EP3099760A1 - Mélange ignifuge solide exempt d'halogènes et utilisation correspondante - Google Patents

Mélange ignifuge solide exempt d'halogènes et utilisation correspondante

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Publication number
EP3099760A1
EP3099760A1 EP15701669.2A EP15701669A EP3099760A1 EP 3099760 A1 EP3099760 A1 EP 3099760A1 EP 15701669 A EP15701669 A EP 15701669A EP 3099760 A1 EP3099760 A1 EP 3099760A1
Authority
EP
European Patent Office
Prior art keywords
aluminum
chloride
flame retardant
halogen
acetate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15701669.2A
Other languages
German (de)
English (en)
Inventor
Harald Bauer
Sebastian HÖROLD
Martin Sicken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Priority to EP19152592.2A priority Critical patent/EP3505598A1/fr
Priority to EP19152589.8A priority patent/EP3505596B1/fr
Priority to EP19152590.6A priority patent/EP3505597B1/fr
Priority to EP19152591.4A priority patent/EP3521402B1/fr
Priority to EP19152594.8A priority patent/EP3505599A1/fr
Publication of EP3099760A1 publication Critical patent/EP3099760A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic 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
    • C09K21/06—Organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/84—Flame-proofing or flame-retarding additives

Definitions

  • Halogen-free solid flame retardant mixture and its use.
  • Flame retardant mixtures of various types are used for the flame-retardant finishing of polymers. It is necessary that in the typical process for polymer production, the components to be added, including the flame retardants, have good flowability and flowability in order to be distributed evenly in the polymer, so that its properties are not adversely affected.
  • the fluidity is influenced by grain properties such. B. grain size, particle size distribution, surface texture of the grains, water content or moisture and different particle shapes. Depending on the particle size or frequency of the particles of different sizes, they roll off each other differently. Round particles with a uniform surface should flow more easily than those with an irregular shape. Depending on the chemical surface, humidity or
  • WO 2003 / 035736A1 describes Melamincyanurataggregate by
  • Binders are held together. The task there is in the
  • the aforementioned aggregates can u. a. be prepared by dispersing the particles in advance in an aqueous slurry and adding a water-soluble auxiliary.
  • EP-1522551 A1 describes phosphorus-containing flame retardant agglomerates of low bulk density, the aggregates and / or primary particles
  • Flammschutzmittelagglomerats with low bulk density and still low dust Low tendency to dust is important, since dusting may cause the dosage to be uneven when incorporated into polymers in extruders, resulting in an inhomogeneous distribution of the flame retardant in the extruder
  • the EP-1522551 A1 is concerned only with the increase of the flowability or flowability, but not with the improvement of the uniformity of
  • JP-2003138264A1 and JP-2003138265A1 describe a good flowability for halogen-containing flame retardants by using particularly large particles (0.8 to 2 mm).
  • JP-2005171206A1 Flammschutzstoffschmischungen with good
  • WO-2010075087A1 describes a free-flowing
  • Flame retardant composition is absorbed from a liquid phosphorus-containing flame retardant in the latter on a support.
  • Flame-retardant polymer molding compounds are u. a. For example, prepared in which the flame retardant components on the side feeder of a
  • Polymer melt are incorporated. Glass fibers are added - if necessary - via a second side feed. The resulting homogenized polymer strand is stripped off, cooled in a water bath and then granulated.
  • the present invention is therefore based on the object to provide a flame retardant mixture with uniform flowability available. Another object of the present invention is the prevention of process disturbances in the manufacture of flame retardant
  • the flame retardant mixtures according to the invention contain no
  • the halogen-free flame retardant mixtures according to the invention have a uniform flowability and at the same time achieve a good flameproofing effect.
  • the invention therefore relates to a halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a solid
  • Diethylphosphinic acid salt of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base and 0.005 to 15% by weight contains non-combustible additives and component B is aluminum phosphite.
  • the halogen-free flame retardant mixture particularly preferably contains from 20 to 80% by weight of component A and from 20 to 80% by weight of component B.
  • the component A contains the halogen-free
  • Aluminiumdiethylphosphinkland 0.5 to 8 wt .-% non-combustible additives.
  • the additives are preferably dialkylphosphinic salts of the formula (IV)
  • R 1 and R 2 are the same or different and are independently ethyl, butyl, hexyl and / or octyl and M is Mg, Ca, Al, Sb, SN, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr , Mn, Li, Na, K and / or a protonated nitrogen base means with the proviso that R 1 and R 2 are not simultaneously ethyl; and / or that the additives are sulfates, phosphates, phosphonates, nitrates, chlorides, sulfites and / or acetates, and the sulfates, phosphates, phosphonates, nitrates, chlorides, sulfites and / or acetates are compounds with cations the alkali metals, the alkaline earth metals, the third main group, the subgroups of the Periodic Table and / or protonated nitrogen bases.
  • dialkylphosphinic acid salts of the formula (IV) are preferably ethyl-butylphosphinic acid salts, butyl-butylphosphinic acid salts, ethyl-hexylphosphinic acid salts, butyl-hexylphosphinic acid salts and / or hexyl-hexylphosphinic acid salts.
  • the cations are preferably those of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and / or K.
  • the protonated nitrogen bases are preferably ammonia, primary, secondary, tertiary and / or quaternary amines.
