U.S. patent application number 14/445175 was filed with the patent office on 2014-11-13 for thermoplastic polycarbonate copolymer compositions, methods of their manufacture, and uses thereof.
The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to Roland Sebastian Assink, Paul Dean Sybert, Robert Dirk van de Grampel, Mark Adrianus Johannes van der Mee.
Application Number | 20140335298 14/445175 |
Document ID | / |
Family ID | 47846217 |
Filed Date | 2014-11-13 |
United States Patent
Application |
20140335298 |
Kind Code |
A1 |
van der Mee; Mark Adrianus Johannes
; et al. |
November 13, 2014 |
THERMOPLASTIC POLYCARBONATE COPOLYMER COMPOSITIONS, METHODS OF
THEIR MANUFACTURE, AND USES THEREOF
Abstract
This disclosure relates to thermoplastic compositions comprising
a polycarbonate copolymer, the polycarbonate copolymer comprising
first repeating carbonate units and second repeating units selected
from carbonate units that are different from the first carbonate
units, polysiloxane units, and a combination comprising at least
one of the foregoing unit; and an organophosphorus flame retardant
in an amount effective to provide 0.1 to 1.0 wt % phosphorus based
on the total weight of the composition, wherein an article molded
from the composition has a smoke density after 4 minutes (Ds-4) of
less than or equal to 600 determined according to ISO 5659-2 on a 3
mm thick plaque, and a material heat release of less than or equal
to 160 kW/m.sup.2 determined according to ISO 5660-1 on a 3 mm
thick plaque.
Inventors: |
van der Mee; Mark Adrianus
Johannes; (Breda, NL) ; van de Grampel; Robert
Dirk; (Tholen, NL) ; Assink; Roland Sebastian;
(Middelburg, NL) ; Sybert; Paul Dean; (Evansville,
IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
BERGEN OP ZOOM |
|
NL |
|
|
Family ID: |
47846217 |
Appl. No.: |
14/445175 |
Filed: |
July 29, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13780324 |
Feb 28, 2013 |
8841366 |
|
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14445175 |
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|
61604845 |
Feb 29, 2012 |
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Current U.S.
Class: |
428/36.92 ;
428/220; 521/154; 521/180; 524/127 |
Current CPC
Class: |
Y10T 428/1397 20150115;
B32B 5/00 20130101; C08K 5/523 20130101; C09K 21/12 20130101; C09K
21/14 20130101 |
Class at
Publication: |
428/36.92 ;
524/127; 521/180; 521/154; 428/220 |
International
Class: |
C08K 5/523 20060101
C08K005/523 |
Claims
1. A thermoplastic composition comprising 60 to 99.5 wt % based on
the weight of the composition of a polycarbonate copolymer
comprising first repeating units repeating units and second
repeating units, wherein the second repeating units are
polysiloxane units; and an organophosphorus compound in an amount
effective to provide 0.1-1 wt % phosphorus, based on the total
weight of the polycarbonates in the composition; wherein the first
carbonate units are of the formula ##STR00024## wherein R.sup.a and
R.sup.b are each independently a C.sub.1-12 alkyl group, p and q
are each independently integers of 0 to 4, and X.sup.a is a single
bond, --O--, --S--, --S(O)--, --S(O).sub.2--, --C(O)--, a
C.sub.1-12 alkylidene of formula --C(R.sup.c)(R.sup.d)-- wherein
R.sup.c and R.sup.d are each independently hydrogen or C.sub.1-11
alkyl, or a group of the formula --C(.dbd.R.sup.e)-- wherein
R.sup.e is a divalent C.sub.1-11 hydrocarbon group; and the second
repeating units are siloxane units of the formulas ##STR00025## or
a combination comprising at least one of the foregoing, wherein R
is each independently a C.sub.1-13 monovalent hydrocarbon group Ar
is each independently a C.sub.6-C.sub.30 aromatic group, R.sup.2 is
each independently a C.sub.2-8 alkylene group, E has an average
value of 2 to 200; and wherein an article molded from the
composition has a smoke density after 4 minutes (Ds-4) of equal to
or less than 600 as determined according to ISO 5659-2 on a 3 mm
thick plaque, a maximum average rate of heat emission (MAHRE) of
less than or equal to 160 kW/m.sup.2 as determined according to ISO
5660-1 on a 3 mm thick plaque, and a multiaxial impact energy equal
to or higher than 100 J as determined according to ISO 6603 on a
3.2 mm thick disc.
2. The composition of claim 1, wherein the first units are
bisphenol-A carbonate units.
3. The composition of claim 1, wherein the siloxane units are of
the formula ##STR00026## or a combination comprising at least one
of the foregoing, wherein E has an average value of 2 to 200.
4. The composition of claim 1, wherein the siloxane units are of
the formula ##STR00027## wherein R is each independently a
C.sub.1-13 monovalent hydrocarbon group, R.sup.3 is independently a
divalent C.sub.2-8 aliphatic group, M is each independently a
halogen, cyano, nitro, C.sub.1-8 alkylthio, C.sub.1-8 alkyl,
C.sub.1-8 alkoxy, C.sub.2-8 alkenyl, C.sub.2-8 alkenyloxy group,
C.sub.3-8 cycloalkyl, C.sub.3-8 cycloalkoxy, C.sub.6-10 aryl,
C.sub.6-10 aryloxy, C.sub.7-12 arylalkyl, C.sub.7-12 arylalkoxy,
C.sub.7-12 alkylaryl, or C.sub.7-12 alkylaryloxy, or a combination
comprising at least one of the foregoing, n is each independently
0, 1, 2, 3, or 4, and E has an average value of 2 to 200.
5. The composition of claim 4, wherein the siloxane units are of
the formula ##STR00028## or a combination comprising at least one
of the foregoing, wherein E has an average value of 5 to 60.
6. The composition of claim 5, wherein the siloxane units are
present in an amount effective to provide 0.3% to 10% of siloxane
units based on the weight of the composition.
7. The composition of claim 1, wherein the polycarbonate copolymer
is present in an amount of 80 to 99.95 wt % based on the weight of
the composition.
8. The composition of claim 1, wherein the polycarbonate copolymer
is present in an amount of 90 to 99.95 wt % based on the weight of
the composition.
9. The composition of claim 1, wherein the aromatic
organophosphorus compound is bisphenol-A bis(diphenyl phosphate),
triphenyl phosphate, resorcinol bis(diphenyl phosphate), tricresyl
phosphate, or a combination comprising at least one of the
foregoing.
10. The composition of claim 9, wherein the organophosphorus
compound is present in an amount effective to provide 0.3% to 0.85%
of phosphorus, based on the weight of the composition.
11. The composition of claim 1, further comprising a processing
aid, a heat stabilizer, an antioxidant, an ultra violet light
absorber, a colorant, or a combination comprising at least one of
the foregoing in a total amount of 0.1 to 5 wt %, based on the
weight of the composition.
12. The composition of claim 1, wherein no or substantially no
flame retarding brominated compounds, flame retardant salts, or a
combination comprising at least one of the foregoing are present in
the composition.
13. The composition of claim 12, wherein the brominated compound is
a brominated polycarbonate, and the flame retardant salt is
potassium perfluorobutane sulfonate, potassium perfluorooctane
sulfonate, tetraethylammonium perfluorohexane sulfonate, potassium
diphenylsulfone sulfonate, Na.sub.2CO.sub.3, K.sub.2CO.sub.3,
MgCO.sub.3, CaCO.sub.3, and BaCO.sub.3, an inorganic phosphate
salt, Li.sub.3AlF.sub.6, BaSiF.sub.6, KBF.sub.4, K.sub.3AlF.sub.6,
KAlF.sub.4, K.sub.2SiF.sub.6, Na.sub.3AlF.sub.6, or a combination
comprising at least one of the foregoing.
14. The composition of claim 12, wherein no or substantially no
brominated polycarbonate, boron phosphate, or C.sub.1-6 alkyl
sulfonate salt is present in the composition.
15. The composition of claim 1, having a transparency of more than
85% and a haze of less than 3%, each measured according to ASTM D
1003 (2007) using illuminant C on plaques with 3 mm thickness.
16. The composition of claim 1, having a melt volume flow rate
greater than or equal to 10 cc/10 min, determined according to ISO
1133.
17. The composition of claim 1, having an MAI of 100 J or higher,
determined at 23.degree. C., 4.4 m/second in accordance with ISO
6603 on discs with a thickness of 3.2 mm.
18. An article comprising the composition of claim 1, selected from
a molded article, a thermoformed article, an extruded film, an
extruded sheet, a foamed article, a layer of a multi-layer article,
a substrate for a coated article, or a substrate for a metallized
article.
19. The article of claim 18, having a thickness of 0.1 to 10
mm.
20. The article of claim 18, having a thickness of 0.5 to 5 mm.
21. The article of claim 18, wherein the article is a
transportation component.
22. The article of claim 18, selected from a train or aircraft
interior component, wherein the component is a partition, a room
divider, a seat back, a food tray, a trim panel, an interior
display panel, an interior wall, a side wall, an end wall, a
ceiling panel, a door lining, a flap, a box, a hood, a louver, an
insulation material, a handle, a body shell for a window, a window
frame, an enclosure for an electronic device, a door, a luggage
rack, a luggage container, an interior side of a gangway membrane,
an interior lining of a gangway, or a component of a luggage
compartment, a display unit, a television, a refrigerator door, a
tray table, a food cart, a magazine rack, an air flow regulator, a
door, a table, or a seat.
23. A method of manufacture of an article, comprising molding,
extruding, foaming, or casting the composition of claim 1.
24. A thermoplastic composition comprises, based on the total
weight of the composition, an organophosphorus compound effective
to provide 0.1 to 1.0 wt % phosphorus based on the total weight of
the composition, wherein the organophosphorus comprises bisphenol-A
bis(diphenyl phosphate), tetraphenyl resorcinol diphosphate, or a
combination thereof; 90 to 98 wt % of a polycarbonate copolymer
comprising first repeating units and second repeating units,
wherein the second repeating units are polysiloxane units; and
optionally up to 5 wt % of an additive selected from a processing
aid, a heat stabilizer, an ultra violet light absorber, a colorant,
or a combination comprising at least one of the foregoing, wherein
the component has a smoke density value of equal to or less than
600 determined according to ISO 5659-2 on a 3 mm thick plaque, and
a material heat release of less than 160 kW/m.sup.2 determined
according to ISO 5660-1 on a 3 mm thick plaque.
25. The composition of claim 24, wherein the first units are
bisphenol-A carbonate units; and the siloxane units are of the
formula ##STR00029## or a combination comprising at least one of
the foregoing, wherein E has an average value of 5 to 60.
26. A thermoplastic composition consisting of, based on the total
weight of the composition, an organophosphorus compound effective
to provide 0.1 to 1.0 wt % phosphorus based on the total weight of
the composition, wherein the organophosphorus comprises bisphenol-A
bis(diphenyl phosphate), tetraphenyl resorcinol diphosphate, or a
combination thereof; 90 to 98 wt % of a polycarbonate copolymer
comprising first repeating units and second repeating units,
wherein the second repeating units are polysiloxane units; and
optionally up to 5 wt % of an additive selected from a processing
aid, a heat stabilizer, an ultra violet light absorber, a colorant,
or a combination comprising at least one of the foregoing, wherein
the component has a smoke density value of equal to or less than
600 determined according to ISO 5659-2 on a 3 mm thick plaque, and
a material heat release of less than 160 kW/m.sup.2 determined
according to ISO 5660-1 on a 3 mm thick plaque.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application of U.S.
patent application Ser. No. 13/780,324, filed Feb. 28, 2013, which
claims the benefit of U.S. Patent Application No. 61/604,845, filed
Feb. 29, 2012, all of the foregoing being incorporated by reference
in their entirety herein.
BACKGROUND
[0002] This disclosure is directed to flame retardant thermoplastic
compositions comprising polycarbonate, their method of manufacture,
and methods of use thereof and in particular to thermoplastic
polycarbonate copolymer compositions having low smoke density and
low heat release.
[0003] Polycarbonates are useful in a wide variety of applications
at least in part because of their good balance of properties, such
as moldability, heat resistance and impact properties among others.
