Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2003-02-06
2004-11-23
Woodward, Ana (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S448000, C524S449000, C524S451000, C524S514000, C525S180000, C525S183000
Reexamination Certificate
active
06822032
ABSTRACT:
FIELD OF THE INVENTION
This invention generally relates to impact modification of blends containing polyimides and polyamides using olefinic copolymers containing zinc carboxylate moieties.
BACKGROUND OF THE INVENTION
Blends of polyimide resins (PI) and polyamide resins (PA) (sometimes referred to herein as “PI/PA blends”) possess various useful properties and are described in U.S. Pat. Nos. 5,013,799 and 4,657,897 and European Patent 0 104 659 B1. These polymer blends afford combined performance features not generally observed in the individual resins. The polyamide resins (also known as nylon resins) improves PI melt processability and solvent resistance while the PI resin improves the dimensional stability of the PA. While PI/PA blends have many useful features their practical impact is too low for many applications
European Patent Appl. 0 410 514 A1 discloses use of a either (a) compound having both an ethylenically unsaturated carbon-carbon double bond and a carboxylic acid, acid anhydride, acid amide, imido, carboxylic acid ester, amino or hydroxyl group or (b) an epoxy compound and 0 to 40 parts by weight of a rubber polymer. The compositions are described as reducing the notch sensitivity and brittleness of PI/PA blends. However, there still exists a need to modify PI/PA blends to improve practical toughness while still having good appearance and melt stability to allow the blends to be formed into parts without significant decomposition of any of the components of the blends.
DESCRIPTION OF THE INVENTION
The present inventor has unexpectedly found that the use of rubbery olefinic copolymers containing zinc carboxylate moieties resulted in PI/PA blends having good appearance, good melt stability and improved impact resistance. Surprisingly, the use of a very similar olefin copolymer containing sodium carboxylate moieties did not result in the same improvements to properties of PI/PA blends as olefinic copolymers containing zinc carboxylate moieties. The zinc carboxylate containing copolymers of the present invention are substantially free of carbon-carbon double bonds. By “substantially free of carbon-carbon double bonds” is meant olefinic copolymers containing less than one mole % olefinic groups
In a preferred embodiment of the invention, the compositions and articles thereof contain three major components: polyimide resin(s), polyamide resin(s) and olefinic copolymer(s) containing zinc carboxylate moieties and may further optionally contain one or more of antioxidants, stabilizers, lubricants, pigments, dyes, modifying agents, fillers, and reinforcing agents.
In another embodiment, the compositions and articles of the present invention are free of the modifying mixtures as described in European Patent Appl. 0 410 514 A1 which are based on low molecular weight compounds containing unsaturated carboxylic acids, anhydrides, acid amide, imido, carboxylic ester, amino, hydroxy, or epoxy compounds.
Useful thermoplastic poly(imide) resins have the general formula (I)
wherein a is more than about 10, typically 10 to about 1000 or more, and preferably about 50 to about 500; and V is a tetravalent linker without limitation, as long as the linker does not impede synthesis or use of the polyimide. Suitable linkers include but are not limited to: (a) substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having about 5 to about 50 carbon atoms, (b) substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl groups having 1 to about 30 carbon atoms; or combinations thereof. Suitable substitutions and/or linkers include, but are not limited to, ethers, amides, esters, and combinations thereof. Preferred linkers include but are not limited to tetravalent aromatic radicals of formula (II), such as
wherein W is a divalent moiety selected from the group consisting of -O-, -S-, -C(O)-, -SO
2
-, C
y
H
2y
- (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups, 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 wherein Z includes, but is not limited, to divalent radicals of formula (III).
R in formula (I) includes but is not limited to substituted or unsubstituted divalent organic radicals such as: (a) aromatic groups or halogenated, ether, sulfo, sulfone or carbonyl derivatives thereof; (b) straight or branched chain alkylene radicals having about 2 to about 20 carbon atoms; (c) cycloalkylene radicals having about 3 to about 20 carbon atoms, or (d) divatent radicals of the general formula (IV)
wherein Q includes but is not limited to a divalent moiety selected from the group consisting of -O-, -S-, -C(O)-, -SO
2
-, C
y
H
2y
- (y being an integer from 1 to 5), and halogenated derivatives thereof, including perfluoroalkylene groups.
Preferred classes of polyimide polymers include polyamide imide polymers and polyetherimide polymers, particularly those polyetherimide polymers known in the art which are melt processable, such as those whose preparation and properties are described in U.S. Pat. Nos. 3,803,085 and 3,905,942.
Preferred polyetherimide resins comprise more than 10, typically about 10 to about 1000 or more, and more preferably about 50 to about 500 structural units, of the formula (V)
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 wherein Z includes, but is not limited, to divalent radicals of formula (III) as defined above.
In one embodiment, the polyetherimide may be a copolymer which, in addition to the etherimide units described above, further contains polyimide structural units of the formula (VI)
wherein R is as previously defined for formula (I) and M includes, but is not limited to, radicals of formula (VII).
The polyetherimide can be prepared by any of the methods known to those skilled in the art, including the reaction of an aromatic bis-ether anhydride of the formula (VIII)
with an organic diamine of the formula (IX)
H
2
N-R-NH
2
(IX)
wherein T and R are defined as described above in formulas (I) and (IV).
Included among the many methods of making the polyimides, particularly polyetherimide polymers, are those disclosed in U. S. Pat. Nos. 3,847,867, 3,814,869, 3,850,885, 3,852,242, 3,855,178, 3,983,093, and 4,443,591. These patents are provided for the purpose of teaching, by way of illustration, general and specific methods for preparing polyimides.
Examples of specific aromatic bis- anhydrides and organic diamines are disclosed, for example, in U.S. Pat. Nos. 3,972,902 and 4,455,410.
Illustrative examples of thermoplastic polyimides of the invention can be derived from reaction of aromatic dianhydrides or aromatic tetracarboxylic acids or their derivatives capable of forming cyclic anhydrides and aromatic diamines,or chemically equivalent derivatives, to form cyclic imide linkages.
Illustrative examples of aromatic bis anhydrides include: 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 2,2-bis([4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; -4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicar
General Electric Company
Woodward Ana
LandOfFree
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