US008735474B2

(12) United States Patent (10) Patent No.: US 8,735,474 B2 Kniesel et al. (45) Date of Patent: May 27, 2014

(54) FLAME RETARDANT COMPOSITIONS WITH 6,365,071 B1 4/2002 Jenewein POLYMERC OSPERSINGAGENTS 6,509,401 B1 1/2003 Jenewein 8,221,658 B2 * 7/2012 Bauer et al...... 252/.609 2001/0005745 A1 6/2001 Kersjes et al. (75) Inventors: Simon Kniesel, Heidelberg-Dossenheim 2003/0193045 A1 * 10, 2003 Takeuchi et al...... 252,601 (DE); Rudolf Pfaendner, Rimbach (DE) 2004.0049063 A1 3/2004 Hoerold et al. 2005/0250885 A1 11/2005 Mercx et al. (73) Assignee: BASFSE, Ludwigshafen (DE) 2006.0020064 A1 1/2006 Bauer et al. 2009.0054592 A1 2/2009 Keijzer De et al. (*) Notice: Subject to any disclaimer, the term of this 2010/01792.58 A1 7/2010 Sakata patent is extended or adjusted under 35 U.S.C. 154(b) by 71 days. FOREIGN PATENT DOCUMENTS DE 19614424 A1 10, 1997 (21) Appl. No.: 13/059,241 DE 19734437 A1 2, 1999 DE 19737727 A1 7, 1999 (22) PCT Filed: Aug. 20, 2009 EP OOO6568 A1 1, 1980 EP O484.832 A1 5, 1992 PCT/EP2009/060786 EP O545496 A1 6, 1993 (86). PCT No.: EP O617079 A2 9, 1994 S371 (c)(1), EP O70703.6 A1 4f1996 EP O78599 A1 7/1997 (2), (4) Date: Mar. 18, 2011 EP 1070754 A2 1, 2001 EP 1095.030 A1 5, 2001 (87) PCT Pub. No.: WO2010/023155 EP 1396524 A 3, 2004 EP 1624015 A 2, 2006 PCT Pub. Date: Mar. 4, 2010 EP 1772491 A 4/2007 EP 21542O1 A 2, 2010 (65) Prior Publication Data GB 1468.188 3/1977 WO 97.39053 A1 10, 1997 US 2011 FO190428A1 Aug. 4, 2011 WO O1984.01 A1 12/2001 WO 2005,116139 A 12/2005 (30) Foreign Application Priority Data WO 2008. 149892 A 12/2008 Aug. 27, 2008 (EP) ...... O8163O29 OTHER PUBLICATIONS Patent Abstracts of Japan 2005.133059 A May 26, 2005. (51) Int. Cl. Patent Abstracts of Japan 54040855 A Mar. 31, 1979. CSK 3/3492 (2006.01) English Language Abstract of EP 0006568 Jan. 9, 1980. CSK 5/533 (2006.01) CSK 3/28 (2006.01) * cited by examiner CSK 3/32 (2006.01) (52) U.S. Cl. Primary Examiner — Kriellion Sanders USPC ...... 524/100; 524/126; 524/133; 524/135; 524/416 (74) Attorney, Agent, or Firm — Tyler A. Stevenson (58) Field of Classification Search USPC ...... 524/100, 126, 133, 135, 416 (57) ABSTRACT See application file for complete search history. The invention relates to a flame retardant composition, wherein the following components: a) At least one flame (56) References Cited retardant component selected from the group consisting of phosphinic salts and nitrogen containing compounds; U.S. PATENT DOCUMENTS and b) At least one polymeric dispersing agent selected from 3,915,777 A 10/1975 Kaplan the group consisting of styrenemaleic acid anhydride copoly 4,010, 137 A 3/1977 Brady mers, long chain carboxylic acid salts and aliphatic polyether 5,210,120 A 5/1993 Cipolli Substituted by acidic groups; and c) A polymer Substrate; are 5,331,030 A 7/1994 Cipolli present. 6,031,032 A 2/2000 Horacek 6,207,736 B1 3, 2001 Nass 6.255,371 B1 7/2001 Schlosser 18 Claims, No Drawings US 8,735,474 B2 1. 2 FLAME RETARDANT COMPOSITIONS WITH test methods especially in polyamide glass fiber reinforced POLYMERC OSPERSINGAGENTS compositions where conventional flame retardants tend to fail. The invention relates to flame retardant compositions The compositions according to the invention are character which comprise a mixture of nitrogen containing compounds ized by favourable flame retardancy in combination with or salts of phosphinic acid and a selected polymeric dispers mechanical characteristics. In the context of the description ing agent. of the invention, mechanical stability is defined as the ability Flame retardants are added to polymeric materials (syn to withstand mechanical stress caused by tensile, bending or thetic or natural) to enhance the flame retardant properties of impact. the polymers. Depending on their composition, flame retar 10 The compositions, as defined above, comprise the follow dants may act in the Solid, liquid or gas phase either chemi ing components: cally, e.g. as a spumescent by liberation of nitrogen, and/or Componenta) physically, e.g. by producing a foam coverage. Flame retar The term salt of phosphinic acid comprises within its scope dants interfere during a particular stage of the combustion 15 preferably a metal salt, for example an alkali metal or alkaline process, e.g. during heating, decomposition, ignition or flame earth metal salt, e.g. the sodium, potassium, magnesium or spread. calcium salt or the iron(II), iron(III), zinc or boron salt. There is still an urgent need for flame retardant composi According to a preferred embodiment, the composition tions with improved properties that can be used in different comprises the aluminium salt of phosphinic acid. polymer Substrates. Increased standards with regard to safety According to an alternative embodiment, the term salts and environmental requirements result in stricter regulations. comprises non-metallic salts, e.g. the acid addition salts Particularly known halogen containing flame retardants no obtainable by reaction of phosphinic acid with ammonia or longer match all necessary requirements. Therefore, halogen amines, e.g. the (C-C alkyl)-N', (C-C alkyl)-NH. (C- free flame retardants are preferred, particularly in view of CalkylOH)N", (C-C alkylOH)NH", (C-C alkylOH)4N their better performance interms of smoke density associated 25 (CH), (C-C alkylOH)NHCH", (CHS),N', (CHS) with fire. Improved thermal stability and less corrosion of NH, (CHCH)N", (CHCH)NH" or the NH." salt. manufacturing equipment are further benefits of halogen free Among the acid addition salts the ammonium, (C- flame retardant compositions. Calkyl) ammonium or (2-hydroxy-ethyl)ammonium, Nitrogen-containing flame retardants, especially those e.g. tetramethylammonium, tetraethylammonium or the based on melamine, have been known for a longtime and are, 30 2-hydroxyethyl-trimethylammonium salt are particularly in Some cases, commercially available. Some of those preferred. melamine derivatives also contain . Examples of publications relating to Such flame retardants are, interalia, The term phosphinic acid comprises within its scope EP-A-782599, EP-A-1 095 030 and U.S. Pat. Nos. 4,010, 137 derivatives of phosphinic acid, HP(=O)CH, wherein one or and 3,915,777. 35 two hydrogenatoms, which are directly attached to the phos Combinations of nitrogen-containing flame retardants phorus atom, have been Substituted by organic Substituents, with flame retardants based on phosphorus compounds are particularly C-Calkyl, aryl, e.g. phenyl, aryl-C-C alkyl, also known. In that respect, particular reference is made to, e.g. benzyl or 1- or 2-phenethyl, or (C-C alkyl)-aryl. for example, DE-A-19734437, DE-A-19737 727, WO-A- According to a preferred embodiment, Suitable phosphinic 97/39053, EP-A-1 070 754, EP-A-6568 and DE-A-196 14 40 are represented by the structural formulae 424. Particular phosphates and phosphinates in combination with nitrogen-containing compounds are also known as flame retardants, for example from EP-A-484 832, EP-A-545 496, (I) EP-A-707 036, WO-A-01/98401, GB-A-1 468 188 and EP A-617 O79. 45 R-P-OH or There is a continuing need for flame retardants that have improved thermal and mechanical properties and that can be (II) used in various polymer Substrates. O O It has surprisingly been found that the mechanical proper ties and/or the flame retardant efficacy of flame retardant 50 HO-P-R-P-OH,| compositions can be improved by the addition of selected dispersants based on fatty acids, fatty amines, maleic acid anhydrides polymers and copolymers thereof. The present invention relates to a composition, particularly in which a flame retardant composition, comprising 55 R", R represents a linear or branched C-C alkyl radical, a) At least one flame retardant component selected from the , or a phenyl radical; and group consisting of phosphinic acid salts and nitrogen con taining compounds; and R represents a linear or branched C-Cloalkylene, arylene, b) At least one polymeric dispersing agent selected from the alkylarylene, or arylalkylene radical; group consisting of styrene-maleic acid anhydride copoly 60 The term phosphinic acid comprises within its scope the mers, long chain carboxylic acid salts, long chain carboxy tautomeric form HP(OH), wherein the hydrogenatom which lic amines and aliphatic polyether Substituted by acidic is directly attached to the phosphorus atom is substituted by groups; and an organic Substituent, particularly C-Calkyl, aryl, e.g. phe c) A polymer Substrate nyl, aryl-C-C-alkyl, e.g. benzyl or 1- or 2-phenethyl, or The compositions according to the invention attain the 65 (C-C alkyl)-aryl. desirable V-0 rating, according to UL-94 (Underwriters According to a particularly preferred embodiment, the salt Laboratories Subject 94) and other excellent ratings in related of a phosphinic acid (I) is represented by the formula US 8,735,474 B2 3 4 -continued (I) (VI) R R2 O w M | N N R-j-o Mi", R2 o={ X=0. / N R R4 in which (VII) R", R represents a linear or branched C-Csalkyl radical, 10 R x(+) or a phenyl radical, M represents (C-C alkyl)-N, (C-C alkyl)-NH. (C- 1. xH' CalkylCH)N, (C-C alkylCH)NH. (C-C alkylOH)N N1 NN 0 (X). (CH), (C-C alkylOH)NHCH (CHs)..N. (CHs)NH, 15 R3 us Nals R (CHCH).N. (CHCH)NH, NH, an alkali metal or iii. earth alkali metal , or an aluminium, Zinc, iron or boron (VIII) 1On; m is a numeral from 1-3 and indicates the number of pi positive charges on M, and R v O|| /R2 N -CN N n is a numeral from 1-3 and indicates the number of phos -C-y and pinic acid anions corresponding to M'. R R4 HO1 C NN1 C No A highly preferred embodiment relates to a composition, (IX) wherein the salt of a phosphinic acid (I) is represented by the R pi formula 25 1. an