However, standards for flame retardancy properties such as flame
spread, heat release, and smoke generation upon burning have become
increasingly stringent, particularly in applications used in mass
transportation (aircraft, trains, and ships), as well as building
and construction. For example, the European Union has approved the
introduction of a new harmonized fire standard for rail
applications, namely EN-45545, to replace all currently active
different standards in each member state. This standard will impose
stringent requirements on heat release and smoke density properties
allowed for materials used in these applications. Smoke density
(Ds-4) in EN-45545 is the smoke density after four minutes
determined in accordance with ISO 5659-2, and heat release in
EN-45545 is the maximum average rate of heat emission (MAHRE)
determined in accordance with ISO 5660-1.
[0004] It is exceptionally challenging to develop materials that
meet stringent smoke density standards and heat release standards
in addition to other material requirements. It is particularly
challenging to develop materials that meet these standards and that
have good mechanical properties (especially impact/scratch
resistance) and processability. Accordingly there remains a need
for thermoplastic compositions that have a combination of low smoke
and low heat release properties. It would be a further advantage
the compositions could be rendered low smoke and low heat release
without a significant detrimental effect on one or more of material
cost, processability, and mechanical properties. It would be a
still further advantage if the materials could be readily
thermoformed or injection molded. It would be a still further
advantage if such materials were in compliance with European
Railway standard EN-45545, for example, without having a
detrimental effect on material cost, processability, and mechanical
properties.
SUMMARY
[0005] Disclosed herein is a thermoplastic composition comprising a
polycarbonate copolymer, comprising first repeating carbonate units
and second repeating units selected from carbonate units that are
different from the first carbonate units, polysiloxane units, and a
combination comprising at least one of the foregoing unit; and an
organophosphorus flame retardant in an amount effective to provide
0.1 to 1.0 wt % phosphorus based on the total weight of the
composition, wherein an article molded from the composition has a
smoke density after 4 minutes (Ds-4) of less than or equal to 600
determined according to ISO 5659-2 on a 3 mm thick plaque, and a
material heat release of less than or equal to 160 kW/m.sup.2
determined according to ISO 5660-1 on a 3 mm thick plaque.
[0006] A method of manufacture of the thermoplastic compositions
comprises extruding or melt-blending the components of the
thermoplastic compositions to form the thermoplastic
compositions.
[0007] In yet another embodiment, an article comprises the
thermoplastic compositions, including a molded article, a
thermoformed article, an extruded film, an extruded sheet, a foamed
article, a layer of a multi-layer article, a substrate for a coated
article, or a substrate for a metallized article. The article can
be a transportation component, for example a component of a train,
a floor for a train compartment, a train compartment, cladding, or
seating for a train.
[0008] A method of manufacture of an article comprises molding,
extruding, foaming, or casting the above-described thermoplastic
composition to form the article.
[0009] The above described and other features are exemplified by
the following Detailed Description, Examples, and Claims.
DETAILED DESCRIPTION
[0010] The inventors hereof have discovered that thermoplastic
compositions having low smoke density as well as lower heat release
can unexpectedly be obtained by combining certain polycarbonate
copolymers with a relatively small amount of organophosphorus
compounds. In particular, the inventors have discovered that the
combination of the small amounts of organophosphorus compounds with
specific polycarbonate copolymers results in a decrease in the
smoke density (Ds-4) of the copolymers as determined in accordance
with ISO 5659-2, in addition to decreasing the material heat
release values as determined in accordance with ISO 5660-1. For
example, the thermoplastic composition can have a smoke density of
less than 600 as determined in accordance with ISO 5659-2 on a 3 mm
thick plaque. The thermoplastic compositions can further have a
maximum average rate of heat emission ("MAHRE") of less than 160
kW/m.sup.2, as determined in accordance with ISO 5660-1 on a 3 mm
thick plaque.
[0011] In particular, the thermoplastic compositions contain a
polycarbonate copolymer comprising first repeating carbonate units
and second repeating units that are different from the first
carbonate units. The first carbonate units are bisphenol carbonate
units that can be derived from a bisphenol-A compound. The second
repeating units can be repeating carbonate units different from the
first carbonate units; siloxane units; or a combination comprising
at least one of the foregoing types of units. The thermoplastic
compositions further contain a organophosphorus compound, effective
to provide 0.1-1.0%, 0.3 to 0.8%, or 0.5 to 0.7% based on the
weight of the composition, of phosphorus, whereby an article formed
from the composition has a smoke density of less than 600 as
determined in accordance with ISO 5659-2 on a 3 mm thick plaque and
MAHRE of less than 160 kW/m.sup.2 as determined in accordance with
ISO 5660-1 on a 3 mm thick plaque.
[0012] Without being bound by theory, it is believed that the
unexpected combination of low smoke density and low heat release
values are obtained by careful selection and balancing of the
relative amounts and ratios of the first and second repeating units
of the polycarbonate copolymer, including the block size of the
first and second repeating units in the polycarbonate copolymer,
the total amount of siloxane units in the composition when present,
and the total amount and choice of the organophosphorus compounds
used in the composition.
[0013] The polycarbonate copolymers have first repeating first
units that are bisphenol carbonate units of formula (1)
##STR00001##
wherein R.sup.a and R.sup.b are each independently C.sub.1-12
alkyl, p and q are each independently 0 to 4, and X.sup.a is a
bridging group between the two arylene groups, and is a single
bond, --O--, --S--, --S(O)--, --S(O).sub.2--, --C(O)--, a
C.sub.1-12 alkylidene of formula --C(R.sup.c)(R.sup.d)-- wherein
R.sup.c and R.sup.d are each independently hydrogen or C.sub.1-11
alkyl, or a group of the formula --C(.dbd.R.sup.e)-- wherein
R.sup.e is a divalent C.sub.1-11 hydrocarbon group. Exemplary
X.sup.a groups include methylene, ethylidene, neopentylidene, and
isopropylidene. The bridging group X.sup.a and the carbonate oxygen
atoms of each C.sub.6 arylene group can be disposed ortho, meta, or
para (specifically para) to each other on the C.sub.6 arylene
group.
[0014] In a specific embodiment, R.sup.a and R.sup.b are each
independently a C.sub.1-3 alkyl group, p and q are each
independently 0 to 1, and X.sup.a is a single bond, --O--,
--S(O)--, --S(O).sub.2--, --C(O)--, a C.sub.1-9 alkylidene of
formula --C(R.sup.c)(R.sup.d)-- wherein R.sup.c and R.sup.d are
each independently hydrogen or C.sub.1-8 alkyl, or a group of the
formula --C(.dbd.R.sup.e)-- wherein R.sup.e is a divalent C.sub.1-9
hydrocarbon group. In another specific embodiment, R.sup.a and
R.sup.b are each independently a methyl group, p and q are each
independently 0 to 1, and X.sup.a is a single bond, a C.sub.1-7
alkylidene of formula --C(R.sup.c)(R.sup.d)-- wherein R.sup.c and
R.sup.d are each independently hydrogen or C.sub.1-6 alkyl. In
another embodiment, p and q is each 1, and R.sup.a and R.sup.b are
each a C.sub.1-3 alkyl group, specifically methyl, disposed meta to
the oxygen on each ring. The bisphenol carbonate units (1) can be
derived from bisphenol-A, where p and q are both 0 and X.sup.a is
isopropylidene.
[0015] The polycarbonate units in the copolymers can be produced
from dihydroxy compounds of formula (2)
HO--R.sup.1--OH (2)
wherein R.sup.1 is a bridging moiety. Thus, the bisphenol carbonate
units (1) are generally produced from the corresponding bisphenol
compounds of formula (3)
##STR00002##
wherein R.sup.a and R.sup.b, p and q, and X.sup.a are the same as
in formula (1).
[0016] Some illustrative examples of specific bisphenol compounds
(3) that can be used include 4,4'-dihydroxybiphenyl,
bis(4-hydroxyphenyl) methane, 1,2-bis(4-hydroxyphenyl)ethane,
2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,
1,2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-ethyl-4-hydroxyphenyl)propane,
2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,
2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,
2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,
2,2-bis(3-allyl-4-hydroxyphenyl)propane,
2,2-bis(3-methoxy-4-hydroxyphenyl)propane,
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone,
1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane,
2,2-bis(4-hydroxyphenyl) propane (hereinafter "bisphenol-A" or
"BPA"), 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl)
octane, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl)
n-butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, or a
combination comprising at least one of the foregoing bisphenolic
compounds.
[0017] As stated above, the polycarbonate copolymers further
comprise second repeating units. The second repeating units can be
bisphenol carbonate units (provided that they are different from
the bisphenol carbonate units (1)), siloxane units, or a
combination comprising at least one of the foregoing.
[0018] In an embodiment, the second units are repeating bisphenol
carbonate units of formula (4)
##STR00003##
wherein R.sup.a and R.sup.b are each independently C.sub.1-12
alkyl, p and q are each independently integers of 0 to 4, and
X.sup.b is C.sub.1-32 bridging hydrocarbon group that is not the
same as the X.sup.a in carbonate units (1). The bridging group
X.sup.b and the carbonate oxygen atoms of each C.sub.6 arylene
group can be disposed ortho, meta, or para (specifically para) to
each other on the C.sub.6 arylene group.
[0019] In an embodiment, X.sup.b in formula (4) is a substituted or
unsubstituted C.sub.5-32 alkylidene of formula
--C(R.sup.c)(R.sup.d)-- wherein R.sup.c and R.sup.d are each
independently hydrogen, C.sub.4-12 cycloalkyl, C.sub.6-12 aryl,
C.sub.7-12 arylalkylene, C.sub.1-12 heteroalkyl, a substituted or
unsubstituted group of the formula --C(.dbd.R.sup.e)-- wherein
R.sup.e is a divalent C.sub.12-31 hydrocarbyl, a substituted or
unsubstituted C.sub.5-18 cycloalkylidene, a substituted or
unsubstituted C.sub.5-18 cycloalkylene, a substituted or
unsubstituted C.sub.3-18 heterocycloalkylidene, or a group of the
formula --B.sup.1-G-B.sup.2-- wherein B.sup.1 and B.sup.2 are the
same or different C.sub.1-6 alkylene group and G is a C.sub.3-12
cycloalkylidene group or a C.sub.6-16 arylene group.
[0020] For example, X.sup.b in formula (4) can be a substituted
C.sub.3-18 heterocycloalkylidene of formula (5)
##STR00004##
wherein R.sup.r, R.sup.p, R.sup.q, and R.sup.t are each
independently hydrogen, oxygen, or C.sub.1-12 organic groups; I is
a direct bond, a carbon, or a divalent oxygen, sulfur, or --N(Z)--
where Z is hydrogen, halogen, hydroxy, C.sub.1-12 alkyl, C.sub.1-12
alkoxy, or C.sub.1-12 acyl; h is 0 to 2, j is 1 or 2, i is an
integer of 0 or 1, and k is an integer of 0 to 3, with the proviso
that at least two of R.sup.r, R.sup.p, R.sup.q, and R.sup.t taken
together are a fused cycloaliphatic, aromatic, or heteroaromatic
ring. It will be understood that where the fused ring is aromatic,
the ring as shown in formula (3) will have an unsaturated
carbon-carbon linkage where the ring is fused. When k is one and i
is 0, the ring as shown in formula (5) contains 4 carbon atoms,
when k is 2, the ring contains 5 carbon atoms, and when k is 3, the
ring contains 6 carbon atoms. In an embodiment, two adjacent groups
(e.g., R.sup.q and R.sup.t taken together) form an aromatic group,
and in another embodiment, R.sup.q and R.sup.t taken together form
one aromatic group and R.sup.r and R.sup.p taken together form a
second aromatic group. When R.sup.q and R.sup.t taken together form
an aromatic group, R.sup.p can be a double-bonded oxygen atom,
i.e., a ketone.
[0021] Specific second bisphenol carbonate repeating units of this
type are phthalimidine carbonate units of formula (6)
##STR00005##
wherein R.sup.a, R.sup.b, p, and q are as in formula (4), R.sup.3
is each independently a C.sub.1-6 alkyl group, j is 0 to 4, and
R.sub.4 is hydrogen, C.sub.1-6 alkyl, phenyl optionally substituted
with 1 to 5 C.sub.1-6 alkyl groups. In particular, the
phthalimidine carbonate units are of formula (6a)
##STR00006##
wherein R.sup.5 is hydrogen, C.sub.1-6 alkyl, or phenyl optionally
substituted with 1 to 5 C.sub.1-6 alkyl groups. In an embodiment,
R.sup.5 is hydrogen, phenyl or methyl. Carbonate units (6a) wherein
R.sup.5 is phenyl can be derived from 2-phenyl-3,3'-bis(4-hydroxy
phenyl)phthalimidine (also known as N-phenyl phenolphthalein
bisphenol, or "PPPBP") (also known as
3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one).
