WO2012045414A1 - Flammschutzmittel- stabilisator-kombination für thermoplastische polymere - Google Patents
Flammschutzmittel- stabilisator-kombination für thermoplastische polymere Download PDFInfo
- Publication number
- WO2012045414A1 WO2012045414A1 PCT/EP2011/004887 EP2011004887W WO2012045414A1 WO 2012045414 A1 WO2012045414 A1 WO 2012045414A1 EP 2011004887 W EP2011004887 W EP 2011004887W WO 2012045414 A1 WO2012045414 A1 WO 2012045414A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- weight
- flame retardant
- stabilizer combination
- hydroxide
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-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
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- 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
- C08K5/34922—Melamine; Derivatives thereof
-
- 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
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
- 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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- 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
Definitions
- the invention relates to a flame retardant stabilizer combination for thermoplastic polymers and to polymeric molding compositions and moldings which contain such flame retardant stabilizer combinations.
- thermoplastics take place predominantly in the melt.
- the associated structural and state changes hardly survive a plastic without changing its chemical structure.
- antioxidants and stabilizers are used so that the plastic without chemical damage survives the processing and then for a long time against external influences such as heat,
- UV light, weather and oxygen (air) is stable.
- lubricants prevent too much sticking
- Plastics are processed during processing in the melt.
- Flame retardants must often be added in high dosages in order to ensure a sufficient flame retardancy of the plastic according to international standards. Due to their chemical reactivity, which for the
- Flame retardants affect the processing stability of plastics. For example, increased polymer degradation, crosslinking reactions, outgassing or discoloration may occur.
- Polyamides are z. B. stabilized by small amounts of copper halides and aromatic amines and hindered phenols, with the achievement of long-term stability at high continuous service temperatures in the foreground (H. Zweifel (Ed.): "Plastics Additives Handbook", 5 th Edition, Carl Hanser Verlag , Kunststoff, 2000, pages 80 to 84).
- Phosphinic acids have proven to be effective flame-retardant additives (DE-A-2 252 258 and DE-A-2 447 727). Calcium and aluminum phosphinates have been described as being particularly effective in polyesters, and
- Flame retardants act more effectively than the phosphinates alone (PCT / EP97 / 01664 and DE-A-19 73 4437 and DE-A-19 737 727).
- Polymer molding compounds with phosphorus-containing flame retardants can be stabilized with carbodiimides, isocyanates and isocyanurates
- Polyamides proved the effect of the stabilizers described so far as insufficient, especially to suppress the effects occurring during processing such as discoloration and molecular weight reduction.
- DE-A-19 933 901 describes phosphinates in combination with melamine polyphosphate as
- Polyamide molding compounds containing as flame retardants an aluminum phosphinate in combination with an aluminum hydroxide, an aluminum phosphate and / or an aluminum phosphonate In a polybutylene terephthalate with 30% glass fibers is in 20% dosage of the flame retardant mixture with
- Aluminum phosphinate and aluminum monomethyl phosphonate V-0 The measured elongation at break is 1.2%. For technical applications in injection molding but much higher elongations at break of at least 2% are required so that the ejector pins of the injection molding machines do not damage the components.
- thermoplastics in particular for polyamides and polyesters, which in addition to the film resistance also have good mechanical properties and low polymer degradation, have a stabilizing effect on the plastic lead to moldings and not to efflorescence from the plastics.
- the lead in addition to the film resistance also have good mechanical properties and low polymer degradation, have a stabilizing effect on the plastic lead to moldings and not to efflorescence from the plastics.
- Flame retardant stabilizer combinations of the invention to better values at the elongation at break.
- phosphorous acid also referred to as phosphonic acid
- HP 0
- OH OH
- component C further nitrogen or phosphorus-nitrogen-containing flame retardants
- the invention therefore provides a flame retardant stabilizer combination for thermoplastic polymers comprising as component A from 20 to 99% by weight of a dialkylphosphinic acid salt of the formula (I) and / or of a diphosphinic acid salt of the formula (II) and / or its polymers,
- R 1 , R 2 are the same or different and C 1 -C 6 -alkyl, linear or branched;
- R 3 C Cio-alkylene, linear or branched, C 6 -Cio-arylene, C 7 -C 2 o alkylarylene or C 7 -C 2 o arylalkylene;
- M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
- component B from 1 to 80% by weight of a salt of phosphorous acid having the general formula (III)
- M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and / or K and m is 1 to 4
- component C 0 to 30 wt .-% of a nitrogen-containing synergist and / or a phosphorus / nitrogen flame retardant
- component D 0 to 10 wt .-% of a zinc salt and / or a basic and / or amphoteric oxide, hydroxide, carbonate, silicate, borates, stannates, mixed oxide-hydroxide, oxide-hydroxide-carbonate, hydroxide silicate and / or Hydroxide borates and / or mixtures of these substances, as component E 0 to 3 wt .-% of a phosphonite and / or a mixture of a phosphonite and a phosphite and as component F 0 to 3 wt .-% of an ester and / or salt of long-chain aliphatic carboxylic acids (fatty acids), which typically have chain lengths of C
- fatty acids which typically have chain lengths of C
- inventive combinations of salts of dialkylphosphinic acids with salts of phosphorous acid have a good flame retardancy combined with improved stability during incorporation into the polymers.
- the polymer degradation is prevented or greatly reduced and there are no moldings and no efflorescence observed.
- the combinations according to the invention also reduce the discoloration of the plastics during processing in the melt and
- R 1 , R 2 are the same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
- R 3 is methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; Phenylene or naphthylene; Methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene,
- the flame retardant stabilizer combination preferably contains
- component F 0.1 to 2% by weight of component F.
- the flame retardant stabilizer combination also contains
- component F 0.1 to 2% by weight of component F.
- the flame retardant-stabilizer combination also contains
- Component B is preferably reaction products of phosphorous acid with aluminum compounds.
- Component B is preferably aluminum phosphite
- Aluminum phosphite [Al (OH) (H 2 P0 3 ) 2 * 2aq], aluminum phosphite tetrahydrate
- Al 2 (HP0 3) 3 * 4aq] Aluminiumphosphonat, Al 7 (HP0 3) 9 (OH) 6 (1, 6- hexanediamine) i5 1 * 12H 2 0, Al 2 (HP0 3) 3 * xai 2 0 3 * nH 2 0 with x 2.27 - 1 and / or
- Component C is preferably condensation products of melamine and / or reaction products of melamine with polyphosphoric acid and / or reaction products of condensation products of melamine with polyphosphoric acid or mixtures thereof.
- the component C is Meiern, melam, melon, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate,
- Component C is preferably nitrogen-containing phosphates of the formulas (NH 4 ) y H 3 -y P0 4 or (NH 4 P0 3 ) 2 , with y being 1 to 3 and z being 1 to 10 000.
- component D is magnesium oxide,
- the phosphonites are those of the general structure - [P (ORi) 2 ], (IV) where
- R is a mono- or polyhydric aliphatic, aromatic or heteroaromatic organic radical
- R 2 independently of one another are C 1 -C 4 -alkyl (linear or branched), C 1 -C 2 -alkoxy,
- m 1 to 4.
- Component F is preferably alkali metal, alkaline earth metal,
- the invention also relates to a flameproof plastic molding composition comprising a flame retardant-stabilizer combination according to one or more of claims 1 to 14, characterized in that it is the plastic to thermoplastic polymers and / or elastomers of the type
- Polystyrene HI high-impact
- polyphenylene ethers polyphenylene ethers
- polyamides polyamides
- polyesters polystyrene HI (high-impact)
- ABS acrylonitrile-butadiene-styrene
- PC polycarbonate / acrylonitrile-butadiene-styrene
- PPE polyethylene / HIPS (polyphenylene ether / polystyrene-H) plastics and that they are
- the invention also relates to polymer moldings, films, filaments and fibers comprising a flame retardant-stabilizer combination according to one or more of claims 1 to 14, characterized in that the polymer is polystyrene-HI (high-impact ), Polyphenylene ethers, polyamides, polyesters, polycarbonates and blends or polymer blends of the ABS type
- the plastic or the polymer is particularly preferably polyamides and / or polyesters.
- Preferred salts of phosphorous acid are water-insoluble or sparingly soluble salts.
- Particularly preferred salts of phosphorous acid are aluminum, calcium and zinc salts.
- Component B is particularly preferably a reaction product of phosphorous acid and an aluminum compound.
- Preference is given to mixtures of aluminum phosphite and aluminum hydroxide of the composition 5 to 95% by weight Al 2 (HPO 3 ) 3 * nH 2 O and 95 to 5% by weight Al (OH) 3 , particularly preferably 10 to 90% by weight Al 2 (HPO 3 ) 3 * nH 2 O and 90-10% by weight Al (OH) 3 , very particularly preferably 35-65% by weight Al 2 (HPO 3 ) 3 * nH 2 O and 65-35 Wt .-% Al (OH) 3 and each n 0 to 4
- the aluminum phosphites have particle sizes of 0.2 to 100 ⁇ .
