Classifications

• • 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
• • 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
  • C09K21/14—Macromolecular materials
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
  • C07D251/56—Preparation of melamine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
  • C07D251/70—Other substituted melamines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
  • C07D487/16—Peri-condensed 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
  • C07F9/547—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
  • C07F9/657172—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 one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
  • C08G79/04—Phosphorus linked to oxygen or to oxygen and 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • 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
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • 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
  • C08K5/5205—Salts of P-acids with N-bases
• • 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'

Definitions

• the present invention relates to flame retardant compositions containing triazine-intercalated metal phosphates with open framework structures (open framework), their use, such metal phosphates and their preparation.
• organophilic layer silicates which have been prepared, for example, by ion exchange, as filling materials for thermoplastic materials and for thermosets, whereby nanocomposites are obtained.
• suitable organophilic layer silicates as fillers, the physical and mechanical properties of the moldings produced in this way are considerably improved.
• the increase in stiffness with at least constant toughness is particularly good.
• nanocomposites which contain the layered silicate in exfoliated form. These nanocomposites are preferably used as flame retardants or as synergists.
• organophilic sheet silicates are known, which are prepared by treating a natural or synthetic sheet silicate or a mixture of such silicates, with a salt of a - optionally quaternary - cyclic melamine compound or a mixture of such salts.
• melamine-metal phosphates are described in WO-A 2009/015772. However, these compounds have - as shown on the aluminum compound - only a limited (thermal) intrinsic stability, which is not sufficient for incorporation into polyamides (see Examples 7 and 8).
• Melamine-intercalated zirconium (layer) phosphates are known from Solid State Sciences 2009, H, 1007-1015. The use as plastic additives, especially as flame retardants is not described herein. Other melamine-intercalated (metal) layer phosphates are not documented in the literature.
• Ethylenediamine bis-zinc phosphate is claimed in US 5994435 and US 6207735 as a flame retardant.
• JP 8269230 describes amine zinc phosphate which also comprises the anions HP0 4 , H 2 P0 4 , Zn 2 (HPO 4 ) 3 and Zn 4 [(P0 4 ) 2 (HPO 4 ) 2 ].
• JP9040686, JP10259275, JP11152373, JP11199708, JP11246754, JP11269187, JP11293155, JP2000063562, JP2000063563, JP2000154283, JP2000154287, JP2000154324 and JP2001031408 describe processes for the preparation of specific applications as well as combinations of ethylenediamine zinc phosphate. However, the processes are uneconomical because they either work with H 3 P0 4 excess or emanate from Zn (en) 3 complexes.
• JP9169784 and JP2001011462 publish diethylenetriamine or piperazine zinc phosphate complexes as flame retardants.
• Inorganic phosphates with open framework structures are described in an article in Angew. Chem. 1999, 1 ⁇ , 3466-3492.
• a disadvantage of the compounds of the prior art mentioned are the limited (thermal) intrinsic stability and the unfavorable mechanical properties resulting after incorporation into the polymer substrate.
• the object is to provide flame retardant compositions which have a high degree of (thermal) intrinsic stability and impart excellent mechanical properties to the polymer after incorporation.
• each M is independently Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO, ZrO, VO, B, Si, Al, Sb, La, Ti, Zr, Ce or Sn; a 1 to 6,
• the flame retardant compositions comprising the triazine-intercalated metal phosphates (a) of the formula (I) have open framework structures.
• the triazine derivatives like melon, are known as chemical precursors for carbon nitride (C 3 N 4 ) X.
• Triazine-intercalated metal phosphates especially with open framework structures, which are preferably prepared by direct reaction of (aqueous) acidic metal phosphates with melamine and subsequent annealing from the corresponding (precursor) precursor stages, show a high thermal stability during processing combined with excellent Dispersing action and interfacial adhesion. These systems are characterized by surprisingly good layer separation, combined with excellent adhesion to a variety of polymers and fillers. It is furthermore surprising that the triazine-intercalated metal phosphates according to the invention with open framework structures are not only excellent fillers for improving the mechanical properties of polymers, but also act as flame retardants.
• the triazine-intercalated (metal) phosphates with open framework structures can also be made of chain (band) phosphates (catena-type), leaf phosphates (ladder or phyllo type - all with 1-D structures), layered phosphates - with 2-D structures) or 3-D-phosphates (zeolite type).
• component (b) is at least one metal compound which is not
• Metal phosphate of component (a) is or / and at least one metal-free
• This at least one metal compound (b) is preferably a metal oxide, a metal hydroxide, a metal phosphate, a metal pyrophosphate, a hydrotalcite, a cationically or anionically modified organoclay, a stannate or molybdate salt, a metal borate or metal phosphinate of the formula (III):
• Organoclays are understood to mean organophilically modified clay minerals (mainly montmorillonites) based on cation exchange such as triethanol tallow ammonium montmorillonite and triethanol tallow ammonium hectorite (Dr. G. Beyer, Confederation Fire Resistance in Plastics 2007).
