U.S. patent application number 14/379842 was filed with the patent office on 2015-10-08 for nor-hals compounds as flame retardants.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Holger Hoppe, Gregor Huber, Andre Le Gal, Gerard Lips.
Application Number | 20150284535 14/379842 |
Document ID | / |
Family ID | 49160324 |
Filed Date | 2015-10-08 |
United States Patent
Application |
20150284535 |
Kind Code |
A1 |
Lips; Gerard ; et
al. |
October 8, 2015 |
NOR-HALS COMPOUNDS AS FLAME RETARDANTS
Abstract
The present invention relates to the use of NOR-HALS compounds
in flame retardant polymer compositions. These compositions are
especially useful for the manufacture of flame retardant
compositions based on thermoplastic polymers, especially polyolefin
homo- and copolymers, polycondensates, such as polyamines or
polyesters and duroplastic polymers, such as polyepoxides.
Inventors: |
Lips; Gerard; (Huningue,
FR) ; Huber; Gregor; (Basel, SE) ; Hoppe;
Holger; (Loerrach, DE) ; Le Gal; Andre;
(Huningue, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
49160324 |
Appl. No.: |
14/379842 |
Filed: |
March 13, 2013 |
PCT Filed: |
March 13, 2013 |
PCT NO: |
PCT/IB2013/052003 |
371 Date: |
August 20, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61611620 |
Mar 16, 2012 |
|
|
|
Current U.S.
Class: |
524/102 ;
546/188 |
Current CPC
Class: |
C08K 5/49 20130101; C08K
5/0066 20130101; C07D 211/94 20130101; C08K 5/3435 20130101; C08K
5/5333 20130101 |
International
Class: |
C08K 5/3435 20060101
C08K005/3435; C08K 5/5333 20060101 C08K005/5333 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 16, 2012 |
EP |
12159919.5 |
Claims
1. Use of a NOR-HALS compound of the formula ##STR00014## Wherein
R.sub.1 and R.sub.2 represent C.sub.1-C.sub.30alkyl, for inducing
the flame retardancy in polymers.
2. Use according to claim 1 of a NOR-HALS compound (I), Wherein
R.sub.1 and R.sub.2, independently of one another, represent
n-butyl, n-undecyl or n-octadecyl.
3. Use according to claim 1 of a NOR-HALS compound (I), Wherein
R.sub.1 and R.sub.2 represent n-undecyl.
4. A composition, which comprises a) At least one NOR-HALS compound
of the formula ##STR00015## Wherein R.sub.1 and R.sub.2 represent
C.sub.1-C.sub.30alkyl; b) At least one flame retardant compound
selected from the group consisting of
tris(tribromoneopentyl)phosphate, resorcinol-bis-diphenylphosphate,
pentaerythritol-di-methyl phosphonate, guanidine phenylphosphonate,
melamine phenylphosphonate, dimethylaluminium phosphinate,
methyl-ethylaluminiumphosphinate, diethylaluminiumphosphinate,
poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]
and ammonium polyphosphate; and c) A polymer substrate.
5. A composition according to claim 4, which comprises a) At least
one NOR-HALS compound (I), wherein R.sub.1 and R.sub.2 represent
n-undecyl; b) At least one flame retardant compound selected from
the group consisting of tris(tribromoneopentyl)phosphate,
resorcinol-bis-diphenylphosphate, pentaerythritol-di-methyl
phosphonate, guanidine phenylphosphonate, melamine
phenylphosphonate, dimethylaluminium phosphinate,
methyl-ethylaluminiumphosphinate, diethylaluminiumphosphinate,
poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]
and ammonium polyphosphate; and c) A polymer substrate.
6. A composition according to claim 4, which comprises as an
optional component additional flame retardants and additives
selected from the group consisting of tetraalkylpiperidine
additives, polymer stabilizers, fillers, reinforcing agents and
so-called anti-dripping agents that reduce the melt flow of
thermoplastic polymers and reduce the formation of drops at higher
temperatures.
7. A composition according to claim 6, which comprises as an
additional flame retardant a nitrogen containing compound selected
from the group consisting of melamine polyphosphate, ammonium
polyphosphate, melamine ammonium phosphate, melamine ammonium
polyphosphate, melamine ammonium pyrophosphate, a condensation
product of melamine with phosphoric acid and other reaction
products of melamine with phosphoric acid and mixtures thereof.
8. A process for inducing the flame retardancy in polymers, which
comprises adding to a polymer substrate a combination of a) At
least one NOR-HALS compound of the formula ##STR00016## Wherein
R.sub.1 and R.sub.2 represent C.sub.1-C.sub.30alkyl; with b) At
least one flame retardant compound selected from the group
consisting of tris(tribromoneopentyl)phosphate,
resorcinol-bis-diphenylphosphate, pentaerythritol-di-methyl
phosphonate, guanidine phenylphosphonate, guanidine
phenylphosphonate, dimethylaluminium phosphinate,
methyl-ethylaluminiumphosphinate, diethylaluminiumphosphinate,
poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]
and aluminium polyphosphate.
9. Use of the composition according to claim 4 for inducing the
flame retardancy in polymers.
Description
[0001] The present invention relates to the use of NOR-HALS
compounds in flame retardant polymer compositions. These
compositions are especially useful for the manufacture of flame
retardant compositions based on thermoplastic polymers, especially
polyolefin homo- and copolymers, polycondensates, such as
polyamines or polyesters, and duroplastic polymers, such as
polyepoxides.
[0002] Flame retardants are added to polymeric materials (synthetic
or natural) to enhance the flame retardant properties of the
polymers. Depending on their composition, flame retardants may act
in the solid, liquid or gas phase either chemically, e.g. as a
spumescent by liberation of nitrogen, and/or physically, e.g. by
producing a foam coverage. Flame retardants interfere during a
particular stage of the combustion process, e.g. during heating,
decomposition, ignition or flame spread.
[0003] There is still a need for flame retardant compositions with
improved properties that can be used in different polymer
substrates. Increased standards with regard to safety and
environmental requirements result in stricter regulations.
Particularly known halogen containing flame retardants no longer
match all necessary requirements. Therefore, halogen free flame
retardants are preferred, particularly in view of their better
performance in terms of smoke density associated with fire.
