DE102015009598A1 - Process for the preparation of a halogen-free flame retardant - Google Patents

Abstract

The present invention relates to a process for preparing a halogen-free flame retardant containing metal (M), nitrogen (N) and phosphorus (P) (MNP derivative) obtainable by reacting melamine orthophosphate, melamine pyrophosphate or melamine metaphosphate with a metal (hydr) oxide, metal oxohydroxide or Metal (hydroxy) carbonate at a temperature of 120 to 350 ° C and the use of these products as flame retardants.

Description

The present invention relates to a process for preparing a halogen-free flame retardant containing metal (M), nitrogen (N) and phosphorus (P) (MNP derivative) obtainable by reacting melamine orthophosphate, melamine pyrophosphate or melamine metaphosphate with a metal (hydr) oxide, metal oxohydroxide or Metal (hydroxy) carbonate at a temperature of 120 to 350 ° C and the use of these products as flame retardants.

Background and technical problem of the invention

It is known that intumescent agents have a flame retardant effect by heating under strong heating, for. B. under the action of a fire, to foam a flame-retardant insulating layer and this u. a. suppress the dripping of molten, possibly burning material.

Melamine polyphosphate is a known N- and P-containing synergistically-active, commercially-available NP flame retardant. A formulation already on the market based on melamine polyphosphate is known in EP 1 537 173 B1 described. Thus, several processes for the preparation of melamine polyphosphates are described, for example in WO 00/02869 . EP 1 789 475 . WO 97/44377 and EP 0 974 588 , However, these processes are time-consuming to produce and are associated with very high energy consumption because of the high reaction temperatures (340 to 400 ° C.). In addition, urea is used as a further additive.

Intumescent metal-containing melamine phosphates are already in EP 2 183 314 B1 and EP 3 371 890 described and known commercially as Safire ^® 200, 400, and 600. This method involves a very tedious wet chemical reaction starting from metal hydrogen phosphate and melamine, followed by filtration and drying. WO 2014/060003 describes the preparation of azine metal phosphates of the formula [(AH) ⁽⁺⁾ [M ^{m +} (PO ₄ ) _x ^(3-) (P ₂ O ₇ ) _y ^(4-) ] ^(-) . pH ₂ O] _z of melamine, (metal (hydr) oxide and phosphoric acid.

The object of the present invention was therefore to provide more effective flame retardants that are accessible by a more efficient process.

An object of the present invention is therefore also in the provision of such flame retardants. These should also be easily accessible and produced by a dry process. They are referred to below as MNP derivatives.

Description of the invention

MNP derivatives

The object has been achieved in the present invention by providing MNP derivatives obtainable by reacting melamine orthophosphate, melamine pyrophosphate (melamine diphosphate) or melamine metaphosphate with a metal (hydr) oxide, metal oxohydroxide or metal (hydroxy) carbonate at a temperature of 120 to 350 ° C, in particular at 200 to 320 ° C and especially at 250 to 300 ° C surprisingly dissolved, wherein the metal (hydr) oxide, metal oxohydroxide or metal (hydroxy) carbonate is selected from the series of oxides, hydroxides or layered double hydroxides (LDH) of magnesium, zinc or aluminum.

This product group consists mainly of MgO, Mg (OH) ₂ , Al ₂ O ₃ , Al (O) OH (boehmite), ZnO, Zn (OH) ₂ and Mg, Al, Zn, Al and Mg / Zn, Al Hydrotalcite or hydromagnesite, (bas.) MgCO ₃ or (bas.) ZnCO ₃ .

Preferably, MgO and Mg (OH) ₂ . Particularly preferred is ZnO.

Another preference is for melamine orthophosphate and melamine pyrophosphate.

The molar ratio of the melamine phosphates to the metal (hydr) oxides, metal oxohydroxides and metal (hydroxy) carbonates is 1: 1 to 15: 1. Preferably 1: 1 to 10: 1 and most preferably 1: 1 to 2: 1.

It has surprisingly been found that the MNP derivatives of the present invention are thermally more stable than the compounds used in conventional flame retardants. In addition, they are easy to produce in a one-step process. The process for their production is energy efficient and economical, since the separate production of metal dihydrogen phosphates is eliminated. This is particularly advantageous because metal dihydrogen phosphates are stable in storage only in the heat in the majority of cases and tend to form precipitates at room temperature after a certain time. However, this rainfall is again difficult to solubilize.

