CA2467711A1 - Flame retardant compositions - Google Patents
Flame retardant compositions Download PDFInfo
- Publication number
- CA2467711A1 CA2467711A1 CA002467711A CA2467711A CA2467711A1 CA 2467711 A1 CA2467711 A1 CA 2467711A1 CA 002467711 A CA002467711 A CA 002467711A CA 2467711 A CA2467711 A CA 2467711A CA 2467711 A1 CA2467711 A1 CA 2467711A1
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- group
- hydrogen
- alkyl
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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 low molecular weight sterically hindered alkoxyamine stabilizer, (ii) at least one high molecular weight sterically hindered alkoxyamine stabilizer and (iii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorus containing and melamine based flame retardants. 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 alkoxyamine and at least one conventional flame retardant, while allowing normally high levels of flame-retardant fillers to be greatly reduced or eliminated.
Claims (20)
1. A flame retardant composition which comprises (A) an organic polymer substrate and (B) an effective flame retarding amount of a synergistic mixture of (i) at least one low molecular weight sterically hindered alkoxyamine stabilizer, (ii) at least one high molecular weight sterically hindered alkoxyamine stabilizer and (iii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorus containing and melamine based flame retardants.
2. A composition according to claim 1 containing no antimony compounds or antimony compounds in an amount less than about 1% by weight based on the weight of the polymer component (A).
3. A composition according to claim 1 containing no flame-retardant filler or a flame-retardant filler in an amount less than about 3% by weight based on the weight of the polymer component (A).
4. A composition according to claim 1 in which the organic polymer substrate (A) is a thermoplastic polymer.
5. A composition according to claim 1 in which the stabilizers of component (i) have a molecular weight ranging from 200 to 1000 glmol and the stabilizers of component (ii) have a molecular weight ranging from 1200 to 10000 g/mol.
6. A composition according to claim 1 in which the stabilizers of component (i) and (ii) are 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 stabilizers of components (i) and (ii) conform to formulae 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, for example an acyl radical of an aliphatic carboxylic acid having 2-18 C atoms, 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, for example an acyl radical of an aliphatic dicarboxylic acid having 2-18 C atoms, 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 D1 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 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, for instance T8 and T9 together are 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, C2-C12 aralkyl, or R5 is also hydrogen, or R5 and R'5 together are C2-C8alkylene 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-C12alkylene, C6-C15arylene or C6-C12cycloalkylene, or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- wherein Z' is hydrogen, C1-C15alkyl, allyl, benzyl, C2-C12alkanoyl or benzoyl;
Q1 is -N(R8)- or -O-; E7 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; for example a copolymer of ethylene and ethyl acrylate, 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, for instance T5 and T6 are each methyl, M and Y are independently methylene or carbonyl, and T4 is ethylene where n is 2;
T7 is the same as R7, and T7 is for example octamethylene where n is 2, 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, for instance a and c are each 3, b is 2 and f is 1; and e is 2, 3 or 4, for example 4;
T13 is the same as R2 with the proviso that T13 cannot be hydrogen when n is 1;
E1 and E2, being different, each are -CO- or -N(E5)- where E5 is hydrogen, C1-alkyl or C4-C22 alkoxycarbonylalkyl, for instance E1 is -CO- and E2 is -N(E5)-, 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, for example methyl, 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-T1 (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, for instance cyclohexyl, R5 is alkyl of 1 to 12 carbon atoms, for example n-butyl, where in the compound of formula II or IIA when R is propyl, cyclohexyl or octyl, T and Ti 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 E1 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-piperidin-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-X1 with X1 being C1-C12acyl or (C1-Cl2alkoxy)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 3 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;
R13a R14 and R15, which are identical or different, are hydrogen, C1-C18alkyl, 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 (le');
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-C18alkenyl, 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.