- the preparation of the preferred aluminum phosphites is usually accomplished by reacting an aluminum source with a source of phosphorus and optionally a template in a solvent at 20 to 200 ° C for a period of up to 4 days.
- Aluminum source and phosphorus source are mixed, heated under hydrothermal conditions or at reflux, filtered off, washed and dried.
- Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).
- Preferred sources of phosphorus are phosphorous acid, (acidic)
- Ammonium phosphite alkali phosphites or alkaline earth phosphites.
- Preferred alkali metal phosphites are disodium phosphite, disodium phosphite hydrate, trisodium phosphite, potassium hydrogen phosphite.
- Preferred Dinatriumphosphithydrat is Brüggolen ® H10 of the company. Brüggemann.
- Preferred templates are 1, 6-hexanediamine, guanidine carbonate or ammonia.
- Preferred alkaline earth metal phosphite is calcium phosphite.
- the preferred ratio of aluminum to phosphorus to solvent is 1: 1: 3.7 to 1: 2.2: 100 mol.
- the ratio of aluminum to template is 1: 0 to 1: 17 mol.
- the preferred pH of the reaction solution is 3 to 9.
- Preferred solvent is water.
- component F 0 to 2% by weight of component F.
- Flame retardant stabilizer combinations are also according to the invention.
- component F 0.1 to 2% by weight of component F.
- Flame retardant stabilizer combinations with 50 to 94.8% by weight of component A are also according to the invention.
- component F 0.1 to 2% by weight of component F.
- component C is melamine cyanurate.
- component C is around
- Ammonium hydrogen phosphate, ammonium dihydrogen phosphate and / or ammonium polyphosphate is provided.
- Suitable components C are also compounds of the formulas (VII) to (XII) or mixtures thereof
- R 5 to R 7 are hydrogen, C 1 -C 8 -alkyl, C 5 -C 16 -cycloalkyl or -alkylcycloalkyl, possibly substituted by one hydroxy or one
- Ci-C 4 -hydroxyalkyl function C 2 -C 8 alkenyl, C 8 alkoxy, acyl, acyloxy, C 6 -C 2 aryl or arylalkyl, -OR 8 and -N (R 8 ) R 9 , as well as N-alicyclic or N-aromatic,
- R 8 is hydrogen, CC 8 alkyl, C 5 -C 6 cycloalkyl or -alkylcycloalkyl, possibly substituted with a hydroxy or a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 -C 8 -alkoxy, -acyl,
- R 9 to R 13 have the same groups as R 8 and -OR 8 ,
- n and n independently of one another 1, 2, 3 or 4,
- Particularly suitable components C are benzoguanamine,
- Component D is particularly preferably boehmite, dihydrotalcite, zinc borate and / or zinc stannate.
- M is calcium, aluminum or zinc.
- Protonated nitrogen bases are preferably understood to mean the protonated bases of ammonia, melamine, triethanolamine, in particular NH 4 + .
- Suitable phosphinates are described in PCT / WO97 / 39053, which is incorporated herein by reference.
- Particularly preferred phosphinates are aluminum, calcium and
- the same salt of phosphinic acid as the phosphorous acid is used in the application, so z.
- phosphinic acid aluminum dialkylphosphinate together with aluminum phosphite or Zinkdialkylphosphinat together with zinc phosphite.
- compositions A and B and optionally C, D, E and F additives can be added, such.
- Suitable antioxidants include alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol; 1,2-alkylthiomethylphenols, e.g. B. 2,4-dioctylthiomethyl-6-tert-butylphenol; Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol; Tocopherols, e.g. Cc-tocopherol, beta-tocopherol,
- ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E); Hydroxylated thiodiphenyl ethers, e.g. B. 2.2 (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thio-bis- (6-tert-thio-bis butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec-amylphenol), 4,4'-bis (2,6-di-methyl-4-hydroxyphenyl) -disulfic acid; Alkylidene Bisphenols, e.g. B. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol;
- benzyl compounds e.g. B. 3,5,3 ⁇ 5'-tetra-tert-butyl-4,4'-dihydroxydi benzyl ether; hydroxybenzylated malonates, e.g. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate; Hydroxybenzyl aromatics, e.g. B.
- Suitable UV absorbers and light stabilizers are, for example
- 2-hydroxybenzophenones such as.
- Esters of optionally substituted benzoic acids such as. B. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di- tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl- 4,6-di-tert-butylphenyl ester; Acrylates, such as. B. cc-cyano-ß, ß-diphenyl
- methyl ⁇ -carbomethoxycinnamate methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate or butyl ester, methyl oc-carbomethoxy-p-methoxycinnamate, N- ( ⁇ -carbomethoxy- ⁇ -cyanovinyl) -2-methyl-indoline.
- nickel compounds such as. Example, nickel complexes of 2,2'-thio-bis [4 (1, 1, 3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n Butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 2,2'-thio-bis [4 (1, 1, 3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n Butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of
- 4-Hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as methyl or ethyl esters, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands; sterically hindered amines, such as. Bis (2,2,6,6-tetramethylpiperidyl) sebacate; Oxideklarediamide, such as. 4,4'-dioctyloxyoxanilide; 2- (2-hydroxyphenyl) -1, 3,5-triazines, such as. B.
- Suitable metal deactivators are, for. B. ⁇ , ⁇ '-diphenyloxalic diamide,
- N-Salicylal-N'-saiicyloylhydrazine N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino 1, 2,4-triazole, bis (benzylidene) oxalic dihydrazide, oxanilide, isophthalic dihydrazide,
- Suitable peroxide-destroying compounds are, for.
- esters of ⁇ -thiopropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester
- Mercaptobenzimidazole the zinc salt of 2-mercaptobenzimidazole
- Zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis ( ⁇ -dodecylmercapto) propionate Suitable polyamide stabilizers are, for. B. copper salts in combination with
- Suitable basic co-stabilizers are melamine, polyvinylpyrrolidone,
- Suitable nucleating agents are for.
- the fillers and reinforcing agents include, for. As calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite and others.
- flame retardants As further flame retardants z. As aryl phosphates, phosphonates, salts of hypophosphorous acid and red phosphorus suitable. To the other additives counts z. As plasticizers, expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
- Additional additives can be added to the polymers before, together with or after addition of the flame retardants.
- the dosing of both these additives as well as the flame retardants can be carried out as a solid, in solution or melt, as well as in the form of solid or liquid mixtures or as masterbatches / concentrates.
- the radicals are preferred for the phosphonites
- Ri is a compound of structure (IX) or (X) with
- R 2 independently of one another are C 1 -C 8 -alkyl (linear or branched), C 1 -C 6 -alkoxy, cyclohexyl;
- Ci.C 8 alkylene linear or branched
- Ci.C 8 alkylidene linear or branched
- R is cyclohexyl, phenyl, phenylene, biphenyl and biphenylene
- Ri is a compound of structure (IX) or (X) with
- R 2 independently of one another Ci.Ce-alkyl (linear or branched), Ci.Ce-alkoxy, cyclohexyl
- Suitable as component F are esters or salts of long-chain aliphatic carboxylic acids (fatty acids), which typically have chain lengths of C 4 to C 40 .
- the esters are reaction products of said carboxylic acids with conventional polyhydric alcohols, such as. As ethylene glycol, glycerol, trimethylolpropane or pentaerythritol.
- Suitable salts of the carboxylic acids mentioned are, in particular, alkali metal or alkaline earth metal salts or aluminum and zinc salts.
- the component F is esters or salts of stearic acid such as. As glycerol monostearate or calcium stearate.
- Component F is preferably reaction products of montan wax acids with ethylene glycol.
- reaction products are preferably a mixture of ethylene glycol mono-montan wax acid ester, ethylene glycol di-montan wax acid ester, montan wax acids and ethylene glycol.
- Component F is preferably reaction products of montan wax acids with a calcium salt.
- reaction products are particularly preferably a mixture of 1,3-budanediol mono-montan wax acid ester, 1,3-budanediol di-montan wax acid ester, montan wax acids, 1,3-butanediol, calcium montanate and the calcium salt.
- the flame retardant-stabilizer combination contains 20 to 99 wt .-% of component A, 1 to 80 wt .-% of component B and 0 to 30 wt .-% of component C.
- the components D, E and F are added independently in 0 to 3%.
- the plastic is particularly preferably polyamides, polyesters and PPE / HIPS blends.
- the flame retardant-stabilizer combination in the plastic molding composition in a total amount of 2 to 50 wt .-%, based on the
- Plastic molding compound used.
- the total amount of the plastic molding compound is then 50 to 98 wt .-%.
- the flame retardant-stabilizer combination in the plastic molding composition in a total amount of 10 to 30 wt .-%, based on the plastic molding composition used.