Improved thermal stability and less corrosive behaviour are further
benefits of halogen free flame retardant compositions.
[0004] NOR-HALS compounds are known from EP 1 731 508 as
stabilizers for synthetic resins to protect these substrates from
degradation caused by the action of chemicals and acid rain.
[0005] It has surprisingly been found that thermoplastic or
duroplastic polymers with excellent flame retardant properties are
prepared in the event that selected NOR-HALS compounds are added to
the polymer substrate.
[0006] These compositions have excellent thermal stability and are
therefore especially suited for the application in engineering
thermoplastics and epoxy laminates used for the manufacture of
electrical and electronic parts and devices. By using the instant
flame retardant additives in thermoplastic and duroplastic resins,
conventional halogen containing flame retardants and halogenated
epoxy resins, antimony compounds, and inorganic fillers may largely
be reduced or replaced.
[0007] The present invention relates to the use of a NOR-HALS
compound of the formula
##STR00001## [0008] Wherein [0009] R.sub.1 and R.sub.2 represent
C.sub.1-C.sub.30alkyl, [0010] for inducing the flame retardancy in
polymers.
[0011] Examples of C.sub.1-C.sub.30alkyl groups represented by
R.sub.1 and R.sub.2 in the above formula (I) are linear, or where
possible, branched alkyl groups, such as methyl, ethyl, n-propyl,
iso-propyl, n-butyl, tert-butyl, isobutyl, n-pentyl, sec-pentyl,
tert-pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, iso-octyl,
2-ethylhexyl, tert-octyl, n-nonyl, isononyl, n-decyl, n-undecyl,
n-dodecyl (lauryl), n-tridecyl, n-tetradecyl (myristyl),
n-pentadecyl, n-hexadecyl (cetyl), n-octadecyl etc.
[0012] The polymer compositions wherein the compounds (I), as
defined above, are present, attain the desirable ratings related
established flame retardant test methods, especially in polyolefin
compositions.
[0013] This compound (I) is preferably contained in the flame
retardant compositions according to the invention in an amount from
about 0.005-90.0 wt. %, preferably about 0.02-20.0 wt. %, most
preferably between 0.10-15.0 wt.-%, based on the total weight of
the composition.
[0014] The term polymer and substrate comprises within its scope
thermoplastic and duroplastic polymers and thermosets.
[0015] A list of suitable thermoplastic polymers is given below:
[0016] 1. Polymers of monoolefins and diolefins, for example
thermoplastic polyolefins (TPO), such as polypropylene,
polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,
polyvinylcyclohexane, polyisoprene or polybutadiene, as well as
polymers of cycloolefins, for instance of cyclopentene or
norbornene, polyethylene (which optionally can be cross linked),
for example high density polymethylene (HDPE), high density and
high molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), (VLDPE) and (ULDPE). [0017]
Polyolefins, i.e. the polymers of monoolefins exemplified in the
preceding para-graph, preferably polyethylene and polypropylene,
can be prepared by different and especially by the following
methods: [0018] a) Radical polymerisation (normally under high
pressure and at elevated temperature). [0019] b) Catalytic
polymerisation using a catalyst that normally contains one or more
than one metal of groups IVb, Vb, VIb or VIII of the Periodic
Table. These metals usually have one or more than one ligand,
typically oxides, halides, alcoholates, esters, ethers, amines,
alkyls, alkenyls and/or aryls that may be either .alpha.- or
.pi.-bond coordinated. These metal complexes may be in the free
form or fixed on substrates, typically on activated magnesium
chloride, titanium(III) chloride, and alumina or silicon oxide.
These catalysts may be soluble or insoluble in the polymerisation
medium. The catalysts can be used by themselves in the
polymerisation or further activators may be used, typically metal
alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or
metal alkyloxanes, said metals being elements of groups Ia, IIa
and/or IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, and amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler-Natta), TNZ (DuPont), metallocene or
single site catalysts (SSC). [0020] 2. Mixtures of the polymers
mentioned under 1), for example mixtures of polypropylene with
polyisobutylene, polypropylene with polyethylene (for example
PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene
(for example LDPE/HDPE). [0021] 3. Copolymers of monoolefins and
diolefins with each other or with other vinyl monomers, for example
ethylene/propylene copolymers, linear low density polyethylene
(LLDPE) and mixtures thereof with low density polyethylene (LDPE),
propylene/but-1-ene copolymers, propylene/isobutylene copolymers,
ethylene/but-1-ene copolymers, ethylene/hexene copolymers,
ethylene/methylpentene copolymers, ethyl-ene/heptene copolymers,
ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers,
ethylene/cycloolefin copolymers (e.g. ethylene/norbomene like COC),
ethylene/1-olefins copolymers, where the 1-olefin is generated
in-situ; propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl
acrylate copolymers, such as ethylene-n-butyl acrylate or
methacrylate, ethylene/alkyl methacrylate copolymers,
ethylene/vinyl acetate copolymers or ethylene/acrylic acid
copolymers and their salts (ionomers) as well as terpolymers of
ethylene with propylene and a diene such as hexadiene,
dicyclopentadiene or ethylidene-norbomene; and mixtures of such
copolymers with one another and with polymers mentioned in 1)
above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides. [0022] 4. Hydrocarbon
resins (for example C.sub.5-C.sub.9) including hydrogenated
modifications thereof (e.g. tackifiers) and mixtures of
polyalkylenes and starch; [0023] The homopolymers and copolymers
mentioned above may have a stereo structure including syndiotactic,
isotactic, hemi-isotactic or atactic; where atactic polymers are
preferred. Stereo block polymers are also included. [0024] 5.
Polystyrene, poly(p-methylstyrene), poly(.alpha.-methylstyrene).
[0025] 6. Aromatic homopolymers and copolymers derived from vinyl
aromatic monomers including styrene, .alpha.-methylstyrene, all
isomers of vinyl toluene, especially p-vinyl toluene, all isomers
of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl
naphthalene, and vinyl anthracene, and mixtures thereof.
