CA2501384A1

CA2501384A1 - Flame retardant compositions

Info

Publication number: CA2501384A1
Application number: CA002501384A
Authority: CA
Inventors: Nikolas Kaprinidis; Nicola Lelli
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 2002-10-17
Filing date: 2003-10-09
Publication date: 2004-04-29
Anticipated expiration: 2023-10-09
Also published as: EP1554336B1; MY136645A; AU2003282026A1; WO2004035671A1; TW200512279A; EP1554336A1; US20040097620A1; JP4490276B2; CN100439434C; ATE462749T1; DE60331938D1; ES2342054T3; KR101010588B1; US7109260B2; CN1705705A; TWI291478B; KR20050083756A; CA2501384C; JP2006503138A

Abstract

Organic polymeric substrates, for example polyolefins such as polypropylene, can be made flame retardant by the incorporation of a synergistic mixture of (i) at least one sterically hindered amine stabilizer, (ii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorous containing, isocyanurate and melamine based flame retardants and (iii) at least one acid scavenger. The compositions of the invention combine good flame retardant properties with light stability and good mechanical properties. Polyolefin molded articles are stabilized against light, heat and oxygen and made flame retardant with the incorporation of at least one sterically hindered amine and at least one conventional flame retardant, while allowing normally high levels of flame-retardant fillers to be greatly reduced or eliminated.

Claims

1. A flame retardant polymer composition which comprises (a) an organic polymer substrate and (b) an effective flame retarding amount of a synergistic mixture of (i) at least one sterically hindered amine stabilizer and (ii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorus containing, isocyanurate and melamine based flame retardants and (iii) at least one acid scavenger.

2. A composition according to claim 1 containing no filler or a filler in an amount less than about 3% by weight based on the weight of the polymer component (a).

3. A composition according to claim 1 containing no antimony or antimony com-pounds in an amount less than about 1 % by weight based on the weight of component (a).

4. A composition according to claim 1 in which the polymer component (a) is a thermoplastic polymer.

5. A composition according to claim 1 in which the polymer component (a) is selected from the group of resins consisting of the polyolefins, the thermoplastic polyolefins, styrenic polymers and copolymers, ABS and polymers which contain hetero atoms, double bonds or aromatic rings.

6. A composition according to claim 1 in which the stabilizer of component (i) is of the formula where G1 and G2 are independently alkyl of 1 to 8 carbon atoms or are together pentamethylene, Z1 and Z2 are each methyl, or Z1 and Z2 together form a linking moiety which may additionally be substituted by an ester, ether, amide, amino, carboxy or urethane group, and E is oxyl, hydroxyl, alkoxy, cycloalkoxy, aralkoxy, aryloxy, -O-CO-OZ3, -O-Si(Z4)3, -O-PO(OZ5)2 or -O-CH2-OZ6 where Z3, Z4, Z5 and Z6 are selected from the group consisting of hydrogen, an aliphatic, araliphatic and aromatic moiety; or E is -O-T-(OH)b, T is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 carbon atoms; and b is 1, 2 or 3 with the proviso that b cannot exceed the number of carbon atoms in T, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atoms of T.

7. A composition according to claim 6 in which the stabilizer of component (i) is one of formula A-R

wherein E is oxyl, hydroxyl, alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or aralkoxy of 7 to 15 carbon atoms, or E is -O-T-(OH)b, T is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the proviso that b cannot exceed the number of carbon atoms in T, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atoms of T;
R is hydrogen or methyl, m is 1 to 4, when m is 1, R2 is hydrogen, C1-C18alkyl or said alkyl optionally interrupted by one or more oxygen atoms, C2-C12alkenyl, C6-C10aryl, C7-C18aralkyl, glycidyl, a monovalent acyl radical of an aliphatic,cycloaliphatic or aromatic carboxylic acid, or a carbamic acid, of a cycloaliphatic carboxylic acid having 5-12 C atoms or of an aromatic carboxylic acid having 7-15 C atoms, or wherein x is 0 or 1, wherein y is 2-4;
when m is 2, R2 is C1-C12alkylene, C4-C12alkenylene, xylylene, a divalent acyl radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid or of a dicarbamic acid, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C atoms;
wherein D, and D2 are independently hydrogen, an alkyl radical containing up to 8 carbon atoms, an aryl or aralkyl radical including 3,5-di-t-butyl-4-hydroxybenzyl radical, D3 is hydrogen, or an alkyl or alkenyl radical containing up to 18 carbon atoms, and d is 0-20;
when m is 3, R2 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic tricarboxylic acid;