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, for example an acyl radical of an aliphatic carboxylic acid having 2-18 C atoms, 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, for example an acyl radical of an aliphatic dicarboxylic acid having 2-18 C atoms, 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 D1 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 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, for instance T8 and T9 together are 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, C2-C12 aralkyl, or R5 is also hydrogen, or R5 and R'5 together are C2-C8alkylene 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-C12alkylene, C6-C15arylene or C6-C12cycloalkylene, or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- wherein Z' is hydrogen, C1-C15alkyl, allyl, benzyl, C2-C12alkanoyl or benzoyl;
Q1 is -N(R8)- or -O-; E7 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; for example a copolymer of ethylene and ethyl acrylate, 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, for instance T5 and T6 are each methyl, M and Y are independently methylene or carbonyl, and T4 is ethylene where n is 2;
T7 is the same as R7, and T7 is for example octamethylene where n is 2, 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, for instance a and c are each 3, b is 2 and f is 1; and e is 2, 3 or 4, for example 4;
T13 is the same as R2 with the proviso that T13 cannot be hydrogen when n is 1;
E1 and E2, being different, each are -CO- or -N(E5)- where E5 is hydrogen, C1-alkyl or C4-C22 alkoxycarbonylalkyl, for instance E1 is -CO- and E2 is -N(E5)-, 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, for example methyl, 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-T1 (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, for instance cyclohexyl, R5 is alkyl of 1 to 12 carbon atoms, for example n-butyl, where in the compound of formula II or IIA when R is propyl, cyclohexyl or octyl, T and Ti 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 E1 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-piperidin-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-X1 with X1 being C1-C12acyl or (C1-Cl2alkoxy)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 3 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;
R13a R14 and R15, which are identical or different, are hydrogen, C1-C18alkyl, 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 (le');
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-C18alkenyl, 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 5 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-piperidin-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;
and 2,4-bis(N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butyl-amino}-6-(2-hydroxyethylamino)-s-triazine;
and the stabilizer of component (ii) is selected from the group consisting of the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-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.
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-piperidin-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;
and 2,4-bis(N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butyl-amino}-6-(2-hydroxyethylamino)-s-triazine;
and the stabilizer of component (ii) is selected from the group consisting of the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-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 stabilizers of components (i) and (ii), in total, are present in an amount from 0.05 to 20 % by weight based on the polymer substrate (A).
10. A composition according to claim 9 in which components (i) and (ii) are present in a weight ratio (i):(ii) of from 1:100 to 100:1.
11. A composition according to claim 1 in which component (iii) is present in an amount from 0.5 to 45 % by weight based on the polymeric substrate (A).
12. A composition according to claim 1 in which the flame retardants of component (iii) are selected from the group consisting of chloroalkyl phosphate esters, polybrominated diphenyl oxide, decabromodiphenyl oxide, tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, bis(2,3-dibromopropyl ether) of bisphenol A, brominated epoxy resin, ethylene-bis(tetrabromophthalimide), bis(hexachlorocyclopentadieno)cyclooctane, chlorinated paraffins, 1,2-bis(tribromophenoxy)ethane, tetrabromo-bisphenol A, ethylene bis-(dibromo-norbornanedicarboximide), bis-(hexachlorocyclopentadieno) cyclooctane, tris-(2,3-dibromopropyl)-isocyanurate, ethylene-bis-tetrabromophthalimide, tetraphenyl resorcinol diphosphite, triphenyl phosphate, ammonium polyphosphate, resorcinol diphosphate oligomer, melamine phosphates, melamine pyrophosphates and ethylenediamine diphosphate.
13. 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, sterically hindered amines, metal passivators, metal oxides, organophosphorus compounds, hydroxylamines, further flame retardants, and mixtures thereof.
14. A composition according to claim 13 in which the further component is selected from the group consisting of phenolic antioxidants, calcium stearate, zinc stearate, phosphite and phosphonite stabilizers, benzofuranone stabilizers, UV absorbers of the 2-(2'-hydroxyphenyl)benzotriazole and 2-(2-hydroxyphenyl)-1,3,5-triazine classes, and sterically hindered amines.
15. A process for imparting light stability and flame retardancy to an organic polymer substrate, which process comprises adding to said polymer substrate (i) at least one low molecular weight sterically hindered alkoxyamine stabilizer, (ii) at least one high molecular weight sterically hindered alkoxyamine stabilizer and (iii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorus containing and melamine based flame retardants.
16. A flame retardant additive combination comprising (i) at least one low molecular weight sterically hindered alkoxyamine stabilizer, (ii) at least one high molecular weight sterically hindered alkoxyamine stabilizer and (iii) at least one conventional flame retardant selected from the group consisting of the organohalogen, phosphorus containing and melamine based flame retardants.