Process for the preparation of MNP derivatives according to the invention

A component of the invention is also a process for the preparation of the MNP derivatives according to the invention described above by reacting a
Melamine phosphate derivatives (A)
with a metal (hydr) oxide (derivative) (B)
wherein the melamine phosphate derivative (A) is selected from
Melamine orthophosphate (melamine monophosphate) of the formula (A-1) (Mel) .H ₃ PO ₄ (A-1) Melamine pyrophosphate (melamine diphosphate) of the formula (A-2) (Mel) ₂ .H ₄ P ₂ O ₇ (A-2) and melamine metaphosphate of the formula (A-3) (Mel) .H ₃ PO ₃ (A-3) where Mel is melamine and the metal (hydr) oxide (derivative) is (B)
is selected from metal (hydr) oxides (B-1),
Metal oxohydroxides (B-2)
or
Metal (hydroxy) carbonates (B-3)
wherein the metal (hydr) oxide, metal oxohydroxide or metal (hydroxy) carbonate is selected from the series of oxides, hydroxides or layered double hydroxides (LDH) of magnesium, zinc or aluminum.

This product group consists mainly of MgO, Mg (OH) ₂ , Al ₂ O ₃ , Al (O) OH (boehmite), ZnO, Zn (OH) ₂ and Mg, Al, Zn, Al and Mg / Zn, Al Hydrotalcite or hydromagnesite, (bas.) MgCO ₃ or (bas.) ZnCO ₃

Preferably, MgO and Mg (OH) ₂ . Particularly preferred is ZnO.

Another preference is for melamine orthophosphate and melamine pyrophosphate.

In principle, mixtures of two or more of the abovementioned compounds can also be used as the metal (hydr) oxide (derivative) (B).

The molar ratio of the melamine phosphates to the metal (hydr) oxides (derivatives), metal oxohydroxides and metal (hydroxy) carbonates is 1: 1 to 15: 1. Preferably 1: 1 to 10: 1 and most preferably 1: 1 to 2: 1.

• 1) Mischen bzw. Vermahlen und Homogenisieren von Melaminphosphat(Derivat) (A) und Metall(hydr)oxid(Derivat), Metall(hydroxy)karbonat (B) in einem Mischer;
• 2) Umsetzung bei einer Temperatur von 120 bis 350°C, insbesondere bei 200 bis 320°C und ganz besonders bei 250 bis 300°C

The method preferably comprises the following steps:

• 1) Mixing and homogenizing melamine phosphate (derivative) (A) and metal (hydr) oxide (derivative), metal (hydroxy) carbonate (B) in a mixer;
• 2) Reaction at a temperature of 120 to 350 ° C, especially at 200 to 320 ° C and especially at 250 to 300 ° C.

The comminution of educts can also take place before step (1) in a ball mill, hammer mill, jet mill or in a single-track jet mill.

Preferred facilities for calcination are heating / cold air mixers, calcination furnaces, and kneaders. Examples include Henschel mixers, AVA mixers, Banbury mixers, ribbon mixers, vacuum kneaders, BUSS kneaders, rotary kilns or a Far-IR rays conveyor furnace. A representative overview of these reactors can be found in EP 2 615 061 A1 ,

Particularly preferably, step (1) can be followed by a step (2) successively in the same apparatus.

The heat treatment of the reaction product is typically carried out at 120 to 350 ° C, preferably at 250 to 300 ° C.

MNP derivatives and their compositions

Furthermore, it has unexpectedly been found that compositions obtained by adding synergists or co-components can further optimize the profile of action of MNP derivatives in terms of flame retardancy and intumescent behavior. These other components may be metal-containing or metal-free.

The present invention thus also relates to a composition which comprises the above-described MNP derivatives component (i) and a further metal-containing component (ii) other than component (i) and optionally a metal-free component (iii).

wobei R¹ und R² unabhängig voneinander Wasserstoff, lineares oder verzweigtes C₁-C₆-Alkyl oder Phenyl sind; Mt¹ Ca, Mg, Zn oder Al ist, m = 2 oder 3 ist und Mt Ca, Mg, Zn, Al, Sn, Zr, TiO, ZrO, Ce, MoO, WO₂, VO, Mn, Bi oder Sb ist, D = O oder S ist und n 2 oder 3 ist.The additional metal-containing component (ii) may in particular metal (hydr) oxide, metal oxohydroxide, metal (double) carbonate, hydrotalcite, Hydrokalumit isnbesondere metal phosphate, metal pyrophosphate, cationic or anionic modified organoclay, stannate or molybdate salt, metal borate or metal phosphinate of the formulas (a) or (b) or metal phosphonate of the formula (c), prepared according to WO2014 / 060004 or aluminum, tris-methyl methane phosphonate,

wherein R ¹ and R ^{2 are} independently hydrogen, linear or branched C ₁ -C ₆ alkyl or phenyl; Mt ^{1 is} Ca, Mg, Zn or Al, m is 2 or 3 and Mt is Ca, Mg, Zn, Al, Sn, Zr, TiO, ZrO, Ce, MoO, WO ₂ , VO, Mn, Bi or Sb , D = O or S and n is 2 or 3.