- the total amount of the plastic molding compound is then 70 to 90 wt .-%.
- the polymer moldings, films, filaments and fibers contain the flame retardant stabilizer combination in a total amount of 2 to 50 wt .-%, based on the polymer content.
- the amount of polymer is then 50 to 98 wt .-%.
- the polymer moldings, films, filaments and fibers contain the flame retardant-stabilizer combination in a total amount of 10 to 30 wt .-%, based on the polymer content. The amount of polymer is then 70 to 90 wt .-%.
- additives can be introduced into the plastic in a wide variety of process steps. So it is possible with polyamides or polyesters, already at the beginning or at the end of the polymerization / polycondensation or in a subsequent compounding the additives in the
- the flame retardant-stabilizer combination is present as granules, flakes, fine particles, powders and / or micronisate.
- the flame retardant-stabilizer combination is preferably present as a physical mixture of the solids, as a melt mixture, as a compactate, as an extrudate or in the form of a masterbatch.
- the flame retardant stabilizer combination according to the invention can be used in thermoplastic polymers.
- Suitable polyesters are derived from dicarboxylic acids and their esters and diols and / or from hydroxycarboxylic acids or the corresponding lactones.
- Terephthalic acid and ethylene glycol, propane-1,3-diol and butane-1, 3-diol are particularly preferably used.
- Suitable polyesters include polyethylene terephthalate, polybutylene terephthalate (Celanex ® 2500, Celanex ® 2002, from Celanese;. Ultradur ®, BASF), poly-1, 4- dimethylolcyclohexane terephthalate, polyhydroxybenzoates as well as block polyether esters derived from polyethers having hydroxyl end groups; also with polycarbonates or MBS modified polyester.
- the flame-retardant polyester molding compositions prepared according to the invention are preferably used in polyester moldings.
- Preferred polyester moldings are threads, fibers, films and moldings themselves, which contain as the dicarboxylic acid component mainly terephthalic acid and as the diol component mainly ethylene glycol.
- the resulting phosphorus content in threads and fibers produced from flame-retardant polyester is preferably from 0.1 to 18, preferably from 0.5 to 15, and in films from 0.2 to 15, preferably from 0.9 to 12,% by weight.
- Suitable polystyrenes are polystyrene, poly (p-methylstyrene) and / or poly (alphamethylstyrene).
- the suitable polystyrenes 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 and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength of styrene copolymers and another polymer, such as.
- styrene such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
- the suitable polystyrenes are also um
- Graft copolymers of styrene or alpha-methylstyrene such as. As styrene on
- Copolymers styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and
- the polymers are preferably polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2, 2, polyamide 4, Polyamide 4,6, polyamide 6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6,66, polyamide 7,7, polyamide 8,8, polyamide 9,9, polyamide 10 , 9, polyamide 10,10, polyamide 11, polyamide 12, etc. These are z. B under the
- aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for.
- poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted
- Polypropylene glycol or polytetramethylene glycol Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").
- the invention also relates to a process for the preparation of
- flame-retardant polymer moldings characterized in that flame-retardant polymer molding compositions according to the invention are produced by injection molding (for example, Aarburg Allrounder injection molding machine) and presses,
- Foam injection molding, internal gas pressure injection molding, blow molding, film casting, calendering, lamination or coating at higher temperatures to the flame-retardant polymer molding is processed.
- thermosetting polymers are preferably unsaturated polyester resins (UP resins) which are more saturated and more stable to copolyesters
- UP resins are cured by free-radical polymerization with initiators (eg peroxides) and accelerators.
- Preferred unsaturated dicarboxylic acids and derivatives for the preparation of the polyester resins are maleic anhydride and fumaric acid.
- Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid,
- Terephthalic acid Terephthalic acid, tetrahydrophthalic acid, adipic acid.
- Preferred diols are 1, 2 propanediol, ethylene glycol, diethylene glycol and
- Preferred vinyl compound for crosslinking is styrene.
- Preferred hardener systems are peroxides and metal co-initiators, e.g. B.
- Preferred hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permalate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-chlorobenzoyl peroxide and dicyclohexyl peroxide dicarbonate ,
- initiators are used in amounts of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight, calculated on the mass of all comonomers.
- Preferred metal co-initiators are cobalt, manganese, iron, vanadium, nickel or lead compounds. Preference is given to using metal co-initiators in amounts of from 0.05 to 1% by weight, calculated on the mass of all comonomers.
- Preferred aromatic amines are dimethylaniline, dimethyl-p-toluene, diethylaniline and phenyldiethanolamine.
- compositions are characterized in that a thermosetting resin with a flame retardant stabilizer combination according to the invention according to one or more of claims 1 to 16 and optionally other flame retardants,
- the polymers are preferably crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic
- Suitable glycidyl compounds are bisphenol A diglycidyl esters, bisphenol F diglycidyl esters, polyglycidyl esters of phenol formaldehyde resins and cresol formaldehyde resins, polyglycidyl esters of pthalthalene, isophthalic and
- Suitable hardeners are aliphatic, cycloaliphatic, aromatic and
- heterocyclic amines or polyamines such as ethylenediamine, diethylenetriamine triethylenetetramine, propan-1,3-diamine, hexamethylenediamine, aminoethylpiperazine, isophoronediamine, polyamidoamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenol sulfones, aniline-formaldehyde resins, 2,2,4-trimethylhexane-1,6 diamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 3-aminomethyl-3,55-trimethylcyclohexylamine (Isophorone diamine), polyamidoamines, cyanoguanidine and dicyandiamide, as well as polybasic acids or their anhydrides such. Phthalic anhydride,
- Methylhexahydrophthal Acidanhydrid and phenols such.
- Phenol aralkyl resin Phenol aralkyl resin, phenoltrimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol-kocondensate resin, naphthol-cresol-kocondensate resin, biphenol-modified phenol resin, and aminotriazine-modified phenol resin. All hardeners can be used alone or in combination with each other.
- Polymerization are tertiary amines, benzyldimethylamine, N-alkylpyridines, imidazole, 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, metal salts of organic acids, Lewis Acids and amine complex salts.
- the formulation of the invention may also contain other additives conventionally used in epoxy resin formulations, such as pigments, dyes and stabilizers.
- Epoxy resins are suitable for casting electrical or electronic components and for impregnation and impregnation processes. In electrical engineering, epoxy resins are predominantly rendered flame retardant and used for circuit boards and insulators.
- 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 crosslinkable Acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester 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.
- Preferred polyols are alkene oxide adducts of ethylene glycol, 1,2-propanediol, bisphenol A, trimethylolpropane, glycerol, pentaerythrol, sorbitol, sugar, degraded starch, ethylenediamine, diaminotoluene and / or aniline, which serve as initiator.
- the preferred oxyalkylating agents 7 preferably contain 2 to
- Preferred polyester polyols are obtained by polycondensation of a
- Polyalcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, glucose and / or sorbitol with a dibasic acid such as oxalic acid, malonic acid, Succinic, tartaric, adipic, sebacic, maleic, fumaric, phthalic and / or terephthalic acid. These polyester polyols may be used alone or in combination.
- Suitable polyisocyanates are aromatic, alicyclic or aliphatic
- Polyisocyanates containing not less than two isocyanate groups and mixtures thereof Preference is given to aromatic polyisocyanates such as tolyl diisocyanate,
- Diisocyanatodicyclohexylmethane isomers 1, 4-cyclohexyl diisocyanate, Desmodur ® grades (Bayer) and lysine diisocyanate and mixtures thereof.
- Suitable polyisocyanates are modified products obtained by reaction of polyisocyanate with polyol, urea, carbodiimide and / or biuret.
- the weight ratio of the polyisocyanate to polyol is 170 to
- the weight ratio of the catalyst is preferably 0.1 to 4 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the polyisole.
- the polymers are preferably thermoplastic elastomers.
- Thermoplastic elastomers are materials which are thermoplastically processable and have rubber-like performance properties.
- Thermoplastic elastomers are very easy to form because they go through the plastic state during processing. They can be produced in all hardnesses from 5 Shore A to over 70 Shore D.
- Thermoplastic elastomers have physical properties in some areas
- Block copolymers have hard and soft segments within one molecule.
- the plastic thus consists of a type of molecule in which both properties are distributed.
- Elastomer alloys are polyblends, ie mixtures (mixtures) of finished polymers, the plastic thus consists of several types of molecules. By different mixing ratios and aggregate to get custom-made materials (for example, polyolefin elastomer Polypropylene (PP) and natural rubber (NR) - depending on the ratio they cover a wide range of hardness).
- PP polyolefin elastomer Polypropylene
- NR natural rubber
- TPE-0 or TPO Thermoplastic elastomers based on olefins, mainly PP / EPDM, eg. B. Santoprene ® (AES / Monsanto)
- TPE-V or TPV crosslinked thermoplastic elastomers based on olefins, predominantly PP / EPDM, e.g. B. Sarlink ® (DSM)
- TPE-U or TPU urethane-based thermoplastic elastomers, e.g. B.
