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
  • C08K5/16—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
• • 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

Definitions

• the present invention relates to a flame retardant composition, which comprises a combination of a phosphonite or a phosphite with a nitrogen containing flame retardant and polyurethane polymer base.
• Thermoplastic polyurethanes are useful for many technical applications. Particular reference is made to Kunststoff-Handbuch, Vol. VII, Polyurethane, Carl Hanser Verlag D-M ⁇ n- chen, 1st Edition 1966, Editors R. Vieweg and A. H ⁇ chtlen, and 2nd Edition, Editor G. Oertel.
• High molecular weight polyhydroxy compounds which form the flexible base, for example polyoxyalkylene glycols, such as poly- oxypropylene or polyoxyethylene glycol, polyoxypropylene polyoxyethylene glycol, polyoxy- butylene glycol, polyoxybutylene polyoxyethylene glycol or polyoxybutylene polyoxypropylene glycol, or polyesterdiols, such as alkanediol polyadipates, are reacted with aromatic or aliphatic diisocyanates, e.g.
• TPU diphenylmethane-4,4'-diisocyanate
• HDI hexamethylene-1 ,6- diisocyanate
• low molecular weight chain extenders for the formation of rigid seg- ments, for example alkanediols or dialkylene glycols, such as 1 ,4-butanediol or diethylene glycol.
• alkanediols or dialkylene glycols such as 1 ,4-butanediol or diethylene glycol.
• a disadvantage of TPU is their easy inflammability.
• Flame retardants are added to polymeric materials (synthetic or natural) to enhance the flame retardant properties of the polymers. Depending on their composition, flame retardants may act in the solid, liquid or gas phase either chemically, e.g. as a spumescent by liberation of nitrogen, and/or physically, e.g. by producing a foam coverage. Flame retardants interfere during a particular stage of the combustion process, e.g. during heating, decomposition, ignition or flame spread.
• Nitrogen-containing flame retardants especially those based on melamine, have been known for a long time and are, in some cases, commercially available. Some of those mela- mine derivatives also contain phosphorus. Examples of publications relating to such flame retardants are, inter alia, EP-A-782 599, EP-A-1 095 030 and U.S. Patent Specification Nos. 4,010, 137 and 3,915, 777.
• Combinations of nitrogen-containing flame retardants with flame retardants based on phosphorus compounds are also known.
• Particular phosphates in combination with nitrogen-containing compounds are also known as flame retardants, for example from EP-A-484 832, EP-A-545 496, EP-A-707 036, WO-A-01/98401, GB-A-1 468 188 and EP-A-617 079.
• flame retardants that have improved thermal and mechanical properties and that can be used in various polymer substrates.
• the present invention relates to a composition, which comprises a) At least one ester derivative of a phosphorus containing oxo acid selected from the group consisting of oxaphosphorinoxide, phosphonous acid and phosphorous acid; b) At least one flame retardant component based on a nitrogen compound; and c) A polyurethane polymer base.
• the present invention relates to a composition, which comprises a) At least one ester derivative of a phosphorus containing oxo acid selected from the group consisting of phosphonous and phosphorous acid; b) At least one flame retardant component based on a nitrogen compound; and c) A polyurethane polymer base.
• compositions according to the invention attain the desirable V-O rating, according to UL- 94 (Underwriter's Laboratories Subject 94) and other excellent ratings in related test methods while preserving the excellent mechanical, chemical and thermal properties of thermoplastic polyurethanes, such as colour and light stability.
• composition as defined above, comprises the following components: Component a)
• composition according to the present invention comprises as component a) at least one ester derivative of a phosphorus containing oxo acid selected from the group consisting of oxaphosphorinoxide, phosphonous acid and phosphorous acid.
• composition according to the present invention comprises as component a) at least one ester derivative of a phosphorus containing oxo acid selected from the group consisting of phosphonous and phosphorous acid.
• Oxaphosphorinoxide has a cyclic structure and is represented by the following general formula:
• the phosphorous atom and one oxygen atom are part of a cyclic structure, particularly a five or six membered ring, as represented by the following representative compound:
• DOPO 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide
• Phosphonous acid is represented by the following general formula:
• the acid is a member of the large group of phosphorus containing oxo acids, which includes other members, such as phosphoric, phosphorous or phosphinous acid. Phosphonous acid does not exist in its free form in an aqueous solution.
