Drug – bio-affecting and body treating compositions – Dentifrices – Phosphate compound containing
Reexamination Certificate
1999-12-16
2002-05-28
Acquah, Samuel A. (Department: 1711)
Drug, bio-affecting and body treating compositions
Dentifrices
Phosphate compound containing
C525S329700, C525S329800, C525S330300, C525S340000, C525S403000, C525S418000, C526S274000, C526S278000, C524S081000
Reexamination Certificate
active
06395259
ABSTRACT:
BACKGROUND TO THE INVENTION
Phosphonylation of organic compounds and polymers has been documented in the prior art. Early applications focused on mass phosphonylation of non-functional polymers to introduce phosphonylate groups randomly along their carbon chain by allowing a solution of these polymers in phosphorous trichloride to interact with gaseous oxygen (U.S. Pat. Nos. 3,097,194; 3,278,464). For example, U.S. Pat. No. 3,097,194 to Leonard is directed to a process for preparing elastomeric phosphonylated amorphous copolymers of ethylene and propylene which are essentially free of low molecular weight polymer oils. Phosphorylation, or esterification of the copolymer, is conducted in situ of the copolymer solution mass after inactivating a polymerization catalyst with water and oxygen to convert the catalyst to an inert metal oxide. Oxygen is then bubbled through the reaction mass in the presence of phosphorous trichloride to obtain the phosphorylated copolymer.
An example of phosphonated polymers is provided in U.S. Pat. No. 3,278,464 to Boyer et al. In accordance therewith, ethylenically unsaturated polymers are reacted with an organic-substituted phosphorous compound to produce phosphonated polymers. Like the process described above, attachment of the phosphorous groups results in near-homogeneous, or mass, phosphonylation within the polymer and phosphorous compounds are combined in a solvent system.
Moreover, in U.S. Pat. No. 4,207,405 to Masler et al., polyphosphates are provided that are the homogeneous reaction products, in an organic solvent, of phosphorous acid or phosphorous trichloride and a water-soluble carboxyl polymer. U.S. Nat. Nos., 3,069,372 to Schroeder et al., U.S. Pat. No. 4,678,840 to Fong et al., U.S. Pat. No. 4,774,262 to Blanquet et al., U.S. Pat. No. 4,581,415 to Boyle Jr., et al., and U.S. Pat. No. 4,500,684 to Tucker show various phosphorous-containing polymer compounds.
U.S. Pat. Nos. 4,814,423 and 4,966,934 to Huang et al., describe adhesives for bonding polymeric materials to the collagen and calcium of teeth. For bonding to calcium, the adhesive employs an ethylenically unsaturated polymeric monophosphate component. A tooth is coated with the adhesive and then a filling is applied.
More recently, restricting the phosphonylation to the surface of polymeric substrates was achieved to produce articles with surface-phosphonylate functionalities and practically intact bulk (U.S. Pat. Nos. 5,491,198 and 5,558,517 to Shalaby et al.). This was achieved by gas phase phosphonylation of a preformed article with PCl
3
and O
2
or passing through a solution of PCl
3
in a non-reactive organic liquid that is also a non-solvent for the polymeric article. In effect, a process for phosphonylating the surface of an organic polymeric preform and the surface-phosphonylated preforms produced thereby are provided. Organic polymeric preforms made from various polymers including polyethylene, polyether-ether ketone, polypropylene, polymethyl methacrylate, polyamides and polyester, and formed into blocks, films, and fibers may have their surfaces phosphonylated according to that process. The process involves the use of a liquid medium that does not dissolve this organic polymeric preform but does dissolve a phosphorous halide such as phosphorous trichloride, and the like. The process allows for surface phosphonylation of the organic polymeric preform such that up to about 30 percent but preferably up to about 20 percent, of the reactive carbon sites in the polymer are phosphonylated. The phosphonylated organic polymers are particularly useful as orthopedic implants because hydroxyapatite-like surfaces which can be subsequently created on the organic implants allow for co-crystallization of hydroxyapatite to form chemically bound layers between prosthesis and bone tissue.
