(12) United States Patent (10) Patent No.: US 8,415,414 B2 Maider Et Al

Home , Phosphorous acid, Pyrophosphoric acid

USOO8415414B2

(12) United States Patent (10) Patent No.: US 8,415,414 B2 Maider et al. (45) Date of Patent: Apr. 9, 2013

(54) POLYURETHANE FLAME RETARDANT (58) Field of Classification Search ...... 524/99-101, COMPOSITIONS 524/147, 151,153 See application file for complete search history. (75) Inventors: Dietmar Mäder, Oberursel (DE); Pierre Rota-Graziosi, Mulhouse (FR) (56) References Cited (73) Assignee: BASFSE, Ludwigshafen (DE) U.S. PATENT DOCUMENTS

5,837,760 A 11/1998 Hacklet al...... 524/127 (*) Notice: Subject to any disclaimer, the term of this $35: E. 239: Ryhidaprinidis . . et. . . . al...... 38 past its, G adjusted under 35 2002/0115782 A1 8/2002 Brauer et al...... 524f710 .S.C. 154(b) by 0 days. 2003/0207969 A1 * 1 1/2003 Capocci et al...... 524/236 2004/0002559 A1 1/2004 Troutman et al...... 524/100 (21) Appl. No.: 11/991,812 2004/0138351 A1* 7/2004 Kaprinidis et al. ... 524/100 2004/O147648 A1 7/2004 Corcoran ...... 524, 186 (22) PCT Filed: Sep. 6, 2006 2004/0254270 A1* 12/2004 Harashina ...... 524.86 2006/00741.54 A1* 4/2006 Harashina et al...... 524/115 (86). PCT No.: PCT/EP2006/066O45 OTHER PUBLICATIONS S371 (c)(1), Patent Abstracts of Japan Publication No. 09020743, Jan. 21, 1997. (2), (4) Date: Mar. 23, 2011 S. Levchik et al., Polymer International, vol. 53, (2004), pp. 1585 1610. (87) PCT Pub. No.: WO2007/031450 * cited by examiner PCT Pub. Date: Mar. 22, 2007 O O Primary Examiner — Peter Szekely (65) Prior Publication Data (74) Attorney, Agent, or Firm — Tyler A. Stevenson US 2011 FO2306O4A1 Sep. 22, 2011 (57) ABSTRACT (30) Foreign Application Priority Data The invention relates to a flame retardant composition, which comprises a) At least one ester of a phosphorus containing Sep. 16, 2005 (EP) ...... 05108520 oXo acid selected from the group consisting of phosphonous and phosphorous acid; b) At least one flame retardant com (51) Int. Cl. ponent based on a nitrogen compound; particularly melamine CSK 3/3492 (2006.01) cyanurate, and c) A polyurethane polymer base. (52) U.S. Cl. USPC ...... 524/101:524/147; 524/151:524/153 5 Claims, No Drawings US 8,415,414 B2 1. 2 POLYURETHANE FLAME RETARDANT nous and phosphorous acid results in improved thermal and COMPOSITIONS mechanical properties of TPU. Therefore, the present invention relates to a composition, The present invention relates to a flame retardant compo which comprises sition, which comprises a combination of a phosphonite or a a) At least one ester derivative of a phosphorus containing phosphite with a nitrogen containing flame retardant and oxoacid selected from the group consisting of oxaphos polyurethane polymer base. phorinoxide, phosphonous acid and phosphorous acid; Thermoplastic polyurethanes (TPU) are useful for many b) At least one flame retardant component based on a technical applications. Particular reference is made to Kunst nitrogen compound; and stoff-Handbuch, Vol. VII, Polyurethane, Carl Hanser Verlag 10 c) A polyurethane polymer base. D-Minchen, 1st Edition 1966, Editors R. Vieweg and A. According to a preferred embodiment, the present inven Höchtlen, and 2nd Edition, Editor G. Oertel. tion relates to a composition, which comprises Many methods for preparing polyurethanes are known. a) At least one ester derivative of a phosphorus containing High molecular weight polyhydroxy compounds, which form oxoacid selected from the group consisting of phospho the flexible base, for example polyoxyalkylene glycols. Such 15 nous and phosphorous acid; as polyoxypropylene or polyoxyethylene glycol, polyox b) At least one flame retardant component based on a ypropylene polyoxyethylene glycol, polyoxybutylene glycol, nitrogen compound; and polyoxybutylene polyoxyethylene glycolor polyoxybutylene c) A polyurethane polymer base. polyoxypropylene glycol, or polyesterdiols, such as The compositions according to the invention attain the alkanediol polyadipates, are reacted with aromatic or ali desirable V-0 rating, according to UL-94 (Underwriters phatic diisocyanates, e.g. diphenylmethane-4,4'-diisocyanate Laboratories Subject 94) and other excellent ratings in related (MDI) or hexamethylene-1,6-diisocyanate (HDI), and low test methods while preserving the excellent mechanical, molecular weight chain extenders for the formation of rigid chemical and thermal properties of thermoplastic polyure segments, for example alkanediols or dialkylene glycols, 25 thanes, such as colour and light stability. Such as 1,4-butanediol or diethylene glycol. A disadvantage The composition, as defined above, comprises the follow of TPU is their easy inflammability. ing components: Flame retardants are added to polymeric materials (syn Componenta) thetic or natural) to enhance the flame retardant properties of The composition according to the present invention com the polymers. Depending on their composition, flame retar 30 dants may act in the Solid, liquid or gas phase either chemi prises as componenta) at least one ester derivative of a phos cally, e.g. as a spumescent by liberation of nitrogen, and/or phorus containing oxo acid selected from the group consist physically, e.g. by producing a foam coverage. Flame retar ing of oxaphosphorinoxide, phosphonous acid and dants interfere during a particular stage of the combustion phosphorous acid. process, e.g. during heating, decomposition, ignition or flame 35 According to a preferred embodiment the composition spread. according to the present invention comprises as componenta) Nitrogen-containing flame retardants, especially those at least one ester derivative of a phosphorus containing oxo based on melamine, have been known for a longtime and are, acid selected from the group consisting of phosphonous and in Some cases, commercially available. Some of those phosphorous acid. melamine derivatives also contain phosphorus. Examples of 40 Oxaphosphorinoxide has a cyclic structure and is repre publications relating to Such flame retardants are, interalia, sented by the following general formula: EP-A-782599, EP-A-1 095 030 and U.S. Pat. Nos. 4,010, 137 and 3,915,777. Combinations of nitrogen-containing flame retardants (I) with flame retardants based on phosphorus compounds are 45 also known. In that respect particular reference is made to, for example, DE-A-19734437, DE-A-19737 727, WO-A-97/ O OsH 39053, EP-A-1 070 754, EP-A-6568 and DE-A-19614 424. Particular phosphates in combination with nitrogen-contain ing compounds are also known as flame retardants, for 50 The phosphorous atom and one oxygen atom are part of a example from EP-A-484832, EP-A-545496, EP-A-707036, cyclic structure, particularly a five or six membered ring, as WO-A-01/98401, GB-A-1 468 188 and EP-A-617079. represented by the following representative compound: There is a continuing need for flame retardants that have improved thermal and mechanical properties and that can be used in various polymer Substrates. In particular, increased 55 safety and environmental requirements mean that hitherto known flame retardants are no longer capable of satisfying all demands. The use of melamine or melamine derivatives as flame retardants for TPU has been proposed in various references. 60 As a further development, the use of melamine cyanurate in combination with organic phosphate in TPU compositions has been proposed, e.g. U.S. Pat. No. 5,837,760. Which can be named as 6H-dibenzc.e. 1.2 oxaphospho It has now been found that the use of a combination of rin-6-oxide, 3.4:5,6-dibenzo-2H-1,2-oxaphosphorin-2-oxide selected flame retardants, particularly flame retardants based 65 or 9,10-dihydro-9-Oxa-10-phosphorylphenanthrene-10-ox on melamine, with esters derivative of a phosphorus contain ide, abbreviated as DOPO (C.A. RN35948-25-5). Such com ing oxoacid selected from the group consisting of phospho pound is commercially available from Sanko HCA. US 8,415,414 B2 3 4 Phosphonous acid is represented by the following general Wherein R represents an organic ester group. formula: A preferred embodiment relates to compositions compris ing as componenta) ester derivatives of phosphorous acid as represented by the following general formulae: 5 (II) (A) R R4