For example, hydrotalcite and hydrocalumite have the composition Mg ₆ Al ₂ (OH) ₁₆ CO ₃ and Ca ₄ Al ₂ (OH) ₁₂ CO ₃ . Organoclays are understood by the skilled artisan to be organophil modified clay minerals (mainly montmorillonites) based on cation exchange such as triethanol tallow ammonium montmorillonite and triethanol tallow ammonium hectorite as described in US Pat Dr. G. Beyer; Conf. Fire Resistance in Plastics, 2007 described. Anionic organoclays mean organophil-modified hydrotalcites based on anion exchange with alkali sarcosates, unsaturated and saturated fatty acid salts, and long-chain alkyl-substituted sulfonates and sulfates.

Metal oxides are preferably di-antimony trioxide, di-antimony tetroxide, di-antimony pentoxide or zinc oxide.

Wherein the metal (hydr) oxides of magnesium hydroxide (MDH, brucite), aluminum trihydroxide are preferred (ATH, gibbsite, Apyral ^®) or aluminum monohydroxide (boehmite Apyral ^®) as well as the carbonates, magnesite, hydromagnesite, hydrozincite and Doppelkarbonate huntite (Ultracarb ^®) and dolomite. In addition to GIbbsit and boehmite, the other modifications of aluminum trihydroxides, namely bayerite, nordstrandite and diaspore are also to be cited.

As metal phosphates, metal pyrophosphates are preferred. Particularly preferred are aluminum and zinc pyrophosphate and zinc and aluminum triphosphate as well as aluminum and zinc metaphosphate and aluminum and zinc orthophosphate.

Among the cationically or anionically modified organoclays, the alkyl sulfate or fatty acid carboxylate-modified hydrotalcites or long-chain quaternary ammonium-modified clay minerals are particularly preferred.

Also preferred with respect to molybdate or stannate salts are ammonium heptamolybdate, ammonium octamolybdate, zinc stannate or zinc hydroxystannate or mixtures thereof. These also act as smoke reducers and thus give the flame retardants of the present invention particularly advantageous properties.

From the class of metal borates alkali, alkaline earth or zinc borate are preferred. Also to be mentioned are aluminum borate, barium borate, calcium borate, magnesium borate, manganese borate, melamine borate, potassium borate, zinc boron phosphate or mixtures thereof.

Metal phosphinates are preferably salts in which Mt ^{1 is} selected from Ca, Mg, Zn or Al. Preferred metal phosphinates are phenylphosphinate, diethyl (methyl, ethyl) phosphinate, especially in combination with the aforementioned metals.

Among the hypophosphites, the Mg, Ca, Zn and Al salts are particularly preferred.

Preferred metal phosphinates (b) and metal phosphonates (c) are salts with Mt selected from Ca, Mg, Zn or Al. Particularly preferred is the use of a metal phosphinate (VI) prepared from 6H-dibenz [c, e] [1,2] oxaphosphorine 6-oxide [CAS #: 35948-25-5) in water without the use of caustic becomes. Also particularly preferred is the use of metal phosphonates (c), which are accessible for example by thermal cyclization of precursors (b). Very particular preference is given to zinc phosphonates or aluminum phosphonates and thiophosphonates (c). The (thio) phosphonates are preferably prepared from the (thio) phosphonic acids (CAS No: 36240-31-0 and CAS No: 62839-09-2). All phosphorus precursors are available as commercial products.

The metal-free (co) component (component (iii) of the inventive composition) comprises in particular red phosphorus, oligomeric phosphate esters, oligomeric phosphonate esters, cyclic phosphonate esters, thiopyrophosphoric acid esters, melamine orthophosphate or melamine pyrophosphate, di-melamine phosphate, melam (polyphosphate), melem, ammonium polyphosphate, melamine Phenylphosphonat and its half ester salt, as in WO 2010/063623 described, melamine-benzenephosphinate, as in WO 2010/057851 described hydroxyalkyl-phosphine oxides, as in WO 2009/034023 Tetrakishydroxymethylphosphoniumsalze and phospholane (oxide) - or phosphole derivatives and Bisphosphoramidate with piperazine as a bridge member or a phosphinate ester, the class of compounds of the NOR-HALS compounds (non-basic amino ether Hindered Amine Light Stabilizer) and mixtures thereof.

