Note: Descriptions are shown in the official language in which they were submitted.
W O 92/16~86 PC~r/US92102209
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POLYMETHYLPENTENE COMPOSITIONS
BACKGROUND OF THE INVENTION
This invention relates to high strength,
thermally re6istant, fire retardant, polymethylpentene
compositions.
Polymethylpentene, also known as PMP, has
long been known in the art. Although many methods are
known in the art for improving the performance -
characteristics of compositions like polyethylene and
polypropylene, these same methods tend not to work in
the higher alpha olefins, like PMP. Recently, great
emphasis has been pIaced upon modi~ying the PMP polymer
structure in order to improve the performance
characteristics of this polymer. Most of these methods
deal with creating a more interactive surface between
the PNP polymer structure and the other constituents in
the composition. It has been noted though, that the
majority of these methods of improving PMP performance
characteristics tend to be time consuming and somewhat
expensive. Therefore, a method of producing a high
strength, thermally resistant, ~ire retardant, PMP
composition, in which the PNP polymer matrix does not
have to be substantially altered, would be of great
scientific and economic value.
SUMMARY OF IHE INVENTION
It is an object of this invention to provide
an improved PNP composition.
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It is another object of this invention to
provide a PMP composition with improved thermal
resistance.
It is still another object of thi~ invention
to provide a PMP composition with improved fire
retardant capabilities.
It is yet another ob;ect of thi8 invention to
provide a PMP composition with high strength and
improved thermal resistance.
It is still another object of this invention
to provide a PMP composition with high strength and
improved fire retardant capabilities.
It is still another ob~ect of this invention
to provide a PMP composition with high strength,
improved thermal resistance, and improved fire
retardant capabilities.
In accordance w~th this invention, a
composition of matter i8 provided which comprises (A)
about 99.5 to about 75 weight percent of unmodified
polymethylpentene where the weight percent of
polymethylpentene is based on the total weight of A and
B: and tB) about 0.5 to about 25 weight percent of
polyphenylene sulfide where the weight percent of
polyphenylene sulfide is based on the total weight of
A, and B; (C) about l0 to about 67 weight percent of a
reinforcer where the weight percent of the reinforcer
is based on the total weight of A, B, c, and D; (D)
optionally about 5 to about 45 weight percent of a
flame retardant where the weight percent of the flame
retardant is based on the total weight A, B, C and D.
D~TAILED DESCRIPTION OF THE INVENTION
Polvmethylpentene fPMP~
The polymethylpentene utilized in the present
invention is a homopolymer or a copolymer of a methyl-
branched pentene, preferably 4-methyl-l-pentene, and
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another alpha olefin. Generally, applicable comonomers
have from about 2 to about 18 carbon atoms and
preferably, have from about 8 to about 16 carbon atoms.
Most preferably, the co~onomer or comonomers are linear
alpha-olefins. Longer chain linear alpha-olefins are
preferred in that they are easier to copolymerize with
polymethylpentene and can, in part, increase clarity,
stability, and impact strength to the resulting
composition. Exemplary comonomers include, but are not
limited to, l-octene, l-decene, l-dodecene, l- -
tetradecene, l-hexadecene, and other higher alpha-
olefins.
Generally the PMP should have a melt
viscosity, measured as the melt flow rate, of about 0.5
to 500 grams per l0 minutes according to ASTM Dl238,
procedure B, under a load ~f 5 kilograms and a
temperature of 260-C., and preferably 5 to 150 grams
per lO minutes. ~hese flow rates tend to provide the
most desired polymer composition processing rates.
The amount of polymethylpentene to utilize in
this invention is from about 75 weight percent to about
99.5 weight percent. More preferably, it is from about
9l weight percent to about 99 weight percent and most
preferably it is from about 92 weight percent to about
98 weight percent, based on the total weight of PMP and
PPS. Other additives, which do not interfere with the
compositions at hand, such as stabilizers, corrosion
inhibitors, and colorants, etc., can be added to the
PMP composition to provide additional desired
variations from the main PMP compositions disclosed
herein. If any additives are added then the weight of
PMP used in the calculations of the weight percents in
this specification is equal to the weight of PMP plus
the weight of the additives. However, it should~be
noted that the P~2 polymer structure is unmodified. By
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the term ~unmodified~ it is meant that the polymer has
no grafting agents acting upon it in order to modify
its polymer matrix.
PolY~henylene sul~i~e (PPS~
The polyphenylene sulfides utilized in the
present invention are well known in the art and are
described in U.S. Patents 3,354,129; 3,396,110;
3,919,177; and 4,025,582; which are hereby incorporated
by reference. The polyphenylene sulfide useful in
accordance with this invention preferably has a melt
flow, when tested in accordance with ASTM D-1238 at
315-C. using a 5 kilogram weight, of 1 to about 2,500
grams per 10 minutes.
The amount of PPS to utilize in this
invention is from about 0.5 weight percent to about 25
weight percent where the weight percent of PPS is based
on the weight of PMP and PPS. More preferably, it is
from about 1 to about 9 weight percent and most
preferably it i5 from about 2 to about 8 weight
percent. The rationale for these ranges is that, while
increasing the amount of polyphenylene sulfide in the
composition tends to increase the thermal resistance of
the polymethylpentene composition, the benefit of
adding additional large increments of polyphenylene
sulfide does not outweigh the cost. Indeed,
practically speaking, small amounts of PPS can be used
to obtain large increments of thermal resistance 80
that further additions of PPS do not bring cost
effective advantages.