O-P P-O The acid is a member of the large group of phosphorus R.C.-- (X) / s containing oxoacids, which includes other members, such as \ / Y, c/ - phosphoric, phosphorous orphosphinous acid. Phosphonous R3 R6 acid does not exist in its free form in an aqueous solution. 15 Ester derivatives of phosphonous acid are represented by Wherein the following general formula One of R. R. and R and one of R. Rs and R represent hydrogen and the other ones represent C-Calkyl oraryl-C- Calkyl; or (II) R. R. and R and R. Rs and R represent C-Calkyl; or RO P-R', (B) RO 25 R-O-P Wherein R represents an organic ester group and R' repre sents hydrogen or an organic Substituent which is directly attached to the phosphorus atom. Wherein R and R' represent Co-Coalkyl; or In the event that R' represents hydrogen, the formula II' 30 comprises within its scope the following tautomeric struc ture: (C) R RO P2 35 ==75R, 3 N 3: RO H

40 Wherein Phosphorous acid is represented by the following general R. R. and R represent C-C salkyl; or formula: one or two of R. R. and R represent hydrogen and the other ones represent C-C salkyl, or

(III) 45 HO (D) P-OH. HO

50 The acid is a further member of the large group of phos phorus 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 Wherein one of R, R and R represents methyl and the term phosphites. They are represented by the following gen 55 other ones represent C-C alkyl, or eral formula: R. R. and R independently of one another represent C-C alkyl; and R, and R, represent methyl or ethyl; or 60 (III) (E) RO P-OR, RO 65 US 8,415,414 B2 5 6 Wherein R, R and R independently of one another rep resent phenyl or Cs-Coalkyl; or (G) O-(C-Calk-O), (R-O--P (F) 5 V R- O- (C-C3alk-O), P-O-H-(C-Calk-O), R-O 10 Whereinx represents one or a numeral greater than one and Wherein X represents two or a numeral greater than two; y y and Z represent two or a numeral greater than two. represents one or a numeral greater than one and R and R- A preferred embodiment relates to compositions compris independently of one another represent phenyl or ing as component a) ester derivatives of phosphonous and Cs-Coalkyl, or phosphorous acid selected from the group consisting of

(CH3)3C C(CH3)3

P- O CoH 19 P-O R P CH3 3. s M s O 3

(CH3)3C C(CH3)3 (Irgafos(R) TNPP, Doverphos(R) HiPure 4) (IRGAFOS 168, DOVERPHOSS-480, S-680) (IRGAFOSP-EPQ, Sandostab(R) P-EPQ)

(CH3)3C C(CH3)3

O O OS/ V PV s HC-CH fP-F O O

C(CH3)3 (CH3)3C (Ethanox(R)398) (Ultranox(R) 641) C(CH3)3 (CH3)3C O V P s / O (CH3)3C C(CH3)3 O 2 O / V O-P P-O (XO OW

(DOVERPHOSS-9228) US 8,415,414 B2 7 8 -continued C(CH3)3 C(CH3)3 (CH3)3C (CH3)3C

O O V V P-O-CHCH N, P-O-CH2CH(CHo)CH2CH, / / O O

(CH3)3C (CH3)3C C(CH3)3 3 C(CH3)3 (IRGAFOS 12), (Mark HP-10)

(ULTRANOX626, IRGAFOS 126)

O O O O / V CH 3. It co-o-Yus-u- VP-O-C18H37, HC o-R -o V O O O O

(MARK PEP36) (Weston(R) 618) t HC-C-CH O P-OCH2CH3. HC Y. CH HC1 \ 3 CH3 2 (IRGAFOS 38)

Another preferred embodiment relates to compositions -continued comprising as componenta) a cyclic oxaphosphorinoxide of O O the formula / V 45 is cut-o-r O O -o-isch, CAS RN26544-27-4) O O

culti-o-Y18137-u- Y-o-ch- u-u1813, P 50 N / o1 HSoS. O O CAS RN35948-25 5 CAS RN 3806-34-6)

or an ester derivative of phosphonous or phosphorous acid 55 selected from the group consisting of dipropylene glycol cut---0-( ). phosphite CAS RN 40305-86-0. CAS RN 2082-80-6)

Bu-t t-Bu 60 sci-Fi-o-( ). CAS RN 26544-23-0)

