U.S. patent application number 10/207674 was filed with the patent office on 2003-08-07 for flame retardant compositions.
Invention is credited to Andrews, Stephen Mark, Davis, Leonard Harris, Dyas, Darrell David JR., Gray, Robert Leo, Gupta, Anunay, Hein, Bruce Vincent, Horsey, Douglas Wayne, Puglisi, Joseph Stephen, Ravichandran, Ramanathan, Shields, Paul, Srinivasan, Rangarajan.
Application Number | 20030149143 10/207674 |
Document ID | / |
Family ID | 26729310 |
Filed Date | 2003-08-07 |
United States Patent
Application |
20030149143 |
Kind Code |
A1 |
Horsey, Douglas Wayne ; et
al. |
August 7, 2003 |
Flame retardant compositions
Abstract
Polyolefins, especially polypropylene, can be made flame
retardant by the incorporation therein of a synergistic mixture of
a selected hindered amine substituted by an alkoxy, cycloalkoxy or
hydroxyalkoxy moiety and a selected organic or inorganic brominated
and/or phosphorus containing flame retardant, such as ammonium
polyphosphate or decabromodiphenyl oxide wherein the amount of
organic or inorganic flame retardant required to achieve an
acceptable level of flame retardancy is significantly reduced
compared to that needed when the hindered amine is not present.
Inventors: |
Horsey, Douglas Wayne;
(Briarcliff Manor, NY) ; Andrews, Stephen Mark;
(New Fairfield, CT) ; Davis, Leonard Harris; (New
City, NY) ; Dyas, Darrell David JR.; (Kennesaw,
GA) ; Gray, Robert Leo; (West Lafayette, IN) ;
Gupta, Anunay; (Edison, NJ) ; Hein, Bruce
Vincent; (Marietta, GA) ; Puglisi, Joseph
Stephen; (Crompond, NY) ; Ravichandran,
Ramanathan; (Nanuet, NY) ; Shields, Paul;
(Rivervale, NJ) ; Srinivasan, Rangarajan;
(Tarrytown, NY) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
26729310 |
Appl. No.: |
10/207674 |
Filed: |
July 29, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10207674 |
Jul 29, 2002 |
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09502239 |
Nov 3, 1999 |
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6472456 |
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09502239 |
Nov 3, 1999 |
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09104718 |
Jun 25, 1998 |
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60051331 |
Jun 30, 1997 |
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Current U.S.
Class: |
524/99 ; 524/102;
524/103 |
Current CPC
Class: |
C09K 15/30 20130101;
C08K 5/3435 20130101; C08K 5/34926 20130101; C07D 211/94 20130101;
C08K 5/0066 20130101; C07D 401/14 20130101 |
Class at
Publication: |
524/99 ; 524/102;
524/103 |
International
Class: |
C08J 003/00; C08K
005/34; C08L 001/00 |
Claims
What is claimed is:
1. A flame retardant composition which comprises (a) a polymer
substrate, and (b) an effective flame retarding amount of a
synergistic mixture of (i) a hindered amine of formula A 16wherein
E is 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).sub.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, R.sub.2 is hydrogen,
C.sub.1-C.sub.18alkyl or said alkyl optionally interrupted by one
or more oxygen atoms, C.sub.2-C.sub.12alkenyl,
C.sub.6-C.sub.10aryl, C.sub.7-C.sub.18aralkyl, glycidyl, a
monovalent acyl radical of an aliphatic, cycloaliphatic or aromatic
carboxylic acid, or a carbamic acid, preferably 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 17wherein x is 0
or 1, 18wherein y is 2-4; when m is 2, R.sub.2 is
C.sub.1-C.sub.12alkylene, C.sub.4-C.sub.12alkenylene, xylylene, a
divalent acyl radical of an aliphatic, cycloaliphatic, araliphatic
or aromatic dicarboxylic acid or of a dicarbamic acid, preferably
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; 19wherein D.sub.1 and D.sub.2
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, D.sub.3 is hydrogen, or an
alkyl or alkenyl radical containing up to 18 carbon atoms, and d is
0-20; when m is 3, R.sub.2 is a trivalent acyl radical of an
aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic
tricarboxylic acid; when m is 4, R.sub.2 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-enetetracarboxylic, and 1,2,3,5- and
1,2,4,5-pentanetetracarboxylic acid; 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'-ethylened-
iiminodipropylamine;
N,N',N"-tris{2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetram-
ethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodiprop-
ylamine, and bridged derivatives as described by formulas I, II,
IIA and
IIIR.sub.1NH--CH.sub.2CH.sub.2CH.sub.2NR.sub.2CH.sub.2CH.sub.2NR.sub.3CH.-
sub.2CH.sub.2CH.sub.2NHR.sub.4 (I)T--E.sub.1--T.sub.1
(II)T--E.sub.1 (IIA)G--E.sub.1--G.sub.1--E.sub.1--G.sub.2
(III)where in the tetraamine of formula I R.sub.1 and R.sub.2 are
the s-triazine moiety E; and one of R.sub.3 and R.sub.4 is the
s-triazine moiety E with the other of R.sub.3 or R4 being hydrogen,
E is 20R is methyl, propyl, cyclohexyl or octyl, preferably
cyclohexyl, R.sub.5 is alkyl of 1 to 12 carbon atoms, preferably
n-butyl, where in the compound of formula II or IIA when R is
propyl, cyclohexyl or octyl, T and T.sub.1 are each a substituted
by R.sub.1-R.sub.4 as is defined for formula I, where (1) one of
the s-triazine moieties E in each tetraamine is replaced by the
group E.sub.1 which forms a bridge between two tetraamines T and
T.sub.1, E.sub.1 is 21(2) the group E.sub.1 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 E.sub.1 group, or
(3) all three s-triazine substituents of tetraamine T can be
E.sub.1 such that one E.sub.1 links T and T.sub.1 and a second
E.sub.1 has both termini in tetraamine T, L is propanediyl,
cyclohexanediyl or octanediyl; where in the compound of formula III
G, G.sub.1 and G.sub.2 are each tetraamines substituted by
R.sub.1-R.sub.4 as defined for formula I, except that G and G.sub.2
each have one of the s-triazine moieties E replaced by E.sub.1, and
G.sub.1 has two of the triazine moieties E replaced by E.sub.1, so