Also particularly preferred are phosphinate esters such as benzene monophenyl ester derivatives or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenzo (c, e) (1,2) -oxaphosphorin-6-one) derivatives ,

Also preferred are polyols, aminouracils, POSS compounds, trishydroxyethyl isocyanurate, melamine cyanurate, expandable graphite or mixtures thereof. POSS compounds (polyhedral oligomeric silsesquioxanes) and their derivatives are described in more detail by Prof. Giovanni Camino in POLYMER, Vol. 46, pp. 7855-7866 , Particularly preferred are POSS derivatives based on methylsiloxane.

Of the polyols, especially preferred are polyols based on pentaerythritol, dipentaerythritol and polypentaerythritol, especially preferred are Charmor ^™ PM, DP and PP100.

Further, tris-hydroxyethyl isocyanurate polyterephthalates and triazine polymers having piperazine-1,4-diyl bridge members and morpholin-1-yl end groups may also be contained in the flame retardants of the present invention.

Further, the following additives may be included 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 form (R 2 SiO) r or (R 2 SiO 1.5) r.

In principle, mixtures of two or more of the compounds described above may also be present in the compositions of the present invention.

Use of the MNP derivatives according to the invention

A particular embodiment of the invention relates to the use of the MNP derivative of the invention in a polymer or a polymer mixture as a flame retardant. The present invention thus further relates to compositions, as described above, which additionally contain a polymer or a polymer mixture. Preference is given to first preparing the above-described composition comprising components (i), (ii) and, if appropriate, (iii), and incorporating this composition 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 granules obtained is z. B. 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. Suitable compounding units are single-screw extruder or single-screw extruder z. B. Berstorff GmbH, Hannover and or the Fa. Leistritz, Nuremberg, multi-zone screw extruder with three-zone screws and / or short compression screws, Ko-Kneader z. B. Fa. Coperion Buss Compounding Systems, CH-Pratteln, z. B. MDK / E46-11 D and / or laboratory kneader (MDK 46 Fa. Buss, Switzerland with L = 11D); Twin-screw extruder z. Coperion Werner Pfleiderer GmbH & Co. KG, Stuttgart (ZSK 25, ZSk 30, ZSK 40, ZSK 58, ZSK MEGAcompounder 40, 50, 58, 70, 92, 119, 177, 250, 320, 350, 380) and / or Berstorff GmbH, Hanover, Leistritz Extrusionstechnik GmbH, Nuremberg; TSE 24 MC twin-screw extruder from Thermo Scientific, Karlsruhe; Ring extruder z. B. the Fa. 3 + Extruder GmbH, running with a ring of three to twelve small screws that rotate around a static core and / or planetary roller extruder z. As the Fa. Entex, Bochem and / or Entgassungsextruder and / or cascade extruder and / or Maillefer screws; Compounder with counter-rotating twin screw z. B. Complex 37- or -70 types of the company. Krauss -Maffei Berstorff.

The polymer is typically a thermoplastic, preferably selected from the group consisting of polyamide, polycarbonate, polyolefin, polystyrene, polyester, polyvinyl chloride, polyvinyl alcohol, ABS and polyurethane, or a thermosetting resin, preferably selected from the group consisting of epoxy resin (with hardener), phenolic resin and melamine resin.

It is also possible to use mixtures of two or more polymers, in particular thermosets and / or thermosets, in which the MNP derivative according to the invention is used as flame retardant.