P(-O-isoCH7), P( O—CH-7), P(-O-isoCoH) Bu-t t-Bu 65 33 P(-O-CHs), CAS RN 80693-00-1) US 8,415,414 B2 9 10 (CHs O-)PI( O CH). CAS RN57077-45-9. According to a particularly preferred embodiment the (CHs O—)P O—CH(CH)CH O P( O— invention relates to compositions, wherein component a) is CH5)2. present in an amount equal or higher than 1% by weight based (CHs O-)P2(—OCH5)(CHs O—P) CAS on the total weight of the composition. RN 67383-54-4, Component b) (CHs O-)P2(—OCH(CH)CH2)(CHs O—P) The composition according to the invention comprises as CAS RN 80584-86-7, Component b) at least one nitrogen compound selected from and tris 2-(2-hydroxypropoxy)-1-methylethylphospho the group consisting of rous acid ester CAS RN 13474-96-9. A particularly preferred embodiment relates to composi 10 tions comprising as component a) ester derivatives of phosphonous and phosphorous acid selected from the group (III) consisting of triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl)phosphite, trilau ryl phosphite, trioctadecyl phosphite, distearylpentaerythri 15 tol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diiso decyl pentaerythritol diphosphite, bis(2,4-di-tert butylphenyl)pentaerythritol diphosphite, bis(2,4-di (IV) cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-bu tyl-6-methylphenyl)pentaerythritol diphosphite, bis(2.4.6- tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'- biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra 25 tert-butyl-12H-dibenzdg-1,3,2-dioxaphosphocin, bis(2,4- (V) di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8. 10-tetra-tert-butyl-12-methyl-dibenzd.g-1,3,2- dioxaphosphocin, 2.2.2"-nitrilo triethyltris(3,3',5,5'-tetra 30 tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 2-ethylhexyl (3.3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-diox (VI) aphosphirane. A highly preferred embodiment relates to compositions 35 comprising as componenta) esterderivatives of phosphonous and phosphorous acid selected from the group consisting of aryl organo phosphites, such as tris nonylphenyl phosphite (TNPPDOVERPHOS4), triphenylphosphite (TPPDOVER PHOS 10) or diphenyl phosphite (DPP DOVERPHOS 213), 40 (VII) aryl-alkyl organophosphites, such as phenyl diisodecylphos phite (PDDP DOVERPHOS 7), diphenyl isodecyl phosphite (DPDP DOVERPHOS 8), diphenylisooctyl phosphite (DPIOP DOVERPHOS 9), tetraphenyl dipropylene glycol diphosphite (THOP DOVERPHOS 11), poly (dipropylene 45 glycol) phenylphosphite (DHOPDOVERPHOS 12) or dode cyl diphenylphosphite (DDPP), and alkyl organo phosphites, (VIII) such as triisodecylphosphite (TDP DOVERPHOS 6), tris tridecyl phosphite (TTDP DOVERPHOS 49) or trilauryl phosphite (TLP DOVERPHOS 53). 50 A further highly preferred embodiment of the invention and relates to compositions comprising as component a) an ester derivative of phosphonous orphosphorous acid selected from the group consisting of 9,10-dihydro-9-Oxa-10-phospho (IX) rylphenanthrene-10-oxide (DOPO), bis(2,6-di-tert-butyl-4- 55 methylphenyl)-pentaerythritol diphosphite CAS RN80693 00-1), (CH, O )PI( O CH). CAS RN 57077 45-9. (CHs O-)P( OCH5)(CHs O—P) CAS RN 67383-54-4 and triphenyl phosphite. The ester derivatives of phosphonous and phosphorous 60 acid are known compounds and are commercially available. According to a particularly preferred embodiment the Wherein in the compounds (III), (VII) and (IX): invention relates to compositions, which comprises as com R. R. or R independently of one another represent Sub ponenta) ester derivatives of phosphonous and phosphorous stituents selected from the group consisting of C-Csalkyl, acid selected from the group consisting of the commercial 65 Cs-Cecycloalkyl and C-C alkyl-Cs-Cecycloalkyl with products IRGAFOS 126, 168, 38, PEPQ, 12, TNPP and hydroxy as an optional Substituent; or represent Substituents DDPP, WESTON 618 and Mark PEP 36. selected from the group consisting of C-Calkenyl, C-Cs US 8,415,414 B2 11 12 alkoxy, C-Csalkenyl: C-Calkoxy, acyl, acyloxy, the group consisting of C-C alkyl, cyclopentyl, cyclohexyl, C-Caryl, -O-R' and - N(R')R’, wherein R' and R' methylcyclohexyl, hydroxy-C-C alkyl, C-Calkenyl, independently of one another represent hydrogen, C-Calkoxy, phenyl, phenyl, which is substituted by 1 to 3 C-C alkyl, Cs-Cecycloalkyl, C-Csalkenyl, Substituents selected from the group consisting of methyl, C-C hydroxyalkyl or C-Caryl; or methoxy and halogen and by —OR' wherein R' represents One of R. R. and R represents hydrogen and two of R, hydrogen, C-C alkyl, hydroxy-C-C-alkyl, cycloalkyl, R and R represent the substituents as defined above; or methylcyclohexyl, phenyl or phenyl, which is substituted by Two of R. RandR represent hydrogen and one of R, R 1 to 3 Substituents selected from the group consisting of and R represents a substituent as defined above: methyl, methoxy and halogen. X represents the anion of a protonic acid; 10 X is a numeral that represents the number of protons trans According to a particularly preferred embodiment the ferred from the latter to the triazine compound; and composition comprises as Component b) a nitrogen com y is a numeral that represents the number of protons pound selected from the group consisting of benzoguanamine abstracted from the protonic acid; (formula III, R=phenyl, R=R —NH), tris(hydroxyeth provided that 15 yl)isocyanurate (formula IV, R=R-R =—CH2—CH2— In compounds (VII) one group is present that is capable of OH), allantoin (formula V. R=R-R-R-Rs—H), gly adding a proton; and coluril (formula VI, R=R R=REH), melamine Compounds (III) are excluded, wherein R, R2 and R phosphate, dimelamine phosphate, melamine pyrophosphate, represent groups of the partial formula N(R')R and R' and melamine polyphosphate, melamine borate (all of formula R represent hydrogen; VII type), urea cyanurate (formula VIII type), melamine cya And wherein in the compounds (IV), (V), (VI) and (VIII): nurate (formula IX type), melam or melem phosphate, melam R. R. R. R. and Rs independently of one another repre or melem polyphosphate, ammonium polyphosphate and sent hydrogen or Substituents selected from the group con melamine ammonium phosphate, pyrophosphate and poly sisting of C-Calkyl, Cs-Cecycloalkyl and C-C alkyl-Cs phosphate. Cecycloalkyl with hydroxy as an optional Substituent; or 25 The nitrogen compounds as defined and described above represent Substituents selected from the group consisting of are known compounds or are obtainable by known methods. C-Csalkenyl, C-C-alkoxy, C-Csalkenyl, C-Csalkoxy, Some of them are commercially available. acyl, acyloxy, Ca-Caryland—O-R', wherein R' repre According to a particularly preferred embodiment the sents hydrogen, C-C alkyl, Cs-Cecycloalkyl, C-Csalkenyl, composition comprises as Component b) a nitrogen com C-Chydroxyalkyl or C-Caryl. 