Homopolymers and copolymers may have a stereo structure including
syndiotactic, isotactic, hemi-isotactic or atactic; where atactic
polymers are preferred. Stereo block polymers are also included;
[0026] a) Copolymers including aforementioned vinyl aromatic
monomers and comonomers selected from ethylene, propylene, dienes,
nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and
vinyl chloride or acrylic derivatives and mixtures thereof, for
example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene
(interpolymers), styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene. [0027] b) Hydrogenated aromatic
polymers derived from hydrogenation of polymers mentioned under
6.), especially including polycyclohexylethylene (PCHE) prepared by
hydrogenating atactic polystyrene, often referred to as
polyvinylcyclohexane (PVCH). [0028] c) Hydrogenated aromatic
polymers derived from hydrogenation of polymers mentioned under
6a). Homopolymers and copolymers may have a stereo structure
including syndiotactic, isotactic, hemi-isotactic or atactic; where
atactic polymers are preferred. Stereo block polymers are also
included. [0029] 7. Graft copolymers of vinyl aromatic monomers,
such as styrene or .alpha.-methylstyrene, for example styrene on
polybutadiene, styrene on polybutadiene-styrene or
polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile
(or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and
methyl methacrylate on polybutadiene; styrene and maleic anhydride
on polybutadiene; styrene, acrylonitrile and maleic anhydride or
maleimide on polybutadiene; styrene and maleimide on polybutadiene;
styrene and alkyl acrylates or methacrylates on polybutadiene;
styrene and acrylonitrile on ethylene/propylene/diene terpolymers;
styrene and acrylonitrile on polyalkyl acrylates or polyalkyl
methacrylates, styrene and acrylonitrile on acrylate/butadiene
copolymers, as well as mixtures thereof with the copolymers listed
under 6), for example the copolymer mixtures known as ABS, MBS, ASA
or AES polymers. [0030] 8. Halogen-containing polymers such as
polychloroprene, chlorinated rubbers, chlorinated and brominated
copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated
or sulphochlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for
example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride, polyvinylidene fluoride, as well as copolymers thereof
such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl
acetate or vinylidene chloride/vinyl acetate copolymers. [0031] 9.
Polymers derived from .alpha.,.beta.-unsaturated acids and
derivatives thereof such as poly-acrylates and polymethacrylates;
polymethyl methacrylates, polyacrylamides and polyacrylonitriles,
impact-modified with butyl acrylate. [0032] 10. Copolymers of the
monomers mentioned under 9) with each other or with other
unsaturated monomers, for example acrylonitrile/butadiene
copolymers, acrylonitrile/alkyl acrylate copolymers,
acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide
copolymers or acrylonitrile/alkyl methacrylate/butadiene
terpolymers. [0033] 11. Polymers derived from unsaturated alcohols
and amines or the acyl derivatives or acetals thereof, for example
polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl
benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate
or polyallyl melamine; as well as their copolymers with olefins
mentioned in 1 above. [0034] 12. Homopolymers and copolymers of
cyclic ethers such as polyalkylene glycols, polyethylene oxide,
polypropylene oxide or copolymers thereof with bisglycidyl ethers.
[0035] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes, which contain ethylene oxide as a co-monomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS. [0036] 14. Polyphenylene oxides and sulphides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides. [0037]
15. Polyamides and co-polyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4, -trimethylhexamethylene
terephthalamide or poly-m-phenylene isophthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or co-polyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0038] 16. Polyureas, polyimides, polyamide imides, polyether
imides, polyester imides, polyhydantoins and polybenzimidazoles.
[0039] 17. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene
naphthalate (PAN) and polyhydroxybenzoates, as well as block
co-polyether esters derived from hydroxyl-terminated polyethers;
and also polyesters modified with polycarbonates or MBS. [0040] 18.
Polyketones. [0041] 19. Polysulphones, polyether sulphones and
polyether ketones. [0042] 20. Blends of the aforementioned polymers
(polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA,
PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE,
PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,
POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers,
PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC. [0043] 21.
Polycarbonates that correspond to the general formula:
[0043] ##STR00002## [0044] Such polycarbonates are obtainable by
interfacial processes or by melt processes (catalytic
transesterification). The polycarbonate may be either branched or
linear in structure and may include any functional substituents.
Polycarbonate copolymers and polycarbonate blends are also within
the scope of the invention. The term polycarbonate should be
interpreted as inclusive of copolymers and blends with other
thermoplastics. Methods for the manufacture of polycarbonates are
known, for example, from U.S. Pat. Nos. 3,030,331; 3,169,121;
4,130,458; 4,263,201; 4,286,083; 4,552,704; 5,210,268; and
5,506,007. A combination of two or more polycarbonates of different
molecular weights may be used. [0045] Preferred are polycarbonates
obtainable by reaction of a diphenol, such as bisphenol A, with a
carbonate source. Examples of suitable diphenols are:
[0045] ##STR00003## ##STR00004## [0046]
4,4'-(2-norbomylidene)bis(2,6-dichlorophenol); or
fluorene-9-bisphenol:
[0046] ##STR00005## [0047] The carbonate source may be a carbonyl
halide, a carbonate ester or a haloformate. Suitable carbonate
halides are phosgene or carbonylbromide. Suitable carbonate esters
are dialkylcarbonates, such as dimethyl- or diethylcarbonate,
diphenyl carbonate, phenyl-alkylphenylcarbonate, such as
phenyl-tolylcarbonate, dialkylcarbonates, such as dimethyl- or
diethylcarbonate, di-(halophenyl)carbonates, such as
di-(chlorophenyl)carbonate, di-(bromophenyl)carbonate,
di-(trichlorophenyl)carbonate or di-(trichlorophenyl)carbonate,
di-(alkylphenyl)carbonates, such as di-tolylcarbonate,
naphthylcarbonate, dichloronaphthylcarbonate and others. [0048] The
polymer substrate mentioned above, which comprises polycarbonates
or polycarbonate blends is a polycarbonate-copolymer, wherein
isophthalate/terephthalate-resorcinol segments are present. Such
polycarbonates are commercially available, e.g. Lexan.RTM. SLX
(General Electrics Co. USA). Other polymeric substrates of
component b) may additionally contain in the form as admixtures or
as copolymers a wide variety of synthetic polymers including
polyolefins, polystyrenes, polyesters, polyethers, polyamides,
poly(meth)acrylates, thermoplastic polyurethanes, polysulphones,
polyacetals and PVC, including suitable compatibilizing agents. For
example, the polymer substrate may additionally contain
thermoplastic polymers selected from the group of resins consisting
of polyolefins, thermoplastic polyurethanes, styrene polymers and
copolymers thereof. Specific embodiments include polypropyl-ene
(PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate
(PBT), polyethylene terephthalate (PET), glycol-modified
polycyclohexylenemethylene terephthalate (PCTG), polysulphone
(PSU), polymethylmethacrylate (PMMA), thermoplastic polyurethane
(TPU), acrylonitrile-butadiene-styrene (ABS),
acrylonitrile-styrene-acrylic ester (ASA),
acrylonitrile-ethylene-propylene-styrene (AES), styrene-maleic
anhydride (SMA) or high impact polystyrene (HIPS).