when m is 4, R2 is a tetravalent acyl radical of a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid including 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-ene-tetracarboxylic , and 1,2,3,5- and 1,2,4,5-pentanetetracarboxylic acid;
p is 1, 2 or 3, R3 is hydrogen, C1-C12alkyl, C5-C7cycloalkyl, C7-C9aralkyl, C2-C18alkanoyl, C3-C5alkenoyl or benzoyl;
when p is 1, R4 is hydrogen, C1-C18alkyl, C5-C7cycloalkyl, C2-C8alkenyl, unsubstituted or substituted by a cyano, carbonyl or carbamide group, aryl, aralkyl, or it is glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; or a group of the formulae or where h is 0 or 1, R3 and R4 together, when p is 1, can be alkylene of 4 to 6 carbon atoms or 2-oxo-polyalkylene the cyclic acyl radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid, when p is 2, R4 is a direct bond or is C1-C12alkylene, C6-C12arylene, xylylene, a -CH2CH(OH)-CH2 group or a group -CH2-CH(OH)-CH2-O-X-O-CH2-CH(OH)-CH2- wherein X is C2-C10alkylene, C6-C15arylene or C6-C12cycloalkylene; or, provided that R3 is not alkanoyl, alkenoyl or benzoyl, R4 can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can be the group -CO-; or R4 is where T8 and T9 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T8 and T9 together are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene;
when p is 3, R4 is 2,4,6-triazinyl, n is 1 or 2, when n is 1, R5 and R'5 are independently C1-C12 alkyl, C2-C12 alkenyl, C7-C12 aralkyl, or R5 is also hydrogen, or R5 and R'5 together are C2-C6alkylene or hydroxyalkylene or C4-C22acyloxyalkylene;
when n is 2, R5 and R'5 together are (-CH2)2C(CH2-)2;
R6 is hydrogen, C1-C12alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl;
when n is 1, R7 is hydrogen, C1-C12alkyl, C3-C5alkenyl, C7-C9aralkyl, C5-C7cycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C10 aryl, glycidyl, a group of the formula -(CH2)t-COO-Q
or of the formula -(CH2)t-O-CO-Q wherein t is 1 or 2, and Q is C1-C4alkyl or phenyl; or when n is 2, R7 is C2-C12alkylene, C6-C12arylene, a group -CH2CH(OH)-CH2-O-X-O-CH2-CH(OH)-CH2- wherein X is C2-C10alkylene, C6-C15arylene or C6-C12cycloalkylene, or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- wherein Z' is hydrogen, C1-C18alkyl, allyl, benzyl, C2-C12alkanoyl or benzoyl;
Q1 is -N(R8)- or -O-; E, is C1-C3 alkylene, the group -CH2-CH(R9)-O- wherein R9 is hydrogen, methyl or phenyl, the group -(CH2)3-NH- or a direct bond;

R10 is hydrogen or C1-C18 alkyl, R8 is hydrogen, C1-C18alkyl, C5-C7cycloalkyl, C12aralkyl, cyanoethyl, C6-C10aryl, the group -CH2-CH(R9)-OH wherein R9 has the meaning defined above; a group of the formula or a group of the formula wherein G4 is C2-C6alkylene or C6-C12arylene; or R8 is a group -E7-CO-NH-CH2-OR10;
Formula F denotes a recurring structural unit of a polymer where T3 is ethylene or 1,2-propylene, is the repeating structural unit derived from an alpha-olefin copolymer with an alkyl acrylate or methacrylate; and where k is 2 to 100;
T4 has the same meaning as R4 when p is 1 or 2, T5 is methyl, T6 is methyl or ethyl, or T5 and T6 together are tetramethylene or pentamethylene, M and Y are independently methylene or carbonyl, and T4 is ethylene where n is 2;
T7 is the same as R7, T10 and T11 are independently alkylene of 2 to 12 carbon atoms, or T11 is T12 is piperazinyl, -NR11-(CH2)d-NR11- or where R11 is the same as R3 or is also a, b and c are independently 2 or 3, and f is 0 or 1; and e is 2, 3 or 4;
T13 is the same as R2 with the proviso that T13 cannot be hydrogen when n is 1;

