EP4028406A1 - Metal complexes, manufacturing method thereof, flame-retardant polymer composition comprising the same and their use - Google Patents
Metal complexes, manufacturing method thereof, flame-retardant polymer composition comprising the same and their useInfo
- Publication number
- EP4028406A1 EP4028406A1 EP20765313.0A EP20765313A EP4028406A1 EP 4028406 A1 EP4028406 A1 EP 4028406A1 EP 20765313 A EP20765313 A EP 20765313A EP 4028406 A1 EP4028406 A1 EP 4028406A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- flame
- complex
- formula
- polymer composition
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- 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
- C08K5/5398—Phosphorus bound to sulfur
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- Metal complexes, manufacturing method thereof, flame-retardant polymer composition comprising the same and their use
- the present invention relates to novel flame retardants and to manufacturing methods thereof, to flame-retardant polymer compositions, as well as to their uses.
- Plastics usually need to be equipped with flame retardants in order to be able to meet the high flame-retardant requirements required by plastics processors and, in some cases, by the legislation.
- flame retardants Preferably - also for ecological reasons - non- halogenated flame-retardant systems are used that form only small or no smoke gases.
- DOPO may be synthesized by reaction of 2-phenylphenol with phosphorus trichloride in the presence of zinc chloride.
- the reaction product 6-chlorine (6H)-dibenz[c,e][1,2] oxaphosphorine (DOP-CI) is produced in high yields at high temperatures under hydrochlorine breakdown. When heating the DOP-CI at high temperatures in the presence of water DOPO is quantitatively produced in high purity.
- DOPO is a white crystalline solid which is present in the form of two tautomers, 6/-/-dibenzo[c,e][1 ,2]oxaphosphorine-6-one (tautomer I) and 6-hydroxy-(6/-/)- dibenzo-[c,e][1 ,2]oxaphosphorin (tautomer II). This latter compound hydrolyses in the presence of water to 2'-hydroxydiphenyl-2-phosphinic acid.
- DOPO derivatives have been synthesized, particularly for use in epoxy resins for electrical and electronic applications that are more hydrolysis stable and have significantly higher melting points.
- DOPO and and its derivatives are well known flame retardants in polymers, e.g. in polyesters.
- Metal salt based DOPO-derivatives can help overcoming these issues.
- salts of diorganyl phosphinic acid, in particular their alkali metal and alkaline earth metal salts, and their use as flame retardant for polyesters and polyamides are known, e.g. from patents DE 2252258 and DE 2447727.
- JP 2001-139586 A describes the use of zinc and aluminum salts of 10-hydroxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as flame-retardants for organic polymers. Both salts are synthesized by a double conversion starting from sodium phosphonate and metal chloride or metal sulfate.
- the zinc salt is also prepared by reacting zinc acetate (hydrate) in ethanol with 10-hydroxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as described in JPS 53-127484 A.
- JP2003-306585 describes magnesium-bis-2-hydroxydiphenyl-2 'phosphinate and the Mg-salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as nucleating agents for polypropylene. Use as a flame retardant is not published.
- JPH07-330963 describes the same salts as clarifiers for polypropylene. Use as a flame retardant is not published.
- JPH04-252245 describes barium-bis (1'-hydroxy-2,2'-biphenylenephosphinate) in combination with inorganic fillers for use in polyolefins for improving the mechanical properties. A use as flame retardant is not published.
- JPH03-223354 describes zinc bis (1'-hydroxy-2,2'-biphenylenephosphinate) in combination with inorganic fillers for improving mechanical properties in polyolefins. A use as flame retardant is not published.
- EP 1657972 A1 describes a reaction product which is obtained by double conversion of DOPO with NaOH / water and ZnCl 2 .
- the precipitation product thus obtained has the composition of zinc-bis-2-hydroxydiphenyl-2 phosphinate.
- a homologous aluminum salt is also mentioned as an example in this document.