- TPE-E or TPC thermoplastic copolyester, e.g. Hytrel ® (DuPont)
- TPE-S or TPS styrene block copolymers (SBS, SEBS, SEPS, SEEPS and MBS), e.g. B. ® Septon (Kuraray) or thermal load ® (Kraiburg TPE)
- TPE-A or TPA thermoplastic copolyamides, eg. B. PEBAX ® (Arkema)
- thermoplastic elastomers are thermoplastic copolyesters, thermoplastic copolyamides and thermoplastic polyurethanes.
- the mixture is used in a molding composition of a polyamide or a polyester.
- Suitable polyamides are, for. As described in DE-A-19 920 276.
- the polyamides are preferably those of the amino acid type and / or of the diamine-dicarboxylic acid type.
- Preferred polyamides are polyamide 6 and / or polyamide 66.
- the polyamides are preferably unchanged, dyed, filled, unfilled, reinforced, unreinforced or otherwise modified.
- the polyesters are preferably polyethylene terephthalate or polybutylene terephthalate.
- the polyesters are preferably unchanged, dyed, filled, unfilled, reinforced, unreinforced or otherwise modified.
- Polyamide 6.6 (PA 6.6 GV): Ultramid ® A27 (BASF AG, Germany.)
- Polyamide 6T / 66 Zytel ® HTN FE 8200 (DuPont, USA.)
- PBT Polybutylene terephthalate
- Polyamide 46 Stanyl PA 46 ® TE 300 (DSM, NL)
- DEPAL diethylphosphinic acid
- PHOPAL Aluminum salt of phosphorous acid
- Melamine polyphosphate (as MPP hereinafter) Melapur ® 200 (Messrs. Ciba SC, CH) melamine cyanurate (referred to as MC) Melapur ® MC50 (Messrs. Ciba SC, CH) melem, Delacal ® 420, Delacal ® 360 (Fa. Delamin Ltd, UK )
- the flame retardant components were mixed in the ratio indicated in the table with the phosphonite, the lubricants and stabilizers and via the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D type) at temperatures of 260 to 310 ° C in PA 6.6 or at 250 - 275 ° C incorporated in PBT.
- the glass fibers were added via a second side feed.
- the homogenized polymer strand was stripped off, cooled in a water bath and then granulated.
- Injection molding machine (type Arburg 320 C Allrounder) processed to test specimens at melt temperatures of 250 to 300 ° C and based on the UL 94 test
- V-0 no afterburning for more than 10 seconds, sum of afterburning times for 10 flame treatments not more than 50 seconds, no burning dripping, no complete burning off of the sample, no afterglowing of the samples longer than 30 seconds after end of flame.
- V-1 no afterburning for more than 30 seconds after end of flame, sum of afterburning times for 10 flame treatments not greater than 250 seconds, no afterglow Samples longer than 60 sec after flaming end, other criteria as in V-0.
- V-2 Ignition of the cotton by burning dripping, other criteria as in V-1.
- the flowability of the molding compositions was determined by determining the
- Table 1 shows, as by successive replacement of DEPAL by
- Aluminum phosphite the afterburning time in the UL 94 test is significantly lower up to an aluminum phosphite content of 3.75 wt .-%. At higher
- Aluminum phosphite content increases the afterburning time again.
- Table 1 PA 66 GF 30 test results.
- V1 is a comparative example
- Component B PHOPAL 1, 25 2.5 3.75 5
- Figure 1 shows the course of the afterburning times in the UL 94 test.
- Table 2 shows Comparative Examples V2 to V4 in which a
- Examples B5, B6 and B7 show that the mixture according to the invention consists of the components DEPAL and PHOPAL and, if appropriate,
- Flammwidrmaschine also no discoloration, no efflorescence, low
- Table 5 shows that with the inventive combination of DEPAL and PHOPAL a V-0 classification with significantly better mechanical values is obtained as without the PHOPAL addition. Small additions from PHOPAL significantly reduce the corrosion observed with DEPAL in PA 6T / 66.
- Glass fiber reinforced polyamide 46 can be flame retarded with DEPAL or DEPAL and zinc borate, as shown in Comparative Examples V14 - V15 in Table 6. However, in the UL 94 test with 20 - 22 wt .-%
- the flame retardant stabilizer mixture according to the invention exhibits a significantly higher flame retardancy in PA 46 GF30, so that the higher UL 94 class V-0 can be reliably achieved with a smaller input quantity of 18-20% by weight, as in Examples B17 and B18 can be seen in Table 6.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Artificial Filaments (AREA)
- Fireproofing Substances (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013532062A JP2013538926A (ja) | 2010-10-09 | 2011-09-30 | 熱可塑性ポリマーのための難燃剤−安定化剤の組み合わせ |
CN201180048585.9A CN103154110B (zh) | 2010-10-09 | 2011-09-30 | 用于热塑性聚合物的阻燃剂-稳定剂-组合物 |
ES11771018.6T ES2610188T3 (es) | 2010-10-09 | 2011-09-30 | Combinación de agentes ignifugantes y estabilizadores para polímeros termoplásticos |
US13/878,145 US20130190432A1 (en) | 2010-10-09 | 2011-09-30 | Flame Retardant-Stabilizer Combination For Thermoplastic Polymers |
KR1020137011974A KR101967602B1 (ko) | 2010-10-09 | 2011-09-30 | 열가소성 중합체를 위한 난연제-안정제 배합물 |
EP11771018.6A EP2625220B1 (de) | 2010-10-09 | 2011-09-30 | Flammschutzmittel- stabilisator-kombination für thermoplastische polymere |
US16/192,043 US20190153197A1 (en) | 2010-10-09 | 2018-11-15 | Flame Retardant-Stabilizer Combination For Thermoplastic Polymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010048025.8 | 2010-10-09 | ||
DE201010048025 DE102010048025A1 (de) | 2010-10-09 | 2010-10-09 | Flammschutzmittel- Stabilisator-Kombination für thermoplastische Polymere |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/878,145 A-371-Of-International US20130190432A1 (en) | 2010-10-09 | 2011-09-30 | Flame Retardant-Stabilizer Combination For Thermoplastic Polymers |
US16/192,043 Continuation US20190153197A1 (en) | 2010-10-09 | 2018-11-15 | Flame Retardant-Stabilizer Combination For Thermoplastic Polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012045414A1 true WO2012045414A1 (de) | 2012-04-12 |
Family
ID=44883156
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/004887 WO2012045414A1 (de) | 2010-10-09 | 2011-09-30 | Flammschutzmittel- stabilisator-kombination für thermoplastische polymere |
Country Status (9)
Country | Link |
---|---|
US (2) | US20130190432A1 (de) |
EP (1) | EP2625220B1 (de) |
JP (3) | JP2013538926A (de) |
KR (1) | KR101967602B1 (de) |
CN (1) | CN103154110B (de) |
DE (1) | DE102010048025A1 (de) |
ES (1) | ES2610188T3 (de) |
TW (1) | TWI519633B (de) |
WO (1) | WO2012045414A1 (de) |
Cited By (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013083247A1 (de) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Flammschutzmittel-mischungen enthaltend flammschutzmittel und aluminiumphosphite, verfahren zu ihrer herstellung und ihre verwendung |
WO2014044471A1 (de) | 2012-09-19 | 2014-03-27 | Basf Se | Flammgeschützte polyamide mit heller farbe |
WO2014135256A1 (de) * | 2013-03-08 | 2014-09-12 | Clariant International Ltd | Flammhemmende polyamidzusammensetzung |
WO2014200082A1 (ja) * | 2013-06-13 | 2014-12-18 | 株式会社クラレ | ポリアミド樹脂組成物およびそれからなる成形品 |
WO2015013370A1 (en) | 2013-07-24 | 2015-01-29 | Chemtura Corporation | Phosphorus containing flame retardants |
WO2015019882A1 (ja) * | 2013-08-05 | 2015-02-12 | 東洋紡株式会社 | 難燃性ポリアミド樹脂組成物 |
US9175160B2 (en) | 2013-08-28 | 2015-11-03 | Sabic Global Technologies B.V. | Blend of poly(phenylene ether) particles and polyoxymethylene, article thereof, and method of preparation |
