Core-shell flow improver
A flow improver comprising a plurality of core-shell particles that can be formed by emulsion polymerization. The core of the core-shell particles can include a drag reducing polymer, while the shell of the particles can include repeat units of a hydrophobic compound and an amphiphilic compound. The flow improver can demonstrate increased pumping stability over conventionally prepared latex flow improvers.
1. A process for making a flow improver comprising:
(a) forming a plurality of core particles of a drag reducing polymer by emulsion polymerization, the drag reducing polymer having a weight average molecular weight (M w ) of at least about 5×10 6 g/mol; and
(b) forming a shell around each of the plurality of core particles by emulsion polymerization to thereby produce a plurality of core-shell particles,
wherein the forming of (b) comprises polymerizing one or more shell-forming monomers and at least one polymerizable surfactant so the shell comprises repeat units of the one or more shell-forming monomers and repeat units of the at least one polymerizable surfactant,
wherein a weight ratio of repeat units of the one or more shell-forming monomers and repeat units of the at least one polymerizable surfactant in the shell is in a range of from about 0.5:1 to about 40:1.
2. The process of claim 1 , wherein the emulsion polymerization of (a) is carried out in a first reaction mixture comprising a first liquid continuous phase, wherein the emulsion polymerization of (b) is carried out in a second reaction mixture comprising a second liquid continuous phase and at least a portion of the core particles, wherein the second liquid continuous phase comprises at least a portion of the first liquid continuous phase.
3. The process of claim 2 , wherein the second liquid continuous phase comprises substantially all of the first liquid continuous phase.
4. The process of claim 1 , wherein the one or more shell-forming monomers comprise an acrylate monomer, a methacrylate monomer, or a combination thereof.
5. The process of claim 1 , wherein the one or more shell-forming monomers and the at least one polymerizable surfactant do not chemically react with the core particles during the forming of (b).
6. A process for making a flow improver, comprising:
(a) forming a plurality of core particles of a drag reducing polymer by emulsion polymerization; and
(b) forming polymeric shells around at least a portion of the core particles by emulsion polymerization to thereby produce a plurality of core-shell particles,
wherein the polymeric shell is formed around the core particle by emulsion polymerizing at least one hydrophobic monomer and at least one polymerizable surfactant in the presence of the core particle,
wherein the emulsion polymerization carried out to form the polymeric shells comprises using a first non-ionic polymerizable surfactant and a second ionic polymerizable surfactant, wherein the polymeric shells comprise repeat units of the first non-ionic polymerizable surfactant in an amount in the range of from about 2 to about 50 weight percent and repeat units of the second ionic polymerizable surfactant in an amount in the range of from about 0.05 to about 30 weight percent,
wherein the core-shell particles have a mean particle size of less than 10 microns, and
wherein the polymeric shell comprises repeat units of the at least one hydrophobic monomer in an amount in the range of from about 25 to about 98 weight percent.
7. The process of claim 6 , wherein the at least one hydrophobic monomer is a methacrylate monomer, an acrylate monomer, or a combination thereof.
8. The process of claim 6 , wherein the plurality of core-shell particles have a mean particle size less than about 1 micron, wherein the average thickness of the polymeric shell is in the range of from about 0.5 to about 30 nanometers.
9. The process of claim 6 , wherein the at least one hydrophobic monomer is selected from the group consisting of:
wherein R 1 is H or a C 1 -C 10 alkyl radical, and R 2 is H, a C 1 -C 30 alkyl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, an aryl-substituted C 1 -C 10 alkyl radical, a —(CH 2 CH 2 O) x —R A or —(CH 2 CH(CH 3 )O) x —R A radical wherein x is in the range of from 1 to 50 and R A is H, a C 1 -C 30 alkyl radical, or a C 6 -C 30 alkylaryl radical;
(B) R 3 -arene-R 4
wherein arene is a phenyl, naphthyl, anthracenyl, or phenanthrenyl, R 3 is CH═CH 2 or CH 3 —C═CH 2 , and R 4 is H, a C 1 -C 30 alkyl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, Cl, SO 3 , OR B , or COOR C , wherein R B is H, a C 1 -C 30 alkyl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, or an aryl-substituted C 1 -C 10 alkyl radical, and wherein R c is H, a C 1 -C 30 alkyl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, or an aryl-substituted C 1 -C 10 alkyl radical;
wherein R 5 is H, a C 1 -C 30 alkyl radical, or a C 6 -C 20 substituted or unsubstituted aryl radical;
wherein R 6 is H, a C 1 -C 30 alkyl radical, or a C 6 -C 20 substituted or unsubstituted aryl radical;
wherein R 7 is H or a C 1 -C 1 alkyl radical, and R 8 is H, a C 1 -C 18 alkyl radical, or Cl;
wherein R 9 and R 10 are independently H, a C 1 -C 30 alkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R 11 and R 12 are independently H, a C 1 -C 30 alkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R 13 and R 14 are independently H, a C 1 -C 30 alkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals; and
wherein R 15 is H, a C 1 -C 30 alkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.
10. The process of claim 6 , wherein the at least one hydrophobic monomer is selected from the group consisting of:
wherein R 16 is H, a C 1 -C 30 alkyl radical, or a C 6 -C 20 aryl radical,
wherein R 17 and R 18 are independently H, a C 1 -C 30 alkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals; and
wherein R 19 and R 20 are independently H, a C 1 -C 30 alkyl radical, a C 6 -C 20 substituted or unsubstituted aryl radical, a C 5 -C 30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.
11. The process of claim 1 , wherein the one or more shell-forming monomers comprise repeat units of a hydrophobic monomer.
12. The process of claim 11 , wherein the repeat units of the at least one polymerizable surfactant comprise repeat units of a non-ionic polymerizable surfactant, an ionic polymerizable surfactant, or both.
13. The process of claim 12 , wherein a weight ratio of repeat units of the non-ionic polymerizable surfactant to repeat units of the ionic polymerizable surfactant in the shell is in the range of from about 0.25:1 to about 30:1.
14. The process of claim 11 , wherein the at least one polymerizable surfactant is polyethylene glycol methacrylate and/or the hydrophobic monomer is 2-ethylhexyl methacrylate.
15. A process for reducing pressure loss associated with turbulent flow of a fluid through a conduit, the process comprising:
using a pump to inject a flow improver formed by the process of claim 1 into the fluid flowing through the conduit.
16. A process for reducing pressure loss associated with turbulent flow of a fluid through a conduit, the process comprising:
using a pump to inject a flow improver formed by the process of claim 6 into the fluid flowing through the conduit.
17. A process for making a flow improver comprising:
(a) forming a plurality of core particles of a drag reducing polymer by emulsion polymerization; and
(b) forming shells around at least a portion of the core particles by emulsion polymerization to thereby produce a plurality of core-shell particles,
wherein the shells comprise repeat units of a hydrophobic monomer, a non-ionic polymerizable surfactant, and an ionic polymerizable surfactant, wherein the weight ratio of repeat units of the hydrophobic monomer to repeat units of the non-ionic polymerizable surfactant in the shells is in the range of from about 0.5:1 to about 40:1, wherein the weight ratio of repeat units of the non-ionic polymerizable surfactant to repeat units of the ionic polymerizable surfactant in the shells is in the range of from about 0.25:1 to about 30:1.