Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~31S~9
HOE 87/H 012J
This invention relates to flame-retardant polymer compo-
sitions containing an intumescent flame-retardant system com-
prised substantially of a phosphorus component and an organic
nitrogen component.
In U.S. Patent No. 4,140,66a it has been suggested that
phosphonic acid derivatives of isocyanuric acid are useful
for imparting flame-retardant properties to polyurethanes.
U.S. Patent No. 4,001,177 also describes a combination of me-
lamine and isocyanuric acid derivatives for imparting flame-
lû retardant properties to polyamides.
U.S. Patent No. 3,810,862 appears to be the first refe-
rence to disclose the use of an intumescent mixture for im-
parting flame-retardant properties to polyolefins; this mix-
ture consists of ammonium polyphosph~ate, melamine and dipen-
taerythrltol or melamine pyrophosphate and dipentaerythritol.In U.S. Patent No. 4,312,805 (DE-OS 28 Oû 891), a three-com-
ponent mixture of ammonium polyphosphate, melamine and poly-
amide 6 (cf. Example 6) is suggested, and in U.S. Patent No.
4,198,493~(~E-OS 28 39 710) a further series of three-compo-
nent mixtures are suggested consisting of ammonium polyphos-
phatej melamine and tris-(2-hydroxyethyl)-isocyanurate (cf.
; Examples 2, 5, 6, 7, 8) or ammonium polyphosphate, pentaery-
thritol or tripentaerythritol and tris-(2-hydroxyethyl)-iso-
cyanurate (cf. Examples 4, 9) or ammonium polyphosphate,
cyanuric acid and tris-(2-hyroxyethyl)-isocyanurate (cf.
~ Examples 13, 14) as intumescent agents imparting flame-retar-
; dant properties to polyolefins. It has also been disclosed
(cf. U.S. Patent No. 4,461,862) that a combination ~f ammo-
~1 3 1 ~ ~ ~ 9 23343-826
nium polyphosphate and the reaction product of an oxygen acid
of phosphorus with a hyclroxy-alkyl deriva~ive o i60cyanuric
acid can conveniently be used for this purpose.
We have now unexpectedly found that a two component
system, consisting of ammonium polyphosphate and tri~-(2~hy-
droxyethyl)-isocyanurate also imparts very good flame-retar-
dant properties to polyolefins. This was more particularly an
unexpected result as the other components of the three-compo-
nent system specified hereinabove when used in a two-component
system with ammonium polyphosphate did not have any flame-
retardant activlty whatever ~cf comparative Examples 1-12
herein).
The present invention now provides a flame retardant
polyolefin composition, containing an intu~escent flame-
retardant system consisting essentially o~ a phosphorus
component and an organic nitrogen component, wherein the lame-
retardant system iæ a two component mixture of ammonium
polyphosphate and tris-(2-hydroxyethyl~-isocyanurate.
Further preferred and optional features of the flame-
: retardant polymer composltion of this invention provide:
a) for the ammonium polyphosphate to contain Q.5 to 25
~eight % of a water-insoluble artificial, preferably
cured, resin enoapsulating the individual ammonium
~: polyphosphate particles;
b) for the ammonium polyphosphate to contain O.S to 25
weight % of a reaction product of a polyisocyanate
with a carbodiimidizatlon catalyst, the polycarbodi-
lmlde formecl encapsulating ~he individual a~monium
polyphosphate particles;
~ ',.
5~ I
~31~9
c) for the ammonium polyphosphate to contain 0.5 to 25
weight % of a reaction product of a polyisocyanate and a
polyhydroxy compound, the polyurethane formed encapsu-
lating the individual ammoniurn polyphosphate particles;
d) for the ammonium polyphosphate to contain 0.5 to 25
weight % of a reaction product of a polyisocyanate with
a trimerization catalyst, the polyisocyanurate formed
encapsulating the individual ammonium polyphosphate
particles;
e) for the ammonium polyphosphate to contain 0.5 to 25
weight % of a reaction product of a polyisocyanate:and
water, the ?olyurea formed encapsulating the individual
: ammonium polyphosphate particles;
f) for the ammonium polyphosphate to contain 0.5 to 25
weight % o a cured melamine/formaldehyde-resin, the me-
lamine/formaldehyde resin encapsulating the indivldual
~: ~ ammonium polyphosphate particles;
g) for the ammonium polyphosphate to contain 0.5 to 25
: weight % of a cured epoxlde resin, the epoxide resin en-
capsulating the individual ammonium polyphosphate par-
~ ticles;
: h) for the flame-retardant system to contain from:80 to 50
:
: weight % ammonium polyphosphate and 20 to 50 weight %
; ~ tris-(2-hydroxyethyl)-isocyanurate;
i) or the ammonium polyphosphate used to be a free-flow-
: ing, pulverulent, sparingly water~soluble ammonium poly-
phosphate of the formula (NH4P03)n, in which n is an
integer from 200 to 1000, preferably about 700;
~ 3 ~
j) for more than 99 % of the ammoniurn polyphosphate to have
a particle size of less than 45 ~rn;
k) for the flame-retardant polymer composition to contain
the flame-retardant system in an amount from 15 to 40
weight %;
l) for the flame-retardant polymer composition to be a
thermoplast;
m) for the flame-retardant polymer composition to be an
olefin.