- the synthesis proceeds in anhydrous isopropanol as solvent by reacting aluminum alcoholate and DOPO. Both syntheses are therefore not sustainable.
- DE 102010026973 A1 describes a flame-retardant combination which reduces the degradation reaction of plastics and the corrosion behavior during processing. This effect can be achieved by adding metal oxides or metal hydroxides.
- Objective of the present invention is the provision of novel flame retardants which can be used alone or in combination with other flame-retardants in polymer compositions. These flame-retardants impart excellent flame-retardant properties to polymers without deteriorating their mechanical properties.
- complexes comprising a selected metal and a combination of ligands based on DOPO, 10-hydroxy-group containing DOPO (also referred as DOPO-OH) or their thio analogues and hydroxide ions can be generated by reacting metal precursors on the DOPO or DOPO-OH sodium, potassium or lithium phosphinates (or their thio analogues) in combination with hydroxide ions and that these new structures can be used, alone or in combination with other additives as flame retardants.
- DOPO or DOPO-OH or their thio analogues correspond to the formula (I) shown below wherein
- Y represents 0 or S
- W represents hydrogen or OH.
- the present invention relates to metal complexes comprising a metal Me selected from the group consisting of Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, TiO, VO, Cr, WO2, MoO, Al, Sb, La, Zr, ZrO, Ce and/or Sn, a hydroxy group ligand and another ligand of formula (II), (III) or (IV) wherein Y represents 0 or S.
- Me is a metal selected from the group consisting of Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, TiO, VO, Cr, W0 2 , MoO, Al, Sb, La, Zr, ZrO, Ce and/or Sn
- Y is 0 or S, preferably 0, x is 2, 3 or 4, preferably 2 or 3, a is 1 or 2, preferably 1 , b is a number with value a + x, and c is a number 31 , preferably 1 -10 and most preferably 1 , with the proviso that in case the complex contains more than one Me-ions some of the Me-ions in the complex may contain no OH -ion ligands.
- Me-ions in a complex comprising several Me-ions contain at least one OH--ion ligand.
- the number of ligands in formulae (V), (VI) and (VII) is chosen in a way that the resulting complex is electroneutral, thus that the positive charge of Me is compensated by the negative charges of the ligands.
- the metal ions Me included in the complexes of the present invention are preferably selected from the group consisting of independently from each other from Mg, Ca, Zn, Mn, Fe, Ti, TiO, Al, Ce or Sn, most perferably selected from the group consisting of Zn, TiO, Al and/or Ce.
- a complex can contain one or more metal ions Me of the same metal or more metal ions Me from different metals.
- a complex contains one or more metal ions Me of the same metal.
- a complex contains one metal ions Me.
- Fe, Ti, TiO, Al, Ce or Sn can be present in the ligands of formulae (V), (VI) and (VII) simultaneously and in all combinations.
- the metal complexes comprising ligands derived from DOPO can either contain oxidized ligands, such as in complexes of formula (VII), and/or can contain hydrogenated ligands, such as in complexes of formula (V), and/or can contain hydrated ligands, such as in complexes of formula (VI).
- the oxidized species of ligands is in equilibrium with the corresponding hydrogen ated or hydrated species of ligands. Depending on the present conditions and the previous history (e.g. the production conditions), the equilibrium can be shifted towards the oxidized species or towards the hydrogenated or hydrated species. In extreme cases, even only the oxidized or hydrogenated or hydrated species might be present.
- metal complexes comprising besides hydroxy ions ligands of formulae (III) and (IV).
- metal complexes comprising besides hydroxy ions ligands of formula (IV).
- the complexes contain a combination of formulae (V) and (VII).
- the complexes of formula (VII) are in equilibrium with complexes of formula (V) and may be obtained by liberation of hydrogen from complexes of formula (V).
- complexes containing a combination of formulae (VI) and (VII) a similar effect can be observed.