[0022] Other bisphenol carbonate repeating units of this type are
the isatin carbonate units of formula (6b) and (6c)
##STR00007##
wherein R.sup.a and R.sup.b are each independently C.sub.1-12
alkyl, p and q are each independently 0 to 4, and R.sup.i is
C.sub.1-12 alkyl, phenyl, optionally substituted with 15 to
C.sub.1-10 alkyl, or benzyl optionally substituted with 1 to 5
C.sub.1-10 alkyl. In an embodiment, R.sup.a and R.sup.b are each
methyl, p and q are each independently 0 or 1, and R.sup.i is
C.sub.1-4 alkyl or phenyl.
[0023] Examples of bisphenol carbonate units (4) wherein X.sup.b is
a substituted or unsubstituted C.sub.3-18 cycloalkylidene include
the cyclohexylidene-bridged, alkyl-substituted bisphenol of formula
(7)
##STR00008##
wherein R.sup.a and R.sup.b are each independently C.sub.1-12
alkyl, R.sup.g is C.sub.1-12 alkyl, p and q are each independently
1 to 4, and t is 0 to 10. In a specific embodiment, at least one of
each of R.sup.a and R.sup.b are disposed meta to the
cyclohexylidene bridging group. In an embodiment, R.sup.a and
R.sup.b are each independently C.sub.1-4 alkyl, R.sup.g is
C.sub.1-4 alkyl, p and q are each 0 or 1, and t is 0 to 5. In
another specific embodiment, R.sup.a, R.sup.b, and R.sup.g are each
methyl, r and s are each 0 or 1, and t is 0 or 3, specifically
0.
[0024] Examples of other bisphenol carbonate units (4) wherein
X.sup.b is a substituted or unsubstituted C.sub.3-18
cycloalkylidene include adamantyl units (8) and units (9)
##STR00009##
wherein R.sup.a and R.sup.b are each independently C.sub.1-12
alkyl, and p and q are each independently 1 to 4. In a specific
embodiment, at least one of each of R.sup.a and R.sup.b are
disposed meta to the cycloalkylidene bridging group. In an
embodiment, R.sup.a and R.sup.b are each independently C.sub.1-3
alkyl, and p and q are each 0 or 1. In another specific embodiment,
R.sup.a, R.sup.b are each methyl, p and q are each 0 or 1.
Carbonates containing units (6a-c), (7), (8), and (9) are useful
for making polycarbonate polymers with high glass transition
temperatures (Tg) and high heat distortion temperatures.
[0025] Bisphenol carbonate units (4) are generally produced from
the corresponding bisphenol compounds of formula (10)
##STR00010##
wherein R.sup.a, R.sup.b, p, q, and X.sup.b are the same as in
formula (4). Specific examples of bisphenol compounds of formula
(10) include bis(4-hydroxyphenyl)diphenylmethane,
1,1-bis(4-hydroxy-t-butylphenyl) propane, 1,6-dihydroxynaphthalene,
2,6-dihydroxynaphthalene,
6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane
("spirobiindane bisphenol"), 2,6-dihydroxydibenzo-p-dioxin,
2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathiin,
2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran,
3,6-dihydroxydibenzothiophene, 2,7-dihydroxycarbazole, and
2,6-dihydroxythianthrene 3,3-bis(4-hydroxyphenyl) phthalimidine,
2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), and
1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinations
comprising at least one of the foregoing dihydroxy compounds can
also be used.
[0026] The mole ratio of first bisphenol carbonate units (1) and
second bisphenol carbonate units (4) can vary from 99:1 to 1:99,
depending on the desired characteristics of the thermoplastic
composition, including Ds-4 smoke density, MAHRE, glass transition
temperature, impact strength, ductility, melt flow rate, and like
considerations. For example, the mole ratio of units (1):units (4)
can be from 90:10 to 10:90, from 80:20 to 20:80, from 70:30 to
30:70, or from 60:40 to 40:60. When repeating bisphenol carbonate
units (1) are derived from bisphenol-A, the bisphenol-A units are
generally present in an amount from 50 to 99 mole %, based on the
total moles of units in the polycarbonate copolymer. For example,
when bisphenol carbonate units (1) are derived from bisphenol-A,
and bisphenol units (4) are derived from PPPBP, the mole ratio of
units (1) to units (4) can be from 99:1 to 50:50, or from 90:10 to
55:45.
[0027] Other carbonate units can be present in any of the
polycarbonate copolymers comprising units (1) and (4), in
relatively small amounts, for example less than 20 mole %, less
than 10 mole %, or less than 5 mole %, based on the total moles of
units in the polycarbonate copolymer. The other carbonate units can
be derived from C.sub.1-32 aliphatic or C.sub.6-32 aromatic
dihydroxy compounds, for example resorcinol, 5-methyl resorcinol,
5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol,
5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol,
catechol, hydroquinone, 2-methyl hydroquinone, 2-ethyl
hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone,
2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl
hydroquinone, 2,3,5,6-tetramethyl hydroquinone, and
2,3,5,6-tetra-t-butyl hydroquinone. In an embodiment no carbonate
derived from aliphatic aromatic dihydroxy compounds are present.
The polycarbonate copolymers comprising a combination of units (1)
and (4) can have an intrinsic viscosity, as determined in
chloroform at 25.degree. C., of about 0.3 to about 1.5 deciliters
per gram (dl/gm), specifically about 0.45 to about 1.0 dl/gm. The
polycarbonate copolymers can have a weight average molecular weight
(M.sub.W) of about 10,000 to about 200,000 grams per mole (g/mole),
specifically about 20,000 to about 100,000 g/mole, as determined by
gel permeation chromatography (GPC), using a cross-linked
styrene-divinylbenzene column and calibrated to polycarbonate
references. GPC samples are prepared at a concentration of about 1
mg per ml, and are eluted at a flow rate of about 1.5 ml per
minute.
[0028] In an embodiment, the polycarbonate copolymers comprising a
combination of units (1) and (4) have flow properties useful for
the manufacture of thin articles. Melt volume flow rate (often
abbreviated MVR) measures the rate of extrusion of a thermoplastic
melt through an orifice at a prescribed temperature and load. For
example, the polycarbonate copolymers comprising a combination of
units (1) and (4) can have an MVR measured at 300.degree. C. under
a load of 1.2 kg according to ASTM D1238-04, of 0.5 to 100 cubic
centimeters per 10 minutes (cc/10 min), specifically 1 to 75 cc/10
min, and more specifically 1 to 50 cc/10 min.
[0029] Combinations of polycarbonate copolymers of different flow
properties and weight average molecular weights can be used to
achieve the overall desired flow property. It is desirable for such
combinations to have an MVR measured at 300.degree. C./1.2 kg load,
of about 5 to about 150 cc/10 min., specifically about 7 to about
125 cc/10 min, more specifically about 9 to about 110 cc/10 min,
and still more specifically about 10 to about 100 cc/10 minute.
Polycarbonates useful for the formation of thin articles can have
an MVR, measured at 300.degree. C./1.2 kg load, of about 9 to about
21 cc/10 min, specifically about 9.4 to about 21.4 cc/10 min.
[0030] Polycarbonates can be manufactured by processes such as
interfacial polymerization and melt polymerization. Although the
reaction conditions for interfacial polymerization can vary, an
exemplary process generally involves dissolving or dispersing a
dihydric phenol reactant in aqueous caustic soda or potash, adding
the resulting mixture to a water-immiscible solvent medium, and
contacting the reactants with a carbonate precursor in the presence
of a catalyst such as, for example, a tertiary amine or a phase
transfer catalyst, under controlled pH conditions, e.g., 8 to 10.
The water immiscible solvent can be, for example, methylene
chloride, 1,2-dichloroethane, chlorobenzene, toluene, and the
like.
[0031] Exemplary carbonate precursors include a carbonyl halide
such as carbonyl bromide or carbonyl chloride, or a haloformate
such as a bishaloformates of a dihydric phenol (e.g., the
bischloroformates of bisphenol A, hydroquinone, or the like) or a
glycol (e.g., the bishaloformate of ethylene glycol, neopentyl
glycol, polyethylene glycol, or the like). Combinations comprising
at least one of the foregoing types of carbonate precursors can
also be used. In an embodiment, an interfacial polymerization
reaction to form carbonate linkages uses phosgene as a carbonate
precursor, and is referred to as a phosgenation reaction.
[0032] Among tertiary amines that can be used are aliphatic
tertiary amines such as triethylamine and tributylamine,
cycloaliphatic tertiary amines such as N,N-diethyl-cyclohexylamine,
and aromatic tertiary amines such as N,N-dimethylaniline. Among the
phase transfer catalysts that can be used are catalysts of the
formula (R.sup.3).sub.4Q.sup.+X.sup.-, wherein each R.sub.3 is the
same or different, and is a C.sub.1-10 alkyl group; Q is a nitrogen
or phosphorus atom; and X is a halogen atom or a C.sub.1-8 alkoxy
group or C.sub.6-18 aryloxy group. Exemplary phase transfer
catalysts include (CH.sub.3(CH.sub.2).sub.3).sub.4N.sup.+X.sup.-,
(CH.sub.3(CH.sub.2).sub.3).sub.4P.sup.+X.sup.-,
(CH.sub.3(CH.sub.2).sub.5).sub.4N.sup.+X.sup.-,
(CH.sub.3(CH.sub.2).sub.6).sub.4N.sup.+X.sup.-,
(CH.sub.3(CH.sub.2).sub.4).sub.4N.sup.+X.sup.-,
CH.sub.3(CH.sub.3(CH.sub.2).sub.3).sub.3N.sup.+X.sup.-, and
CH.sub.3(CH.sub.3(CH.sub.2).sub.2).sub.3N.sup.+X.sup.-, wherein X
is Cl.sup.-, Br.sup.-, a C.sub.1-8 alkoxy group or a C.sub.6-18
aryloxy group. An effective amount of a phase transfer catalyst can
be 0.1 to 10 wt. %, or 0.5 to 2 wt. %, each based on the weight of
bisphenol in the phosgenation mixture.
[0033] Alternatively, melt processes can be used to make the
polycarbonates. Melt polymerization may be conducted as a batch
process or as a continuous process. In either case, the melt
polymerization conditions used may comprise two or more distinct
reaction stages, for example, a first reaction stage in which the
starting dihydroxy aromatic compound and diaryl carbonate are
converted into an oligomeric polycarbonate and a second reaction
stage wherein the oligomeric polycarbonate formed in the first
reaction stage is converted to high molecular weight polycarbonate.
Such "staged" polymerization reaction conditions are especially
suitable for use in continuous polymerization systems wherein the
starting monomers are oligomerized in a first reaction vessel and
the oligomeric polycarbonate formed therein is continuously
transferred to one or more downstream reactors in which the
oligomeric polycarbonate is converted to high molecular weight
polycarbonate. Typically, in the oligomerization stage the
oligomeric polycarbonate produced has a number average molecular
weight of about 1,000 to about 7,500 Daltons. In one or more
subsequent polymerization stages the number average molecular
weight (Mn) of the polycarbonate is increased to between about
8,000 and about 25,000 Daltons (using polycarbonate standard).
[0034] The term "melt polymerization conditions" is understood to
mean those conditions necessary to effect reaction between a
dihydroxy aromatic compound and a diaryl carbonate in the presence
of a transesterification catalyst. Typically, solvents are not used
in the process, and the reactants dihydroxy aromatic compound and
the diaryl carbonate are in a molten state. The reaction
temperature can be about 100.degree. C. to about 350.degree. C.,
specifically about 180.degree. C. to about 310.degree. C. The
pressure may be at atmospheric pressure, supra-atmospheric
pressure, or a range of pressures from atmospheric pressure to
about 15 torr in the initial stages of the reaction, and at a
reduced pressure at later stages, for example about 0.2 to about 15
torr. The reaction time is generally about 0.1 hours to about 10
hours.