that there is a bridge between G and G.sub.1 and a second bridge
between G.sub.1 and G.sub.2; which mixture is prepared by reacting
two to four equivalents of
2,4-bis[(1-hydrocarbyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-t-
riazine with one equivalent of
N,N'-bis(3-aminopropyl)ethylenediamine; or the hindered amine is a
compound of the formula IIIb 22in which the index n ranges from 1
to 15; R.sub.12 is C.sub.2-C.sub.12alkylene,
C.sub.4-C.sub.12alkenylene, C.sub.5-C.sub.7cycloalkylene,
C.sub.5-C.sub.7cycloalkylenedi(C.sub.1-C.sub.4alkylene),
C.sub.1-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylene),
phenylenedi(C.sub.1-C.sub.4alkylene) or C.sub.4-C.sub.12alkylene
interrupted by 1,4-piperazinediyl, --O-- or >N--X.sub.1 with
X.sub.1 being C.sub.1-C.sub.12acyl or
(C.sub.1-C.sub.12alkoxy)carbonyl or having one of the definitions
of R.sub.14 given below except hydrogen; or R.sub.12 is a group of
the formula (Ib') or (Ic'); 23with m being 2 or 3, X.sub.2 being
C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl;
phenyl which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; and the radicals
X.sub.3 being independently of one another
C.sub.2-C.sub.12alkylene; R.sub.13, R.sub.14 and R.sub.15, which
are identical or different, are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
1, 2 or 3 C.sub.1-C.sub.4alkyl; C.sub.3-C.sub.18alkenyl, phenyl
which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl or
C.sub.2-C.sub.4alkyl which is substituted in the 2, 3 or 4 position
by --OH, C.sub.1-C.sub.8alkoxy, di(C.sub.1-C.sub.4alkyl)a- mino or
a group of the formula (Ie'); 24with Y being --O--, --CH.sub.2--,
--CH.sub.2CH.sub.2-- or >N--CH.sub.3, or --N(R.sub.14)(R.sub.15)
is additionally a group of the formula (Ie'); the radicals A are
independently of one another --OR.sub.13, --N(R.sub.14)(R.sub.15)
or a group of the formula (IIId); 25X is --O-- or >N--R.sub.16;
R.sub.16 is hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl, a
group of the formula (IIIf), 26or C.sub.2-C.sub.4alkyl which is
substituted in the 2, 3 or 4 position by --OH,
C.sub.1-C.sub.8alkoxy, di(C.sub.1-C.sub.4alkyl)amino or a group of
the formula (Ie'); R.sub.11 has one of the definitions given for
R.sub.16; and the radicals B have independently of one another one
of the definitions given for A; (ii) a brominated and/or phosphorus
containing flame retardant with the proviso that when the polymeric
substrate is polypropylene, the flame retardant is not a
halogenated hydrocarbyl phosphate or phosphonate.
2. A composition according to claim 1 wherein the polymer substrate
is selected from the group of resins consisting of the polyolefins,
the thermoplastic olefins, styrenic polymers and copolymers, and
ABS.
3. A composition according to claim 2 wherein the polymer substrate
is polypropylene, polyethylene, thermoplastic olefin (TPO), ABS and
high impact polystyrene.
4. A composition according to claim 3 wherein the polymer substrate
is polypropylene, polyethylene or thermoplastic olefin (TPO).
5. A composition according to claim 1 wherein the effective flame
retarding amount of a hindered amine of component (i) is 0.05 to
10% by weight based on the polymer substrate.
6. A composition according to claim 5 wherein the effective flame
retarding amount of a hindered amine of component (i) is 0.5 to 8%
by weight based on the polymer substrate.
7. A composition according to claim 6 wherein the effective flame
retarding amount of a hindered amine of component (i) is 0.5 to 2%
by weight based on the polymer substrate.
8. A composition according to claim 1 where in the hindered amine
of formula A of component (i) E is alkoxy of 1 to 18 carbon atoms,
cycloalkoxy of 5 to 12 carbon atoms or aralkoxy of 7 to 15 carbon
atoms.
9. A composition according to claim 8 wherein E is methoxy,
propoxy, cyclohexyloxy or octyloxy.
10. A composition according to claim 9 wherein E is propoxy,
cyclohexyloxy or octyloxy.
11. A composition according to claim 10 wherein E is
cyclohexyloxy.
12. A composition according to claim 1 wherein the effective flame
retarding amount of the synergistic mixture of component (b) is 0.5
to 30% by weight based on component (a).
13. A composition according to claim 1 wherein the flame retardant
component (ii) is selected from the group consisting of
polybrominated diphenyl oxide (DE-60F) decabromodiphenyl oxide
(DBDOP), bis(2,3-dibromopropyl ether) of bisphenol A (PE68),
ammonium polyphosphate (APP) or (HOSTAFLAM.RTM. AP750), resorcinol
diphosphate oligomer (RDP), brominated epoxy resin,
ethylene-bis(tetrabromophthalimid- e) (BT93),
1,2-bis(tribromophenoxy)ethane (FF680), and tetrabromo-bisphenol A
(SAYTEX.RTM. RB100).
14. A composition according to claim 13 wherein the flame retardant
compound (ii) is ammonium polyphosphate or decabromodiphenyl
oxide.
15. A composition according to claim 1 wherein the coadditive is a
phosphorus compound selected from the group consisting of
tris(2,4-di-tert-butylphenyl) phosphite,
bis(2,4-di-tert-butyl-6-methylph- enyl) ethyl phosphite,
2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-
-butyl-1,1'-biphenyl-2,2'-diyl) phosphite],
tetrakis(2,4-di-butylphenyl) 4,4'-biphenylene-diphosphonite,
tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)
pentaerythrityl diphosphite,
2,2'-ethylidenebis(2,4-di-tert-butylphenyl) fluorophosphite and
2-butyl-2-ethylpropan-1,3-diyl 2,4,6-tri-tert-butylphenyl
phosphite; or a UV absorber selecte from the group consisting of
2-(2-hydroxy-3,5-di-.alp- ha.-cumylphenyl)-2H-benzotriazole,
2-(2-hydroxy-5-methylphenyl)-2H-benzotr- iazole,
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,
2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate,
2-hydroxy-4-n-octyloxybenzophenone and
2,4-bis(2,4-dimethyphenyl)-6-(2-hy-
droxy-4-octyloxyphenyl)-s-triazine.