R2 l Nals R3 Ho1 CnSN1 C No

30 Wherein in the compounds (III), (VII) and (IX): R. R. or R independently of one another represent Sub stituents selected from the group consisting of C-Calkyl, The composition according to the invention comprises as Cs-Cecycloalkyl and C-C alkyl-Cs-Cecycloalkyl with Component a) a flame retardant compound wherein at least 35 hydroxy as an optional Substituent; or represent Substituents one nitrogenatom is present. This flame retardant compound selected from the group consisting of C-Calkenyl, C-C- is present in the composition in combination with the phos alkoxy, C-Csalkenyl, C-Calkoxy, acyl, acyloxy, phinic acid salts defined above or as an alternative thereto C-Caryl, -O-R' and - N(R')R’, wherein R' and R' (and/or-relationship). independently of one another represent hydrogen, Suitable flame retardant compounds falling with the scope 40 of the definition “flame retardant compound wherein at least C-C alkyl, Cs-Cecycloalkyl, C-Calkenyl, one nitrogen atom is present are selected from the group C-Chydroxyalkyl or C-Caryl; or consisting of: One of R. R. and R represents hydrogen and two of R, R and R represent the substituents as defined above; or 45 Two of R, R and R represent hydrogen and one of R, R (III) and R represents a substituent as defined above: R X represents the anion of a protonic acid; X is a numeral that represents the number of protons trans ferred from the latter to the triazine compound; and s 50 y is a numeral that represents the number of protons l als abstracted from the protonic acid; R2 N R3, provided that O (IV)IV In compounds (VII) one group is present that is capable of adding a proton; and R 'NN ls 1.R2, 55 Compounds (III) are excluded, wherein R, R2 and R represent groups of the partial formula N(R')R and R' and R represent hydrogen; ---, And wherein in the compounds (IV), (V), (VI) and (VIII): R. R. R. R. and Rs independently of one another repre l 3 60 sent hydrogen or Substituents selected from the group con O R (V) s sisting of C-Calkyl, Cs-Cecycloalkyl and C-C alkyl-Cs Cecycloalkyl with hydroxy as an optional Substituent; or represent Substituents selected from the group consisting of R l 1s C-Calkenyl, C-C-alkoxy, C-Csalkenyl, C-Csalkoxy, 65 acyl, acyloxy, Co-C2aryl and —O R', wherein R' repre s^^rs.R4 R3 R2 sents hydrogen, C-C alkyl, Cs-Cecycloalkyl, C-Csalkenyl, C-Chydroxyalkyl or C-Caryl. US 8,735,474 B2 5 6 According to a preferred embodiment of the invention the melamine ammonium phosphate, melamine ammonium composition comprises as Componenta) at least one nitrogen polyphosphate, melamine ammonium , a con compound selected from the group consisting of ammonium densation product of melamine with and polyphosphate, melamine ammonium phosphate, melamine other reaction products of melamine with phosphoric acid ammonium polyphosphate, melamine ammonium pyrophos and mixtures thereof. phate, a condensation product of melamine with phosphoric According to a highly preferred embodiment the compo acid and other reaction products of melamine with phospho sition comprises as Component a) a nitrogen compound ric acid and mixtures thereof. selected from the group consisting of benzoguanamine, tris The symbol X in formula VII represents, for example, an (hydroxyethyl)isocyanurate, isocyanurate, allantoin, gly anion of phosphoric acid, polyphosphoric acid (linear or 10 coluril, melamine cyanurate, melamine phosphate, branched), pyrophosphoric acid, phosphinic acid, phospho dimelamine phosphate, melamine pyrophosphate, urea cya nic acid or boric acid. nurate, melamine polyphosphate, melamine borate, ammo According to a preferred embodiment the composition nium polyphosphate, melamine ammonium polyphosphate, comprises as Componenta) compounds (III), (VII) and (IX), melamine ammonium pyrophosphate, the condensation wherein R, R or Rs independently of one another represent 15 product of melamine selected from the group consisting of Substituents selected from the group consisting of melem, melam, melon and higher condensed compounds and C-C alkyl, cyclopentyl, cyclohexyl, methylcyclohexyl, other reaction products of melamine with phosphoric acid C-C hydroxyalkyl, C-Calkenyl, C-C alkoxy, phenyl, and mixtures thereof. phenyl, which is substituted by 1 to 3 substituents selected Special emphasis is given to dimelamine pyrophosphate, from the group consisting of methyl, methoxy and by halo melamine polyphosphate, melem polyphosphate, melam gen, —OR" and by N(R')R’, wherein R' and Rindepen polyphosphate, and/or a mixed polysalt thereof, particularly dently of one another represent hydrogen, C-C alkyl, melamine polyphosphate. hydroxy-C-C alkyl, cycloalkyl, methylcyclohexyl, phenyl According to a highly preferred embodiment the compo or phenyl, which is substituted by 1 to 3 substituents selected sition comprises as Componenta) melamine cyanurate. Such from the group consisting of methyl, methoxy and by halo 25 as the ones commercially available under the designation gen. MELAPUR MC, MC 15, MC 25 or MC 50, or melamine According to a particularly preferred embodiment the polyphosphate such as the one commercially available under composition comprises as Component a) compounds (III), the designation MELAPUR 200. (VII) and (IX), wherein one of R, R and R represents According to a particularly preferred embodiment the hydrogen and two of R. R. and R represent the substituents 30 invention relates to compositions, wherein component a) is as defined above; or two of R, R2 and R represent hydrogen present in an amount equal or higher than 1% by weight based and one of R, R and R represents a substituent as defined on the total weight of the composition. above. Component a) is admixed to the polymer Substrate c) in According to another preferred embodiment the composi concentrations of 0.05-35.0 wt.%, preferably 0.1-20.0 wt.%. tion comprises as Component a) compounds (IV), (V), (VI) 35 Component b) and (VIII), wherein R. R. R. R. and Rs independently of A suitable polymeric dispersing agent consists of a poly one another represent hydrogen or Substituents selected from meric chain and at least one so-called anchoring groups. The the group consisting of C-C alkyl, cyclopentyl, cyclohexyl, polymeric chain provides properties within the methylcyclohexyl, hydroxy-C-C alkyl, C-Calkenyl, polymeric Substrate as well as steric stabilization and deter C-C alkoxy, phenyl, phenyl, which is substituted by 1 to 3 40 mines the compatibility with the polymer system, whereas the Substituents selected from the group consisting of methyl, anchoring group is connected with the flame retardant mol methoxy and halogen and by —OR' wherein R' represents ecule itself. hydrogen, C-C alkyl, hydroxy-C-C-alkyl, cycloalkyl, Suitable polymeric dispersing agents are characterized by methylcyclohexyl, phenyl or phenyl, which is substituted by their effect of wetting solid flame retardant molecules, pre 1 to 3 Substituents selected from the group consisting of 45 vent viscosity buildup by dispersed flame retardant particles methyl, methoxy and halogen. and prevent such particles from reflocculation. According to a particularly preferred embodiment the Suitable polymeric dispersing agents are commercially composition comprises as Component a) a nitrogen com available items e.g. under the product name SMARResins pound selected from the group consisting of benzoguanamine (Sartomer Corp.). Such as the styrene-maleic acid anhydride (formula III, R-phenyl, R=RE NH), tris(hydroxy 50 copolymers which correspond to the general formula: ethyl) isocyanurate (formula IV, R=R-R=—CH2— CH-OH), allantoin (formula V. R—R—R=Ra–Rs—H), glycoluril (formula VI, R=R-R-R-H), melamine phosphate, dimelamine (X) phosphate, melamine pyrophosphate, melamine polyphos 55 phate, melamine borate (all of formula VII type), urea cya nurate (formula VIII type), melamine cyanurate (formula IX type), melam or melem phosphate, melam or melem poly phosphate, ammonium polyphosphate and melamine ammo nium phosphate, pyrophosphate and polyphosphate. 60 The nitrogen compounds as defined and described above are known compounds or are obtainable by known methods. Some of them are commercially available. According to a particularly preferred embodiment the composition comprises as Component a) a nitrogen com 65 wherein —X— represents —O— —NH- or —NR—, pound selected from the group consisting of compounds wherein R represents C-C alkyl or aryl, particularly phenyl, (VII), compounds (IX), ammonium polyphosphate, m is a numeral from 1-50 and n is a numeral from 1-5, US 8,735,474 B2 7 8 particularly the product SMAR 1000P. This product is a low a) Radical polymerisation (normally under high pressure molecular weight styrene, maleic anhydride copolymer with and at elevated temperature). an approximately 1:1 mol ratio. b) Catalytic polymerisation using a catalyst that normally Other suitable products are so-called styrene maleic anhy contains one or more than one metal of groups IVb, Vb, dride copolymers, particularly the products SMA 1000F, VIb or VIII of the Periodic Table. These metals usually 17352P, 2000F, 2000P, 2625F, 2625P, 3000F, 3000P. 3840F, have one or more than one ligand, typically oxides, 17352F, 1440, 17352H, 1000H, 2625H, 1440H, 1000H or halides, alcoholates, esters, ethers, amines, alkyls, alk 3000H or so-called styrene maleimide resins, particularly the enyls and/or aryls that may be either it or O-coordinated. products SMA 3000I, 4000I or 2000I. These metal complexes may be in the free form or fixed 10 on Substrates, typically on activated magnesium chlo According to an alternative embodiment, Suitable poly ride, titanium(III) chloride, alumina or silicon oxide. meric dispersing agents are commercially available items These catalysts may be soluble or insoluble in the poly under the product designation Ciba REFKAR) “Processing merisation medium. The catalysts can be used by them aids and Surface modifiers for polymer systems', with a Suit selves in the polymerisation or further activators may be able molecular weight range is from 4000-20 000. 15 used, typically metal alkyls, metal hydrides, metal alkyl A suitable product is an aliphatic polyether substituted by halides, metal alkyl oxides or metal alkyloxanes, said acidic groups, as represented by the formula metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conve niently with further ester, ether, and amine or silyl ether (XI) groups. These catalyst systems are usually termed Phil R-O o lips, Standard Oil Indiana, Ziegler-Natta), TNZ (Du |- y -OH, Pont), metallocene or single site catalysts (SSC). O O 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypro 25 pylene with polyethylene (for example PP/HDPE, Wherein R represents a Cs-Csalkyl group and n represents PP/LDPE) and mixtures of different types of polyethylene a numeral from 5 to 10, such as the product EFKAR8530 (for example LDPE/HDPE). (aliphatic polyether with acidic groups). 