17. A molded polymer article comprising a composition of claim 1.
18. A polymer article according to claim 17 which is a polyolefin article which is 0.1 mm to 2.5 mm thick.
19. A polymer article according to claim 18 which comprises a pigment selected from titanium dioxide and carbon black.
20. A polymer article according to claim 17 which is a construction article selected from the group consisting of roofing membranes, window profiles, siding and moldings.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33909901P | 2001-12-10 | 2001-12-10 | |
| US60/339,099 | 2001-12-10 | ||
| US41662502P | 2002-10-07 | 2002-10-07 | |
| US60/416,625 | 2002-10-07 | ||
| PCT/EP2002/013664 WO2003050175A2 (en) | 2001-12-10 | 2002-12-03 | Flame retardant conpositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2467711A1 true CA2467711A1 (en) | 2003-06-19 |
| CA2467711C CA2467711C (en) | 2011-11-01 |
Family
ID=26991490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2467711A Expired - Lifetime CA2467711C (en) | 2001-12-10 | 2002-12-03 | Flame retardant compositions |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US20030207969A1 (en) |
| EP (1) | EP1465943B1 (en) |
| JP (1) | JP4406869B2 (en) |
| KR (1) | KR100873719B1 (en) |
| CN (1) | CN1602334A (en) |
| AT (1) | ATE420916T1 (en) |
| AU (1) | AU2002358584A1 (en) |
| CA (1) | CA2467711C (en) |
| DE (1) | DE60230922D1 (en) |
| ES (1) | ES2318059T3 (en) |
| TW (1) | TWI281931B (en) |
| WO (1) | WO2003050175A2 (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2837614B1 (en) * | 2002-03-22 | 2004-06-18 | Nexans | INSULATING COMPOSITION FOR ELECTRIC SECURITY CABLE |
| WO2004031286A1 (en) * | 2002-10-03 | 2004-04-15 | Ciba Specialty Chemicals Holding Inc. | Flame retardant compositions |
| US7109260B2 (en) * | 2002-10-17 | 2006-09-19 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
| JP4158559B2 (en) * | 2003-03-07 | 2008-10-01 | 東洋インキ製造株式会社 | Flame retardant resin composition and sheet using the same |
| AU2003304555A1 (en) * | 2003-11-21 | 2005-06-08 | Indian Petrochemicals Corporation Limited | Flame retardant polyolefin blends |
| WO2005090307A1 (en) * | 2004-03-15 | 2005-09-29 | Ciba Specialty Chemicals Holding Inc. | A process for the synthesis of amine ethers |
| US20060068317A1 (en) * | 2004-09-30 | 2006-03-30 | Klei Steven R | Poly(arylene ether) composition |
| CN1321149C (en) * | 2004-12-09 | 2007-06-13 | 中山大学 | Crease-proof fire-proof heat-conductive and electrically insulating plastic composition and its prepn |
| US8415414B2 (en) * | 2005-09-16 | 2013-04-09 | Basf Se | Polyurethane flame retardant compositions |
| CN101405306B (en) * | 2006-03-16 | 2011-07-27 | 克莱里安特财务(Bvi)有限公司 | Modified waxes, a process for their preparation, and their use |
| DE102006049519A1 (en) * | 2006-10-20 | 2008-04-24 | Lanxess Deutschland Gmbh | Flame retardant for curable molding materials comprises ethylenediamine phosphate, a halogen-free phosphorus compound and a halogen-free nitrogen compound |
| CA2667457A1 (en) * | 2006-10-25 | 2008-05-02 | Dow Global Technologies Inc. | Polyolefin dispersions, froths, and foams |
| WO2008151986A1 (en) * | 2007-06-14 | 2008-12-18 | Basf Se | Flame retardant compositions |
| US20110046250A1 (en) * | 2007-07-06 | 2011-02-24 | Stowell Jeffrey K | Flame retardant composition and flexible polyurethane foam prepared therewith |
| EP2130854B1 (en) | 2008-05-09 | 2016-10-19 | MCA Technologies GMBH | Polytriazinyl compounds as flame retardants and light stabilizers |
| US7947768B2 (en) * | 2009-03-02 | 2011-05-24 | Saudi Arabian Oil Company | Ultraviolet (UV) radiation stability and service life of woven films of polypropylene (PP) tapes for the production of jumbo bags |
| US20120108712A1 (en) * | 2009-07-06 | 2012-05-03 | Basf Se | Phenylphosphonate flame retardant compositions |
| JP5373586B2 (en) * | 2009-12-21 | 2013-12-18 | 住江織物株式会社 | Flooring |
| US20120245260A1 (en) * | 2009-12-22 | 2012-09-27 | Basell Poliolefine Italia, s.r.l. | Polyolefin Composition for Membranes |