Rein~oxcing Aaents
The reinforcing agents usable in the present
invention include, for example, glass fiber, carbon
fiber, boron fiber, and other inorganic substances,
etc. Glass fiber reinforcements are available i~ a
variety of compositions, filament diameters, sizings,
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and forms. The most commonly used composition for
reinforced thermoplastics is E Glass, a
boroaluminosilicate.
The diameter of the glass fiber i8 preferably
less than 20 micrometers, but may vary from about 3 to
about 30 micrometers. Glass fiber diameters are
usually given a letter designation between A and Z.
The most common diameters encountered in glass
reinforced thermoplast~cs are G-f~lament (about 9
micrometers) and K-filament (about 13 micrometers).
Several types of glass fiber products can be used for
reinforcing thermoplastics. These include yarn, woven
fabrics, chopped strands, mats, etc. Continuous
filament strands are generally cut into lengths of 1/8,
3/16, 1/4, 1/2, 3/4, and 1 inch or longer for
compounding efficiency in various processes and
products.
The glass fiber products are usually sized
during the fiber ~ormation process or in a post
treatment. Sizing compositions usually contain a
lubricant, which provides protection for the glass `
fiber strand; a film former or binder that gives the
glass fiber strand integrity and wor~ability; and a
coupling agent that provides better adhesion between
the glass fiber strand and the polymeric materials that
are reinforced with the glass fiber strand. Additional
agents that may be used in sizing compositions include
emulsifiers, wetting agents, nucleating agents, and the
like.
The amount of sizing on the glass fiber
product typically ranges from about O.2 to 1.5 weight
percent based on the weight of the glass, although
loadings up to lO percent may be added to mat products.
Examples of film formers include polyesters, ep~xy
resins, polyurethanes, polyacrylates, polyvinyl
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acetates, polyvinyl alcohols, starchs, a~d the like.
Usually the coupling agent is a silane coupling agent
that has a hydrolyzable moiety for bonding to the glass
and a reactive organic moiety that is compat~ble with
the polymeric ~aterial that i6 to be reinforced with
the glass fibers.
Preferably the amount of reinforcers used are
present in about 10 to about 67 weight percent, based
on the weight of PMP, PPS, the reinforcer and the
lo optional flame retardant. Preferably, the glass fibers
are present in the range of about 10 to about 55 weight
percent, and most preferably in the range of about 10
to about 45 weight percent. Not enough glass fiber
does not improve the polymer properties and too much
glass fiber results in not enough polymer to coat the
glass fiber, i.e., the $ibers are not wetted ~ut.
El~m~ Retardants
Fla~e retardants utilized in the present
invention include, but are not limited to, phosphate
acid esters such as tricresyl phosphate, tributyl
phosphate, tris(dichloropropyl)phosphate, and tris(2,3-
dibromopropyl)phosphate; halogenated hydrocarbons such
as chlorinated or brominated, ethane, propane, butane,
and cyclodecane; halogenated polymers such as
chlorinated or brominated, polyethylene, polypropylene,
polystyrene, and polycarbonates; brominated or
chlorinated diphenyl oxides such as octabromodiphenyl
oxide, and decabromodiphenyl oxide; antimony type
compounds such as antimony trioxide, antimony potassium
tartarate; boron type compound such as borax, zinc
borate, barium metaborate: and metallic hydroxides such
as magnesium hydroxide, aluminum hydroxide, calcium
hydroxide, barium hydroxide, etc. Most preferably the
flame retardant is selected from the group consi~tin~
of antimo~y type compounds, boron type compounds,
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polybrominated diphenyl oxides, brominated
polystyrenes, polydibromophenylene oxides, brominated
polycarbonate derivatives, or mixtures thereof.
Preferably the amount of flame retardant used
is between about 5 weight percent to about 45 weight
percent based on the weight of PMP, PPS, reinforcer,
and flame retardant. More preferably, the amount used
is between about 10 weight percent to about 40 weight
percent, and most preferably is from about 15 to about
36 weight percent.
EXAMP~ES
~ hese examples are provided to further assist
a person skilled in the art with understanding this
invention. The particular reactants, conditions, and
the like, are intended to be generally illustrative of
this invention and are not meant to be construed a8
unduly lim~ting the reasonable scope of thi6 invention.
The following ASTM test procedures were
utilized in the testing.
Analysis ASTM Method No.
Tensile Strength at Break D638, at 5 mm/min.
Elongation at Break D638, at 5 mm/min.
Flexural Strength D790, 2 inch span,
1 mm/min. crosshead speed
Flexural Modulus D790, 2 inch span,
1 mm/min. crosshead speed
Izod Impact Strength, D256
Notched and Unnotched
Heat Deflection Temperature D648, at 264 psi
(HDT) (-C.)
Experiment~ ials
Dry blends of polymethylpentene (PM~) ~nd
polypropylene (PP~ were prepared, respectively, by drum
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tumbling 10 Xilograms of resin with 5 grams of
Mg4A12(OH)12CO3 3H2O (DHT-4A), 50 grams of Irganox
1010, 50 grams of Anoxsyn 442 and 10 grams of Weston
619 for 30 minutes. Since the total mass of each mix
amounted to 10115 grams, a 101.15 gram portion was
equivalent, respectively, to 100 parts PMP or PP, 0.05
phr DHT-4A, 0.5 phr Irganox 1010, 0.5 phr Anoxsyn 442
and 0.1 phr Weston 619.
