Particular preference is given to using butane or carbon dioxide and / or nitrogen. Frequently, nitrogen is used as co-blowing agent.
  • butane a technical mixture of n- and iso-butane is often used in practice.
  • the at least one blowing agent is generally used in an amount of 1 to 50 wt .-%, preferably 1 to 30 wt .-%, particularly preferably 2 to 25 wt .-%, each based on the granules. It can be fed at once or in partial portions.
  • the reactor contents are generally heated to an impregnation temperature of usually at least 100 ° C.
  • the addition of propellant may take place before, during or after the heating of the reactor contents, preferably before heating.
  • the impregnation temperature should be in the vicinity of the softening temperature of the polyolefin, for example 40 ° C below to 25 ° C above the melting temperature (crystallite melting point) of the polyolefin.
  • polypropylene impregnation temperatures of 1 10 to 180 ° C, in particular 130 to 160 ° C are preferred.
  • a pressure arises in the closed reactor which is generally from 2 to 100 bar (absolute). If necessary, one can regulate the pressure by a pressure regulating valve or by repressing blowing agent. Due to the elevated temperature and the overpressure present at the impregnation conditions, blowing agent diffuses into the polymer granulate particles.
  • the impregnation time is generally 0.3 to 10 hours.
  • step (c) After step (c) according to the invention, a granulate laden with propellant is obtained in suspension.
  • Step (d) Step (d) of the process of the invention comprises relaxing and cooling the suspension obtained in step (c) by contacting it with a suitable coolant (quenching process) to obtain foam particles.
  • a suitable quenching process is described, for example, in EP 2336225, in which quenching is effected by adding a certain amount of coolant.
  • the suspension is expanded by a suitable device.
  • the suspension initially leaves the impregnation vessel through a valve.
  • this can then be preferably passed through a short piece of an expansion tube, which carries a pinhole at the end. Due to the length and diameter of the expansion tube and the diameter of the pinhole, the relaxation time can be controlled.
  • the expanded particles can be separated from the suspension in the usual way, for example by filtration, for example with a mesh or curved screen or a continuously operating centrifuge.
  • suspending and / or suspending agents still adhering before or after separation can optionally be removed.
  • the expanded polyolefin particles can then be washed and dried.
  • the expanded polyolefin particles obtained after step (d) of the process according to the invention preferably have a bulk density of from 5 to 300 kg / m 3 , particularly preferably from 10 to 200 kg / m 3 , for example 25-40 kg / m 3 .
  • the expanded particles (expanded particles I) obtained in step (d) are further foamed in order to obtain expanded particles II having a lower bulk density.
  • This step is also called "post-foaming.”
  • This additional step is particularly used to take advantage of the transport and storage advantages of high bulk density particles, so that a required low bulk density can only be produced on demand
  • obtained expanded particles I further foam are known in the art and are described for example in EP 1 533 335 B1.
  • the polyolefin particles obtained in step (d), ie as expanded polyolefin particles I may optionally be provided with an antifogging agent prior to post-foaming. This is done in a preferred embodiment by coating. Typical bonding agents are also described in EP 1 533 335 B1.
  • the ratio of bulk density of the expanded particles I to the bulk density of the re-foamed expanded particles II, the so-called expansion factor is particularly preferably from 1.2 to 3.
  • the expanded polyolefin particles (expanded particles I or II) produced according to the invention generally have a cell count of 1 to 500 cells / mm 2 , preferably 2 to
  • the expanded particles I or II are generally at least approximately spherical and usually have a diameter of 0.2 to 20 mm, preferably 0.5 to 15 mm and in particular 1 to 12 mm. For non-spherical, z. As elongated or cylindrical particles, by diameter is meant the longest dimension.
  • the present application also relates to expanded particles, preparable and preferably produced by the process according to the invention.
  • the polyolefin particles may optionally after foaming, i. H. as expanded polyolefin particles I, which are obtained in step (d) and the expanded polyolefin particles II produced therefrom, are provided with an antistatic agent. This is done in a preferred embodiment by coating.
  • foams from the expanded polyolefin particles I or II, for example by welding them together in a closed mold under the action of heat.
  • the particles are filled into the mold and, after closing the mold, initiates water vapor or hot air, whereby the particles expand further and join together
  • Foam preferably with a density in the range of 8 to 300 kg / m 3 , welding.
  • the foams can be semi-finished products, such as plates, profiles or webs, or finished moldings with simple or complicated geometry. Accordingly, the term includes polyolefin foam, semifinished foam products and foam moldings.
  • a preferred method of making a foam molding comprising at least the steps
  • step (ii) foaming the foam particles of step (i) in a suitable mold to obtain a molded article.
  • initially expanded particles are prepared according to steps (a), (b), (c) and (d) as described above.
  • the particles II can additionally be produced from the expanded particles I by post-foaming. The statements made with respect to steps (a) to (d) therefore apply accordingly.
