US2013224462A1PendingUtilityA1
Thermoplastic compositions having low smoke, methods of their manufacture, and uses thereof
Assignee: SABIC INNOVATIVE PLASTICS IPPriority: Feb 29, 2012Filed: Feb 28, 2013Published: Aug 29, 2013
Est. expiryFeb 29, 2032(~5.6 yrs left)· nominal 20-yr term from priority
Inventors:Mark Adrianus Johannes Van Der MeeRobert Dirk Van De GrampelRoland Sebastian AssinkPaul Dean Sybert
C08G 73/1046B32B 5/00C08G 77/448C08L 83/10C08L 79/08C09K 21/14C08L 79/04C08L 69/00B32B 27/365C08L 2201/02C08L 69/005C08K 5/49
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Claims
Abstract
A low smoke density thermoplastic composition comprising, based on the total weight of the thermoplastic composition, 70 to 95 wt % of a polycarbonate copolymer comprising first repeating units and second repeating units, wherein the first repeating units are not the same as the second repeating units, and wherein the first repeating units are bisphenol carbonate units of the formula wherein R a and R b are each independently C 1-12 alkyl, C 1-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy, p and q are each independently 0 to 4, and X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, a C 1-11 alkylidene of formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen or C 1-10 alkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-10 hydrocarbon group; and the second repeating units comprise bisphenol carbonate units that are not the same as the first repeating bisphenol carbonate units, siloxane units, arylate ester units, or a combination of arylate ester units and siloxane units; and 5 to 30 wt % of a polyetherimide based on the weight of the composition, wherein an article molded from the composition has a smoke density (Ds-4) value of equal to or less than 300 as measured by ISO 5659-2 on a 3 mm thick plaque.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
1 . A thermoplastic composition comprising, based on the total weight of the thermoplastic composition,
70 to 95 wt % of a polycarbonate copolymer comprising first repeating units and second repeating units, wherein the first repeating units are not the same as the second repeating units, and wherein
the first repeating units are bisphenol carbonate units of the formula
wherein
R a and R b are each independently C 1-12 alkyl, C 1-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy,
p and q are each independently 0 to 4, and
X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, a C 1-11 alkylidene of formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen or C 1-10 alkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-10 hydrocarbon group; and
the second repeating units comprise bisphenol carbonate units that are not the same as the first repeating bisphenol carbonate units, siloxane units, arylate ester units, or a combination of arylate ester units and siloxane units; and
to 30 wt % of a polyetherimide based on the weight of the composition, wherein an article molded from the composition has smoke density after 4 minutes (Ds-4) of less than or equal to 300 as measured by ISO 5659-2 on a 3 mm thick plaque.
2 . A thermoplastic composition comprising, based on the total weight of the thermoplastic composition,
70 to 95 wt % of a polycarbonate copolymer comprising first repeating units and second repeating units, wherein the first repeating units are not the same as the second repeating units, and wherein
the first repeating units are bisphenol carbonate units of the formula
wherein R a and R b are each independently C 1-12 alkyl, C 1-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy, p and q are each independently 0 to 4, and X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, a C 1-11 alkylidene of formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen or C 1-10 alkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-10 hydrocarbon group; and
the second repeating units comprise bisphenol carbonate units that are not the same as the first repeating bisphenol carbonate units, siloxane units, arylate ester units, or a combination of arylate ester units and siloxane units; and
to 30 wt % of a polyetherimide based on the 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 300 as measured by ISO 5659-2 on a 3 mm thick plaque;
a multiaxial impact energy determined according to ISO 6603 on a 3.2 mm thick disc within 20% of the same composition without the polyetherimide.
3 . The composition of claim 2 , having a multiaxial impact energy determined according to ISO 6603 on a 3.2 mm thick disc within 10% of the same composition without the polyetherimide.
4 . The composition of claim 2 , having a multiaxial impact energy determined according to ISO 6603 on a 3.2 mm thick disc within 5% of the same composition without the polyetherimide.