  • the sulfates are sodium sulfates
  • the phosphates are preferably aluminum phosphates
  • Aluminum hydrogenphosphates aluminum chloride phosphate
  • Calcium chloride phosphates calcium aluminum phosphate, calcium carbonate phosphate, calcium phosphates, cerium phosphates, ceric acid phosphate, lithium phosphate, lithium hydrogen phosphate, magnesium phosphates,
  • the phosphonates are preferably mono- (Cn 8 -alkyl) -
  • Phosphonates mono (C 6 -C 10 -aryl) phosphonates and / or mono- (C 1-8 -aralkyl) -phosphonates.
  • the nitrates are aluminum nitrate, calcium nitrate, cerium nitrate, iron nitrates, potassium nitrate, lithium nitrate, magnesium nitrate,
  • the acetates are preferably aluminum acetate, calcium acetate, cerium acetate, iron acetate, lithium acetate, potassium acetate, sodium acetate,
  • the sulfites are potassium sulfites
  • Potassium hydrogen sulfites potassium metabisulfite, sodium sulfites, sodium metabisulfite, sodium hydrogen sulfites, ammonium sulfites and / or their hydrates.
  • the chlorides are aluminum chloride,
  • Calcium acetate chloride calcium chloride, iron chloride, iron magnesium chloride, iron manganese chloride, iron chloride, lithium chloride, magnesium chloride, titanium chloride, titanium oxide chloride, zinc chloride, zinc aluminum chloride, zinc oxide chloride, tin chloride, zirconyl chloride, aluminum chloride hydroxide, calcium chloride chloride, iron hydroxide chloride, lithium hydroxide chloride, magnesium hydroxide chloride,
  • Manganese chloride, potassium chloride, potassium aluminum chloride and / or their hydrates are those of
  • y is 2.63 to 3.5
  • Aluminum phosphite tetrahydrate [Al 2 (HPO 3 ) 3 * 4aq] to give aluminum phosphonate, Al 7 (HPO 3 ) 9 (OH) 6 (1,6-hexanediamine) 1 , 5 * 12H 2 O, Al 2 (HPO 3 ) 3 * xAl 2 O 3 * nH 2 O with x 2.27-1, around Al 4 H 6 Pi 6 0i 8 and / or around mixtures of 0-99.9% by weight
  • the aluminum phosphite is preferably a mixture of 50-99% by weight Al 2 (HPO 3 ) 3 ⁇ (H 2 O) q in which q is 0 to 4 and 1 to 50% by weight sodium aluminum phosphite.
  • the aluminum phosphite is preferably also a mixture of 50-99% by weight Al 2 (HPO 3 ) 3 ⁇ (H 2 O) q in which q is 0 to 4 and 1-50% by weight Al 2 , ooM z (HPO 3 ) y (OH) v x (H 2 O) w (II) in the M sodium, z 0.005 to 0.15, y 2.8 to 3, 1, v 0 to 0.4 and w is 0 to 4.
  • Component A has a mean particle size d50 of 0.05 to 10 ⁇ and the
  • Component B has a mean particle size d50 of 0.05 to 10 pm and a residual moisture content of 0.05 to 8 wt .-%.
  • the invention also relates to a process for the preparation of a halogen-free flame retardant mixture according to one or more of claims 1 to 17, characterized in that the components A and B are mixed together in powder form and optionally sieved.
  • the invention further relates to a process for the preparation of the halogen-free flame retardant mixture, characterized in that one
  • the invention also relates to the use of a halogen-free
  • Sequestering agent as a mineral oil additive, as a corrosion inhibitor, in detergent and cleaner applications, in electronic applications.
  • a halogen-free flame retardant mixture according to one or more of claims 1 to 13 in or as flame retardants, as flame retardants for clearcoats and intumescent coatings, in or as flame retardants for wood and other cellulose-containing products, in or as reactive and / or non-reactive flame retardants for Polymers, for the preparation of flame-retardant polymer molding compositions, for the production of
  • the invention also relates to flame-retardant thermoplastic or thermosetting polymer molding compounds, polymer moldings, films, filaments and / or fibers, containing 0.1 to 45 wt .-% halogen-free flame retardant mixture according to one or more of claims 1 to 13, 55 to 99.9 wt .-%
  • thermoplastic or thermosetting polymer or mixtures thereof 0 to 55 wt .-% of additives and 0 to 55 wt .-% filler or
  • Reinforcement materials wherein the sum of the components is 100 wt .-%.
  • thermoplastic or thermosetting polymer molding compositions Preference is given to flame-retardant thermoplastic or thermosetting polymer molding compositions, polymer moldings, films, filaments and / or fibers, containing 1 to 30 wt .-% halogen-free flame retardant mixture according to one or more of claims 1 to 13, 10 to 97 parts by weight.
  • % thermoplastic or thermosetting polymer or mixtures thereof 1 to 30 wt .-% additives and 1 to 30 wt .-% filler or reinforcing materials, wherein the sum of the components is 100 wt .-%.
  • the invention further relates to flame-retardant thermoplastic or
  • the polymer is thermoplastic polymers of the type polystyrene HI ( High-impact), polyphenylene ethers, polyamides, polyesters, polycarbonates and blends or polymer blends of the ABS (acrylonitrile-butadiene-styrene) or PC / ABS (polycarbonate / acrylonitrile-butadiene-
  • the polymer is polyamide 4/6
  • Component A preferably contains 99.1 to 99.95% by weight of solid aluminum diethylphosphinate and 0.05 to 0.9% by weight of non-combustible additives.
  • diethylphosphinic acid salt always includes a diethylphosphinic salt of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.