The following Examples and Tables are intended to il-
lustrate the invention which is na-turally not limited there-
to.
Example 1 (Comparative Example)
;~ 5000 9 of ~HOSTALEN PPU 0180 P~(a registered Trade Mark
: 15 of HOECHST AKTIENGESELLSCHAFT, Frankfurt) - a polypropylene
powder having a melt index: MFI 230/5 of about 55 9/10 minu-
tes;
;1500 9 of ~EXOLIT 422 (a registe:red Trade Mark of
HOECHST AKTIENGESELLSCHAFT, Frankfurt) - a fine particulate,
sparingly water-soluble ammonium polyphosphate of the formula
: : (NH4P03)n, in which:n is about 700 and more than 99 % of the
particles have a size of less than 45 ,um;
500 9 of melamine;
ao 9 of ~ RONOS CL Z20 (a registered Trade Mark of
Kronos Titan GmbH, Leverkusen) - a titanium dioxlde pigment
(rutile grade);
10 9 calcium stearate;
lû g of ~HOSTANOX û3 (a registered Trade Mark of HOECHST
AKTIENGESEILSCHAFT, Frankfurt) - an antioxidan~ based on
~L 3 ~ 9
polynuclear phenols;
10 9 of ~HOSTANOX SE 10 (a registered Trade Mark of
HOECHST AKTIENGESELLSCHAFT, frankfurt) - an antioxidant based
on dialkyl sulfides, and
10 9 of QHOSTANOX PA~ 24 (a registered Trade Mark of
HûECHST AKTIENGESELLSCHAFT, Frankfurt) - an aromatic phos-
phite(tris-(2,4-ditert.-butylphenol)-phosphite)
were mixed in a SPANGENBERG intensive mixer (20 1 capa-
city), extruded at 180-200C in a WEBER small extruder (20 mm
screw diameter) and granulated in a DREHER laboratory granu-
lator.
The dried, granulated material was introduced into a
steam-heated BECKER-VAN-HULLEN molding press and molded at a
temperature of 195C and under a pressure of 2-3 bars (5-10
.
15 mlnutes) or 30û bars (2 minutes) into test plates 1.6 mm
thick and 3.2 mm thick.
The flammability of the composition was tested in accor-
dance with the Underwriters Laboratories procedure "Test for
Flammability of Plastic Material - UL 94" dated as of May 2,
2û ~975, on specimens 127 mm long, 12.7 mm wide and 1.6 and 3.2
mm thick, and the oxygen lndex was determined substantially
in accordance with ASTM-D ~2863 in a modified apparatus.
The results of the flammability tests are reported in
Table 1.
Example 2 (Comparative Example)
The procedure of Example l was repeated but 1000 9 of
~3EXOLIT 422 and 1000 g of melamine were used. Tha results of
the flammability tests are listed in Table 1.
..
~31 5~
Example 3 (Comparative Example)
The procedure of Example 1 was repeated but 50û 9 of
~EXOLIT 422 and 1500 9 of melamine were used. The results of
the flammability tests are listed in Table 1.
Example 4 (Comparative Example)
The procedure of Example 1 was repeated but the mela-
mine was replaced by 500 g of cyanuric acid. The results of
the flammability tests are listed in Table 1.
Example 5 (Comparative Example)
lû The procedure of Example 2 was repeated but the mela-
mine was replaced by 1000 9 of cyanuric acid. The results of
the flammability tests are listed in Table 1.
Example 6 (Comparative Example)
The procedure of Example 3 was repeated but the mela-
mine was replaced by 1500 9 of cyanuric acid. The results of
the fl~ammabillty tests are listed in Table 1.
Example 7 (Comparative Example)
The procedure of Exàmple 1 was repeated but the mela-
mine was replaced by 500 9 of melamine cyanurate. The re-
sults of the flammability tests are listed in Table 2.
Example 8 (Comparative Example)
The procedure ~of Example 2 was repeated but the mela-
mine was replaced by 1000 9 of melamine cyanurate. The re-
sults of the flammability tests are listed in Table 2.
~: :
25. Example 9 (Comparative Example)
The procedure of Example 3 was repeated but the mela-
mine was replaced by 1500 9 of melamine cyanurate. The re-
sults of the flammability tests are listed in Table 2.
13~5~
Example 10 (Comparative Exampla)
The procedure of Example 1 was repeated but the mela-
mine was replaced by 500 9 of ~ ADURIT MW 909 (a registered
Trade Mark of HOECHST AKTIENGESELLSCHAFT, Frankfurt) which
was used in the form of a melamine/formaldehyde-resin cured
for 2 hours at 180C prior to use. ~ AOURIT MW gO9 is an un-
plastlcized melamine/formaldehyde-resin commercially avail-
able in the form of a white powder. A 50 weight % percent
solution has a dynamic viscosity of about 30 mPa.s, a pH of
9.0-10.0 and a density (at 20C) of 1.21-1.225 gjml. The
results of the flammability tests are listed in Table 2.