• – Polymere von Mono- und Diolefinen, z. B. Polypropylen, Polyisobutylen, Polybuten-1, Poly-4-methylpenten-1, Polyvinylcyclohexan, Polyisopren oder Polybutadien und Polymerisate von Cycloolefinen, z. B. von Cyclopenten oder Norbornen und Polyethylen (auch vernetzt), z. B. High Density Polyethylen (HDPE) oder High Molecular Weight (HDPE-HMW), High Density Polyethylen mit Ultra-High Molecular Weight (HDPE-UHMW), Medium Density Polyethylen (MDPE), Low Density Polyethylen (LDPE), Green Polyethylen^® und Linear Low Density Polyethylen (LLDPE), (VLDPE) und (ULDPE) sowie Copolymere von Ethylen und Vinylacetat (EVA) (z. B. Escorene^TM);
• – Polyurethane: thermoplastische Polyurethan-Elastomere (TPU): aliphatische- und aromatische-TPU; Polyester- und Polyether-Polyurethane sowie Polycaprolactone. Beispiele hierfür sind: Elastollan^®, Irogran^®, Irostic^® und Avalon^®
• – Polystyrole, Poly(p-methylstyrol), Poly(α-methylstyrol);
• – Copolymere sowie Propfcopolymere von Polybutadien-Styrol oder Polybutadien und (Meth)Acrylnitril wie z. B. ABS und MBS;
• – Halogenhaltige Polymere, wie z. B. Polychloropren, Polyvinylchlorid (PVC); Polyvinylidenchlorid (PVDC), Copolymere von Vinylchlorid/Vinylidenchlorid, Vinylchlorid/Vinylacetat oder Vinylchlorid/Vinylacetat;
• – Poly(meth)acrylate, Polymethylmethacrylate (PMMA), Polyacrylamid und Polyacrylnitril (PAN);
• – Polymere von ungesättigten Alkoholen und Aminen oder ihren Azylderivaten bzw. Azetalen, wie z. B. Polyvinylalkohol (PVA), Polyvinylacetate, -stearate, -benzoate oder -maleate, Polyvinylbutyral, Polyallylphthalate und Polyallylmelamine;
• – Homo- und Copolymere von cyclischen Ethern, wie Polyalkylenglykole, Polyethylenoxide, Polypropylenoxide und deren Copolymere mit Bisglycidylethern;
• – Polyacetale, wie beispielsweise Polyoxymethylene (POM) sowie Polyurethan und Acrylat-modifizierte Polyazetale;
• – Polyphenylenoxide und -sulfide und deren Gemische mit Styrolpolymeren oder Polyamiden;
• – Polyamide und Copolyamide hergeleitet von Diaminen und Dicarbonsäuren und/oder von Aminocarbonsäuren oder den entsprechenden Laktamen, wie z. B. Polyamid 4, Polyamid 6, Polyamid 6/6, 6/10, 6/9, 6/12, 12/12, Polyamid 11, Polyamid 12, aromatische Polyamide, hergeleitet vom m-Xylylendiamin und Adipinsäure und Copolyamide modifiziert mit EPDM oder ABS. Beispiele von Polyamiden und Copolyamiden sind hergeleitet von ε-Kaprolaktam, Adipinsäure, Sebacinsäure, Dodekansäure, Isophthalsäure, Terephthalsäure, Hexamethylendiamin, Tetramethylendiamin, 2-Methyl-pentamethylendiamin, 2,2,4-Trimethylhexamethylendiamin, 2,4,4-Trimethylhexamethylendiamin, m-Xylylendiamin oder Bis(3-Methyl-4-aminozyklohexyl)methan;
• – Polyharnstoffe, Polyimide, Polyamidimide, Polyetherimide, Polyesterimide, Polyhydantoine und Polybenzimidazole.
• – Polyester, hergeleitet von Dicarbonsäuren und Dialkoholen und/oder Hydroxycarbonsäuren oder den entsprechenden Laktonen, wie z. B. Polyethylenterephthalat, Polypropylenterephthalat, Polybutylenterephthalat, Poly-1,4-dimethylzyklohexanterephthalat, Polyalkylennaphthalat (PAN) und Polyhydroxybenzoate, Polymilchsäureester und Polyglykolsäureester;
• – Polycarbonate und Polyestercarbonate;
• – Polyketone;
• – Mischungen bzw. Legierungen von o. g. Polymeren z. B. PP/EPDM, PA/EPDM oder ABS, PVC/EVA, PVC/ABS, PBC/MBS, PC/ABS, PBTP/ABS, PC/AS, PC/PBT, PVC/CPE, PVC/Acrylat, POM/thermoplastisches PUR, PC/thermoplastisches PUR, POM/Acrylat, POM/MBS, PPO/HIPS, PPO/PA6.6 und Copolymere, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS oder PBT/PET/PC, sowie TPE-O, TPE-S und TPE-E;
• – Biopolymere der Klasse Polymilchsäure (PLA), zellulosebasiertes PH, Polycaprolate (PCl), Polybutyleneterephthalat (PBT), Polyhydroxyalkanoate (PHA), Green Polyethylenterephthalat (GPET), Poly-D-Lactid (PDLA) und Poly-L-Lactid (PLLA) und ggf. einen Weichmacher
• – Duroplaste wie PF, MF oder UF oder Mischungen davon;
• – Epoxidharze-Thermoplaste und Duroplaste;
• – Phenolharze;
• – Wood-Plastic-Composites (WPC) sowie Polymere auf PLA-, PHB- und Stärke-Basis.