  • the particularly preferred additives are dialkylphosphinic acid telomers, such as, for example, B. ethyl-butylphosphinic acid salts, butyl-butylphosphinic acid salts, ethyl hexylphosphinic acid salts, butyl-hexylphosphinic acid salts, hexyl hexylphosphinic acid salts and other metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe , Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.
  • Preferred here is a halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a Diethylphosphinklasalzes the above metals and 0.005 to 15 wt % non-combustible additives and component B is aluminum phosphite.
  • a halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a Diethylphosphinklasalzes the above metals and 0.005 to 15 wt % non-combustible additives and component B is aluminum phosphite.
  • a halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a Diethylphosphinklasalzes of the aforementioned metals and 0.005 to 15 wt % non-combustible additives and component B is aluminum phosphite.
  • a halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 92 to 99.9 wt .-% of a Diethylphosphinklarsalzes of the aforementioned metals and 0.1 to 8 wt .-% non-combustible additives and it is in the component B to
  • Aluminum phosphite acts.
  • Particularly preferred non-combustible additives are dialkylphosphinic acid
  • Preferred halogen-free flame retardant mixtures according to the invention which contain dialkylphosphinic acid telomers as non-combustible additive: I) Halogen-free flame retardant mixture comprising 1 to 99% by weight of component A and 1 to 99% by weight of aluminum phosphite, component A being from 85 to 99.995% by weight .-% Diethylphosphinklad and 0.005 to 15 wt .-% dialkylphosphinic telomers contains. II) Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein
  • Component A contains from 85 to 99.995% by weight of diethylphosphinic acid salt and from 0.005 to 5% by weight of dialkylphosphinic acid telomers.
  • Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein
  • Component A contains from 85 to 99.995% by weight of diethylphosphinic acid salt and from 0.005 to 15% by weight of dialkylphosphinic telomers.
  • the non-combustible additives may preferably also be sulfates. Preferred sulfates are then those with cations of the alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of
  • alkaline earth metals with cations of the elements of the third main group; with cations of the subgroup elements.
  • Particularly preferred subgroup elements are titanium, iron, zinc and mixtures thereof.
  • Preferred sulfates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.
  • Particularly preferred sulfates are sodium sulfate, sodium aluminum sulfate and alunite.
  • Aluminite (AI 2 (OH) 4 (S0 4) 7H 2 O), Metabasaluminite (Al 4 (OH) 0 (SO 4)),
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklad and 0.005 to 5 wt .-% sulfate.
  • Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% sulfate.
  • Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% sulfate.
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 99.1 to 99.99 wt .-% Diethylphosphinklarsalz and 0.01 to 0.9 wt .-% sulfate.
  • the non-combustible additives may preferably also be phosphates.
  • Preferred phosphates are those with cations of the alkali metals and with cations of protonated nitrogen bases z.
  • alkaline earth metals with cations of the elements of the third main group; with cations of the subgroup elements.
  • Particularly preferred subgroup elements are titanium, iron, zinc and mixtures thereof.
  • Preferred phosphates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated one
  • Preferred phosphates are aluminum phosphate AlPO 4, Al 2 0 3 * P 2 O5, AI 36 P36Oi 44, AL 16 Pi 6 0 64 AI 8 P 8 O 22, Al 2 O 3 * x P 2 0 5, Al 2 O 3 * 0.95P 2 O 5 , Al 2 O 3 * 0.86P 2 O 5 , Al 12 P 12 O 48 , Al 2 P 6 0i8, Aluminum phosphate hydrate Al 2 P 1 I94 O 7 , 85 * 2H 2 O, AIPO 4 * xH 2 O, AIPO4 * 0.45H 2 O, Al 32 P 32 O 128 * xH 2 O, Al 6 P 6 O 24 * 4H 2 O, AIPO 4 * 1, 67H 2 O, Al 4 (P 2 O 7 ) 3 * 12H 2 O,
  • Lithium hydrogen phosphate Li 3 HP 2 0 7 * H 2 O
  • Preferred halogen-free flame retardant mixtures according to the invention which contain phosphate as non-combustible additive:
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% phosphate.
  • Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% phosphate.
  • Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein Component A 95 to 99.995 wt .-% Diethylphosphinklaresalz and 0.005 to 5 wt .-% phosphate.
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 99.3 to 99.95 wt .-% Diethylphosphinklaresalz and 0.05 to 0.7 wt .-% phosphate.
  • the non-combustible additives may preferably also be
  • Preferred organophosphonates are those with cations of the alkali metals and with cations of protonated nitrogen bases z.
  • alkaline earth metals with cations of the elements of the third main group; with cations of the subgroup elements.
  • Particularly preferred subgroup elements are titanium, iron, zinc and mixtures thereof.
  • Preferred organophosphonates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.
  • Preferred organophosphonates are, for example, monoorganylphosphonates, such as
  • Mono- (Ci- 8 alkyl) phosphonates mono (C 6 -C 0 aryl) phosphonates, mono (C 7 --i 8 - aralkyl) phosphonates, particularly Monomethylphosphonate thereof,
  • Monoethyl phosphonates Monobutyl phosphonates, monohexyl phosphonates, monophenyl phosphonates, monobenzyl phosphonates, etc.
  • Preferred halogen-free flame retardant mixtures according to the invention which contain organophosphonate as non-combustible additive:
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein component A 95 to 99.995 wt .-% Diethylphosphinklaresalz and 0.005 to 5 wt .-% Organophosphonat contains.
