WO2014060004A1 - Procédé de production de métal-hydroxydiphényl-2' -(thio)phosphinates et de métal-diphénylène-(thio)phosphonates, compositions les contenant et leur utilisation comme agents ignifuges - Google Patents

Procédé de production de métal-hydroxydiphényl-2' -(thio)phosphinates et de métal-diphénylène-(thio)phosphonates, compositions les contenant et leur utilisation comme agents ignifuges Download PDF

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WO2014060004A1
WO2014060004A1 PCT/EP2012/004330 EP2012004330W WO2014060004A1 WO 2014060004 A1 WO2014060004 A1 WO 2014060004A1 EP 2012004330 W EP2012004330 W EP 2012004330W WO 2014060004 A1 WO2014060004 A1 WO 2014060004A1
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metal
formula
oxide
composition according
melamine
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PCT/EP2012/004330
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German (de)
English (en)
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Wolfgang Wehner
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Wolfgang Wehner
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4841—Aromatic acids or derivatives (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the invention relates to a process for the preparation of metal (thio) phosphinates starting from (6H) -dibenz (c, e) (1,2) -oxaphosphorin-6-one / thione (oxide / sulfide) or from 10-hydroxy- 9,10-Dihydro-9-oxa-phosphaphenanthrene-10-oxide (on) or of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide / (thione) and
  • WPC wood plastic composites
  • 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1,2] oxaphosphorine-6-oxide) and its polymeric derivatives are indeed flame retardants in certain polyesters
  • 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide (6H-dibenz [c, e] [1, 2] oxa-phosphorin-6 oxide) or polymeric derivatives thereof are not readily processable or metered and necessary for processing
  • 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1,2] oxa-phosphorine-6-oxide) derivatives based on metal salts can remedy this situation.
  • Salts of diorganylphosphinic acids, in particular their alkali metal and alkaline earth metal salts, and their use as flame retardants for polyesters and polyamides are known, for example, from DE 225 2258 and DE 244 7727. Mixtures of these salts with nitrogen bases and their use as effective flame retardants are described, for example, in WO 97/39053.
  • Diorganylphosphinic acids especially since the Monoorganylphosphin Acid Acid, which still have a P-H bond, are expressly referred to as disadvantageous, because they because of their light
  • Oxidability are unstable and thereby lose their flame retardancy over time.
  • JP 2001-139586 discloses the use of the zinc and aluminum salts of 10-hydroxy-9,0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as flame retardants for organic polymers.
  • the synthesis of these two salts takes place by double reaction starting from sodium phosphonate and metal chloride or metal sulfate.
  • precipitates difficult to filter are obtained, which also have a high residual chloride content.
  • the process is also not environmentally friendly because wastewater ballast must be disposed of with a high salt load.
  • the starting phosphonic acid is only by oxidation with
  • the zinc salt is also obtainable by reacting zinc acetate (hydrate) in ethanol and 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (JP 53127484). This process is uneconomical, since the alcohol
  • JP2003-306585 describes magnesium-bis-2-hydroxydiphenyl-2 phosphinate 'and the Mg-salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as nucleating agents for polypropylene. A use as a flame retardant is not published.
  • JP07-330963 describes the same salts as transparency improver for
  • JP04-252245 describes barium bis (1'-hydroxy-2,2'-biphenylenephosphinate) in combination with inorganic fillers for use in polyolefins for improving the mechanical properties.
  • JP03-223354 also describes zinc bis (1'-hydroxy-2,2'-biphenylene phosphinate) in combination with inorganic fillers for the improvement of
  • EP 1 657 972 A1 discloses a reaction product which is obtained by double reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1, 2] oxa phosphoric-6-oxide) with NaOH / H 2 O with ZnC ⁇ .
  • the precipitation product thus obtained has the composition of zinc-bis-2-hydroxydiphenyl-2 '- phosphinate.
  • a homologous aluminum salt is also exemplified in this document.