• Ester derivatives of phosphonous acid are represented by the following general formula - A -
• R represents an organic ester group and R' represents hydrogen or an organic sub- stituent which is directly attached to the phosphorus atom.
• Phosphorous acid is represented by the following general formula:
• the acid is a further member of the large group of phosphorus containing oxo acids and does not exist in aqueous solution in its free form as well.
• Ester derivatives of phosphorous acid are defined by the term phosphites. They are represented by the following general formula:
• R represents an organic ester group.
• a preferred embodiment relates to compositions comprising as component a) ester derivatives of phosphorous acid as represented by the following general formulae:
• R-i, R 2 and R3 and one of R 4 , R 5 and Re represent hydrogen and the other ones represent CrC 8 alkyl or aryl-Ci-C 4 alkyl; or
• Ri, R 2 and R 3 and R 4 , R 5 and R 6 represent d-C 8 alkyl
• R and R' represent Cg-C 2 oalkyl
• Ri, R 2 and R 3 represent CrCi 8 alkyl; or one or two of Ri, R 2 and R 3 represent hydrogen and the other ones represent d-Ci 8 alkyl; or
• R-i, R 2 and R 3 represents methyl and the other ones represent C 3 -C 4 alkyl; or Ri, R 2 and R 3 independently of one another represent CrC 4 alkyl; and
• R 3 and R b represent methyl or ethyl
• R 1 , R 2 and R 3 independently of one another represent phenyl or C 5 -C 2 oalkyl; or
• a preferred embodiment relates to compositions comprising as component a) ester derivatives of phosphonous and phosphorous acid selected from the group consisting of
• compositions comprising as component a) a cyclic oxaphosphorinoxide of the formula
• a particularly preferred embodiment relates to compositions comprising as component a) ester derivatives of phosphonous and phosphorous acid selected from the group consisting of triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert- butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-
• a highly preferred embodiment relates to compositions comprising as component a) ester derivatives of phosphonous and phosphorous acid selected from the group consisting of aryl organo phosphites, such as tris nonylphenyl phosphite (TNPP DOVERPHOS 4), triphenyl phosphite (TPP DOVERPHOS 10) or diphenyl phosphite (DPP DOVERPHOS 213), aryl-alkyl organo phosphites, such as phenyl diisodecyl phosphite (PDDP DOVERPHOS 7), diphenyl isodecyl phosphite (DPDP DOVERPHOS 8), diphenylisooctyl phosphite (DPIOP DOVERPHOS 9), tetraphenyl dipropylene glycol diphosphite (THOP DOVERPHOS 11 ), poly (dipropylene glycol) phenyl phosphit
• a further highly preferred embodiment of the invention relates to compositions comprising as component a) an ester derivative of phosphonous or phosphorous acid selected from the group consisting of 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO), bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite [CAS RN 80693-00-1],
• DOPO 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide
• DOPO 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide
• ester derivatives of phosphonous and phosphorous acid are known compounds and are commercially available. According to a particularly preferred embodiment the invention relates to compositions, which comprises as component a) ester derivatives of phosphonous and phosphorous acid selected from the group consisting of the commercial products IRGAFOS 126, 168, 38, PEPQ, 12, TNPP and DDPP, WESTON 618 and Mark PEP 36.
• the invention relates to compositions, whe- rein component a) is present in an amount equal or higher than 1 % by weight based on the total weight of the composition.