Examples of such polymers are:

• Polymers of monoolefins and diolefins, e.g. As polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyvinylcyclohexane, polyisoprene or polybutadiene and polymers of cycloolefins, z. B. of cyclopentene or norbornene and polyethylene (also crosslinked), z. As High Density Polyethylene (HDPE) or high molecular weight (HDPE-HMW), high density polyethylene ultra-high molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), polyethylene Green ^® and linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE) as well as copolymers of ethylene and vinyl acetate (EVA) (Escorene ^™ eg.);
• - Polyurethanes: thermoplastic polyurethane elastomers (TPU): aliphatic and aromatic TPU; Polyester and polyether polyurethanes and polycaprolactones. Examples include: Elastollan ^®, Irogran ^{®, ®} and Irostic Avalon ^®
• - polystyrenes, poly (p-methylstyrene), poly (α-methylstyrene);
• - Copolymers and graft copolymers of polybutadiene-styrene or polybutadiene and (meth) acrylonitrile such. ABS and MBS;
• - Halogen-containing polymers, such as. For example, polychloroprene, polyvinyl chloride (PVC); Polyvinylidene chloride (PVDC), copolymers of vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinyl chloride / vinyl acetate;
• Poly (meth) acrylates, polymethyl methacrylates (PMMA), polyacrylamide and polyacrylonitrile (PAN);
• - Polymers of unsaturated alcohols and amines or their Azylderivaten or acetals, such as. Polyvinyl alcohol (PVA), polyvinyl acetates, stearates, benzoates or maleates, polyvinyl butyral, polyallyl phthalates and polyallylamines;
• - Homo- and copolymers of 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;
• - Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides;
• - 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. Examples of polyamides and copolyamides are derived from ε-caprolactam, adipic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, hexamethylenediamine, tetramethylenediamine, 2-methyl-pentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, m- Xylylenediamine or bis (3-methyl-4-aminocyclohexyl) methane;
• Polyureas, polyimides, polyamide-imides, polyether-imides, polyester-imides, polyhydantoins and polybenzimidazoles.
• - Polyester, derived from dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones, such as. Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, polylactic acid esters and polyglycolic acid esters;
• - polycarbonates and polyestercarbonates;
• - polyketones;
• - Mixtures or alloys of the above polymers z. 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;
• - Polylactic acid (PLA) biopolymers, cellulose-based PH, polycaprolates (PCl), polybutylene terephthalate (PBT), polyhydroxyalkanoates (PHA), green polyethylene terephthalate (GPET), poly-D-lactide (PDLA) and poly-L-lactide (PLLA) and optionally a plasticizer
• Thermosets such as PF, MF or UF or mixtures thereof;
• - epoxy resin thermoplastics and thermosets;
• - phenolic resins;
• - Wood-plastic composites (WPC) as well as polymers based on PLA, PHB and starch.

These polymers are used either as engineering plastics (engineering plastics) in the electrical and electronics industry (PCBs, cables, cable sheathing, components for E & E) or form the matrix in various applications such as paints and coatings, as well as in coating of metal surfaces in construction and transport (rail, ships and aircraft), fibers and textiles.

The concentration of the flame retardant preparations according to the invention, consisting of the MNP derivative (component (i)) and the additional metal-containing component (ii) in a polymer or a polymer mixture is preferably from 0.1 to 60% by weight, based on the polymer or the polymer mixture , The component ratio in the composition consisting of MNP derivative (i) and co-components (ii) and (iii) is in the range of 1: 1 to 1:10.

According to a preferred embodiment of the invention, the polymer material according to the invention may comprise further fillers which are preferably selected from the group consisting of metal hydroxides and / or metal oxides, preferably alkaline earth metal hydroxides, for example magnesium hydroxide and aluminum hydroxide, silicates, preferably phyllosilicates such as bentonite, kaolinite, muscovite, pyrophyllite , Marcasite and talc, or other minerals such as wollastonite, silica, such as quartz, mica, feldspar, and titanium dioxide, alkaline earth metal silicates and alkali metal silicates, carbonates, preferably calcium carbonate, and talc, clay, mica, silica, calcium sulfate, barium sulfate, pyrite, glass fibers, Glass particles, glass beads and glass beads, wood flour, cellulose powder, carbon black, graphite, chalk and pigments.

These fillers can impart further desired properties to the polymeric material. In particular, z. B. by a reinforcement with glass fibers, the mechanical stability can be increased or colored by the addition of dyes of the plastic.

According to a further embodiment, the polymer materials may contain further additives such as antioxidants, light stabilizers, process aids, nucleating agents, antistatic agents, lubricants such as calcium and zinc stearate, viscosity improvers, impact modifiers and in particular compatibilizers and dispersants.