30 pound selected from the group consisting of compounds According to another embodiment of the invention the composition comprises as Component b) at least one nitrogen (VII), compounds (IX), ammonium polyphosphate, compound selected from the group consisting of ammonium melamine ammonium phosphate, melamine ammonium polyphosphate, melamine ammonium phosphate, melamine polyphosphate, melamine ammonium pyrophosphate, a con ammonium polyphosphate, melamine ammonium pyrophos 35 densation product of melamine with phosphoric acid and phate, a condensation product of melamine with phosphoric other reaction products of melamine with phosphoric acid acid and other reaction products of melamine with phospho and mixtures thereof. ric acid and mixtures thereof. According to a highly preferred embodiment the compo The symbol X in formula VII represents, for example, an sition comprises as Component b) a nitrogen compound anion of phosphoric acid, polyphosphoric acid (linear or 40 selected from the group consisting of benzoguanamine, tris branched), pyrophosphoric acid, phosphinic acid, phospho (hydroxyethyl)isocyanurate, allantoin, glycoluril, melamine nic acid or boric acid. cyanurate, melamine phosphate, dimelamine phosphate, According to a preferred embodiment the composition melamine pyrophosphate, urea cyanurate, melamine poly comprises as Component b) compounds (III), (VII) and (IX), phosphate, melamine borate, ammonium polyphosphate, wherein R, R or Rs independently of one another represent 45 melamine ammonium polyphosphate, melamine ammonium Substituents selected from the group consisting of pyrophosphate, the condensation product of melamine C-C alkyl, cyclopentyl, cyclohexyl, methylcyclohexyl, selected from the group consisting of melem, melam, melon C-C hydroxyalkyl, C-Calkenyl, C-C alkoxy, phenyl, and higher condensed compounds and other reaction prod phenyl, which is substituted by 1 to 3 substituents selected ucts of melamine with phosphoric acid and mixtures thereof. from the group consisting of methyl, methoxy and by halo 50 Special emphasis is given to dimelamine pyrophosphate, gen, —OR" and by N(R')R’, wherein R' and R indepen melamine polyphosphate, melem polyphosphate, melam dently of one another represent hydrogen, C-C alkyl, polyphosphate, and/or a mixed polysalt thereof, particularly hydroxy-C-C alkyl, cycloalkyl, methylcyclohexyl, phenyl melamine polyphosphate. or phenyl, which is substituted by 1 to 3 substituents selected According to a highly preferred embodiment the compo from the group consisting of methyl, methoxy and by halo 55 sition comprises as Component b) melamine cyanurate. Such gen. as the ones commercially available under the designation According to a particularly preferred embodiment the MELAPURMC, MC 15, MC 25, MC 50. composition comprises as Component b) compounds (III), The ratio of components a) and b) may vary within wide (VII) and (IX), wherein one of R, R and R represents limits and is dependent upon the intended use. Examples of hydrogen and two of R. R. and R represent the Substituents 60 ratios a:b (ratios by weight) are from 5:95 to 95:5, e.g. from as defined above; or 10:90 to 90:10, preferably from 20:80 to 80:20, especially two of R, R2 and R represent hydrogen and one of R, R from 30:70 to 70:30 and from 40:60 to 60:40. and R represents a substituent as defined above. Component c) According to another preferred embodiment the composi The composition according to the invention comprises as tion comprises as Component b) compounds (IV), (V), (VI) 65 Component c) a polyurethane polymer base and (VIII), wherein R. R. R. R. and Rs independently of The polymer base may be a thermoplastic polyurethane one another represent hydrogen or Substituents selected from (TPU), a PU elastomer, artificial leather, PU skin, PU stray US 8,415,414 B2 13 14 coating or reaction injection molding (RIM), a cast PU, a in the course of the industrial preparation of isocyanates. It is silylated polyurethane (SPUR), a PU hot melt adhesive or a additionally possible to use any desired mixtures of the PU hot melt adhesive. above-mentioned polyisocyanates. The polyurethanes are obtainable, for example, by reacting Particular preference is given in general to the polyisocy polyethers, polyesters and polybutadienes which containter anates which are readily obtainable industrially, for example minal hydroxyl groups, i.e. polyols, with aliphatic or aro aromatic isocyanates such as 2.4- and 2,6-tolylene diisocy matic polyisocyanates. anate and any desired mixtures of these isomers (“TDI), Polyethers and polyesters having terminal hydroxyl groups polyphenyl-polymethylene-polyisocyanates as prepared by are known and are prepared, for example, by polymerizing aniline-formaldehyde condensation followed by phosgeniza epoxides such as ethylene oxide, propylene oxide, butylene 10 tion ("crude MDI), and polyisocyanates containing carbo oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with diimide, urethane, allophanate, isocyanurate, urea orbiuret themselves, for example in the presence of BF, or by addi groups (“modified polyisocyanates'). tion reaction of these epoxides, alone or as a mixture or in Polyurethane is preferably prepared from liquid starting Succession, with starting components containing reactive components, i.e. the starting materials to be reacted with one hydrogen atoms, such as alcohols, ammonia or amines, for 15 another being mixed together in a one-shot process. example ethylene glycol, propylene 1.3- and 1.2-glycol, tri The polymer base of component c) may additionally con methylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, tain in the form as admixtures or as copolymers a wide variety ethanolamine or ethylenediamine. Sucrose polyethers are of other synthetic polymers including polyolefins, polysty also suitable in accordance with the invention. In many cases renes, polyesters, polyethers, polyamides, poly(meth)acry preference is given to those polyethers which predominantly lates, thermoplastic polyurethanes, polysulphones, polyac (up to 90% by weight, based on all OH groups present in the etals and PVC, including Suitable compatibilizing agents. For polyether) contain primary OH groups. Furthermore, poly example, the polymer base may additionally contain thermo ethers modified by vinyl polymers, as are formed, for plastic polymers selected from the group of resins consisting example, by polymerizing styrene and acrylonitrile in the of polyolefins, thermoplastic polyurethanes, styrene poly presence of polyethers, are suitable, as are polybutadienes 25 mers and copolymers thereof. Specific embodiments include containing OH groups. polypropylene (PP), polyethylene (PE), polyimide (PA), These compounds generally have molecular weights of 40 polybutylene terephthalate (PBT), polyethylene terephtha and are polyhydroxy compounds, especially compounds con late (PET), glycol-modified polycyclohexylenemethylene taining from two to eight hydroxyl groups, especially those of terephthalate (PCTG), polysulphone (PSU), polymethyl molecular weight from 800 to 10 000, preferably from 1000 30 methacrylate (PMMA), thermoplastic polyurethane (TPU). to 6000, for example polyethers containing at least 2, gener acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene ally 2 to 8, but preferably 2 to 4, hydroxyl groups, as are acrylic ester (ASA), acrylonitrile-ethylene-propylene-sty known for the preparation of homogeneous polyurethanes rene (AES), styrene-maleic anhydride (SMA) or high impact and cellular polyurethanes. polystyrene (HIPS). It is of course possible to employ mixtures of the above 35 A list of suitable synthetic polymers is given below: compounds containing at least two isocyanate-reactive 1. Polymers of monoolefins and diolefins, for example hydrogen atoms, in particular with a molecular weight of polypropylene, polyisobutylene, poly-but-1-ene, poly-4- 400-10 OOO. methylpent-1-ene, polyvinylcyclohexane, polyisoprene or Suitable polyisocyanates are aliphatic, cycloaliphatic, polybutadiene, as well as polymers of cycloolefins, for araliphatic, aromatic and heterocyclic polyisocyanates, for 40 instance of cyclopentene or norbornene, polyethylene example ethylene diisocyanate, 1,4-tetramethylene diisocy (which optionally can be crosslinked), for example high anate, 1.6-hexamethylene diisocyanate, 1,12-dodecane diiso density polyethylene (HDPE), high density and high cyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1.3- and molecular weight polyethylene (HDPE-HMW), high den -1,4-diisocyanate and also any desired mixtures of these iso sity and ultrahigh molecular weight polyethylene (HDPE mers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcy 45 UHMW), medium density polyethylene (MDPE), low clohexane, 2.4- and 