- complexes of formula (VII) are in equilibrium with complexes of formula (VI) and may be obtained by liberation of water from complexes of formula (VI).
- a first manufacturing method A two subsequent steps are performed.
- Method A conversion A1 : DOPO and alkali metal hydroxide (KatOH), preferably sodium, potassium or lithium hydroxide, are reacted in an aqueous phase (see scheme 1).
- Alcohols can be added.
- DOPO and alkali hydroxide are applied in a molar ratio from 0.8 : 1 to 1 : 0.8, preferably 0.95 : 1 to 1 : 0.95 and most preferred in equimolar amounts.
- Method A proceeds at temperatures below 100 °C, preferably from 20 °C to 90 °C, and most preferred from 30 °C to 70 °C, if normal pressure is applied. In case of higher pressures temperatures are applied at which liquid water is present in the reaction mixture.
- Method A therefore initially yields the alkali metal salt of DOPO conversion products (Kat-DOPO) as a solution as depicted in scheme 1.
- the product from method A, conversion A1 is converted in a subsequent step, where two options are available by either using metal halides or metal sulfates.
- EP 1657972 A1 quotes the Zn salt of DOPO as flame retardant, obtained from the conversion of DOPO with NaOH and ZnCl 2 in water.
- the synthesis can be performed in the present case, method A, conversion A2.
- Method A conversion A2
- Kat-DOPO and alkali hydroxide are preferably applied in conversion step A2 in a molar ratio from 0.8 : 1 to 1 : 0.8, preferably 0.95 : 1 to 1 : 0.95 and most preferred in equimolar amounts.
- Kat-DOPO and alkali hydroxide are preferably applied in conversion step A3 in a molar ratio from 0.8 : 1 to 1 : 0.8, preferably 0.95 : 1 to 1 : 0.95 and most preferred in equimolar amounts.
- Kat-DOPO and alkali hydroxide are preferably applied in conversion step A4 in a molar ratio from 0.8 : 1 to 1 : 0.8, preferably 0.95 : 1 to 1 : 0.95 and most preferred in equimolar amounts.
- the reactions depicted in schemes 1 , 2, 3 and 4 can be performed using DOPO- OH or all thio-analogues of DOPO and DOPO-OH instead of DOPO as a starting material.
- the resulting precipitation products comprising the metal complexes of this invention, preferably the complexes of formulae (V), (VI) and/or (VII), are filtered off and washed with water.
- mixtures of the different metal halides or metal sulfates can be used in combination in one step. From this, mixed complexes can be obtained.
- the use of sulfates exhibits technical advantages over the use of halides, namely an improvement of the precipitation.
- sulfates exhibits technical advantages over the use of halides, namely an improvement of the precipitation.
- smaller quantities of water are required to wash of the resulting salts and therefore low conductivity values can be reached faster than from the halides pathway.
- waste water amounts can be reduced significantly.
- a granulation process can be used.
- Preferred methods comprise spray driers, spray granulators (top spray, bottom spray, and counter current flow), fluidized bed granulators or paddle dryers. During this process, water remaining from method A can be removed unless a desired degree of residual moisture is reached.
- Granulation can be conducted by spray drying of an aqueous suspension of the reaction products from method A at higher temperatures, for example at 70 - 80 °C.
- a spray granulation starting with a mixture of the educts (flow bed) and spraying of water on to the flow bed with subsequent drying step is feasible.
- the flow bed temperature is adjusted to elevated temperatures, for example to 70 - 80 °C, so granulate can be dried and a free-flowing non-dusting granulate is obtained. Residual moisture of this process is between 0,5 - 1 ,0 %.
- the obtained products can be dried in a static way either in vacuum or at ambient pressure at elevated temperatures, for example at 70 - 100 °C and then be used as is.
- a metal complex containing besides metal Me and a hydroxy group a ligand of formula (II) or (III), preferably a complex of formula (V) or (VI), is treated in a calcination step taking place at elevated temperatures, preferably from 130 °C to 270 °C, more preferred at 170 °C to 220 °C, and most preferred between 180 °C and 200 °C.