| US9315731B2 (en) * | 2010-03-21 | 2016-04-19 | Bromine Compounds Ltd. | High impact polystyrene flame retarded compositions |
| TWI471350B (en) * | 2010-05-12 | 2015-02-01 | Taiwan Union Technology Corp | Halogen-free flame-retardant epoxy resin composition, and prepreg and printed wiring board using the same |
| JP2013532749A (en) * | 2010-07-28 | 2013-08-19 | ビーエーエスエフ ソシエタス・ヨーロピア | Phosphinic hydrazide flame retardant composition |
| CN103339172A (en) * | 2011-01-31 | 2013-10-02 | 巴斯夫欧洲公司 | Methods of flame retarding polyethylene processed at high temperatures |
| WO2014099397A1 (en) * | 2012-12-20 | 2014-06-26 | Polyad Services Llc | Flame retardant polymer compositions |
| US9777206B2 (en) * | 2013-12-10 | 2017-10-03 | General Cable Technologies Corporation | Thermally conductive compositions and cables thereof |
| KR101707732B1 (en) * | 2015-05-13 | 2017-02-28 | 주식회사 남전산업 | The method of preparing fire retardant poly propylenfiber adding fire retardant of reaction |
| JP6771538B2 (en) * | 2015-07-20 | 2020-10-21 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Flame-retardant polyolefin articles |
| CN105504477A (en) * | 2016-01-11 | 2016-04-20 | 长园电子（东莞）有限公司 | Halogen-free and red-phosphorus-free flame-retardant thermal shrinkage identification tube and preparing method thereof |
| CN107663332A (en) | 2016-07-28 | 2018-02-06 | Sabic环球技术有限责任公司 | Fire retardant propylene compositions |
| WO2018069530A1 (en) | 2016-10-14 | 2018-04-19 | Basf Se | Stabilizer composition |
| WO2019002315A1 (en) * | 2017-06-26 | 2019-01-03 | Sabic Global Technologies B.V. | Uv and heat stable flame-retardant glass filled polymer composition and reinforced articles therefrom |
| CN109503887A (en) * | 2017-09-14 | 2019-03-22 | 衢州市中通化工有限公司 | A kind of preparation method of silane fire retardant |
| EP3608360A1 (en) * | 2018-08-08 | 2020-02-12 | Sabo S.p.A. | N-alkoxy amine based stabilizer combinations |
| EP3911698A1 (en) * | 2019-01-16 | 2021-11-24 | Basf Se | Stabilizer composition for sealants and adhesives |
| CN109801737B (en) * | 2019-01-24 | 2021-04-20 | 广州澳通电线电缆有限公司 | Inorganic mineral insulating layer of cable |
| CN114805646B (en) * | 2021-01-22 | 2023-02-17 | 中国科学院化学研究所 | Polyvinyl phosphorus flame retardant and preparation method and application thereof |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5204473A (en) * | 1987-09-21 | 1993-04-20 | Ciba-Geigy Corporation | O-substituted N-hydroxy hindered amine stabilizers |
| US5124378A (en) * | 1987-09-21 | 1992-06-23 | Ciba-Geigy Corporation | Stabilization of ambient cured coatings |
| US5112890A (en) * | 1987-09-21 | 1992-05-12 | Ciba-Geigy Corporation | Stabilization of acid catalyzed thermoset resins |
| US5096950A (en) * | 1988-10-19 | 1992-03-17 | Ciba-Geigy Corporation | Polyolefin compositions stabilized with NOR-substituted hindered amines |
| US5004770A (en) * | 1988-10-19 | 1991-04-02 | Ciba-Geigy Corporation | Polymeric substrates stabilized with N-substituted hindered amines |
| US5145893A (en) * | 1989-03-21 | 1992-09-08 | Ciba-Geigy Corporation | Non-migrating 1-hydrocarbyloxy hindered amine derivatives as polymer stabilizers |
| US5216156A (en) * | 1992-05-05 | 1993-06-01 | Ciba-Geigy Corporation | Non-migrating 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine 1,3,5-triazine derivatives |
| US5393812A (en) * | 1993-08-31 | 1995-02-28 | Hercules Incorporated | Flame retardant, light stable composition |
| US6262161B1 (en) * | 1997-06-26 | 2001-07-17 | The Dow Chemical Company | Compositions having improved ignition resistance |
| US5844026A (en) * | 1997-06-30 | 1998-12-01 | Ciba Specialty Chemicals Corporation | N,N',N''-tris{2,4-bis Hydrocarbyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)alkylamino!-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamines, their isomers and bridged derivatives and polymer compositions stabilized therewith |
| US6472456B1 (en) * | 1997-06-30 | 2002-10-29 | Ciba Specialty Chemicals Corp. | Flame retardant compositions |
| AU735643B2 (en) | 1997-06-30 | 2001-07-12 | Ciba Specialty Chemicals Holding Inc. | Flame retardant compositions |