Although various phosphonylated polymers are known, the prior art is deficient in affording phosphorous-containing groups randomly and covalently attached to carbon atoms of aliphatic chains and pendant side groups of organo-soluble polymers such as polyalkylene oxides, polyamides, polyesters, and acrylate polymers, that are tailored for use in specified technology areas.
SUMMARY OF THE INVENTION
In one aspect the present invention is directed to a randomly phosphonylated acrylate polymeric composition which includes an acrylic polymer and phosphorous-containing functional groups, wherein the phosphorous atom of each functional group is covalently bonded to a carbon atom of the acrylic polymer and wherein the phosphorous atoms comprise at least about 0.1 percent by weight of the polymeric composition.
Preferably, the acrylic polymer is polymethyl-methacrylate and the phosphorous atoms comprise at least 0.5 percent by weight of the polymeric composition. Optionally, the acrylic polymer is based on methyl-methacrylate and methacrylic acid repeat units. It is also within the scope of the present invention that the acrylic polymer includes at least one polymerizable side group per chain, preferably a group derived from a bis-acrylate monomer, most preferably, ethylene bis-methacrylate.
A preferred application for the phosphonylated acrylate polymeric composition of the present invention is as a dental product such as a varnish or sealer, preferably one which includes fluoride ions which may be released on a controlled manner. It is also desirable that the dental product made in accordance with the present invention includes bioactive compounds such as antimicrobials, anti-inflammatory drugs, or pain-relieving agents, with the polymeric composition being capable of regulating the release of the bioactive compounds.
In another aspect the present invention is directed to a randomly phosphonylated polyalkylene oxide polymeric composition which includes a polyalkylene oxide polymer and phosphorous-containing functional groups, wherein the phosphorous atom of each of the functional groups is covalently bonded to a carbon atom of the polyalkylene oxide polymer and wherein the phosphorous atoms comprise at least about 0.1 percent by weight of the polymeric composition. Preferably the alkylene group of the polyalkylene oxide polymer has from two to six carbon atoms.
In yet another aspect the present invention is directed to a randomly phosphonylated polyamide composition which includes a polyamide polymer and phosphorous-containing functional groups, wherein the phosphorous atom of each of the functional groups is covalently bonded to a carbon atom of the polyamide polymer and wherein the phosphorous atoms comprise at least about 0.1 percent by weight of the composition. Preferably, the polyamide is the polymerization product of N-alkyl laurolactam.
In a still further aspect the present invention is directed to a randomly phosphonylated polyester composition which includes a polyester polymer and phosphorous-containing functional groups, wherein the phosphorous atom of each of the functional groups is covalently bonded to a carbon atom of the polyester polymer and wherein the phosphorous atoms comprise at least about 0.1 percent by weight of the composition. Preferably the polyester is poly-68-caprolactone. The present polyester composition is especially useful as a flame retardant additive for polyesters and polyurethanes.
All of the present inventive polymeric compositions may include a bioactive compound linked to the phosphonyl functionality.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention deals with novel phosphonylated derivatives of polyalkylene oxides, N-substituted aliphatic polyamides, and acrylate polymers, and preferably, specifically, polyethylene oxide (PEO), N-ethyl, Nylon 12 (N-12) [description of alkylated N-12 can be found in Shalaby et al.,
J. Polym. Sci.
-
Polym. Phys.Ed.,
11,939 (1973)], and polymethyl methacrylate (PMMA). Generally, the phosphonylation of the representative members of these groups of polymers occurs by bubbling oxygen through a polymer solution in PCl
3
with or without a non-reactive organic solvent. The resulting phosphonyldihalide-bea
Acquah Samuel A.
Gregory Leigh P.
Poly-Med, Inc.
LandOfFree
Phosphonylated derivatives of aliphatic heterochain and... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Phosphonylated derivatives of aliphatic heterochain and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Phosphonylated derivatives of aliphatic heterochain and... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2867213