E, and E2, being different, each are -CO- or -N(E5)- where E5 is hydrogen, C1-alkyl or C4-C22 alkoxycarbonylalkyl, E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, said phenyl or said naphthyl substituted by chlorine or by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or said phenylalkyl substituted by alkyl of 1 to 4 carbon atoms, E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or E3 and E4 together are polymethylene of 4 to 17 carbon atoms, or said polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms, E6 is an aliphatic or aromatic tetravalent radical, R2 of formula (N) is a previously defined when m is 1;
G1 a direct bond, C1-C12 alkylene, phenylene or -NH-G'-NH wherein G' is C1-C12 alkylene; or wherein the hindered amine compound is a compound of the formula I, II, III, IV, V, VI, VII, VIII, IX, X or XI
wherein E1, E2, E3 and E4 are independently alkyl of 1 to 4 carbon atoms, or E1 and E2 are independently alkyl of 1 to 4 carbon atoms and E3 and E4 taken together are pentamethylene, or E1 and E2; and E3 and E4 each taken together are pentamethylene, R1 is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, a bicyclic or tricyclic hydrocarbon radical of 7 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 8 carbon atoms, R2 is hydrogen or a linear or branched chain alkyl of 1 to 12 carbon atoms, R3 is alkylene of 1 to 8 carbon atoms, or R3 is -CO-, -CO-R4-, -CONR2-, or -CO-R4 is alkylene of 1 to 8 carbon atoms, R5 is hydrogen, a linear or branched chain alkyl of 1 to 12 carbon atoms, or or when R4 is ethylene, two R5 methyl substituents can be linked by a direct bond so that the triazine bridging group -N(R5)-R4-N(R5)- is a piperazin-1,4-diyl moiety, R6 is alkylene of 2 to 8 carbon atoms or R6 is with the proviso that Y is not -OH when R6 is the structure depicted above, A is -O- or -NR7-where R7 is hydrogen, a straight or branched chain alkyl of 1 to 12 carbon atoms, or R7 is T is phenoxy, phenoxy substituted by one or two alkyl groups of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms or -N(R2)2 with the stipulation that R2 is not hydrogen, or T is X is -NH2, -NCO, -OH, -O-glycidyl, or -NHNH2, and Y is -OH, -NH2, -NHR2 where R2 is not hydrogen; or Y is -NCO, -COOH, oxiranyl, -O-glycidyl, or -Si(OR2)3; or the combination R3-Y- is -CH2CH(OH)R2 where R2 is alkyl or said alkyl interrupted by one to four oxygen atoms, or R3-Y- is -CH2OR2;
or wherein the hindered amine compound is a mixture of N,N',N"'-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine;
N,N',N"-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine, and bridged derivatives as described by formulas I, II, IIA and III

R1NH-CH2CH2CH2NR2CH2CH2NR3CH2CH2CH2NHR4 (I) T-E1-T, (II) T-E1 (IIA) G-E1-G1-E1-G2 (III) where in the tetraamine of formula I

R1 and R2 are the s-triazine moiety E; and one of R3 and R4 is the s-triazine moiety E
with the other of R3 or R4 being hydrogen, E is R is methyl, propyl, cyclohexyl or octyl, R5 is alkyl of 1 to 12 carbon atoms, where in the compound of formula II or IIA when R is propyl, cyclohexyl or octyl, T and T1 are each a tetraamine substituted by R1-R4 as is defined for formula I, where (1) one of the s-triazine moieties E in each tetraamine is replaced by the group E1 which forms a bridge between two tetraamines T and T1, E1 is or (2) the group E1 can have both termini in the same tetraamine T as in formula IIA
where two of the E moieties of the tetraamine are replaced by one E1 group, or (3) all three s-triazine substituents of tetraamine T can be E, such that one E1 links T
and T1 and a second E1 has both termini in tetraamine T, - L is propanediyl, cyclohexanediyl or octanediyl;

where in the compound of formula III

G, G1 and G2 are each tetraamines substituted by R1-R4 as defined for formula I, except that G and G2 each have one of the s-triazine moieties E replaced by E1, and G1 has two of the triazine moieties E replaced by E1, so that there is a bridge between G
and G1 and a second bridge between G1 and G2;

which mixture is prepared by reacting two to four equivalents of 2,4-bis[(1-hydrocarbyl-oxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine with one equivalent of N,N'-bis(3-aminopropyl)ethylenediamine;
or the hindered amine is a compound of the formula IIIb in which the index n ranges from 1 to 15;
R12 is C2-C12alkylene, C4-C12alkenylene, C5-C7cycloalkylene, C5-C7cycloalkylene-di(C1-C4alkylene), C1-C4alkylenedi(C5-C7cycloalkylene), phenylenedi(C1-C4alkylene) or C4-C12alkylene interrupted by 1,4-piperazinediyl, -O- or > N-X, with X1 being C1-C12acyl or -(C1-C12alkoxy)carbonyl or having one of the definitions of R14 given below except hydrogen;
or R12 is a group of the formula (Ib') or (Ic');
with m being 2 or 3, X2 being C1-C18alkyl, C5-C12cycloalkyl which is unsubstituted or substituted by 1, 2 or C1-C4alkyl; phenyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl or C1-C4alkoxy; C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; and the radicals X3 being independently of one another C2-C12alkylene;
R13, R14 and R15, which are identical or different, are hydrogen, C1-C16alkyl, C12cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl;
C3-C18alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl or C1-C4alkoxy; C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl;
tetrahydrofurfuryl or C2-C4alkyl which is substituted in the 2, 3 or 4 position by -OH, C1-C8alkoxy, di(C1-C4alkyl)amino or a group of the formula (Ie');
with Y being -O-, -CH2-, -CH2CH2- or > N-CH3, or -N(R14)(R15) is additionally a group of the formula (Ie');
the radicals A are independently of one another -OR13, -N(R14)(R15) or a group of the formula (IIId);

