Method of Altering the Wettability of a Subterranean Surface to Enhance Protection of Hydrocarbons

A method of imparting hydrophobicity and/or oleophobicity to a surface of a subterranean formation penetrated by a well during production of hydrocarbons from the subterranean formation comprising:

• (a) pumping into the well hydroxy containing nanoparticles surface modified with a surface modifying wettability agent and a difunctional linking agent containing a blocking moiety, —OB, wherein B is independently selected from C1-C20 branched or unbranched alkyl or aryl group and further wherein the surface modifying wettability agent is of the structure:
• ZmX(OR)n (II)
• wherein:
• X is an anchor selected from the group consisting of aluminum, silicon and a transition metal;
• each Z is a hydrophobic and/or oleophobic moiety attached to the anchor, the moiety comprising a substantially non-branched fluorinated monomer of a member selected from the group consisting of a C3-C40 alkyl, C3-C40 aryl, C3-C40 fluorinated alkyl, C3-C40 fluorinated aryl, C3-C40 fluorinated ethylenically unsaturated monomer and perfluoroalkylene ether;
• each R is independently selected from a C1-C20 branched or unbranched alkyl or aryl group;
• and
• m+n is defined by the valence state of the anchor provided neither m nor n are zero;
• (b) aligning the hydroxy containing nanoparticles to the surface of the subterranean formation such that the hydrophobic and/or oleophobic moiety is directed away from the surface of the formation;
• and
• (c) forming a condensation reaction product directly or indirectly onto the surface of the formation from the one or more blocking moieties and a hydroxy group on the surface of the formation.

A method of imparting hydrophobicity and/or oleophobicity to a surface of a subterranean formation penetrated by a well during production of hydrocarbons from the subterranean formation comprising:

• (a) pumping into the well a (i) difunctional linking agent having a blocking moiety, —OB, at one terminal end and a —OH, —COOH or amino group at the other terminal end;
• and (ii) hydroxy containing nanoparticles altered with a surface modifying wettability agent of the structure:
• ZmX(OR)n (II)
• wherein:
• X is an anchor selected from the group consisting of aluminum, silicon and a transition metal;
• Each Z is independently selected from a hydrophobic and/or oleophobic moiety attached to the anchor, the moiety comprising the hydrophobic and/or oleophobic functional group independently selected from the group consisting of a C3-C40 alkyl, C3-C40 aryl, C3-C40 fluorinated alkyl, C3-C40 fluorinated aryl, C3-C40 fluorinated ethylenically unsaturated monomer and perfluoroalkylene ether;
• each R and B are independently selected from C1-C20 branched or unbranched alkyl or aryl group;
• and
• m+n is defined by the valence state of the anchor provided neither m nor n are zero;
• (b) forming a condensation product between the —OB of the difunctional linking agent and a free hydroxy group on the surface of the formation;
• and
• (c) forming a condensation product with the terminal end of the difunctional linking agent and a hydroxy group attached to the surface of the formation.