  • This patent also discloses a combination of melamine polyphosphate and melamine cyanurate, respectively, prepared by the method described above
  • Zinc phosphinate described in relation to the burning behavior of polyamide.
  • step (b) optionally reacting the metal (thio) phosphinates of the formula (I) from step (a) in a cyclization reaction for the preparation of
  • Mt is selected from Cu, Ca, Mg, Zn, Mn, Fe, Al, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, W0 2 , VO, B, Si, La, Ti, Bi or Sb;
  • Mt is selected from Al, Ca, Cu, Mg, Zn or Zr.
  • Particular preference is given to a process which uses metal metal oxides CaO, MgO, ZnO as starting materials and Ca (OH) 2 , Mg (OH) 2 , Zn (OH) 2 and / or Al (OH) 3 as metal hydroxides.
  • ZnO and Ca (OH) 2 and Mg (OH) 2 are particularly preferred as starting materials.
  • starting materials in particular basic copper carbonate, basic magnesium carbonate, basic zinc carbonate, basic zirconium carbonate and basic aluminum carbonate.
  • Particularly preferred starting materials are basic magnesium carbonate (hydromagnesite) and basic zinc carbonate (hydrozincite).
  • mixtures of two or more of the abovementioned compounds can also be used as starting materials.
  • step (a) is preferably carried out in the aqueous phase, if appropriate in the presence of alcohols. Furthermore, step (a) is preferably carried out at a temperature of 20 to 90 ° C, more preferably at 30 to 70 ° C.
  • a granulation process can be followed by step (a). This may be preferred as spray agglomeration either in the spray dryer,
  • Spray granulator top spray or bottom spray, countercurrent process
  • Fluidized bed granulator or in a paddle mixer or horizontal dryer, wherein the introduced water is removed until the desired residual moisture is obtained.
  • the granulation can take place by spray-drying an aqueous suspension of a metal (thio) phosphinate of the formula (I) at 70-80 ° C. or alternatively as spray granulation starting from a
  • Eduktmischung and spraying water onto the fluidized bed and subsequent drying can be obtained.
  • the fluidized bed temperature is kept constant between 70-80 ° C, the granules dry at the same time and a free-flowing, non-dusting granules formed.
  • the residual water content is approx. 0.5 - 1%.
  • the preparation of metal phosphonates (III) in step (b) is preferably anhydrous by thermal cyclization of metal (thio) phosphinates (I). This can be done in a mixer or dryer, electric oven, rotary kiln or in one High-speed mixer to be performed. Particularly preferably, the cyclization is carried out in a vertical or horizontal paddle mixer.
  • the cyclization is typically carried out at 130 to 270 ° C, preferably at 170 to 220 ° C and more preferably at 180 to 200 ° C.
  • a flame retardant composition according to the invention has an improved flame retardancy in a variety compared to the individual components
  • synergistic compositions are used. These other components may be metal-containing or metal-free.
  • the present invention thus further relates to a composition
  • a composition comprising (i) a metal (thio) phosphonate of the formula (III), optionally in
  • synergistic components (ii-a) and (ii-b) of the composition according to the invention are shown below.
  • the other metal-containing component (ii-a) other than component (i) may in particular comprise metal hydroxide, metal phosphate, metal pyrophosphate, hydrotalcite, hydrocalumite, cationic or anionic modified organoclay, stannate salt or molybdate salt, metal borate or a metal phosphinate of formula (IV) .
  • R and R 2 are independently hydrogen, linear or branched CC 6 alkyl or phenyl, Mt 1 is Ca, Mg, Zn or Al and m is 2 or 3.
  • component (ii-a) are melamine metal phosphates such as
  • M 2 ZP 2 bis-melamine zinc diphosphate
  • M 2 AP 3 bis-melamine magnesium diphosphate
  • M 2 AP 3 bis-melamine aluminum triphosphate
  • component (ii) are azine metal phosphates of the general formula [I],
  • M is selected from Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO, ZrO, VO, B, Si, Al, Sb, La, Ti, Zr, Ce, Bi or Sn,
  • n 2 or 3
  • x and y are independently 0 or 1
  • p is an integer from 0 to 4.