In addition, foaming agents can be added to the polymer in addition to the MNP derivative 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, as well as other guanidine salts or allantoins and glycolurils.

In addition, a polymer containing the MNP derivative of the present invention may also contain antidripping agents, especially polytetrafluoroethylene-based. The concentration of such anti-dripping agents is preferably 0.01 to 15 wt .-%, based on the polymer to be processed.

The following representative selection of examples serves to further explain the invention.

Examples

The following commercially available materials are used: melamine orthophosphate (CAS No .: 20208-95-1), melamine pyrophosphate (CAS No: 15541-60-3), zinc oxide (CAS No .: 1314-13-2), magnesium hydroxide (CAS no .: 1309-42-8, aluminum hydroxide (CAS No .: 21645-51-2)

example 1

896 g of melamine orthophosphate and 162 g of ZnO were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 250 to 290 ° C, 3-5 h with stirring. This resulted in 950 g of a white powder.

Example 2

1720 g of melamine pyrophosphate and 324 g of ZnO were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 250 to 290 ° C, 2-3 h with stirring. This resulted in 1890 g of a white powder.

Example 3

1792 g of melamine orthophosphate and 324 g of ZnO were homogenized at RT in a laboratory mixer (vertical mixer KM / HU 23, ZEPPELIN). The thus homogenized mixture was thermally treated at 250 to 290 ° C for 1-2 h with stirring. This resulted in 1950 g of a white powder.

Example 4

1793 g of melamine orthophosphate and 233 g of magnesium hydroxide were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 270 to 290 ° C, 3-5 h with stirring. This resulted in 1250 g of a white powder.

Example 5

1721 g of melamine pyrophosphate and 233 g of magnesium hydroxide were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 250 to 290 ° C, 3-5 h with stirring. This resulted in 1260 g of a white powder.

Example 6

1345 g of melamine orthophosphate and 156 g of aluminum hydroxide were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 250 to 290 ° C, 3-5 h with stirring. This resulted in 1030 g of a white powder.

Example 7

1290 g of melamine pyrophosphate and 156 g of aluminum hydroxide were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 270 to 290 ° C, 2-3 h with stirring. This resulted in 1000 g of a white powder.

Example 8

2241 g of melamine orthophosphate and 81 g of ZnO were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 270 to 290 ° C, 3-5 h with stirring. This resulted in 2000 g of a white powder.

Example 9

2151 g of melamine pyrophosphate and 81 g of ZnO were homogenized in a laboratory mixer (laboratory mixer HTL 50-90, AVA) at RT. The thus homogenized mixture was thermally treated at 270 to 290 ° C, 3-5 h with stirring. This resulted in 1990 g of a white powder.

Comparative Example 1

Melamine poly (zinc phosphate) was prepared according to WO2012 / 025362 produced.

Comparative Example 2

Zn (2'-hydroxy [1,1'-biphenyl-2-yl-2-phosphinate) 2 was prepared according to WO2014 / 060004 produced.

Example 10

Determination of heat release with the Cone Calorimeter according to ( ISO 5660-1 ); Dual Cone Calorimeter from the company Fire Testing Technology, England.

The components according to formulations V-1 and V-2 (Table 1) were compounded in a laboratory kneader to a homogeneous mass and then pressed into a press plate;
Pattern 9.1 cm × 9.1 cm × 0.3 cm; Irradiance: (35 kW / m2) Table 1: Cone calorimeter result components V-1 (SdT) (% by weight) V-2 (% by weight) PE Exact 8201 Polyolefin Elastomer (ExxonMobil) 10 10 Fussabond MB226D Maleic Anhydride grafted PE (Du Pont) 30 30 ATH APYRAL 40CD (Nabaltec) 60 52 Product (Example 1) - 8th Peak Heat Release PHR (kW / m ² ) 180 130

The comparison (Tab. 1 and ) shows that the inventive formulation (V-2) compared to the SdT (V-1) results in a significant reduction (> 25%) in the heat release and thus a high flame retardancy is generated. Another advantage of the products is that no release of ammonia was observed during combustion. This is in contrast to the observations of C. Hoffendahl et. al., RSC Advances, 2014, 4 (39): p. 20185 to 20199

Example 11

Determination of flame retardancy in PA 6.6

compounding:

Materials: PA 6.6 (Akulon ^® S 223-D, from DSM.); Glass fiber (Chopvantage HP 3660, PPG company); Melamine-poly (zinc phosphate) (Comparative Example 1); Zn (2'-hydroxy [1,1'-biphenyl-2-yl-2-phosphinate) ₂ (Comparative Example 2) and MNP derivative (Example 1).