  • Halogen-free flame retardant mixture containing 0 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein
  • Component A contains from 95 to 99.995% by weight of diethylphosphinic acid salt and from 0.005 to 5% by weight of organophosphonate.
  • Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein
  • Component A contains from 95 to 99.995% by weight of diethylphosphinic acid salt and from 0.005 to 5% by weight of organophosphonate.
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A contains 98 to 99.95% by weight of diethylphosphinic acid salt and 0.05 to 2% by weight of organophosphonate.
  • the non-combustible additives may preferably also be nitrates.
  • the nitrates are those with cations of
  • Subgroup elements are titanium, iron, zinc and mixtures thereof.
  • Preferred nitrates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.
  • Preferred nitrates are aluminum nitrate (Al (NO 3 ) 3), calcium nitrate (Ca (NO 3 ) 2 ), cerium (II) nitrate (Ce (NO 3 ) 2 ), cerium (III) nitrate (Ce (NO 3 ) 3 ) , Cerium (IV) nitrate (Ce (NO 3 ) 4 ), Cerium nitrate (Ce (N0 3) x), iron nitrate (Fe (NO 3) x), iron (II) nitrate (Fe (NO 3) 2),
  • halogen-free flame retardant mixtures according to the invention which contain nitrate as non-combustible additive:
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% nitrate.
  • Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% nitrate.
  • Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% nitrate.
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 99.79 to 99.99 wt .-% Diethylphosphinklarsalz and 0.01 to 0.21 wt .-% nitrate.
  • the non-combustible additives may preferably also be chlorides.
  • Preferred chlorides are those with cations of the alkali metals and with cations of protonated nitrogen bases z.
  • Subgroup elements are titanium, iron, zinc and mixtures thereof.
  • Preferred chlorides are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base
  • Preferred chlorides include:
  • Aluminum chloride acetate (C 4 H 6 AICIO), aluminum hydrogenchloride acetate,
  • Iron manganese chloride hydrate Mn 0i 5Feo, 5Cl 2 * nH 2 O,
  • Titanoxidchloridhydrat Ti 2 9O CI 42 32 * 0 H 2 O, Ti 2 O 2 CI 4 * 2H 2 O,
  • Aluminum chloride hydroxide hydrate Ali 3 CI 15 (OH) 24 * 37.5H 2 O
  • Preferred halogen-free flame retardant mixtures according to the invention which contain chloride as non-combustible additive:
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% chloride.
  • Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% chloride.
  • Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% chloride.
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 99.5 to 99.99 wt .-% Diethylphosphinklaresalz and 0.01 to 0.5 wt .-% chloride.
  • the non-combustible additives may preferably also be acetates.
  • Preferred acetates are those with cations of the alkali metals and with cations of protonated nitrogen bases z.
  • Subgroup elements are titanium, iron, zinc and mixtures thereof.
  • Preferred acetates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base
  • suitable acetates are about:
  • Aluminum acetate Ali / 3 (C 2 H 4 O 2)
  • calcium acetate Cai / 2 (C 2 H 4 O 2)
  • cerium (II) acetate cerium (III) acetate (Ce / 3 (C 2 H 4 O 2 )
  • Cerium (IV) acetate Ce 1 4 (C 2 H 4 O 2 )
  • iron acetate Aluminum acetate (Ali / 3 (C 2 H 4 O 2)
  • calcium acetate Cai / 2 (C 2 H 4 O 2)
  • cerium (II) acetate cerium (III) acetate (Ce / 3 (C 2 H 4 O 2 )
  • Cerium (IV) acetate Ce 1 4 (C 2 H 4 O 2 )
  • iron acetate Ali / 3 (C 2 H 4 O 2)
  • calcium acetate Cai / 2 (C 2 H 4 O 2)
  • cerium (II) acetate cerium (III) acetate (Ce / 3 (C 2 H 4
  • ziri / 2 (C2H 4 O 2) zirconium (III) acetate and / or zirconium (IV) acetate (Zri / 4 (C 2 H 4 O 2 )).
  • Preferred halogen-free flame retardant mixtures according to the invention which contain acetate as non-combustible additive: I) Halogen-free flame retardant mixture containing 1 to 99% by weight of a component A and 1 to 99% by weight of aluminum phosphite, where
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% acetate.
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • Component A 99.25 to 99.99 wt .-% Diethylphosphinklaresalz and 0.01 to 0.75 wt .-% acetate.
  • the non-combustible additives may preferably also be sulfites.
  • Preferred sulfites are those with cations of the alkali metals and with cations of protonated nitrogen bases z.
  • Subgroup elements are titanium, iron, zinc and mixtures thereof.
  • Preferred sulfites are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base Sodium metabisulfite, sodium sulfite, sodium bisulfite, potassium metabisulfite, potassium sulfite, potassium bisulfite and potassium hydrogen sulfate.
  • Preferred halogen-free flame retardant mixtures according to the invention which contain sulfite as non-combustible additive:
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein Component A 95 to 99.995 wt .-% Diethylphosphinklaresalz and 0.005 to 5 wt .-% sulfite.
  • Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% sulfite.
  • Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein
  • Component A 95 to 99.995 wt .-% Diethylphosphinklarsalz and 0.005 to 5 wt .-% sulfite.
  • Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein
  • halogen-free flame retardant mixtures which contain 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 95 to 99.995 wt .-% of a
  • aluminum phosphite covers a number of compounds, as defined below.