[0049] A preferred embodiment of the invention relates to the use
of NOR-HALS compounds (I) in thermoplastic polymers. Preferred
thermoplastic polymers include polyamides, polyesters and
polycarbonates.
[0050] Another preferred embodiment of the invention relates to a
composition, wherein component c) is a duroplastic polymer
substrate of the polyepoxide type.
[0051] A particularly preferred embodiment of the invention relates
to the use of a NOR-HALS compound (I), wherein R.sub.1 and R.sub.2,
independently of one another, represent n-butyl, n-undecyl or
n-octadecyl, for inducing flame retardancy in polymers.
[0052] A highly preferred embodiment of the invention relates to
the use of a NOR-HALS compound (I), wherein R.sub.1 and R.sub.2
represent n-undecyl, for inducing flame retardancy in polymers.
[0053] A further embodiment of the invention relates to a
composition, which comprises [0054] a) At least one NOR-HALS
compound of the formula
[0054] ##STR00006## [0055] Wherein [0056] R.sub.1 and R.sub.2
represent C.sub.1-C.sub.30alkyl; [0057] b) At least one flame
retardant compound selected from the group consisting of
tris(tribromoneopentyl)phosphate:
[0057] ##STR00007## [0058] resorcinol-bis-diphenylphosphate:
[0058] ##STR00008## [0059] pentaerythritol-di-methyl
phosohonate:
[0059] ##STR00009## [0060] guanidine phenylphosphonate, melamine
phenylphosphonate, dimethylaluminium phosphinate,
methyl-ethylaluminiumphosphinate, diethylaluminiumphosphinate,
poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]
and ammonium polyphosphate; and [0061] c) A polymer substrate.
[0062] The use of the composition defined above for inducing the
flame retardancy in polymers is also subject matter of the present
invention.
[0063] Another preferred embodiment relates to a composition, which
comprises [0064] a) At least one NOR-HALS compound (I), wherein
R.sub.1 and R.sub.2 represent n-undecyl; [0065] b) At least one
flame retardant compound selected from the group consisting of
tris(tribromoneopentyl)phosphate, resorcinol-bis-diphenylphosphate,
pentaerythritol-di-methyl phosphonate, guanidine phenylphosphonate,
melamine phenylphosphonate, dimethylaluminium phosphinate,
methyl-ethylaluminiumphosphinate, diethylaluminiumphosphinate,
poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]
and aluminium polyphosphate; and [0066] c) A polymer substrate.
[0067] The combination of the NOR-HALS (I) and the additional flame
retardants defined above is preferably contained in the flame
retardant compositions according to the use defined above in an
amount from about 0.005-90.0 wt. %, preferably about 0.02-20.0 wt.
%, most preferably between 0.10-15.0 wt.-%, based on the total
weight of the composition.
[0068] The instant invention further pertains to the use of
compounds (I) in flame retardant compositions and to the
above-defined compositions which comprise, in addition to the
components defined above, optional components, such as additional
flame retardants and/or further additives selected from the group
consisting of tetraalkylpiperidine additives, smoke suppressants,
polymer stabilizers, fillers, reinforcing agents and so-called
anti-dripping agents that reduce the melt flow of thermoplastic
polymers and reduce the formation of drops at higher
temperatures.
[0069] Such additional flame retardants are phosphorus containing
flame retardants, for example selected from the group consisting of
phosphorus and/or nitrogen containing flame retardants,
organo-halogen containing flame retardants and inorganic flame
retardants.
[0070] Phosphorus containing flame retardants are, for example,
resorcinol phenylphosphate oligomer (Fyrolflex.RTM. RDP, Akzo
Nobel), triphenyl phosphate, bisphenol A phenylphosphate oligomer
(Fyrolflex.RTM. BDP), tris(2,4-di-tert-butylphenyl)phosphate,
ethylenediamine diphosphate (EDAP), tetra(2,6-dimethylphenyl)
resorcinol diphosphate, diethyl-N,N-bis(2-hydroxyethyl)-aminomethyl
phosphonate, hydroxyalkyl esters of phosphorus acids, salts of
hypophosphoric acid (H.sub.3PO.sub.2), particularly the Ca.sup.2+,
Zn.sup.2+, or Al.sup.3+ salts, tetrakis(hydroxymethyl)phosphonium
sulphide, triphenylphosphine, triphenyl phosphine oxide,
tetraphenyldiphosphine monoxide, phosphazenes and
9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and
its derivatives, such as
2-(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)-1,4-benzenediol.
[0071] Nitrogen containing flame retardants are, for example,
isocyanurate flame retardants, such as polyisocyanurate, esters of
isocyanuric acid or isocyanurates. Representative examples are
hydroxyalkyl isocyanurates, such as
tris-(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate,
tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl
isocyanurate.
[0072] Nitrogen containing flame-retardants furthermore include
melamine-based flame retardants. Representative examples are:
melamine cyanurate, melamine borate, melamine phosphate, melamine
pyrophosphate, melamine polyphosphate, melamine ammonium
polyphosphate, melamine ammonium pyrophosphate, dimelamine
phosphate and dimelamine pyrophosphate.
[0073] Further examples are: benzoguanamine, allantoin, glycoluril,
urea cyanurate, ammonium polyphosphate, and a condensation product
of melamine from the series melem, melam, melon and/or a higher
condensed compound or a reaction product of melamine with
phosphoric acid or a mixture thereof.