• composition according to the invention comprises as Component b) at least one nitrogen compound selected from the group consisting of:
• Ri, R 2 or R 3 independently of one another represent substituents selected from the group consisting of C-i-C ⁇ alkyl, C 5 -C 6 cycloalkyl and CrC 4 alkyl-C 5 -C 6 cycloalkyl with hydroxy as an optional substituent; or represent substituents selected from the group consisting of C 2 - C 8 alkenyl, CrC 8 -alkoxy, C 2 -C 8 alkenyl; d-C 8 alkoxy, acyl, acyloxy, C 6 -Ci 2 aryl, -0-R 1 and -N(R 1 )R 2 , wherein R 1 and R 2 independently of one another represent hydrogen, CrC 4 alkyl, C 5 -C 6 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 4 hydroxyalkyl or C 6 -Ci 2 aryl; or
• R-i, R 2 and R 3 represents hydrogen and two of R-i, R 2 and R 3 represent the substitu- ents as defined above; or Two of Ri, R 2 and R 3 represent hydrogen and one of Ri, R 2 and R 3 represents a substituent as defined above;
• X represents the anion of a protonic acid
• x is a numeral that represents the number of protons transferred from the latter to the triazine compound
• y is a numeral that represents the number of protons abstracted from the protonic acid
• R 1 , R 2 and R 3 represent groups of the partial formula -N(R 1 )R 2 and R 1 and R 2 represent hydrogen;
• R-i, R 2 , R3, R 4 and R 5 independently of one another represent hydrogen or substituents selected from the group consisting of CrC 8 alkyl, C 5 -C 6 cycloalkyl and Ci-C 4 alkyl-C 5 -C 6 cycloalkyl with hydroxy as an optional substituent; or represent substituents selected from the group consisting of C 2 -C 8 alkenyl, CrC 8 -alkoxy, C 2 -C 8 alkenyl, Ci-C 8 alkoxy, acyl, acyloxy, C 6 -Ci 2 aryl and -O-R 1 , wherein R 1 represents hydrogen, Ci-C 4 alkyl, C 5 -C 6 cycloalkyl, C 2 -C 8 alkenyl, CrC 4 hydroxyalkyl or C 6 -Ci 2 aryl.
• the composition comprises as Component b) at least one nitrogen compound selected from the group consisting of ammonium polyphosphate, melamine ammonium phosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid and mixtures thereof.
• X in formula VII represents, for example, an anion of phosphoric acid, polyphos- phoric acid (linear or branched), pyrophosphoric acid, phosphinic acid, phosphonic acid or boric acid.
• the composition comprises as Component b) compounds (III), (VII) and (IX), wherein R 1 , R 2 or R 3 independently of one another represent substituents selected from the group consisting of CrC 4 alkyl, cyclopentyl, cyclohexyl, methylcy- clohexyl, CrC 4 hydroxyalkyl, C 2 -Cealkenyl, CrC 4 alkoxy, phenyl, phenyl, which is substituted by 1 to 3 substituents selected from the group consisting of methyl, methoxy and by halogen, -OR 1 and by -N(R 1 )R 2 , wherein R 1 and R 2 independently of one another represent hydrogen, CrC 4 alkyl, hydroxy-C 2 -C 4 alkyl, cycloalkyl, methylcyclohexyl, phenyl or phenyl, which is sub- stituted by 1 to 3 substituents selected from the group consisting
• the composition comprises as Component b) compounds (III), (VII) and (IX), wherein one of Ri, R 2 and R 3 represents hydrogen and two of R-i, R 2 and R 3 represent the substituents as defined above; or two of R-i, R 2 and R 3 represent hydrogen and one of R-i, R 2 and R 3 represents a substituent as defined above.
• the composition comprises as Component b) compounds (IV), (V), (Vl) and (VIII), wherein R 1 , R 2 , R 3 , R 4 and R 5 independently of one an- other represent hydrogen or substituents selected from the group consisting of CrC 4 alkyl, cyclopentyl, cyclohexyl, methylcyclohexyl, hydroxy-C 2 -C 4 alkyl, C 2 -C 6 alkenyl, Ci-C 4 alkoxy, phenyl, phenyl, which is substituted by 1 to 3 substituents selected from the group consisting of methyl, methoxy and halogen and by -OR 1 wherein R 1 represents hydrogen, Ci-C 4 alkyl, hydroxy-C 2 -C 4 alkyl, cycloalkyl, methylcyclohexyl, phenyl or phenyl, which is substituted by 1 to 3 substituents selected from the group consisting of methyl, methoxy and
• the composition comprises as Component b) a nitrogen compound selected from the group consisting of compounds (VII), compounds (IX), ammonium polyphosphate, melamine ammonium phosphate, melamine amimo- nium polyphosphate, melamine ammonium pyrophosphate, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid and mixtures thereof.
• a nitrogen compound selected from the group consisting of compounds (VII), compounds (IX), ammonium polyphosphate, melamine ammonium phosphate, melamine amimo- nium polyphosphate, melamine ammonium pyrophosphate, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid and mixtures thereof.