| US6599963B2 (en) * | 1997-06-30 | 2003-07-29 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
| ITMI980366A1 (en) * | 1998-02-25 | 1999-08-25 | Ciba Spec Chem Spa | PREPARATION OF STERICALLY PREVENTED AMINE ETHERS |
| EP1086263A4 (en) * | 1998-04-20 | 2007-05-02 | Bba Nonwovens Simpsonville Inc | Nonwoven fabric having both uv stability and flame retardancy and related method for its manufacture |
| US6271377B1 (en) * | 1999-02-25 | 2001-08-07 | Ciba Specialty Chemicals Corporation | Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith |
| EP1038912A3 (en) * | 2000-06-22 | 2000-12-27 | Ciba SC Holding AG | High molecular weight hindered hydrocarbyloxyamine stabilizers |
| TWI273115B (en) * | 2000-12-12 | 2007-02-11 | Ciba Sc Holding Ag | Improved weatherability of flame retardant polyolefin |
| JP2004530785A (en) * | 2001-06-29 | 2004-10-07 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Synergistic combination of sterically hindered nanoscale fillers with amine light stabilizers |
| US7109260B2 (en) * | 2002-10-17 | 2006-09-19 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
| MY139230A (en) * | 2002-10-17 | 2009-08-28 | Ciba Holding Inc | Flame retardant polymeric electrical parts |
-
2002
- 2002-12-03 AT AT02792865T patent/ATE420916T1/en not_active IP Right Cessation
- 2002-12-03 JP JP2003551197A patent/JP4406869B2/en not_active Expired - Lifetime
- 2002-12-03 DE DE60230922T patent/DE60230922D1/en not_active Expired - Lifetime
- 2002-12-03 EP EP02792865A patent/EP1465943B1/en not_active Expired - Lifetime
- 2002-12-03 WO PCT/EP2002/013664 patent/WO2003050175A2/en active Application Filing
- 2002-12-03 ES ES02792865T patent/ES2318059T3/en not_active Expired - Lifetime
- 2002-12-03 CN CNA028245644A patent/CN1602334A/en active Pending
- 2002-12-03 KR KR1020047008977A patent/KR100873719B1/en active IP Right Grant
- 2002-12-03 CA CA2467711A patent/CA2467711C/en not_active Expired - Lifetime
- 2002-12-03 AU AU2002358584A patent/AU2002358584A1/en not_active Abandoned
- 2002-12-06 US US10/313,754 patent/US20030207969A1/en not_active Abandoned
- 2002-12-09 TW TW091135526A patent/TWI281931B/en not_active IP Right Cessation
-
2006
- 2006-04-04 US US11/397,273 patent/US20060197069A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US20060197069A1 (en) | 2006-09-07 |
| TWI281931B (en) | 2007-06-01 |
| DE60230922D1 (en) | 2009-03-05 |
| KR20040074072A (en) | 2004-08-21 |
| ATE420916T1 (en) | 2009-01-15 |
| WO2003050175A2 (en) | 2003-06-19 |
| EP1465943A2 (en) | 2004-10-13 |
| AU2002358584A1 (en) | 2003-06-23 |
| AU2002358584A8 (en) | 2003-06-23 |
| WO2003050175A3 (en) | 2004-06-24 |
| TW200301282A (en) | 2003-07-01 |
| CA2467711C (en) | 2011-11-01 |
| ES2318059T3 (en) | 2009-05-01 |
| KR100873719B1 (en) | 2008-12-12 |
| JP2005511842A (en) | 2005-04-28 |
| EP1465943B1 (en) | 2009-01-14 |
| CN1602334A (en) | 2005-03-30 |
| JP4406869B2 (en) | 2010-02-03 |
| US20030207969A1 (en) | 2003-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2467711A1 (en) | Flame retardant compositions | |
| CA2501384A1 (en) | Flame retardant compositions | |
| US10316169B2 (en) | NOR-HALS compounds as flame retardants | |
| EP0996669B1 (en) | Flame retardant compositions | |
| JP5631392B2 (en) | Phenylphosphonate flame retardant composition | |
| US6599963B2 (en) | Flame retardant compositions | |
| JP2006528254A5 (en) | ||
| JP2005511842A5 (en) | ||
| WO2011117266A1 (en) | Flame retardant compositions of phosphinic acid salts and nitroxyl derivatives | |
| US20030130384A1 (en) | Flame retardant compositions | |
| CA2476294A1 (en) | Flame retardant compositions | |
| CA2455841A1 (en) | Flame retardant compositions | |
| EP2598565B1 (en) | Phosphinic acid hydrazide flame retardant compositions | |
| US20150148464A1 (en) | Flame retardant compositions of phosphinic acid salts and nitroxyl derivatives | |
| WO2012013565A1 (en) | Phosphinic acid hydrazide flame retardant compositions | |
| MXPA00000239A (en) | Flame retardant compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20221205 |