  • z is an integer> 5,
  • hydrotalcite and hydrokalumite have, for example, the composition Mg 6 Al 2 (OH) i 6 CO 3 and Ca 1 OH 2 CO 3 .
  • Organoclays are understood as meaning organophilically modified clay minerals (mainly montmorillonites) based on cation exchange, such as triethanol-tallow-ammonium-montmorillonite and triethanol-tallow-ammonium-hectorite, as described in Dr. med. G. Beyer; Conf. Fire Resistance in Plastics, 2007.
  • Anionic organoclays are preferably organophil-modified hydrotalcites based on anion exchange with alkali metal roosinates, unsaturated and saturated fatty acid salts and long-chain alkyl-substituted sulfonates and sulfates.
  • Metal oxides are preferably selected from diantimony trioxide, diantimony tetroxide, diantimony pentoxide, zinc oxide or mixtures thereof.
  • metal phosphate metal pyrophosphates are preferred. Particularly preferred are aluminum and zinc pyrophosphate, zinc and aluminum triphosphate, aluminum and zinc metaphosphate, aluminum and zinc orthophosphate or mixtures thereof.
  • the alkyl sulfate or fatty acid carboxylate-modified hydrotalcites or long-chain quaternary ammonium-modified clay minerals are particularly preferred.
  • Aluminum trihydroxide ATH, gibbsite
  • aluminum monohydroxide boehmite
  • hydromagnesite and hydrozincite hydromagnesite and hydrozincite.
  • gibbsite and boehmite the other modifications of aluminum hydroxides, namely bayerite, nordstrandite and diaspore are also mentioned.
  • Zinkhydroxystannat or mixtures thereof also act as
  • metal borates alkali, alkaline earth or zinc borate are preferred. Also to be mentioned are aluminum borate, barium borate, calcium borate,
  • Metal phosphinates are preferably salts in which Mt is selected from Ca, Mg, Zn or Al.
  • Preferred metal phosphinates are phenylphosphinate diethyl (methyl, ethyl) phosphinate, especially in combination with the aforementioned metals.
  • the Mg, Ca, Zn and Al salts are particularly preferred.
  • Composition includes in particular red phosphorus, oligomeric
  • Phosphate esters oligomeric phosphonate esters, cyclic phosphonate esters,
  • Thiopyrophosphoric acid ester melamine orthophosphate or melamine pyrophosphate, di- Melamine phosphate, melamine polyphosphate, melam (polyphosphate), and, Meiern and Diguanidinphosphat, Melaminphenylphosphinat, monomeric, oligomeric and polymeric Melaminphenylphosphonat, ammonium polyphosphate, melamine phenylphosphonate and its half ester salt, as in WO 2010/063623
  • melaminebenzene phosphinate as described in WO 2010/057851, hydroxyalkyl-phosphine oxides, as described in WO 2009/034023, tetrakis-hydroxymethyl-phosphonium salts and phospholane (oxide) - or phosphole derivatives and bisphosphoramidates with piperazine as a bridge member or a phosphinate ester, the substance class of NOR-HALS compounds (non-basic aminoether hindered amine light stabilizer) and mixtures thereof.
  • NOR-HALS compounds non-basic aminoether hindered amine light stabilizer
  • oligomeric phosphate esters are phosphate esters of formula (VI) or formula (VII),
  • y is 0 or 2.
  • Particularly preferred is bis [5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-ate) methyl] methyl phosphonate P, P ' dioxide.
  • hydroxyalkyl-phosphine oxides preference is given to isobutyl-bis-hydroxymethyl-phosphine oxide and its combination with epoxy resins, as in WO-A
  • the tetrakis-hydroxyalkyl phosphonium salts are particularly preferred.
  • the bis-di-ortho-xylylester are particularly preferred with piperazine as a bridge member.