• the composition comprises as Component b) a nitrogen compound selected from the group consisting of benzoguanamine, tris(hydroxy- ethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, dimel- amine phosphate, melamine pyrophosphate, urea cyanurate, melamine polyphosphate, melamine borate, ammonium polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, the condensation product of melamine selected from the group consisting of melem, melam, melon and higher condensed compounds and other reaction products of melamine with phosphoric acid and mixtures thereof.
• a nitrogen compound selected from the group consisting of benzoguanamine, tris(hydroxy- ethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, dimel- amine phosphate,
• the composition comprises as Component b) melamine cyanurate, such as the ones commercially available under the designation MELAPUR MC, MC 15, MC 25, MC 50.
• ratios a) and b) may vary within wide limits and is dependent upon the intended use.
• ratios a : b ratios by weight are from 5 : 95 to 95 : 5, e.g. from 10 : 90 to 90 : 10, preferably from 20 : 80 to 80 : 20, especially from 30 : 70 to 70 : 30 and from 40 : 60 to 60 : 40.
• composition according to the invention comprises as Component c) a polyurethane polymer base
• the polymer base may be a thermoplastic polyurethane (TPU), a PU elastomer, artificial leather, PU skin, PU stray coating or reaction injection molding (RIM), a cast PU, a silylated polyurethane (SPUR), a PU hot melt adhesive or a PU hot melt adhesive.
• TPU thermoplastic polyurethane
• RIM reaction injection molding
• SPUR silylated polyurethane
• SPUR silylated polyurethane
• the polyurethanes are obtainable, for example, by reacting polyethers, polyesters and poly- butadienes which contain terminal hydroxyl groups, i.e. polyols, with aliphatic or aromatic polyisocyanates.
• Polyethers and polyesters having terminal hydroxyl groups are known and are prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 , or by addition reaction of these epoxides, alone or as a mixture or in success- sion, with starting components containing reactive hydrogen atoms, such as alcohols, ammonia or amines, for example ethylene glycol, propylene 1 ,3- and 1 ,2-glycol, trimethylolpro- pane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine.
• epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin
• starting components containing reactive hydrogen atoms such
• Sucrose polyethers are also suitable in accordance with the invention. In many cases preference is given to those polyethers which predominantly (up to 90% by weight, based on all OH groups present in the polyether) contain primary OH groups. Furthermore, polyethers modified by vinyl polymers, as are formed, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers, are suitable, as are polybutadienes containing OH groups.
• These compounds generally have molecular weights of 40 and are polyhydroxy compounds, especially compounds containing from two to eight hydroxyl groups, especially those of molecular weight from 800 to 10 000, preferably from 1000 to 6000, for example polyethers containing at least 2, generally 2 to 8, but preferably 2 to 4, hydroxyl groups, as are known for the preparation of homogeneous polyurethanes and cellular polyurethanes. It is of course possible to employ mixtures of the above compounds containing at least two isocyanate-reactive hydrogen atoms, in particular with a molecular weight of 400 - 10 000.
• Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, for example ethylene diisocyanate, 1 ,4-tetramethylene diisocyanate, 1 ,6- hexamethylene diisocyanate, 1 ,12-dodecane diisocyanate, cyclobutane 1 ,3-diisocyanate, cy- clohexane 1 ,3- and -1 ,4-diisocyanate and also any desired mixtures of these isomers, 1-iso- cyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate and also any desired mixtures of these isomers, hexa hydro- 1 ,3- and/or -1 ,4-phe- nylene diisocyanate, perhydro-2,4
• isocyanate group-containing distillation residues as they are or dissolved in one or more of the above-mentioned polyisocyanates, which are obtained in the course of the industrial preparation of isocyanates. It is additionally possible to use any desired mixtures of the above-mentioned polyisocyanates.
• polyisocyanates which are readily obtainable industrially, for example aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate and any desired mixtures of these isomers (“TDI”), polyphenyl-polymethylene-polyisocyanates as prepared by aniline-formaldehyde condensation followed by phosgenization (“crude MDI”), and polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups (“modified polyisocyanates”).
• Polyurethane is preferably prepared from liquid starting components, i.e. the starting materials to be reacted with one another being mixed together in a one-shot process.