X is -O- or > N-R16;
R16 is hydrogen, C1-C18alkyl, C3-C16alkenyl, C5-C12cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl; C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; tetrahydrofurfuryl, a group of the formula (IIIf), or C2-C4alkyl which is substituted in the 2, 3 or 4 position by -OH, C1-C8alkoxy, di(C1-C4alkyl)amino or a group of the formula (Ie');
R11 has one of the definitions given for R16; and the radicals B have independently of one another one of the definitions given for A.

8. A composition according to claim 7 wherein the stabilizer of component (i) is selected from the group consisting of 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxy-ethylamino-s-triazine;
bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate;
2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine;
1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine;
1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine;

1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate;
2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butyl-amino}-6-(2-hydroxyethylamino)-s-triazine;
the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-butylamino]-6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine) and the compound of formula in which n is from 1 to 15.

9. A composition according to claim 1 in which the stabilizer of component (i) are present from about 0.05% to about 20% by weight based on the polymer substrate (a).

10. A composition according to claim 1 in which the conventional flame retardant of component (ii) is selected from the group consisting of chloroalkyl phosphate esters, tris(2-chloroethyl)phosphate, polybrominated diphenyl oxide, decabromodiphenyl oxide, tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl)phosphate, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, bis-(N,N'-hydroxyethyl)tetrachlorphenylene diamine, poly-.beta.-chloroethyl triphosponate mixture, tetrabromobisphenol A bis(2,3-dibromopropyl) ether, brominated epoxy resin, ethylene-bis(tetrabromophthalimide), bis(hexachlorocyclopentadieno)cyclooctane, chlorinated paraffins, octabromodiphenyl ether, hexachlorocyclopentadiene derivatives, 1,2-bis(tribromophenoxy)ethane, tetrabromo-bisphenol A, ethylene bis-(dibromo-norbornanedicarboximide), bis-(hexachlorocyclopentadieno) cyclooctane, PTFE
tris-(2,3-dibromopropyl)-isocyanurate, and ethylene-bis-tetrabromophthalimide, tetraphenyl resorcinol diphosphite, triphenyl phosphate, trioctyl phosphate, tricresyl phosphate, tetrakis(hydroxymethyl)phosphonium sulfide, diethyl-N,N-bis(2-hydroxyethyl)-aminomethyl phosphonate, hydroxyalkyl esters of phosphorus acids, ammonium polyphosphate, resorcinol diphosphate oligomer, phosphazene flame retardants, ethylenediamine diphosphate, polyisocyanurate, esters of isocyanuric acid, isocyanurates, hydroxyalkyl isocyanurates, melamine cyanurate, melamine borate, melamine phosphates, melamine polyphosphates and melamine pyrophosphates.

11. A composition according to claim 1 in which the conventional flame retardant of component (ii) is present in an amount from about 0.5% to about 45% by weight based on the polymeric substrate (a).

12. A composition according to claim 1 in which the acid scavenger of component (iii) is selected from the group consisting of hydrotalcites and amorphous basic aluminum magnesium carbonates.

13. A composition according to claim 1 in which the acid scavenger of component (iii) is present from about 0.1% to about 1.0% by weight based on component (a).

14. A composition according to claim 1 comprising a further component selected from the group consisting of pigments, dyes, plasticizers, phenolic antioxidants, thixotropic agents, levelling assistants, basic costabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, UV absorbers, further sterically hindered amines, metal passivators, metal oxides, organophosphorus compounds, hydroxylamines, and mixtures thereof; especially phenolic antioxidants, calcium stearate, zinc stearate, phosphite and phosphonite stabilizers, benzofuranone stabilizers, UV absorbers of the 2-(2'-hydroxyphenyl)benzotriazole, the hydroxybenzophenones and the 2-(2-hydroxyphenyl)-1,3,5-triazine classes, and further sterically hindered amines.

15. A flame retardant additive combination comprising (i) at least one sterically hindered amine stabilizer and (ii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorus containing, isocyanurate and melamine based flame retardants and (iii) at least one acid scavenger, as of component (b) of claim 1.

16. A process for imparting light stability and flame retardancy to an organic polymer substrate, which process comprises adding to said polymer substrate the flame retardant additive combination of claim 15.

17. A composition according to claim 1, which is a molded polymer article, preferably a construction article selected from the group consisting of roofing membranes, window profiles, siding and moldings.

18. Use of the flame retardant additive combination of claim 15 for imparting light stability and flame retardancy to an organic polymer substrate or molded polymer article.