[0074] Representative organo-halogen flame retardants are, for
example:
[0075] Polybrominated diphenyl oxide (DE-60F, Chemtura Corp.),
decabromodiphenyl oxide (DBDPO; Saytex.RTM. 102E),
tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate (PB 370.RTM., FMC
Corp.), tris(2,3-dibromopropyl)phosphate,
tris(2,3-dichloropropyl)phosphate, chlorendic acid,
tetrachlorophthalic acid, tetrabromophthalic acid, polychloroethyl
triphosphonate mixture, tetrabromobisphenol A bis(2,3-dibromopropyl
ether) (PE68), brominated epoxy resin,
ethylene-bis(tetrabromophthalimide) (Saytex.RTM. BT-93),
bis(hexachlorocyclopentadieno)cyclooctane (Declorane Plus.RTM.),
chlorinated paraffins, octa-bromodiphenyl ether,
1,2-bis(tribromophenoxy)ethane (FF680), tetrabromo-bisphenol A
(Saytex.RTM. RB100), ethylene bis-(dibromo-norbomanedicarboximide)
(Saytex.RTM.BN-451), bis-(hexachlorocyclopentadieno) cyclooctane,
PTFE, tris-(2,3-dibromopropyl)isocyanurate, and
ethylene-bis-tetrabromophthalimide.
[0076] The organohalogen flame retardants mentioned above are
routinely combined with an inorganic oxide synergist. Most common
for this use are zinc or antimony oxides, e.g. Sb.sub.2O.sub.3 or
Sb.sub.2O.sub.5. Boron compounds are suitable, too.
[0077] Representative inorganic flame retardants include, for
example, aluminium trihydroxide (ATH), boehmite (AlOOH), magnesium
dihydroxide (MDH), hydrotalcite, zinc borates, CaCO.sub.3,
(organically modified) layered silicates, (organically modified)
layered double hydroxides, and mixtures thereof.
[0078] The above-mentioned additional flame retardant classes are
advantageously contained in the composition of the invention in an
amount from about 0.5% to about 75.0% by weight of the organic
polymer substrate; for instance about 10.0% to about 70.0%; for
example about 25.0% to about 65.0% by weight, based on the total
weight of the corn-position.
[0079] According to another embodiment, the invention relates to
compositions which additionally comprise as additional component
so-called anti-dripping agents.
[0080] These anti-dripping agents reduce the melt flow of the
thermoplastic polymer and inhibit the formation of drops at high
temperatures. Various references, such as U.S. Pat. No. 4,263,201,
describe the addition of anti-dripping agents to flame retardant
compositions.
[0081] Suitable additives that inhibit the formation of drops at
high temperatures include glass fibres, polytetrafluoroethylene
(PTFE), high temperature elastomers, carbon fibres, glass spheres
and the like.
[0082] The addition of polysiloxanes of different structures has
been proposed in various references; cf. U.S. Pat. Nos. 6,660,787,
6,727,302 or 6,730,720.
[0083] According to a further embodiment, the invention relates to
compositions which additionally comprise as additional components
fillers and reinforcing agents. Suitable fillers are, for example,
glass powder, glass-microspheres, silica, mica, wollastonite and
talcum.
[0084] Stabilizers are preferably halogen-free and selected from
the group consisting of nitroxyl stabilizers, nitrone stabilizers,
amine oxide stabilizers, benzofuranone stabilizers, phosphite and
phosphonite stabilizers, quinone methide stabilizers and
monoacrylate esters of 2,2'-alkylidenebisphenol stabilizers.
[0085] As mentioned above, the composition according to the
invention may additionally contain one or more conventional
additives, for example selected from the group consisting of
pigments, dyes, plasticizers, antioxidants, thixotropic agents,
levelling assistants, basic co-stabilizers, metal passivators,
metal oxides, organophosphorus compound, UV-absorbers and further
light stabilizers and mixtures thereof, especially pigments,
phenolic antioxidants, calcium stearate, zinc stearate and UV
absorbers of the 2-hydroxy-benzophenone,
2-(2'-hydroxyphenyl)benzotriazole and/or
2-(2-hydroxyphenyl)-1,3,5-triazine and benzoate groups, such as
2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate
(TINUVIN 120) or hexadecyl 3,5-bis-tert-butyl-4-hydroxybenzoate
(Cytec Cyasorb.RTM.UV 2908.
[0086] Preferred additional additives for the compositions as
defined above are processing stabilizers, such as the
above-mentioned phosphites and phenolic antioxidants, and light
stabilizers, such as benzotriazoles. Preferred specific
antioxidants include octadecyl 3-(3,5-di-tert-butyl-hydroxyphenyl)
propionate (IRGANOX 1076),
pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]
(IRGANOX 1010), tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate
(IRGANOX 3114),
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene
(IRGANOX 1330),
triethyleneglycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate-
] (IRGANOX 245), and
N,N'-hexane-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamid-
e] (IRGANOX 1098). Specific processing stabilizers include
tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168),
3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphas-piro[5-
.5]undecane (IRGAFOS 126),
2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1-biphenyl-2,-
2'-diyl)]phosphite (IRGAFOS 12), and
tetrakis(2,4-di-tert-butylphenyl)-[1,1-biphenyl]-4,4'-diylbisphosphonite
(IRGAFOS P-EPQ). Specific light stabilizers include
2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
(TINUVIN 234),
2-(5-chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol
(TINUVIN 326),
2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol
(TINUVIN 329),
2-(2H-benzotriazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol
(TINUVIN 350),
2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)ph-
enol) (TINUVIN 360), and
2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (TINUVIN
1577), 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (TINUVIN P),
2-hydroxy-4-(octyloxy)benzophenone (CHI-MASSORB 81),
1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-{[(2'-cyano-3',3'--
diphenylacryloyl)oxy]methyl}-propane (UVINUL 3030, BASF),
ethyl-2-cyano-3,3-diphenylacrylate (UVINUL 3035, BASF), and
(2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINUL 3039,
BASF).
[0087] According to a further embodiment the compositions comprise
as an optional component the additional flame retardants defined
above and additives selected from the group consisting of polymer
stabilizers and tetraalkylpiperidine derivatives.