16. A composition according to claim 1 wherein the NOR or NOROL
hindered amine of component (i) is (a) the mixture of compounds of
formula I, II, IIA and III where R is cyclohexyl; (b)
1-cyclohexyloxy-2,2,6,6-tetramethy- l-4-octadecylaminopiperidine;
(c) bis(1-octyloxy-2,2,6,6-tetramethylpiperi- din-4-yl) sebacate;
(d) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperi-
din-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine; (e)
bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; (f)
the oligomeric compound which is the condensation product of
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and
2,4dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]--
s-triazine end-capped with
2-chloro-4,6-bis(dibutylamino)-s-triazine; (g) the oligomeric
compound which is the condensation product of
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and
2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butyla-
mino]-s-triazine end-capped with
2-chloro-4,6-bis(dibutylamino)-s-triazine- ; (h)
2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-
-s-triazine; (i)
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-t-
etramethylpiperidine; or (j) the compound of formula 27
17. A composition according to claim 16 wherein the NOR or NOROL
hindered amine of component (i) is (a) the mixture of compounds of
formula I, II, IIA and III where R is cyclohexyl; (c)
bis(1-octyloxy-2,2,6,6-tetramethyl- piperidin-4-yl) sebacate; (i)
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyl-
oxy-2,2,6,6-tetramethylpiperidine; or (j) the compound of formula
28
Description
[0001] This application claims the benefit under 35 USC 119(e) of
U.S. Provisional Application Serial No. 60/051,331, filed on Jun.
30, 1997; and is a continuation-in-part of application Ser. No.
09/104,718, filed on Jun. 25, 1998.
[0002] The instant invention pertains to a method of flame
retarding a polymeric substrate by adding thereto an effective
flame retarding amount of a synergistic mixture of a selected
hindered amine compound and an organic or inorganic flame retardant
which contains bromine and/or phosphorus moieties.
BACKGROUND OF THE INVENTION
[0003] The hindered amines have long been recognized as light
and/or as thermal stabilizers for a host of organic materials
subject to degradation induced by oxygen, heat or actinic light.
The patent and academic publication literature is replete with
references to these hindered amine compounds and their valuable
stabilizing efficacies. There is no mention or suggestion in any of
such references that the hindered amines themselves are also flame
retardants per se.
[0004] Particularly relevant are U.S. Pat. Nos. 5,004,770;
5,096,950; 5,204,473; 5,300,544 and 5,844,026 as well as copending
applications Ser. Nos. 09/257,711 and 09/253,161. These references
pertain to various N-hydrocarbyloxy substituted hindered amines (so
called NOR and NOROL hindered amines) and to various compositions
stabilized therewith. As mentioned above, none of these reference
disclose or even hint that the compositions stabilized with the NOR
or NOROL hindered amines alone are flame retardant. This inherent
property was never discovered, not even serendipitously, until the
present invention was made. That this is so, is in itself evidence
that even those of considerable skill in the hindered amine
stabilizer art were quite surprised by this unexpected discovery.
The fact that a large amount of an inorganic or organic classical
bromine and/or phosphorus containing flame retardant could be
substituted by a small amount of a NOR or NOROL hindered amine and
still achieve very acceptable flame retardancy was also quite
unexpected. This is highly beneficial for the environment and for
safety reasons. Accordingly, polymeric substrate compositions made
flame retardant by incorporating therein a synergistic mixture of a
NOR or NOROL hindered amine plus a classic inorganic or organic
bromine and/or phosphorus containing flame retardant is also quite
surprising, unexpected and clearly not obvious to those of skill in
this stabilizer art. This invention affords the public a valuable
method for flame retarding polymers which cannot be gleaned from
any of the prior art references.
[0005] U.S. Pat. No. 5,393,812 does describe polyolefin
compositions which are made flame retardant by a combination of a
halogenated hydrocarbyl phosphate or phosphonate ester flame
retardant in combination with a alkoxyamine functional hindered
amine, but there is no suggestion that the hindered amine itself is
responsible for the flame retardancy, but rather that the hindered
amine is preventing delustering and other undesirable effects from
occurring in these polyolefin compositions.
[0006] European Application No. 0 792 911 A2, published after the
filing date of the parent provisional application Serial No.
60/051,331, discloses that alkoxyamine functional hindered amines
may have some flame retarding properties, but are quite effective
when used to enhance the flame retarding efficacy of
tris(trihalogenopentyl) phosphate flame retardants. This
publication is somewhat ambivalent as to whether the alkoxyamine
functional hindered amine are really themselves flame retardants in
the absence of the recognized phosphate flame retardant.
[0007] The flame retardant (FR) market today is comprised of
products which function to interfere with the combustion process by
chemical and/or physical means. Mechanistically these FRs have been
proposed to function during combustion of an article in either the
gas phase, the condensed phase or both. The organohalogens are
proposed to generate halogen species (e.g. HX) which interferes in
the gas phase with free radical organic "fuel" from the polymer
substrate. Synergists are proposed to react with HX to form
additional chemical species with interfere with combustion in the
gas phase, such as reaction of antimony oxide with HX to form
antimony halide and water vapor. Still other flame retardant
classes are proposed to impart efficacy in the "condensed" phase
such as forming a protective char layer on the polyester, or
forming an intumescent or foaming on the polymer surface. The char
or intumescent layer is thought either to prevent organic fuel from
migrating from the polymer into the vapor phase where it can fuel
combustion, or the char can act as a thermal shield to protect the
underlying polymer article from thermally induced decomposition and
generation of fuel. Phosphorus compound of various classes (e.g.
halo- or non-halogenated) are an example. Further still, other
classes of compounds are proposed to function in the condensed
and/or vapor phase. Metal hydrates or metal oxides are proposed to
generate water vapor under thermal conditions, the water acting to
dilute the fuel mix in the combustion zone and to remove heat from
the flame zone via conversion of water to vapor. Alumina
trihydrate, magnesium hydroxide or oxide, and other compounds are
reported to function in this way.