5 . The composition of claim 1 , having a multiaxial impact ductility determined according to ISO 6603 on a 3.2 mm thick disc within 20% of the same composition without the polyetherimide.
6 . The composition of claim 1 , wherein in the polycarbonate copolymer, the first repeating units are bisphenol-A carbonate units.
7 . The composition of claim 1 , wherein in the polycarbonate copolymer, the second repeating units are carbonate units of the formula
wherein
R a and R b are each independently C 1-12 alkyl, C 1-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy,
p and q are each independently integers of 0 to 4, and
X b is C 2-32 bridging hydrocarbon group that is not the same as the X a in the first repeating bisphenol carbonate units.
8 . The composition of claim 7 , wherein the second repeating units are carbonate units of the formula
wherein
R a and R b are each independently a C 1-3 alkyl group,
p and q are each independently integers of 0 to 4,
R 3 is each independently a C 1-6 alkyl group,
j is 0 to 4, and
R 4 is hydrogen, C 1-6 alkyl, or phenyl optionally substituted with 1 to 5 C 1-6 alkyl groups.
9 . The composition of claim 8 , wherein the second repeating units are carbonate units of the formula
wherein R 5 is hydrogen, C 1-6 alkyl, or phenyl optionally substituted with 1 to 5 C 1-6 alkyl groups.
10 . The composition of claim 9 , wherein R 5 is phenyl.
11 . The composition of claim 1 , wherein the second repeating units are siloxane units of the formula
wherein
R is each independently a C 1-13 monovalent hydrocarbon group, and
E has an average value of 2 to 500.
12 . The composition of claim 11 , wherein the second repeating units are siloxane units of the formulas
or a combination comprising at least one of the foregoing wherein
R is each independently a C 1-13 monovalent hydrocarbon group,
Ar is each independently a C 6-30 aromatic group,
R 2 is each independently a C 2-8 alkylene group, and
E has an average value of 2 to 200.
13 . The composition of claim 12 , wherein the siloxane units are of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 200.
14 . The composition of claim 12 , wherein the siloxane units are of the formula
wherein
R is each independently a C 1-13 monovalent hydrocarbon group,
R 3 is independently a divalent C 2-8 aliphatic group,
M is each independently a halogen, cyano, nitro, C 1-8 alkylthio, C 1-8 alkyl, C 1-8 alkoxy, C 2-8 alkenyl, C 2-8 alkenyloxy group, C 3-8 cycloalkyl, C 3-8 cycloalkoxy, C 6-10 aryl, C 6-10 aryloxy, C 7-12 arylalkyl, C 7-12 arylalkoxy, C 7-12 alkylaryl, or C 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.
15 . The composition of claim 14 , wherein the siloxane units are of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 30 to 80.
16 . The composition of claim 1 , wherein the second repeating units comprise arylate ester units of the formula
wherein Ar 1 is a C 6-32 hydrocarbyl group containing at least one aromatic group.
17 . The composition of claim 16 , wherein the second repeating units comprise arylate ester units of the formula
optionally, monoaryl carbonate units of the formula
and
optionally, bisphenol ester units of the formula
wherein, in the foregoing formulas
R h is each independently a C 1-10 hydrocarbon group,
n is 0 to 4,
R a and R b are each independently a C 1-12 alkyl,
p and q are each independently integers of 0 to 4, and
X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a C 1-13 alkylidene of formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen or C 1-12 alkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-12 hydrocarbon group.
18 . The composition of claim 17 , wherein the polycarbonate copolymer comprises
2 to 20 mol % of bisphenol-A carbonate units, 60 to 98 mol % of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally, 1 to 20 mol % resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol-A ester units, or a combination thereof.
19 . The composition of claim 18 , wherein an article molded from the composition has a smoke density (Ds-4) value of equal to or less than 150 as measured by ISO 5659-2 on a 3 mm thick plaque.
20 . The composition of claim 16 , wherein arylate ester units are units of the formula
wherein
R a and R b are each independently C 1-12 alkyl, C 1-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy, p and q are each independently 0 to 4, and
X a is a bridging group between the two arylene groups, and is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, a C 1-11 alkylidene of the formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen or C 1-10 alkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-10 hydrocarbon group.