  • the aluminum phosphites according to the invention include an alkali-aluminum mixed phosphite of the formula
  • Example 78 The X-ray powder data of sodium aluminum phosphite are given in Example 78 and the X-ray powder data of Al 2 (HPO 3) 3 * 4H 2 O for comparison in Example 82.
  • Aluminum phosphite according to the invention is also a mixture of
  • a preferred aluminum phosphite according to the invention is a mixture of
  • an inventive aluminum phosphite of a mixture of 5-75 wt .-% Al 2 (HPO 3) 3 * nH 2 0 and 5-25 wt .-%
  • An aluminum phosphite which can be used according to the invention is also an alkali-aluminum mixed phosphite according to the formula
  • a usable aluminum phosphite according to the invention is also a mixture of the following composition:
  • phosphate 0-10% by weight of phosphate
  • aluminum phosphite which is of the following composition:
  • the usable aluminum phosphites according to the invention also include the aluminum hydrogen phosphite of the formula (III)
  • Aluminum phosphite which can be used according to the invention is also a mixture of aluminum phosphite with sparingly soluble aluminum salts and nitrogen-free foreign ions containing 80 to 99.898% by weight of aluminum phosphite of the formula (I)
  • the sparingly soluble aluminum salts are
  • the nitrogen-free foreign ions are chlorides, complex chlorides, bromides; hydroxides, peroxides, peroxide hydrate, sulphites, sulphates, sulphate hydrates, acid sulphates, hydrogen sulphates, peroxosulphates,
  • Peroxodisulfate to nitrates; carbonates, percarbonates, stannates; Borates, perborates, perborate hydrates; formates, acetates, propionates, lactates and / or ascorbates and / or cations of the elements Li, Na, K, Mg, Ca, Ba, Pb, Sn, Cu, Zn, La, Ce, Ti, Zr, V, Cr , Mn, Fe, Co and / or Ni.
  • aluminum phosphite which can be used according to the invention is also a
  • the aluminum phosphites which can be used according to the invention include, inter alia, aluminum phosphite (Al (H 2 PO 3 ) 3), secondary aluminum phosphite, basic aluminum phosphite (Al (OH) (H 2 PO 3 ) 2 * 2aq),
  • Flame retardant mixture 0.01 to 10 wt .-%, in particular 0.1 to 2 wt .-%.
  • the average particle size d 50 of the halogen-free flame retardant mixture according to the invention is preferably from 0.1 to 1000 ⁇ m, in particular from 10 to 100 ⁇ m.
  • the bulk density of the halogen-free invention is preferably
  • Flame retardant mixture is determined according to Pfrengle (DIN ISO 4324 surfactants, powders and granules, determination of Schüttwinkels, Dec. 1983, Beuth Verlag Berlin). Thereafter, the aforementioned flowability is determined by determining the height of the cone of a powder or granules or the ratio of bevel radius to cone height.
  • the cone is generated by passing a special amount of the substance to be examined in a defined apparatus a special funnel is poured out.
  • the defined bevel radius is created by pouring the cone until the product overflows over a circular plate raised from the ground. The radius of the plate is fixed.
  • the funnel has an inside diameter of 10 mm.
  • the plate has a radius of 50 mm. 5 determinations are carried out and averaged.
  • the height is measured in millimeters with a measuring strip from the plate, measured to the apex of the cone.
  • the ratio of bevel radius (50 mm) to cone height is calculated from the mean value.
  • the halogen-free flame retardant mixtures according to the invention can be prepared by various methods.
  • aluminum diethylphosphinate is mixed directly with the non-combustible additive and aluminum phosphite.
  • aluminum diethylphosphinate containing the non-combustible additive is mixed with aluminum phosphite.
  • the aluminum diethylphosphinate containing the non-combustible additive is prepared by reacting diethylphosphinic acid with elemental metal or a metal salt at 0 to 300 ° C for 0.01 to 1 hours.
  • Preferred metal salts are metal oxides, mixed metal oxide hydroxides, hydroxides, etc.
  • the non-combustible additive-containing aluminum diethylphosphinate is prepared by reacting a Diethylphosphinklare with a free base for 0.01 to 1 hours at 0 to 300 ° C.
  • the non-combustible additive-containing Aluminiumdiethylphosphinat is prepared by a
  • Preferred alkali metal salts are sodium and potassium salts.
  • Preferred salts which provide the desired cations are acetates, hydroxoacetates, chlorides, hydroxochlorides, nitrates, sulfates, hydroxosulfates, phosphonates and phosphites.
  • Their concentration in aqueous solution is preferably from 5 to 95% (anhydrous solid), more preferably from 20 to
  • the non-combustible additive-containing Aluminiumdiethylphosphinat is prepared by a
  • Diethylphosphinklare in the form of a reactive derivative with a derivative of the desired cation for 0.01 to 1 hours at 0 to 300 ° C.
  • Preferred diethylphosphinic acid derivatives are diethylphosphinic esters, pyroesters, chlorides, phosphates, acetates, phenolates, etc.
  • dialkylphosphinic telomers as a non-combustible additive, the dialkylphosphinic telomer content is 50 ppm to 15 wt .-%, more preferably 1000 ppm to 8 wt .-%.
  • the sulphate content is from 50 ppm to 5% by weight, more preferably from 100 ppm to 9000 ppm.
  • the phosphate content is 50 ppm to
  • Organylphosphonat contains as a non-combustible additive is the
  • Organylphosphonate content 50 ppm to 5 wt .-%, particularly preferably 500 ppm to 2 wt .-%.
  • the nitrate content is 50 ppm to 5 wt%, more preferably 100 ppm to 2100 ppm.