[0008] These state of the art chemistries described above have
various detrimental aspects in addition to the effective flame
retarding attributes mentioned. Certain organobrominated compounds
are under governmental scrutiny for the generation of toxic
by-products during the production or combustion such as dioxanes
from polybrominated diphenyl oxides. Certain metal-containing flame
retardants, notably antimony oxides, are under scrutiny for worker
exposure and toxicity reasons. Antimony oxides often contain trace
amounts of arsenic compounds which are suspected cancinogens.
Overall, a growing concern has arisen regarding the generation of
smoke and toxic gases which are evolved from these flame retardants
during a fire. While the classic FRs may be effective combustion
suppressants, the toxic gases they form pose a threat to human
exposure.
[0009] The instant invention alleviates some of the detrimental
aspects of the current state of the art which the use of large
amounts of commercial flame retardants pose. The instant NOR or
NOROL hindered amines are non-halogenated and free of heavy metals,
thus avoiding generation of corrosive HX gases and avoiding
exposure to toxic metals. In some applications, the instant
invention provides a direct replacement for current FR systems
where the instant NOR or NOROL hindered amine compounds provide a
complimentary enhancment or synergistic system for heavy metals
(e.g. antimony oxide replacement in ABS) where good flame
retardancy can be achieved by using less classic FR agent in the
presence of the instant NOR or NOROL hindered amine compound.
DETAILED DISCLOSURE
[0010] The instant invention pertains to a flame retardant
composition which comprises
[0011] (a) a polymer substrate, preferably a polyolefin, most
preferably polypropylene, and
[0012] (b) an effective flame retarding amount of a synergistic
mixture of
[0013] (i) a hindered amine of formula A 1
[0014] wherein
[0015] E is 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).sub.b, preferably E is methyoxy, propoxy,
cyclohexyloxy or octyloxy, most preferably cyclohexyloxy,
[0016] 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;
[0017] 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;
[0018] R is hydrogen or methyl,
[0019] m is 1 to 4,
[0020] when m is 1,
[0021] R.sub.2 is hydrogen, C.sub.1-C.sub.18alkyl or said alkyl
optionally interrupted by one or more oxygen atoms,
C.sub.2-C.sub.12alkenyl, C.sub.6-C.sub.10aryl,
C.sub.7-C.sub.18aralkyl, glycidyl, a monovalent acyl radical of an
aliphatic,cycloaliphatic or aromatic carboxylic acid, or a carbamic
acid, preferably 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 2
[0022] wherein x is 0 or 1, 3
[0023] wherein y is 2-4;
[0024] when m is 2,
[0025] R.sub.2 is C.sub.1-C.sub.12alkylene,
C.sub.4-C.sub.12alkenylene, xylylene, a divalent acyl radical of an
aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic
acid or of a dicarbamic acid, preferably 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; 4
[0026] wherein D.sub.1 and D.sub.2 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, D.sub.3
is hydrogen, or an alkyl or alkenyl radical containing up to 18
carbon atoms, and d is 0-20;
[0027] when m is 3, R.sub.2 is a trivalent acyl radical of an
aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic
tricarboxylic acid;
[0028] when m is 4, R.sub.2 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-enetetracarboxylic, and 1,2,3,5- and
1,2,4,5-pentanetetracarboxylic acid; or
[0029] 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
R.sub.1NH--CH.sub.2CH.sub.2CH.sub.2NR.sub.2CH.sub.2CH.sub.2NR.sub.3CH.sub.-
2CH.sub.2CH.sub.2NHR.sub.4 (I)
T--E.sub.1--T.sub.1 (II)
T--E.sub.1 (IIA)
G--E.sub.1--G.sub.1--E.sub.1--G.sub.2 (III)
[0030] where in the tetraamine of formula I
[0031] R.sub.1 and R.sub.2 are the s-triazine moiety E.sub.2; and
one of R.sub.3 and R.sub.4 is the s-triazine moiety E.sub.2 with
the other of R.sub.3 or R.sub.4 being hydrogen,
[0032] E.sub.2 is 5
[0033] R is methyl, propyl, cyclohexyl or octyl, preferably
cyclohexyl,
[0034] R.sub.5 is alkyl of 1 to 12 carbon atoms, preferably
n-butyl,
[0035] where in the compound of formula II or IIA when R is propyl,
cyclohexyl or octyl,
[0036] T and T.sub.1 are each a substituted by R.sub.1-R.sub.4 as
is defined for formula I, where
[0037] (1) one of the s-triazine moieties E.sub.2 in each
tetraamine is replaced by the group E.sub.1 which forms a bridge
between two tetraamines T and T.sub.1,
[0038] E.sub.1 is 6
[0039] (2) the group E.sub.1 can have both termini in the same
tetraamine T as in formula IIA where two of the E.sub.2 moieties of
the tetraamine are replaced by one E.sub.1 group, or
[0040] (3) all three s-triazine substituents of tetraamine T can be
E.sub.1 such that one E.sub.1 links T and T.sub.1 and a second
E.sub.1 has both termini in tetraamine T,
[0041] L is propanediyl, cyclohexanediyl or octanediyl;
[0042] where in the compound of formula III
[0043] G, G.sub.1 and G.sub.2 are each tetraamines substituted by
R.sub.1-R.sub.4 as defined for formula I, except that G and G.sub.2
each have one of the s-triazine moieties E.sub.2 replaced by
E.sub.1, and G.sub.1 has two of the triazine moieties E.sub.2
replaced by E.sub.1, so that there is a bridge between G and
G.sub.1 and a second bridge between G.sub.1 and G.sub.2;
[0044] which mixture is prepared by reacting two to four
equivalents of
2,4-bis[(1-hydrocarbyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-t-
riazine with one equivalent of
N,N'-bis(3-aminopropyl)ethylenediamine;
[0045] or the hindered amine is a compound of the formula IIIb
7
[0046] in which the index n ranges from 1 to 15;
[0047] R.sub.12 is C.sub.2-C.sub.12alkylene,
C.sub.4-C.sub.12alkenylene, C.sub.5-C.sub.7cycloalkylene,
C.sub.5-C.sub.7cycloalkylenedi(C.sub.1-C.su- b.4alkylene,
C.sub.1-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylene),
phenylenedi(C.sub.1-C.sub.4alkylene) or C.sub.4-C.sub.12alkylene
interrupted by 1,4-piperazinediyl, --O-- or >N--X.sub.1 with
X.sub.1 being C.sub.1-C.sub.12acyl or
(C.sub.1-C.sub.12alkoxy)carbonyl or having one of the definitions
of R.sub.14 given below except hydrogen; or