The PMP/PPS formulations were compounded in a
Werner & Pfleiderer ZSX-30 twin screw extruder (general
purpose compounding screw/barrel configuration) at 250
rpm and 260-290-C. temperature profile. The
compositions were stranded, pelletized and dried
overnight at 110-C. The PP/PPS formulations were
compounded in a Werner & Pfleiderer zsX-30 twin screw
extruder at 250 rpm and 200-230 C. profile. These
compositions were also stranded, pelletized and dried
overnight at 110-C.
The pelletized compositions were molded into
ASTM test samples on a Engel Model EC88 injection
molding machine with a 55 ton clamp force. The PMP/PPS
blends were molded with a 136-C. mold temperature, 280-
295-C. barrel temperature and 30 second cycle time.
The PP/PPS blends were molded with a 90-C. mold
temperature, 220-240-C. barrel temperature and 30
second cycle time. Molded parts were annealed for one
hour at 150-C. be~ore testing.
The formulations of the PMP and PP are
illustrated along with the other materials in Table EM.
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Wo92~6s86 PCT/US92/02209
TABLE EM .
A. Polymethvlmentene Base Formulation
100.00 phr PMP PMP Homopolymer, ~18 MFR)
0.05 phr DHT-4A hydrotalcite, available
Srom Mitsui
Petrochemicals, Inc.
0.50 phr Irganox 1010 tetrakis (methylene 3-
(3,5-di-t-butyl-4-
hydroxyphenyl)-
propionate)methane,
available from Ciba-Geigy
0.50 phr Anoxsyn 442 aliphatic thio compound,
available from Atochem
0.10 phr Weston 619 distearyl pentaerythritol :
diphosphite, available
from General Electric
~. Polypromvlene
100.00 phr PP PP Homopolymer, (12 MFR)
O.05 phr DHT-4A hydrotalcite, a~ailable
from Mitsui
Petrochemicals, Inc.
0.50 phr Irganox 1010 tetrakis (methylene 3-
(3,5-di-t-butyl-4-
hydroxyphenyl)-
propionate)methane,
available from Ciba-Geigy
0.50 phr Anoxsyn 442 aliphatic thio compound,
available from Atochem
0.10 phr Weston 619 distearyl pentaerythritol
diphosphite, available
from General Electric
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C. PolyDhenvlene Sulfide
Approximate
Grade Flow Rate Type Wash
A 2500 uncured water
B 900 cured water
C 120 cured water
D 300 uncured acid
E 160 uncured water
lASTM D1238 at 315-C. and 5 kg load, modified
with a 5 minut~ preheat instead of a 6 minute preheat.
D. Glas~s ~ein~orcemen~ P~o~cts
Manu-
facturer Product Sizingl Diameter2 Length (in) L0I3
oCF4 457BA6 pp K 3/16 0.90
OCF 408BC PBT K 3/16 0.70
OCF 492AA Nylon/PET G 1/8 1.10
OCF 497DC PPS X 1/8 0.35
CertainTeed5 930 PB~ K 3/16 0.80
CertainTeed 93B Nylon/PET G 1/8 1.00
lIndicates the resin for which the sizing
package was optimized: PP represents polypropylene,
PBT represents polybutylene terephthalate and PET
repre~ents polyethylene terephthalate.
2G-filament nominal diameter is 9 ~m.
K-filament nominal dizmeter is 13 ~m.
3LOI is ~he nominal ignition loss of the
product. This is the percent organic solids of the
sizing package.
4Owens Corning FiberglasTM Corp
5CertainTeed Glass Corporation
i
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6All examples used OCF 457BA unless specified
otherwise.
~xa~le I
~his example i8 provided to illustrate that
the effect observed in polymethylpentene compositions
does not occur in polypropylene compositions.
Referring to the data in Table I it is evident that
relatively small amounts of PPS did not enhance the HDT
values in Runs 12, 13, and 14. Furthermore, it appears
that PPS functions only as a filler in the
polypropylene compositions.
TABLE I
pP and PPS Blends:
Pro~erti~s as a Function o$ Polv~henylene Sulfide Level
(30% Glass Reinforced~
Run Number 11 12 13 14
Percent PPS ~Grade B) 0 5 10 25
Tensile Strength,
Break (ksi) 7.77.5 7.36.7
Flexural Strength (ksi)10.8 10.7 10.4 9.8
Flexural Modulus (ksi) 806 821 803 849
Unnotched Izod
Impact (ft-lb/in) 2.62.5 2.22.2
HDT ~ 264 psi (-C.) 150.1149.9 150.0149.8
~HDT/wt~ PPS -0.04 -0.01-0.01
~xam~le II
This example is provided to illustrate the
effect observed in polymethylpentene/polyphenylene
culfide/reinforced compositions. It is evident from
the data below that relative small amounts of PPS
enhanced the HDT values in PMP/PPS resins. For
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example, in Run 22, at a 5 weight percent PPS level,
the HDT value was approximately 56% greater than the
HDT value in Run 21 which contained no PPS.
Furthermore, it can be seen from the data below, in the
~HDT/weight percent PPS row, that increasing the weight
percent of PPS does not proportionally increase the
change in the heat deflection temperature.
