IP Library Granted Patent US 8,981,015
Granted Patent B2
US 8,981,015 · App. 13/251,122 · Granted Mar 17, 2015

Flame retardant poly(siloxane) copolymer compositions, methods of manufacture, and articles formed therefrom

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Quick Facts
Patent No.
US 8,981,015
App. No.
13/251,122
Granted
Mar 17, 2015
Kind
B2
Abstract

A poly(siloxane) copolymer composition comprising: a first polymer comprising a first repeating unit, and a poly(siloxane) block unit, a second polymer different from the first polymer and comprising of bromine; and optionally, one or more third polymers different from the first polymer and second polymer; wherein siloxane units are present in the composition in an amount of at least 0.3 wt %, and bromine is present in the composition in an amount of at least 7.8 wt %, each based on the sum of the wt % of the first, second, and optional one or more third polymers; and further wherein an article molded from the composition has an OSU integrated 2 minute heat release test value of less than 65 kW-min/m 2 and a peak heat release rate of less than 65 kW/m 2 , and an E662 smoke test Dmax value of less than 200.

Claims (102)

1. A composition comprising:

a first polymer comprising (a) a first repeating unit, and (b) a poly(siloxane) block unit, the polysiloxane block unit having the formula:

 wherein

R is each independently a C 1 -C 30 hydrocarbon group, and

E has an average value of 5 to 200; and

wherein the poly(siloxane) block unit of the first polymer is derived from a polysiloxane bisphenol of the formula:

a second polymer different from the first polymer and comprising bromine; and

optionally, one or more third polymers different from the first polymer and second polymer, wherein the one or more third polymers are polymers comprising carbonate units, imide units, etherimide units, arylene ether sulfone units, arylene ether units, or a combination of units comprising at least one of the foregoing;

wherein

the wt % of the first polymer, second polymer, and optional one or more third polymers sum to 100 wt %,

siloxane units are present in the composition in an amount of at least 0.3 wt %, based on the sum of the wt % of the first, second, and optional one or more third polymers, and

bromine is present in the composition in an amount of at least 7.8 wt %, based on the sum of the wt % of the first, second, and optional one or more third polymers; and

further wherein an article molded or formed from the composition has

an OSU integrated 2 minute heat release test value of less than 65 kW-min/m 2 and a peak heat release rate of less than 65 kW/m 2 as measured using the method of FAR F25.4, in accordance with Federal Aviation Regulation FAR 25.853 (d), and

an E662 smoke test Dmax value of less than 200 when measured at a thickness of 1.6 mm.

2. The composition of claim 1 , wherein the siloxane block unit of the first polymer is present in an amount of at least 2.0 wt %, based on the weight of the first polymer.

3. The composition of claim 1 , wherein the bromine is present in the second polymer in an amount of at least 30 wt %, based on the weight of the second polymer.

4. The composition of claim 1 , wherein the first repeating unit comprises a carbonate unit, an ester unit, an arylene ether unit, an arylene sulfone unit, an arylene ether sulfone unit, an arylene ether ketone unit, or a combination comprising at least one of the foregoing units.

5. The composition of claim 1 , further comprising an additional polymer having (a) a first repeating unit, and (b) a poly(siloxane) block unit having the formula:

wherein

R is each independently a C 1 -C 30 hydrocarbon group, and

E has an average value of 5 to 200,

wherein the additional polymer is not the same as the first polymer.

6. The composition of claim 1 , wherein the second polymer is a brominated polycarbonate.

7. The composition of claim 1 , wherein the second polymer is a polycarbonate comprising 25 to 35 mol % of units derived from 2,2′6,6′ tetrabromo-4,4′-isopropylidenediphenol and 65 to 75 mole % of units derived from Bisphenol A.

8. The composition of claim 1 , wherein the second polymer is a brominated epoxy polymer.

9. The composition of claim 1 , further comprising an additional polymer comprising bromine, wherein the additional polymer is not the same as the first polymer or the second polymer.

10. The composition of claim 1 , comprising 1 to 85 wt % of the first polymer, and at least 15 wt % of the second polymer, each based on the total weight of the composition.

11. The composition of claim 1 , wherein

the poly(siloxane) block unit is present in an amount of 1.5 to 3.5 wt % based on the sum of the wt % of the first, second, and third polymers,

the bromine is present in an amount of 7.8 to 13 wt % based on the sum of the wt % of the first, second, and third polymers; and

the third polymer is present in an amount of 8 to 50 wt % based on the sum of the first, second, and third polymers.