WO2016014113A1 (en) | 2014-07-22 | 2016-01-28 | Chemtura Corporation | Phosphorus containing flame retardants |
WO2016018484A1 (en) | 2014-07-29 | 2016-02-04 | Chemtura Corporation | Salts of pyrophonic acid as flame retardants |
WO2016165966A1 (de) * | 2015-04-13 | 2016-10-20 | Clariant International Ltd | Verfahren zur herstellung flammwidriger, nicht korrosiver und stabiler polyamidformmassen |
US9493621B2 (en) | 2013-07-23 | 2016-11-15 | Sabic Global Technologies B.V. | Rigid foam and associated article and method |
US9505904B2 (en) | 2011-12-05 | 2016-11-29 | Clariant International Ltd. | Mixtures of aluminum hydrogenphosphites with aluminum salts, process for the production thereof and the use thereof |
US9534108B2 (en) | 2015-03-13 | 2017-01-03 | Chemtura Corporation | Flame retardant epoxy resins comprising phosphorus containing flame retardants |
DE102016203221A1 (de) | 2016-02-29 | 2017-08-31 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzung |
US9752009B2 (en) | 2015-01-26 | 2017-09-05 | Lanxess Solutions Us Inc. | Flame retardant polymer compositions comprising heat treated phosphorus compounds and melam |
US9758640B2 (en) | 2015-01-09 | 2017-09-12 | Lanxess Solutions Us Inc. | Process stabilization of polymer compositions comprising phosphorous containing flame retardants |
US9765204B2 (en) | 2013-07-24 | 2017-09-19 | Lanxess Solutions Us Inc. | Halogen free high temperature polyamide compositions comprising phosphorus containing flame retardants |
US20180244899A1 (en) * | 2013-03-08 | 2018-08-30 | Clariant International Ltd. | Flame-Retardant Polyamide Composition |
DE102017212098A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung |
DE102017212099A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für Kunststoffe, lasermarkierbare Polymerzusammensetzungen enthaltend diese und deren Verwendung |
DE102017212100A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für Kunststoffe, lasermarkierbare Polymerzusammensetzungen enthaltend diese und deren Verwendung |
WO2019011789A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende graue polyamidzusammensetzungen und deren verwendung |
DE102017212096A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende schwarze Polyamidzusammensetzungen und deren Verwendung |
US10202549B2 (en) | 2011-12-05 | 2019-02-12 | Clariant International Ltd. | Mixtures of aluminum phosphite with sparingly soluble aluminum salts and foreign ions, process for the production thereof and the use thereof |
DE102017214046A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen und deren Verwendung |
DE102017214051A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung |
DE102017214045A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen und deren Verwendung |
WO2019030252A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzungen mit hoher glühdrahtentzündungstemperatur und deren verwendung |
DE102017215779A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammschutzmittelkombinationen für Polymerzusammensetzungen und deren Verwendung |
DE102017215775A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung |
DE102017215777A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammschutzmittelkombinationen für Polymerzusammensetzungen und deren Verwendung |
DE102017215780A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Synergistische Flammschutzmittelkombinationen für Polymerzusammensetzungen und deren Verwendung |
DE102017215773A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyesterzusammensetzungen und deren Verwendung |
DE102017215776A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyesterzusammensetzungen und deren Verwendung |
DE102017218453A1 (de) | 2017-10-16 | 2019-04-18 | Clariant Plastics & Coatings Ltd | Flammwidrige und farbstabile Polyamidformmassen |
KR20190053910A (ko) * | 2016-09-15 | 2019-05-20 | 클라리언트 플라스틱스 앤드 코팅즈 리미티드 | 열가소성 플라스틱 중합체용 난연제-안정제 배합물 |
US10421909B2 (en) | 2011-12-05 | 2019-09-24 | Clariant International Ltd. | Mixed alkali-aluminum phosphites, method for producing same, and the use thereof |
US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
WO2020132095A1 (en) | 2018-12-20 | 2020-06-25 | Lanxess Solutions Us Inc. | Method for preparing readily processable, thermally-stable, phosphorus-containing flame retardant material |
WO2020165017A1 (en) | 2019-02-11 | 2020-08-20 | Clariant Plastics & Coatings Ltd | Flame retardant mixture for thermoplastic polymers |
WO2020201811A1 (en) | 2019-04-02 | 2020-10-08 | Italmatch Chemicals S.P.A. | Non-flammable hypophosphite metal salt based powders and their use as flame retardant ingredients |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3002943B1 (fr) * | 2013-03-11 | 2015-03-27 | Arkema France | Sirop (meth)acrylique liquide d'impregnation d'un substrat fibreux, procede d'impregnation d'un substrat fibreux, materiau composite obtenu apres polymerisation dudit substrat pre-impregne. |
US9447227B2 (en) | 2013-10-03 | 2016-09-20 | Sabic Global Technologies B.V. | Flexible polyurethane foam and associated method and article |
WO2015087099A1 (en) * | 2013-12-12 | 2015-06-18 | Italmatch Chemicals S.P.A. | Halogen-free flame retardant polyamide moulding compositions with increased glow wire and fire resistance |
CN104371142B (zh) * | 2014-10-29 | 2016-07-13 | 广州金凯新材料有限公司 | 一种用于聚合物的添加剂组合物和其制备方法及由其组成的阻燃热塑性聚合物模塑材料 |
EP3034553A1 (de) * | 2014-12-19 | 2016-06-22 | LANXESS Deutschland GmbH | Polyamidzusammensetzungen |
CN105085988B (zh) * | 2014-12-26 | 2017-06-30 | 肖群 | 一种用于聚合物的添加剂组合物和其制备方法及由其组成的阻燃热塑性聚合物模塑材料 |
DE102015004661A1 (de) * | 2015-04-13 | 2016-10-13 | Clariant International Ltd. | Flammhemmende Polyamidzusammensetzung |
DE102015211728A1 (de) | 2015-06-24 | 2016-12-29 | Clariant International Ltd | Antikorrosive Flammschutzformulierungen für thermoplastische Polymere |
ES2751693T3 (es) * | 2015-08-21 | 2020-04-01 | Basf Se | Poliuretano termoplástico ignífugo |
JP6788967B2 (ja) * | 2015-12-25 | 2020-11-25 | 太平化学産業株式会社 | 難燃性樹脂組成物 |
EP3559104A1 (de) | 2016-12-22 | 2019-10-30 | DSM IP Assets B.V. | Verbesserte wärme- und elektrisch resistive thermoplastische harzzusammensetzungen |
WO2019060117A1 (en) * | 2017-09-21 | 2019-03-28 | E. I. Du Pont De Nemours And Company | FLAME RETARDANT POLYAMIDE COMPOSITIONS |
CN107603210B (zh) * | 2017-09-22 | 2019-11-15 | 杭州本松新材料技术股份有限公司 | 一种阻燃聚酰胺组合物及其制备方法和应用 |
US11407639B2 (en) | 2017-10-11 | 2022-08-09 | Taihei Chemical Industrial Co., Ltd. | Aluminum phosphite and composition containing aluminum phosphite |
US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
CN107938885B (zh) * | 2017-10-20 | 2019-07-19 | 芜湖易法网络科技有限公司 | 空间租赁用阻燃隔断墙的制备方法 |
CN107936297A (zh) * | 2017-11-22 | 2018-04-20 | 江苏利思德新材料有限公司 | 玻纤增强尼龙用无卤阻燃复配体系及其在无卤阻燃玻纤增强尼龙材料中的应用 |
CN107698798A (zh) * | 2017-11-22 | 2018-02-16 | 江苏利思德新材料有限公司 | 玻纤增强尼龙用不含氮无卤阻燃复配体系及其应用 |
CN107778527A (zh) * | 2017-11-22 | 2018-03-09 | 江苏利思德新材料有限公司 | 一种基于磷铝化合物的无卤阻燃复配体系及其在玻纤增强工程塑料中的应用 |
CN108794806B (zh) * | 2018-06-28 | 2019-07-02 | 浙江大学 | 二烷基二硫代次磷酸盐与无机亚磷酸盐协同的无卤阻燃体系及其应用 |
CN109181294B (zh) * | 2018-08-09 | 2020-12-15 | 浙江大学 | 利用无机和烷基亚磷酸金属盐提高热塑性聚合物或其复合物的高温热稳定方法 |