  • phosphinate esters such as
  • Benzene monophenyl ester derivatives or phosphaphenanthrene derivatives for example, 9,10-dihydro-9-0xa-10-phosphaphenanthrene-10-oxide or 6H-dibenzo (c, e) (1,2) -oxa-hosphorin-6-one) derivatives, such as shown in the following formulas.
  • dihydro-oxa-phospha-anthracene can also be used oxide (on) can be used. An overview of this can be found in WO-A 2008/1 19693.
  • R ' CH 3 , nC 4 H 9 , or cC 6 Hn
  • polyols polyols, aminouracils, POSS compounds, trishydroxyethyl isocyanurate, melamine cyanurate, expandable graphite or mixtures thereof.
  • POSS compounds polyhedral oligomeric silsesquioxanes
  • POSS derivatives based on methylsiloxane.
  • Triazine polymers having piperazine-1,4-diyl bridge members and morpholine-1-yl end groups may be included in the flame retardants of the present invention.
  • the following additives may be present in the flame retardants of the present invention: bis-azine pentaerythritol diphosphate salts, hexa-aryloxy triphosphazenes, polyaryloxy phosphazenes and siloxanes, for example of the general formula (R 2 SiO) r or (RSiO-i, 5 ) r.
  • mixtures of two or more of the compounds described above may also be present in the compositions of the present invention.
  • Particularly preferred are the following combinations.
  • MZP or MAP 2 (melamine zinc phosphate / melamine aluminum diphosphate)
  • M 2 ZP 2 or M 2 AP 3 (Dimelamin-zinc diphosphate / Dimelamin-aluminum triphosphate) and Mg (2 '-hydroxy [1, 1' -biphenyl-2-yl-2-phosphinate) 2, Zn (2 '-hydroxy [1, 1' -biphenyl-2-yl-2-phosphinate) 2,
  • MZP or MAP 2 (melamine zinc phosphate / melamine aluminum diphosphate)
  • M 2 ZP 2 or M 2 AP 3 (dimelamine zinc diphosphate / dimelamine aluminum triphosphate)
  • MZP or MAP 2 melamine-zinc phosphate / melamine Aluminiumdiphosphat
  • Mg 2 '-hydroxy [, 1' -biphenyl-2-yl-2-phosphinate
  • M 2 ZP 2 or M 2 AP 3 (Dimelamin-zinc diphosphate / Dimelamin-aluminum triphosphate) and Mg (2 '-hydroxy [1, 1' -biphenyl-2-yl-2-phosphinate) 2,
  • MZP or MAP 2 (melamine zinc phosphate / melamine aluminum diphosphate) and Mg (2 '-hydroxy [1, 1' -biphenyl-2-yl-2-phosphinate) 2
  • M 2 ZP 2 or M 2 AP 3 (Dimelamin-zinc diphosphate / Dimelamin-Aluminiumtripho ⁇ and Mg (2 '-hydroxy [, 1' -biphenyl-2-yl-2-phosphinate) 2,
  • a particular embodiment of the invention relates to the use of the compositions described above, which -phosphinates inventive metal-2-hydroxydiphenyl-2, 'and the metal phosphonates prepared therefrom by cyclization contained in a polymer as a flame retardant.
  • the present invention thus further relates to compositions, as described above, which additionally contain a polymer or a polymer mixture.
  • the composition described above comprising component (i), (ii-a) and / or (ii-b) is first prepared and this composition incorporated into the polymer or the polymer mixture.
  • the invention also relates to a process for the preparation of flame-retardant polymer molding compositions, characterized in that the stabilized flame retardants according to the invention are homogenized with the polymer granules and any additives in a compounding unit at higher temperatures in the polymer melt and then the homogenized polymer strand is withdrawn, cooled and portioned.
  • the resulting granules are e.g. dried at 90 ° C in a convection oven.
  • the compounding unit preferably comes from the group of single-screw extruders, multizone screws or twin-screw extruders.
  • Compounding units are single-screw extruders or single-screw extruders, e.g. the company Berstorff GmbH, Hannover and or the company Leistritz, Nuremberg,
  • Short-Compression Screws Ko-Kneader eg Fa.