[0035] The diaryl carbonate ester can be diphenyl carbonate, or an
activated diphenyl carbonate having electron-withdrawing
substituents on the aryl groups, such as
bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate,
bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate,
bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl)
carboxylate, bis(4-acetylphenyl) carboxylate, or a combination
comprising at least one of the foregoing.
[0036] Catalysts used in the melt polymerization of polycarbonates
can include alpha or beta catalysts. Beta catalysts are typically
volatile and degrade at elevated temperatures. Beta catalysts are
therefore preferred for use at early low-temperature polymerization
stages. Alpha catalysts are typically more thermally stable and
less volatile than beta catalysts.
[0037] The alpha catalyst can comprise a source of alkali or
alkaline earth ions. The sources of these ions include alkali metal
hydroxides such as lithium hydroxide, sodium hydroxide, and
potassium hydroxide, as well as alkaline earth hydroxides such as
magnesium hydroxide and calcium hydroxide. Other possible sources
of alkali and alkaline earth metal ions include the corresponding
salts of carboxylic acids (such as sodium acetate) and derivatives
of ethylene diamine tetraacetic acid (EDTA) (such as EDTA
tetrasodium salt, and EDTA magnesium disodium salt). Other alpha
transesterification catalysts include alkali or alkaline earth
metal salts of a non-volatile inorganic acid such as
NaH.sub.2PO.sub.3, NaH.sub.2PO.sub.4, Na.sub.2HPO.sub.3,
KH.sub.2PO.sub.4, CsH.sub.2PO.sub.4, Cs.sub.2HPO.sub.4, and the
like, or mixed salts of phosphoric acid, such as NaKHPO.sub.4,
CsNaHPO.sub.4, CsKHPO.sub.4, and the like. Combinations comprising
at least one of any of the foregoing catalysts can be used.
[0038] Possible beta catalysts can comprise a quaternary ammonium
compound, a quaternary phosphonium compound, or a combination
comprising at least one of the foregoing. The quaternary ammonium
compound can be a compound of the structure
(R.sup.4).sub.4N.sup.+X.sup.-, wherein each R.sup.4 is the same or
different, and is a C.sub.1-20 alkyl group, a C.sub.4-20 cycloalkyl
group, or a C.sub.4-20 aryl group; and X.sup.- is an organic or
inorganic anion, for example a hydroxide, halide, carboxylate,
sulfonate, sulfate, formate, carbonate, or bicarbonate. Examples of
organic quaternary ammonium compounds include tetramethyl ammonium
hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium
acetate, tetramethyl ammonium formate, tetrabutyl ammonium acetate,
and combinations comprising at least one of the foregoing.
Tetramethyl ammonium hydroxide is often used. The quaternary
phosphonium compound can be a compound of the structure
(R.sup.5).sub.4P.sup.+X.sup.-, wherein each R.sup.5 is the same or
different, and is a C.sub.1-20 alkyl group, a C.sub.4-20 cycloalkyl
group, or a C.sub.4-20 aryl group; and X.sup.- is an organic or
inorganic anion, for example a hydroxide, halide, carboxylate,
sulfonate, sulfate, formate, carbonate, or bicarbonate. Where
X.sup.- is a polyvalent anion such as carbonate or sulfate it is
understood that the positive and negative charges in the quaternary
ammonium and phosphonium structures are properly balanced. For
example, where R.sup.20-R.sup.23 are each methyl groups and X.sup.-
is carbonate, it is understood that X.sup.- represents
2(CO.sub.3.sup.-2). Examples of organic quaternary phosphonium
compounds include tetramethyl phosphonium hydroxide, tetramethyl
phosphonium acetate, tetramethyl phosphonium formate, tetrabutyl
phosphonium hydroxide, tetrabutyl phosphonium acetate (TBPA),
tetraphenyl phosphonium acetate, tetraphenyl phosphonium phenoxide,
and combinations comprising at least one of the foregoing. TBPA is
often used.
[0039] The amount of alpha and beta catalyst used can be based upon
the total number of moles of dihydroxy compound used in the
polymerization reaction. When referring to the ratio of beta
catalyst, for example a phosphonium salt, to all dihydroxy
compounds used in the polymerization reaction, it is convenient to
refer to moles of phosphonium salt per mole of the dihydroxy
compound, meaning the number of moles of phosphonium salt divided
by the sum of the moles of each individual dihydroxy compound
present in the reaction mixture. The alpha catalyst can be used in
an amount sufficient to provide 1.times.10.sup.-2 to
1.times.10.sup.-8 moles, specifically, 1.times.10.sup.-4 to
1.times.10.sup.-7 moles of metal per mole of the dihydroxy
compounds used. The amount of beta catalyst (e.g., organic ammonium
or phosphonium salts) can be 1.times.10.sup.-2 to
1.times.10.sup.-5, specifically 1.times.10.sup.-3 to
1.times.10.sup.-4 moles per total mole of the dihydroxy compounds
in the reaction mixture.
[0040] Branched polycarbonate blocks can be prepared by adding a
branching agent during polymerization. These branching agents
include polyfunctional organic compounds containing at least three
functional groups selected from hydroxyl, carboxyl, carboxylic
anhydride, haloformyl, and mixtures of the foregoing functional
groups. Specific examples include trimellitic acid, trimellitic
anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane,
isatin-bis-phenol, tris-phenol TC
(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA
(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl
benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid,
and benzophenone tetracarboxylic acid. The branching agents can be
added at a level of about 0.05 to about 5 wt. %. Combinations
comprising linear polycarbonates and branched polycarbonates can be
used.
[0041] All types of polycarbonate end groups are contemplated as
being useful in the polycarbonate composition, provided that such
end groups do not significantly adversely affect desired properties
of the compositions. A chain stopper (also referred to as a capping
agent) can be included during polymerization. The chain stopper
limits molecular weight growth rate, and so controls molecular
weight in the polycarbonate. Exemplary chain stoppers include
certain mono-phenolic compounds, mono-carboxylic acid chlorides,
and/or mono-chloroformates. Mono-phenolic chain stoppers are
exemplified by monocyclic phenols such as phenol and
C.sub.1-C.sub.22 alkyl-substituted phenols such as p-cumyl-phenol,
resorcinol monobenzoate, and p- and tertiary-butyl phenol; and
monoethers of diphenols, such as p-methoxyphenol. Alkyl-substituted
phenols with branched chain alkyl substituents having 8 to 9 carbon
atom can be specifically mentioned. Certain mono-phenolic UV
absorbers can also be used as a capping agent, for example
4-substituted-2-hydroxybenzophenones and their derivatives, aryl
salicylates, monoesters of diphenols such as resorcinol
monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their
derivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their
derivatives, and the like. Mono-carboxylic acid chlorides can also
be used as chain stoppers. These include monocyclic,
mono-carboxylic acid chlorides such as benzoyl chloride,
C.sub.1-C.sub.22 alkyl-substituted benzoyl chloride, toluoyl
chloride, halogen-substituted benzoyl chloride, bromobenzoyl
chloride, cinnamoyl chloride, 4-nadimidobenzoyl chloride, and
combinations thereof; polycyclic, mono-carboxylic acid chlorides
such as trimellitic anhydride chloride, and naphthoyl chloride; and
combinations of monocyclic and polycyclic mono-carboxylic acid
chlorides. Chlorides of aliphatic monocarboxylic acids with less
than or equal to about 22 carbon atoms are useful. Functionalized
chlorides of aliphatic monocarboxylic acids, such as acryloyl
chloride and methacryoyl chloride, are also useful. Also useful are
mono-chloroformates including monocyclic, mono-chloroformates, such
as phenyl chloroformate, alkyl-substituted phenyl chloroformate,
p-cumyl phenyl chloroformate, toluene chloroformate, and
combinations thereof.
[0042] Additionally, the polycarbonate copolymers can be prepared
from polyester blocks. The polyester blocks can also be prepared by
interfacial polymerization. The polyesters can also be obtained by
melt-process condensation as described above, by solution phase
condensation, or by transesterification polymerization wherein, for
example, a dialkyl ester such as dimethyl terephthalate can be
transesterified with the dihydroxy reactant using acid catalysis,
to generate the polyester blocks. Branched polyester blocks, in
which a branching agent, for example, a glycol having three or more
hydroxyl groups or a trifunctional or multifunctional carboxylic
acid has been incorporated, can be used. Furthermore, it can be
desirable to have various concentrations of acid and hydroxyl end
groups on the polyester blocks, depending on the ultimate end use
of the composition.
[0043] All types of polycarbonate end groups are contemplated as
being useful in the thermoplastic composition, provided that such
end group does not significantly adversely affect desired
properties of the compositions such as smoke density and maximum
average rate of heat release, ductility, transparency and the like.
Branched polycarbonate blocks can be prepared by adding a branching
agent during polymerization. These branching agents include
polyfunctional organic compounds containing at least three
functional groups selected from hydroxyl, carboxyl, carboxylic
anhydride, haloformyl, and mixtures of the foregoing functional
groups. Specific examples include trimellitic acid, trimellitic
anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane,
isatin-bis-phenol, tris-phenol TC
(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA
(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl
benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid,
and benzophenone tetracarboxylic acid. The branching agents can be
added at a level of about 0.05 to about 2.0 wt %. Mixtures
comprising linear polycarbonates and branched polycarbonates can be
used.
[0044] In another embodiment, the second units of the polycarbonate
copolymers are siloxane units. Such poly(carbonate-siloxane)
(PC-siloxane or PC--Si)copolymers contain bisphenol carbonate units
(1), for example bisphenol-A carbonate units, and repeating
siloxane units (also known as "diorganosiloxane units"). The
polysiloxane units are of formula (11)
##STR00011##
wherein each R is independently a C.sub.1-13 monovalent hydrocarbyl
group. For example, each R can independently be a C.sub.1-13 alkyl
group, C.sub.1-13 alkoxy group, C.sub.2-13 alkenyl group,
C.sub.2-13 alkenyloxy group, C.sub.3-6 cycloalkyl group, C.sub.3-6
cycloalkoxy group, C.sub.6-14 aryl group, C.sub.6-10 aryloxy group,
C.sub.7-13 arylalkyl group, C.sub.7-13 arylalkoxy group, C.sub.7-13
alkylaryl group, or C.sub.7-13 alkylaryloxy group. The foregoing
groups can be fully or partially halogenated with fluorine,
chlorine, bromine, or iodine, or a combination thereof. In an
embodiment no halogens are present. Combinations of the foregoing R
groups can be used in the same copolymer. In an embodiment, the
polysiloxane comprises R groups that have minimal hydrocarbon
content. In a specific embodiment, an R group with minimal
hydrocarbon content is a methyl group.
[0045] The average value of E, denoting the siloxane-containing
block size in formula (11), can vary widely depending on the type
and relative amount of each component in the thermoplastic
composition, whether the polymer is linear, branched or a graft
copolymer, the desired properties of the composition (e.g.
transparency), and like considerations. In an embodiment, E has an
average value of 2 to 500, 5 to 200, or 5 to 100, 10 to 100, 10 to
80 or 3 to 60. In an embodiment E has an average value of 16 to 50,
more specifically 20 to 45, and even more specifically 25 to 45. In
another embodiment, E has an average value of 4 to 50, 4 to 15,
specifically 5 to 15, more specifically 6 to 15, and still more
specifically 7 to 10.
[0046] In an embodiment, the polysiloxane units are structural
units of formula (11a)
##STR00012##
wherein E is as defined above; each R can independently be the same
or different, and is as defined above; and each Ar can
independently be the same or different, and is a substituted or
unsubstituted C.sub.6-30 compound containing an aromatic group,
wherein the bonds are directly connected to the aromatic moiety.
The Ar groups in formula (11a) can be derived from a C.sub.6-30
dihydroxy aromatic compound, for example a bisphenol compound as
described above or monoaryl dihydroxy compound such as resorcinol
for example. Combinations comprising at least one of the foregoing
dihydroxy aromatic compounds can also be used. Exemplary dihydroxy
aromatic compounds are resorcinol (i.e., 1,3-dihydroxybenzene),
4-methyl-1,3-dihydroxybenzene, 5-methyl-1,3-dihydroxybenzene,
4,6-dimethyl-1,3-dihydroxybenzene, 1,4-dihydroxybenzene,
1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane,
2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane,
2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane,
1,1-bis(4-hydroxyphenyl) n-butane,
2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4-hydroxyphenyl)
cyclohexane, bis(4-hydroxyphenyl sulfide), and
1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinations comprising
at least one of the foregoing dihydroxy compounds can also be used.
