Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From sulfur-containing reactant
Reexamination Certificate
1998-08-25
2001-01-09
Moore, Margaret G. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From sulfur-containing reactant
C525S056000, C525S057000, C525S058000, C525S059000, C525S090000, C525S09200D, C525S09200D, C525S09200D, C525S09200D, C525S09200D, C525S09200D, C525S088000, C525S093000, C525S094000
Reexamination Certificate
active
06172180
ABSTRACT:
BACKGROUND OF THE INVENTION
One useful attribute of block copolymers is their ability to combine the disparate properties of different materials into a single material. For example, a polymer of styrene-butadiene-styrene, a thermoplastic elastomer, draws its elastomeric qualities from the low glass transition, viscoelastic butadiene segments, and its dimensional stability and melting behavior from the high glass transition, rigid styrene segments. This combination of properties is achieved by arranging the constituent monomers in a particular sequential architecture, i.e., a so-called block copolymer.
An additional feature of block copolymers is their ability to localize at the interface of two materials thereby modifying the chemical and physical bond between the two. In order to localize in this manner, the block copolymer must be comprised of segments which have a specific chemical or physical affinity for the respective materials. This feature has been employed for the compatibilizing blends and improving adhesion.
The ability of certain polymer segments of block copolymers to localize at the air/material interface to thereby modify the surface has also been noted. In each instance, such a surface modification employs low surface energy polymer segments that are not highly branched to provide the physical driving force to enrich the surface with these polymer segments.
SUMMARY OF THE INVENTION
The present invention provides polymers, which by virtue of their composition and architecture, unexpectedly modify the surface of an article that contains these polymers. The present invention generally provides a block copolymer having 1 to 50 first polymer segments, each first polymer segment having monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 2,000 kDa, and 1 to 50 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 to 0.5 and an average molecular weight range of 5 to 2,000 kDa. The first polymer segments are 5 to 95% by weight of the block copolymer, and the second polymer segments are 5 to 95% by weight of the block copolymer. The ratio of the average mole fraction of monomers possessing a branch point of the second polymer segments to the average mole fraction of monomers possessing a branch point of the first polymer segments is 0 to 0.5. The block copolymer may have 1 to 10, 1 to 5, or 1 to 2 first polymer segments. The first polymer segments may be terminally or internally located in the block copolymer. Likewise, the block copolymer may have 1 to 10, 1 to 5, or 1 to 2 second polymer segments. The second polymer segments may be terminally or internally located. More specifically, the block copolymer has 1 to 2 first polymer segments, and 1 to 2 second polymer segments.
In a particular example, the block copolymer may have a total molecular weight of 10 to 2,000 kDa. The molecular weight may be determined by gel permeation chromatography, viscometry, light scattering, osmometry or any other proper methods.
The first polymer segment may be poly(ethylene oxide), poly(propylene oxide), ethylene oxide/propylene oxide copolymer, poly(acrylic acid), poly(methacrylic acid), poly(acryl amide), poly(vinyl alcohol), poly(vinyl sulfonic acid), poly(styrene sulfonate), polycarbonate, polyolefin, poly(vinyl phosphoric acid), poly(ethylene imine), poly(amino acid), or mixture thereof. The second polymer segment may be polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinychloride copolymer, poly(vinylidene fluoride), fluoropolymer, or a mixture thereof.
One example of the copolymer of the present invention is a block copolymer in which the first polymer segment is poly(ethylene oxide) or ethylene oxide/propylene oxide copolymer and the second polymer segment is polysulfone. The block copolymer includes (i) 1-3 first polymer segments, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 200 kDa, and (ii) 1-3 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 and an average molecular weight range of 20 to 200 kDa. The first polymer segments are 20 to 60% by weight of the block copolymer, and the second polymer segments are 40 to 80% by weight of the block copolymer.
The present invention additionally provides an article having an aggregate of block copolymer molecules, the block copolymer molecules having 1 to 50 first polymer segments, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 2,000 kDa, and 1 to 50 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 to 0.5 and an average molecular weight range of 5 to 2,000 kDa. The first polymer segments are 5 to 95% by weight of the block copolymer, and the second polymer segments are 5 to 95% by weight of the block copolymer. The ratio of the average mole fraction of monomers possessing a branch point of the second polymer segment to that of the first polymer segment is 0 to 0.5.
The article may contain block copolymer molecules wherein the first polymer segment is poly(ethylene oxide), poly(propylene oxide), ethylene oxide/propylene oxide copolymer, poly(acrylic acid), poly(methacrylic acid), poly(acryl amide), polyvinyl alcohol, poly(vinyl sulfonic acid), poly(styrene sulfonate), poly(vinyl phosphoric acid), poly(ethylene imine), poly(amino acid) or mixture thereof; and wherein the second polymer segment is polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinychloride copolymer, poly(vinylidene fluoride), fluoropolymer, or mixture thereof.
The article may further contain a bulk polymer wherein the second polymer segments are miscible with the bulk polymer. The bulk polymer may be polycarbonate, polyolefin, polysulfone, polyethersulfone, polyetherketone, polyimide, polysulfonamide, polyamide, polyacrylonitrile, polyacrylonitrile/polyvinychloride copolymer, poly(vinylidene fluoride), or fluoropolymer. In one embodiment, the article contains a bulk polymer of polysulfone, and each of the second polymer segments of the block copolymer is polysulfone.
The present invention also provides a solution for preparing a polymer article. The solution having 0.5 to 80% by weight of block copolymer molecules and 20 to 99.5% by weight of a solvent. The block copolymer molecules are dissolved in the solvent and each of these molecules has 1 to 50 first polymer segments, each first polymer segment having an average mole fraction of monomers possessing a branch point of 0.0001 to 1 and an average molecular weight range of 5 to 2,000 kDa; and 1 to 50 second polymer segments, each second polymer segment having an average mole fraction of monomers possessing a branch point of 0 to 0.5 and an average molecular weight range of 5 to 2,000 kDa. The first polymer segments are attached by covalent bonding to the second polymer segments. The first polymer segments are 5 to 95% by weight of the block copolymer, and the second polymer segments are 5 to 95% by weight of the block copolymer. The ratio of the average mole fraction of monomers possessing a branch point of the second polymer segment to that of the first polymer segment is 0 to 0.5.
The solution for preparing the polymer article may have 1 to 50% or 1 to 30% by weight of block copolymer molecules. The first polymer segment of block copolymer molecules may be poly(ethylene oxide), poly(propylene oxide), ethylene oxide/propylene oxide copolymer, poly(acrylic acid), poly(methacrylic acid), poly(acryl amide), poly(vinyl alcohol), poly(vinyl sulfonic acid), poly(styrene sulfonate), poly(vinyl phosphoric acid), poly(ethylene i
Fagan Stephen M.
Hancock Lawrence F.
Mullon Claudy J.-P.
Circe Biomedical, Inc.
Fish & Richardson P.C.
Moore Margaret G.
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