IP Library Granted Patent US 9,006,319
Granted Patent B2
US 9,006,319 · App. 13/020,897 · Granted Apr 14, 2015

Hydrostable polyetherimide blends, methods of manufacture, and articles formed therefrom

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Quick Facts
Patent No.
US 9,006,319
App. No.
13/020,897
Granted
Apr 14, 2015
Kind
B2
Abstract

A composition comprising, based on the total weight of the composition, from 10 to 90 wt. % of a polyetherimide with a weight average molecular weight from 10,000 to 80,000 Daltons; from 10 to 90 wt. % of a polymer selected from polycarbonates, polyester-polycarbonates, polyalkylene terephthalates, or a combination thereof, from 0.005 to 1 wt. % of a hydrotalcite having a particle size of less than 10 micrometer and a magnesium oxide to aluminum oxide mole ratio of 1.0 to 5.0; from 0.01 to 1.0 wt. % of a phosphorus-containing stabilizer; from 0.01 to 1.00 wt. % of a hindered phenol stabilizer; optionally, from 0 to 3 wt. % of a polyolefin; and optionally, from 0 to 5 wt. % of an inorganic metal oxide.

Claims (88)

1. A composition comprising, based on the total weight of the composition,

from 10 to 90 wt. % of a polyimide with a weight average molecular weight of from 10,000 to 80,000 Daltons, of the formula

wherein

a is greater than 1,

V is a tetravalent aromatic group of the formula

 wherein W is a divalent moiety selected from —O—, —O—Z—O—, —SO 2 —, or a combination thereof, wherein the divalent bonds of the —O—, the —O—Z—O—, and the —SO 2 —group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions, and wherein Z is a monocyclic or polycyclic moiety having 6 to 24 carbon atoms and optionally substituted with 1 to 8 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, and

R is selected from an aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a divalent group of the formula

 wherein Q 1 is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — wherein y is 1 to 5, and a halogenated derivative thereof;

from 10 to 90 wt. % of a polymer selected from a polycarbonate, polyester-polycarbonate, polyalkylene terephthalate, or a combination thereof;

from 0.005 to 1 wt. % of a hydrotalcite having a particle size of less than 10 micrometer and a magnesium oxide to aluminum oxide mole ratio of 1.0 to 5.0;

from 0.01 to 1.0 wt. % of a phosphorus-containing stabilizer;

from 0.01 to 1.0 wt. % of a hindered phenol stabilizer;

optionally, from 0 to 3 wt. % of a polyolefin; and

optionally, from 0 to 5.0 wt. % of an inorganic metal oxide,

wherein when the composition is exposed to a temperature of 110° C. for 10 days under steam and under pressure, the composition has a melt flow rate increase that is less than 100%, as compared to the melt flow rate, at 295° C. with 6.7 Kg, of the composition at 0 days steam and pressure exposure.

2. The composition of claim 1 , having less than 100 ppm by weight of the composition of a sodium aryl phosphinate salt.

3. The composition of claim 1 , wherein the polyimide is the product of a halo-displacement manufacturing process.

4. The composition of claim 1 , wherein the phosphorus-containing stabilizer is tris(2,4-di-tert-butyl-phenyl) phosphite having a molecular weight of greater than 300 Daltons.

5. The composition of claim 1 comprising the polyolefin, wherein the polyolefin is a high-density polyethylene.

6. The composition of claim 1 comprising the metal oxide, wherein the metal oxide is a titanium dioxide having a mean particle size of less than 5 micrometers.

7. The composition of claim 1 , wherein the hydrotalcite is calcined.

8. The composition of claim 7 , wherein the calcined hydrotalcite has less than 30 ppm of mercury, lead, cadmium, arsenic, bismuth, or a combination thereof.

9. The composition of claim 1 , wherein the polyester-polycarbonate comprises, based on the total weight of the polyester-polycarbonate,

from greater than zero to 90 weight percent of a polymer containing recurring units of the formula:

wherein

x is 20 to 100 and y is more than zero to 80, based on 100 parts by weight of the polymer,

Ar is divalent aromatic residue of a dicarboxylic acid or combination of dicarboxylic acids and

Ar′ is the divalent aromatic residue of a dihydric phenol or a mixture of dihydric phenols of the formula

wherein R a and R b are each independently a halogen or a C 1-12 alkyl, X a is a single bond, —O—, —S—, —S(O)—, —S(O)— 2 —, —C(O)—, or a C 1-18 organic group, and p and q are each independently 0 to 4.

10. The composition of claim 9 , wherein X a is a substituted or unsubstituted C 3-18 cycloalkylidene, a C 1-25 alkylidene of the formula —C(R c )(R d )— wherein R c and R d are each independently hydrogen, C 1-12 alkyl, C 1-12 cycloalkyl, C 7-12 arylalkyl, C 1-12 heteroalkyl, or cyclic C 7-12 heteroarylalkyl, or a group of the formula —C(═R e )— wherein R e is a divalent C 1-12 hydrocarbon group.