2.6-hexahydrotolylene diisocyanate and density polyethylene (LDPE), linear low density polyeth also any desired mixtures of these isomers, hexahydro-1,3- ylene (LLDPE), (VLDPE) and (ULDPE). The polymers of and/or -1,4-phenylene diisocyanate, perhydro-2,4'- monoolefins exemplified in the preceding paragraph, pref and/or-4,4'-diphenylmethanediisocyanate, 1.3- and 1,4-phe erably polyethylene and polypropylene, can be prepared by nylene diisocyanate, 2.4- and 2,6-tolylene diisocyanate, and 50 different, and especially by the following, methods: also any desired mixtures of these isomers, diphenylmethane a) Radical polymerisation (normally under high pressure 2,4'-and/or-4,4'-diisocyanate, naphthylene 1,5-diisocyanate, and at elevated temperature). triphenylmethane 4,4',4'-triisocyanate, polyphenyl-polym b) Catalytic polymerisation using a catalyst that normally ethylene polyisocyanates as are obtained by aniline-formal contains one or more than one metal of groups IVb, Vb, dehyde condensation followed by phosgenization, m- and 55 VIb or VIII of the Periodic Table. These metals usually p-isocyanatophenylsulphonyl isocyanates, perchlorinated have one or more than one ligand, typically oxides, aryl polyisocyanates, polyisocyanates containing carbodiim halides, alcoholates, esters, ethers, amines, alkyls, alk ide groups, polyisocyanates containing allophanate groups, enyls and/or aryls that may be either L- or O-coordi polyisocyanates containing isocyanurate groups, polyisocy nated. These metal complexes may be in the free form or anates containing urethane groups, polyisocyanates contain 60 fixed on Substrates, typically on activated magnesium ing acylated urea groups, polyisocyanates containing biuret chloride, titanium(III) chloride, alumina or silicon groups, polyisocyanates containing ester groups, reaction oxide. These catalysts may be soluble or insoluble in the products of the above-mentioned isocyanates with acetals, polymerisation medium. The catalysts can be used by and polyisocyanates containing polymeric fatty acid radicals. themselves in the polymerisation or further activators It is also possible to employ the isocyanate group-contain 65 may be used, typically metal alkyls, metal hydrides, ing distillation residues as they are or dissolved in one or more metal alkylhalides, metal alkyl oxides or metal alkylox of the above-mentioned polyisocyanates, which are obtained anes, said metals being elements of groups Ia, IIa and/or US 8,415,414 B2 15 16 IIIa of the Periodic Table. The activators may be modi example a polyacrylate, a diene polymer or an ethylene/ fied conveniently with further ester, ether, and amine or propylene?diene terpolymer; and block copolymers of silyl ether groups. These catalyst Systems are usually styrene Such as styrene?butadiene/styrene, styrenefiso termed Phillips, Standard Oil Indiana, Ziegler-Natta), prene?styrene, styrene? ethylene/butylene?styrene or sty TNZ (DuPont), metallocene or single site catalysts rene? ethylene/propylene?styrene. (SSC). b) Hydrogenated aromatic polymers derived from hydro 2. Mixtures of the polymers mentioned under 1), for example genation of polymers mentioned under 6.), especially mixtures of polypropylene with polyisobutylene, polypro including polycyclohexylethylene (PCHE) prepared by pylene with polyethylene (for example PP/HDPE, hydrogenating atactic polystyrene, often referred to as PP/LDPE) and mixtures of different types of polyethylene 10 polyvinylcyclohexane (PVCH). (for example LDPE/HDPE). 3. Copolymers of monoolefins and diolefins with each other c) Hydrogenated aromatic polymers derived from hydro or with other vinyl monomers, for example ethylene/pro genation of polymers mentioned under 6a). Homopoly pylene copolymers, linear low density polyethylene (LL mers and copolymers may have a stereo structure includ DPE) and mixtures thereof with low density polyethylene 15 ing syndiotactic, isotactic, hemi-isotactic or atactic; (LDPE), propylene/but-1-ene copolymers, propylene/ where atactic polymers are preferred. Stereo block poly isobutylene copolymers, ethylene/but-1-ene copolymers, mers are also included. ethylene/hexene copolymers, ethylene/methylpentene 7. Graft copolymers of vinyl aromatic monomers such as copolymers, ethylene/heptene copolymers, ethylene? styrene or C.-methylstyrene, for example styrene on polyb octene copolymers, ethylene/vinylcyclohexane copoly utadiene, styrene on polybutadiene-styrene or polybutadi mers, ethylene/cycloolefin copolymers (e.g. ethylene/nor ene-acrylonitrile copolymers; styrene and acrylonitrile(or bornene like COC), ethylene/1-olefins copolymers, where methacrylonitrile) on polybutadiene; styrene, acrylonitrile the 1-olefin is generated in-situ; propylene/butadiene and methyl methacrylate on polybutadiene; styrene and copolymers, isobutylenefisoprene copolymers, ethylene? maleic anhydride on polybutadiene; styrene, acrylonitrile vinylcyclohexene copolymers, ethylene/alkyl acrylate 25 and maleic anhydride or maleimide on polybutadiene; Sty copolymers, ethylene/alkyl methacrylate copolymers, eth rene and maleimide on polybutadiene; styrene and alkyl ylene/vinyl acetate copolymers or ethylene? acrylic acid acrylates or methacrylates on polybutadiene; styrene and copolymers and their salts (ionomers) as well as terpoly acrylonitrile on ethylene/propylene?diene terpolymers; mers of ethylene with propylene and a diene Such as hexa styrene and acrylonitrile on polyalkyl acrylates or poly diene, dicyclopentadiene or ethylidene-norbornene; and 30 alkyl methacrylates, styrene and acrylonitrile on acrylate/ mixtures of Such copolymers with one another and with butadiene copolymers, as well as mixtures thereof with the polymers mentioned in 1) above, for example polypropy copolymers listed under 6), for example the copolymer lene/ethylene-propylene copolymers, LDPE/ethylene-vi mixtures known as ABS, MBS, ASA or AES polymers. nyl acetate copolymers (EVA), LDPE/ethylene-acrylic 8. Halogen-containing polymers such as polychloroprene, acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and 35 chlorinated rubbers, chlorinated and brominated copoly alternating or random polyalkylene/carbon monoxide mer of isobutylene-isoprene (halobutyl rubber), chlori copolymers and mixtures thereof with other polymers, for nated or Sulphochlorinated polyethylene, copolymers of example polyamides. ethylene and chlorinated ethylene, epichlorohydrinhomo 4. Hydrocarbon resins (for example Cs-Co.) including hydro and copolymers, especially polymers of halogen-contain genated modifications thereof (e.g. tackifiers) and mixtures 40 ing vinyl compounds, for example polyvinyl chloride, of polyalkylenes and starch; polyvinylidene chloride, polyvinyl fluoride, polyvi The homopolymers and copolymers mentioned above may nylidene fluoride, as well as copolymers thereof Such as have a stereo structure including syndiotactic, isotactic, vinyl chloride/vinylidene chloride, vinyl chloride/vinyl hemi-isotactic or atactic; where atactic polymers are acetate or vinylidene chloride/vinyl acetate copolymers. preferred. Stereo block polymers are also included. 45 9. Polymers derived from C.B-unsaturated acids and deriva 5. Polystyrene, poly(p-methylstyrene), poly(C.-methylsty tives thereof such as polyacrylates and polymethacrylates; rene). polymethyl methacrylates, polyacrylamides and polyacry 6. Aromatic homopolymers and copolymers derived from lonitriles, impact-modified with butyl acrylate. vinyl aromatic monomers including styrene, C.