TA8LE II
PMP and PpS ~lends:
Pro~ç~ies a~ ly~ ig~_oo_,~lyphçnylene Sulfide Level
(3Q~Gl~ss Reinforced~
Run Number 21 22 23 24 25
Percent PPS (Grade B) 0 5 1025 50
Tensile Strength,
Break (~si) 6.3 6.2 6.1 6.36.3
Flexural Strength (~si) 9.7 9.1 9.1 9.3 9.6
Flexural Modulus (ksi) 674 738 804 890 1,020
Unnotched Izod
Impact (ft-lb/in) 2.1 2.2 2.5 2.31.4
HDT ~ 264 psi (-C.)111.0 173.3 176.2 195.1217.7
~HDT/wt% PPS12.5 6.5 3.4 2.1
Example III
Additional data was gathered to confirm the
findings observed in Example II. This data is
illustrated in Table III. It is apparent from the
data, that at very low levels of PPS, a significant
amount of thermal resistance can be attained.
Further~ore, it can be seen from the data below, in the
~HDT/wt% PPS row, that increasing the weight percent of
PPS does not proportionally increase the change ~in the
heat deflection temperature. This is illustrated by
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the ~HDT/weight percent PPs row whic:h shows a dra~natic
decline from a 2.5 wsight percent loading to a 20
weight percent loading.
TA~E III
R~P and PPS ~e~ls:
~e~ties as a E~on of Polv~lene
~lfide Level
r30% Gla~ Reinfor~
R~n No. 31 32 33 34 35 36
.
P~.t PPS (OE~e 8) 0 2.5 5.0 7.510.0 20.0
. .
qensile Strer~h ~ksi) 6.7 6.9 6.76.9 7.0 7.3
El~n (S) 3.1 3.1 3.1 3.03.0 3.1
Fle~ral StL~Ul ~ksi) 9.3 8.9 8.8 8.58.9 9.1
Ele~al ~ulus (ksi) 815 809 822 805856 891
Notd~ed Izod (ft-lb/in) 0.9 1.0 0.90.9 o.9 0.8
~t~ Izcd (~t-lb/in) 2.S 2.7 2.6 2.72.9 2.2
HDr at 264 psi (-C.) 104.7 156.1 165.1 163.2 167.2 184.1
/wtS E~ 20.6 12.1 7.8 6.3 4.0
Exam~le IV
This example shows the properties of
injection molded sample~ prepared from PMP/PPS molding
compositions containing different grades of PPS at the
5 weight percent PPS level. The different grades of
PPS are identified in Table EM. Results are sl~mmarized
in Table IV.
Referring to the HDT values in Runs 41-45, it
can be seen that this property varied over a range
157.3 to 164.2-C. This is a dramatic enhancement of
HDT relative to the HDT value of 104.7-C. exhibited by
the sample in Control ~un 31 which contain no ~S. The
general enhancement of HDT values in Runs 41-45
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indicate that any of the five different types of PPS
are suitable for use in the inventive composition.
TABLE IV
PMP and PPS Blends:
5Effe~t of PPS Variant on Pro~erties
~0% Glass Reinforced)
Run No. 41 42 43 44 45
PPS Grade A B C D E
Tensile Strength ~ksi) 7.1 6.9 6.6 6.8 7.1
Elongation (%) 3.2 3.2 3.2 3.2 3.2
Flexural Strength (ksi) 9.1 8.8 9.o 9.1 9.1
Flexural ~odulus (ksi) 831 826 821 842 832
Notched Izod (ft-lb/in) 0.9 1.0 1.0 1.0 0.9
Unnotched Izod (ft-lb/in~ 2.4 4.5 3.1 3.1 2.5
HDT at 264 p8i (-C.) 158.~ 157.3 160.9 157.5 164.2
~xample V
This example ~hows the properties of
injection molded samples prep red from 30% glass
reinforced PMP/PPS molding compositions containing six
different types of glasæ reinforcement. The different
types of glass reinforcements are identified in Table
EM. The polyphenylene 8Ul fide was Grade B at the 5
weight percent level. The results are ~ummarizsd in
Table V.
Referring to Runs 53 and 56 in Table V, it is
evident that the ~ystems containing, respectively, OCF
492AA and Certainteed 93B gave the highest HDT values
of 184.5 and 17SØ These glass reinforcements are
- sized for compatibility with Nylon/PET resins. The
smaller filament diameters of these glass reinfo~ce-
ments perhaps accounted for the superior HDT values
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exhibited by the molded samples in Runs 53 and 56. The
glass reinforcements sized for compatibility with
polypropylene, polybutylene terephthalate and Nylon/PET
resins imparted comparable mechanical properties to
molded samples, respectively, in Runs 51, 52, 53, 55,
and 56. Surprisingly, the glass reinforcement sized
for compatibility with PPS (Run 54) providsd molding
samples which exhibited the lowest HDT values of the
series.
~t is noteworthy that all of the HDT values
in Table V (regardless of the type of glass
reinforcement) were significantly greater than that of
control run 31.
q~E V
~P and P$S Elends:
Effec~ Of Glass Reinfor~E~t cn Pnox~ties
t30% Gl s Reinfo~d)
Run No. 5152 53 54 55 56
Glass Reinfon#~ænt 457B~408EC 492AA 497DC 93093B
-
Tens;le Stn~th (ksi) 6.5 6.8 6.8 5.8 7.1 6.4
Elongation (%) 1.6 1.6 1.4 1.5 1.6 1.6
25 Flex~ S~U-(ksi) 8.7 8.6 8.7 7.7 9.3 8.2
Flex~ Moh~us (ksi) 800 789 832 789 83~ 789
No~d Izod tft-lb/in) 0.9 1.1 1.2 1.0 1.2 1.0
UnnJ3~{d Izod (ft-Ib/in) 2.9 2.9 3.6 3.0 3.1 3.4
HDT at 264 p6i t 'C.)164.1 165.7 184.5 lS5.9 169.8 175.0
ExamDle VI
This example shows the properties of
injection molded samples prepared from 30% glass
reinforced PMP/PPS molding compositions under somewhat
varied processing conditions. The polyphenylene
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sulfide was Grade B at a 5S by weight level. The
results are summarized in Table VI.
