Monolayer polymeric coatings for modifying metal oxide surfaces
The invention is directed to methods of modifying metal oxide or hydroxylated polymer surfaces using compositions of water soluble polymers that adsorb onto such surfaces and that contain functional groups which directly modify such surfaces without further processing. In some embodiments, compositions used in such methods include water-soluble oxide-adsorbing polymers having water solubility in an indicated temperature range, an indicated concentration in the aqueous solution, and a molecular weight range, wherein each of the water-soluble oxide-adsorbing polymers comprises a linear copolymer comprising a first monomer having at least one hydrophilic moiety and a second monomer having at least one lipophilic moiety and wherein a first monomer: second monomer molecular ratio is at least 3:1.
1. A method of disposing a polymeric monolayer on a metal oxide or hydroxylated polymer surface, the method comprising contacting an aqueous or organic-aqueous solution containing one or more water-soluble oxide-adsorbing polymers having (i) water solubility in a temperature range between about 20° C. and about 50° C., (ii) a concentration in the aqueous solution in a range between about 0.001% and about 10% weight/volume, (iii) a molecular weight in the range between about 5×10 3 and about 1×10 6 daltons; wherein each of the water-soluble oxide-adsorbing polymers comprises a linear copolymer comprising a first monomer having at least one hydrophilic moiety and a second monomer having at least one protected functionality and wherein a first monomer:second monomer molecular ratio is at least 3:1.
2. The method of claim 1 wherein said first monomer is a (N,N-dialkyl)acrylamide or a vinylpyrrolidone.
3. The method of claim 1 wherein said at least one protected functionality comprises a protected amino, a protected carboxyl, a protected thiol, a protected carbonyl, a protected hydroxyl, or a protected phosphoryl.
4. The method of claim 1 further comprising the steps of deprotecting said protected functionality and reacting the deprotected functionality with a complementary functionality of a surface modifying moiety.
5. The method of claim 4 wherein said surface-modifying moiety is a lipophilic moiety.
6. The method of claim 1 wherein said hydrophilic moiety is the same or different and is selected from the group consisting of C1 to C3 alkyl; halo-substituted C1 to C3 alkyl; methoxy-substituted C1 to C3 alkyl; and hydroxyl-substituted C1 to C3 alkyl.
7. A method of disposing a polymeric monolayer on a metal oxide or hydroxylated polymer surface, the method comprising contacting such surface with an aqueous or an organic-aqueous solution containing one or more water-soluble oxide-adsorbing polymers having (i) water solubility in a temperature range between about 20° C. and about 50° C., (ii) a concentration in the aqueous solution in a range between about 0.001% and about 10% weight/volume, (iii) a molecular weight in the range between about 5×10 3 and about 1×10 6 daltons; wherein each of the water-soluble oxide-adsorbing polymers comprises a linear copolymer comprising a first monomer having at least one hydrophilic moiety and a second monomer having at least one surface-modifying moiety and wherein a first monomer:second monomer molecular ratio is at least 3:1.
8. The method of claim 7 wherein said surface-modifying moiety is a lipophilic moiety.
9. The method of claim 8 wherein said lipophilic moiety may be the same or different and is selected from the group consisting of C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alky, C17 alkyl, C18 alkyl, C19 alkyl, and C20 alkyl.
10. The method of claim 7 wherein said first monomer is a (N,N-dialkyl)acrylamide or a vinylpyrrolidone.
11. A method of disposing a lipophilic coating on a metal oxide or hydroxylated polymer surface, the method comprising contacting such surface with an aqueous or an organic-aqueous solution containing one or more water-soluble oxide-adsorbing polymers having (i) water solubility in a temperature range between about 20° C. and about 50° C., (ii) a concentration in the aqueous solution in a range between about 0.001% and about 10% weight/volume, (iii) a molecular weight in the range between about 5×10 3 and about 1×10 6 daltons; wherein each of the water-soluble oxide-adsorbing polymers comprises a linear copolymer comprising a first monomer having at least one hydrophilic moiety and a second monomer having at least one lipophilic moiety and wherein a first monomer: second monomer molecular ratio is at least 3:1.
12. The method of claim 11 wherein said first monomer is a (N,N-dialkyl)acrylamide or a vinylpyrrolidone.
13. A method of coating a metal oxide or hydroxylated polymer surface with a surface-modifying group, the method comprising the steps of:
forming a polymer composition comprising water-soluble oxide-adsorbing polymers each comprising a linear copolymer comprising a first monomer having at least one hydrophilic moiety and a second monomer having at least one protected functionality, wherein each water-soluble oxide-adsorbing polymer of the composition has a first monomer:second monomer molecular ratio of at least 3:1;
activating the protected functionalities of the linear copolymer to form reactive functionalities;
reacting a surface-modifying group with the reactive functionalities to form a surface-modifying polymer composition which has (i) water solubility in a temperature range between about 20° C. and about 50° C.; (ii) a concentration in the aqueous solution in a range between about 0.001% and about 10% weight/volume; and (iii) a molecular weight in the range between about 5×10 3 and about 1×10 6 daltons; and
exposing in an aqueous or an organic-aqueous solution the metal oxide or hydroxylated polymer surface to the surface-modifying polymer composition.
14. The method of claim 13 wherein said first monomer is a (N,N-dialkyl)acrylamide or a vinylpyrrolidone.
15. The method of claim 13 wherein said surface-modifying group is C12 to C20 alkyl.
16. The method of claim 13 wherein said hydrophilic moiety is the same or different and is selected from the group consisting of C1 to C3 alkyl; halo-substituted C1 to C3 alkyl; methoxy-substituted C1 to C3 alkyl; and hydroxyl-substituted C1 to C3 alkyl.