3. Copolymers of monoolefins and diolefins with each other Other suitable products are or with other vinyl monomers, for example ethylene/pro EFKAR5054 (High molecular weight carboxylic acid salt) 30 pylene copolymers, linear low density polyethylene (LL EFKAR8462 (Modified polyacrylate) DPE) and mixtures thereof with low density polyethylene EFKAR8530 (Aliphatic polyether with acidic groups) (LDPE), propylene/but-1-ene copolymers, propylene/ EFKAR8531 (Modified polyester) isobutylene copolymers, ethylene/but-1-ene copolymers, EFKAR8532 (Acidic polyether) ethylene/hexene copolymers, ethylene/methylpentene EFKAR8533 (Modified polyether) 35 copolymers, ethylene/heptene copolymers, ethylene? EFKAR8534 (Partial amide and salt of high-molecular octene copolymers, ethylene/vinylcyclohexane copoly weight unsaturated carboxylic acid) mers, ethylene/cycloolefin copolymers (e.g. ethylene/nor EFKAR8536 (Polycarbonic acid-adduct, anionic) bornene like COC), ethylene? 1-olefins copolymers, where The amount of Component b) present in the composition is the 1-olefin is generated in-situ; propylene/butadiene not critical and may vary within broad ranges. According to a 40 copolymers, isobutylenefisoprene copolymers, ethylene? preferred embodiment, the amount of Component a) present vinylcyclohexene copolymers, ethylene/alkyl acrylate in the composition is within a concentration range of 0.05 copolymers, ethylene/alkyl methacrylate copolymers, eth 10.0 wt.-%, particularly 0.5-5.0 wt.-%. ylene/vinyl acetate copolymers or ethylene? acrylic acid The mixture of components a) and b) is added to the sub copolymers and their salts (ionomers) as well as terpoly 45 mers of ethylene with propylene and a diene Such as hexa strate of component c) in an amount of about 0.1-40.0% by diene, dicyclopentadiene or ethylidene-norborene; and weight, preferably 0.2-20.0% by weight. mixtures of Such copolymers with one another and with Component c) polymers mentioned in 1) above, for example polypropy The term polymer Substrate comprises within its scope lene/ethylene-propylene copolymers, LDPE/ethylene-vi thermoplastic polymers or thermosets. 50 nyl acetate copolymers (EVA), LDPE/ethylene-acrylic A list of suitable synthetic polymers is given below: acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and 1. Polymers of monoolefins and diolefins, for example alternating or random polyalkylene/carbon monoxide polypropylene, polyisobutylene, polybut-1-ene, poly-4- copolymers and mixtures thereof with other polymers, for methylpent-1-ene, polyvinylcyclohexane, polyisoprene or example polyamides. polybutadiene, as well as polymers of cycloolefins, for 55 4. Hydrocarbon resins (for example Cs-Co.) including hydro instance of cyclopentene or norbornene, polyethylene genated modifications thereof (e.g. tackifiers) and mixtures (which optionally can be crosslinked), for example high of polyalkylenes and starch; density polyethylene (HDPE), high density and high The homopolymers and copolymers mentioned above may molecular weight polyethylene (HDPE-HMW), high den have a stereo structure including syndiotactic, isotactic, sity and ultrahigh molecular weight polyethylene (HDPE 60 hemi-isotactic or atactic; where atactic polymers are UHMW), medium density polyethylene (MDPE), low preferred. Stereo block polymers are also included. density polyethylene (LDPE), linear low density polyeth 5. Polystyrene, poly(p-methylstyrene), poly(C.-methylsty ylene (LLDPE), (VLDPE) and (ULDPE). rene). Polyolefins, i.e. the polymers of monoolefins exemplified 6. Aromatic homopolymers and copolymers derived from in the preceding paragraph, preferably polyethylene and 65 vinyl aromatic monomers including styrene, C.-methylsty polypropylene, can be prepared by different and espe rene, all isomers of vinyl toluene, especially p-vinyl tolu cially by the following methods: ene, all isomers of ethyl styrene, propyl Styrene, vinyl US 8,735,474 B2 10 biphenyl, vinyl naphthalene, and vinyl anthracene, and late or acrylonitrile/vinyl halide copolymers or acryloni mixtures thereof. Homopolymers and copolymers may trile/alkyl methacrylate/butadiene terpolymers. have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are pre 11. Polymers derived from unsaturated alcohols and amines ferred. Stereo block polymers are also included: or the acyl derivatives or acetals thereof, for example poly a) Copolymers including aforementioned vinyl aromatic vinyl alcohol, polyvinyl acetate, polyvinyl Stearate, poly monomers and comonomers selected from ethylene, vinylbenzoate, polyvinyl maleate, polyvinylbutyral, poly propylene, dienes, nitriles, acids, maleic anhydrides, allyl phthalate or polyallyl melamine; as well as their maleimides, vinyl acetate and vinyl chloride or acrylic copolymers with olefins mentioned in 1. above. derivatives and mixtures thereof, for example styrene/ 10 12. Homopolymers and copolymers of cyclic ethers such as butadiene, styrene/acrylonitrile, styrene/ethylene (inter polyalkylene glycols, polyethylene oxide, polypropylene polymers), styrenefalkyl methacrylate, Styrenefbutadi oxide or copolymers thereof with bisglycidyl ethers. ene/alkyl acrylate, styrene/butadiene/alkyl 13. Polyacetals such as polyoxymethylene and those poly methacrylate, styrene/maleic anhydride, styrenefacry oxymethylenes, which contain ethylene oxide as a lonitrile/methyl acrylate; mixtures of high impact 15 strength of styrene copolymers and another polymer, for comonomer, polyacetals modified with thermoplastic example a polyacrylate, a diene polymer or an ethylene/ polyurethanes, acrylates or MBS. propylene?diene terpolymer; and block copolymers of 14. Polyphenylene oxides and sulphides, and mixtures of styrene Such as styrene?butadiene/styrene, styrenefiso polyphenylene oxides with styrene polymers or polya prene?styrene, styrene? ethylene/butylene?styrene or sty mides. rene? ethylene/propylene?styrene. 15. Polyurethanes derived from hydroxyl-terminated poly b) Hydrogenated aromatic polymers derived from hydro ethers, polyesters or polybutadienes on the one hand and genation of polymers mentioned under 6.), especially aliphatic or aromatic polyisocyanates on the other, as well including polycyclohexylethylene (PCHE) prepared by as precursors thereof. hydrogenating atactic polystyrene, often referred to as 25 polyvinylcyclohexane (PVCH). 16. Polyamides and copolyamides derived from diamines and c) Hydrogenated aromatic polymers derived from hydro dicarboxylic acids and/or from aminocarboxylic acids or genation of polymers mentioned under 6a). Homopoly the corresponding lactams, for example polyamide 4. mers and copolymers may have a stereo structure includ polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, ing syndiotactic, isotactic, hemi-isotactic or atactic; 30 polyamide 11, polyamide 12, aromatic polyamides starting where atactic polymers are preferred. Stereo block poly from m-Xylene diamine and adipic acid; polyamides pre mers are also included. pared from hexamethylenediamine and isophthalic or/and 7. Graft copolymers of vinyl aromatic monomers such as terephthalic acid and with or without an elastomeras modi styrene or C.-methylstyrene, for example styrene on polyb fier, for example poly-2,4,4-trimethylhexamethylene utadiene, styrene on polybutadiene-styrene or polybutadi 35 terephthalamide or poly-m-phenylene isophthalamide: ene-acrylonitrile copolymers; styrene and acrylonitrile (or and also block copolymers of the aforementioned polya methacrylonitrile) on polybutadiene; styrene, acrylonitrile mides with polyolefins, olefin copolymers, ionomers or and methyl methacrylate on polybutadiene; styrene and chemically bonded or grafted elastomers; or with poly maleic anhydride on polybutadiene; styrene, acrylonitrile ethers, e.g. with polyethylene glycol, polypropylene glycol and maleic anhydride or maleimide on polybutadiene; Sty 40 rene and maleimide on polybutadiene; styrene and alkyl or polytetramethylene glycol; as well as polyamides or acrylates or methacrylates on polybutadiene; styrene and copolyamides modified with EPDM or ABS; and polya acrylonitrile on ethylene/propylene?diene terpolymers; mides condensed during processing (RIM polyamide sys styrene and acrylonitrile on polyalkyl acrylates or poly tems). alkyl methacrylates, styrene and acrylonitrile on acrylate? 45 17. Polyureas, polyimides, polyamide imides, polyether imi butadiene copolymers, as well as mixtures thereof with the des, polyester imides, polyhydantoins and polybenzimida copolymers listed under 6), for example the copolymer Zoles. mixtures known as ABS, MBS, ASA or AES polymers. 18. Polyesters derived from dicarboxylic acids and diols and/ 8. Halogen-containing polymers such as polychloroprene, or from hydroxycarboxylic acids or the corresponding lac chlorinated rubbers, chlorinated and brominated copoly 50 tones, for example polyethylene terephthalate, polybuty mer of isobutylene-isoprene (halobutyl rubber), chlori lene terephthalate, poly-1,4-dimethylolcyclohexane nated or Sulphochlorinated polyethylene, copolymers of terephthalate, polyalkylene naphthalate (PAN) and poly ethylene and chlorinated ethylene, epichlorohydrinhomo hydroxybenzoates, as well as block copolyether esters and copolymers, especially polymers of halogen-contain derived from hydroxyl-terminated polyethers; and also ing vinyl compounds, for example polyvinyl chloride, 55 polyesters modified with polycarbonates or MBS. polyvinylidene chloride, polyvinyl fluoride, polyvi 19. Polyketones. nylidene fluoride, as well as copolymers thereof Such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl 20. Polysulphones, polyether sulphones and polyether acetate or vinylidene chloride/vinyl acetate copolymers. ketones. 9. Polymers derived from C.B-unsaturated acids and deriva 60 21. Blends of the aforementioned polymers (polyblends), for tives thereof Such as polyacrylates and polymethacrylates; example PP/EPDM, Polyamide/EPDM or ABS, PVC/ polymethyl methacrylates, polyacrylamides and polyacry EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, lonitriles, impact-modified with butyl acrylate. PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/ther 10. Copolymers of the monomers mentioned under 9) with moplastic PUR, PC/thermoplastic PUR, POM/acrylate, each other or with other unsaturated monomers, for 65 POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, example acrylonitrile/butadiene copolymers, acrylonitrile? PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/ alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acry PC. US 8,735,474 B2 11 12 22. Polycarbonates that correspond to the general formula: bisphenol C:

*-i-R-O--O-- OH O 5 C Such Polycarbonates are obtainable by interfacial pro- o cesses or by melt processes (catalytic transesterifica- C tion). The polycarbonate may be either branched or lin- 10 ear in structure and may include any functional Substituents. Polycarbonate copolymers and polycar OH, bonate blends are also within the scope of the invention. The term polycarbonate should be interpreted as inclu sive of copolymers and blends with other thermoplas- 15 tics. Methods for the manufacture of polycarbonates are known, for example, from U.S. Pat. Nos. 3,030,331; bisphenol E: 3,169,1214,130,458; 4,263,2014,286,083; 4,552,704; 5,210,268; and 5,606,007. A combination of two or CH 3 maymore be polycarbonates used. of different molecular weights 20 HO ( ) ( ) OH, Preferred are polycarbonates obtainable by reaction of a diphenol. Such as bisphenol A, with a carbonate source. H Examples of suitable diphenols are: Bisphenol A: 25 bisphenol F:

OH OH O O H H,

bisphenol AF: 35

CF to-() ()-ol bisphenol M: CF 40 bisphenol AP: HO ( ) ( ) OH,

45

bisphenol P:

50 HO ( ) ( ) ( ) OH, HO OH,

55 bisphenol B:

HO OH, bisphenol S: 60

65 t US 8,735,474 B2 13 14 bisphenol TMC: styrene-acrylic ester (ASA), acrylonitrile-ethylene-propy lene-styrene (AES), styrene-maleic anhydride (SMA) or high impact polystyrene (HIPS). OH, According to a preferred embodiment, the polymer Sub strate of component c) is a polyamide or co-polyamide derived from diamines and dicarboxylic acids or aminocar boxylic acids or the corresponding lactams. A further embodiment of the invention relates to a mixture comprising 10 a) At least one flame retardant component selected from the group consisting of nitrogen containing compounds and bisphenol Z: salts of phosphinic acid; and b) At least one polymeric dispersing agent selected from the group consisting of Styrene-maleic acid anhydride 15 copolymers, long chain carboxylic acid salts and ali phatic polyether substituted by acidic groups. A further embodiment relates to process for imparting flame retardancy to a polymer Substrate, which process com HO ( ) ( ) OH, prises adding to a polymer Substrate the mixture as defined above. Additional Components 4,4'-(2-norbornylidene)bis(2,6-dichlorophenol); or The instant invention further pertains to a composition, fluorene-9-bisphenol: which comprises, in addition to the components a) b) and c). as defined above, further additives selected from the group 25 consisting of so-called anti-dripping agents, polymer stabi lizers and additional flame-retardants, such as phosphorus containing flame-retardants, nitrogen containing flame-retar dants, halogenated flame-retardants and inorganic flame-re tardants. 30 According to a preferred embodiment the invention relates composition, which additionally comprises further additives HO OH. selected from the group consisting of polymer stabilizers and additional flame retardants. According to another embodiment, the invention relates to The carbonate source may be a carbonylhalide, a carbon 35 a composition which additionally comprises as additional ate ester or a haloformate. Suitable carbonate halides are component so-called anti-dripping agents. phosgene or carbonylbromide. Suitable carbonate esters are These anti-dripping agents reduce the melt flow of the dialkylcarbonates, such as dimethyl- or diethylcarbonate, thermoplastic polymer and inhibit the formation of drops at diphenyl carbonate, phenyl-alkylphenyl-carbonate, such as high temperatures. Various references, such as U.S. Pat. No. phenyl-tolylcarbonate, dialkylcarbonates, such as dimethyl 40 4.263,201, describe the addition of anti-dripping agents to or diethylcarbonate, di-(halophenyl)carbonates, such as di flame retardant compositions. (chlorophenyl)carbonate, di-(bromophenyl)-carbonate, di Suitable additives that inhibit the formation of drops at (trichlorophenyl)carbonate or di-(trichlorophenyl)carbonate, high temperatures include glass fibers, polytetrafluoroethyl di-(alkylphenyl)-carbonates, such as di-tolylcarbonate, naph ene (PTFE), high temperature elastomers, carbon fibers, glass thylcarbonate, dichloronaphthylcarbonate and others. 45 spheres and the like. The polymer substrate mentioned above, which comprises The addition of polysiloxanes of different structures has polycarbonates or polycarbonate blends is a polycarbonate been proposed in various references; cf. U.S. Pat. Nos. 6,660, copolymer, wherein isophthalate?terephthalate-resorcinol 787, 6,727,302 or 6,730,720. segments are present. Such polycarbonates are commercially Stabilizers are preferably halogen-free and selected from 50 phenolic antioxidants, stabilizers, nitrone stabilizers, available, e.g. Lexan R SLX (General Electrics Co. USA). amine oxide stabilizers, benzofuranone stabilizers, phosphite Other polymeric substrates of component b) may additionally and phosphonite stabilizers, quinone methide stabilizers and contain in the form as admixtures or as copolymers a wide monoacrylate esters of 2,2'-alkylidenebisphenol stabilizers. variety of synthetic polymers including polyolefins, polysty Additional flame-retardants as of present component are renes, polyesters, polyethers, polyamides, poly(meth)acry 55 known components, items of commerce or can be obtained by lates, thermoplastic polyurethanes, polysulphones, polyac known methods. etals and PVC, including Suitable compatibilizing agents. For Representative phosphorus containing flame-retardants, in example, the polymer Substrate may additionally contain addition to the ones defined above with regard to component thermoplastic polymers selected from the group of resins a), are for example: consisting of polyolefins, thermoplastic polyurethanes, sty 60 Tetraphenyl resorcinol diphosphite (FYROLFLEX(R) RDP. rene polymers and copolymers thereof. Specific embodi Akzo Nobel), tetrakis(hydroxymethyl)phosphonium sul ments include polypropylene (PP), polyethylene (PE), polya phide, , diethyl-N,N-bis(2-hydroxy mide (PA), polybutylene terephthalate (PBT), polyethylene ethyl)-aminomethyl phosphonate, hydroxyalkyl esters of terephthalate (PET), glycol-modified polycyclohexylenem phosphorus acids, ammonium polyphosphate (APP) or (HO ethylene terephthalate (PCTG), polysulphone (PSU), polym 65 STAFLAMR AP750), resorcinol diphosphate oligomer ethylmethacrylate (PMMA), thermoplastic polyurethane (RDP), phosphazene flame-retardants and ethylenediamine (TPU), acrylonitrile-butadiene-styrene (ABS), acrylonitrile diphosphate (EDAP). US 8,735,474 B2 15 16 Nitrogen containing flame-retardants are, for example, iso Hydroquinones and alkylated hydroquinones, for example cyanurate flame-retardants, such as polyisocyanurate, esters 2,6-di-tert-butyl-4-methoxyphenol. 