  • Step (ii) comprises foaming the expanded particles of step (i) in a corresponding mold to obtain a molded article.
  • step (ii) is carried out, for example, by heat-welding together the expanded particles obtained in step (i) in a closed mold.
  • the particles are preferably filled into the mold and, after closing the mold, initiates steam or hot air, whereby the particles expand further and together with each other to the molded part, preferably with a density in the range of 8 to
  • the ratio of the density of the molding to the bulk density of the expanded particles is generally> 1.1.
  • the moldings are obtained by methods known to the person skilled in the art, such as pressure filling or compression methods, the exchange edge method, or crack-gap method or after prior pressure loading. Corresponding methods are disclosed in DE-A 25 42 453 and EP-A-0 072 499.
  • the molding composition of the invention is characterized by excellent flame-retardant properties even at low levels, in particular together with organic phosphorus compounds. They are particularly suitable for injection-molded polyolefin molding compounds and for thin polyolefin films or polyolefin foams. These are used as film, packaging material, for thermal insulation, for building applications, as packaging or housing for fittings and systems in the field of heating, sanitation and ventilation, as a composite molding, in the automotive industry, in shipbuilding or in wind turbines. Examples
  • PP Moplen RP320M, polypropylene Random Copolymer from lyondellbasell having a density of 0.900 g / cc and a melt flow rate (MFR 230 ° C / 2.16 kg) of 8.0 g / 10 min.
  • Calcilite 1 G (calcium carbonate) from Alpha Calcite Gearstoff GmbH & Co: KG
  • FR1 Commercially available as Disflamoll® TP from Lanxess.
  • FR2 Commercially available as Fyrolflex® RDP from ICL-I P Europe BV.
  • FR3 Commercially available as Fyrolflex® BDP from ICL-I P Europe BV.
  • FR4 Synthesized according to WO201 1/083009 A1.
  • FR5 Commercially available as Aflammit PCO 900 (mp 245 ° C) from THOR GmbH.
  • FR6 Synthesized according to WO2010 / 063623 A1.
  • FR7 Synthesized according to WO2010 / 057851 A1.
  • FR8 Commercially available as Fyroflex® Sol-DP from ICL-I P Europe BV
  • FR9 Commercially available as Aflammit PCO 800 (white powder with particle size max.
  • FR10 Commercially available as Aflammit PCO 700 (white powder with particle size max.
  • the melting point was the temperature of the peak maximum in the second run.
  • the degree of compaction VG is the ratio of molding density (FT density) to bulk density (SD).
  • FT density molding density
  • SD bulk density
  • the flame retardancy of films or of multilayer film bodies was carried out in a small burner test analogous to DIN 4102.
  • the compound according to the invention or used as a comparative example in the form of a strand, granules or minigranules, on a hydraulic laboratory hand press PW 40 (Weber, 73630 Remshalden ) at 170 ° C to films with thicknesses of 100 - 150 ⁇ compressed.
  • the films were then formed into multilayer film balls with a diameter of about 5 cm.
  • the assessment of the fire behavior with a flame time of three seconds is carried out by the classification "burns down" or "self-extinguishing", with simultaneous documentation of the afterburning times (in seconds after the end of the flame treatment).
  • the flame resistance of the molding compositions was determined by the method UL94-V (Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", p. 14-18, Northbrook, 1996).
  • the flame retardancy of the foam moldings was determined by the UL94-HBF method (Underwriters Laboratories Inc Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pp. 28-33, Northbrook, 1996).
  • Polypropylene Moplen RP320M was melted in a DSM extruder (DSM Micro 15) and flame retardant (FR) and flame retardant synergist (S) at a melt temperature of 210 ° C for 5 min. homogeneously incorporated.
  • the type and amount of the flame retardant and synergist, in weight percent based on the flame-retardant polypropylene melt, are summarized in Table 3.
  • the polymer melt was then discharged as a strand and then pressed on a hydraulic lab hand press PW 40 (Weber, 73630 Remshalden) at 170 ° C to give films with thicknesses of 100-150 ⁇ .
  • the films were then formed into multilayer film balls with a diameter of about 5 cm.
  • the assessment of the fire behavior was carried out in a small burner test analogous to DIN 4102 with a flame time of three seconds with simultaneous documentation of the afterburning time in seconds after the end of the flame treatment). The results of the small burner test are summarized in Table
  • V10 - 2,0 S2 burns off /> 20
  • V1 1 - 5.0 S2 burns off /> 20
  • V12 - 2,5 S3 burns off /> 20
  • Polypropylene Moplen RP320M was melted in a DSM extruder (DSM Micro 15) and flame retardant (FR) and flame retardant synergist (S) at a melt temperature of 210 ° C for 5 min. homogeneously incorporated.
  • the type and amount of the flame retardant and synergist, in weight percent based on the flame-retardant polypropylene melt, are summarized in Table 4.
  • the polymer melt was then sprayed with a 10cc Injection Molding Machine (DSM) at a temperature of 210 ° C and a mold temperature of 60 ° C to UL94 firesticks of thickness 1, 6 mm.
  • DSM 10cc Injection Molding Machine
  • the minigrams MG1 - MG12 were used with a particle weight of about 1 mg, whose composition is described in Table 5.
  • the moldings were produced on a commercial EPP molding machine (type EHV-C-PP 870/670 from Erlenbach GmbH). It became with tools of dimensions
  • the moldings were stored at 80 ° C for 16 h.
  • Table 5 Composition of the minigranules MG1 - MG12, data in% by weight based on MW