  • the chloride content is 50 ppm to 5 wt%, more preferably 100 ppm to 5000 ppm.
  • the acetate content is 50 ppm to 5 wt%, more preferably 100 ppm to 7500 ppm.
  • the acetate content is 50 ppm to 5 wt%, more preferably 100 ppm to 8200 ppm.
  • the invention also encompasses flame-retardant polymer molding compositions containing 1 to 50% by weight of the halogen-free compounds according to the invention
  • the invention preferably comprises flameproofed polymer molding compositions containing
  • the polymers preferably originate from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the thermosetting polymers.
  • the polymers are preferably polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, and also polymers of
  • Cycloolefins such. From cyclopentene or norbornene; also polyethylene (which may be optionally crosslinked), e.g. High density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density polyethylene and ultrahigh molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene Density (LLDPE), branched low density polyethylene (VLDPE), as well as mixtures thereof.
  • HDPE High density polyethylene
  • HDPE-HMW high density polyethylene
  • HDPE-UHMW high density polyethylene and ultrahigh molecular weight
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene Density
  • VLDPE branched low density polyethylene
  • the polymers are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as.
  • LDPE low density polyethylene
  • propylene-butene-1 copolymers propylene-isobutylene copolymers
  • ethylene-butene-1 copolymers ethylene-hexene copolymers
  • ethylene-methylpentene copolymers ethylene-heptene copolymers
  • Ethylene-octene copolymers propylene-butadiene copolymers
  • Isobutylene-isoprene copolymers ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their
  • the polymers are preferably hydrocarbon resins (eg C5-C9) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.
  • the polymers are preferably polystyrene (polystyrene 143E (BASF), poly (p-methylstyrene), poly (alpha-methylstyrene).
  • the polymers are copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate
  • styrene-maleic anhydride styrene-acrylonitrile-methyl acrylate
  • Blends of high impact strength of styrene copolymers and another polymer such as.
  • block copolymers of styrene such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
  • the polymers are graft copolymers of styrene or alpha-methylstyrene, such as. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (resp.
  • the polymers are preferably halogen-containing polymers, such as.
  • halogen-containing polymers such as.
  • chlorinated rubber chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated
  • halogen-containing vinyl compounds such as. B. polyvinyl chloride
  • Copolymers such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
  • the polymers are preferably polymers which are derived from alpha, beta-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethyl methacrylates which have been modified with butyl acrylate, polyacrylamides and polyacrylonitriles and copolymers of said monomers with one another or with other unsaturated monomers , such as Acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
  • the polymers are preferably polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate,
  • Polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins are examples of polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins.
  • the polymers are preferably homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • the polymers are preferably polyacetals, such as
  • Polyoxymethylene as well as those polyoxymethylenes, the comonomers, such as.
  • ethylene oxide Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • the polymers are preferably polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.
  • the polymers are preferably polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof.
  • the polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2/12, polyamide 4 (poly-4-aminobutyric acid, Nylon® 4, Fa. DuPont), polyamide 4/6
  • Polyamide 6/10 poly (hexamethylene sebacamide), nylon ® 6/10, from DuPont
  • polyamide 6/12 poly (hexamethylene dodecanediamide), nylon ® 6/12, from DuPont
  • polyamide 6/66 Poly (hexamethylene adipamide-co-caprolactam), nylon ® 6/66, from DuPont
  • polyamide 7 poly-7-aminoheptanoic acid, nylon ® 7, from DuPont), polyamide 7/7
  • polydecamethylensebacamid Nylon ® 10/10 Fa. DuPont
  • polyamide aminoundecanoic acid, poly-11, Nylon ® 1, Fa. DuPont
  • polyamide 12 polylauryllactam, Nylon ® 12, Fa. DuPont, Grillamid ® L20, Fa Ems Chemie
  • aromatic polyamides starting from m-xylene, diamine and adipic acid
  • Polyhexamethylenisophthalamid polyhexamethylene terephthalamide and optionally an elastomer as a modifier, for.
  • poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide As poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide.
  • Polypropylene glycol or polytetramethylene glycol Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").
  • aromatic polyamides such as PA4T, PA6T,
  • the polymers are preferably also polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and
  • the polymers are preferably polyesters which differ from
  • Derive dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones such as polyethylene terephthalate,
  • Polybutylene terephthalate (Celanex ® 2500, Celanex ® 2002, from Celanese;. Ultradur ®, BASF), poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters derived from hydroxyl-terminated polyethers; also with polycarbonates or MBS modified polyester.
  • the polymers are preferably polycarbonates and polyestercarbonates and also polysulfones, polyethersulfones and polyetherketones.
  • the polymers are preferably crosslinked polymers which are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
  • the polymers are drying and non-drying alkyd resins.
  • the polymers are preferably unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids
  • the polymers are crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. B. of epoxy acrylates,
  • the polymers are preferably alkyd resins, polyester resins and acrylate resins which are blended with melamine resins, urea resins, isocyanates,
  • Isocyanurates, polyisocyanates or epoxy resins are crosslinked.
  • the polymers are preferably crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic
  • Derive glycidyl compounds for. B. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, by conventional hardeners such. As anhydrides or amines can be crosslinked with or without accelerators.
  • the polymers are mixtures (polyblends) of the aforementioned polymers, such as.