In an embodiment, the dihydroxy aromatic compound is unsubstituted,
or is does not contain non-aromatic hydrocarbyl substituents such
as alkyl, alkoxy, or alkylene substituents.
[0047] In a specific embodiment, where Ar is derived from
resorcinol, the polysiloxane units are of the formula (11a-1)
##STR00013##
or where Ar is derived from bisphenol-A, the polysiloxane has the
formula (11a-2)
##STR00014##
or a combination comprising at least one of the foregoing can be
used, wherein E has an average value as described above,
specifically an average value of 5 to 200.
[0048] In another embodiment, polydiorganosiloxane units are units
of formula (11b)
##STR00015##
wherein R and E are as described for formula (11), and each R.sup.2
is independently a divalent C.sub.1-30 alkylene or C.sub.7-30
arylene-alkylene. In a specific embodiment, where R.sup.2 is
C.sub.7-30 arylene-alkylene, the polydiorganosiloxane units are of
formula (11b-1)
##STR00016##
wherein R and E are as defined for formula (11), and each R.sup.3
is independently a divalent C.sub.2-8 aliphatic group. Each M in
formula (11b-1) can be the same or different, and can be a halogen,
cyano, nitro, C.sub.1-8 alkylthio, C.sub.1-8 alkyl, C.sub.1-8
alkoxy, C.sub.2-8 alkenyl, C.sub.2-8 alkenyloxy group, C.sub.3-8
cycloalkyl, C.sub.3-8 cycloalkoxy, C.sub.6-10 aryl, C.sub.6-10
aryloxy, C.sub.7-12 arylalkyl, C.sub.7-12 arylalkoxy, C.sub.7-12
alkylaryl, or C.sub.7-12 alkylaryloxy, wherein each n is
independently 0, 1, 2, 3, or 4. For example, M is bromo or chloro,
an alkyl group such as methyl, ethyl, or propyl, an alkoxy group
such as methoxy, ethoxy, or propoxy, or an aryl group such as
phenyl, chlorophenyl, or tolyl; R.sup.3 is a dimethylene,
trimethylene or tetramethylene group; and R is a C.sub.1-8 alkyl,
haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as
phenyl, chlorophenyl or tolyl. In another embodiment, R is methyl,
or a combination of methyl and trifluoropropyl, or a combination of
methyl and phenyl. In still another embodiment, M is methoxy, n is
0 or 1, R.sup.3 is a divalent C.sub.1-3 aliphatic group, and R is
methyl.
[0049] In a specific embodiment, the polysiloxane units are of
formula (11b-2)
##STR00017##
where E has an average value as described above, specifically 5 to
80. In another specific embodiment, the polysiloxane units are of
formula (11b-3)
##STR00018##
where E has an average value as defined above, specifically an
average value of 5 to 80.
[0050] The relative amount of carbonate units (1) and polysiloxane
units (11) in the poly(carbonate-siloxane) copolymers depends on
the desired properties of the thermoplastic compositions, such as
transparency, impact resistance, smoke density, heat release, and
melt viscosity. In particular the polycarbonate copolymer is
selected to have an average value of E that provides good impact
and/or transparency properties, as well as to provide the desired
weight percent of siloxane units in the thermoplastic composition.
For example, the polycarbonate copolymers can comprise siloxane
units in an amount of 0.3 to 30 weight percent (wt %), specifically
0.5 to 25 wt %, or 0.5 to 15 wt %, based on the total weight of the
polymers in the thermoplastic composition, with the proviso that
the siloxane units are provided by polysiloxane units covalently
bonded in the polymer backbone of the polycarbonate copolymer.
[0051] A specific poly(carbonate-siloxane) comprises first
carbonate units (1) derived from bisphenol-A, and second repeating
siloxane units (11b-2), (11b-3), or a combination thereof. This
polycarbonate copolymer can comprise the siloxane units in an
amount of 0.1 to 25 weight percent (wt %), 0.2 to 10 wt %, 0.2 to 6
wt % 0.2 to 5 wt %, or 0.25 to 2 wt %, based on the total weight of
the polycarbonate copolymer, with the proviso that the siloxane
units are covalently bound to the polymer backbone of the
polycarbonate copolymer. For example, the siloxane units are
present in an amount effective to provide 0.3 wt % to 10 wt %, 0.3
wt % to 8.0 wt %, 0.3 wt % to 7.5 wt %, 0.5 wt % to 7.5 wt %, 1.0
wt % to 6.0 wt % siloxane based on the weight of the composition.
In an embodiment, the remaining units are bisphenol units (1).
[0052] Methods for the manufacture of the PC-siloxane copolymers
are known. The poly(carbonate-siloxane) copolymers can have an
intrinsic viscosity, as determined in chloroform at 25.degree. C.,
of 0.3 to 1.5 deciliters per gram (dl/g), specifically 0.45 to 1.0
dl/g. The poly(carbonate-siloxane) can have an M.sub.W of 10,000 to
100,000 g/mol, as determined by gel permeation chromatography (GPC)
using a cross linked styrene-divinyl benzene column, at a sample
concentration of 1 milligram per milliliter, and as calibrated with
polycarbonate standards.
[0053] Poly(siloxane) copolymers suitable for use can have an MVR,
measured at 300.degree. C. under a load of 1.2 kg according to ASTM
D1238-04, of 0.5 to 80 cc/10 min. Also, the poly(siloxane)
copolymers can have an intrinsic viscosity, as determined in
chloroform at 25.degree. C., of 0.3 to 1.5 dl/g, specifically 0.45
to 1.0 dl/g.
[0054] The low smoke density and low heat release thermoplastic
compositions comprise the above-described polycarbonate copolymers
and poly(carbonate-siloxane) copolymers in combination with an
organophosphorus flame retardant in an amount effective to provide
0.1 to 1.0 wt % phosphorus, based on the weight of the composition.
Such compounds include aromatic organophosphorus compounds having
at least one organic aromatic group and at least one
phosphorus-containing group, as well as organic compounds having at
least one phosphorus-nitrogen bond.
[0055] In the aromatic organophosphorus compounds that have at
least one organic aromatic group, the aromatic group can be a
substituted or unsubstituted C.sub.3-30 group containing one or
more of a monocyclic or polycyclic aromatic moiety (which can
optionally contain with up to three heteroatoms (N, O, P, S, or
Si)) and optionally further containing one or more nonaromatic
moieties, for example alkyl, alkenyl, alkynyl, or cycloalkyl. The
aromatic moiety of the aromatic group can be directly bonded to the
phosphorus-containing group, or bonded via another moiety, for
example an alkylene group. In an embodiment the aromatic group is
the same as an aromatic group of the polycarbonate backbone, such
as a bisphenol group (e.g., bisphenol-A), a monoarylene group
(e.g., a 1,3-phenylene or a 1,4-phenylene), or a combination
comprising at least one of the foregoing.
[0056] The phosphorus-containing group can be a phosphate
(P(.dbd.O)(OR).sub.3), phosphite (P(OR).sub.3), phosphonate
(RP(.dbd.O)(OR).sub.2), phosphinate (R.sub.2P(.dbd.O)(OR)),
phosphine oxide (R.sub.3P(.dbd.O)), or phosphine (R.sub.3P),
wherein each R in the foregoing phosphorus-containing groups can be
the same or different, provided that at least one R is an aromatic
group. A combination of different phosphorus-containing groups can
be used. The aromatic group can be directly or indirectly bonded to
the phosphorus, or to an oxygen of the phosphorus-containing group
(i.e., an ester).
[0057] In an embodiment the aromatic organophosphorus compound is a
monomeric phosphate. Representative monomeric aromatic phosphates
are of the formula (GO).sub.3P.dbd.O, wherein each G is
independently an alkyl, cycloalkyl, aryl, alkylarylene, or
arylalkylene group having up to 30 carbon atoms, provided that at
least one G is an aromatic group. Two of the G groups can be joined
together to provide a cyclic group. In some embodiments G
corresponds to a monomer used to form the polycarbonate, e.g.,
resorcinol. Exemplary phosphates include phenyl bis(dodecyl)
phosphate, phenyl bis(neopentyl) phosphate, phenyl
bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate,
2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl
phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate,
tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl
phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl
bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl
phosphate, and the like. A specific aromatic phosphate is one in
which each G is aromatic, for example, triphenyl phosphate,
tricresyl phosphate, isopropylated triphenyl phosphate, and the
like.
[0058] Di- or polyfunctional aromatic phosphorus-containing
compounds are also useful, for example, compounds of the formula
(12)
##STR00019##
[0059] wherein each G.sup.2 is independently a hydrocarbon or
hydrocarbonoxy having 1 to 30 carbon atoms. In some embodiments G
corresponds to a monomer used to form the polycarbonate, e.g.,
resorcinol.
[0060] Specific aromatic organophosphorus compounds have two or
more phosphorus-containing groups, and are inclusive of acid esters
of formula (13)
##STR00020##
wherein R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are each
independently C.sub.1-8 alkyl, C.sub.5-6 cycloalkyl, C.sub.6-20
aryl, or C.sub.7-12 arylalkylene, each optionally substituted by
C.sub.1-12 alkyl, specifically by C.sub.1-4 alkyl and X is a mono-
or poly-nuclear aromatic C.sub.6-30 moiety or a linear or branched
C.sub.2-30 aliphatic radical, which can be OH-substituted and can
contain up to 8 ether bonds, provided that at least one of
R.sup.16, R.sup.17, R.sup.18, R.sup.19, and X is an aromatic group.
In some embodiments R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are
each independently C.sub.1-4 alkyl, naphthyl,
phenyl(C.sub.1-4)alkylene, or aryl groups optionally substituted by
C.sub.1-4 alkyl. Specific aryl moieties are cresyl, phenyl,
xylenyl, propylphenyl, or butylphenyl. In some embodiments X in
formula (13) is a mono- or poly-nuclear aromatic C.sub.6-30 moiety
derived from a diphenol. Further in formula (13), n is each
independently 0 or 1; in some embodiments n is equal to 1. Also in
formula (13), q is from 0.5 to 30, from 0.8 to 15, from 1 to 5, or
from 1 to 2. Specifically, X can be represented by the following
divalent groups (14), or a combination comprising one or more of
these divalent groups,
##STR00021##
wherein the monophenylene and bisphenol-A groups can be
specifically mentioned.
[0061] In these embodiments, each of R.sup.16, R.sup.17, R.sup.18,
and R.sup.19 can be aromatic, i.e., phenyl, n is 1, and p is 1-5,
specifically 1-2. In some embodiments at least one of R.sup.16,
R.sup.17, R.sup.18, R.sup.19, and X corresponds to a monomer used
to form the polycarbonate, e.g., bisphenol-A or resorcinol. In
another embodiment, X is derived especially from resorcinol,
hydroquinone, bisphenol-A, or diphenylphenol, and R.sup.16,
R.sup.17, R.sup.18, and R.sup.19, is aromatic, specifically phenyl.
A specific aromatic organophosphorus compound of this type is
resorcinol bis(diphenyl phosphate), also known as RDP. Another
specific class of aromatic organophosphorus compounds having two or
more phosphorus-containing groups are compounds of formula (15)
##STR00022##
wherein R.sup.16, R.sup.17, R.sup.18, R.sup.19, n, and q are as
defined for formula (13) and wherein Z is C.sub.1-7 alkylidene,
C.sub.1-7 alkylene, C.sub.5-12 cycloalkylidene, --O--, --S--,
--SO.sub.2--, or --CO--, specifically isopropylidene. A specific
aromatic organophosphorus compound of this type is bisphenol-A
bis(diphenyl phosphate), also known as BPADP, wherein R.sup.16,
R.sup.17, R.sup.18, and R.sup.19 are each phenyl, each n is 1, and
q is from 1 to 5, from 1 to 2, or 1.