[0048] R.sub.12 is a group of the formula (Ib') or (Ic'); 8
[0049] with m being 2 or 3,
[0050] X.sub.2 being C.sub.1-C.sub.18alkyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
1, 2 or 3 C.sub.1-C.sub.4alkyl; phenyl which is unsubstituted or
substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.4alkoxy; C.sub.7-C.sub.9phenylalkyl which is
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4alkyl; and
[0051] the radicals X.sub.3 being independently of one another
C.sub.2-C.sub.12alkylene;
[0052] R.sub.13, R.sub.14 and R.sub.15, which are identical or
different, are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
1, 2 or 3 C.sub.1-C.sub.4alkyl; C.sub.3-C.sub.18alkenyl, phenyl
which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl or
C.sub.2-C.sub.4alkyl which is substituted in the 2, 3 or 4 position
by --OH, C.sub.1-C.sub.8alkoxy, di(C.sub.1-C.sub.4alkyl)amino or a
group of the formula (Ie'); 9
[0053] with Y being --O--, --CH.sub.2--, --CH.sub.2CH.sub.2-- or
>N--CH.sub.3, or --N(R.sub.14)(R.sub.15) is additionally a group
of the formula (Ie');
[0054] the radicals A are independently of one another --OR.sub.13,
--N(R.sub.14)(R.sub.15) or a group of the formula (IIId); 10
[0055] X is --O-- or >N--R.sub.16;
[0056] R.sub.16 is hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl, a
group of the formula (IIIf), 11
[0057] or C.sub.2-C.sub.4alkyl which is substituted in the 2, 3 or
4 position by --OH, C.sub.1-C.sub.8alkoxy,
di(C.sub.1-C.sub.4alkyl)amino or a group of the formula (Ie');
[0058] R.sub.11 has one of the definitions given for R.sub.16;
and
[0059] the radicals B have independently of one another one of the
definitions given for A;
[0060] (ii) a brominated and/or a phosphorus containing flame
retardant with the proviso that when the polymeric substrate is
polypropylene, the flame retardant is not a halogenated hydrocarbyl
phosphate or phosphonate.
[0061] Preferably the hindered amine compounds are the mixture of
compounds of formula I, II, IIA and III where R is cyclohexyl;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine, or the compound of formula 12
[0062] In the structures A to R, if any substituents are
C.sub.1-C.sub.18 alkyl, they are for example methyl, ethyl,
n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,
2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-hexadecyl or n-octadecyl. Typical cycloalkyl groups
include cyclopentyl and cyclohexyl; typical cycloalkenyl groups
include cyclohexenyl; while typical aralkyl groups include benzyl,
alpha-methyl-benzyl, alpha, alpha-dimethylbenzyl or phenethyl.
C.sub.1-C.sub.12 alkyl and cyclohexyl are preferred.
[0063] If R.sub.2 is a monovalent acyl radical of a carboxylic
acid, it is for example an acyl radical of acetic acid, stearic
acid, salicylic acid, benzoic acid or
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid.
[0064] If R.sub.2 is a divalent acyl radical of a dicarboxylic
acid, it is for example an acyl radical of oxalic acid, adipic
acid, succinic acid, suberic acid, sebacic acid, phthalic acid
dibutylmalonic acid, dibenzylmalonic acid or
butyl-(3,5-di-tert-butyl-4-hydropxybenzyl)-maloni- c acid, or
bicycloheptenedicarboxylic acid, with succinates, sebacates,
phthalates and isophthalates being preferred.
[0065] If R.sub.2 is a divalent acyl radical of a dicarbamic acid,
it is for example an acyl radical of hexamethylenedicarbamic acid
or of 2,4-toluylenedicarbamic acid.
[0066] The instant NOR hindered amine compounds as described above
are known in the prior art and are prepared as taught in U.S. Pat.
Nos. 5,004,770; 5,096,950; 5,204,473, 5,300,544 and 5,844,026; and
copending patent application Ser. Nos. 09/253,161 and
09/257,711.
[0067] Preferably, the polymer substrate is selected from the group
of resins consisting of the polyolefins, the thermoplastic olefins,
styrenic polymers and copolymers, and ABS.
[0068] More preferably, the polymer substrate is polypropylene,
polyethylene, thermoplastic olefin (TPO), ABS and high impact
polystyrene.
[0069] Most preferably, polymer substrate is polypropylene,
polyethylene or thermoplastic olefin (TPO).
[0070] Preferably, the NOR or NOROL hindered amine of component (i)
is
[0071] (a) the mixture of compounds of formula I, II, IIA and III
where R is cyclohexyl;
[0072] (b)
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;
[0073] (c) bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate;
[0074] (d)
2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)buty-
lamino]-6-(2-hydroxyethylamino-s-triazine;
[0075] (e) bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
adipate;
[0076] (f) the oligomeric compound which is the condensation
product of
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and
2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-
-s-triazine end-capped with
2-chloro-4,6-bis(dibutylamino)-s-triazine;
[0077] (g) the oligomeric compound which is the condensation
product of
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and
2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-yl)butylami-
no]-s-triazine end-capped with
2-chloro-4,6-bis(dibutylamino)-s-triazine;
[0078] (h)
2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-c-
hloro-s-triazine;
[0079] (i)
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetrame-
thylpiperidine; or
[0080] (j) the compound of formula 13
[0081] Most preferably, the compound of component (i) is
[0082] (a) the mixture of compounds of formula I, II, IIA and III
where R is cyclohexyl;
[0083] (c) bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate;
[0084] (i)
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetrame-
thylpiperidine; or
[0085] (j) the compound of formula 14
[0086] The effective flame retarding amount of the hindered amine
is that needed to show flame retarding efficacy as measured by one
of the standard methods used to assess flame retardancy. These
include the NFPA 701 Standard Methods of Fire Tests for
Flame-Resistant Textiles and Films, 1989 and 1996 editions; the UL
94 Test for Flammability of Plastic Materials for Parts in Devices
and Appliances, 5th Edition, Oct. 29, 1996; Limiting Oxygen Index
(LOI), ASTM D-2863; and Cone Calorimetry, ASTM E-1354.