-methylsty 10. Copolymers of the monomers mentioned under 9) with rene, all isomers of vinyl toluene, especially p-vinyl tolu 50 each other or with other unsaturated monomers, for ene, all isomers of ethyl styrene, propyl Styrene, vinyl example acrylonitrile/butadiene copolymers, acrylonitrile? biphenyl, vinyl naphthalene, and vinyl anthracene, and alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acry mixtures thereof. Homopolymers and copolymers may late or acrylonitrile/vinyl halide copolymers or acryloni have a stereo structure including syndiotactic, isotactic, trile/alkyl methacrylate/butadiene terpolymers. hemi-isotactic or atactic; where atactic polymers are pre 55 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 60 copolymers with olefins mentioned in 1. above. derivatives and mixtures thereof, for example styrene/ 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 65 oxymethylenes, which contain ethylene oxide as a lonitrile/methyl acrylate; mixtures of high impact comonomer, polyacetals modified with thermoplastic strength of styrene copolymers and another polymer, for polyurethanes, acrylates or MBS. US 8,415,414 B2 17 18 14. Polyphenylene oxides and sulphides, and mixtures of consisting of polymer stabilizers and additional flame-retar polyphenylene oxides with styrene polymers or polya dants selected from the group consisting of phosphorus con mides. taining flame-retardants, halogenated flame-retardants and 15. Polyamides and copolyamides derived from diamines and inorganic flame-retardants. dicarboxylic acids and/or from aminocarboxylic acids or Stabilizers are preferably halogen-free and selected from the corresponding lactams, for example polyamide 4. nitroxyl stabilizers, nitrone stabilizers, amine oxide stabiliz polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, ers, benzofuranone stabilizers, phosphite and phosphonite polyamide 11, polyamide 12, aromatic polyamides starting stabilizers, quinone methide Stabilizers and monoacrylate from m-Xylene diamine and adipic acid; polyamides pre esters of 2,2'-alkylidenebisphenol stabilizers. pared from hexamethylenediamine and isophthalic or/and 10 Additional flame-retardants as of present component d) are terephthalic acid and with or without an elastomeras modi known components, items of commerce or can be obtained by fier, for example poly-2,4,4-trimethylhexamethylene known methods. terephthalamide or poly-m-phenylene isophthalamide; Representative phosphorus containing flame-retardants, in and also block copolymers of the aforementioned polya addition to the ones defined above with regard to component mides with polyolefins, olefin copolymers, ionomers or 15 a), are for example: chemically bonded or grafted elastomers; or with poly Tetraphenyl resorcinol diphosphite (FYROLFLEX(R) RDP. ethers, e.g. with polyethylene glycol, polypropylene glycol Akzo Nobel), tetrakis(hydroxymethyl)phosphonium sul or polytetramethylene glycol; as well as polyamides or phide, triphenyl phosphate, diethyl-N,N-bis(2-hydroxy copolyamides modified with EPDM or ABS; and polya ethyl)-aminomethyl phosphonate, hydroxyalkyl esters of mides condensed during processing (RIM polyamide sys phosphorus acids, resorcinol diphosphate oligomer (RDP), tems). phosphaZene flame-retardants or ethylenediamine diphos 16. Polyureas, polyimides, polyamide imides, polyether imi phate (EDAP). des, polyester imides, polyhydantoins and polybenzimida Representative halogenated flame-retardants are, for Zoles. example: 17. Polyesters derived from dicarboxylic acids and diols and/ 25 Polybrominated diphenyl oxide (DE-60F, Great Lakes or from hydroxycarboxylic acids or the corresponding lac Corp.), decabromodiphenyl oxide (DBDPO; SAYTEX(R) tones, for example polyethylene terephthalate, polybuty 102E), tris3-bromo-2,2-bis(bromomethyl)propylphos lene terephthalate, poly-1,4-dimethylolcyclohexane phate (PB 370R, FMC Corp.), tris(2,3-dibromopropyl)phos terephthalate, polyalkylene naphthalate (PAN) and poly phate, tris(2,3-dichloropropyl)phosphate, chlorendic acid, hydroxybenzoates, as well as block copolyether esters 30 tetrachlorophthalic acid, tetrabromophthalic acid, poly-B- derived from hydroxyl-terminated polyethers; and also chloroethyl triphosphonate mixture, tetrabromobisphenol A polyesters modified with polycarbonates or MBS. bis(2,3-dibromopropyl ether) (PE68), brominated epoxy 18. Polyketones. resin, ethylene-bis(tetrabromophthalimide) (SAYTEXOR) 19. Polysulphones, polyether sulphones and polyether BT-93), bis(hexachlorocyclopentadieno)cyclooctane (DE ketones. 35 CLORANE PLUS(R), chlorinated paraffins, octabromo 20. Blends of the aforementioned polymers (polyblends), for diphenyl ether, hexachlorocyclopentadiene derivatives, 1.2- example PP/EPDM, Polyamide/EPDM or ABS, PVC/ bis(tribromophenoxy)ethane (FF680), tetrabromobisphenol EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, A (SAYTEX(R) RB100), ethylene bis-(dibromo-norbor PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/ther nanedicarboximide) (SAYTEXR BN-451), bis-(hexachloro moplastic PUR, PC/thermoplastic PUR, POM/acrylate, 40 cycloentadeno)cyclooctane, PTFE, tris-(2,3-dibromopro POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, pyl)-isocyanurate, and ethylene-bis-tetrabromophthalimide. PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/ The flame-retardant mentioned above are routinely com PC. bined with an inorganic oxide synergist. Most common for The preparation of the compositions according to the this use are Zinc or antimony oxides, e.g. Sb2O, or Sb2Os. invention may be carried out either by adding or applying the 45 Boron compounds are Suitable, too. flame retardants consisting of components a) and b) accord The above-mentioned flame-retardant classes are advanta ing to the invention or, however, by adding or applying the geously contained in the composition of the invention in an individual components separately. amount from about 0.5% to about 45.0% by weight of the Preference is given to the use of components a) and b), each organic polymer substrate; for instance about 3.0% to about independently of the other, in a concentration of from 0.1 to 50 40.0%; for example about 5.0% to about 35.0% by weight of 30.0% by weight, for example from 0.2 to 20.0% by weight, the polymer. For example, the flame-retardant of component preferably from 0.2 to 15.0% by weight, based on weight of b) is employed from about 0.5% to about 10.0% by weight, the polymer base. from about 1.0% to about 10.0%, from about 3.0% to about The compositions according to the invention contain the 10.0% or from about 5.0% to about 10.0% by weight, based flame retardant consisting of components a) and b) in an 55 on the weight of the polymer Substrate. For example, compo amount of for example, from 0.1 to 50.0% by weight, pref nent b) is employed from about 0.5% to about 8.0%, from erably from 0.3 to 40.0% by weight, especially from 0.3 to about 0.5% to about 6.0%, from about 0.5% to about 5.0%, or 30.0% by weight or from 0.8 to 30.0% by weight, based on the from about 0.5% to about 3.0% by weight, based on the composition. weight of the polymer substrate. The flame-resistant polymer compositions are Suitable, 60 As mentioned above, the composition according to the inter alia, for the production of moulded articles, films, invention may additionally contain one or more conventional threads and fibres, for example by injection-moulding, extru additives, for example selected from pigments, dyes, plasti sion or compression-moulding. cizers, antioxidants, thixotropic agents, levelling assistants, Additional Components basic co-stabilizers, metal passivators, metal oxides, organo The instant invention further pertains to a composition, 65 phosphorus compounds, further light stabilizers and mixtures which comprises, in addition to the Components a), b) and c). thereof, especially pigments, phenolic antioxidants, calcium as defined above, d) further additives selected from the group stearate, zinc stearate, UV absorbers of the 2-hydroxy-ben