  • PP / EPDM polyamide / EPDM or ABS
  • PVC / EVA polyvinyl / polyethylene
  • PVC / ABS polyvinyl / polyethylene
  • PVC / MBS polyvinyl / polyethylene
  • PC / ABS polyvinyl / polyethylene
  • PBTP / ABS PC / ASA
  • PC / PBT PC / PBT
  • PA / HDPE PA / PP
  • PA / PPO PA / PC / ABS or PBT / PET / PC.
  • Flame retardant mixtures are z. B. synergists.
  • the synergists used are melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetrakis melamine triphosphate, hexakismelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphates, melampolyphosphates,
  • Melamine polyphosphates and / or melon polyphosphates are preferred. Furthermore, as synergists melamine condensation products such as melam, Meiern and / or melon are preferred.
  • synergists are oligomeric esters of tris (hydroxyethyl) isocyanurate with aromatic polycarboxylic acids,
  • Benzoguanamine tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and / or guanidine.
  • synergists are furthermore preferably nitrogen-containing
  • Preferred further additives in the flame retardant compositions of the invention are zinc compounds, e.g. Zinc oxide, zinc hydroxide,
  • Preferred further additives in the flame retardant compositions according to the invention are those from the group of carbodiimides and / or (poly) isocyanates.
  • Preferred further additives are from the group of sterically hindered phenols (e.g., B. Hostanox OSP ® 1), sterically hindered amines, and
  • Light stabilizers z. B. Chimasorb ® 944, Hostavin ® types
  • phosphonites and antioxidants eg. B. Sandostab ® P-EPQ of Fa. Clariant
  • Preferred further fillers in the flame retardant compositions according to the invention are oxygen compounds of silicon
  • Magnesium compounds e.g. B. metal carbonates of metals of the second
  • magnesium oxide magnesium hydroxide, hydrotalcites, dihydrotalcite, magnesium carbonates or magnesium calcium carbonates, calcium compounds, eg. Calcium hydroxide, calcium oxide,
  • Hydrocalumite aluminum compounds, eg. Example, alumina, aluminum hydroxide, boehmite, gibbsite or aluminum phosphate, red phosphorus, zinc or
  • Twin screw extruder z. Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart (ZSK 25, ZSK30, 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.
  • Compounding units that can be used in accordance with the invention are ring extruders, eg. 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. B. the Fa. Entex, Bochum and / or degassing extruder and / or cascade extruder and / or Maillefer-Peck.
  • Compounding units which can be used according to the invention are compounders with counter-rotating twin screw z.
  • Effective screw lengths according to the invention are 20 to 40D in single-screw extruders or single-screw extruders.
  • Screw lengths effective in accordance with the invention in twin-screw extruders are 8 to 48D.
  • the flame retardant components are mixed with the polymer granulate and any additives and via the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D type) at temperatures of 230 to 260 ° C
  • glass fiber reinforced PBT glass fiber reinforced PBT
  • the glass fibers were over a second side feed
  • Injection molding machine (type Arburg 320 C Allrounder) at melt temperatures of 240 to 300 ° C to test specimens processed and based on the UL 94 test
  • the 31 P NMR spectra are measured with a Jeol JNM-ECS-400 instrument, a 400 MHz NMR instrument from JEOL (Germany) GmbH.
  • 100 - 150 mg is dissolved in 2 ml of 10 wt .-% NaOD / D 2 O by gently warming the sample to about 40 ° C.
  • the measurement is performed in ⁇ 1 H ⁇ decoupling mode with 2048 scans.
  • the 31 P NMR signals of the telomers can be taken from a 31 P NMR spectrum.
  • the assignment of the chemical structures of the telomers to the 31 P NMR signals can be done by combining the 31 P NMRs and a) the intensities of the signals with LC / MS (combination of liquid chromatography and mass spectroscopy analysis), b) by targeted Synthesis of telomeres and backfilling of 31 P samples with reference materials thus obtained or c) by combination of 31 P NMR and 13 C NMR spectroscopy.
  • Diethyiphosphinate with molecular weight 122 g / mol is the most intense peak in LC-MS and also in 31 P-NMR. Molecular mass 122 admits only the structure diethyiphosphinate, the 31 P NMR chemical shift found is listed in Table 9.
  • n-butyl ethyl phosphinate and sec-butyl ethyl phosphinate have the LC-MS
  • N-butyl ethyl phosphinate and "sec-butyl ethyl phosphinate” to.
  • n-butyl is in LC / MS and more intense in P-NMR than sec-butyl. Consequently, the more intense signal (to the right of diethyl) is the n-butyl ethyl phosphinate, the less intense signal (to the left of diethyl) the sec-butyl ethyl phosphinate.
  • the signal layers found are listed in Table 9.
  • Aluminum tri (n-butylethylphosphinate) can be chemically prepared in several steps by butyl group addition to hypophosphorous acid, hereinafter
  • the CH group characteristic of the sec-butyl group (-CH (-CH 3 ) -CH 2 -CH 3 ) gives a signal at 33.7 ppm (with a Jpc coupling of 91 Hz) 1 Jpc coupling defined as the coupling of the phosphorus core via a covalent bond to the next carbon nucleus.
  • An aluminum diethylphosphinate containing telomeres as an additive is prepared by dissolving 2.2 kg (20.7 moles) of sodium hypophosphite 1-hydrate in 8 kg (7.62 liters) of acetic acid and precipitating out in a 16 liter jacketed pressure reactor Steel enamel submitted. After the reaction mixture had been heated to 85 ° C., ethylene was introduced into the reactor through a reducing valve set at 7 bar until saturation. The reaction was carried out with constant stirring by metering in a solution of 56 g
  • Reaction temperature in the reactor at a jacket temperature of 80 ° C with constant supply of ethylene at an average pressure of about 7 bar did not rise above 95 ° C.