• the polymer base of component c) may additionally contain in the form as admixtures or as copolymers a wide variety of other synthetic polymers including polyolefins, polystyrenes, polyesters, polyethers, polyamides, poly(meth)acrylates, thermoplastic polyurethanes, poly- sulphones, polyacetals and PVC, including suitable compatibilizing agents.
• the polymer base may additionally contain thermoplastic polymers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof.
• Specific embodiments include polypropylene (PP), polyethylene (PE), polyam- ide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), glycol-modified polycyclohexylenemethylene terephthalate (PCTG), polysulphone (PSU), polymethylmethacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA), acrylonitrile-ethylene-propylene-styrene (AES), styrene-maleic anhydride (SMA) or high impact polystyrene (HIPS).
• PP polypropylene
• PE polyethylene
• PA polyam- ide
• PBT polybutylene terephthalate
• PET polyethylene terephthalate
• PCTG glycol-modified polycyclohexylenemethylene terephthal
• polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, poly- but-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadi- ene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
• HDPE high density polyethylene
• HDPE-HMW high density and high molecular weight polyethylene
• HDPE-UHMW high density and ultrahigh molecular weight polyethylene
• MDPE low density polyethylene
• the polymers of monoolefins exemplified in the preceding paragraph can be prepared by different, and especially by the following, methods: a) Radical polymerisation (normally under high pressure and at elevated temperature). b) Catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
• ligand typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
• These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium.
• the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Ma and/or IMa of the Periodic Table.
• the activators may be modified conveniently with further ester, ether, and amine or silyl ether groups.
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethyl- ene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.,
• ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ
• propylene/butadiene copolymers isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethyl- ene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-no- rbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethylene-propylene copolymers,
• the homopolymers and copolymers mentioned above may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included. 5. Polystyrene, poly (p-methylstyrene), poly( ⁇ -methylstyrene).
• Homopolymers and copolymers may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.
• Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, sty- rene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylon it- rile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block
• Hydrogenated aromatic polymers derived from hydrogenation of polymers men- tioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
• PCHE polycyclohexylethylene
• PVCH polyvinylcyclohexane
• Homopolymers and copolymers may have a stereo structure in- eluding syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.
• Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene- acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; s
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sul- phochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichloro- hydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvi- nylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
• halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobut
• Polymers derived from ⁇ , ⁇ -unsatu rated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacry- lonitriles, impact-modified with butyl acrylate.
• Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
• Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl ben- zoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1. above.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes, which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyam- ide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polyte
• ABS ABS; and polyamides condensed during processing (RIM polyamide systems).
• Polyureas Polyureas, polyimides, polyamide imides, polyether imides, polyester imides, polyhydan- toins and polybenzimidazoles.
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxy l-term in ated polyethers; and also polyesters modified with polycarbonates or MBS.
• Blends of the aforementioned polymers for example PP/EPDM, Polyam- ide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, 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/ABS or PBT/PET/PC.
• polyblends for example PP/EPDM, Polyam- ide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate
• compositions according to the invention may be carried out either by adding or applying the flame retardants consisting of components a) and b) according to the invention or, however, by adding or applying the individual components separately.
• components a) and b), each independently of the other in a concentration of from 0.1 to 30.0% by weight, for example from 0.2 to 20.0% by weight, preferably from 0.2 to 15.0 % by weight, based on weight of the polymer base.
• compositions according to the invention contain the flame retardant consisting of components a) and b) in an amount of, for example, from 0.1 to 50.0 % by weight, preferably from 0.3 to 40.0% by weight, especially from 0.3 to 30.0% by weight or from 0.8 to 30.0% by weight, based on the composition.
• the flame-resistant polymer compositions are suitable, inter alia, for the production of moulded articles, films, threads and fibres, for example by injection-moulding, extrusion or compression-moulding. Additional Components
• the instant invention further pertains to a composition, which comprises, in addition to the Components a), b) and c), as defined above, d) further additives selected from the group consisting of polymer stabilizers and additional flame-retardants selected from the group consisting of phosphorus containing flame-retardants, halogenated flame-retardants and inorganic flame-retardants.
• Stabilizers are preferably halogen-free and selected from nitroxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methide stabilizers and monoacrylate esters of 2,2'-alkylidenebisphenol stabiliz- ers.
• Additional flame-retardants as of present component d) are known components, items of commerce or can be obtained by known methods.