CN108997612A (zh) * | 2018-08-09 | 2018-12-14 | 江苏利思德新材料有限公司 | 利用无机亚磷酸金属盐提高热稳定性的磷氮无卤阻燃剂组合物及其应用 |
CN109181295A (zh) * | 2018-08-09 | 2019-01-11 | 浙江大学 | 利用无机和烷基亚磷酸盐提高热稳定性的磷氮无卤阻燃剂组合物及其应用 |
CN109181293B (zh) * | 2018-08-09 | 2021-03-05 | 浙江大学 | 利用无机和烷基亚磷酸金属盐提高三聚氰胺衍生物类阻燃剂高温热稳定方法及其产品和应用 |
CN108912676A (zh) * | 2018-08-09 | 2018-11-30 | 江苏利思德新材料有限公司 | 利用无机亚磷酸金属盐提高三聚氰胺衍生物类阻燃剂高温热稳定方法及其产品和应用 |
CN108997611B (zh) * | 2018-08-09 | 2020-04-21 | 江苏利思德新材料有限公司 | 利用烷基亚磷酸金属盐提高三聚氰胺衍生物类阻燃剂的高温热稳定方法及其产品和应用 |
CN109251526A (zh) * | 2018-08-09 | 2019-01-22 | 江苏利思德新材料有限公司 | 利用烷基亚磷酸盐提高热稳定性的磷氮无卤阻燃剂组合物及其应用 |
CN109082115A (zh) * | 2018-08-09 | 2018-12-25 | 江苏利思德新材料有限公司 | 利用无机亚磷酸金属盐提高热塑性聚合物或其复合物的高温热稳定方法 |
KR102161362B1 (ko) * | 2018-12-24 | 2020-10-05 | 주식회사 하이플럭스 | 내화 조성물 |
CN118063856A (zh) | 2019-01-16 | 2024-05-24 | 科莱恩国际有限公司 | 阻燃剂混合物 |
TWI830717B (zh) * | 2019-01-16 | 2024-02-01 | 瑞士商克萊瑞特國際股份有限公司 | 阻燃劑混合物 |
WO2020153330A1 (ja) * | 2019-01-23 | 2020-07-30 | 東洋紡株式会社 | 耐衝撃性に優れた難燃性ポリアミド樹脂組成物 |
DE102019201824A1 (de) * | 2019-02-12 | 2020-08-13 | Clariant Plastics & Coatings Ltd | Flammschutzmittelmischungen, flammhemmende Polymerzusammensetzungen, damit ausgerüstete Kabel und deren Verwendung |
CN111662323A (zh) * | 2019-03-07 | 2020-09-15 | 黎杰 | 二烷基次膦酸-烷基亚磷酸金属复合盐,其制备方法和用途 |
JP2022539211A (ja) * | 2019-06-28 | 2022-09-07 | セラニーズ・インターナショナル・コーポレーション | 耐燃焼性ポリマー組成物およびそれから作製した物品 |
WO2021043929A1 (en) * | 2019-09-06 | 2021-03-11 | Dsm Ip Assets B.V. | Flame retardant polyamide-based 3d printing extrusion materials |
KR102346106B1 (ko) * | 2019-10-10 | 2022-01-03 | 주식회사 경동원 | 고난연성 유기 변성 실리케이트를 이용한 유무기 복합 합성수지 및 이의 제조방법 |
WO2021106888A1 (ja) * | 2019-11-28 | 2021-06-03 | 株式会社クラレ | ポリアミド樹脂組成物及びその成形体 |
EP3926002A1 (de) | 2020-06-15 | 2021-12-22 | Clariant International Ltd | Flammschutzmittel-stabilisator-kombination für thermoplastische polymere |
US20230220194A1 (en) | 2020-06-15 | 2023-07-13 | Dupont Polymers, Inc. | Improved polyetherester |
JP2024518436A (ja) | 2021-05-07 | 2024-05-01 | デュポン ポリマーズ インコーポレイテッド | 改良されたポリマー組成物 |
EP4086302A1 (de) * | 2021-05-07 | 2022-11-09 | Clariant International Ltd | Flammschutzmittelstabilisatorkombination für thermoplastische polymere |
CN113621249B (zh) * | 2021-08-24 | 2022-07-26 | 浙江鼎富橡塑科技有限公司 | 一种防异响的tpe防尘套及其生产工艺 |
WO2023126320A1 (en) * | 2021-12-28 | 2023-07-06 | Sabic Global Technologies B.V. | Article comprising an object and a layer |
CN115433456B (zh) * | 2022-09-14 | 2024-05-10 | 广东聚石化学股份有限公司 | 一种高阻燃、高抗冲的三聚氰胺氰尿酸盐阻燃尼龙组合物及其制备方法和应用 |
US20240117157A1 (en) | 2022-10-05 | 2024-04-11 | Ascend Performance Materials Operations Llc | Flame retardant polyamide compositions with improved glow wire performance |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2252258A1 (de) | 1972-10-25 | 1974-05-09 | Hoechst Ag | Schwerentflammbare thermoplastische polyester |
DE2447727A1 (de) | 1974-10-07 | 1976-04-08 | Hoechst Ag | Schwerentflammbare polyamidformmassen |
EP0699708A2 (de) | 1994-08-31 | 1996-03-06 | Hoechst Aktiengesellschaft | Flammengeschützte Polyesterformmassen |
DE19614424A1 (de) | 1996-04-12 | 1997-10-16 | Hoechst Ag | Synergistische Flammschutzmittel-Kombination für Polymere |
DE19734437A1 (de) | 1997-08-08 | 1999-02-11 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Polymere |
DE19737727A1 (de) | 1997-08-29 | 1999-07-08 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Kunststoffe |
EP0964886A1 (de) | 1997-03-04 | 1999-12-22 | Ticona GmbH | Flammgeschützte polymerformmassen |
DE19920276A1 (de) | 1999-05-04 | 2000-11-09 | Basf Ag | Thermoplastische Formmassen |
DE19933901A1 (de) | 1999-07-22 | 2001-02-01 | Clariant Gmbh | Flammschutzmittel-Kombination |
WO2003078523A1 (de) * | 2002-03-15 | 2003-09-25 | Bayer Chemicals Ag | Stabilisator-kombinationen für polymersysteme |
EP1607400A2 (de) * | 2004-05-11 | 2005-12-21 | Clariant GmbH | Dialkylphosphinsäure-Salze, ein Verfahren zu ihrer Herstellung und ihre Verwendung |
EP1705220A1 (de) * | 2005-03-26 | 2006-09-27 | Clariant Produkte (Deutschland) GmbH | Phosphorhaltige thermostabilisierte Flammschutzmittelagglomerate |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4951187B2 (ja) * | 2002-12-26 | 2012-06-13 | ポリプラスチックス株式会社 | 難燃性樹脂組成物 |
DE10309385B4 (de) * | 2003-03-03 | 2007-01-18 | Clariant Produkte (Deutschland) Gmbh | Flammschutzmittel-Stabilisator-Kombination für thermoplastische Polymere und ihre Verwendung sowie flammfest ausgerüstete Kunststoff-Formmassen |
DE10320465A1 (de) * | 2003-05-08 | 2004-12-02 | Clariant Gmbh | Flammschutzmittel-Nanocomposite-Kombination für thermoplastische Polymere |
DE102004035508A1 (de) * | 2004-07-22 | 2006-02-16 | Clariant Gmbh | Flammgeschützte Polymerformmassen |
DE102004048876A1 (de) * | 2004-09-13 | 2006-03-30 | Bayer Ag | Halogenfreie flammgeschützte thermoplastische Formmassen auf Basis von Polyamid mit erhöhter Glühdrahtbeständigkeit |
WO2007007663A1 (ja) * | 2005-07-08 | 2007-01-18 | Polyplastics Co., Ltd. | 難燃性樹脂組成物 |
PL2252653T3 (pl) | 2008-03-03 | 2021-11-22 | Clariant International Ltd | Sposób wytwarzania poliamidowych i poliestrowych mas do formowania o zmniejszonej palności, niekorozyjnych i o dobrej zdolności płynięcia |
JP2010222486A (ja) * | 2009-03-24 | 2010-10-07 | Unitika Ltd | 難燃性ガラス繊維強化ポリアミド樹脂組成物 |
-
2010
- 2010-10-09 DE DE201010048025 patent/DE102010048025A1/de not_active Withdrawn
-
2011
- 2011-09-30 JP JP2013532062A patent/JP2013538926A/ja active Pending
- 2011-09-30 WO PCT/EP2011/004887 patent/WO2012045414A1/de active Application Filing
- 2011-09-30 EP EP11771018.6A patent/EP2625220B1/de active Active
- 2011-09-30 KR KR1020137011974A patent/KR101967602B1/ko active IP Right Grant
- 2011-09-30 ES ES11771018.6T patent/ES2610188T3/es active Active
- 2011-09-30 CN CN201180048585.9A patent/CN103154110B/zh active Active
- 2011-09-30 US US13/878,145 patent/US20130190432A1/en not_active Abandoned
- 2011-10-05 TW TW100136076A patent/TWI519633B/zh active
-
2016
- 2016-06-30 JP JP2016129548A patent/JP6391180B2/ja active Active
-
2018
- 2018-05-29 JP JP2018102486A patent/JP6768741B2/ja active Active
- 2018-11-15 US US16/192,043 patent/US20190153197A1/en not_active Abandoned
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2252258A1 (de) | 1972-10-25 | 1974-05-09 | Hoechst Ag | Schwerentflammbare thermoplastische polyester |
DE2447727A1 (de) | 1974-10-07 | 1976-04-08 | Hoechst Ag | Schwerentflammbare polyamidformmassen |
EP0699708A2 (de) | 1994-08-31 | 1996-03-06 | Hoechst Aktiengesellschaft | Flammengeschützte Polyesterformmassen |
DE19614424A1 (de) | 1996-04-12 | 1997-10-16 | Hoechst Ag | Synergistische Flammschutzmittel-Kombination für Polymere |
WO1997039053A1 (de) | 1996-04-12 | 1997-10-23 | Clariant Gmbh | Synergistische flammschutzmittel-kombination für thermoplastische polymere |
EP0964886A1 (de) | 1997-03-04 | 1999-12-22 | Ticona GmbH | Flammgeschützte polymerformmassen |
DE19734437A1 (de) | 1997-08-08 | 1999-02-11 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Polymere |
DE19737727A1 (de) | 1997-08-29 | 1999-07-08 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Kunststoffe |
DE19920276A1 (de) | 1999-05-04 | 2000-11-09 | Basf Ag | Thermoplastische Formmassen |
DE19933901A1 (de) | 1999-07-22 | 2001-02-01 | Clariant Gmbh | Flammschutzmittel-Kombination |