In Runs 61 and 62 samples were molded at the
higher temperature of 136-C. The sample in Run 62 was
annealed for two hours at 150-C. whereas the sample in
Run 61 was not annealed. Since the HDT values in Runs
61 and 62 were essentially the same (162 V8. 167),
there appeared to be no annealing effect perhaps
indicating that both PMP and PPS, especially the PPS,
attained maximum crystallization at the 136-F. mold
temperature.
In Runs 63 and 64 samplec were molded at the
lower temperature of 38-C. The sample in Run 64 was
annealed for two hours at 150-C. whereas the sample in
Run 63 was not annealed. Since the HDT values in Runs
63 and 64 were not comparable (147 vs. 165), there
appeared to be an annealing effect in the sample of Run
64. Although the properties of molded samples at the
lower mold temperature were comparable, it is
noteworthy that the HDT value of the sample in Run 64
was significantly greater than that of the non-annealed
sample in Run 63. Perhaps this indicates that the PPS
did not completely crystallize at the lower mold
temperature of 38-C. It should be noted, however, that
even at the lower mold temperature the HDT value of the
non-annealed 6ample in Run 63 tl47) was significantly
greater than that of the sample in Control Run 31.
The results in Table VI indicate that higher
mold temperatures should be used on the inventive
molding compositions to realize maximum enhancement of
HDT values in the injection molded samples.
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~LE VI
Eff~ of E~x~essina Conditions on Properties
(30% Glass Reinforced)
R~n No. 61 62 63 64
Mbld Tecperature ('C.) 136 136 38 38
Arnealing No Yes No Yes
Tensile Strength (ksi) 6.8 7.1 6.8 7.0
Elongation (%) 3.4 3.2 3.2 3.0
FlexLral SI~U. (ksi) 8.4 8.7 8.1 8.6
Flex~ral Mbdulus tksi) 741 752 720 729
N~ Izod (~t-lb/in) 0.9 0.9 1.0 1.0
Il~LJbdh d Izod (ft-Ib/in) 2.6 2.6 2.6 2.8
HDr at 264 pd (-C.) 162.1 166.7 147.1 165.3
GENERAL NOTES FOR ALL FLAME RETARDANT EXAMPLES
The weight ratio of the flame retardant to
the antimony oxide 6ynergist in each formulation was
3:1. The samples, in each of the following examples,
were tested according to ANSI/UL94 Standard for tests
for flamability of plastic materials for parts and
devices and appliances. The speciman thickness was 1/8
of an inch. In these UL94 tests a result of V-o is
better than a V-l and both of these results are better
than a fail.
~xample VII
This example describes flame retarded glass
reinforced PMP molding compositions containing 2.5 to
10 weight percsnt PPS and 18 to 27 weight percent of
decabromodiphenyloxide, a commercial flame retardant
available as DE-83R from Great Lzkes Chemical
~J~S~ITl~E SHtET
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Corporation. Table VIIA shows the properties of
injection molded samples prepared from compositions
containing 18 weight percent DE-83R and 0, 2.5, 5 and
10 weight percent PPS. Table VII8 shows the properties
of injection molded samples prepared from compositions
containing 22. 5 weight percent DE-83R and 0, 2. 5, 5 and
10 weight percent PPS. Table VIIC shows the properties
of injection molded samples prepared from compositions
containing 27 weight percent DE-83R and 0, 2.5, 5 and
10 weight percent PPS.
Part A
Referring to runs 71A and 72A in Table VIIA,
neither of which contained PPS, it is evident that the
glass reinforced PMP sample without flame retardant
(run 72~) exhibited higher property values (except for
îlexural modulus) than did the sample of run 71A which
contained 18 we~ght percent flame retardant ~DE-83R).
It is noteworthy that the samples of runs 71A and 72A
failed to obtain V-O (self extinguishing) ratings in
the UL94 flammability test. Thus, the presence of a
flame retardant in a glass reinforced PMP formulation
was detrimental to the physical properties of the
molded sample and did not render the composition flame
resistant. Inventive runs 74A and 75A in Table VIIA
show that the PPS at 5 and 10 weight percent levels
enhanced flexural modulus and HDT values as well as
flame retardancy. The samples of runs 74A and 75A
rated V-O in the UL94 test. Run 73A is noteworthy
because it shows that 2. 5 weight percent PPS is
insufficient to enhance flame retardancy to a V-O
rating with only an 18 weight percent flame retardant
loading. The HDT value in run 73A, however, was
significantly greater than the observed values in runs
71A and 72A . Therefore it can be concluded that the
addition of this flame retardant lowers the mechanical
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WO92/16~B6 PCT/US92/02209
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performance of the polymethylpentene composition.
However, the addition of PPS restores both the
mechanical performa~ce as well as improving the ,lame
retardancy of t~e co~bined composition.