12. The composition of claim 1 , having a density of less than 1.31 g/cc.

13. The compositions of claim 1 , having a density of less than 1.30 g/cc.

14. The composition of claim 1 , wherein an article molded from the composition has a room temperature notched Izod impact of greater than 500 J/m as measured according to ASTM D 256-10 at a 0.125 inch (3.2 mm) thickness.

15. The composition of claim 1 , wherein an article molded from the composition has a haze less of less than 15% and a transmission greater than 75%, each measured using the color space CIE1931 (Illuminant C and a 2° observer) at a 0.125 inch (3.2 mm) thickness.

16. The composition of claim 15 , wherein an article molded from the composition has a room temperature notched Izod impact of greater than 500 J/m as measured according to ASTM D 256-10 at a 0.125 inch (3.2 mm) thickness.

17. The composition of claim 1 , further comprising 0.5 to 3 parts by weight of titanium dioxide per hundred parts by weight of the sum of the of the first, second, and optional third polymers.

18. The composition of claim 1 , wherein the composition is substantially free of a fibrillated, fluorinated polyolefin.

19. An article selected from a molded article, a foamed article, a thermoformed article, an extruded film, an extruded sheet, one or more layers of a multi-layer article, a substrate for a coated article or a substrate for a metallized article made from the composition of claim 1 .

20. The article of claim 16 , wherein the article is a component of an aircraft interior or a train interior.

21. The article of claim 16 , wherein the article is selected from an access panel, access door, air flow regulator, air gasper, air grille, arm rest, baggage storage door, balcony component, cabinet wall, ceiling panel, door pull, door handle, duct housing, enclosure for an electronic device, equipment housing, equipment panel, floor panel, food cart, food tray, galley surface, handle, housing for television, light panel, magazine rack, telephone housing, partition, part for trolley cart, seat back, seat component, railing component, seat housing, shelve, side wall, speaker housing, storage compartment, storage housing, toilet seat, tray table, tray, trim panel, window molding, window slide, or window.

22. The composition of claim 1 , wherein the first polymer is a poly(siloxane-carbonate) comprising polysiloxane units in an amount of 0.3 to 30 weight percent, based on the total weight of the poly(siloxane-carbonate), with the remainder being carbonate units.

23. A composition comprising a first polymer comprising (a) a first repeating unit, and (b) a poly(siloxane) block unit, the polysiloxane block unit having the formula:

wherein

R is each independently a C 1 -C 30 hydrocarbon group, and

E has an average value of 5 to 200;

a second polymer different from the first polymer and comprising bromine; and

optionally, one or more third polymers different from the first polymer and second polymer, wherein the one or more third polymers are polymers comprising carbonate units, imide units, etherimide units, arylene ether sulfone units, arylene ether units, or a combination of units comprising at least one of the foregoing;

wherein

the wt % of the first polymer, second polymer, and optional one or more third polymers sum to 100 wt %,

siloxane units are present in the composition in an amount of at least 0.3 wt %, based on the sum of the wt % of the first, second, and optional one or more third polymers, and

bromine is present in the composition in an amount of at least 7.8 wt %, based on the sum of the wt % of the first, second, and optional one or more third polymers; and

further wherein an article molded or formed from the composition has

an OSU integrated 2 minute heat release test value of less than 65 kW-min/m 2 and a peak heat release rate of less than 65 kW/m 2 as measured using the method of FAR F25.4, in accordance with Federal Aviation Regulation FAR 25.853 (d), and

an E662 smoke test Dmax value of less than 200 when measured at a thickness of 1.6 mm;

wherein the first repeating unit comprises carbonate units of the formula

wherein R 1 is derived from bisphenol compounds of the formula:

wherein

each of R a and R b is independently a halogen atom or a monovalent hydrocarbon group;

p and q are each independently integers of 0 to 4; and

X a is a single bond or a group of the formula:

wherein each R c and R d is independently hydrogen, C 1-12 alkyl, C 1-12 cycloalkyl, C 7-12 arylalkyl, C 1-12 heteroalkyl, or cyclic C 7-12 heteroarylalkyl, and R e is a divalent C 1-12 hydrocarbon group.

24. The composition of claim 23 , wherein the poly(siloxane) block unit of the first polymer is derived from a polysiloxane bisphenol of the formula:

or a combination thereof,

wherein

R is each independently a C 1 -C 12 hydrocarbon group,

R 2 is each independently a C 7 -C 30 hydrocarbon group,

Ar is a C 6 -C 30 aromatic group, and

E has an average value of 5 to 100.