- the calcination preferably takes place in vacuum or at ambient pressure.
- two possible reactions occur depending on the starting materials, metal complexes comprising ligands derived from DOPO or from DOPO-OH (or from their respective thio-analogues).
- Scheme 5 shows the conversion of metal complexes comprising ligands derived from DOPO, meaning ligands of formula (II).
- hydrogen is liberated from the precipitation product of formula (VIII) and the resulting material is a cyclization product of formula (IX), given full conversion of starting material (VIII).
- Scheme 6 shows the conversion of metal complexes comprising ligands derived from DOPO-OH, meaning ligands of formula (III).
- water is liberated from the precipitation product of formula (X) and the resulting material is a cyclization product of formula (XI), given full conversion of starting material (X).
- calcination is carried out in a mixer or dryer, electric furnace, rotary furnace or high-speed mixer. Most preferably, a vertical or horizontal paddle mixer is used.
- Products resulting from the calcination step can contain remaining starting material in any proportion without limiting the scope of the present invention.
- the present invention relates to a first process for the preparation of complexes comprising Me, a hydroxy group and a ligand of formulae (II) or (III) said first process comprising the steps: i) reacting DOPO, DOPO-OH or a thio-analogue of DOPO or of DOPO-OH and an alkali metal hydroxide in an aqueous phase at temperatures above 20 °C to obtain an alkali metal salt of a ring-opened conversion product of DOPO, DOPO-OH or a thio-analogue of DOPO or of DOPO-OH, ii) adding a metal halide Me x+ (Hal-) x and an aqueous solution of an alkali metal hydroxide to the product obtained from step i) and reacting this mixture at temperatures above 20 °C until a precipitate comprising the complex is formed, and iii) removing the liquid phase from the reaction mixture obtained in step ii) to obtain the complex comprising ME,
- the present invention relates to a second process for the preparation of complexes comprising ME, a hydroxy group and a ligand of formulae (II) or (III) said second process comprising the steps: i) reacting DOPO, DOPO-OH or a thio-analogue of DOPO or of DOPO-OH and an alkali metal hydroxide in an aqueous phase at temperatures above 20 °C to obtain an alkali metal salt of a ring-opened conversion product of DOPO, DOPO-OH or a thio-analogue of DOPO or of DOPO-OH, iia) adding a metal sulfate Me 2+ (S04 2- ) or (Me 3+ )2(S04 2- )3 and an aqueous solution of an alkali metal hydroxide to the product obtained from step i) and reacting this mixture at temperatures above 20 °C until a precipitate comprising the complex is formed, and iii) removing the liquid phase from the reaction
- the present invention relates to a third process for the preparation of complexes comprising ME, a hydroxy group and a ligand of formula (IV) said third process comprising the step: iv) calcinating a metal complex containing besides metal Me, a hydroxy group and a ligand of formula (II) or (III), preferably a complex of formula (V) or (VI), at temperatures from 130 °C to 270 °C in vacuum or at ambient pressure to result in a liberation of hydrogen or water.
- the complexes of the present invention described above are particularly suitable as flame-retardants.
- a flame-retardant composition comprising selected components as described below show a synergistic performance in different plastic articles, e.g. a better compatibility, processability or flame-retardant performance than the single components of said composition.
- the present invention thus relates to a flame-retardant polymer composition
- a flame-retardant polymer composition comprising: a) a polymer, b) a metal complex comprising a metal Me selected from the group consisting of Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, TiO, VO, Cr, W0 2 , MoO, Al, Sb, La, Zr, ZrO, Ce and/or Sn, a hydroxy group ligand and another ligand of formula (II), (III) or (IV) as defined above, and optionally c) a metal complex comprising a metal Me selected from the group consisting of Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, TiO, VO, Cr, W0 2 , MoO, Al, Sb, La, Zr, ZrO, Ce and/or Sn, and at least two ligands of formula (II), (III) or (IV) as defined
- the amount of polymer a) in the flame-retardant polymer composition of the invention may vary in a broad range.