[0087] The effective amount of hindered amine needed to achieve
flame retardancy is from 0.05 to 10% by weight based on the
polymeric substrate; preferably 0.5 to 8% by weight; and most
preferably 0.5 to 2% by weight.
[0088] The effective flame retarding amount of the synergistic
mixture (b) containing components (i) and (ii) is 0.5 to 30% by
weight based on component (a).
[0089] In that synergistic mixture (b), the effective flame
retarding amount of a hindered amine is 0.5 to 10% by weight based
on component (a); and preferably is 0.5 to 8% by weight based on
component (a).
[0090] More particularly, the flame retardant compounds useful in
the instant invention are preferably selected from the group
consisting of
[0091] polybrominated diphenyl oxide (DE-60F, Great Lakes
Corp.)
[0092] decabromodiphenyl oxide (DBDPO; SAYTEX.RTM. 102E)
[0093] bis(2,3-dibromopropyl ether) of bisphenol A (PE68),
[0094] ammonium polyphosphate (APP) or (HOSTAFLAM.RTM. AP750),
[0095] brominated epoxy resin,
[0096] ethylene-bis(tetrabromophthalimide) (BT93),
[0097] 1,2-bis(tribromophenoxy)ethane (FF680), and
[0098] tetrabromo-bisphenol A (SAYTEX.RTM. RB100).
[0099] The following examples are meant for illustrative purposes
only and are not to be construed to limit the scope of this
invention in any manner whatsoever.
[0100] Coadditives found useful for use with the instant
NOR-hindered amine compounds in flame retardant compositions are as
follows:
[0101] Phosphorus Compounds:
[0102] tris(2,4-di-tert-butylphenyl) phosphite, (IRGAFOS.RTM. 168,
Ciba Specialty Chemicals Corp.);
[0103] bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,
(IRGAFOS.RTM. 38, Ciba Specialty Chemicals Corp.);
[0104]
2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biph-
enyl-2,2'-diyl) phosphite], (IRGAFOS.RTM. 12, Ciba Specialty
Chemicals Corp.);
[0105] tetrakis(2,4-di-butylphenyl) 4,4'-biphenylenediphosphonite,
(IRGAFOS.RTM. P-EPQ, Ciba Specialty Chemicals Corp.);
[0106] tris(nonylphenyl) phosphite, (TNPP.RTM., General
Electric);
[0107] bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite,
(ULTRANOX.RTM. 626, General Electric);
[0108] 2,2'-ethylidenebis(2,4-di-tert-butylphenyl) fluorophosphite,
(ETHANOX.RTM. 398, Ethyl Corp.)
[0109] 2-butyl-2-ethylpropan-1,3-diyl 2,4,6-tri-tert-butylphenyl
phosphite, (ULTRANOX.RTM. 641, General Electric).
[0110] Flame retardants:
[0111] tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate, (PB
370.RTM., FMC Corp.)
[0112] decabromodiphenyl oxide, (DBDPO);
[0113] ethylene bis-(tetrabromophthalimide), (SAYTEX.RTM.
BT-93);
[0114] ethylene bis-(dibromo-norbornanedicarboximide), (SAYTEX.RTM.
BN-451)
[0115] UV absorbers:
[0116] 2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole,
(TINUVIN.RTM. 234, Ciba Specialty Chemicals Corp.);
[0117] 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, (TINUVIN.RTM.
P, Ciba Specialty Chemicals Corp.);
[0118]
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,
(TINUVIN.RTM. 327, Ciba Specialty Chemicals Corp.);
[0119] 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,
(TINUVIN.RTM. 328, Ciba Specialty Chemicals Corp.);
[0120]
2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole,
(TINUVIN.RTM. 928, Ciba Specialty Chemicals Corp.);
[0121] 2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate,
(TINUVIN.RTM. 120, Ciba Specialty Chemicals Corp.);
[0122] 2-hydroxy-4-n-octyloxybenzophenone, (CHIMASSORB.RTM. 81,
Ciba Specialty Chemicals Corp.);
[0123]
2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazin-
e, (CYASORB.RTM. 1164, Cytec).
Test Methods
[0124] NFPA 701 Standard Methods of Fire Tests for Flame-Resistant
Textiles and Films, 1989 and 1996 editions;
[0125] UL 94 Test for Flammability of Plastic Materials for Parts
in Devices and Appliances, 5th Edition, Oct. 29, 1996;
[0126] Limiting Oxygen Index (LOI), ASTM D-2863;
[0127] Cone Calorimetry, ASTM E-1 or ASTM E 1354;
[0128] ASTM D 2633-82, burn test.
Test Compounds
[0129] NOR-1 is the mixture of compounds of formula I, II, IIA and
III where R is cyclohexyl.
[0130] NOR-3 is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate, (TINUVIN.RTM. 123, Ciba Specialty Chemicals Corp.).
[0131] NOR-9 is
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-te-
tramethylpiperidine.
[0132] NOR-10 is the compound of formula 15
[0133] FR-4 is ammonium polyphosphate/synergist blend,
HOSTAFLAM.RTM. AP750.
[0134] FR-5 is decabromodiphenyl oxide, SAYTEX.RTM. 102E.
[0135] FR-7 is melamine phosphate, MELAPUR.RTM. P 46.
[0136] FR-8 is ammonium polyphosphate, EXOLIT.RTM. AP752.
EXAMPLE 1
[0137] Fiber grade polypropylene, containing 0.05% by weight of
calcium stearate and 0.05% of tris(2,4-di-tert-butylphenyl)
phosphite and 0.05% of a N,N-dihydroxylamine made by the direct
oxidation of N,N-di(hydrogenated tallow)amine is dry blended with
the test additives and then melt compounded at 234.degree. C.
(450.degree. F.) into pellets. The pelletized fully formulated
resin is then spun at 246.degree. C. (475.degree. F.) into fiber
using a Hills laboratory model fiber extruder. The spun tow of 41
filaments is stretched at a ratio of 1:3.2 to give a final denier
of 615/41.