The components were compounded on a twin screw extruder TSE 24 at 290 ° C and granulated. From these granules standard test specimens (127 × 12.7 × 1.6 mm) were produced by injection molding. The test specimens were conditioned at 105 ° C, 16 h.

The fire test test was performed according to UL94 test. The results are summarized in Table 2. Table 2: Results of the UL94 study components V-3 (% by weight) V-4 (SdT) (wt.%) PA 6.6 45.0 45.0 glass fiber 30.0 30.0 Irganox B 1171 0.2 0.2 calcium stearate 0.2 0.2 Flame retardant components: Zn (2'-hydroxy [1,1'-biphenyl-2-yl-2-phosphinate) ₂ (Comparative Example 2) 12.6 12.6 Melamine-poly (zinc phosphate) (Comparative Example 1) - 12.0 MNP derivative (Example 3) 12.0 - UL94 test V-0 V-0

The experiments show that the MNP derivative (V-3) according to the invention can replace the wet-process melamine-poly (zinc phosphate) (V-4) in an efficiency comparison, resulting in an economic advantage.

Brief description of the picture

: Heat release in Cone calorimeter

Cited patent literature

• WO 00/02869 .
• EP 1 789 475 .
• WO 97/44377
• EP 0 974 588 ,
• EP 2 183 314 B1
• EP 2 371 890 B1
• EP 2 615 061 A1
• WO 2014/060004
• WO 2010/063623
• WO 2010/057851
• WO 2009/034023
• WO 2012/025362
• WO 2014/060004

Cited non-patent literature

• Dr. G. Beyer; AMI Conference; Fire Resistance in Plastics, 2007
• Prof. G. Camino, POLYMER, Vol. 46, pp. 7855-7866
• C. Hoffendahl et. al., RSC Advances, 2014, 4 (39): p. 20185 to 20199

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 1537173 B1 [0003]
• WO 00/02869 [0003]
• EP 1789475 [0003]
• WO 97/44377 [0003]
• EP 0974588 [0003]
• EP 2183314 B1 [0004]
• EP 3371890 [0004]
• WO 2014/060003 [0004]
• EP 2615061 A1 [0021]
• WO 2014/060004 [0026, 0069]
• WO 2010/063623 [0037]
• WO 2010/057851 [0037]
• WO 2009/034023 [0037]
• WO 2012/025362 [0068]

Cited non-patent literature

• Dr. G. Beyer; Conf. Fire Resistance in Plastics, 2007 [0027]
• Prof. Giovanni Camino in POLYMER, Vol. 46, pp. 7855-7866 [0039]
• ISO 5660-1 [0070]
• C. Hoffendahl et. al., RSC Advances, 2014, 4 (39): p. 20185-20199 [0072]

Claims (6)

Process for the preparation of a halogen-free flame retardant comprising metal (M), nitrogen (N) and phosphorus (P) (MNP derivative), obtainable by reacting melamine orthophosphate, melamine pyrophosphate or melamine metaphosphate (component A) with a metal (hydr) oxide, metal oxohydroxide, Metal (hydroxy) carbonates or layered double hydroxides (LDH) of Mg, Zn and Al (component B) at a temperature of 120 to 350 ° C. A process for the preparation of MNP derivatives according to claim 1, characterized in that the reaction is carried out at a temperature of 120 to 350 ° C, in particular at 200 to 320 ° C and especially at 250 to 300 ° C. Process for the preparation of MNP derivatives according to Claims 1 to 2, characterized in that the components (A) :( B) in a molar ratio of 1: 1 to 15: 1, preferably 1: 1 to 10: 1 and most preferably 1 : 1 to 2: 1. Process according to Claims 1 to 3, characterized in that it is carried out in a horizontal or vertical mixer, in a rotary kiln, preferably a paddle mixer or vertical high-speed mixer. Use of the MNP derivatives prepared according to claims 1 to 4, as flame retardants or as flame retardant component for polymers, polymer blends, paper, textiles or wood plastic composites (WPC). Use according to claim 5, characterized in that the polymer is a thermoplastic, preferably selected from the group consisting of polyamide, polycarbonate, polyolefin in particular polyethylene, EVA, polystyrene, polyester, polyvinyl chloride, polyvinyl alcohol, ABS, polyurethanes and biopolymers, based on polylactic acid (PLA) and / or starch, or a thermoset, preferably selected from the group consisting of epoxy resin, phenolic resin and melamine resin.

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