  • Planetary roller extruder e.g. Entex, Bochum and / or degassing extruders and / or cascade extruders and / or Maillefer screws; Compounder with counter-rotating twin screw e.g. Complex 37- or -70-types of the company Krauss-Maffei Berstorff.
  • the polymer is typically a thermoplastic, which is preferably selected from the group consisting of polyamide, polycarbonate, polyolefin, polystyrene, polyester, polyvinyl chloride, polyvinyl alcohol, ABS and polyurethane, or a
  • Duroplast is, which is preferably selected from the group consisting of epoxy resin (with hardener), phenolic resin and melamine resin.
  • thermosets and / or thermosets, in which the azine-metal phosphate according to the invention is used as flame retardant.
  • Polymers of mono- and diolefins e.g. Polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyvinylcyclohexane, polyisoprene or
  • Polybutadiene and polymers of cycloolefins e.g. of cyclopentene or norbornene and polyethylene (also cross-linked), e.g. High Density Polyethylene (HDPE) or High Molecular Weight (HDPE-HMW), High Density Polyethylene with Ultra-High Molecular Weight (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE) and Linear Low Density Polyethylene ( LLDPE), (VLDPE) and (ULDPE) as well as copolymers of ethylene and vinyl acetate (EVA);
  • HDPE High Density Polyethylene
  • HDPE-HMW High Molecular Weight
  • HDPE-UHMW High Density Polyethylene with Ultra-High Molecular Weight
  • MDPE Medium Density Polyethylene
  • LDPE Low Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • VLDPE Linear Low Density Polyethylene
  • ULDPE Linear Low Density
  • Polystyrenes poly (p-methylstyrene), poly ( ⁇ -methylstyrene);
  • Polybutadiene and (meth) acrylonitrile such as ABS and MBS
  • Halogen-containing polymers for example polychloroprene, polyvinyl chloride (PVC);
  • PVDC Polyvinylidene chloride
  • Vinyl chloride / vinyl acetate or vinyl chloride / vinyl acetate Vinyl chloride / vinyl acetate.
  • PMMA polymethyl methacrylates
  • PAN polyacrylonitrile
  • Polymers of unsaturated alcohols and amines or their Azylderivaten or acetals such.
  • Polyvinyl alcohol (PVA) polyvinyl acetates, stearates, benzoates or maleates, polyvinyl butyral, polyallyl phthalates and polyallyl melamines;
  • cyclic ethers such as polyalkylene glycols, polyethylene oxides, polypropylene oxides and their copolymers with bisglycidyl ethers;
  • Polyacetals such as polyoxymethylene (POM) and polyurethane and acrylate modified polyacetals;
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams e.g. Polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylylenediamine and adipic acid and copolyamides modified with EPDM or ABS.
  • Copolyamides are derived from ⁇ -caprolactam, adipic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, hexamethylenediamine,
  • Tetramethylenediamine 2-methyl-pentamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, m-xylylenediamine or bis (3-methyl-4-aminocyclohexyl) methane;
  • Polyureas polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
  • Hydroxycarboxylic acids or the corresponding lactones e.g.
  • Polyhydroxybenzoates polylactic acid esters and polyglycolic acid esters
  • polyketones Mixtures or alloys of above-mentioned polymers, eg PP / EPDM, PA / EPDM or ABS, PVC / EVA, PVC / ABS, PBC / MBS, PC / ABS, PBTP / ABS, PC / AS, PC / PBT, PVC / CPE, PVC / Acrylate, POM / Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and Copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC, as well as TPE-O, TPE-S and TPE-E;
  • Thermosets such as PF, MF or UF or mixtures thereof;
  • Wood-plastic composites as well as polymers based on PLA, PHB and starch.
  • PA Preference is given to PA, PET, PBT, PUR, PC and epoxy resins. Particularly preferred are glass fiber reinforced PA and PBT.