~ VIIA
~action with Flame Retu~brt
Dooi~nT~d1~henyloxide 18 Wt% Flame Ret~ebrt
(30 Wk~ Glass Reinfoxxd~
_
Run 71A 72A 73A 74A 75A
% nE-83~a 18.0 Oo~x~ 18.0 18.018.0
% PFS (Gra~e B) o o 2.5 5.010.0
lensile Stn~h, B~k (ksi) 5.4 6.1 6.2 6.9 6.7
Fle~n~l Sbn~h (ksi) 7.4 8.6 8.3 8.4 8.6
Fle~n~l ~Y~US (ksi) 920 710 ggo 995 1,080
No~d Izod ~p~ (ft-lb/in) 0.5 0.8 0.5 0.6 0.6
Unn*l~cd Izcd ~xwk (ft-Ib/in) 1.3 2.2 1.5 1.7 1.5
HDT ~ 264 p6i ~ C.) 122.5 124.3 157.3 165.2 161.7
UL94 V-l ~1 V-1 V-0 V-0
Limiting ~ n ~x
(LDI)b (%) 31.5 25.5 29.2 30.0 31.5
a DE-83R represents decabromodiphenyloxide
(DBDP0) (83% Br), available from Great Lakes
Chemical Corporation.
b The limiting oxygen index (LOI) is
expressed as the minimum volume percent of
oxygen necessary in an oxygen/nitrogen
mixture to sustain combustion of a burning
sample. The magnitude of LOI numbers i8
directly proportional to flame retardant
effectiveness.
aUBSTlTI JTE SHEET
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Part B
Referring to runs 71B and 72B in Table VII8,
neither of which contained PPS, it can be seen that the
flame retardant reduced the property values (except for
modulus) in run 71B but the sample rated V-0 in the
UL94 flammability test. Control run 72B without flame
retardant failQd the UL94 test. Inventive runs 73B,
74B and 75B in Table VIIB show that the PPS at 2.5, 5
and 10 weight percent levels enhanced flame retardancy
(~ee higher LOI values compared to the LOI values of
runs 71B and 72B), modulus values and ~DT values.
Thus, at the 22.5 vQight percent loading of flame
retardant, the PPS enhanced both the flame retardancy
to the point of being self-extinguishing and the
physical properties of the injection molded samples.
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DecabrcmLdi~henvloxide 2~.5 Wk% Flame Frtard3nt
(30 Wk% Glass ReinfcrGed)
: `
R~n 71B 72B 73B 74B 75B
S DE n3R 22.5Ccntrol 22.5 22.5 22.5
S PæS (Gra~e B) 0 2.5 5.0 10.0
Tens~le ~ , Ereak (ksi) 5.4 6.1 6.0 6.4 6.4
FlexLral Strength ~ksi) 7.4 8.6 8.2 8.3 7.6
FlexLral McdLlus (ksi) 1,100 710 1,100 1,060 1,160
Nbkched Izod l~pact (ft-Ib/in)0.5 0.8 0.5 0.5 0.5
13~YJldho~ Izod Impact~ft-lb/in) 1.2 2.2 1.6 1.6 1.1
H~ ~ 264 Fsi (-C.) 120.0 124.3 160.0 159.4 165.3
U~4 V-0 Fail V~ V-0 V-0
Limitir~ Qx~en ~c
(LOI) (%)29.2 25.5 30.8 32.1 33.6
.
Part C
Referring to runs 71C and 72C in Table VIIC,
neither of which contained PPS, it is evident that
properties (except for flexural modulus) were reduced
by the flame retardant (run 71C) but the sample did
rate V-0 in the UL94 test and possessed a desirably
high LOI value of 33. The glass reinforced PMP sample
(run 72C) without flame retardant failed the UL94 test.
Inventive runs 73C, 74C and 75C in Table VIIC show that
the PPS additive at 2.5, 5 and 10 weight percent levels
maintained fla~e retardancy and enhanced HDT values of
camples containing 27 weight percent :Elame retardant.
SUBSTITLJTE SHE~T
WO 92/16S86 P~US92/02209
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,q~E VlIC
;~actia~ with Fq# Eb~
DecobrorLdi~henvloxide 27 Wk% Flame PeeDrd~nt
(30 Wk% Gl~e Reinforced~ ~
:
Run 71C 72C 73C 74C 75C
% DE-83R 27.0 Cbnkrcl27.0 27.027.0
% PFS (Grade B) 0 2.5 5.010.0
~,
lersile Strength, Ereak (ksi) 5.1 6.1 5.8 5.9 6.4
FlexLral SLLe~Uh (ksi) 7.2 8.6 7.4 6.7 7.2
Flo^~n~al M~dulus (ksi) 1,190 7101,200 1,1601,300
Nbtdhed Izod Impact (ft-Ib/in) 0.5 0.8 0.5 0.4 0.5
~rr~h~ 3a Impact (ft-Ib/in) 0.9 2.2 1.0 0.9 0.9
HDr 0 264 p6i (-C.) 120.3 124.3160.0 171.2177.8
UI94 V-0 F~l V-0 V-0 V-0
L~miting a~n ~Y~X -:
(LDI) (%) 33.0 25.5 33.6 34.935.4
Example.YIII
This example describes flame retardant glass
reinforced PMP molding compositions containing 2.5 to
10 weight percent PPS and 18 to 27 weight percent o~
brominated polystyrene, a commercial flame retardant
available as Pyro-Chek 68PB (68S bromine) ~rom Ferro
Corporation. Table VIIIA shows the properties of
injection ~olded samples prepared from compositions
containing 18 weight percent Pyro-Chek 68PB and 0, 2.5,
5 and 10 weight percent PPS. Table VIIIB shows the
properties of injection molded samples prepared from
compositions containing 22.5 weight percent Pyro-Chek
68PB and 0, 2.5, 5 and 10 weight percent PPS. Table
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WO92/16~6 PCT~US92/02209
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VIIIC shows the properties of in~ection molded samples
prepared from compositions containing 27 weight percent
Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS.