- the amount of component a) is 40 to 95 % by weight, preferably 50 to 90 % by weight and most preferred 60 to 85 % by weight, referring to the total amount of the polymer composition.
- the amount of flame-retardant b) in the flame-retardant polymer composition of the invention may also vary in a broad range.
- the amount of component b) is 5 to 40 % by weight, preferably 7.5 to 30 % by weight and most preferred 10 to 25 % by weight, referring to the total amount of the polymer composition.
- the amount of flame-retardant c) in the flame-retardant polymer composition of the invention may also vary in a broad range.
- the amount of component c) is 1 to 25 % by weight, preferably 2 to 15 % by weight and most preferred 5 to 15 % by weight, referring to the total amount of the polymer composition.
- the component ratio in the flame-retardant polymer composition comprising components a), b) and optionally c) may vary over a broad range.
- the flame-retardant polymer composition contains only one or more metal complexes of component b).
- the weight ratio of component(s) b) to component(s) c) is preferably between 1 : 10 and 10: 1 , more preferred between 1: 1 and 1: 4.
- Preferred metal complexes b) in the flame-retardant polymer compositions of this invention are metal complexes with structures of formulae (V), (VI) or (VII) defined above.
- Preferred component c) in the flame-retardant polymer compositions of this invention are compounds of formulae (XII), (XIII) and (XIV) wherein Me is a metal selected from the group consisting of Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, TiO, VO, Cr, W0 2 , MoO, Al, Sb, La, Zr, ZrO, Ce and/or Sn, Y is O or S, preferably O, x is 2, 3 or 4, preferably 2 or 3, d is a number with value x, and e is a number 31 , preferably 1-10 and most preferably 1.
- Particularly preferred components c) are the following individual components: Mg(2'-hydroxy [1,1 '-biphenyl-2 -yl-2-phosphinate)2, CAS No. [165597-56-8], Zn(2'-hydroxy [1,1 '-biphenyl-2 -yl-2-phosphinate)2, CAS No. [139005-99-5], AI(2'-hydroxy[1 , 1 '-biphenyl-2 -yl-2-phosphinate) 3 , CAS No.
- these compounds or mixtures of two or more thereof are included as component c) in the flame-retardant polymer compositions of the present invention.
- Additional preferred components c) are Zn(10-oxy-9,10-dihydro-9-oxa- phosphaphenanthrene-10-sulfide-ate) 2 , Al(10-oxy-9, 10-dihydro-9-oxa- phosphaphenanthrene-10-oxide-ate)3 and Zn(2'-hydroxy[1 , 1 ' -biphenyl-2 -yl-2- phosphinate)2.
- Component a) of the flame-retardant polymer compositions of the invention can be any natural polymer including modifications by chemical treatment or any synthetic polymer. Polymer blends may also be used. Suitable polymers a) include thermoplastic polymers, thermoplastic elastomeric polymers, elastomers or duroplastic polymers.
- thermoplastic polymers are used as component a).
- Preferred thermoplastic polymers are selected from the group consisting of polyamides, polycarbonates, polyolefins, polystyrenes, polyesters, polyvinyl chlorides, polyvinyl alcohols, ABS and polyurethanes.
- duroplastic polymers may be used. These are preferably selected from the group consisting of epoxy resins, phenolic resins and melamine resins.
- thermoplastics and/or thermosets may be used.
- polymers preferably used as component a) in the polymer compositions of the present invention are: polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1 , poly-4-methylpentene-1 , polyvinylcyclohexane, polyisoprene or polybutadiene and polymers of cycloolefins, for example of cyclopentene or norbornene, polyethylene (including crosslinked PE), e.g.