WO2003078523A1 (de) * | 2002-03-15 | 2003-09-25 | Bayer Chemicals Ag | Stabilisator-kombinationen für polymersysteme |
EP1607400A2 (de) * | 2004-05-11 | 2005-12-21 | Clariant GmbH | Dialkylphosphinsäure-Salze, ein Verfahren zu ihrer Herstellung und ihre Verwendung |
EP1705220A1 (de) * | 2005-03-26 | 2006-09-27 | Clariant Produkte (Deutschland) GmbH | Phosphorhaltige thermostabilisierte Flammschutzmittelagglomerate |
Non-Patent Citations (1)
Title |
---|
H. ZWEIFEL: "Plastics Additives Handbook, 5th Edition", 2000, CARL HANSER VERLAG, pages: 80 - 84 |
Cited By (89)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9505904B2 (en) | 2011-12-05 | 2016-11-29 | Clariant International Ltd. | Mixtures of aluminum hydrogenphosphites with aluminum salts, process for the production thereof and the use thereof |
US9481831B2 (en) | 2011-12-05 | 2016-11-01 | Clariant International Ltd. | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
US20140336325A1 (en) * | 2011-12-05 | 2014-11-13 | Clariant Finance (Bvi) Limited | Mixtures of Flame Protection Means Containing Flame Protection Means and Aluminium Phosphites, Method for Production and Use Thereof |
US10421909B2 (en) | 2011-12-05 | 2019-09-24 | Clariant International Ltd. | Mixed alkali-aluminum phosphites, method for producing same, and the use thereof |
US10202549B2 (en) | 2011-12-05 | 2019-02-12 | Clariant International Ltd. | Mixtures of aluminum phosphite with sparingly soluble aluminum salts and foreign ions, process for the production thereof and the use thereof |
WO2013083247A1 (de) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Flammschutzmittel-mischungen enthaltend flammschutzmittel und aluminiumphosphite, verfahren zu ihrer herstellung und ihre verwendung |
WO2014044471A1 (de) | 2012-09-19 | 2014-03-27 | Basf Se | Flammgeschützte polyamide mit heller farbe |
JP2016509114A (ja) * | 2013-03-08 | 2016-03-24 | クラリアント・インターナシヨナル・リミテツド | 難燃性ポリアミド組成物 |
US20180244899A1 (en) * | 2013-03-08 | 2018-08-30 | Clariant International Ltd. | Flame-Retardant Polyamide Composition |
KR20150126932A (ko) * | 2013-03-08 | 2015-11-13 | 클라리언트 인터내셔널 리미티드 | 난연성 폴리아미드 조성물 |
KR102297586B1 (ko) * | 2013-03-08 | 2021-09-07 | 클라리언트 인터내셔널 리미티드 | 난연성 폴리아미드 조성물 |
WO2014135256A1 (de) * | 2013-03-08 | 2014-09-12 | Clariant International Ltd | Flammhemmende polyamidzusammensetzung |
EP3009478A4 (de) * | 2013-06-13 | 2017-03-08 | Kuraray Co., Ltd. | Polycarbonatharzzusammensetzung und daraus hergestellter formartikel |
JPWO2014200082A1 (ja) * | 2013-06-13 | 2017-02-23 | 株式会社クラレ | ポリアミド樹脂組成物およびそれからなる成形品 |
WO2014200082A1 (ja) * | 2013-06-13 | 2014-12-18 | 株式会社クラレ | ポリアミド樹脂組成物およびそれからなる成形品 |
US10364339B2 (en) | 2013-06-13 | 2019-07-30 | Kuraray Co., Ltd. | Polyamide resin composition and molded article produced therefrom |
US9493621B2 (en) | 2013-07-23 | 2016-11-15 | Sabic Global Technologies B.V. | Rigid foam and associated article and method |
US9745449B2 (en) | 2013-07-24 | 2017-08-29 | Lanxess Solutions Us Inc. | Phosphorus containing flame retardants |
US9765204B2 (en) | 2013-07-24 | 2017-09-19 | Lanxess Solutions Us Inc. | Halogen free high temperature polyamide compositions comprising phosphorus containing flame retardants |
WO2015013370A1 (en) | 2013-07-24 | 2015-01-29 | Chemtura Corporation | Phosphorus containing flame retardants |
KR20160039578A (ko) * | 2013-08-05 | 2016-04-11 | 도요보 가부시키가이샤 | 난연성 폴리아미드 수지 조성물 |
JP5800096B2 (ja) * | 2013-08-05 | 2015-10-28 | 東洋紡株式会社 | 難燃性ポリアミド樹脂組成物 |
WO2015019882A1 (ja) * | 2013-08-05 | 2015-02-12 | 東洋紡株式会社 | 難燃性ポリアミド樹脂組成物 |
KR101932808B1 (ko) * | 2013-08-05 | 2018-12-27 | 도요보 가부시키가이샤 | 난연성 폴리아미드 수지 조성물 |
US9175160B2 (en) | 2013-08-28 | 2015-11-03 | Sabic Global Technologies B.V. | Blend of poly(phenylene ether) particles and polyoxymethylene, article thereof, and method of preparation |
US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
WO2016014113A1 (en) | 2014-07-22 | 2016-01-28 | Chemtura Corporation | Phosphorus containing flame retardants |
WO2016018484A1 (en) | 2014-07-29 | 2016-02-04 | Chemtura Corporation | Salts of pyrophonic acid as flame retardants |
US10035896B2 (en) | 2014-07-29 | 2018-07-31 | Lanxess Solutions Us Inc. | Salts of pyrophosphonic acid as flame retardants |
US9758640B2 (en) | 2015-01-09 | 2017-09-12 | Lanxess Solutions Us Inc. | Process stabilization of polymer compositions comprising phosphorous containing flame retardants |
US9752009B2 (en) | 2015-01-26 | 2017-09-05 | Lanxess Solutions Us Inc. | Flame retardant polymer compositions comprising heat treated phosphorus compounds and melam |
US9988520B2 (en) | 2015-03-13 | 2018-06-05 | Lanxess Solutions Us Inc. | Flame retartdant epoxy resins comprising phosphorus containing flame retardants |
US9994696B2 (en) | 2015-03-13 | 2018-06-12 | Lanxess Solutions Us Inc. | Flame retardant resins comprising phosphorous containing flame retardants |
US9534108B2 (en) | 2015-03-13 | 2017-01-03 | Chemtura Corporation | Flame retardant epoxy resins comprising phosphorus containing flame retardants |
US10053555B2 (en) | 2015-03-13 | 2018-08-21 | Chemtura Corporation | Flame retardant resins comprising phosphorus containing flame retardants |
WO2016165966A1 (de) * | 2015-04-13 | 2016-10-20 | Clariant International Ltd | Verfahren zur herstellung flammwidriger, nicht korrosiver und stabiler polyamidformmassen |
DE102016203221A1 (de) | 2016-02-29 | 2017-08-31 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzung |
WO2017148721A1 (de) | 2016-02-29 | 2017-09-08 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzung |
KR20190053910A (ko) * | 2016-09-15 | 2019-05-20 | 클라리언트 플라스틱스 앤드 코팅즈 리미티드 | 열가소성 플라스틱 중합체용 난연제-안정제 배합물 |
KR102513665B1 (ko) | 2016-09-15 | 2023-03-24 | 클라리언트 인터내셔널 리미티드 | 열가소성 플라스틱 중합체용 난연제-안정제 배합물 |
WO2019011792A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für kunststoffe, lasermarkierbare polymerzusammensetzungen enthaltend diese und deren verwendung |
DE102017212096A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende schwarze Polyamidzusammensetzungen und deren Verwendung |
WO2019011788A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende schwarze polyamidzusammensetzungen und deren verwendung |
DE102017212097A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende graue Polyamidzusammensetzungen und deren Verwendung |
WO2019011789A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende graue polyamidzusammensetzungen und deren verwendung |
US11739195B2 (en) | 2017-07-14 | 2023-08-29 | Clariant International Ltd | Additive mixtures for plastics, laser-markable polymer compositions comprising them and the use thereof |
WO2019011791A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für kunststoffe, lasermarkierbare polymerzusammensetzungen enthaltend diese und deren verwendung |
WO2019011790A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzungen mit hoher wärmeformbeständigkeit und deren verwendung |
DE102017212100A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für Kunststoffe, lasermarkierbare Polymerzusammensetzungen enthaltend diese und deren Verwendung |
DE102017212099A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für Kunststoffe, lasermarkierbare Polymerzusammensetzungen enthaltend diese und deren Verwendung |