2,5-di-tert-butylhy of isocyanuric acid or isocyanurates. Representative droquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphe examples are hydroxyalkyl isocyanurates, such as tris-(2- nyl-4-Octadecyloxyphenol, 2,6-di-tert-butylhydro hydroxyethyl)isocyanurate, tris(hydroxy-methyl)isocyanu quinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3.5-di rate, tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl iso tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4- cyanurate. hydroxyphenyl Stearate, bis(3,5-di-tert-butyl-4- Representative organohalogen flame-retardants are, for hydroxyphenyl) adipate. example: Tocopherols, for example Cl-, 3-, y-, 6-tocopherol and mix 10 tures thereof (vitamin E). Polybrominated diphenyl oxide (DE-60F, Great Lakes Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis Corp.), decabromodiphenyl oxide (DBDPO; SAYTEX(R) (6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphe 102E), tris3-bromo-2,2-bis(bromomethyl)propylphos nol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'- phate (PB 370R, FMC Corp.), tris(2,3-dibromopropyl)phos thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6- phate, tris(2,3-dichloropropyl)phosphate, chlorendic acid, 15 di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4- tetrachlorophthalic acid, tetrabromophthalic acid, poly-B- hydroxyphenyl)disulphide. chloroethyl triphosphonate mixture, tetrabromobisphenol A Alkylidenebisphenols, for example 2,2'-methylenebis(6- bis(2,3-dibromopropyl ether) (PE68), brominated epoxy tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert resin, ethylene-bis(tetrabromophthalimide) (SAYTEXOR) butyl-4-ethylphenol), 2,2'-methylenebis 4-methyl-6- BT-93), bis(hexachlorocyclopentadieno)-cyclooctane (DE (C.-methylcyclohexyl)phenol. 2,2'-methylenebis(4- CLORANE PLUS(R), chlorinated paraffins, octabromo methyl-6-cyclohexylphenol), 2,2'-methylenebis(6- diphenyl ether, hexachlorocyclopentadiene derivatives, 1.2- nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert bis(tribromophenoxy)ethane (FF680), tetrabromobisphenol butylphenol), 2,2'-ethylidenebis(4,6-di-tert A (SAYTEX(R) RB100), ethylene bis-(dibromo-norbor butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4- nanedicarboximide) (SAYTEXR BN-451), bis-(hexachloro 25 isobutylphenol), 2,2'-methylenebis G-(C.- cycloentadeno)cyclooctane, PTFE, tris-(2,3-dibromopro methylbenzyl)-4-nonylphenol. 2,2'-methylenebis(5- pyl)-isocyanurate, and ethylene-bis-tetrabromophthalimide. (C.C.-dimethylbenzyl)-4-nonylphenol. 4,4'- The flame-retardant mentioned above routinely combined methylenebis(2,6-di-tert-butylphenol), 4,4'- with an inorganic oxide synergist. Most common for this use methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5- are zinc or antimony oxides, e.g. SbO or SbOs. Boron 30 tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis compounds are Suitable, too. (3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- The above-mentioned additional flame-retardant classes methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2- are advantageously contained in the composition of the inven methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy tion in an amount from about 0.5% to about 45.0% by weight 2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene of the organic polymer substrate; for instance about 1.0% to 35 glycol bis3.3-bis(3'-tert-butyl-4'-hydroxyphenyl)bu about 40.0%; for example about 5.0% to about 35.0% by tyrate, bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)di weight of the polymer substrate. cyclopentadiene, bis 2-(3'-tert-butyl-2'-hydroxy-5'-me As mentioned above, the composition according to the thylbenzyl)-6-tert-butyl-4-methylphenylterephthalate, invention may additionally contain one or more conventional 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2.2-bis additives, for example selected from pigments, dyes, plasti 40 (3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2.2-bis cizers, antioxidants, thixotropic agents, levelling assistants, (5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dode basic co-stabilizers, metal passivators, metal oxides, organo cylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4- phosphorus compounds, further light stabilizers and mixtures hydroxy-2-methylphenyl)pentane. thereof, especially pigments, phenolic antioxidants, calcium O-, N- and S-benzyl compounds, for example 3.5.3',5'- stearate, zinc stearate, UV absorbers of the 2-hydroxy-ben 45 tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octade Zophenone, 2-(2-hydroxyphenyl)benzotriazole and/or 2-(2- cyl-4-hydroxy-3,5-di methyl benzylmercaptoacetate, hydroxyphenyl)-1,3,5-triazine groups. More specific tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoac examples are the following components: etate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis 1. Antioxidants (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiot Alkylated monophenols, for example 2,6-di-tert-butyl-4- 50 erephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) methylphenol, 2-tert-butyl-4,6-dimethylphenol. 2,6-di Sulphide, isooctyl-3,5-di-tert-butyl-4- tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-bu hydroxybenzylmercaptoacetate. tylphenol. 2,6-di-tert-butyl-4-isobutylphenol. 2.6- Hydroxybenzylated malonates, for example dioctadecyl dicyclopentyl-4-methylphenol, 2-(C.- 2.2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, methylcyclohexyl)-4,6-dimethylphenol, 2,6- 55 di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylben dioctadecyl-4-methylphenol, 2.4.6- Zyl)malonate, di-dodecylmercaptoethyl-2.2-bis(3,5-di tricyclohexylphenol, 2,6-di-tert-butyl-4- tert-butyl-4-hydroxybenzyl)malonate, bis4-(1,1,3,3- methoxymethylphenol, nonylphenols which are linear tetramethylbutyl)phenyl-2.2-bis(3,5-di-tert-butyl-4- or branched in the side chains, for example 2,6-di-nonyl hydroxybenzyl)malonate. 4-methylphenol. 2,4-dimethyl-6-(1'-methylundec-1-yl) 60 Aromatic hydroxybenzyl compounds, for example 1.3.5- phenol. 2,4-dimethyl-6-(1'-methylheptadec-1-yl)phe tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimeth nol. 2,4-dimethyl-6-(1'-methyltridec-1-yl)phenol and ylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- mixtures thereof. 2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl Alkylthiomethylphenols, for example 2,4-dioctylthiom 4-hydroxybenzyl)phenol. ethyl-6-tert-butylphenol. 2,4-dioctylthiomethyl-6-me 65 Triazine compounds, for example 2.4-bis(octylmercapto)- thylphenol. 2,4-dioctylthiomethyl-6-ethylphenol. 2.6- 6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, di-dodecylthiomethyl-4-nonylphenol. 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxya

US 8,735,474 B2 21 22 -continued 13. Additional benzofuranones and indolinones, for example (F) those disclosed in U.S. Pat. Nos. 4,325,863; 4,338,244; O O 5,175,312: 5,216,052; or 5,252,643; DE-A-4316611; DE It us-u-co-o-Y Y-o-cult- u-ust13, A-4316622: DE-A-431 6876; EP-A-0589839 or EP-A- N / 5 O O 0591 102 or 3-4-(2-acetoxyethoxy)phenyl-5,7-di-tert (G) butylbenzofuran-2-one, 5,7-di-tert-butyl-3-4-(2- CH stearoyloxyethoxy)phenylbenzofuran-2-one, 3,3'-bis(5, 7-di-tert-butyl-3-(4-2-hydroxyethoxyphenyl) HC-C-CH benzofuran-2-one, 5,7-di-tert-butyl-3-(4-ethoxyphenyl) 10 O P-OCH2CH benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5, 7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4- HC pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, V -C CH 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2- HC V one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran CH3 15 2 2-one. Preferred additional additives for the compositions as 5. Further nitrones, for example N-benzyl-alpha-phenylni defined above are processing stabilizers, such as the above trone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-hep mentioned phosphites and phenolic antioxidants, and light tylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl- 20 stabilizers, such as benzotriazoles. Preferred specific antioxi alpha-tridecylnitrone, N-hexadecyl-alpha dants include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphe pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, nyl) propionate (IRGANOX 1076). Specific processing sta N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-al bilizers include tris-(2,4-di-tert-butylphenyl) phosphite pha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylni (IRGAFOS 168) and tetrakis(2,4-di-tert-butylphenyl) 1,1- trone, N-octadecyl-alpha-hexadecylnitrone, nitrone 25 biphenyl-4,4'-diylbisphosphonite (IRGAFOS P-EPQ). Spe derived from N,N-dialkylhydroxylamine derived from cific light stabilizers include 2-(2H-benzotriazole-2-yl)-4,6- hydrogenated tallow amine. bis(1-methyl-1-phenylethyl)phenol (TINUVIN 234), 2-(5- 6. Thiosynergists, for example dilauryl thiodipropionate or chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl) distearyl thiodipropionate. phenol (TINUVIN326), 2-(2H-benzotriazole-2-yl)-4-(1,1,3, 7. Peroxide scavengers, for example esters of B-thiodipropi- 30 3-tetramethylbutyl)phenol (TINUVIN 329), 2-(2H onic acid, for example the lauryl, Stearyl, myristyl or tride benzotriazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol cyl esters, mercaptobenzimidazole or the Zinc salt of (TINUVIN 350), 2,2'-methylenebis(6-(2H-benzotriazol-2- 2-mercaptobenzimidazole, Zinc dibutyldithiocarbamate, yl)-4-(1,1,3,3-tetramethylbutyl)phenol) (TINUVIN 360), dioctadecyl disulphide, pentaerythritol tetrakis(B-dode and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)-oxy-phe cylmercapto)propionate. 35 nol (TINUVIN 1577). 8. Polyamide stabilisers, for example copper salts in combi The additives mentioned above are preferably contained in nation with iodides and/or phosphorus compounds and an amount of 0.01 to 10.0%, especially 0.05 to 5.0%, relative salts of divalent manganese. to the weight of the polymer substrate c). 9. Basic co-stabilisers, for example melamine, polyvinylpyr The incorporation of the additive components a) and b) and rolidone, dicyandiamide, triallyl cyanurate, urea deriva- 40 optional further components into the polymer component c) tives, polyamides, polyurethanes, alkali metal salts and is carried out by known methods such as dry blending in the alkaline earth metal salts of higher fatty acids, for example form of a powder, or wet mixing in the form of Solutions, calcium Stearate, Zinc Stearate, magnesium behenate, mag dispersions or Suspensions for example in an inert Solvent, nesium Stearate, sodium ricinoleate and potassium palmi water or oil. The additive components a) and b) and optional tate, antimony pyrocatecholate or Zinc pyrocatecholate. 45 further additives may be incorporated, for example, before or 10. Nucleating agents, for example inorganic Substances, after molding or also by applying the dissolved or dispersed Such as talcum, metal oxides, such as titanium dioxide or additive or additive mixture to the polymer material, with or magnesium oxide, phosphates, carbonates or Sulphates of without Subsequent evaporation of the solvent or the Suspen preferably, alkaline earth metals; organic compounds, such sion/dispersion agent. They may be added directly into the as mono- or polycarboxylic acids and the salts thereof, e.g. 50 processing apparatus (e.g. extruders, internal mixers, etc.), 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, e.g. as a dry mixture or powder, or as a solution or dispersion Sodium Succinate or sodium benzoate; polymeric com or Suspension or melt. pounds. Such as ionic copolymers (ionomers). Especially The addition of the additive components to the polymer preferred are 1.3:2.4-bis(3',4'-dimethylbenzylidene)sorbi Substrate c) can be carried out in customary mixing machines tol, 1.3:2,4-di(paramethyldibenzylidene)sorbitol, and 1.3: 55 in which the polymer is melted and mixed with the additives. 2,4-di(benzylidene)sorbitol. Suitable machines are known to those skilled in the art. They 11. Further fillers and reinforcing agents, for example cal are predominantly mixers, kneaders and extruders. cium carbonate, silicates, glass fibres, glass bulbs, stainless The process is preferably carried out in an extruder by steel fibres, aramide fibers, asbestos, talc, kaolin, mica, introducing the additive during processing. barium Sulphate, metal oxides and hydroxides, carbon 60 Particularly preferred processing machines are single black, graphite, wood flour and flours or fibers of other screw extruders, contra-rotating and co-rotating twin-screw natural products, synthetic fibres. extruders, planetary-gear extruders, ring extruders or 12. Other additives, for example blend compatibilizing co-kneaders. It is also possible to use processing machines agents, plasticisers, lubricants, emulsifiers, pigments, rhe provided with at least one gas removal compartment to which ology additives, catalysts, flow-control agents, optical 65 a vacuum can be applied. brighteners, flame proofing agents, antistatic agents and Suitable extruders and kneaders are described, for blowing agents. example, in Handbuch der Kunststoffextrusion, Vol. 1 Grund US 8,735,474 B2 23 24 lagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. ratings according to the UL 94 V test are compiled in the 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, following table (times are indicated for one specimen): ISBN 3-446-14329-7). For example, the screw length is 1-60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the 5 screw is preferably 10-600 rotations per minute (rpm), pref Rating After-flame Time Burning Drips erably 25-300 rpm. W-O <1OS No V-1 <30S No The maximum throughput is dependent on the screw diam V-2 <30S Yes eter, the rotational speed and the driving force. The process of n.c. (=not >30S the present invention can also be carried out at a level lower 10 classified) than maximum throughput by varying the parameters men tioned or employing weighing machines delivering dosage amountS. STANDARD PROCEDUREAEXAMPLES If a plurality of components is added, these can be pre 15 mixed or added individually. The flame retardant additives are dry-mixed and are dried The additive