[0062] Organophosphorus compounds containing at least one
phosphorus-nitrogen bond includes phosphazenes, phosphorus ester
amides, phosphoric acid amides, phosphonic acid amides, phosphinic
acid amides, and tris(aziridinyl) phosphine oxide. Phosphazenes
(16) and cyclic phosphazenes (17)
##STR00023##
in particular can used, wherein w1 is 3 to 10,000 and w2 is 3 to
25, specifically 3 to 7, and each R.sup.w is independently a
C.sub.1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or
polyoxyalkylene group. In the foregoing groups at least one
hydrogen atom of these groups can be substituted with a group
having an N, S, O, or F atom, or an amino group. For example, each
R.sup.w can be a substituted or unsubstituted phenoxy, an amino, or
a polyoxyalkylene group. Any given R.sup.w can further be a
crosslink to another phosphazene group. Exemplary crosslinks
include bisphenol groups, for example bisphenol-A groups. Examples
include phenoxy cyclotriphosphazene, octaphenoxy
cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the
like. A combination of different phosphazenes can be used. A number
of phosphazenes and their synthesis are described in H. R. Allcook,
"Phosphorus-Nitrogen Compounds" Academic Press (1972), and J. E.
Mark et al., "Inorganic Polymers" Prentice-Hall International, Inc.
(1992).
[0063] Accordingly, depending on the particular organophosphorus
compound used, the thermoplastic compositions can comprise from 0.3
to 8.5 wt %, or 0.5 to 8.0 wt %, or 3.5 to 7.5 wt % of the
organophosphorus flame retardant, each based on the total weight of
the composition. Specifically, the organophosphorus compounds can
be bisphenol-A bis(diphenyl phosphate), triphenyl phosphate,
resorcinol bis(diphenyl phosphate), tricresyl phosphate, or a
combination comprising at least one of the foregoing.
[0064] The thermoplastic compositions can include various additives
ordinarily incorporated into flame retardant compositions having
low smoke density and low heat release, with the proviso that the
additive(s) are selected so as to not adversely affect the desired
properties of the thermoplastic composition significantly, in
particular low smoke density and low heat release. Such additives
can be mixed at a suitable time during the mixing of the components
for forming the composition. Exemplary additives include fillers,
reinforcing agents, antioxidants, heat stabilizers, light
stabilizers, ultraviolet (UV) light stabilizers, plasticizers,
lubricants, mold release agents, antistatic agents, colorants such
as such as titanium dioxide, carbon black, and organic dyes,
surface effect additives, radiation stabilizers, additional flame
retardants, and anti-drip agents. A combination of additives can be
used. In general, the additives are used in the amounts generally
known to be effective. The total amount of additives (other than
any filler or reinforcing agents) is generally 0.01 to 25 parts per
parts per hundred parts by weight of the polymers (PHR).
[0065] The use of pigments such as titanium dioxide produces white
compositions, which are commercially desirable. Pigments such as
titanium dioxide (or other mineral fillers) can be present in the
thermoplastic compositions in amounts of 0 to 12 PHR, 0.1 to 9 PHR,
0.5 to 5 PHR, or 0.5 to 3 PHR.
[0066] Exemplary antioxidant additives include organophosphites
such as tris(nonyl phenyl)phosphite,
tris(2,4-di-t-butylphenyl)phosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl
pentaerythritol diphosphite; alkylated monophenols or polyphenols;
alkylated reaction products of polyphenols with dienes, such as
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane;
butylated reaction products of para-cresol or dicyclopentadiene;
alkylated hydroquinones; hydroxylated thiodiphenyl ethers;
alkylidene-bisphenols; benzyl compounds; esters of
beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with
monohydric or polyhydric alcohols; esters of
beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with
monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl
compounds such as distearylthiopropionate, dilaurylthiopropionate,
ditridecylthiodipropionate,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;
amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid,
or combinations comprising at least one of the foregoing
antioxidants. Antioxidants are used in amounts of 0.01 to 0.1
PHR.
[0067] Exemplary heat stabilizer additives include organophosphites
such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite,
and tris-(mixed mono- and di-nonylphenyl)phosphite; phosphonates
such as dimethylbenzene phosphonate, phosphates such as trimethyl
phosphate; or combinations comprising at least one of the foregoing
heat stabilizers. Heat stabilizers are used in amounts of 0.01 to
0.1 PHR.
[0068] Light stabilizers and/or ultraviolet light (UV) absorbing
additives can also be used. Exemplary light stabilizer additives
include benzotriazoles such as
2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and
2-hydroxy-4-n-octoxy benzophenone, or combinations comprising at
least one of the foregoing light stabilizers. Light stabilizers are
used in amounts of 0.01 to 5 PHR.
[0069] Exemplary UV absorbing additives include
hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines;
cyanoacrylates; oxanilides; benzoxazinones;
2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol
(CYASORB.RTM. 5411); 2-hydroxy-4-n-octyloxybenzophenone
(CYASORB.RTM. 531);
2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phe-
nol (CYASORB.RTM. 1164);
2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (CYASORB.RTM.
UV-3638);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-
acryloyl)oxy]methyl]propane (UVINUL.RTM. 3030);
2,2'-(1,4-phenylene) bis(4H-3,1-benzoxazin-4-one);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-
acryloyl)oxy]methyl]propane; nano-size inorganic materials such as
titanium oxide, cerium oxide, and zinc oxide, all with particle
size less than or equal to 100 nanometers; or combinations
comprising at least one of the foregoing UV absorbers. UV absorbers
are used in amounts of 0.01 to 5 PHR.
[0070] Plasticizers, lubricants, and/or mold release agents can
also be used. There is considerable overlap among these types of
materials, which include phthalic acid esters such as
dioctyl-4,5-epoxy-hexahydrophthalate;
tris-(octoxycarbonylethyl)isocyanurate; tristearin;
poly-alpha-olefins; epoxidized soybean oil; silicones, including
silicone oils; esters, for example, fatty acid esters such as alkyl
stearyl esters, e.g., methyl stearate, stearyl stearate,
pentaerythritol tetrastearate, and the like; combinations of methyl
stearate and hydrophilic and hydrophobic nonionic surfactants
comprising polyethylene glycol polymers, polypropylene glycol
polymers, poly(ethylene glycol-co-propylene glycol) copolymers, or
a combination comprising at least one of the foregoing glycol
polymers, e.g., methyl stearate and polyethylene-polypropylene
glycol copolymer in a solvent; waxes such as beeswax, montan wax,
and paraffin wax. Such materials are used in amounts of 0.1 to 1
PHR.
[0071] Flame retardant salts are not needed in order to obtain the
desired low smoke and heat release characteristics. Flame retardant
salts include, for example, salts of C.sub.1-16 alkyl sulfonate
salts such as potassium perfluorobutane sulfonate (Rimar salt),
potassium perfluorooctane sulfonate (KSS), tetraethylammonium
perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate;
salts such as Na.sub.2CO.sub.3, K.sub.2CO.sub.3, MgCO.sub.3,
CaCO.sub.3, and BaCO.sub.3, inorganic phosphate salts, and
fluoro-anion complexes such as Li.sub.3AlF.sub.6, BaSiF.sub.6,
KBF.sub.4, K.sub.3AlF.sub.6, KAlF.sub.4, K.sub.2SiF.sub.6, and/or
Na.sub.3AlF.sub.6. In an embodiment, no or substantially no flame
retardant inorganic salts are present in the thermoplastic
compositions.
[0072] Organic flame retardants can be present, but halogenated
flame retardants are generally avoided, such that the thermoplastic
composition can be essentially free of chlorine and bromine.
"Essentially free of chlorine and bromine" as used herein means
having a bromine and/or chlorine content of less than or equal to
100 parts per million by weight (ppm), less than or equal to 75
ppm, or less than or equal to 50 ppm, based on the total parts by
weight of the composition, excluding any filler.
[0073] Anti-drip agents in most embodiments are not used in the
thermoplastic compositions. Anti-drip agents include a
fibril-forming or non-fibril forming fluoropolymer such as
polytetrafluoroethylene (PTFE). The anti-drip agent can be
encapsulated by a rigid copolymer, for example
styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is
known as TSAN. Antidrip agents are substantially absent or
completely absent from the thermoplastic compositions in some
embodiments.
[0074] In addition to the polycarbonates described above,
combinations of the polycarbonate with other thermoplastic
polymers, for example combinations of the polycarbonate copolymers
with homopolycarbonates, other polycarbonate copolymers, or
polyesters, can be used. Useful polyesters can include, for
example, poly(alkylene dicarboxylates), liquid crystalline
polyesters, and polyester copolymers. The polyesters are generally
completely miscible with the polycarbonates when combined. When
used, other thermoplastic polymers are present in amounts of less
than 20 wt %, less than 10 wt %, or less than 5 wt % of the
compositions. In an embodiment, the thermoplastic compositions
contain no polymers other than the polycarbonate copolymers
described above.
[0075] Methods for forming the thermoplastic compositions can vary.
In an embodiment, the polymers are combined with any additives
(e.g., a mold release agent) such as in a screw-type extruder. The
polymers and any additives can be combined in any order, and in any
form, for example, powder, granular, filamentous, as a masterbatch,
and the like. Transparent compositions can be produced by
manipulation of the process used to manufacture the thermoplastic
composition. One example of such a process to produce transparent
thermoplastic compositions is described in U.S. Pat. No. 7,767,738.
The thermoplastic compositions can be foamed, extruded into a
sheet, or optionally pelletized. Methods of foaming a thermoplastic
composition using frothing or physical or chemical blowing agents
are known and can be used. The pellets can be used for molding into
articles, foaming, or they can be used in forming a sheet of the
flame retardant thermoplastic composition. In some embodiments, the
composition can be extruded (or co-extruded with a coating or other
layer) in the form of a sheet and/or can be processed through
calendaring rolls to form the desired sheet.
[0076] As discussed above, the thermoplastic compositions are
formulated to meet strict smoke density and heat release
requirements. The relative amounts of the polycarbonate copolymer,
in combination with the organophosphorus compound in the
thermoplastic compositions depends on the particular copolymer and
organophosphorus compound used, the heat release and smoke density,
and other desired properties of the thermoplastic composition, such
as impact strength, transparency and melt flow. In an embodiment,
the organophosphorus compound is present in an amount from 0.5 to 8
wt %, based on the total weight of the thermoplastic composition,
and the polycarbonate copolymer is present in an amount of 60 to
99.5 wt %, 65 to 99.5 wt %, 70 to 99.5 wt %, 75 to 99.5 wt %, 80 to
99.5 wt %, 85 to 99.5 wt %, or 90 to 99.5 wt %; and within these
ranges, the specific amount of each with any other additives is
selected to be effective to provide, in an article made from the
compositions, a Ds-4 smoke density of 600 or less determined in
accordance with ISO 5659-2 on a 3 mm thick plaque, and a maximum
average rate of heat emission (MAHRE) of 160 kW/m.sup.2 or less, as
determined according to ISO 5660-1 on a 3 mm thick plaque. In an
embodiment the polycarbonate copolymer is PPPBP-BPA, comprising
first bisphenol-A carbonate repeating units and second
PPPBP-derived repeating units, or a
poly(carbonate-siloxane)copolymer comprising bisphenol-A carbonate
units and siloxane units of formula (9) above. The compositions
further comprise an aromatic organophosphorus compound, e.g., RDP,
BPADP, or a combination comprising at least one of the foregoing
aromatic organophosphorus compounds. The same or similar values can
be obtained in articles having a wide range of thicknesses, for
example from 0.1 to 10 mm, but particularly at 0.5 to 5 mm.
[0077] In addition, the thermoplastic compositions can further have
good melt viscosities, which aid processing. The thermoplastic
compositions can have a melt volume flow rate (MVR, cc/10 min,
according to ISO 1133 of 4 to 30, greater than or equal to 10,
greater than or equal to 12, greater than or equal to 15, greater
than or equal to 16, greater than or equal to 17, greater than or
equal to 18, greater than or equal to 19, or greater than or equal
to 20 cc/min, measured at 300.degree. C./1.2 Kg at 360 second dwell
according to ISO 1133. The same or similar values can be obtained
in articles having a wide range of thicknesses, for example from
0.1 to 10 mm, or 0.5 to 5 mm. The same or similar values can be
obtained in articles having a wide range of thicknesses, for
example from 0.1 to 10 mm, but particularly at 0.5 to 5 mm.
[0078] The thermoplastic compositions can be formulated to have
lower densities, in particular a density of 1.35 g/cc or less, 1.34
g/cc or less, 1.33 g/cc or less, 1.32 g/cc or less, 1.31 g/cc or
less, 1.30 g/cc or less, or 1.29 g/cc or less.