21 . The composition of claim 16 , wherein the polycarbonate copolymer comprises
5 to 50 mol % of bisphenol-A carbonate units, 51 to 95 mol % of phthalate-bisphenol-A ester units.
22 . The composition of claim 1 , wherein the second units comprise a combination of
monoaryl arylate ester units of the formula
siloxane units of the formula
optionally, arylate-bisphenol ester units of the formula
and
optionally monoaryl carbonate units of the formula
wherein in the foregoing formulas
R h is each independently a halogen atom or a C 1-10 hydrocarbon group,
n is 0 to 4,
R a and R b are each independently a C 1-12 alkyl,
p and q are each independently integers of 0 to 4, and
X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a C 1-13 alkylidene of formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen or C 1-12 alkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-12 hydrocarbon group,
R is each independently a C 1-13 monovalent hydrocarbon group, and
E has an average value of 2 to 500.
23 . The composition of claim 22 , wherein the siloxane units are of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 200.
24 . The composition of claim 22 , wherein the siloxane units are of the formula
wherein
R is each independently a C 1-13 monovalent hydrocarbon group,
R 3 is independently a divalent C 2-8 aliphatic group,
M is each independently a halogen, cyano, nitro, C 1-8 alkylthio, C 1-8 alkyl, C 1-8 alkoxy, C 2-8 alkenyl, C 2-8 alkenyloxy group, C 3-8 cycloalkyl, C 3-8 cycloalkoxy, C 6-10 aryl, C 6-10 aryloxy, C 7-12 arylalkyl, C 7-12 arylalkoxy, C 7-12 alkylaryl, or C 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.
25 . The composition of claim 24 , wherein the siloxane units are of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 200.
26 . The composition of claim 22 , wherein the polycarbonate copolymer comprises
1 to 20 mol % of bisphenol-A carbonate units, 60 to 90 mol % of isophthalic acid-terephthalic acid-resorcinol units, and in an amount effective to provide 0.1 to 10 wt % of siloxane units based on the weight of polycarbonate, units of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 80.
27 . The composition of claim 22 , further comprising a second polycarbonate copolymer comprising first repeating units and second repeating units different from the first repeating units, wherein
the first repeating units are bisphenol carbonate units of the formula
wherein R a and R b are each independently C 1-12 alkyl, C 1-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy, p and q are each independently 0 to 4, and X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, a C 1-11 alkylidene of formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen or C 1-10 alkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-10 hydrocarbon group; and
the second repeating units comprise monoaryl arylate ester units of the formula
wherein R h is each independently a C 1-4 alkyl and n is 0 to 1.
28 . The composition of claim 27 , comprising, based on the weight of the polymers in the composition,
20 to 80 wt % of the polycarbonate copolymer, which comprises, based on the copolymer,
1 to 20 mol % of bisphenol-A carbonate units,
60 to 90 mol % of isophthalic acid-terephthalic acid-resorcinol units, and
in an amount effective to provide 0.1 to 10 wt % of siloxane units based on the weight of polycarbonate, units of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 30; and
20 to 80 wt % of a second polycarbonate copolymer, which comprises, based on the second polycarbonate copolymer,
2 to 20 mol % of bisphenol-A carbonate units,
60 to 98 mol % of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally, 1 to 20 mol % resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol-A ester units, or a combination thereof; and
wherein an article molded from the composition has a smoke density (Ds-4) value of less than 150 as determined in accordance with ISO 5659-2 on 3 mm thick plaque.
29 . The composition of claim 11 , further comprising a second polycarbonate, wherein the second polycarbonate is a polycarbonate homopolymer.
30 . The composition of claim 29 , comprising, based on the weight of the polymers in the composition,
20 to 80 wt % of the polycarbonate copolymer, wherein
the first repeating units are bisphenol-A carbonate units, and
the second repeating units are siloxane units of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 80; and
20-80 wt % of the second polycarbonate, wherein the second polycarbonate is a bisphenol-A homopolymer; and
wherein an article molded from the composition has a smoke density (Ds-4) value of equal to or less than 300 as measured by ISO 5659-2 on a 3 mm thick plaque.