components a) and b) and optional further in vacuo for at least 12 hours at 90°C. The mixtures obtained additives can also be sprayed onto the polymer Substrate c). are melt compounded in a co-rotating COPERIONR) ZSK 25 The additive mixture dilutes other additives, for example the WLE twin screw extruder with exhaust unit. conventional additives indicated above, or their melts so that they can be sprayed also together with these additives onto the Processing programme PA 6 compositions: Zones 1-11: polymer Substrate. Addition by spraying during the deactiva 60,230, 240,245, 250->250° C.; Vacuum: <200 mbar, speed tion of the polymerisation catalysts is particularly advanta of rotation: 200 rpm, throughput=8 kg/h; geous; in this case, the steam evolved may be used for deac Processing programme PA 66 GF: Zones 1-11: 50, 240, tivation of the catalyst. In the case of spherically polymerised 25 280->280° C.; Vacuum-200 mbar, speed of rotation=60 rpm, polyolefins, it may, for example, be advantageous to apply the throughput=8 kg/h. additives of the invention, optionally together with other The flame retardant components are incorporated into the additives, by spraying. polymer melt through a lateral feed unit. Single extrusion The additive components a) and b) and optional further experiments are carried out on a HAAKE TW-100 (see: additives can also be added to the polymer in the form of a 30 Tables 2 and 3) counter-rotating twin screw extruder. master batch ("concentrate”) which contains the components Processing programme PA 6 compositions: Medium tem in a concentration of for example, about 1.0% to about 40.0% perature: 260C., vacuum: <400 mbar, speed of rotation: 100 and preferably 2.0% to about 20.0% by weight incorporated in rpm, throughput: 1 kg/h. a polymer. The polymer is not necessarily of identical struc The homogenized polymer Strand is drawn off, cooled in a ture than the polymer where the additives are added finally. In 35 waterbath and then pelletized. After sufficient drying of the Such operations, the polymer can be usedin the form of pow pellets (in vacuo, 12 hours at 90° C.) the formulations are der, granules, solutions, and Suspensions or in the form of processed at melt temperatures of 240-275°C. in an injection lattices. molding machine (ARBURG 370S ALLROUNDER) to give Incorporation can take place prior to or during the shaping test specimens (UL test bar, 1.6 mm thickness; tensile impact operation. The materials containing the additives of the inven 40 tion described herein preferably are used for the production of test bars according to DIN 53448, Form A). molded articles, for example roto-molded articles, injection After conditioning for 24 hours at 25°C. and 50% relative molded articles, profiles and the like, and especially a fiber, humidity the test specimens are tested and classified on the spun melt non-woven, film or foam. basis of the UL 94-V (Underwriter Laboratories) test Thus, present invention further pertains to a molded or 45 described above. The tensile impact test bars are tested in extruded article, a fiber, spun melt non-woven or a foam respect of tensile impact strength at room temperature (23° comprising the composition of the invention. C.) using a ZWICK PSW 5101 test apparatus having a 25J The following examples illustrate the invention but are not pendulum. meant to limit the scope thereof in any manner. Unless stated otherwise, all experiments of each series are Components 50 carried out under identical conditions to ensure comparability Polyamide 6 (PA 6): DURETHAN B40ER, Lanxess AG, (e.g. temperature profiles, screw geometries, addition of Germany; flame retardant additives, injection-molding parameters, Polyamide 66 GF (PA 66 GF): ULRAMID A3EG5 (30% etc.). All amounts are listed by their weight amounts and are GF), BASF AG, Germany: based on the plastic molding composition including the flame Melamine cyanurate: MELAPURMC 50R) (medium par 55 retardant(s) and dispersants. The burning times are given as ticle diameter 50 um), Ciba Specialty Chemicals (Ciba); Sum of burning times for 5 specimen. Melamine polyphosphate: MELAPUR 200R, Ciba; Mixtures of different fatty acid salts (long chain amino): TABLE 1 Ciba R. EFKAR5054, Ciba; Dispersant based on aliphatic polyether with acidic group: 60 PA 6 Compositions (DURETHAN B40 E (R), processed on Ciba R. EFKAR8530, Ciba; COPERION (RZSK2SWLE Styrene maleic anhydride copolymer: SMA 1000PRSAR Elongation TOMER Inc. FR- UL Burning At Test Methods to Assess Flame Retardancy Example 1 Additives Dispersant 94 times (s) Break The UL94 test is performed according to the general rules 65 Referential — ll. C. 635 127.2% described in “Flammability of Plastic Materials for Parts in Comp. 1 Devices and Appliances", 5' edition, Oct. 29, 1996. The US 8,735,474 B2 25 26 TABLE 1-continued TABLE 4 PA 66 GF Compositions (ULTRAMID A3EG5 (R), processed on PA 6 Compositions (DURETHAN B40 E (R), processed on COPERION (RZSK2SWLE COPERION (R) ZSK 25 WLE) Examples Intrinsic Burning 6, 7 FRAdditives Dispersant viscosity UL94 time (s) Elongation Referential 20% MELAPUR - 1.67 V-1 76 FR- UL Burning At Comp. 1 200 (R) Example 1 Additives Dispersant 94 times (s) Break Referential 22.5% MELAPUR- 1.69 V-1 42 10 Comp. 2 200 (R) Example 6 20% MELAPUR 1% EFKA 1.61 W-O 24 Referential 9% V-2 25 12.7% Inventive 200 (R) 5054 Comp. 2 MELAPUR Comp. 1 Example 7 22.5% MELAPUR 1% EFKA 1.59 W-O 32 MC (R) Inventive 200 (R) 5054 Example 1 9% 1.5% V-2 23 45.3% 15 Comp. 2 Inventive MELAPUR EFKA Comp. 1 MC (R) 8530 From the results reported in Table 4 it can be seen that the compositions according to the present invention provide polymers with flame retardant and self-extinguishing proper ties. Shorterburning times can be achieved and a V-0 classi From the results reported in Table 1 it can be seen that the fication using lower concentrations of MELAPUR 200R). compositions according to the present invention provide The invention claimed is: polymers with significantly improved elongation at break 1. A composition comprising without affecting the burning behaviour. a) at least one flame retardant selected from the group consisting of salts of phosphinic acids, where the phos TABLE 2 25 phinic acids are of formulae I or II (I) PA 6 Compositions (DURETHAN B40 E (R), processed on HAAKE O TW-100 extruder, Aluminiumdiethylphosphinate || Tensile R --oil Impact R2 Examples UL Burning Strength (II) 2, 3 FR-Additives Dispersant 94 time (s) KJ/m) O O Referential 10% EXOLIT OP - Il.C. 133 421 Comp. 1 930 (R) HO-P-R-P-OH Example 2 9% EXOLIT OP 1.35% Il.C. 110 767 35 Inventive. 930 (R) SMA 10OOP Comp. 1 Example 3 10% EXOLIT OP 1.5% SMA W-O 2O 634 in which Inventive 930 (R) 1OOOP R", R represents a linear or branched C-Csalkyl radical, Comp. 2 hydrogen, or a phenyl radical and 40 R represents a linear or branched C-Coalkylene, arylene, From the results reported in Table 2 it can be seen that the alkylarylene or arylalkylene radical; b) at least one polymeric dispersing agent selected from the compositions according to the present invention provide group consisting of styrene-maleic acid anhydride polymers with significantly improved tensile impact strength. copolymers, and aliphatic polyethers substituted by 45 acidic groups and TABLE 3 c) a polymer Substrate, PA 6 Compositions (DURETHAN B40 E (R), processed on where the aliphatic polyethers substituted by acidic groups HAAKETW-100 extruder are of formula (V)