• Anionic organoclays are organophilic-modified hydrotalcites based on anion exchange with alkali metal soaps, unsaturated and saturated fatty acid salts, and long-chain alkyl-substituted sulfonates and sulfates.
• the metal oxide is di-antimony trioxide, diantimony tetroxide, diantimony pentoxide or zinc oxide.
• Aluminum hydroxide (ATH) or gibbsite (hydrargillite), aluminum oxohydroxide (boehmite) and magnesium hydroxide (MDH, brucite) and hydromagnesite are particularly preferred as the metal hydroxide.
• gibbsite and boehmite the other modifications of aluminum hydroxides, namely bayerite, nordstrandite and diaspore are also to be cited.
• metal pyrophosphates are preferred. Particularly preferred are aluminum and zinc pyrophosphate and zinc and aluminum triphosphate as well as aluminum metaphosphate and aluminum orthophosphate.
• Preferred hydrotalcite are magnesium aluminum and calcium aluminum hydroxocarbonate.
• the alkyl sulfate or fatty acid carboxylate-modified hydrotalcites or long-chain quaternary ammonium-modified clay minerals are particularly preferred.
• stannate and molybdate salts zinc stannate, zinc hydroxystannate, ammonium heptamolybdate and ammonium cate molybdate are particularly preferred.
• other molybdates also polymolybdates
• calcium zinc molybdate, basic zinc molybdate and calcium molybdate such as calcium zinc molybdate, basic zinc molybdate and calcium molybdate.
• borates are preferred alkali and Erdalkaliborate and zinc borate. Furthermore, lead to aluminum borate, barium borate, calcium borate, magnesium borate, manganese borate, melamine borate, potassium borate and zinc boron phosphate.
• metal phosphinates are preferably Ca, Mg, Zn or Al phosphinates. Particularly preferred are Ca, Mg, Zn or Al-phenyl (benzene) phosphinate and Ca, Mg, Zn or Al diethyl (ethane) phosphinate.
• hypophosphites particularly preferred are the Mg, Ca, Zn and Al salts.
• a further preference of the invention relates to flame retardant compositions comprising as component (b) at least one metal-free phosphorus compound.
• This at least one metal-free phosphorus compound (b) is red phosphorus, an oligomeric phosphate ester, an oligomeric phosphonate ester, a cyclic phosphonate ester, a thiopyrophosphoric acid ester, melamine pyrophosphate, melamine polyphosphate,
• Ammonium polyphosphate, melamine-phenylphosphonate and its half-salt (WO2010 / 063623), melamine-benzenephosphinate (WO2010 / 057851), hydroxyalkyl phosphine oxides (WO2009 / 034023), tetrakis-hydroxymethyl-phosphonium salts and phospholane or phosphole derivatives and bisphosphoramidates with piperazine as
• Oligomeric phosphate esters have formula (IV) or formula (V):
• Gomeric phosphonate esters are preferably characterized by formula (VI):
• R 3 methyl or phenyl and x is 1-20 and R, n is the one given above
• Cyclic phosphonate esters preferably have the following formula (VII):
• Thiopyrophosphoric acid esters are preferably represented by the following formula (VIII)
• hydroxyalkyl-phosphine oxides are preferably isobutyl-bis-hydroxymethyl-phosphine oxide and its combination with epoxy resins (WO-A 2009/034023).
• the tetrakis-hydroxymethyl phosphonium salts are particularly preferred.
• dihydrophosphole (oxide) derivatives and phospholane (oxide) derivatives and their salts are particularly preferred.
• Bisphosphoramichal particularly preferred among the Bisphosphoramilves are the bis-di-ortho-xylylester with piperazine as a bridge member.
• phosphonite esters preferred are benzene-phosphinic acid phenyl esters and their PH-functionalized derivatives and DOPO derivatives.
• DOPO derivatives 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives or 6H-dibenzo (c, e) (l, 2) -oxaphosphorine-6-oxide) derivatives (wherein PH -functionalized derivatives are preferred)
• DOPO derivatives 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives or 6H-dibenzo (c, e) (l, 2) -oxaphosphorine-6-oxide) derivatives (wherein PH -functionalized derivatives are preferred)
• the following compounds are structurally represented (see WO-A 2008/119693): ⁇
• Dihydro-oxa-phospha-anthracene oxide (on) can also replace DOPO.
• An overview of this can be taken from WO-A 2008/119693.