- HDPE high density polyethylene
- HDPE-HMW high molecular weight PE
- HDPE-UHMW medium density polyethylene
- MDPE low density polyethylene
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- VLDPE VLDPE
- ULDPE linear low density polyethylene
- EVA ethylene and vinyl acetate
- polystyrene poly(p-methylstyrene), poly(alpha-methylstyrene)
- halogen-containing polymers such as polychloroprene, polyvinyl chloride (PVC); polyvinylidene chloride (PVDC), copolymers of vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinyl chloride / vinyl acetate; polystyrene, poly(p
- polyamides and copolyamides are those which are derived from e-caprolactam, adipic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, hexamethylene diamine, tetramethylenediamine, 2-methyl-pentamethylene diamine, 2,2,4-trimethyl-hexamethylene diamine, 2,4,4-tri-methylhexamethylenediamine, m-xylylenediamine or bis(3-methyl- 4-aminocyclohexyl) methane; polyureas, polyimides, polyester imides, polyhydantoins and polybenzimidazoles; polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxy-carboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1 , 4- dimethyl cyclohexane
- ABS ABS
- PC / AS PC / PBT
- PVC / CPE PVC / acrylic
- POM / thermoplastic PUR POM / thermoplastic PUR
- PC / thermoplastic PUR POM / acrylate
- POM / MBS PPO / HIPS
- PPO / PA 6.6 and copolymers PA / HDPE, PA / PP, PA / PPO, PBT / PC /
- thermosets such as phenol-formaldehyde resins (PF), melamine- formaldeyhde resins (MF) or urea-formaldehyde-resins (UF) or mixtures thereof; epoxy resins ; phenolic resins; wood-plastic composites (WPC) and polymers based on PLA, PFIB and starch.
- polyamides Preference is given to polyamides, polyesters, preferably to PET and PBT, polyurethanes, polycarbonates and epoxy resins.
- Particularly preferred components a) are polyamided and polyesters and most preferred are glass fiber reinforced polyamides and polyesters.
- the flame-retardant polymer composition of the present invention may contain further additives as component d).
- the amount of component d) may vary in a broad range. Typical amounts of component d) are between 0 and 50 % by weight, preferably between 1 and 20 % by weight and more preferred between 5 and 15 % by weight, referring to the total amount of the flame-retardant polymer composition.
- additives d) are antioxidants, light stabilizers, processing aids, nucleating agents and clarifiers, antistatic agents, lubricants, such as calcium stearate and zinc stearate, viscosity and impact modifiers, compatibilizers and dispersing agents, dyes or pigments, fillers and/or reinforcing agents.
- the flame-retardant polymer composition of the present invention preferably contains additional fillers. These are are preferably selected from the group consisting of metal hydroxides and/or metal oxides, preferably alkaline earth metal, e.g. magnesium hydroxide, 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 beads, glass particles, wood flour, cellulose powder, carbon black, graphite and chalk.
- metal hydroxides and/or metal oxides preferably alkaline earth metal, e.g. magnesium hydroxide, aluminum hydro
- the flame-retardant polymer composition of the present invention preferably contains reinforcing agents, more preferred reinforcing fibers. These are are preferably selected from the group consisting of glass fibers and carbon fibers. Fibers may be staple fibers or filaments, preferably staple fibers.
- additives d) can impart other desired properties to the polymer composition of the invention.
- the mechanical stability can be increased by reinforcement with fibers, preferably with glass fibers.
- the flame-retardant polymer compositions of the invention are preferably prepared by providing the components a), b) and optionally c) and/or d), e.g. by mixing or by incorporation into a masterbatch, and by incorporating the components b) and optionally c) and/or d) into the polymer or polymer mixture.
- the process for the production of flame-retardant polymer compositions is characterized by incorporating and homogenizing the flame retardant, component b) and optionally c), into polymer pellets (optionally together with other additives), in a compounding assembly at elevated temperatures.