  • the concentration of the flame retardant preparations according to the invention consisting of metal (thio) phosphinate or metal (thio) phosphonate (i) and the additional metal-containing component (ii-a) and / or the metal-free component (ii-b) is preferably in a polymer or a polymer mixture 0.1 to 60 wt .-%, based on the polymer or the polymer mixture.
  • Component ratio in the composition consisting of component (i) to the co-components (ii-a) and / or (ii-b) is preferably in the range of 1: 1 to 1: 4.
  • Polymer material according to the invention further contain fillers, which are preferably selected from the group consisting of metal hydroxides and / or
  • Metal oxides preferably alkaline earth metal hydroxides, for example
  • Minerals such as wollastonite, silica such as quartz, mica, feldspar and titanium dioxide, alkaline earth metal silicates and alkali metal silicates, carbonates,
  • fillers can impart further desired properties to the polymer material of the invention.
  • a filler preferably calcium carbonate and talc, clay, mica, silica, calcium sulfate, barium sulfate, pyrite, glass fiber, glass beads, glass particles and glass beads, wood flour, cellulose powder, carbon black, graphite, chalk and pigments.
  • the mechanical stability can be increased or dyed by adding dyes to the plastic.
  • the polymer materials may contain further additives, such as antioxidants, light stabilizers, process auxiliaries,
  • Viscosity improvers impact modifiers and in particular compatibilizers and dispersants.
  • foaming agents can be added to the polymer in addition to the azine metal phosphate of the present invention.
  • Foaming agents are preferably melamine, melamine-formaldehyde resins, urea derivatives such as urea, thiourea, guanamine, benzoguanamine, acetoguanamine and succinylguanamine, dicyandiamide, guanidine and guanidine sulfamate and also other guanidine salts or allantoins and glycolurils.
  • a polymer containing the azine metal phosphate according to the invention may also comprise antidripping agents, in particular
  • Polytetrafluoroethylene base included.
  • concentration of such anti-dripping agents is preferably 0.01 to 15 wt .-%, based on the processed
  • Example 1 shows that the conductivity of the product according to the invention is lower by a factor of 4.7 and is therefore more suitable in electronic applications.
  • Example 3B Spray Method
  • the drying can be carried out by spraying.
  • the nutschfeuchte filter cake is suspended in water and the resulting slurry dried by spray granulation at 70-80 ° C.
  • Magnesium and calcium salts of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were prepared similarly as in Example 7, but starting from magnesium hydroxide or calcium hydroxide (mp> 300 ° C ).
  • Example 13 (Use as flame retardant in PA)
  • PA 6.6 (Durethan A30S, LANXESS); Glass fiber (Thermo Flow ® 671; 10 mx4mm; Fa John Manville.); MPP melamine polyphosphate (Melapur 200; BASF.), (2 '-hydroxy [1, 1' -biphenyl-2-yl-2-phosphinate) 2 Zn (Example 3), Dimelamin- zinc diphosphate (own product).

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Abstract

L'invention concerne un procédé de production de métal-2-Hydroxydiphényl-2'-(Thio)phosphinates de formule (I), à partir de (6H)-Dibenz(c,e)(1,2)-oxaphosphorin-6-on(thion) (II) et de métal(hydr)oxydes ou de carbonates métalliques (basiques), et de métal(Thio)phosphonats (III) obtenus par cyclisation à partir des précédents, Mt = Cu, Ca, Mg, Zn, Mn, Fe, AI, Co, Ni, Sn, Zr, TiO, ZrO, Ce, MoO, W02, VO, B, Si, La, Ti, Bi oder Sb X = H ou OH, Y = O ou S et n = 2 ou 3, ainsi que leurs compositions et l'utilisation desdites compositions comme agents ignifuges pour des polymères, du papier, des textiles ou des composites bois-plastique (CPC).