US 8,415,414 B2 23 24 2.6 Sterically hindered amines, for example bis(2.2.6,6-tet 2.8 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2.4.6- ramethylpiperid-4-yl)sebacate, bis(2.2.6.6-tetramethylpi tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hy perid-4-yl)Succinate, bis(1.2.2.6,6-pentamethylpiperid-4- droxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1, yl)sebacate, bis(1-octyloxy-2.2.6.6-tetramethylpiperid-4- 3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4- yl)sebacate, n-butyl-3,5-di-tert-butyl-4- 5 dimethylphenyl)-1,3,5-triazine, 2.4-bis(2-hydroxy-4- hydroxybenzylmalonic acid bis(1.2.2.6,6- propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, pentamethylpiperidyl)ester, condensation product of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphe 1-hydroxyethyl-2.2.6,6-tetramethyl-4-hydroxypiperidine nyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4, and Succinic acid, linear orcyclic condensation products of 6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy N,N'-bis(2.2.6,6-tetramethyl-4-piperidyl)hexamethylene 10 4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5- diamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triaz triazine, 2-2-hydroxy-4-(2-hydroxy-3- ine, tris(2.2.6,6-tetramethyl-4-piperidyl)nitrilotriacetate, butyloxypropyloxy)phenyl-4,6-bis(2,4-dimethylphenyl)- tetrakis(2.2.6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane 1,3,5-triazine, 2-2-hydroxy-4-(2-hydroxy-3- tetraoate, 1,1'-(1.2-ethane-diyl)bis(3,3,5,5-tetrameth octyloxypropyloxy)phenyl-4,6-bis(2,4-dimethylphenyl)- ylpiperazinone), 4-benzoyl-2.2.6.6-tetramethylpiperidine, 15 1,3,5-triazine, 2-4-(dodecyloxy/tridecyloxy-2- 4-stearyloxy-2.2.6.6-tetramethylpiperidine, bis(1.2.2.6.6- hydroxypropoxy)-2-hydroxyphenyl-4,6-bis(2,4- pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di dimethylphenyl)-1,3,5-triazine, 2-2-hydroxy-4-(2- tert-butylbenzyl)malonate, 3-n-octyl-7.7.9.9-tetramethyl hydroxy-3-dodecyloxypropoxy)phenyl-4,6-bis(2,4- 1.3.8-triazaspiro4.5 decane-2,4-dione, bis(1-octyloxy-2, dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4- 2.6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2.2, hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2- 6,6-tetramethylpiperidyl)Succinate, linear or cyclic hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, condensation products of N,N'-bis(2.2.6,6-tetramethyl-4- 2,4,6-tris 2-hydroxy-4-(3-butoxy-2-hydroxypropoxy) piperidyl)hexamethylenediamine and 4-morpholino-2,6- phenyl-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-meth dichloro-1,3,5-triazine, condensation product of 2-chloro oxyphenyl)-6-phenyl-1,3,5-triazine, 2-2-hydroxy-4-3- 4,6-di(4-n-butylamino-2,26,6-tetramethylpiperidyl)-1,3, 25 (2-ethylhexyl-1-oxy)-2-hydroxypropyloxyphenyl-4,6- 5-triazine and 1.2-bis(3-aminopropylamino)ethane, bis(2,4-dimethylphenyl)-1,3,5-triazine. condensation product of 2-chloro-4,6-di(4-n-butylamino . Metal deactivators, for example N,N'-diphenyloxalic acid 1.2.2.6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis (3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7.7.9, (salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hy 9-tetramethyl-1,3,8-triazaspiro4.5 decane-2,4-dione, 30 droxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2, 3-dodecyl-1-(2.2.6,6-tetramethyl-4-piperidyl)pyrrolidine 4-triazole, bis(benzylidene)oxalic acid dihydrazide, 2,5-dione, 3-dodecyl-1-(1.2.2.6,6-pentamethyl-4-pip oxanilide, isophthalic acid dihydrazide, sebacic acid bis eridyl)pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy phenylhydrazide, N,N'-diacetyladipic acid dihydrazide, and 4-stearyloxy-2.2.6.6-tetramethylpiperidine, conden N,N'-bis-salicyloyloxalic acid dihydrazide, N,N'-bis-sali sation product of N,N'-bis(2.2.6,6-tetramethyl-4-pip 35 cyloylthiopropionic acid dihydrazide. eridyl)hexamethylenediamine and 4-cyclohexylamino-2, . Hydroxylamines, for example N,N-dibenzylhydroxy 6-dichloro-1,3,5-triazine, condensation product of 1,2-bis lamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxy (3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5- lamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhy triazine and 4-butylamino-2.2.6.6-tetramethylpiperidine droxylamine, N,N-dihexadecylhydroxylamine, N.N- (CAS Reg. No. 136504-96-6); condensation product of 40 dioctadecylhydroxylamine, N-hexadecyl-N- 1,6-diaminohexane and 2,4,6-trichloro-1,3,5-triazine and octadecylhydroxylamine, N-heptadecyl-N- also N,N-dibutylamine and 4-butylamino-2,2.6,6-tetram octadecylhydroxylamine, N,N-dialkylhydroxylamine ethylpiperidine (CAS Reg. No. 192268-64-7); N-(2.2.6, from hydrogenated tallow fatty amines. 6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1.2, . Nitrones, for example N-benzyl-alpha-phenylnitrone, 2.6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 45 N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylni 2-undecyl-7.7.9.9-tetramethyl-1-oxa-3,8-diaza-4-oxo trone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha spiro4.5 decane, reaction product of 7.7.9.9-tetramethyl tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, 2-cycloundecyl-1-Oxa-3.8-diaza-4-oxospiro4.5 decane N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al and epichlorohydrin, 1.1-bis(1.2.2.6,6-pentamethyl-4-pi pha-heptadecylnitrone, N-octadecyl-alpha-pentadecylni peridyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'- 50 trone, N-heptadecyl-alpha-heptadecylnitrone, N-octade bis-formyl-N,N'-bis(2.2.6,6-tetramethyl-4-piperidyl)hex cyl-alpha-hexadecylnitrone, nitrones derived from N.N- amethylenediamine, diester of dialkylhydroxylamines prepared from hydrogenated 4-methoxymethylenemalonic acid with 1.2.2.6,6-pentam tallow fatty amines. ethyl-4-hydroxypiperidine, polymethylpropyl-3-oxy-4- . Thiosynergistic compounds, for example thiodipropionic (2.2.6.6-tetramethyl-4-piperidyl)siloxane, reaction prod 55 acid dilauryl ester or thiodipropionic acid distearyl ester. uct of maleic anhydride C-olefin copolymer and 2.2.6.6- . Peroxide-destroying compounds, for example esters of tetramethyl-4-aminopiperidine or 1.2.2.6,6-pentamethyl B-thio-dipropionic acid, for example the lauryl, Stearyl, 4-aminopiperidine. myristylortridecyl ester, mercaptobenzimidazole, the Zinc 2.7 Oxalic acid diamides, for example 4,4'-dioctyloxy oxa salt of 2-mercaptobenzimidazole, zinc dibutyldithiocar nilide, 2,2'-diethoxy oxanilide, 2,2'-dioctyloxy-5,5'-di 60 bamate, dioctadecyldisulphide, pentaerythritol tetrakis(B- tert-butyl oxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyl dodecylmercapto)propionate. oxanilide, 2-ethoxy-2-ethyl oxanilide, N,N'-bis(3-dim . Polyamide stabilisers, for example copper salts in combi ethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'- nation with iodides and/or phosphorus compounds and ethyl oxanilide and a mixture thereof with 2-ethoxy-2'- salts of divalent manganese. ethyl-5,4'-di-tert-butyl oxanilide, mixtures of o- and 65 . Basic co-stabilisers, for example melamine, polyvinylpyr p-methoxy- and also of o- and p-ethoxy-di-substituted oxa rolidone, dicyandiamide, triallyl cyanurate, urea deriva nilides. tives, hydrazine derivatives, amines, polyamides, polyure US 8,415,414 B2 25 26 thanes, alkali metal and alkaline earth metal salts of higher The process is preferably carried out in an extruder by fatty acids, for example calcium Stearate, Zinc Stearate, introducing the additive during processing. magnesium behenate, magnesium Stearate, sodium ricino Particularly preferred processing machines are single leate, potassium palmitate, antimony pyrocatecholate or screw extruders, contra rotating and co-rotating twin-screw Zinc pyrocatecholate. 5 extruders, planetary-gear extruders, ring extruders or co 10. Nucleating agents, for example inorganic Substances, e.g. kneaders. It is also possible to use processing machines pro talc, metal oxides, such as titanium dioxide or magnesium vided with at least one gas removal compartment to which a oxide, phosphates, carbonates or Sulphates of preferably vacuum can be applied. alkaline earth metals; organic compounds, such as mono Suitable extruders and kneaders are described, for or poly-carboxylic acids and their salts, e.g. 4-tert-butyl 10 benzoic acid, adipic acid, diphenylacetic acid, Sodium Suc example, in Handbuch der Kunststoffextrusion, Vol. 1 Grund cinate or Sodium benzoate; polymeric compounds, for lagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. example ionic copolymerisates (ionomers'). Special 3-7, ISBN: 3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, preference is given to 1.3:2.4-bis(3',4'-dimethylben ISBN 3-446-14329-7). Zylidene)sorbitol, 1.3:2,4-di(paramethyldibenzylidene) 15 For example, the screw length is 1-60 screw diameters, sorbitol and 1.3:2,4-di(benzylidene)sorbitol. preferably 35-48 screw diameters. The rotational speed of the 11. Fillers and reinforcing agents, for example calcium car screw is preferably 10-600 rotations per minute (rpm), very bonate, silicates, glass fibres, glass beads, talc, kaolin, particularly preferably 25-300 rpm. mica, barium Sulphate, metal oxides and hydroxides, car The maximum throughput is dependent on the screw diam bon black, graphite, wood powders, and powders and fibres eter, the rotational speed and the driving force. The process of of other natural products, synthetic fibres. the present invention can also be carried out at a level lower 12. Benzofuranones and indolinones, for example as than maximum throughput by varying the parameters men described in U.S. Pat. No. 4,325,863: U.S. Pat. No. 4,338, tioned or employing weighing machines delivering dosage 244: U.S. Pat. No. 5,175,312, U.S. Pat. No. 5,216,052; U.S. amountS. Pat. No. 5,252,643; DE-A-4 316 611; DE-A-4 316 622; 25 If a plurality of components is added, these can be pre DE-A-4 316876; EP-A-0589 839 or EP-A-0591 102, or mixed or added individually. 3-4-(2-acetoxyethoxy)phenyl-5,7-di-tert-butyl-benzofu The additives components a) and b) and optional further ran-2-one, 5,7-di-tert-butyl-3-4-(2-stearoyloxyethoxy) additives can also be sprayed onto the polymer Substrate c). phenylbenzofuran-2-one, 3,3'-bis(5,7-di-tert-butyl-3-(4- The additive mixture dilutes other additives, for example the 2-hydroxyethoxyphenyl)benzofuran-2-one, 5,7-di-tert 30 conventional additives indicated above, or their melts so that butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4- they can be sprayed also together with these additives onto the acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl polymer substrate. Addition by spraying during the deactiva benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxy tion of the polymerisation catalysts is particularly advanta phenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4- geous; in this case, the steam evolved may be used for deac dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 35 tivation of the catalyst. In the case of spherically polymerised 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2- polyolefins it may, for example, be advantageous to apply the OC. additives of the invention, optionally together with other 13. Anti-gas fading agents, for example 1,1,1,1-tetramethyl additives, by spraying. 4,4'-(methylene-di-p-phenylene)disemicarbazide; 1,6- The additive components a) and b) and optional further hexamethylene bis(N,N-dimethylsemicarbazide); 11-6- 40 additives can also be added to the polymer in the form of a (2,2-dimethylhydrazino)carbonyl)aminohexyl)-10,12 master batch ("concentrate”) which contains the components dioxo-bis(2,2-dimethylhydrazide). in a concentration of for example, about 1.0% to about 40.0% 14. Other additives, for example plasticisers, lubricants, and preferably 2.0% to about 20.0% by weight incorporated emulsifiers, pigments, rheology additives, catalysts, flow in a polymer. The polymer is not necessarily of identical improvers, optical brighteners, antistatics, blowing agents. 45 structure than the polymer where the additives are added The further additives of Component c) are added, for finally. In Such operations, the polymer can be used in the example, in concentrations of 0.01 to 10.0%, relative to the form of powder, granules, Solutions, and Suspensions or in the total weight of the composition of this invention. form of lattices. The incorporation of the additive components a) and b) and Incorporation can take place prior to or during the shaping optional further components into the polymer component c) 50 operation. The materials containing the additives of the inven is carried out by known methods such as dry blending in the tion described herein preferably are used for the production of form of a powder, or wet mixing in the form of Solutions, molded articles, for example roto-molded articles, injection dispersions or Suspensions for example in an inert Solvent, molded articles, profiles and the like, and especially a fiber, water or oil. The additive components a) and b) and optional spun melt non-woven, film or foam. further additives may be incorporated, for example, before or 55 Thus, present invention further pertains to a molded or after molding or also by applying the dissolved or dispersed extruded article, a fiber, spun melt non-woven or a foam additive or additive mixture to the polymer material, with or comprising the composition of the invention. without Subsequent evaporation of the solvent or the Suspen A particularly preferred embodiment of the invention sion/dispersion agent. They may be added directly into the relates to a composition, which comprises processing apparatus (e.g. extruders, internal mixers, etc.), 60 a) At least one ester derivative of phosphonous and phospho e.g. as a dry mixture or powder, or as a solution or dispersion rous acid; or Suspension or melt. b) Melamine cyanurate; and The addition of the additive components to the polymer c) A polyurethane polymer base. Substrate c) can be carried out in all customary mixing Another particularly preferred embodiment of the inven machines in which the polymer is melted and mixed with the 65 tion relates to a composition, which comprises additives. Suitable machines are known to those skilled in the a) At least one at least one ester derivative of phosphonous and art. They are predominantly mixers, kneaders and extruders. phosphorous acid selected from the group consisting of