• phosphorus containing flame-retardants are for example: Tetraphenyl resorcinol diphosphite (FYROLFLEX ® RDP, Akzo Nobel), tetrakis(hydroxy- methyl)phosphonium sulphide, triphenyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)-amino- methyl phosphonate, hydroxyalkyl esters of phosphorus acids, resorcinol diphosphate oligomer (RDP), phosphazene flame-retardants or ethylenediamine diphosphate (EDAP).
• FYROLFLEX ® RDP Triphenyl resorcinol diphosphite
• tetrakis(hydroxy- methyl)phosphonium sulphide triphenyl phosphate
• diethyl-N,N-bis(2-hydroxyethyl)-amino- methyl phosphonate hydroxyalkyl esters
• halogenated flame-retardants are, for example: Polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.), decabromodiphenyl oxide (DBDPO; SAYTEX ® 102E), tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370 ® , FMC Corp.), tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl)phosphate, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly- ⁇ -chloroethyl triphosphonate mixture, tetrabromobisphenol A bis(2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylene-bis(tetrabromophthalimide) (SAYTEX ® BT-93), bis(hexachlorocyclopentadieno)
• the flame-retardant mentioned above are routinely combined with an inorganic oxide synergist. Most common for this use are zinc or antimony oxides, e.g. Sb 2 O 3 or Sb 2 O 5 . Boron compounds are suitable, too.
• the above-mentioned flame-retardant classes are advantageously contained in the composition of the invention in an amount from about 0.5% to about 45.0% by weight of the organic polymer substrate; for instance about 3.0% to about 40.0%; for example about 5.0% to about 35.0% by weight of the polymer.
• the flame-retardant of component b) is em- ployed from about 0.5% to about 10.0% by weight, from about 1.0% to about 10.0%, from about 3.0% to about 10.0% or from about 5.0% to about 10.0% by weight, based on the weight of the polymer substrate.
• component b) is employed from about 0.5% to about 8.0%, from about 0.5% to about 6.0%, from about 0.5% to about 5.0%, or from about 0.5% to about 3.0% by weight, based on the weight of the polymer substrate.
• composition according to the invention may additionally contain one or more conventional additives, for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-hydroxy-benzophenone, 2-(2'-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)- 1 ,3,5-triazine groups. More specific examples are the following components:
• Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert- butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimeth- ylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, linear nonylphenols or nonylphenols branched in the side-chain, e.g.
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecyl- thiomethyl-4-nonylphenol.
• Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
• Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (Vitamin E).
• thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) di- sulphide.
• Alkylidene bisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-meth- ylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphe- nol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylbenzyl)- 4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -di-
• Hydroxybenzylated malonates for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, dido- decylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, di[4-(1 ,1 ,3,3- tetramethylbutyl)phenyl] 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Hydroxybenzyl aromatic compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
• Triazine compounds for example 2,4-bisoctyl ⁇ mercapto-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-triaz- ine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris(3,5- di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1
• Benzylphosphonates for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester.
• esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or poly-hydric alcohols for example with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1 ,6-hex- anediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl- hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phos
• esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols for example with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl- hexanediol, trimethylolpropane, 4-hydroxymethyl-1 -pho
• esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or poly-hydric alcohols for example with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxy- ethyl)oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.
• esters of S. ⁇ -di-tert-butvM-hvdroxyphenylacetic acid with mono- or poly-hydric alcohols for example with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nona- nediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxy- ethyl)oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]
• Amine-type antioxidants for example N,N'-di-isopropyl-p-phenvlenediamine, N.N'-di- sec-butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1- ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(2-naph- thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)- N
• 2-(2'-Hvdroxyphenyl)-benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)-ben- zotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert-butyl-2'-hydroxy- phenyl)-benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)-phenyl)-benzotriazole, 2- (3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'- methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotri- azole, 2-(
• 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivative.
• Esters of unsubstituted or substituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenz- oyl)resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyl- phenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hy- droxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di- tert-butylphenyl ester.
• 2.4 Acrylates for example ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester, ⁇ - methoxycarbonylcinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxycinnamic acid methyl ester or butyl ester, ⁇ -methoxycarbonyl-p-methoxycinnamic acid methyl ester, N-( ⁇ - methoxycarbonyl- ⁇ -cyanovinyl)-2-methyl-indoline.