• additives include: polyols, aminouracils, tris-hydroxyethyl isocyanurate (THEIC), melamine (iso) cyanurate, POS S compounds and expandable graphite.
• pentaerythritol dipentaerythritol and tripentaerythritol are particularly preferred.
• aminouracils 1-methyl-6-aminouracil and 1,3-dimethyl-6-aminouracil are particularly preferred.
• POSS Polyhedral Oligomeric Silsesquioxanes
• tris-hydroxyethyl isocyanurate polyterephthalate and triazine polymers with piperazine-1,4-diyl-B backlinker and morpholin-l-yl end groups may be present.
• additives may be present: Bis-Azinpentaerythritdiphosphat- salts, hexa-aryloxy-triphosphazene, poly-aryloxy-phosphazenes and siloxanes (R 2 SiO) r or (RSi0 1> 5 ) r .
• Metal oxides such as titanium dioxide, silicon dioxide; Clay minerals such as kaolinite, muscovite, pyrophyllite, bentonite and talc or other minerals such as wollastonite, quartz, mica, feldspar. Furthermore, dolomite, bentonite, huntite, or silicic acids and their natural or synthetic silicate minerals may additionally be present in the polymer.
• foaming agents may be added to a polymer in addition to the at least one metal phosphate of the present invention.
• the foaming agents which may be mentioned are: melamine, melamine-formaldehyde resins, urea derivatives such as urea, thiourea, guanamine, benzoguanamine, acetoguanamine and succinylguanamine, dicyandiamide, Guanidine and guanidine sulfamate as well as other guanidine salts or allantoins and glycolurils.
• a polymer containing the at least one metal phosphate according to the invention may also contain antidripping agents, in particular based on polytetrafluoroethylene.
• concentration of such Antidrippingstoff is 0.01 to 15 wt .-% based on the polymer to be processed.
• polymers containing the at least one metal phosphate of the present invention may also be added with further components, e.g. Fillers and reinforcing agents, such as glass fibers, glass beads or mineral additives such as chalk.
• Fillers and reinforcing agents such as glass fibers, glass beads or mineral additives such as chalk.
• antioxidants, light stabilizers, lubricants, pigments, nucleating agents and antistatic agents can function.
• the present invention also relates to the use of the triazine-intercalated metal phosphates according to the invention with open framework structures as flame retardants in a polymer, paper, textiles or wood plastic composites (WPC).
• the flame retardants according to the invention are best suited for imparting flame retardancy to synthetic polymers, in particular thermoplastic polymers.
• a particular embodiment of the invention relates to the use of the at least one metal phosphate according to the invention in a polymer as flame retardant, wherein the polymer is 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 thermosetting resin, which is preferably selected from the group consisting of epoxy resin (with hardener), phenolic resin and melamine resin.
• the polymer in which the at least one metal phosphate according to the invention is used as flame retardant is a thermoplastic, polyamide, polyurethane, polystyrene, polyolefin or polyester is preferred. If the polymer in which the at least one metal phosphate according to the invention is used as the flameproofing agent is a thermoset epoxy resin is preferred. It is also possible to use mixtures of one or more polymers, in particular thermosets and / or thermosets, in which the metal phosphate according to the invention is used as flame retardant.
• Polymers of monoolefins 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 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
• EVA ethylene and vinyl acetate
• Halogen-containing polymers e.g. Polychloroprene, polyvinyl chloride (PVC);
• PVDC Polyvinylidene chloride
• Acetals e.g. Polyvinyl alcohol (PVA), polyvinyl acetates, stearates, benzoates or maleates, polyvinyl butyral, polyallyl phthalates and polyallyl melamines;
• PVA Polyvinyl alcohol
• polyacetals such as polyoxymethylene (POM) as well as polyurethane and acrylate modified polyacetals;
• polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams such as 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.
• polyamides and 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;
• polyesters derived from dicarboxylic acids and dialcohols and / or hydroxy carboxylic acids or the corresponding lactones such as e.g. Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, polylactic acid esters and polyglycolic acid esters;
• thermosets such as PF, MF or UF or mixtures thereof;
• WPC Wood-plastic composites
• the concentration of the at least one claimed triazine-intercalated metal phosphate (a) and component (b) in a polymer or a polymer mixture is preferably from 0.1 to 60% by weight, based on the polymer to be processed.
• the flameproofed material by adding the at least one metal phosphate according to the invention can be processed into fibers, films, cast articles and used for the treatment of surfaces.
• the at least one metal phosphate according to the invention can also be used for the surface treatment (impregnation) of fibers, films, textiles or other technical materials.
• the present invention relates to the use of a composition according to the invention in a flame retardant in a polymer, paper, textiles or wood plastic composites (WPC).