[0079] The thermoplastic compositions can further have excellent
impact properties, in particular multiaxial impact (MAI) and
ductility. The compositions can have an MAI of 100 J or higher,
determined at 23.degree. C., 4.4 m/second in accordance with ISO
6603 on discs with a thickness of 3.2 mm. The compositions can have
a ductility at 23.degree. C. equal to or higher than 80%. The same
or similar values can be obtained in articles having a wide range
of thicknesses, for example from 0.1 to 10 mm, but particularly at
0.5 to 5 mm.
[0080] The thermoplastic compositions can further be formulated to
have a haze less than 3% and a transmission greater than 85%, each
determined according to the color space CIE1931 (Illuminant C and a
2.degree. observer) or according to ASTM D 1003 (2007) using
illuminant C at a 0.062 inch (1.5 mm) thickness. In some
embodiments, the thermoplastic compositions can be formulated such
that an article molded from the composition has all three of a haze
less of than 15% and a transmission of greater than 75%, each
determined according to the color space CIE1931 (Illuminant C and a
2.degree. observer) or according to ASTM D 1003 (2007) using
illuminant C at a 0.125 inch (3.2 mm) thickness, and an MAI equal
to or higher than 100 J, determined at 23.degree. C. at an impact
speed of 4.4 m/second in accordance with ISO 6603 on discs with a
thickness of 3.2 mm.
[0081] Shaped, foamed, or molded articles comprising the
thermoplastic compositions are also provided. The thermoplastic
compositions can be molded into useful shaped articles by a variety
of means such as injection molding, extrusion, rotational molding,
blow molding, and thermoforming to form articles. Thus the
thermoplastic compositions can be used to form a foamed article, a
molded article, a thermoformed article, an extruded film, an
extruded sheet, a layer of a multi-layer article, e.g., a
cap-layer, a substrate for a coated article, or a substrate for a
metallized article. These values can be obtained in articles having
a wide range of thicknesses, for example from 0.1 to 10 mm, or 0.5
to 5 mm.
[0082] Illustrative articles include external panels, external
transparent cover panels, external equipment housing, and other
articles that are not in immediate contact with occupants of the
structure where the article is used. Also, access panels, access
doors, air flow regulators air gaspers, air grilles, arm rests,
baggage storage doors, balcony components, cabinet walls, ceiling
panels, door pulls, door handles, duct housing, enclosures for
electronic devices, equipment housings, equipment panels, floor
panels, food carts, food trays, galley surfaces, grilles, handles,
housings for TVs and displays, light panels, magazine racks,
telephone housings, partitions, parts for trolley carts, seat
backs, seat components, railing components, seat housings, shelves,
side walls, speaker housings, storage compartments, storage
housings, toilet seats, tray tables, trays, trim panel, window
moldings, window slides, windows, and the like.
[0083] The thermoplastic compositions provided herein can be
formulated to provide articles that meet certain criteria set forth
in European Railway standard EN-45545 (2013). The European Union
has approved the introduction of a set of fire testing standards
for the railroad industry that prescribe certain flammability,
flame spread rate, heat release, smoke emission, and smoke toxicity
requirements for materials used in railway vehicles, known as
European Railway standard EN-45545 (2013). Based on the vehicle
type, material, end-use, and fire risks, 26 different "Requirement"
categories for qualifying materials have been established
(R1-R26).
[0084] Passenger seat shells (both back and base shell) fall under
the R6 application type. Lighting strips fall under the R3
application type. The R1 application type covers, amongst others,
interior vertical and horizontal surfaces, such as side walls,
front/end walls, doors, ceiling panels, as well as luggage racks,
linings and frames.
[0085] "Hazard Levels" (HL1 to HL3) have been designated,
reflecting the degree of probability of personal injury as the
result of a fire. The levels are based on dwell time and are
related to operation and design categories. HL 1 is the lowest
hazard level and is typically applicable to vehicles that run under
relatively safe conditions (above-ground, easy evacuation of the
vehicle). HL3 is the highest hazard level and represents most
dangerous operation/design categories (difficult and/or
time-consuming evacuation of the vehicle, e.g. in underground rail
cars). For each application type, different test requirements for
the hazard levels are defined. The testing methods, and smoke
density and maximum heat release rate values for the various hazard
levels in the European Railway standard EN-45545 (2013) are shown
in Table 1B for applications qualifying under R6.
TABLE-US-00001 TABLE 1B European Railways Standard EN-45545 for R6
applications Smoke Density, DS-4 Heat release, MAHRE (kW/m.sup.2)
Hazard Level ISO 5659-2 ISO 5660-1 HL-1 .ltoreq.600 -- HL-2
.ltoreq.300 .ltoreq.90 HL-3 .ltoreq.150 .ltoreq.60
[0086] Data in the Examples shows that the compositions herein can
be made to meet the requirements for HL-1.
[0087] Thus, while thermoplastic compositions can be used for the
manufacture of a wide variety of articles, including high occupancy
structures such as rail stations, airports and office buildings,
the thermoplastic compositions are especially useful for the
manufacture of transportation components.
[0088] As used herein, a "transportation component" is an article
or portion of an article used in rolling stock, an aircraft, a
roadway vehicle, or a marine vehicle. "Rolling stock" includes but
is not limited to a locomotive, coach, light rail vehicle,
underground rail vehicle, tram, trolley, magnetic levitation
vehicle, and a cable car. An "aircraft" includes but is not limited
to a jet, an airplane, an airship, a helicopter, a balloon, and a
spacecraft. A "roadway vehicle" includes but is not limited to an
automobile, bus, scooter and a motorcycle. A "marine vehicle"
includes but is not limited to a boat, a ship (including freight
and passenger ships), jet skis, and a submarine.
[0089] Exemplary transportation components for rolling stock (e.g.,
trains), aircraft, and roadway and marine vehicles, particularly
rolling stock, includes interior components (e.g., structure and
coverings) such as ceiling paneling, flaps, boxes, hoods, louvers,
insulation material and the body shell in interiors, side walls,
front walls/end walls, partitions, room dividers, interior doors,
interior lining of the front-/end-wall doors and external doors,
luggage overhead luggage racks, vertical luggage rack, luggage
container, luggage compartments, windows, window frames, kitchen
interiors, surfaces or a component assembly comprising at least one
of the foregoing. In an embodiment any of the foregoing articles
are in compliance with R6 of European Rail Standard EN-45545
(2013), for example meeting HL-1.
[0090] The thermoplastic compositions are particularly useful in
train and aircraft, for example a variety of aircraft compartment
interior applications, as well as interior applications for other
modes of transportation, such as bus, train, subway, marine, and
the like. In a specific embodiment the articles are interior
components for aircraft or trains, including access panels, access
doors, air flow regulators baggage storage doors, display panels,
display units, door handles, door pulls, enclosures for electronic
devices, food carts, food trays, grilles, handles, magazine racks,
seat components, partitions, refrigerator doors, seat backs, side
walls, tray tables, trim panels, and the like. The poly(siloxane)
copolymer compositions can be formed (e.g., molded) into sheets
that can be used for any of the above mentioned components. It is
generally noted that the overall size, shape, thickness, optical
properties, and the like of the polycarbonate sheet can vary
depending upon the desired application. In an embodiment any of the
foregoing articles are in compliance with R6 of European Rail
Standard EN-45545 (2013), for example meeting HL-1.
[0091] In an embodiment, provided herein is a thermoplastic
composition comprising, based on the total weight of the
composition, 90 to 98 wt % of a combination of a
(N-phenylphenolphthaleinylbisphenol, 2,2-bis(4-hydro)-bisphenol-A
copolymer; and 2 to 10 wt %, or 0.3 to 8.5 wt % of an
organophosphorus flame retardant effective to provide 0.1 to 1.0 wt
% phosphorus based on the total weight of the composition,
specifically BPADP or RDP; and optionally up to 5 wt % of an
additive selected from a processing aid, a heat stabilizer, an
ultra violet light absorber, a colorant, or a combination
comprising at least one of the foregoing, wherein the component has
a smoke density value of equal to or less than 600 determined
according to ISO 5659-2 on a 3 mm thick plaque, and a material heat
release of less than 160 kW/m.sup.2 determined according to ISO
5660-1, on a 3 mm thick plaque, and optionally, a 3.3-millimeter
sample molded from the composition has a multiaxial impact of
greater than 110 measured at 23.degree. C., 4.4 m/sec in accordance
with ISO 6603. The same or similar values can be obtained in
components having a wide range of thicknesses, for example from 0.1
to 10 mm, or 0.5 to 5 mm. These thermoplastic compositions are
especially useful in the manufacture of a transportation component,
in particular a train component.
[0092] In another embodiment a thermoplastic composition comprises,
based on the total weight of the composition-based on the total
weight of the composition, 2 to 10 wt %, or 0.3 to 8.5 wt % of an
organophosphorus compound effective to provide 0.1 to 1.0 wt %
phosphorus based on the total weight of the composition,
specifically BPADP or RDP; 90 to 98 wt % of a
poly(carbonate-siloxane) copolymer; and optionally up to 5 wt % of
an additive selected from a processing aid, a heat stabilizer, an
ultra violet light absorber, a colorant, or a combination
comprising at least one of the foregoing, wherein the component has
a smoke density value of equal to or less than 600 determined
according to ISO 5659-2 on a 3 mm thick plaque, and a material heat
release of less than 160 kW/m.sup.2 determined according to ISO
5660-1 on a 3 mm thick plaque. The same or similar values can be
obtained in components having a wide range of thicknesses, for
example from 0.1 to 10 mm, or 0.5 to 5 mm. These thermoplastic
compositions are especially useful in the manufacture of a
transportation component, in particular a train component.
[0093] The thermoplastic compositions having low heat release rates
determined according to ISO 5660-1 and low smoke densities
determined according to ISO 5659-2 are further illustrated by the
following non-limiting examples.
EXAMPLES
[0094] Materials for the following examples are listed in Table 2.
Amounts of each component in the Examples are in wt % unless
otherwise indicated.
TABLE-US-00002 TABLE 2 Component Trade name; chemical description
Source PPPBP- N-phenylphenolphthaleinylbisphenol, SABIC BPA
2,2-bis(4-hydro))-bisphenol-A copolymer, INNOVATIVE 32 mol % PPPBP,
Mw = 23,000 to PLASTICS 27,000 g/mol (determined via GPC using
polycarbonate standards), manufactured by interfacial
polymerization BPA-PC Bisphenol-A polycarbonate, manufactured SABIC
by interfacial polymerization, Mw = INNOVATIVE 28,000 to 32,000
g/mol (determined via PLASTICS GPC using polycarbonate standards)
PC- PDMS (polydimethylsiloxane) - bisphe- SABIC Siloxane nol-A
copolymer, 6 mol wt % siloxane INNOVATIVE having an average block
length of 40-50 PLASTICS units, Mw 21,000 t- 25,0000 g/mol
(determined via GPC using polycarbonate standards), manufactured by
interfacial polymerization BPADP CR-741; Bisphenol-A diphosphate
Nagase (Europa) GmbH RDP FyrfolEX; Tetraphenyl resorcinol ICL- IP
diphosphate Europe BC52 Phenoxy-terminated carbonate oligomer
Various of tetrabromobisphenol-A Boron Boron orthophosphate
Budenheim phosphate Poly- Songflame TP100; Phenol/Bi-phenol Songwon
phosphate polyphosphate Industrial Co. AO IRGAPHOS 168;
Tris(2,4-di-tert- Ciba butylphenyl) phosphite
[0095] The tests performed are summarized in Table 3.
TABLE-US-00003 TABLE 3 Description Test Specimen Property Units
Smoke density ISO plaque 75 .times. Ds-4 [--] 5659-2 75 .times. 3
mm Heat release ISO plaque 100 .times. MAHRE kW/m.sup.2 5660-1 100
.times. 3 mm
[0096] ISO smoke density measurements were performed on
7.5.times.7.5 cm plaques with 3 mm thickness using an NBS Smoke
Density Chamber from Fire Testing Technology Ltd (West Sussex,
United Kingdom). All measurements were performed according to ISO
5659-2, with an irradiance of 50 kW/m.sup.2 at the sample position
and a sample-to-cone distance of 5 cm in view of the charring
behavior of the samples (as prescribed by ISO 5659-2). Ds-4 was
determined as the measured smoke density after 240 seconds.