[0088] Representative examples of tetraalkylpiperidine derivatives
are selected from the group [0089] consisting of [0090]
1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
bis(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, [0091]
2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6--
(2-hy-droxyethylamino-s-triazine, [0092]
bis(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
[0093]
2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6--
chloro-s-triazine, [0094]
1-(2-Hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,
[0095]
1-(2-Hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,
[0096]
1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethy-
lpiperidine, [0097]
bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate, [0098]
bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)
adipate, [0099]
2,4-bis{N-[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-y-
l]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine, [0100] The
reaction product of
2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6--
chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine),
[0101]
2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6--
(2-hy-droxyethylamino)-s-triazine, [0102] The oligomeric compound
which is the condensation product of
4,4'-hexame-thylenebis(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, [0103] The compound of
the formula
[0103] ##STR00010## [0104] and the compound of the formula
##STR00011##
[0104] in which n is a numeral from 1 to 15.
[0105] The additives mentioned above are preferably contained in an
amount of 0.01 to 10.0%, especially 0.05 to 5.0%, relative to the
weight of the polymer substrate of Component c).
[0106] The incorporation of the components defined above into the
polymer component is carried out by known methods such as dry
blending in the form of a powder, or wet mixing in the form of
solutions, dispersions or suspensions for example in an inert
solvent, wa-ter or oil. The additive components may be
incorporated, for example, before or after molding or also by
applying the dissolved or dispersed additive or additive mixture to
the polymer material, with or without subsequent evaporation of the
solvent or the sus-pension/dispersion agent. They may be added
directly into the processing apparatus (e.g. extruders, internal
mixers, etc.), e.g. as a dry mixture or powder, or as a solution or
dispersion or suspension or melt.
[0107] The addition of the additive components to the polymer
substrate can be carried out in customary mixing machines in which
the polymer is melted and mixed with the additives. Suitable
machines are known to those skilled in the art. They are
predominantly mixers, kneaders and extruders.
[0108] The process is preferably carried out in an extruder by
introducing the additive during processing.
[0109] Particularly preferred processing machines are single-screw
extruders, contra-rotating and co-rotating twin-screw extruders,
planetary-gear extruders, ring extruders or co-kneaders. Processing
machines provided with at least one gas removal compartment can be
used to which a vacuum can be applied.
[0110] Suitable extruders and kneaders are described, for example,
in Handbuch der Kunst-stoffextrusion, Vol. 1 Grundlagen, Editors F.
Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4
(Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
[0111] For example, the screw length is 1-60 screw diameters,
preferably 35-48 screw diameters. The rotational speed of the screw
is preferably 10-600 rotations per minute (rpm), preferably 25-300
rpm.
[0112] The maximum throughput is dependent on the screw diameter,
the rotational speed and the driving force. The process of the
present invention can also be carried out at a level lower than
maximum throughput by varying the parameters mentioned or
em-ploying weighing machines delivering dosage amounts.
[0113] If a plurality of components is added, these can be premixed
or added individually.
[0114] The additive components and optional further additives can
also be added to the polymer in the form of a master batch
("concentrate") which contains the components in a concentration
of, for example, about 1.0% to about 80.0% and preferably 2.0% to
about 60.0% by weight incorporated in a polymer. The polymer is not
necessarily of identical structure than the polymer where the
additives are added finally. In such operations, the polymer can be
used in the form of powder, granules, solutions, and suspensions or
in the form of lattices.
[0115] The additive components can also be added to the polymer in
the form of a master batch ("concentrate") which contains the
components in a concentration of, for example, about 1.0% to about
80.0% and preferably 2.0% to about 60.0% by weight incorporated in
a polymer. The polymer is not necessarily of identical structure
than the polymer where the additives are added finally. In such
operations, the polymer can be used in the form of powder,
granules, solutions, and suspensions or in the form of
lattices.
[0116] Incorporation can take place prior to or during the shaping
operation. The materials containing the additives of the invention
described herein preferably are used for the production of molded
articles, for example injection molded or roto-molded articles,
injection molded articles, profiles and the like, and fibres, spun
melt non-woven, films or foams.
[0117] A preferred embodiment relates to a process for inducing the
flame retardancy in polymers, which comprises adding to a polymer
substrate a combination of [0118] a) At least one NOR-HALS compound
of the formula
[0118] ##STR00012## [0119] Wherein [0120] R.sub.1 and R.sub.2
represent C.sub.1-C.sub.30alkyl; with [0121] b) At least one flame
retardant compound selected from the group consisting of
tris(tribromoneopentyl)phosphate, resorcinol-bis-diphenylphosphate,
pentaerythritol-di-methyl phosphonate, guanidine phenylphosphonate,
melamine phenylphosphonate, dimethylaluminium phosphinate,
methyl-ethylaluminiumphosphinate, diethylaluminiumphosphinate,
poly-[2,4-(piperazine-1,4-yl)-6-morpholine-4-yl)-1,3,5-triazine]
and ammonium polyphosphate.
[0122] The polymer substrate suitable for inducing flame retardancy
has been described above.
[0123] The following Examples illustrate the invention:
A) METHODS
[0124] The following standard test methods are used to evaluate the
performance of FR-1 as flame retardant:
DIN 4102-Part 1
[0125] The specimen is positioned vertically and the ignition flame
is applied at the lower edge of the specimen (edge ignition
test).
[0126] Classification is based on the time for flames to spread 150
mm of the specimen.
[0127] If the flame does not reach the 150 mm reference mark within
20 seconds, the tested film passes the test and is classified
B2.
[0128] UL 94-VTM and UL 94-V
[0129] A flame is applied twice to the lower end of the test
specimen positioned vertically.
[0130] UL 94-VTM is a well-known test for classifying the flame
retardancy of very thin material in 3 classes VTM-0, VTM-1 and
VTM-2. The best rating is VTM-0.
[0131] UL 94 test for Flammability of Plastic Materials for Parts
in Devices and Appliances, 5th edition, Oct. 29, 1996. Ratings
according to the UL 94 V test are compiled in the following table
(time periods are indicated for one specimen):
TABLE-US-00001 TABLE After flame time Rating [sec] Burning drips
Burn to clamp V-0 <10 No No V-1 <30 No No V-2 <30 Yes No
n.c. <30 Yes n.c. >30 No n.c.: not classified
Fr-1
##STR00013##
[0132] R.sub.1, R.sub.2: n-undecyl
B) APPLICATION EXAMPLES
Example 1
Flame Retardancy of Fiber Grade Polypropylene (MFI 25) Containing
1% of FR-1
PP Film Manufacture:
[0133] Fiber grade polypropylene (Moplen.RTM. HP 552 (Basell)) is
dry blended with 1% of FR-1 and melt compounded into pellets on a
co-rotating twin-screw extruder type Berstorff 32D (lab size twin
screw extruder, 25 mm screw diameter, 9 heating zones) at a
temperature T.sub.max of 230.degree. C.