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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 matière de moulage contenant a) 65 à 99,5 % en poids d'au moins une polyoléfine (p), b) 0 à 10 % en poids d'au moins un composé organophosphoré en tant qu'agent ignifuge (FR), c) 0,5 à 15 % en poids d'au moins un synergiste ignifuge (S) contenant du soufre, d) 0 à 10 % en poids d'un ou de plusieurs additifs (A), la somme des composants a) à d) étant égale à 100 % en poids, et la proportion de synergiste ignifuge (S) étant supérieure à 5 % en poids si la proportion d'agent ignifuge (FR) est inférieure à 1 % en poids. L'invention concerne également l'utilisation desdits mélanges pour la fabrication de pièces moulées, de films ou de mousses.
EP15724633.1A 2014-05-22 2015-05-22 Mélanges ignifuges sans halogène destinés à des mousses polyoléfines Withdrawn EP3145988A1 (fr)

Applications Claiming Priority (2)

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EP14169449 2014-05-22
PCT/EP2015/061405 WO2015177347A1 (fr) 2014-05-22 2015-05-22 Mélanges ignifuges sans halogène destinés à des mousses polyoléfines

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116355223A (zh) * 2023-04-06 2023-06-30 北京工商大学 一种无卤阻燃体型共聚大分子及其阻燃聚烯烃材料

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10316845A1 (de) * 2003-04-11 2004-11-11 Rehau Ag + Co. Polyolefinrohr
JP5161663B2 (ja) * 2008-06-12 2013-03-13 株式会社カネカ 難燃性ポリオレフィン系樹脂予備発泡粒子およびその型内発泡成形体
CN103415557B (zh) * 2010-12-27 2015-11-25 巴斯夫欧洲公司 阻燃体系
WO2013135701A1 (fr) * 2012-03-13 2013-09-19 Basf Se Synthèse de polyphénolbisulfures

Non-Patent Citations (2)

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Title
None *
See also references of WO2015177347A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116355223A (zh) * 2023-04-06 2023-06-30 北京工商大学 一种无卤阻燃体型共聚大分子及其阻燃聚烯烃材料
CN116355223B (zh) * 2023-04-06 2024-04-16 北京工商大学 一种无卤阻燃体型共聚大分子及其阻燃聚烯烃材料

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