[0138] Socks are knitted from the stabilized polypropylene fiber on
a Lawson-Hemphill Analysis Knitter and tested under NFPA 701
vertical burn procedure. The time in seconds for the knitted sock
to extinguish after the insult flame is removed is reported as
"After Flame". Both the maximum time for any one replicate and the
total time for all ten replicates are shown in the table below.
Efficacy as a flame retardant is demonstrated when low After Flame
times are observed relative to a blank sample containing no flame
retardant.
1 (weight %) Weight Drip Burn Formulation Loss % Time sec Pass/Fail
Control 36 >50 Fail FR-5 (4%) 7 0.8 Pass FR-5 (2%) 10 5 Fail
FR-5 (1%) + 4 0 Pass NOR-1 (0.5%) FR-5 (1%) + 9 0.5 Pass NOR-3
(0.5%) FR-5 (1%) + 5 0 Pass NOR-9 (0.5%) FR-5 (1%) + 0.1 8 Pass
NOR-10 (0.5%)
[0139] In the NFPA 701 test, a vertical piece of fabric is ignited
with a Meeker burner. The flame is held on the fabric for 45
seconds. The drip burn time and the fabric weight loss are measured
after the burning. To pass the NFPA 701 test, a material shoud
loose less than 40% of weight and have a drip burn time of less
than 2 seconds.
[0140] FR-5 at the 2% level fails the NFPA 701 test, but even at
half that concentration in the presence of the instant hindered
amines the flame retardancy performance is vastly improved.
[0141] It is clear that when some of the decabromodiphenyl oxide is
replaced with a selected hindered amine that flame retardancy is
actually enhanced even at a lower total concentration (2% versus
1.5%) enough to pass the NFPA 701 test.
[0142] The combination of decabromodiphenyl oxide and the selected
hindered amine is synergistic. This result is both surprising and
unexpected as well as allowing a lesser amount of a brominated
compound to be used and still obtain adequate flame retardancy.
EXAMPLE 2
[0143] Polypropylene, the base resin containing 0.05% by weight of
calcium stearate, 0.1% by weight of tris(2,4-di-tert-butyl-phenyl)
phosphite and 0.05% by weight of neopentanetetrayl
tetrakis(3,5-di-tert-butyl-4-hydroxy- hydrocinnamate), is melt
compounded on a single-screw extruder at 425.degree. F.
(218.degree. C.) with the respective additives to form the
formulations given in the table below. 125 mil plaques are
compression molded at 400.degree. F.(204.degree. C.).
[0144] The plaques are tested for flame retardancy by the UL 94V
thick section test.
2 1st Flame Time 2nd Flame Time Formulation (average seconds)
(average seconds) FR-4 (5%) 252 ** FR-4 (10%) 103 ** FR-4 (5%) + 3
83 NOR-1 (5%) FR-4 (10%) + 5 4 NOR-1 (5%) FR-4 (25%) 7 11 **no time
is shown for the 2nd flame since the sample is completely consumed
after application of the first flame.
[0145] It is clear that the combination of the hindered amine NOR-1
with inorganic flame retardant at the same total concentration
potentiates the effectiveness of the inorganic flame retardant
allowing for a lower concentration of said inorganic flame
retardant to be used when combined with the hindered amine
component. This is a synergistic effect.
[0146] Even when the inorganic flame retardant is used at very high
levels alone, it cannot provide as much flame retardancy as the
combination of said flame retardant with the hindered amine at a
much lower total concentration.
EXAMPLE 3
[0147] Following the procedure of Example 2, molding grade
polypropylene is dry blended with the test additives and then melt
compounded at 425.degree. F. (218.degree. C.). Plaques (125 mil)
are prepared by injection molding from the formulations using a Boy
Injection Molder at 475.degree. F. (246.degree. C.). The specimens
are tested for flame retardancy according to the UL-94 vertical
burn test specifications. The results are shown below.
3 First Second (weight %) Flame Time Flame Time Formulation (av
seconds) (av seconds) control 194 ** FR-5 (10.5%) 97 55 FR-5
(10.5%) + 27 3 Sb.sub.2O.sub.3 (3.5%) FR-5 (5%) + 22 11 NOR-1
(0.25%) FR-5 (5%) + 12 8 NOR-9 (0.25%) FR-S (5%) + 8 18 NOR-10
(0.25%) **no time is shown for the 2nd flame since the sample is
completely consumed after application of the first flame.
[0148] FR-5 at the 10.5% level does not provide adequate flame
retardancy. However, when only half as much FR-4 (5% level) is
combined with a very small amount of an instant hindered amines
(0.25%), the flame retardancy is greatly improved.
[0149] These data show that antimony oxide can be replaced with a
small amount of an instant hindered amine in order to achieve good
flame retardancy. This is important since the replacement of heavy
metals is of prime concern for safety and environmental
reasons.
EXAMPLE 4
[0150] Polyethylene fibers are prepared from fiber grade
polyethylene by dry blending with test additives and melt
compounding at 400.degree. F. Fibers are extruded from this
formulation using a Hills laboratory scale fiber extruder. Socks
are knitted from the fibers and are tested for flame retardancy
according to NFPA 701 vertical burn method. Polyethylene fibers
contain an instant hindered amine compound in combination with a
classic brominated flame retardant decabromodiphenyl oxide (DBDPO);
bis(2,3dibromopropyl) ether of tetrabromobis phenol A (PE68); or
ethylene bis-tetrabromophthalimide (SAYTEX.RTM. BT-93). These
formulated fibers are tested for flame retardancy according to NFPA
701.
[0151] The fibers containing both an instant hindered amine
compound and a classic brominated flame retardant exhibit enhanced
flame retardancy compared to the classic flame retardant alone.
EXAMPLE 5
[0152] Polyethylene (LDPE) is melt compounded on a twin screw
extruder at 450.degree. F. (232.degree. C.) with the respective
additives to form the formulations given in the table below. 125
mil plaques are compression molded at 400.degree. F. (204.degree.
C.).
[0153] The plaques are tested for flame retardancy by the UL 94V
thick section test.
