Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-07-16
2003-09-30
Short, Patricia A. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C528S205000, C428S457000, C428S458000, C428S461000, C428S462000, C428S463000
Reexamination Certificate
active
06627704
ABSTRACT:
BACKGROUND OF INVENTION
Thermoset molding compositions known in the art are generally thermosetting resins containing inorganic fillers and/or fibers. Upon heating, thermoset monomers initially exhibit viscosities low enough to allow for melt processing and molding of an article from the filled monomer composition. Upon further heating the thermosetting monomers react and cure to form hard resins with high modulus.
There remains a need for thermoset compositions exhibiting improved combinations of properties including curing rate, toughness, stiffness, and heat resistance.
SUMMARY OF INVENTION
One embodiment is a composition comprising: a capped poly(arylene ether); an alkenyl aromatic monomer; and an acryloyl monomer. The present inventors have found that this composition provides a highly desirable combination of fast curing, reduced curing rate oxygen sensitivity, high toughness, high stiffness, and high heat resistance. At least one of these properties is compromised if any of the components is omitted.
Another embodiment is a method of preparing a thermoset composition, comprising: blending a capped poly(arylene ether), an alkenyl aromatic monomer, and an acryloyl monomer to form an intimate blend.
Another embodiment is a cured resin comprising the reaction product of: a capped poly(arylene ether); an alkenyl aromatic monomer; and an acryloyl monomer.
DETAILED DESCRIPTION
One embodiment is a thermoset composition, comprising: a capped poly(arylene ether); an alkenyl aromatic monomer; and an acryloyl monomer.
The composition comprises a capped poly(arylene ether), which is defined herein as a poly(arylene ether) in which at least 50%, preferably at least 75%, more preferably at least 90%, yet more preferably at least 95%, even more preferably at least 99%, of the free hydroxyl groups present in the corresponding uncapped poly(arylene ether) have been functionalized by reaction with a capping agent.
There is no particular limitation on the molecular weight or intrinsic viscosity of the capped poly(arylene ether). In one embodiment, the composition may comprise a capped poly(arylene ether) having a number average molecular weight up to about 10,000 atomic mass units (AMU), preferably up to about 5,000 AMU, more preferably up to about 3,000 AMU. Such a capped poly(arylene ether) may be useful in preparing and processing the composition by reducing its viscosity. In another embodiment, the composition may comprise a capped poly(arylene ether) having an intrinsic viscosity of about 0.15 to about 0.30 deciliters per gram (dl/g), preferably about 0.20 to about 0.25 dl/g, as measured in chloroform at 25° C. Generally, the intrinsic viscosity of the capped poly(arylene ether) will vary insignificantly from the intrinsic viscosity of the corresponding uncapped poly(arylene ether). These intrinsic viscosities may correspond approximately to number average molecular weights of about 5,000 to about 25,000 AMU, preferably about 8,000 to about 20,000 AMU, more preferably about 10,000 to about 15,000 AMU. Such a capped poly(arylene ether) may provide the composition with a desirable balance of toughness and processability. It is expressly contemplated to employ blends of at least two capped poly(arylene ether)s having different molecular weights and intrinsic viscosities.
The capped poly(arylene ether) may be represented by the structure
Q(
J—K
)
y
wherein Q is the residuum of a monohydric, dihydric, or polyhydric phenol, preferably the residuum of a monohydric or dihydric phenol, more preferably the residuum of a monohydric phenol; y is 1 to 100; J comprises recurring units having the structure
wherein m is 1 to about 200, preferably 2 to about 200, and R
1
-R
4
are each independently hydrogen, halogen, primary or secondary C
1
-C
12
alkyl, C
2
-C
12
alkenyl, C
2
-C
12
alkynyl, C
1
-C
12
aminoalkyl, C
1
-C
12
hydroxyalkyl, phenyl, C
1
-C
12
haloalkyl, C
1
-C
12
hydrocarbonoxy, C
2
-C
12
halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or the like; and K is a capping group produced by reaction of a phenolic hydroxyl group on the poly (arylene ether) with a capping reagent. The resulting capping group may be
or the like, wherein R
5
is C
1
-C
12
alkyl, or the like; R
6
-R
8
are each independently hydrogen, C
1
-C
12
alkyl, C
2
-C
12
alkenyl, C
6
-C
18
aryl, C
7
-C
18
alkyl-substituted aryl, C
7
-C
18
aryl-substituted alkyl, C
2
-C
12
alkoxycarbonyl, C
7
-C
18
aryloxycarbonyl, C
7
-C
18
alkyl-substituted aryloxycarbonyl, C
7
-C
18
aryl-substituted alkoxycarbonyl, nitrile, formyl, carboxylate, imidate, thiocarboxylate, or the like; R
9
-R
13
are each independently hydrogen, halogen, C
1
-C
12
alkyl, hydroxy, amino, or the like; and wherein Y is a divalent group such as
or the like, wherein R
14
and R
15
are each independently hydrogen, C
1
-C
12
alkyl, or the like.