Part A
Referring to runs 81A and 82A in Table VIII,
neither of which contained PPS, it can be seen that the
glass reinforced PMP sample without flame retardant
(run 82A) had higher property values in general than
did the sample of run RlA which contained 18 weight
percent flame retardant (Pyro-Chek 68PB). Sa~ples of
both run 81A and 82A failed the UL94 flammability test.
It is noteworthy that the samples in runs 83A and 84A
at the 2.5 and 5 weight % PPS levels failed to enhance
flame retardancy to a V-0 rating but HDT values were
increased to about 155. Inventive run 85A shows that
the PPS at the 10 weight percent levels enhanced
~lexural modulus and HDT ~alues as well as flame
retardancy. The injection molded sample in run 85A
rated V-0 in the UL94 test. The data in Table VII
suggest that between 5 and 10 weight percent PPS at the
18 wt% loading of flame retardant is required to obtain
maximum enhancement of physical properties.
SUBSTITUTE SHEET
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.q~E VmA '
PMP and PPS Blends:
Erominated P~lystvrene 18 Wt% Flame ~eearC3nt
~30 Wk% Glass Reinforced~
~n 81A 82A 83A 84A 85A
% Fyro-Chek 68P~a 18.0 Control 18.0 18.0 18.0
% PPS (Grade B) 0 0 2.5 5.0 10.0
lens;le Strength, Ereak (ksi) 5.46.1 5.9 6.3 6.6
FlexLral Strength (ksi) 7.98.6 8.4 8.6 8.9
Flexural M~dLlus (ksi) 900 710 930 970 1,050
Nbkched Izod Impact (ft-Ib/in) 0.50.8 0.6 0.6 0.7
UCrr~dh d Izod I~pact (ft-Ib/in) 1.4 2.2 1.9 1.7 1.9
264 psi (-C.) 130.8124.3154.3156.9156.8
U~4 FailFail V-l V-l V-0
I1miting Qx~en :~c
(LO~) (%) 27.625.5 29.2 30.0 31.5
a Pyro-Chek 68PB represents a brominated
polystyrene (68% bromine) available from Ferro
Corporation. `
Part B
Referring to runs 81B and 82B in Table VIIIEI,
neither of which contained PPS, it is evident that the
presence of flame retardant at a 22.5 weight percent
loading (run 81B) compromised the physical properties
of a molded sample and the sample failed to rate V-0 in
the UL94 flammability test. Run 82B is a glass rein-
forced PMP sample without flame retardant (control).
Inventive samples 83B, 84B and 85B in Table VIIIB show
that the PPS at the 2.5, 5 and 10 weight percent levels
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snhanced physical properties, particularly HDT values,
and enhanced flame retardancy as evidenced by the
higher L~I values and a V-0 rating in the UL94
flammability test. It is noteworthy that in Table
VIIIB PPS was effective at 2.5 weight percent in runs
wherein the flame retardant was at the 22.5 weight
percent loading. As noted previously, the PPS was
required at the 10 weight percent level to be fully
effective in the presence of only 18 weight percent
flame retardant (see Table VIIIA).
Table VIIIB
PMP and FP5 Elends:
b~ ction with Flame R-t~brt
Broyhxeed P~lYs~n~e 22.S Wt% Flame Rct~brt
(30 Wk% Glass Reinf~xæd~
Run 81B 82B 83B 84B 85B
% Pyn~C~Y~ 68PB 22.5 O~ol 22.5 22.5 22.5
% PPS (G~e B) o o 2.5 5.0 10.0
_ _ _ _
Tensile Sbn~h, B~k (ksi) 5.4 6.1 5.6 5.8 6.4
Flex~21 Stna~h (ksi) 7.7 8.6 8.7 8.5 9.1
Fle~n~l Mo~us (ksi) 940 7101,030 1,050 1,140
N~x~ed Izod ~ t (ft-lb/in) 0.5 0.80.5 0.6 0.6
U~JI~Yd Izcd ~x~ (ft-Ib/in)1.2 2.21.3 1.5 1.5
HDT ~ 264 p6i (-C.) 138.0 124.3 153.9 155.9 159.9
. .
UI~4 V~ 1 V-0 V-0 V-0
T .;mi ting Q~n ~Y~X
(LDI) (%) 28.4 25.5 31.5 31.5 33.0
Part C
Referring to runs &lC and 82C in Table VIIIC,
neither of which contained PPS, it can be seen in run
81C that a 27 weight percent loading of flame retardant
~'JBSTlTUTE SHEET
WO 92tl 6~86 PCT/US92/~2209
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reduced properties except for modest increases in
modulus and HDT values. This sample rated V-0 in the
UL94 test. A contrc~l run (No. 82C) with a glass
reinforced PMP composition without flame retardant
failed the UL94 flammability test.