• Nickel compounds for example nickel complexes of 2,2'-thio-bis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 : 1 or 1 : 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyl dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methyl- phenylundecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.
• additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyl dithi
• Sterically hindered amines for example bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate, bis(2,2,6,6-tetramethylpiperid-4-yl) succinate, bis(1 ,2,2,6,6-pentamethylpiperid-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate, n-butyl-3,5-di-tert-butyl-4-hy- droxybenzylmalonic acid bis(1 ,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-d
• Oxalic acid diamides for example 4,4'-dioctyloxy oxanilide, 2,2'-diethoxy oxanilide, 2,2'- dioctyloxy-5,5'-di-tert-butyl oxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethoxy- 2'-ethyl oxanilide, N,N'-bis(3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl oxanilide, mixtures of o- and p-methoxy- and also of o- and p-ethoxy-di-substituted ox
• Metal deactivators for example N,N'-diphenyloxalic acid diamide, N-salicylal-N'- salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl- propionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, N,N'-diacetyladipic acid dihydrazide, N.N'-bis-salicyloyloxalic acid dihydrazide, N.N'-bis-salicyloylthiopropionic acid dihydrazide.
• Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N 1 N- dihexadecylhydroxylamine, N.N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhy- droxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine from hy- drogenated tallow fatty amines.
• Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptade- cylnitrone, N-octadecyl-alpha-hexadecylnitrone,N
• Thiosynergistic compounds for example thiodipropionic acid dilauryl ester or thio- dipropionic acid distearyl ester.
• Peroxide-destroying compounds for example esters of ⁇ -thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulphide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
• esters of ⁇ -thio-dipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester
• mercaptobenzimidazole the zinc salt of 2-mercaptobenzimidazole
• zinc dibutyldithiocarbamate dioctadecyldisulphide
• Polyamide stabilisers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmi- tate, antimony pyrocatecholate or zinc pyrocatecholate. 10.
• Nucleating agents for example inorganic substances, e.g. talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulphates of preferably alkaline earth metals; organic compounds, such as mono- or poly-carboxylic acids and their salts, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, for example ionic copolymerisates ("ionomers").
• inorganic substances e.g. talc
• metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulphates of preferably alkaline earth metals
• organic compounds such as mono- or poly-carboxylic acids and their salts, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
• polymeric compounds for example ionic copo
• Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black, graphite, wood powders, and powders and fibres of other natural products, synthetic fibres.
• Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black, graphite, wood powders, and powders and fibres of other natural products, synthetic fibres.
• Benzofuranones and indolinones for example as described in U.S. 4,325,863; U.S. 4,338,244; U.S.5, 175,312, U.S. 5,216,052; U.S.
• Anti-gas fading agents for example 1 ,1 ,1',1'-tetramethyl-4,4'-(methylene-di-p-pheny- lene)disemicarbazide; 1 ,6-hexamethylene bis(N,N-dimethylsemicarbazide); 11-[6-[[(2,2-di- methylhydrazino)carbonyl]amino]hexyl]-10,12-dioxo-bis(2,2-dimethylhydrazide).
• additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow improvers, optical brighteners, antistatics, blowing agents.
• the further additives of Component c) are added, for example, in concentrations of 0.01 to 10.0%, relative to the total weight of the composition of this invention.
• the incorporation of the additive components a) and b) and optional further components into the polymer component c) is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
• the additive components a) and b) and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc.), e.g. as a dry mixture or powder, or as a solution or dispersion or suspension or melt.
• the addition of the additive components to the polymer substrate c) can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders. The process is preferably carried out in an extruder by introducing the additive during processing.
• Particularly preferred processing machines are single-screw extruders, contra rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders or co kneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
• the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
• the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm.
• the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
• the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
• the additives components a) and b) and optional further additives can also be sprayed onto the polymer substrate c).
• the additive mixture dilutes other additives, for example the conventional additives indicated above, or their melts so that they can be sprayed also together with these additives onto the polymer substrate.
• Addition by spraying during the deactivation of the polymerisation catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst.
• the additives of the invention optionally together with other additives, by spraying.