In one embodiment, Q is the residuum of a phenol, including polyfunctional phenols, and includes radicals of the structure
wherein R
1
-R
4
are each independently hydrogen, halogen, primary or secondary C
1
-C
12
alkyl, C
1
-C
12
alkenyl, C
1
-C
12
alkynyl, C
1
-C
12
aminoalkyl, C
1
-C
12
hydroxyalkyl, phenyl, C
1
-C
12
haloalkyl, C
1
-C
12
aminoalkyl, C
1
-C
12
hydrocarbonoxy, C
1
-C
12
halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or the like; X may be hydrogen, C
1
-C
12
alkyl, C
6
-C
18
aryl, C
7
-C
18
alkyl-substituted aryl, C
7
-C
18
aryl-substituted alkyl, or any of the foregoing hydrocarbon groups containing at least one substituent such as carboxylic acid, aldehyde, alcohol, amino radicals, or the like; X also may be sulfur, sulfonyl, sulfuryl, oxygen, or other such bridging group having a valence of 2 or greater to result in various bis- or higher polyphenols; y and n are each independently 1 to about 100, preferably 1 to 3, and more preferably about 1 to 2; in a preferred embodiment, y=n.
In one embodiment, the capped poly(arylene ether) is produced by capping a poly (arylene ether) consisting essentially of the polymerization product of at least one monohydric phenol having the structure
wherein R
1
-R
4
are each independently hydrogen, halogen, primary or secondary C
1
-C
12
alkyl, C
2
-C
12
alkenyl, C
2
-C
12
alkynyl, C
1
-C
12
aminoalkyl, C
1
-C
12
hydroxyalkyl, phenyl, C
1
-C
12
haloalkyl, C
1
-C
12
hydrocarbonoxy, C
2
-C
12
halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or the like. Suitable monohydric phenols include those described in U.S. Pat. No. 3,306,875 to Hay, and highly preferred monohydric phenols include 2,6-dimethylphenol and 2,3,6-trimethylphenol. The poly(arylene ether) may be a copolymer of at least two monohydric phenols, such as 2,6-dimethylphenol and 2,3,6-trimethylphenol.
In a preferred embodiment, the capped poly(arylene ether) comprises at least one capping group having the structure
wherein R
6
-R
8
are each independently hydrogen, C
1
-C
12
alkyl, C
2
-C
12
alkenyl, C
6
-C
18
aryl, C
7
-C
18
alkyl-substituted aryl, C
7
-C
18
aryl-substituted alkyl, C
2
-C
12
alkoxycarbonyl, C
7
-C
18
aryloxycarbonyl, C
7
-C
18
alkyl-substituted aryloxycarbonyl, C
7
-C
18
aryl-substituted alkoxycarbonyl, nitrile, formyl, carboxylate, imidate, thiocarboxylate, or the like. Highly preferred capping groups include acrylate (R
6
=R
7
=R
8
=hydrogen) and methacrylate (R
6
=methyl, R
7
=R
8
=hydrogen).
In another preferred embodiment, the capped poly(arylene ether) comprises at least one capping group having the structure
wherein R
5
is C—C alkyl, preferably C—C alkyl, more preferably methyl, ethyl, or isopropyl. The present inventors have surprisingly found that the advantageous properties of their composition can be achieved even when the capped poly(arylene ether) lacks a polymerizable function such as a carbon-carbon double bond.
In yet another preferred embodiment, the capped poly(arylene ether) comprises at least one capping group having the structure
wherein R
9
Colborn Robert Edgar
Yeager Gary William
General Electric Company
Short Patricia A.
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