25. The composition of claim 24 , wherein

R is each independently a C 1 -C 6 hydrocarbon group,

R 2 is each independently a C 7 -C 12 hydrocarbon group,

Ar is a C 6 -C 8 aromatic group, and

E in structure (1) and structure (2) has an average value of 5 to 80.

26. The composition of claim 25 , wherein the polysiloxane bisphenol is of the formula:

27. The composition of claim 25 , wherein the polysiloxane bisphenol is of the formula:

wherein

R is each independently a C 1 -C 6 hydrocarbon group,

R 3 is each 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, 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, wherein each n is independently 0, 1, 2, 3, or 4, and

E has an average value of 5 to 80.

28. The composition of claim 27 , wherein the polysiloxane bisphenol is of the formula:

29. The composition of claim 23 wherein the first repeating unit comprises a carbonate unit derived from bisphenol A.

30. The composition of claim 4 wherein the first repeating unit comprises an arylate ester unit.

31. The composition of claim 4 wherein the first repeating unit comprises an aliphatic ester unit.

32. The composition of claim 4 wherein the first repeating unit comprises a combination of a carbonate unit and an ester unit.

33. The composition of claim 4 wherein the first repeating unit comprises a polyetherimide unit of the formula:

wherein R is m-phenylene, p-arylene diphenylsulfone, or a combination comprising at least one of the foregoing, and Z is 2,2-(4-phenylene)isopropylidene.

34. The composition of claim 4 wherein the first repeating unit comprises an arylene oxide unit of the formula:

wherein

Z 1 is each independently halogen or C 1 -C 12 hydrocarbon group with the proviso that that the hydrocarbon group is not tertiary hydrocarbon group; and

Z 2 is each independently hydrogen, halogen, or C 1 -C 12 hydrocarbon group with the proviso that that the hydrocarbon group is not tertiary hydrocarbyl.

35. The composition of claim 4 wherein the first repeating unit comprises poly(siloxane-arylene ether ketone)s wherein the first repeating unit comprises a unit of the formula:

wherein

Z 1 is each independently halogen or C 1 -C 12 hydrocarbon group with the proviso that that the hydrocarbon group is not tertiary hydrocarbon group; and

Z 2 is each independently hydrogen, halogen, or C 1 -C 12 hydrocarbon group with the proviso that that the hydrocarbon group is not tertiary hydrocarbyl.

36. The composition of claim 4 , wherein the first repeating unit comprises an arylene ether sulfone unit of the formula:

wherein

R 1 , R 2 , and R 3 are each independently a halogen atom, a nitro group, a cyano group, a C 1-12 aliphatic radical, C 3-12 cycloaliphatic radical, or a C 3-12 aromatic radical;

n, m, q are each independently 0 to 4; and

W is a C 3-20 cycloaliphatic radical or a C 3 -C 20 aromatic radical.

Assignments (5)
CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE THE APPLICATION NUMBER 15039474 PREVIOUSLY RECORDED AT REEL: 054528 FRAME: 0467. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Mar 23, 2021
From: SABIC GLOBAL TECHNOLOGIES B.V.
To: SHPP GLOBAL TECHNOLOGIES B.V.
Reel/Frame 057453/0680 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 26, 2020
From: SABIC GLOBAL TECHNOLOGIES B.V.
To: SHPP GLOBAL TECHNOLOGIES B.V.
Reel/Frame 054528/0467 →
CORRECTIVE ASSIGNMENT TO CORRECT THE 12/116841, 12/123274, 12/345155, 13/177651, 13/234682, 13/259855, 13/355684, 13/904372, 13/956615, 14/146802, 62/011336 PREVIOUSLY RECORDED ON REEL 033591 FRAME 0673. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME. Recorded Aug 29, 2014
From: SABIC INNOVATIVE PLASTICS IP B.V.
To: SABIC GLOBAL TECHNOLOGIES B.V.
Reel/Frame 033663/0427 →
CORRECTIVE ASSIGNMENT TO CORRECT REMOVE 10 APPL. NUMBERS PREVIOUSLY RECORDED AT REEL: 033591 FRAME: 0673. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME. Recorded Aug 28, 2014
From: SABIC INNOVATIVE PLASTICS IP B.V.
To: SABIC GLOBAL TECHNOLOGIES B.V.
Reel/Frame 033649/0529 →
CHANGE OF NAME Recorded Aug 22, 2014
From: SABIC INNOVATIVE PLASTICS IP B.V.
To: SABIC GLOBAL TECHNOLOGIES B.V.
Reel/Frame 033591/0673 →