- the resulting homogenized polymer melt is then formed into a strand, cooled and portioned.
- the resulting granules are dried, e.g. at 90 °C in a convection oven.
- the compounding equipment is selected from the group of single-screw extruders, multizone screws, or twin-screw extruders.
- the invention also relates to the use of the above-defined metal complexes comprising a metal Me selected from the group consisting of Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, TiO, VO, Cr, WO2, MoO, Al, Sb, La, Zr, ZrO, Ce and/or Sn, a hydroxy group ligand and another ligand of formula (II), (III) or (IV) as a flame retardant.
- a metal Me selected from the group consisting of Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, TiO, VO, Cr, WO2, MoO, Al, Sb, La, Zr, ZrO, Ce and/or Sn, a hydroxy group ligand and another ligand of formula (II), (III) or (IV) as a flame retardant.
- Conductivity 2110 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 510 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 505 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 517 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 670 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 500 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 514 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 508 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 510 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 353 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 319 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 300 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 470 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- Conductivity 344 ms / cm (10% suspension in distilled water, following centrifugation; measured with a calibrated conductivity meter).
- TGA and DSC thermogravimetric analysis
- % Glass fibers PPG Fiber Glass, HP3610 EC104,5 mm are compounded on a microcompounder
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19196744 | 2019-09-11 | ||
PCT/EP2020/075121 WO2021048154A1 (en) | 2019-09-11 | 2020-09-08 | Metal complexes, manufacturing method thereof, flame-retardant polymer composition comprising the same and their use |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4028406A1 true EP4028406A1 (en) | 2022-07-20 |
Family
ID=67928730
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20765313.0A Withdrawn EP4028406A1 (en) | 2019-09-11 | 2020-09-08 | Metal complexes, manufacturing method thereof, flame-retardant polymer composition comprising the same and their use |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP4028406A1 (en) |
CN (1) | CN114450290A (en) |
WO (1) | WO2021048154A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112745604A (en) * | 2021-02-04 | 2021-05-04 | 陕西理工大学 | Preparation method of flame-retardant modified rice hull powder-polyvinyl chloride composite material |
CN113337007B (en) * | 2021-04-28 | 2023-03-10 | 佳化化学(抚顺)新材料有限公司 | Liquid flame retardant, flame-retardant silicone rubber, and preparation method and application thereof |
EP4296335A1 (en) * | 2021-10-18 | 2023-12-27 | Lg Chem, Ltd. | Phosphorus-based flame retardant and thermoplastic resin composition including same |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA738245B (en) | 1972-10-25 | 1974-09-25 | Hoechst Ag | Flame resistant thermoplastic polyesters |
DE2447727A1 (en) | 1974-10-07 | 1976-04-08 | Hoechst Ag | FLAME RESISTANT POLYAMIDE MOLDING COMPOUNDS |
JPS53127484A (en) | 1977-04-13 | 1978-11-07 | Toyobo Co Ltd | Phosphorus-containing chelate compound |
US4208321A (en) | 1978-04-13 | 1980-06-17 | Pennwalt Corporation | Polyamide resins flame retarded by poly(metal phosphinate)s |
IT1130965B (en) | 1979-03-19 | 1986-06-18 | Sanko Kaihatsu Kagaku Kenk | FLAME RETARDANT AGENT |
JP2906180B2 (en) | 1989-11-11 | 1999-06-14 | チッソ株式会社 | Inorganic filler-containing polyolefin composition |
JP2896610B2 (en) | 1991-01-28 | 1999-05-31 | チッソ株式会社 | Inorganic filler-containing polyolefin composition |