  • the dosing time was a total of 3 hours. Then allowed to react for 3 h at 85 ° C.
  • the reactor was relaxed and on
  • the product contains 15.9 wt .-% Aluminiumbutylethylphosphinat and 0.2 wt .-% residual moisture.
  • Example 2
  • Example 1 is 3 bar ethylene pressure and 95.2 g
  • Aluminum diethylphosphinate and aluminum phosphite are weighed into a polyethylene bottle so that about 1 kg
  • Flame retardant mixture results. In an overhead mixer, mix for about 2 hours until homogeneity is achieved.
  • Aluminiumdiethylphosphinat containing an addition of telomeres with mixtures of Al2 (HPO 3 ) 3 * 4H 2 O and sodium aluminum phosphite from Example 80 or 81, which were previously dried at 220 ° C to 0.5 wt .-% residual moisture, weighed into a polyethylene bottle so that approx. 1 kg of flame retardant mixture is obtained and mixed in an overhead mixer for approx. 2 hours, until
  • Aluminiumdiethylphosphinat containing an additive of sulfate is with
  • Aluminiumdiethylphosphinat containing an addition of phosphate is weighed with aluminum phosphite in a polyethylene bottle so that results in about 1 kg flame retardant mixture and mixed in an overhead mixer for about 2 hours until homogeneity is reached.
  • Experiments show a more uniform flowability in the products of Examples 25 to 33 than in the product without additives from Comparative Example 4.
  • Examples 34 to 42 Aluminiumdiethylphosphinat containing an addition of phosphonate is weighed with aluminum phosphite in a polyethylene bottle so as to give about 1 kg flame retardant mixture. In an overhead mixer, mix is mixed for about 2 hours until homogeneity is achieved. The experiments show more uniform flowability than without additives in Comparative Example 4.
  • Aluminiumdiethylphosphinat containing an additive of nitrate is with
  • Aluminiumdiethylphosphinat containing an addition of chloride is with
  • Aluminiumdiethylphosphinat containing an additive of acetate is with
  • Example 70 flame-retardant polymer molding compositions based on polyamide 6, polyamide 4.6 and polybutylene terephthalate are processed. After drying, the molding compositions on an injection molding machine to
  • Aluminum aluminum phosphite Aluminum Al 2 (HP0 3 ) 3 Aluminum-soluble aluminum phosphites Aluminum-dried
  • Aluminum phosphite basic secondary AI 2 (HP0 3) 3 * secondary mixture of aluminum secondary alkali aluminum AluminiumAluminium4H AluminiumAI 2 0 2 (HP0 3) 3 * hydrogen- AluminiumAluminium- hydrogen- phosphite phosphite phosphite 4H 2 0 with phosphites and phosphite mixing phosphite AI (OH) (H 2 PO 3 ) 2 Al 2 (HPO 3 ) 3 Al 2 (HPO 3 ) 3 heavy Al 2 -Al 2 (HPO 3 ) 3 phosphites
  • Table 8 Composition of flame-retardant polymeric molding compounds and flame retardance tests of flame-retardant polymeric moldings according to UL 94
  • Polybutylene terephthalate Celanex ® 2500, Ticona Fa.
  • Polyamide 6.6 Ultramid ® A3, BASF.
  • Polyamide 6 Zytel ® 730, from Du Pont.
  • Polyamide 4.6 Stanyl ® PA46, DSM company.
  • Fiberglass PBT Vetrotex ® EC 10983, from Saint-Gobain.
  • Glass fibers PA PPG 3540, PPG Industries, Inc

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Abstract

L'invention concerne un mélange ignifuge exempt d'halogènes comprenant entre 1 et 99 % en poids d'un composant A et entre 1 et 99 % en poids d'un composant B. Ledit composant A comporte entre 85 et 99,995 % en poids d'un sel d'acide diéthylphosphinique solide des métaux Mg, Ca, AI, Sb, SN, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K et/ou d'une base azotée protonée et entre 0,005 et 15 % en poids d'additifs incombustibles, et ledit composant B se présente sous la forme de phosphite d'aluminium.
EP15701669.2A 2014-01-29 2015-01-19 Mélange ignifuge solide exempt d'halogènes et utilisation correspondante Withdrawn EP3099760A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP19152592.2A EP3505598A1 (fr) 2014-01-29 2015-01-19 Mélange d'agent ignifuge solide sans halogène et son utilisation
EP19152589.8A EP3505596B1 (fr) 2014-01-29 2015-01-19 Mélange d'agent ignifuge solide sans halogène et son utilisation
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US20160340588A1 (en) 2016-11-24
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US10508238B2 (en) 2019-12-17
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DE102014001222A1 (de) 2015-07-30
EP3505596A1 (fr) 2019-07-03
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KR20160114160A (ko) 2016-10-04
EP3505598A1 (fr) 2019-07-03
CN109796628B (zh) 2021-04-20
EP3521402B1 (fr) 2022-08-31
PL3521402T3 (pl) 2023-01-02
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KR102405986B1 (ko) 2022-06-10
EP3505597B1 (fr) 2022-08-31
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JP2017508832A (ja) 2017-03-30
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CN109810291A (zh) 2019-05-28
ES2914882T3 (es) 2022-06-17
CN105940085B (zh) 2020-03-24

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