[0097] ISO heat release measurements were performed on 10.times.10
cm plaques with 3 mm thickness using a Cone Calorimeter. All
measurements were performed according to ISO 5660-1, with an
irradiation of 50 kW/m.sup.2 at the sample position and a
sample-to-cone distance of 6 cm in view of the charring behavior of
the samples (in accordance with ISO 5660-1). Heat release is
measured as MAHRE in kW/m.sup.2.
[0098] The smoke density and heat release tests executed are
indicative tests. They were performed according to their respective
ISO standards, but were not executed by an officially certified
test institute.
Extrusion and Molding Conditions.
[0099] The compositions were made as follows. All solid additives
(stabilizers, colorants, solid flame retardants) were dry blended
off-line as concentrates using one of the primary polymer powders
as a carrier and starve-fed via gravimetric feeder(s) into the feed
throat of the extruder. The remaining polymer(s) were starve-fed
via gravimetric feeder(s) into the feed throat of the extruder as
well. The liquid flame retardants (e.g., BPADP, RDP) were fed
before the vacuum using a liquid injection system. It will be
recognized by one skilled in the art that the method is not limited
to these temperatures or processing equipment.
[0100] Extrusion of all materials was performed on a 27 mm
Werner-Pfleiderer ZAK twin-screw extruder (L/D ratio of 33:1) with
a vacuum port located near the die face. The extruder has 9 zones,
which were set at temperatures of 40.degree. C. (feed zone),
200.degree. C. (zone 1), 250.degree. C. (zone 2), and 270.degree.
C. (zone 3) and 280-300.degree. C. zone 4 to 8. Screw speed was 300
rpm and throughput was between 15 and 25 kg/hr.
[0101] The compositions were molded after drying at 100-110.degree.
C. for 6 hrs. on a 45-ton Engel molding machine with 22 mm screw or
75-ton Engel molding machine with 30 mm screw operating at a
temperature 270-300.degree. C. with a mold temperature of
70-90.degree. C. It will be recognized by one skilled in the art
that the method is not limited to these temperatures or processing
equipment.
Examples 1-9
[0102] Examples 1-9 demonstrate the effect of adding different
organophosphorus flame retardants (BPADP, RDP, and a
phenol/biphenol polyphosphate) to a polycarbonate copolymer, namely
PPPBP-BPA. Formulations and results are shown in Table 4.
TABLE-US-00004 TABLE 4 Ex1 Ex2 Ex3 Ex4 Ex5 CEx6 CEx7 CEx8 CEx9
Component, wt % PPPBP-BPA 96.17 92.42 96.49 96.17 92.42 99.92 82.34
89.92 98.77 AO 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 PC-Br 0
0 0 0 0 0 17.6 0 0 RDP 0 0 0 3.75 7.5 0 0 0 0 BC52 0 0 0 0 0 0 0 10
0 BPADP 3.75 7.5 0 0 0 0 0 0 0 Boron phosphate 0 0 0 0 0 0 0 0 1.15
TP100 0 0 3.43 0 0 0 0 0 0 P-content 0.33 0.67 0.37 0.82 0 0 0 0
Property Ds-4 ISO 5659-2 571 460 580 424 399 626 1320 732 648 MAHRE
ISO 5660-1 165 171 173 147 139 198 -- -- 195
[0103] The results in Table 4 demonstrate that addition of the
organophosphorus flame retardants to PPPBP-BPA copolymers (Ex1-5)
results in improved smoke density (Ds-4) as measured according to
ISO5659-2 on 3 mm thick plaques, as well as maximum average rate of
heat emission values (MAHRE) as measured according to ISO5660-1 on
3 mm thick plaques compared to the copolymer without an
organophosphorus flame retardant (CEx6).
[0104] The effect of addition of RDP was very similar to BPADP; as
indicated above, the smoke density (Ds-4) is improved compared to
the PPPBP-BPA copolymer without the organophosphorus flame
retardants (BPADP or RDP) (Ex4-5 vs. CEx6). Although the addition
of all of the organophosphorus flame retardants result in improved
smoke density and MAHRE (Ex1-5) compared to the copolymer without
an organophosphorus flame retardant (CEx6), RDP appears to be most
effective. Addition of RDP decreased smoke density (Ds-4) to 424
and MAHRE to 147 kW/m.sup.2 (Ex4) while providing 0.37% phosphorus
content, compared with the smoke density of 460 (Ds-4) as measured
according to ISO5659-1 and MAHRE of 171 kW/m.sup.2 for BPADP
providing 0.67% phosphorus (Ex2).
[0105] Conversely, the addition of brominated polycarbonate (CEx7)
resulted in deterioration of Ds-4 smoke density, yielding the
maximum Ds-4 value of 1320 at 3 mm thickness. The same trend is
observed for a brominated oligomer (CEx8), which also gives a
higher smoke density, with Ds-4 values increasing by about 17% from
626 to 732 at 3 mm thickness (CEx5 vs. CEx7).
[0106] Addition of an inorganic phosphorus source (boron phosphate)
had no positive effect on smoke density or heat release (CEx9),
with Ds-4 of 648 and MAHRE of 195 (CEx9) compared to Ds-4 of 626
and MAHRE of 198 for the composition without a phosphorus component
(CEx6), all measured on 3 mm thick plaques.
[0107] These results demonstrate that the effect of adding
compounds having inherent flame retardant characteristics to
polycarbonate copolymers do not automatically result in an
improvement in smoke density and/or MAHRE or that any improvement
would be to the same degree. All organophosphorus additives (RDP,
BPADP, TP100) had positive effects on smoke density (Ds-4) measured
according to ISO 5659-2 and heat release (MAHRE) measured according
to ISO 5660-1, whereas other common flame retardants such as
brominated additives or an inorganic phosphorus additive have
negative effects or no positive effect, respectively.
Examples 10-13
[0108] Examples 10-13 demonstrate the effect of adding an
organophosphorus flame retardants (BPADP) to
poly(carbonate-siloxane) copolymers. Formulations and results are
shown in Table 5.
TABLE-US-00005 TABLE 5 Ex10 CEx11 CEx12 CEx13 Component, wt % PC 0
0 92.5 100 PC-Si 92.5 100 0 0 BPADP 7.5 0 7.5 0 P-content 0.67 0
0.67 0 Property Ds-4 610 935 1320 1320 MAHRE 153 220 211 236
[0109] The results in Table 5, demonstrate that addition of BPADP
to PC--Si greatly improves the smoke density (Ds-4) measured
according to ISO 5659-2 and heat release (MAHRE) measured according
to ISO 5660-1 of the copolymer. Addition of 7.5 wt % of an
organophosphorus compound (BPADP, Ex10) to PC--Si resulted in a
reduction in the observed Ds-4 smoke density, measured according to
ISO 5659-2 on a 3 mm thick plaque, reducing the value from 935
(CEx11) to 610. The addition of BPADP effectively transforms PC--Si
from a material that would not otherwise meet the European Railway
standard EN-45545 for HL-1 (Ds-4.ltoreq.600) to a material that can
meet these requirements upon optimization of the composition (Ds-4
value of 610 for Ex10 at 3 mm thickness).
[0110] The same effect is not observed when an aromatic
organophosphorus compound is added to a polycarbonate bisphenol-A
homopolymer (CEx12 and CEx13). These results indicate that the
effect of adding an organophosphorus compound, in particular an
aromatic organophosphorus compound to polycarbonate copolymers on
heat release (MAHRE) and smoke density (Ds-4) does not occur with
all polycarbonates, and instead is polymer/copolymer specific.
[0111] Based on the relatively higher effectiveness observed for in
the case of PPPBP-PC (Ex4 and Ex5) compared to BPADP (Ex1 and Ex2),
the addition of RDP in an amount effective to provide 0.67 wt % of
phosphorus can potentially reduce smoke density (Ds-4) to below
600, measured according to ISO 5659-2 on 3 mm thick plaques.
[0112] The singular forms "a," "an," and "the" include plural
referents unless the context clearly dictates otherwise. "Or" means
"and/or." In general, the embodiments can comprise, consist of, or
consist essentially of, any appropriate components herein
disclosed. The embodiments can additionally, or alternatively, be
formulated so as to be devoid, or substantially free, of any
components, materials, ingredients, adjuvants or species used in
the prior art compositions or that are otherwise not necessary to
the achievement of the function and/or objectives as described
herein. The endpoints of all ranges directed to the same component
or property are inclusive and independently combinable (e.g.,
ranges of "less than or equal to about 25 wt %, or, more
specifically, about 5 wt % to about 20 wt %," is inclusive of the
endpoints and all intermediate values of the ranges of "about 5 wt
% to about 25 wt %," etc.).
[0113] Unless defined otherwise, technical and scientific terms
used herein have the same meaning as is commonly understood by one
of skill in the art to which this invention belongs. Compounds are
described using standard nomenclature. For example, any position
not substituted by any indicated group is understood to have its
valency filled by a bond as indicated, or a hydrogen atom. A dash
("-") that is not between two letters or symbols is used to
indicate a point of attachment for a substituent. For example,
--CHO is attached through carbon of the carbonyl group.
[0114] As used herein, the term "hydrocarbyl" refers broadly to a
substituent comprising carbon and hydrogen, optionally with 1 to 3
heteroatoms, for example, oxygen, nitrogen, halogen, silicon, or
sulfur; "alkyl" means a straight or branched chain monovalent
hydrocarbon group; "alkylene" means a straight or branched chain
divalent hydrocarbon group; "alkylidene" means a straight or
branched chain divalent hydrocarbon group, with both valences on a
single common carbon atom; "alkenyl" means a straight or branched
chain monovalent hydrocarbon group having at least two carbons
joined by a carbon-carbon double bond; "cycloalkyl" means a
non-aromatic monovalent monocyclic or multicyclic hydrocarbon group
having at least three carbon atoms, "cycloalkenyl" means a
non-aromatic cyclic divalent hydrocarbon group having at least
three carbon atoms, with at least one degree of unsaturation;
"aryl" means an aromatic monovalent group containing only carbon in
the aromatic ring or rings; "arylene" means an aromatic divalent
group containing only carbon in the aromatic ring or rings;
"alkylaryl" means an aryl group that has been substituted with an
alkyl group as defined above, with 4-methylphenyl being an
exemplary alkylaryl group; "arylalkyl" means an alkyl group that
has been substituted with an aryl group as defined above, with
benzyl being an exemplary arylalkyl group; "alkoxy" means an alkyl
group as defined above with the indicated number of carbon atoms
attached through an oxygen bridge (--O--); and "aryloxy" means an
aryl group as defined above with the indicated number of carbon
atoms attached through an oxygen bridge (--O--).
[0115] Unless otherwise indicated, the groups herein can be
substituted or unsubstituted. "Substituted" means a groups
substituted with at least one (e.g., 1, 2, or 3) substituents
independently selected from a halide (e.g., F.sup.-, Cl.sup.-,
Br.sup.-, I.sup.-), a C.sub.1-6 alkoxy, a nitro, a cyano, a
carbonyl, a C.sub.1-6 alkoxycarbonyl, a C.sub.1-6 alkyl, a
C.sub.2-6 alkynyl, a C.sub.6-12 aryl, a C.sub.7-13 arylalkyl, a
C.sub.1-6 heteroalkyl, a C.sub.3-6 heteroaryl (i.e., a group that
comprises at least one aromatic ring and the indicated number of
carbon atoms, wherein at least one ring member is S, N, O, P, or a
combination thereof), a C.sub.3-6 heteroaryl(C.sub.3-6)alkyl, a
C.sub.3-8 cycloalkyl, a C.sub.5-8 cycloalkenyl, a C.sub.5-6
heterocycloalkyl (i.e., a group that comprises at least one
aliphatic ring and the indicated number of carbon atoms, wherein at
least one ring member is S, N, O, P, or a combination thereof), or
a combination including at least one of the foregoing, instead of
hydrogen, provided that the substituted atom's normal valence is
not exceeded.
[0116] All cited patents, patent applications, and other references
are incorporated herein by reference in their entirety. However, if
a term in the present application contradicts or conflicts with a
term in the incorporated reference, the term from the present
application takes precedence over the conflicting term from the
incorporated reference.
[0117] While typical embodiments have been set forth for the
purpose of illustration, the foregoing descriptions should not be
deemed to be a limitation on the scope herein. Accordingly, various
modifications, adaptations, and alternatives can occur to one
skilled in the art without departing from the spirit and scope
herein.
* * * * *