JP3805388B2 (en) | 1994-04-08 | 2006-08-02 | チッソ株式会社 | Crystalline polyolefin composition |
DE19614424A1 (en) | 1996-04-12 | 1997-10-16 | Hoechst Ag | Synergistic combination of flame retardants for polymers |
JP2001139586A (en) | 1999-11-12 | 2001-05-22 | Sanko Chem Co Ltd | Method for production of organic phosphorus compound and its metal salt |
JP2003306585A (en) | 2002-04-15 | 2003-10-31 | Sekisui Chem Co Ltd | Resin-phyllosilicate composite material and its manufacturing process |
DE102004049614A1 (en) | 2004-10-12 | 2006-04-13 | Schill + Seilacher "Struktol" Ag | New phosphinate complex useful as flame protective agent for polyester, polyamide and epoxide resin and their manufactured products |
DE102010026973A1 (en) | 2010-07-13 | 2012-01-19 | Clariant International Ltd. | Flame retardant stabilizer combination for thermoplastic polymers |
DE102011011928A1 (en) | 2011-02-22 | 2012-08-23 | Clariant International Ltd. | Flame retardant stabilizer combination for thermoplastic polymers |
CN104109173A (en) * | 2014-06-23 | 2014-10-22 | 淮阴师范学院 | HPPP-Zn coordination polymer and synthesis method thereof |
-
2020
- 2020-09-08 WO PCT/EP2020/075121 patent/WO2021048154A1/en unknown
- 2020-09-08 EP EP20765313.0A patent/EP4028406A1/en not_active Withdrawn
- 2020-09-08 CN CN202080050043.4A patent/CN114450290A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CN114450290A (en) | 2022-05-06 |
WO2021048154A1 (en) | 2021-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI582222B (en) | Flame retardant mixtures comprising flame retardant and aluminum phosphites, process for preparation thereof and use thereof | |
CN106573776B (en) | Salts of pyrophosphonic acids as flame retardants | |
EP4028406A1 (en) | Metal complexes, manufacturing method thereof, flame-retardant polymer composition comprising the same and their use | |
CN107641218B (en) | Flame retardant mixtures, their preparation and their use | |
RU2580733C2 (en) | Fireproof compositions, containing triazine-intercalated metal phosphates | |
EP3172217B1 (en) | Phosphorus containing flame retardants | |
US9505793B2 (en) | Azine metal phosphates as flame-retardant materials | |
JPH09235465A (en) | Low combustible polyamide molding material | |
TW201815928A (en) | Flame retardant mixtures and the production and use thereof | |
JP2008143901A (en) | Salts of alkyl ester of carboxy ethyl (alkyl) phosphinic acid | |
US20190292464A1 (en) | Diorganylphosphinic acid salts, method for the production thereof and the use thereof | |
US20140371361A1 (en) | Aluminum Hydrogen Phosphites, A Process for Preparing Them and Their Use | |
JP2022553226A (en) | Process for preparing phosphorus-containing flame retardants and their use in polymer compositions | |
US20150141556A1 (en) | Phosphorus containing flame retardants | |
WO2014060004A1 (en) | Method for producing metal-2-hydroxydiphenyl-2'-(thio)phosphinates and metal-diphenylene-(thio)phosphonates, compositions containing same and use thereof as flame-proofing agents | |
JP2013531615A (en) | Method for producing alkyl phosphonite | |
CN114364729B (en) | Flame retardant composition, polymer molding composition comprising the same and use thereof | |
CN112409638B (en) | Flame retardant combinations for polymer compositions and uses thereof | |
CA2911457C (en) | Phosphorus containing flame retardants | |
JPH04234893A (en) | Flame retardant for polymer | |
CA3186993A1 (en) | Flame retardant and stabilizer combined for use with thermoplastics | |
WO2021048157A1 (en) | Polymer composition comprising heat stabilizer and use thereof | |
RU2812784C1 (en) | Method for obtaining phosphorus-containing fire-resistant agents and their application in polymer compositions | |
WO2023096795A1 (en) | Flame retardant and synergist combined for use with thermoplastics | |
CA3186971A1 (en) | Flame retardant and stabilizer combined for use with thermoplastics |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20220411 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Effective date: 20230517 |