Tensile 50 Impact Examples Burning Strength (V) 4, 5 FRAdditives Dispersant UL94 time (s) (KJ/m) R-O1 V Referent. Il.C. 635 1021 Comp. 1 55 (O O)—o Referent. 3%. MELAPUR V-2 8 762 Comp. 2 MC (R) Example 4 3% MELAPUR 0.5% SMA V-2 24 1024 Inventive MC (R) 1OOOP wherein R represents a C-C salkyl group and n represents Comp. 1 a numeral from 5 to 10. Example 5 3% MELAPUR 0.44% SMA V-2 14 1053 2. A composition according to claim 1, comprising a) Inventive MC (R) 1OOOP 60 Comp. 2

From the results reported in Table 3 it can be seen that the et-P-O | Al". formulations according to the present invention provide poly 65 mers with significantly improved tensile impact strength without affecting the burning behaviour. US 8,735,474 B2 27 28 3. A composition according to claim 1, comprising b) a 8. A composition comprising styrene-maleic acid anhydride copolymer of formula (X) a) at least one flame retardant selected from the group consisting of nitrogen containing compounds, b) an aliphatic polyether Substituted by acidic groups of (X) 5 formula (V)

(V) 10 R - O al-K)-ol O O

wherein R represents a C-C salkyl group and n represents 15 a numeral from 5 to 10 wherein —X— represents —O— —NH- or —NR—, and wherein R represents C-C alkyl or aryl, m is a numeral c) a polymer Substrate. from 1-50 and n is a numeral from 1-5. 9. A composition according to claim 8 comprising a) a 4. A composition according to claim 1, comprising c) a nitrogen containing compound selected from the group con polyamide or co-polyamide derived from diamines and dicar sisting of ammonium polyphosphate, melamine polyphos boxylic acids or aminocarboxylic acids or the corresponding phate, melamine ammonium phosphate, melamine ammo lactams. nium polyphosphate, melamine ammonium pyrophosphate, a 5. A composition according to claim 1, which additionally condensation product of melamine with phosphoric acid, comprises further additives selected from the group consist other reaction products of melamine with phosphoric acid ing of polymer stabilizers and additional flame retardants. 25 6. A mixture comprising and mixtures thereof. a) at least one flame retardant selected from the group 10. A composition according to claim 8 comprising a) consisting of salts of phosphinic acids, where the phos melamine cyanurate. phinic acids are of formulae I or II 11. A composition according to claim 8, comprising c) a 30 polyamide or co-polyamide derived from diamines and dicar boxylic acids or aminocarboxylic acids or the corresponding (I) lactams. O 12. A composition according to claim8, which additionally RI-P-OH comprises further additives selected from the group consist 35 ing of polymer stabilizers and additional flame retardants. k 13. A mixture comprising (II) O O a) at least one flame retardant selected from the group consisting of nitrogen containing compounds, HO-P-R-P-OH b) an aliphatic polyether Substituted by acidic groups of 40 formula (V)

in which R", R represents a linear or branched C-Csalkyl radical, (V) hydrogen, or a phenyl radical and R represents a linear or branched C-Cloalkylene, arylene, 45 R-O al-K)-ol alkylarylene or arylalkylene radical; O O and b) at least one polymeric dispersing agent selected from the group consisting of styrene-maleic acid anhydride wherein R represents a C-C salkyl group and n represents 50 a numeral from 5 to 10 copolymers and aliphatic polyether Substituted by acidic and groups c) a polymer Substrate. where the aliphatic polyethers substituted by acidic groups 14. A process for imparting flame retardancy to a polymer are of formula (V) Substrate, which process comprises adding to a polymer Sub 55 strate the mixture according to claim 13. 15. A composition according to claim 8 comprising (V) a) melamine cyanurate, b) an aliphatic polyether Substituted by acidic groups of formula V R-O al-K)-ol 60 O O (V) wherein R represents a C-C salkyl group and n represents a numeral from 5 to 10. R - O al-K)-ol 7. A process for imparting flame retardancy to a polymer 65 O O Substrate, which process comprises adding to a polymer Sub strate the mixture according to claim 6. US 8,735,474 B2 29 30 wherein R represents a Cs-Calkyl group and n represents in which a numeral from 5 to 10 and R", R represents a linear or branched C-Csalkyl radical, c) a polyamide or co-polyamide derived from diamines and dicarboxylic acids or aminocarboxylic acids or the cor hydrogen, or a phenyl radical and responding lactams. 5 R represents a linear or branched C-Cloalkylene, arylene, 16. A composition according to claim 8 comprising b) an alkylarylene or arylalkylene radical aliphatic polyether substituted by acidic groups of formula V M represents (C-C alkyl)-N, (C-C alkyl)-NH. (C- (V) CalkylCH).N. (C-C alkylCH)NH, (C- CalkylCH), N(CH), (C-C alkylOH)NHCH R-O al-K)-ol 10 (CHs)..N. (CH)NH, (CHCH).N. (CHCH) O O NH, NH, an alkali metal or earth alkali metal ion or an aluminium, zinc, iron or boron ion; wherein R represents a Cs-Calkyl group and n represents m is a numeral from 1-3 and indicates the number of a numeral from 5 to 10. 15 positive charges on M, and 17. A composition according to claim 1 where the phos n is a numeral from 1-3 and indicates the number of phos phinic acid salts are of formula (I) phinic acid anions corresponding to M'. (I) 18. A composition according to claim 1, comprising b) O aliphatic polyethers Substituted by acidic groups. R--o Mint R2