[0134] The pelletized fully formulated resin is cast at a maximum
temperature T.sub.max of 200.degree. C. into 250 .mu.m films using
a cast film equipment Collin CR-136/350 coupled with an extruder
Collin E 30 M.
[0135] Produced films and concentration of additive are listed in
Table 1:
TABLE-US-00002 TABLE 1 Concentration of added additive in the PP
film Film No. Additive Film 1 No addition Film 2 1% FR-1
[0136] Performance of FR-1 as flame retardant:
TABLE-US-00003 TABLE 2 Flame test on 250 .mu.m PP cast films
according to modified DIN 4102-Part 1 (edge ignition) Burning
Damaged DIN time length Burning drips 4102-B2 Film No. [sec] [mm]
paper ignition .sup.f) Rating Film 1 33 190 yes not classified Film
2 8 62 no B2 .sup.f) Rated "yes", if the burning drips ignite the
paper placed underneath the test specimen according to the DIN
4102-Part 1 test norm.
[0137] The burning time of Film 2 containing 1% FR-1 decreases
significantly in comparison to Film 1. Film 2 is classified as B2.
FR-1 contributes to lower the burning time and the damaged length
and, therefore, increases flame retardancy of polypropylene.
TABLE-US-00004 TABLE 3 Flame test on 250 .mu.m PP cast films
according to UL94-VTM Average flaming time .sup.a) Specimen burnt
UL94-VTM Film No. [sec] to holding clamp Rating Film 1 31 Yes not
classified Film 2 13 No VTM-2 .sup.a) Average flaming time per
specimen and after maximum 2 ignitions
[0138] The efficacy of FR-1 as a flame retardant is demonstrated by
a lower average flaming time, with no specimen burnt to the clamp
and VTM-2 classification.
Example 2
Flame Retardancy of Cast Film Grade Polypropylene (MFI 8)
Containing 1% of FR-1
PP Film Manufacture:
[0139] Fiber grade polypropylene (RD204CF (Borealis)) is dry
blended with 1% of FR-1 and melt compounded into pellets on a
co-rotating twin-screw extruder type Berstorff 46D (lab size twin
screw extruder, 25 mm screw diameter at a temperature T.sub.max of
250.degree. C.
[0140] The pelletized fully formulated resin is cast at a maximum
temperature T.sub.max of 230.degree. C. into 250 .mu.m films using
a cast film equipment Collin CR-136/350 coupled with an extruder
Collin E 30 M.
[0141] Produced films and concentration of additive are listed in
Table 4.
TABLE-US-00005 TABLE 4 Concentration of added additive in the PP
film Film No. Additive Film 1 No addition Film 2 1% FR-1
[0142] Performance of FR-1 as flame retardant:
TABLE-US-00006 TABLE 5 Flame test on 250 .mu.m PP cast films
according to modified DIN 4102-Part 1 (edge ignition) Burning
Damaged DIN time length Burning drips 4102-B2 Film No. [sec] [mm]
paper ignition .sup.f) Rating Film 1 30 190 yes not classified Film
2 10 77 no B2 .sup.f) Rated "yes", if the burning drips ignite the
paper placed underneath the test specimen according to the DIN
4102-Part 1 test norm.
[0143] The burning time of Film 2 containing 1% FR-1 decreases
significantly in comparison with Film 1. Film 2 is classified B2.
FR-1 contributes to lower the burning time and the damaged length
and, therefore, increases the flame retardancy of
polypropylene.
TABLE-US-00007 TABLE 6 Flame test on 250 .mu.m PP cast films
according to UL94-VTM Average flaming time .sup.a) Specimen burnt
UL94-VTM Film No. [sec] to holding clamp Rating Film 1 27 Yes not
classified Film 2 7 No VTM-2 .sup.a) Average flaming time per
specimen and after maximum of 2 ignitions
[0144] The efficacy of FR-1 as a flame retardant is demonstrated by
a lower average flaming time, with no specimen burnt to the clamp
and VTM-2 classification.
Example 3
Flame Retardancy of TPO (Thermoplastic Polyolefin) Membrane
Containing 0.8% of FR-1
TPO 1 mm Film Manufacture:
[0145] Roofing membrane grade thermoplastic polyolefin (Hifax.RTM.
CA 10 A Natural (Lyondell BaseII Polymers)) is blended on two
roll-mill equipment at 160.degree. C. with 2% titanium dioxide
pigment, 0.1% calcium stearate and FR-1 and melt compressed at the
temperature of 170.degree. C. into 1 mm plaques by using a hot
press. Produced plaques and concentration of additives are listed
in Table 7.
TABLE-US-00008 TABLE 7 Concentration of added additive in the TPO
Plaques Film No. Additive Plaque 1 No FR-1 Plaque 2 0.8% FR-1
The test method according to DIN 4102-Part 1 is used to evaluate
the performance of FR-1 as flame retardant:
TABLE-US-00009 TABLE 8 Flame test on TPO plaques of 1 mm thickness
according to modified DIN 4102-Part 1 (edge ignition) Burning
Damaged DIN time length Burning drips 4102-B2 Film No. [sec] [mm]
paper ignition f) Rating Plaque 1 75 >150 yes not classified
Plaque 2 23 50 yes B2 f) Rated "yes", if the burning drips ignite
the paper placed underneath the test specimen according to the DIN
4102-Part 1 test norm.
[0146] The burning time as well as the damaged length of Plaque 2
containing 0.8% FR-1 decreases significantly in comparison to
Plaque 1. As a result, Plaque 2 is classified B2.
[0147] FR-1 contributes to lower the burning time and the damaged
length and therefore increases thermoplastic polyolefin flame
retardancy.