• the additive components a) and b) and optional further additives can also be added to the polymer in the form of a master batch ("concentrate") which contains the components in a concentration of, for example, about 1.0% to about 40.0% and preferably 2.0% to about 20.0% by weight incorporated in a polymer.
• concentration a master batch
• the polymer is not necessarily of identical structure than the polymer where the additives are added finally.
• the polymer can be used in the form of powder, granules, solutions, and suspensions or in the form of lattices.
• Incorporation can take place prior to or during the shaping operation.
• the materials contain- ing the additives of the invention described herein preferably are used for the production of molded articles, for example roto-molded articles, injection molded articles, profiles and the like, and especially a fiber, spun melt non-woven, film or foam.
• present invention further pertains to a molded or extruded article, a fiber, spun melt non-woven or a foam comprising the composition of the invention.
• a particularly preferred embodiment of the invention relates to a composition, which comprises a) At least one ester derivative of phosphonous and phosphorous acid; b) Melamine cyanurate; and c) A polyurethane polymer base.
• compositions which comprises a) At least one at least one ester derivative of phosphonous and phosphorous acid selected from the group consisting of
• a particularly preferred embodiment of the invention relates to a composition, which comprises a) At least one ester derivative of phosphonous and phosphorous acid selected from the group consisting of
• compositions which comprises a) At least one ester derivative of phosphonous and phosphorous acid selected from the group consisting of tris nonylphenyl phosphite (TNPP), triphenyl phosphite (TPP), di- phenyl phosphite (DPP), phenyl diisodecyl phosphite (PDDP), diphenyl isodecyl phosphite (DPDP), diphenylisooctyl phosphite (DPIOP), tetraphenyl dipropylene glycol diphosphite(THOP), poly (dipropylene glycol) phenyl phosphite (DHOP), dodecyl diphenyl phosphite (DDPP), triisodecylphosphite (TDP), tris tridecyl phosphite (TTDP) and trilauryl
• compositions which comprises a) At least one ester derivative of phosphonous or phosphorous acid selected from the group consisting of 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO), bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite [CAS RN 80693-00-1], [(C 6 H5-O-)2P]2(-O-C2H 4 )2 [CAS RN 57077-45-9], [(C6H5-O-)2P]2(-OC 2 H5)i4(C6H5-O-P)6 [CAS RN 67383-54-4] and triphenyl phosphite; b) Melamine cyanurate; and c) A polyurethane polymer base
• DOPO 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide
• DOPO 9,10-di
• TPU polyester thermoplastic polyurethane
• Estane®GP 72 DB NAT 021 P Noveon®
• IRGAFOS 126 bis(2,4-di-tert-butyl- phenyl)pentaerythritol diphosphite
• MELAPUR MC 25 25% melamine cyanurate
• IRGANOX 1066 pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propion- ate
• This blend is compounded in twin-screw extruder (Berstorff®) at a temperature up to 220°C. The extrudate is granulated after drawing through a water bath and cooling.
• test panels are moulded from the granules formed by means of an injection-moulding machine (Arburg®320 S) at a temperature up to 220°C (mold temperature: 50°C).
• V-O Very good
• V-1 Good
• V-2 Not sufficient
• polyester thermoplastic polyurethane (TPU) pellets (Estane®58311 Natural 028 P) are mixed to homogeneity in a tumble mixer with different concentrations bis(2,4-di-tert-bu- tylphenyl)pentaerythritol diphosphite (IRGAFOS 126), different concentrations of melamine cyanurate (MELAPUR MC 25) and 1 % pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxy- phenyl)propionate (IRGANOX 1066).
• This blend is compounded in twin-screw extruder (Ber- storff®) at a temperature up to 220°C. The extrudate is granulated after drawing through a water bath and cooling.
• TPU polyester thermoplastic polyurethane
• Estane®58311 Natural 028 P polyester thermoplastic polyurethane pellets
• IRGAFOS 126 different concentrations bis(2,4-di-tert-bu- tylphenyl)pentaerythritol diphosphite
• MELAPUR MC 25 different concentrations of melamine cyanurate
• IRGANOX 1066 pen- taerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate
• This blend is compounded in twin-screw extruder (Berstorff®) at a temperature up to 220°C. The extrudate is granulated after drawing through a water bath and cooling. Injection molding and testing for flame retardancy are carried out in a manner analogous to Example 1.

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