4 1st Flame Time 2nd Flame Time Formulation (average seconds)
(average seconds) Blank 163 FR-4 (10%) 198 ** FR-4 (5%) + 118 --
NOR-1 (5%) FR-4 (10%) + 1 64 NOR-1 (5%) **no time is shown for the
2nd flame since the sample is completely consumed after the
application of the first flame.
[0154] It is clear that the combination of the hindered amine NOR-1
with inorganic flame retardant at the same total concentration
potentiates the effectiveness of the inorganic flame retardant
allowing for a lower concentration of said inorganic flame
retardant to be used when combined with the hindered amine
component. This is a synergistic effect.
EXAMPLE 6
[0155] Foam grade polyethylene is dry blended with test additives
and then melt compounded into pellets. The pelletized fully
formulated resin is then blown into foam.
[0156] The polyethylene foam prepared contains an instant NOR or
NOROL compound in combination with a classic brominated flame
retardant. The formulated foam is tested for flame retardancy
according to the UL-94 burn test method.
[0157] The foam containing both an NOR or NOROL compound and a
classic brominated flame retardant exhibits enhanced flame
retardancy compared to foam containing the classic halogenated
flame retardant alone.
EXAMPLE 7
[0158] Wire & cable grade polyethylene is dry blended with test
additives and then melt compounded into pellets. The pelletized
fully formulated resin is then extruded onto wire.
[0159] Test specimens are tested for flame retardancy using the
ASTM D 2633-82 burn test conditions. The formulations containing
both an NOR or NOROL compound and a classic brominated flame
retardant exhibits enhanced flame retardancy compared to the
classic halogenated flame retardant alone.
EXAMPLE 8
[0160] Fiber grade polyethylene is dry-blended with test additives.
In addition to a hindered amine, selected flame retardants are also
included in the various formulations. Non-woven fabrics are
produced from the polymer blend formulations by a spun-bonded or
melt-blown process.
[0161] The non-woven fabrics made thereby are tested for flame
retardancy according to the NFPA 701 vertical burn test
specifications. The fabrics containing the hindered amine compounds
and selected flame retardants exhibit flame retardancy.
EXAMPLE 9
[0162] Fiber grade polypropylene is dry-blended with test
additives. In addition to a hindered amine, selected brominated
flame retardants are also included in the various formulations.
Non-woven fabrics are produced from the polymer blend formulations
by a spun-bonded or melt-blown process.
[0163] The non-woven fabrics made thereby are tested for flame
retardancy according to the NFPA 701 vertical burn test
specifications. The fabrics containing the hindered amine compounds
and selected brominated flame retardants exhibit flame
retardancy.
EXAMPLE 10
[0164] Molding grade polystyrene is dry-blended with test additives
and then melt compounded. In addition to the hindered amines,
selected brominated flame retardants are also included in the test
formulations. Specimens are injection molded from these test
formulations.
[0165] The specimens are tested for flame retardancy according to
the UL-94 burn test specifications. The molded specimens containing
the hindered amine compounds and selected brominated flame
retardants exhibit flame retardancy.
EXAMPLE 11
[0166] Foam grade polystyrene is dry-blended with test additives
and then melt compounded. In addition to the hindered amines,
selected brominated flame retardants are also included in these
test formulations. Foam polystyrene specimens are prepared from
these test formulations.
[0167] The specimens are tested for flame retardancy according to
the UL-94 burn test specifications. The foam specimens containing
the hindered amine compounds and brominated flame retardants
exhibit flame retardancy.
EXAMPLE 12
[0168] Molding grade ABS is dry blended with the test additives and
then melt compounded at 425.degree. F. (218.degree. C.). Specimens
125 mil (1/8") thick are then injection molded from this
formulation using a Boy Injection Molder at 450.degree. F.
(232.degree. C.). The specimens are tested for flame retardancy
according to the UL-94 vertical burn test specifications. The
results are tabulated below.
5 (weight %) 1st Flame Time 2nd Flame Time Formulation (average
seconds) (average seconds) control 141 ** FR-5 (5%) 68 18 FR-5
(10%) 42 28 FR-5 (7.5%) + 30 13 NOR-1 (0.25%) FR-5 (5%) + 39 20
NOR-1 (0.25%) **no time is shown for the 2nd flame since the sample
is completely consumed after application of the first flame.
[0169] It is clear that the combination of the hindered amine NOR-1
with an organic flame retardant at essentially the same total
concentration potentiates the effectiveness of the organic flame
retardant allowing for a lower concentration of said organic flame
retardant to be used when combined with the hindered amine
component. This is a synergistic effect.
[0170] Even when the organic flame retardant is used at very high
levels alone, it cannot provide as much flame retardancy as the
combination of said flame retardant with the hindered amine at a
much lower total concentration.
EXAMPLE 13
[0171] Following the general procedure of Example 2, molding grade
polypropylene is dry blended with the test additives and then melt
compounded at 425.degree. F. (218.degree. C.). Specimens 125 mil
(1/8") thick are then injection molded from this formulation at
450.degree. F. (232.degree. C.). The specimens are tested for flame
retardancy according to the UL-94 horizontal burn test
specifications. The results are tabulated below.
6 (weight %) Burn Time (seconds) Formulation Specimen 1 Specimen 2
Specimen 3 Total FR-7 (5%) 186 182 180 548 FR-7 (5%) + 3 35 25 63
NOR-1 (0.5%) FR-7 (2.5%) + 132 13 24 169 NOR-1 (1%) FR-7 (2.5%) + 2
1 1 4 NOR-10 (1%) FR-8 (10%) 282 271 172 725 FR-8 (5%) + 3 8 5 16
NOR-1 (1%) FR-8 (5%) + 2 1 2 5 NOR-10 (1%)
[0172] It is clear that the combination of the hindered amine NOR-1
or NOR-10 with an inorganic or organic flame retardant at
essentially the same and even at a lesser total concentration
potentiates the effectiveness of the inorganic or organic flame
retardant allowing for a lower concentration of said inorganic or
organic flame retardant to be used when combined with the hindered
amine component. This is a synergistic effect.
[0173] Even when the inorganic or organic flame retardant is used
at very high levels alone, it cannot provide as much flame
retardancy as the combination of said flame retardant with the
hindered amine at a much lower total concentration.
* * * * *