Inventive runs 83C, 84C and 85C in Table
VIIIC, show that the PPS at the 2.5, 5 and 10 weight
percent levels dramatically enhanced modulus and HDT
values. The enhanced flame retardancy of the sample
was evidenced by the higher values of the L0I.
~E vmc
FMP and PP5 E4ends:
~açticn with Flame ~etosbrt
B~x~s~ted P~lv5~n~ne 27 Wk% Fla~e RYt~nbrt
~30 Wk% Gl~C~ Reinf~xd)
Run 81C 82C 83C 84C 85C
% PynrC~Yk 68PB 27.00o~ol 27.0 27.027.0
% PFS (Grade B) 0 0 2.5 5.010.0
Tensile Stn~th, Bn~k (ksi) 5.1 6.1 5.6 5.8 6.3
Fle~n~l S~n~Ul(ksi) 7.3 8.6 8.4 8.6 9.1
Flex~ Moh~us (Xsi) 980 7101,100 1,160 1,230
Nou~d Izcd ~x~t (ft-lb/in) 0.4 0.8 0.5 0.5 0.5
unn~=tn~ Izcd ~x~t (ft-lb/in) 1.12.2 1.5 1.2 1.0
HDT ~ 264 p6i (-C.) 138.3 124.3152.1 1~.8 158.9
-
UI94 V-0 F~l V-0 V-0 V-o
T;miting Q~n ~x
(LDI) (%)30.8 25.5 33.0 33.6 35.4
_
Exam~le 1~
This example describes a flame retarded
reinforced PMP molding composition containing 10 weight
percent PPS and 22.5 weight percent of a
SUBSTITUTE SH~E-~
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WO92~16586 PCr~US92102209
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polydibromophenylene oxide, a commercial flame
retardant available as PO-64P from Great Lakes Chemical ~ -
Corporation. Table IX shows the properties of
injection molded samples.
s Referring to runs 91 and 92 in Table IX,
neither of which contained PPS, it is evident in run 92
that a 22.5 weight percent loading of fla~e retardant
reduced properties except for ~ome increase in modulus
and HDT values. This sample rated V-0 in the UL94
test. A control run (No. 91) with a glass reinforced
PMP composition without flame retardant failed the UL94
flammability test. Inventive run 93 in Table IX, shows
that the PPS additive at the lO weight percent level
enhanced modulus and HDT values. ~he enhanced flame
retardancy of the sample was reflected by the higher
L~I value (34.9).
TITUTE S~ET
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~ l:X '
Interactial wi~h Plame 8
(30 W~% Glass R~in~or~)
Rl~n 91 92 93
% ~64pa C~trol 22.522.5
~ EeS O O 10.0
_ _
Tensile St~th, B~ealc (ksi)6.1 5.8 6.7
E~e~ral Sl~ (ksi) 8.6 8.3 8.2
~ i) 710 1,0301,200
No~ Izod ~c (~-~b/in) 0.8 0.5 0-5
W~ Izod ~ (~-~b/in) 2.2 1.2 .8
Hl~ 0 264 pgi (-C.) 124.3 150.0160.2
UL94 Eail V~~O V-O
T.im~~ axygen ~c
(IDI) (%)25.5 30.034.9
a PO-64P represents polydibromophenylene
oxide (64% Br) available from Great Lakes Chemical
Corporation.
2S ;~xamDle X
This example describes flame retarded glass
reinforced PMP molding compositions conta~ning 5 and 10
weight percent PPS and 22.5 weight percent of a
tetrabromobisphenol A carbonate oligomer, a commercial
flame retardant available as BC-58 from Great Lalces
Chemical Corporation. Table X shows the properties of
injection molded samples.
Referring to runs 101 and 105 in Table X,
none of which contained PPS, it can be seen that the
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flame retardant in the sample of run lOl and 104
reduced properties except for modulus and rated V-O in
the UL94 flammability test. The control sample in run
105 without rlame retardant failed the UL94
flammability test. Inventive runs 102 and 103 in Table
X show that the PPS at the 5 and 10 weight percent
l~vels enhanced modulus and HDr values. These samples
rated V-O in the UL94 flammability test and possessed
LOI values of about 32-
q~ X
~P a~ PPS ~e~s:
~ elon with Fla~e Rct~bnt
Iet~n~lb~q*~rol A CE~xnate OlioD~r
~30 WC% Glas~s Reinfc ~ d)
Rlm lOl 102 103 104 105
% BC-58a 22.5 22.5 æ.5 27.0 Control
% PPS O 5.0 lO.0 0 O
Tensile Str ~ h, Brealc (Xsi) 4.9 6.0 6.4 4-9 6.1
FlexLral ~ (Xsi) 7-2 8.0 ~.0 7.2 8.6
~e~ral ~ lus (ksi) 1,030 1,020 1,110 1,060 710
ed Izcd ~ act (ft-lb/in) 0.4 0.6 0.6 O.S 0-8
13 tdled T7~ ~ t (ft--lb/in) 1.4 1.3 1.4 .9 2.2
E ~ ~! 264 psi (C) lO9.9 148.1 158.6 114.1 124-3
Ul~4 V-O V-O V-O V-O Fail
Limiting Q~æn ~K~X
(IDI) (%)31-5 31.5 33.0 31.5 25.5
a BC-58 represents tetrabromobisphenol A
carbonate oligomer (58~ Br), a~aila~le from Great Lakes
C~emical Corporation.
.SU~ST~UTE SH~_ i
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