• the polymer is a thermoplastic, preferably selected from the group consisting of polyamide, polycarbonate, polyolefin, polystyrene, polyester, polyvinyl chloride, polyvinyl alcohol, ABS and polyurethane, or a duroplastic, preferably selected from the group consisting of epoxy resin, phenolic resin and melamine resin.
• the present invention further relates to the use of the triazine-intercalated metal phosphates according to the invention with open framework structures for the preparation of paints, adhesives, casting resins, coatings, thixotropic agents and flame retardants for polymers.
• the present invention relates to the use of the at least one metal phosphate according to the invention as a filler in polymers.
• a further subject of the present invention relates to compounds of the general formula (I)
• xi 0 or 1
• x 2 0 or 2
• x 3 1 or
• y 2 or 0
• Another object of the present invention is a process for preparing the metal phosphate according to the invention, wherein a substance (A) with an acidic metal phosphate of the formula H a (+) [M b m + (H 2 P0 4 ) x i ( ) (HP0 4 ) x2 2 (") (P0 4 ) x3 3 (") (P0 3 ) y (") ] (a") * pH 2 0.
• the invention relates to a process for the preparation of the above-mentioned compounds comprising the step
• Another object of the present invention is a compound obtainable by the method according to the invention described above.
• such compounds are characterized in that the gross composition is a melamine-aluminum phosphate [(melamine-H) 2 + [ ⁇ 1 ⁇ 3 ⁇ ] 2 ()) ] ⁇ , the following 3 -M-MAS-NMR shifts ( ⁇ - Values): -10.6ppm, -22.0ppm, -24.5ppm, and -27.6ppm, and a single shift of 40ppm in the 27 AI NMR spectrum.
• the gross composition is a melamine-zinc phosphate [(melamine-H) 2 + [ ⁇ 2 ⁇ 7] 2 (_) ] ⁇ with the following 3 ⁇ -MAS NMR shifts ( ⁇ values): + 6.2 ppm, + 3.7ppm, + 2.0ppm, -2.5ppm, -5.5ppm, -8.2ppm, -10.7ppm, -12, lppm, -22.2ppm and -24.7ppm.
• the respective metal phosphate may e.g. by premixing in the form of powder and / or granules in a blender and then by homogenizing in a polymer melt by compounding (inter alia in a twin-screw extruder).
• the metal phosphate may also be added directly during processing.
• condensed phosphates such as triphosphates or pyrophosphates of the formulas H 2 AlP 3 Oio and H 2 ZnP 2 0 7 in question.
• pyrophosphate or triphosphate as Complex ligands
• the triazine-intercalated metal phosphates according to the invention are incorporated into a suitable polymer matrix.
• suitable polymers which can be used as substrate are known per se.
• Preferred for incorporation are thermoplastic polymers and thermoset polymer systems, rubbers and textiles.
• Melamine is preferred as an intercalate.
• novel intercalates can be represented as follows, where (A - H) (+) (Mel-H) (+) (melamine cation):
• Another object of the present invention is a process for the preparation of a flame-retardant, deformable polymer, wherein the at least one inventive, triazine-intercalated metal phosphate is exfoliated in the polymer.
• Another object of the invention is the achievement of anti-corrosive protective effect by coating metal surfaces.
• Fig. 1 shows an example of a lattice section from an intercalation model of
• Product (A) is heat-treated with frequent mixing for 5 h at 280 ° C almost constant weight.
• the resulting white product has the following composition:
• Example 5 Synthesis of bis-melamine zinko diphosphate
• Product D obtained according to the above procedure is dried for 5 h at 280 ° C, with a weight loss of about 6.0% takes place.
• Example 6 Static thermal treatment of precursor products A and C:
• Example 7 Static thermal treatment of temper products B, D and MPP
• Test strips (15 mm ⁇ 15 mm) are cut out from the skin skins prepared according to I. These are loaded in a METRASTAT test oven IR 700 (DR. STAPFER GmbH, Dusseldorf) at the indicated temperature until significant discoloration.
• the Yl value (yellowness index) according to DIN 53381 is then determined using a Spectro-Guide color measuring device (BYK-GARDNER) and compared with the Yl value of the unloaded rolled surface (zero minute value).
• BYK-GARDNER Spectro-Guide color measuring device
• the rolled skins manufactured above are processed to press plates (120x100x3mm) and subjected to a flame retardance test in accordance with UL94.
• the UL94 test is described in "Flammability of Plastic Materials for Parts in Devices and Appliances", 5th edition, October, 1996.
• Example 8 Testing in soft PVC: The following dry mixes are prepared (Table 3) - Weighed in parts by weight: Tab. 3: Formulations
• Table 5 shows that the mechanical properties of the formulation (R-2) according to the invention are even improved compared to the prior art (R-1).

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