Example 11 (Comparative Example)
The procedure of Example 2 was repeated but the mela-
mine was replaced by 1000 9 of 6MADURIT MW 909, which was in
the form of a melamine/formaldehyde-resin which had been
cured for 2 hours at 180C prior to use. The results of the
flammability tests are listed in Table 2.
Example 12 (Comparative Example)
The procedure of Example 3 was repeated but the mela-
20 mine was replaced by 1500 9 ~MADURIT MW 909, which was used
in the form~of a me1amine/formaldehyde-resin cured for 2
hours at 180C. The results of the flammability tests are
listed in Table 2.
Example 13 (inventionj
The procedure of Example 1 was repeated but the mela-
mine was replaced by 500 9 of tris-(2-hydroxyethyl)-iso-
cyanurate (THEIC). The results of the flammability tests are
listed in Table 3.
~3~5~
Example 14 (invention)
The procedure of Example 2 was repeated but the mela-
mine was replaced by lOûO g of tris-(2-hydroxyethyl)-iso-
cyanurate (THEIC). The results of the flammability tests are
listed in Table 3.
Example 15 (invention)
The procedure of Example 3 was repeated but the mela-
mine was replaced by 1500 g of tris-(2-hydroxyethyl)-iso-
cyanurate ~THEIC). The results of the flammability tests are
listed in Table 3.
Example 16 (invention)
The procedure of Example 1 was repeated but 1312.5 9 of
~EXOLIT 422 and (instead of 500 9 of melamine) 437.5 9 of
THEIC were used. The results of the flammability -tests are
lS listed in Table 3.
Example 17 (invention)
The procedure of Example 2 was repeated but 875 g of
~EXOLIT 422 and (instead of 500 9 melamlne) 875 9 of THEIC
were used. The results of the flammability tests are listed
in Table 3.
Example 18 (invention)
; ~ :
The procedure~ of Example 1 was ~repeated but 1~125 9 of
EXOLIT 422 and (lnstead of 500 9 of melamine) 375 9 of
THEIC were use.d. The results of the flammability tests are
:
listed in Table 3.
Example 19 (invention)
The procedure of Example 1 was repeated but 75C g of
~EXOLIT 422 and (instead of 500 9 of melamine) 750 9 of
THEIC wera used. The results of the flammability tests are
indicated in Table 3.
~31~
Example 20 (invention)
The procedure of Example 16 was repeated but ~EXOLIT
.422 was replaced by 1312.5 9 of ~EXOLIT 462.
The ~-~EXOLIT 462 is a microencapsulated ammonium poly-
phosphate made by the process described in German Specifica-
tion DE-OS 35 31 50û, containing about 10 weight % of en-
capsulating material consisting of a cured melamine/formal-
dehyde resin.
The results of the flammability tests are indicated in
Table 4.
Example 21 (invention)
The procedure of Example 18 was repeated but the
`~EXOLIT 422 was replaced by 1125 9 of EXOLIT 462.
The results of the flammability tests are indicated in
Table 4.
Example 22 (inventlon)
~: The procedure of Example 16 was repeated but the
: ~ XOLIT 422 was replac;ed by 1312.5 9 of ~EXOLIT 470.
~,
The ~EXOLIT 470 is a microencapsulated ammonium poly-
phos,ohate made by the process described in German Specifica-
: tion DE-OS 35 26 006, containing about 10 weight % of encap-
suIating material:cons:isting of the reaction product of a
:: ~ polyisocyanate and a carbodiimldization catalyst.
The reaults of the flammability tests are indicated in
~; ~ 25 Table 4.
Example 23 (invention)
The procedure of Example 18 was repeated but the
G~EXOLIT 422 was replaced by 1125 9 of ~EXOLIT 470.
: 9
~ 3 ~ 9
The results of the flammability tests are indicated in
Table 4.
The comparative materials melamine, cyanuric acid, me-
lamine cyanurate and melamine/formaldehyde-resin (~MADUnIT
MW 909) were found in the flammability tests to be definite-
ly unsuitable for use in a two-component system with ammo-
nium polyphosphate as a flame-retardant composition for
thermoplastic materials; tcf. Tables 1 and 2).
In clear contrast therewith, the ammonium polyphospha-
te/tris-(2-hydroxyethyl)-isocyanurate composition was very
- effectiva (cf. Tables 3 and 4). Specimens 3.2 mm thick made
from material in which 35 parts of this composition were
used per 100 parts of polypropylene could be classified in
class UL g4 V-0.
15 ~ Comparison physical properties for APP/THEIC (inve~n-
tion), typical halogen and 3-component non-halogen flame re-
:~ ~: tardant formulations are presented in Table 5. An excellent
trade-off in property balance is demonstrated for APP/THEIC
formulations (1, 2, 3). Compared with commercial halogen
;20 formulations (5, 6) strengths in tensile, flexural, impact,
: :and low smoke properties, and specific gravity are note-
worthy. The non-halogen 3-component formulations (7, 8, 93
:: show inferior performance in tensile, flexural, elongation
and impact properties.
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