Example 4
Flame Retardancy of Injection Molded Grade Polypropylene (MFI 25)
Containing FR-1
Polymer Component: MOPLEN HP 552 R (Lyondell Basell (PP))
Flame Retardant Components:
[0148] ADK STAB LA-81 (ADEKA):
bis(1-undecanyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate
(FR-1)
[0149] Aflammit.RTM.TL 1260 (THOR GROUP LIMITED):
Pentaerythritol-di-methylphosphonate (FR-2)
[0150] PP, FR-1 and FR-2 are premixed in the amounts indicated and
melt compounded into pellets on a co-rotating twin-screw extruder
Berstorff 32D (lab size twin screw extruder, 25 mm screw diameter)
at a maximum temperature T.sub.max of 230.degree. C.
[0151] UL94-V test specimen of 1.6 mm thickness are prepared by
injection molding (Engel EK 65).
TABLE-US-00010 TABLE 9 Ref. 1 Ref. 2 Inv. 1 PP 100 84 84 FR-1 1
FR-2 16 15 UL 94 V at 1.6 mm n.c. V-2 V-0
[0152] Ref. (Referential Compositions) 1, 2; Inv. (Inventive
Composition) 1: Addition of FR-1 increases significantly the FR
performance of the composition in comparison to Referential
Compositions 1, 2. The efficacy of FR-1 as a flame retardant is
demonstrated by V-0 classification.
Example 5
Flame Retardancy of High Density Polyethylene (HDPE) Containing
FR-1
HDPE Film Manufacture:
[0153] High density polyethylene (Hostalen.RTM. ACP 7740 F2
(Lyondell Basell)) is dry blended with FR-1 and melt compounded
into pellets on a co-rotating twin-screw extruder type Collin 42D
(lab size twin screw extruder, 25 mm screw diameter) at a maximum
temperature T.sub.max of 210.degree. C.
[0154] The pelletized fully formulated resin is extruded and blown
at a maximum temperature T.sub.max of 230.degree. C. into film by
using a blown film extrusion equipment Collin Type 180/400 coupled
with an extruder Collin E 30 P.
[0155] Produced films and concentration of additive are listed in
Table 10.
TABLE-US-00011 TABLE 10 Concentration of added additive in HDPE
blown films Film No. Film Additive 1 100 .mu.m No addition 2 200
.mu.m No addition 3 100 .mu.m 1.5% FR-1 4 200 .mu.m 1.0% FR-1
TABLE-US-00012 TABLE 11 Flame test on 200 .mu.m HDPE blown films
according to DIN 4102-Part 1 (edge ignition) Burning Damaged DIN
time length Burning drips 4102-B2 Film No. [sec] [mm] paper
ignition.sup.f) rating 2 31 >150 yes not classified 4 11 71 yes
B2 .sup.f)Rated "yes", if the burning drips ignite the paper placed
underneath the test specimen according to the DIN 4102-Part 1 test
norm.
[0156] The burning time of Film 4 containing 1% FR-1 decreases
significantly in comparison to Film 2. Film 4 is classified B2.
FR-1 contributes to lower the burning time and the damaged length
and therefore increases high density polyethylene flame
retardancy.
TABLE-US-00013 TABLE 12 Flame test on 100 .mu.m HDPE blown films
according to UL94-VTM Average flaming time.sup.a) Specimen burnt
UL94-VTM Film No. [sec] to holding clamp rating 1 16.sup.b) Yes not
classified 3 7.sup. No VTM-2 .sup.a)Average flaming time per
specimen and after maximum 2 ignitions .sup.b)Specimen completely
burnt after the first ignition.
[0157] The efficacy of FR-1 as a flame retardant is demonstrated by
lower average flaming time, with no specimen burnt to the clamp and
VTM-2 classification.
Example 6
Flame Retardancy of Linear Low Density Polyethylene (LLDPE)
Containing FR-1
LLDPE Film Manufacture:
[0158] Linear low density polyethylene (1002YB (Exxon Mobile)) is
dry blended with 1% FR-1 and melt compounded into pellets on a
co-rotating twin-screw extruder type Collin 42D (lab size twin
screw extruder, 25 mm screw diameter) at a maximum temperature
T.sub.max of 210.degree. C. The pelletized fully formulated resin
is casted at a maximum temperature T.sub.max of 190.degree. C. into
100 and 200 .mu.m film by using a cast film equipment Collin
CR-136/350 coupled with an extruder Collin E 30 M.
[0159] Produced films and concentration of additive are listed in
Table 13.
TABLE-US-00014 TABLE 13 Concentration of added additive in the
LLDPE cast film Film No. Film Additive 1 100 .mu.m without addition
2 200 .mu.m without addition 3 100 .mu.m 1.0% FR-1 4 200 .mu.m 1.0%
FR-1
TABLE-US-00015 TABLE 14 Flame test on 100 and 200 .mu.m LLDPE cast
films according to modified DIN 4102-Part 1 (edge ignition) Burning
Damaged DIN time length Burning drips 4102-B2 Film No. [sec] [mm]
paper ignition.sup.f) Rating Film 1 21 >150 yes not classified
(100 .mu.m) Film 2 3 62 no B2 (100 .mu.m) Film 3 32 >150 yes not
classified (200 .mu.m) Film 4 6 54 yes B2 (200 .mu.m) .sup.f)Rated
"yes", if the burning drips ignite the paper placed underneath the
test specimen according to the DIN 4102-Part 1 test norm.
[0160] The burning time of Film 2 and 4 containing 1.0% FR-1
decreases significantly in comparison to Film 1 and 3. Film 2 and 4
are classified B2. FR-1 contributes to lower the burning time and
the damaged length and, therefore, increases the flame retardancy
in low density polyethylene.
TABLE-US-00016 TABLE 15 Flame test on 100 and 200 .mu.m LLDPE cast
films according to UL94-VTM Average flaming time.sup.a) Specimen
burnt UL94-VTM Film No. [sec] to holding clamp Rating Film 1
14.sup.b) Yes not classified (100 .mu.m) Film 2 4.sup. No VTM-2
(100 .mu.m) Film 3 23.sup.b) Yes not classified (200 .mu.m) Film 4
15.sup. No VTM-2 (200 .mu.m) .sup.a)Average flaming time per
specimen and after maximum 2 ignitions .sup.b)Specimen completely
burnt after the first ignition.
[0161] The efficacy of FR-1 as a flame retardant is demonstrated by
lower average flaming time, with no specimen burnt to the clamp and
VTM-2 classification.
* * * * *