PCT/EP2012/004330 2012-10-16 2012-10-16 Procédé de production de métal-hydroxydiphényl-2' -(thio)phosphinates et de métal-diphénylène-(thio)phosphonates, compositions les contenant et leur utilisation comme agents ignifuges WO2014060004A1 (fr)

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Cited By (9)

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DE102015009598A1 (de) 2015-07-24 2017-01-26 Trupti Dave-Wehner Verfahren zur Herstellung eines halogenfreien Flammschutzmittels
CN106496975A (zh) * 2016-09-29 2017-03-15 中国科学院宁波材料技术与工程研究所 一种聚乳酸/淀粉膨胀阻燃复合材料及其制备方法
CN108681173A (zh) * 2018-05-15 2018-10-19 希腊布莱特公司 具有快速开关特性的电致变色安全玻璃系统
CN112409693A (zh) * 2020-11-26 2021-02-26 浙江旭森非卤消烟阻燃剂有限公司 具有良好阻燃和加工性能的无卤阻燃剂及阻燃树脂组合物
WO2021048155A1 (fr) * 2019-09-11 2021-03-18 Clariant International Ltd Composition ignifuge, composition de moulage polymère la comprenant et son utilisation
WO2021048156A1 (fr) * 2019-09-11 2021-03-18 Clariant International Ltd Composition polymère comprenant un stabilisateur thermique et son utilisation
CN112625340A (zh) * 2020-12-01 2021-04-09 张家港优全汽配有限公司 一种纤维增强聚丙烯复合材料、制备方法及其应用
CN115322439A (zh) * 2022-05-18 2022-11-11 沈阳工业大学 利用水镁石制备的用于环氧树脂的复配阻燃剂的制备方法
EP3714020B1 (fr) * 2017-11-24 2023-09-06 Tesa Se Fabrication d'une masse autoadhésive à base de caoutchouc acrylonitrile-butadiène

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015009598A1 (de) 2015-07-24 2017-01-26 Trupti Dave-Wehner Verfahren zur Herstellung eines halogenfreien Flammschutzmittels
CN106496975A (zh) * 2016-09-29 2017-03-15 中国科学院宁波材料技术与工程研究所 一种聚乳酸/淀粉膨胀阻燃复合材料及其制备方法
EP3714020B1 (fr) * 2017-11-24 2023-09-06 Tesa Se Fabrication d'une masse autoadhésive à base de caoutchouc acrylonitrile-butadiène
CN108681173A (zh) * 2018-05-15 2018-10-19 希腊布莱特公司 具有快速开关特性的电致变色安全玻璃系统
CN114364729B (zh) * 2019-09-11 2023-09-29 科莱恩国际有限公司 阻燃剂组合物，包含它的聚合物模塑组合物及其用途
WO2021048155A1 (fr) * 2019-09-11 2021-03-18 Clariant International Ltd Composition ignifuge, composition de moulage polymère la comprenant et son utilisation
WO2021048156A1 (fr) * 2019-09-11 2021-03-18 Clariant International Ltd Composition polymère comprenant un stabilisateur thermique et son utilisation
CN114364729A (zh) * 2019-09-11 2022-04-15 科莱恩国际有限公司 阻燃剂组合物，包含它的聚合物模塑组合物及其用途
CN112409693B (zh) * 2020-11-26 2023-05-09 浙江旭森阻燃剂股份有限公司 具有良好阻燃和加工性能的无卤阻燃剂及阻燃树脂组合物
CN112409693A (zh) * 2020-11-26 2021-02-26 浙江旭森非卤消烟阻燃剂有限公司 具有良好阻燃和加工性能的无卤阻燃剂及阻燃树脂组合物
CN112625340A (zh) * 2020-12-01 2021-04-09 张家港优全汽配有限公司 一种纤维增强聚丙烯复合材料、制备方法及其应用
CN115322439A (zh) * 2022-05-18 2022-11-11 沈阳工业大学 利用水镁石制备的用于环氧树脂的复配阻燃剂的制备方法
CN115322439B (zh) * 2022-05-18 2023-06-16 沈阳工业大学 利用水镁石制备的用于环氧树脂的复配阻燃剂的制备方法

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