US 8,415,414 B2 29 30 -continued CH3 HC-C-CH O P-OCHCH: H3C Y. CH HC1 \ 3 CH 2 b) Melamine cyanurate; and -continued c) A polyurethane polymer base. 15 CH3 A particularly preferred embodiment of the invention relates to a composition, which comprises HC-C-CH a) At least one ester derivative of phosphonous and phospho O P-OCH2CH: rous acid selected from the group consisting of H3C V - CH H3C CH3

b) Melamine cyanurate; and c) A polyurethane polymer base. 30 Another preferred embodiment of the invention relates to a composition, which comprises a) At least one ester derivative of phosphonous and phospho rous acid selected from the group consisting of tris non 35 ylphenyl phosphite (TNPP), triphenyl phosphite (TPP), diphenyl phosphite (DPP), phenyl diisodecyl phosphite (PDDP), diphenyl isodecyl phosphite (DPDP), diphenyl isooctyl phosphite (DPIOP), tetraphenyl dipropylene gly col diphosphite (THOP), poly (dipropylene glycol) phenyl C(CH3)3 40 phosphite (DHOP), dodecyl diphenyl phosphite (DDPP), (CH3)3C triisodecylphosphite (TDP), tris tridecyl phosphite (TTDP) and trilauryl phosphite (TLP): O V b) Melamine cyanurate; and P s / 45 c) A polyurethane polymer base. O Another particularly preferred embodiment of the inven tion relates to a composition, which comprises C(CH3)3 a) At least one ester derivative of phosphonous or phospho 2 50 rous acid selected from the group consisting of 9,10-dihy O O dro-9-Oxa-10-phosphorylphenanthrene-10-oxide O-P P-O (DOPO), bis(2,6-di-tert-butyl-4-methylphenyl)-pen V A s O O taerythritol diphosphite CAS RN80693-00-1), (CHs O )P( O CH). CAS RN57077-45-9), (CHs 55 O—)P( OCHs)(CH, O—P). CAS RN 67383 C(CH3)3 (CH3)3C 54-4 and triphenyl phosphite; O O M V b) Melamine cyanurate; and H3C O-P P-O CH3, c) A polyurethane polymer base O O 60 A further embodiment of the invention relates to a process C(CH3)3 (CH3)3C for imparting flame retardancy to a polyurethane polymer base, which process comprises adding to said polymer base a mixture, which comprises 65 a) At least one ester derivative of a phosphorus containing oxo acid selected from the group consisting of oxaphosphori noxide, phosphonous acid and phosphorous acid; and US 8,415,414 B2 31 32 b) At least one flame retardant component based on a nitrogen EXAMPLE 3 compound. The following examples illustrate the invention: Materials and Methods 4 kg of polyester thermoplastic polyurethane (TPU) pellets EXAMPLE1 (EstaneR 583 11 Natural 028 P) are mixed to homogeneity in a tumble mixer with different concentrations bis(2,4-di-tert Materials and Methods butylphenyl)pentaerythritol diphosphite (IRGAFOS 126), 4 kg of polyester thermoplastic polyurethane (TPU) pellets different concentrations of melamine cyanurate (MELAPUR (EstaneR GP 72 DB NAT 021 P (Noveon(R) are mixed to MC 25) and the test compounds mentioned in Table 3 and 1% homogeneity in a tumble mixer with 5-10% bis(2,4-di-tert 10 pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphe butylphenyl)pentaerythritol diphosphite (IRGAFOS 126), nyl)propionate (IRGANOX 1066). This blend is com 25% melamine cyanurate (MELAPUR MC 25) and pen pounded in twin-screw extruder (BerstorffR) at a temperature taerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) up to 220° C. The extrudate is granulated after drawing propionate (IRGANOX 1066). This blend is compounded in through a water bath and cooling. twin-screw extruder (BerstorffR) at a temperature up to 220 15 Injection molding and testing for flame retardancy are car C. The extrudate is granulated after drawing through a water ried out in a manner analogous to Example 1. bath and cooling. Results 125mmx13 mmx1.6 mm test panels are moulded from the granules formed by means of an injection-moulding machine TABLE 3 (Arburg R 320 S) at a temperature up to 220° C. (mold tem Test No Amounts Components UL94 rating perature: 50° C.). The samples are tested for flame retardancy by the UL94V thick section test (Underwriter's Laboratories UL94 Flam 25 RMC 25 mability Test: UL94 Test for Flammability of Plastic Materi 59% als for parts in Devices and Appliances, 5" Edition, 1996). 5 25% RMC 25 W-O Results 7.5% 6 30% RMC 25 W-O TABLE 1. 59% 30 7 30% RMC 25 W-O Test No. Amounts 96 Components UL94 rating) 7.5% 8 30% RMC 25 W-O 1 25 MELAPURMC 25 V-2 O% 2 25 MELAPURMC 25 W-O 9 3596. MELAPURMC 25 W-O 5 IRGAFOS 126 59% DOPO 3 25 MELAPURMC 25 W-O 35 O 3596. MELAPURMC 25 W-O 10 IRGAFOS 126 O% DOPO 30:6 MEEEAPERME:2S WO *)V-0: Very good; V-1: Good; V-2: Not sufficient 7:59: AEKSEABPEP-36 2 25% MELAPURMC 25 W-O O% THOP 3 30% MELAPURMC 25 W-O EXAMPLE 2 40 O% THOP A. 25.9% MEEAPERMC.25 VG Materials and Methods 75% EDHOP 4 kg of polyester thermoplastic polyurethane (TPU) pellets S 3.09% NAEEAPRMC.25 WC (EstaneR 583 11 Natural 028 P) are mixed to homogeneity in 9% OHOP 6. 35% MEEEAPERME:2S WO a tumble mixer with different concentrations bis(2,4-di-tert 45 0% BEOR butylphenyl)pentaerythritol diphosphite (IRGAFOS 126), 7 3596. MELAPURMC 25 W-O different concentrations of melamine cyanurate (MELAPUR O% TPP MC 25) and 1% pentaerythritol tetrakis 3-(3,5-di-tert-butyl 4-hydroxyphenyl)propionate (IRGANOX 1066).This blend (VO = Very Good, V1 = Good, V2 = Not Sufficient) is compounded in twin-screw extruder (BerstorffR) at a tem 50 perature up to 220°C. The extrudate is granulated after draw ing through a water bath and cooling. The invention claimed is: Injection molding and testing for flame retardancy are car 1. A composition which comprises ried out in a manner analogous to Example 1. a) at least one ester derivative of Oxaphosphorinoxide, Results 55 b) melamine cyanurate and c) a polyurethane polymer base. TABLE 2 2. A composition according to claim 1, which comprises a) 9,10-dihydro-9-Oxa-10-phosphorylphenanthrene-10 Test No. Amounts 96 Components UL94 rating) oxide (DOPO), 1 30 MELAPURMC 25 V-2 60 b) melamine cyanurate and 30 MELAPURMC 25 W-O 7.5 IRGAFOS 126 c) a polyurethane polymer base. 3 35 MELAPURMC 25 W-O 3. A process for imparting flame retardancy to a polyure 7.5 IRGAFOS 126 thane polymer base, which process comprises adding to said 4 28 MELAPURMC 25 W-O 65 polymer base a mixture which comprises 7.0 IRGAFOS 126 a) at least one ester derivative of oxaphosphorinoxide and b) melamine cyanurate. US 8,415,414 B2 33 34 4. A composition comprising a) tetraphenyl dipropylene glycol diphosphite(THOP) or poly (dipropylene glycol) phenyl phosphite (DHOP), b) melamine cyanurate and c) a polyurethane polymer base. 5. A process for imparting flame retardancy to a polyure thane polymer base, which process comprises adding to said polymer base a mixture which comprises a) tetraphenyl dipropylene glycol diphosphite(THOP) or poly (dipropylene glycol) phenyl phosphite (DHOP) 10 and b) melamine cyanurate.

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