11. The composition of claim 10 , wherein X a is isopropylidene and p and q are each zero.

12. The composition of claim 1 , wherein the polyimide is a polyetherimide of the formula

wherein

T is —O—or a group of the formula —O—Z—O—wherein the divalent bonds of the —O—or the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions and Z is a divalent radical of the formulae

 wherein Q is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5; and

R is a divalent group of 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.

13. The composition of claim 12 , wherein R is m-phenylene, p-phenylene diarylsulfone, or a combination thereof.

14. The composition of claim 12 , wherein the polyimide is a product of the reaction of

a compound of the formula

 wherein X is bromine or chlorine and R is a divalent group of 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, with

a compound of the formula

MO—Z—OM

wherein M is an alkali metal salt and the divalent bonds of the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions and Z is a divalent radical of the formulae

 wherein Q is —O—, —S—,—C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5.

15. The composition of claim 14 , wherein X is chloro, M is sodium, and R is m-phenylene, p-phenylene diaryl sulfone, or a combination thereof.

16. A method of manufacture of a composition, comprising melt blending the components of the composition of claim 1 .

17. A method of forming an article, comprising shaping, extruding, blow molding, or injection molding the composition of claim 1 to form the article.

18. An article comprising the composition of claim 1 .

19. The article of claim 18 , selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

20. A composition comprising, based on the total weight of the composition,

from 10 to 90 wt. % of a polyimide with a weight average molecular weight of from 10,000 to 80,000 Daltons, of the formula

wherein

a is greater than 1,

V is a tetravalent aromatic group of the formula

 wherein W is a divalent moiety selected from —O—, —O—Z—O—, —SO 2 —, or a combination thereof, wherein the divalent bonds of the —O—, the —O—Z—O—, and the —SO 2 — group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions, and wherein Z is a monocyclic or polycyclic moiety having 6 to 24 carbon atoms and optionally substituted with 1 to 8 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, and

R is selected from an aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or a divalent group of the formula

 wherein Q 1 is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — wherein y is 1 to 5, and a halogenated derivative thereof;

from 10 to 90 wt. % of a polymer selected from a polycarbonate, polyester-polycarbonate, polyalkylene terephthalate, or a combination thereof;

from 0.005 to 1 wt. % of a hydrotalcite having a particle size of less than 10 micrometer and a magnesium oxide to aluminum oxide mole ratio of 1.0 to 5.0;

from 0.01 to 1.0 wt. % of a phosphorus-containing stabilizer;

from 0.01 to 1.0 wt. % of a hindered phenol stabilizer;

optionally, from 0 to 3 wt. % of a polyolefin; and

optionally, from 0 to 5.0 wt. % of an inorganic metal oxide, wherein the composition retains at least 60% of its initial tensile strength at yield, after exposure to 110° C. steam for 20 days.

21. The composition of claim 20 , wherein the initial tensile strength at yield is from 9 to 15 MPa.

22. A composition comprising, based on the total weight of the composition,

from 15 to 85 wt. % of a polyimide with a weight average molecular weight (Mw) of from 40,000 to 80,000 Daltons, of the formula

wherein

T is —O— or a group of the formula —O—Z—O— wherein the divalent bonds of the —O— or the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions and Z is a divalent radical of the formulae

 wherein Q is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y —wherein y is an integer from 1 to 5 and

R is a divalent group of formula

 wherein Q is —O—,—S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5;

from 15 to 85 wt. % a polymer selected from a bisphenol A polycarbonate, a polyester-polycarbonate comprising units derived from bisphenol A, isophthalate and terephthalate, or a combination thereof;

from 0.1 to less than 0.8 wt. % of a calcined hydrotalcite having a particle size of less than 10 microns and a magnesium oxide to aluminum oxide mole ratio of 1.0 to 5.0.;

from 0.01 to 0.3 wt. % of a triaryl phosphorus-containing stabilizer with a molecular weight greater than 300 Daltons;

from 0.01 to 0.3 wt. % of a hindered phenol stabilizer with a molecular weight greater than 300 Daltons;

from 0.1 to 5.0 wt. % of a titanium dioxide with a mean particle size of less than 5 micrometers,

wherein when the composition is exposed to a temperature of 110° C. for 10 days under steam and under pressure, the composition has a melt flow rate increase that is less than 100%, as compared to the melt flow rate, at 295° C. with 6.7 Kg, of the composition at 0 days steam and pressure exposure.

23. The composition of claim 22 , wherein the calcined hydrotalcite is present in an amount that is from 0.1 to less than or equal to 0.4 wt. %, based on the total weight of the composition.

24. The composition of claim 22 , wherein the polyimide is a product of the reaction of

a compound of the formula

 wherein X is bromine or chlorine and R is a divalent group of 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, with

a compound of the formula

MO—Z—OM

wherein M is an alkali metal salt and the divalent bonds of the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions and Z is a divalent radical of the formulae

 wherein Q is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5.

Assignments (6)
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 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 1, 2011
From: GALLUCCI, ROBERT RUSSELL; SANNER, MARK A.; ZAFIRIS, GEORGIOS S.
To: SABIC INNOVATIVE PLASTICS IP B.V.
Reel/Frame 025877/0539 →