DE102017212098A1 (de) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung |
DE102017214046A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen und deren Verwendung |
WO2019030250A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzungen und deren verwendung |
CN109385079A (zh) * | 2017-08-11 | 2019-02-26 | 科莱恩塑料和涂料有限公司 | 阻燃性聚酰胺组合物及其用途 |
CN109385080A (zh) * | 2017-08-11 | 2019-02-26 | 科莱恩塑料和涂料有限公司 | 阻燃性聚酰胺组合物及其用途 |
TWI813579B (zh) * | 2017-08-11 | 2023-09-01 | 瑞士商克萊瑞特國際股份有限公司 | 阻燃性聚醯胺組成物及其用途 |
DE102017214051A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung |
US11692097B2 (en) | 2017-08-11 | 2023-07-04 | Clariant International Ltd | Flame-retardant polyamide compositions with a high glow wire ignition temperature and use thereof |
DE102017214045A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen und deren Verwendung |
CN109385079B (zh) * | 2017-08-11 | 2022-04-12 | 科莱恩塑料和涂料有限公司 | 阻燃性聚酰胺组合物及其用途 |
WO2019030252A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzungen mit hoher glühdrahtentzündungstemperatur und deren verwendung |
CN109385081B (zh) * | 2017-08-11 | 2021-09-03 | 科莱恩塑料和涂料有限公司 | 具有高的耐热变形性的阻燃性聚酰胺组合物及其用途 |
CN109385081A (zh) * | 2017-08-11 | 2019-02-26 | 科莱恩塑料和涂料有限公司 | 具有高的耐热变形性的阻燃性聚酰胺组合物及其用途 |
DE102017214051B4 (de) | 2017-08-11 | 2020-07-23 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung |
WO2019030251A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzungen und deren verwendung |
DE102017214048A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Glühdrahtentzündungstemperatur und deren Verwendung |
WO2019030253A1 (de) | 2017-08-11 | 2019-02-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzungen mit hoher wärmeformbeständigkeit und deren verwendung |
CN109467891B (zh) * | 2017-09-07 | 2021-04-06 | 科莱恩塑料和涂料有限公司 | 阻燃性聚酯组合物及其用途 |
DE102017215773A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyesterzusammensetzungen und deren Verwendung |
DE102017215779A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammschutzmittelkombinationen für Polymerzusammensetzungen und deren Verwendung |
DE102017215775A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyamidzusammensetzungen mit hoher Wärmeformbeständigkeit und deren Verwendung |
CN109467891A (zh) * | 2017-09-07 | 2019-03-15 | 科莱恩塑料和涂料有限公司 | 阻燃性聚酯组合物及其用途 |
WO2019048313A1 (de) | 2017-09-07 | 2019-03-14 | Clariant Plastics & Coatings Ltd | Synergistische flammschutzmittelkombinationen für polymerzusammensetzungen und deren verwendung |
WO2019048309A1 (de) | 2017-09-07 | 2019-03-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyesterzusammensetzungen und deren verwendung |
WO2019048307A1 (de) | 2017-09-07 | 2019-03-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyesterzusammensetzungen und deren verwendung |
DE102017215777A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammschutzmittelkombinationen für Polymerzusammensetzungen und deren Verwendung |
WO2019048312A1 (de) | 2017-09-07 | 2019-03-14 | Clariant Plastics & Coatings Ltd | Flammschutzmittelkombinationen für polymerzusammensetzungen und deren verwendung |
DE102017215780A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Synergistische Flammschutzmittelkombinationen für Polymerzusammensetzungen und deren Verwendung |
CN109467890A (zh) * | 2017-09-07 | 2019-03-15 | 科莱恩塑料和涂料有限公司 | 阻燃性聚酯组合物及其用途 |
WO2019048308A1 (de) | 2017-09-07 | 2019-03-14 | Clariant Plastics & Coatings Ltd | Flammhemmende polyamidzusammensetzungen mit hoher wärmeformbeständigkeit und deren verwendung |
CN109467890B (zh) * | 2017-09-07 | 2021-07-06 | 科莱恩塑料和涂料有限公司 | 阻燃性聚酯组合物及其用途 |
WO2019048311A1 (de) | 2017-09-07 | 2019-03-14 | Clariant Plastics & Coatings Ltd | Flammschutzmittelkombinationen für polymerzusammensetzungen und deren verwendung |
DE102017215776A1 (de) | 2017-09-07 | 2019-03-07 | Clariant Plastics & Coatings Ltd | Flammhemmende Polyesterzusammensetzungen und deren Verwendung |
WO2019076688A1 (de) | 2017-10-16 | 2019-04-25 | Clariant Plastics & Coatings Ltd | Flammwidrige und farbstabile polyamidformmassen |
DE102017218453A1 (de) | 2017-10-16 | 2019-04-18 | Clariant Plastics & Coatings Ltd | Flammwidrige und farbstabile Polyamidformmassen |
US11859084B2 (en) | 2017-10-16 | 2024-01-02 | Clariant International Ltd | Flame-retardant and color-stable polyamide molding compounds |
WO2020132095A1 (en) | 2018-12-20 | 2020-06-25 | Lanxess Solutions Us Inc. | Method for preparing readily processable, thermally-stable, phosphorus-containing flame retardant material |
WO2020165017A1 (en) | 2019-02-11 | 2020-08-20 | Clariant Plastics & Coatings Ltd | Flame retardant mixture for thermoplastic polymers |
WO2020201811A1 (en) | 2019-04-02 | 2020-10-08 | Italmatch Chemicals S.P.A. | Non-flammable hypophosphite metal salt based powders and their use as flame retardant ingredients |
Also Published As
Publication number | Publication date |
---|---|
KR20130132432A (ko) | 2013-12-04 |
JP2013538926A (ja) | 2013-10-17 |
JP2017025298A (ja) | 2017-02-02 |
US20130190432A1 (en) | 2013-07-25 |
TWI519633B (zh) | 2016-02-01 |
EP2625220A1 (de) | 2013-08-14 |
CN103154110A (zh) | 2013-06-12 |
TW201229219A (en) | 2012-07-16 |
DE102010048025A1 (de) | 2012-04-12 |
CN103154110B (zh) | 2015-06-03 |
JP2018154842A (ja) | 2018-10-04 |
EP2625220B1 (de) | 2016-11-09 |
JP6768741B2 (ja) | 2020-10-14 |
US20190153197A1 (en) | 2019-05-23 |
KR101967602B1 (ko) | 2019-04-11 |
JP6391180B2 (ja) | 2018-09-19 |
ES2610188T3 (es) | 2017-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2625220B1 (de) | Flammschutzmittel- stabilisator-kombination für thermoplastische polymere | |
EP2563876B1 (de) | Flammschutzmittel-stabilisator-kombination für thermoplastische und duroplastische polymere | |
EP2563877B1 (de) | Flammschutzmittel-stabilisator-kombination für thermoplastische und duroplastische polymere | |
EP2593505B1 (de) | Flammschutzmittel-stabilisator-kombination für thermoplastische polymere | |
EP1537173B1 (de) | Flammschutzmittel-stabilisator-kombination fur thermoplastische polymere | |
EP1454948B1 (de) | Flammschutzmittel-Stabilisator-Kombination für thermoplastische Polymere | |
DE102015004662A1 (de) | Verfahren zur Herstellung flammwidriger, nicht korrosiver und stabiler Polyamidformmassen | |
DE102010018684A1 (de) | Verfahren zur Herstellung von Mischungen aus Alkylphosphonigsäuresalzen und Dialkylphosphinsäuresalzen | |
EP1568731A1 (de) | Flammschutzmittel-Kombination für thermoplastische Polymere | |
WO2012113520A1 (de) | Flammschutzmittel-stabilisator-kombination für thermoplastische polymere | |
WO2019076688A1 (de) | Flammwidrige und farbstabile polyamidformmassen | |
EP2563798A2 (de) | Verfahren zur herstellung von alkylphosphonigsäuresalzen | |
EP3926002A1 (de) | Flammschutzmittel-stabilisator-kombination für thermoplastische polymere |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180048585.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11771018 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2011771018 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011771018 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2013532062 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13878145 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20137011974 Country of ref document: KR Kind code of ref document: A |