31 . The composition of claim 1 , wherein the polyetherimide comprises units of the formula
wherein
R is a C 2-20 hydrocarbon group, and
Z is an aromatic C 6-24 monocyclic or polycyclic group optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, wherein the divalent bonds of the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions.
32 . The composition of claim 31 , wherein
R is a divalent radical of the formula
wherein Q is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — or a halogenated derivative thereof
wherein y is an integer from 1 to 5, and
Z is a divalent group of the formula
wherein Q 1 is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5.
33 . The composition of claim 32 , wherein R is m-phenylene and Q 1 is isopropylidene.
34 . The composition of claim 1 , further comprising an organophosphorus compound in an amount effective to provide 0.1-1 wt % phosphorus, based on the total weight of the composition.
35 . The composition claim 34 , wherein the organophosphorus compound is an aromatic organophosphorus compounds having at least one organic aromatic group and at least one phosphorus-containing group, or an organic compounds having at least one phosphorus-nitrogen bond.
36 . The composition of claim 35 , wherein the aromatic organophosphorus compound comprises a C 3-30 aromatic group and a phosphate group, phosphite group, phosphonate group, phosphinate group, phosphine oxide group, phosphine group, phosphazene, or a combination comprising at least one of the foregoing phosphorus-containing groups.
37 . The composition of claim 36 , wherein the aromatic organophosphorus compound is of the formula
wherein
R 16 , R 17 , R 18 and R 19 are each independently C 1-8 alkyl, C 5-6 cycloalkyl, C 6-20 aryl, or C 7-12 arylalkylene, each optionally substituted by C 1-12 alkyl, and
X is a mono- or poly-nuclear aromatic C 6-30 moiety or a linear or branched C 2-30 aliphatic radical, which can be OH-substituted and can contain up to 8 ether bonds, provided that at least one of R 16 , R 17 , R 18 , R 19 , and X is aromatic,
n is each independently 0 or 1, and
q is from 0.5 to 30.
38 . The composition of claim 37 , wherein
each of R 16 , R 17 , R 18 , and R 19 is phenyl, X is of the formula
each n is 1, and
p is 1-5.
39 . The composition of claim 35 , 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.
40 . The composition of claim 1 , wherein no halogenated compounds are present.
41 . The composition of claim 1 , wherein an increase in fractional concentration of polyetherimide in the composition reduces the smoke density (Ds-4) as measured in accordance with ISO 5659-2 on a 3 mm thick plaque in a non-linear manner, wherein an interaction parameter ‘k’ measured using the equation
Ds
Blend
=
w
POL
Ds
POL
pure
+
kw
PEI
Ds
PEI
pure
w
POL
+
kw
PEI
where Ds Blend is the smoke density of the composition;
w POL is the fractional wt % of the non-polyetherimide polymer(s)/copolymer(s) or their blends based on the weight of the composition;
w PEI is the fractional wt % of the polyetherimide based on the weight of the composition;
Ds POL pure is the smoke density of the composition with only the non-polyetherimide polymer(s)/copolymer(s);
Ds PEI pure is the smoke density of the composition with only polyetherimide; and
k is greater than 4.0.
42 . An article selected from a molded article, a thermoformed article, an extruded film, an extruded sheet, a foamed article, one or more layers of a multi-layer article, a substrate for a coated article, and a substrate for a metallized article comprising the composition of claim 1 .
43 . The article of claim 42 , having a thickness of 0.1 to 10 mm.
44 . The article of claim 43 , having a thickness of 0.5 to 5 mm.
45 . The article of claim 42 , wherein the article is a transportation component.
46 . The article of claim 45 , 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.
47 . A method of manufacture of an article, comprising molding, extruding, or casting the thermoplastic composition of claim 1 to form the article.Join the waitlist — get patent alerts
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