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 flow improver comprising:
solid particles each having a polymeric core and a polymeric shell at least partly surrounding said polymeric core,
wherein said polymeric core comprises a drag reducing polymer, wherein said polymeric shell comprises a shell copolymer having repeat units of a hydrophobic compound and repeat units of a first amphiphilic compound,
wherein an amount of said repeat units of the hydrophobic compound ranges from about 25 to about 98 weight percent of said shell copolymer, and
wherein said polymeric core and said polymeric shell are formed by emulsion polymerization, and said solid particles have a mean particle size of less than 1000 nm.
2. The flow improver of claim 1 , wherein said hydrophobic compound 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;
R 3 -arene-R 4 (B)
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.sub.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.sub.6-C.sub.20 substituted or unsubstituted aryl radical;
wherein R 7 is H or a C 1 -C 18 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;
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;
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 cycloalky radical, or heterocyclic radicals; and
wherein R 10 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.
3. The flow improver of claim 1 , wherein said first amphiphilic compound is a polymerizable surfactant, wherein a weight ratio of repeat units of said hydrophobic compound to repeat units of said first amphiphilic compound in said shell copolymer is in the range of from about 0.5:1 to about 40:1.
4. The flow improver of claim 3 , wherein said hydrophobic compound comprises an acrylate and/or methacrylate.
5. The flow improver of claim 1 , wherein said first amphiphilic compound is polyethylene glycol methacrylate and/or said hydrophobic compound is 2-ethylhexyl methacrylate.
6. The flow improver of claim 1 , wherein said shell copolymer further comprises repeat units of a second amphiphilic compound, wherein said first amphiphilic compound is a non-ionic polymerizable surfactant and said second amphiphilic compound is an ionic polymerizable surfactant, wherein a weight ratio of repeat units of said first amphiphilic compound to repeat units of said second amphiphilic compound in said shell copolymer is in the range of from about 0.25:1 to about 30:1.
7. The flow improver of claim 1 , wherein at least 90 weight percent of said solid particles have a particle size greater than 25 nanometers and at least 90 weight percent of said solid particles have a particle size less than 500 nanometers, wherein the average thickness of said shell is in the range of from about 0.1 to about 20 percent of the average particle diameter of said solid particles.
8. The flow improver of claim 1 , wherein said flow improver is in the form of a latex comprising said solid particles dispersed in a liquid continuous phase, wherein said latex comprises said solid particles in an amount in the range of from about 10 to about 60 weight percent.
9. The flow improver of claim 1 , wherein said hydrophobic compound 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 cycloalky radical, or heterocyclic radicals; and
wherein R 10 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.
10. A latex flow improver comprising:
an aqueous continuous phase and a plurality of polymeric particles dispersed in said continuous phase,
wherein said at least one of said plurality of polymeric particles comprises a core and a shell at least partly surrounding said core,
wherein said core comprises a drag reducing polymer formed by polymerization,
wherein said shell is formed around said core by emulsion polymerizing at least one hydrophobic monomer and at least one polymerizable surfactant in the presence of said core,
wherein said solid particles have a mean particle size of less than 10 microns, and
wherein said shell comprises repeat units of a monomer in an amount in the range of from about 25 to about 98 weight percent.
11. The flow improver of claim 10 , wherein said hydrophobic monomer is a methacrylate or acrylate monomer.
12. The flow improver of claim 10 , wherein said emulsion polymerization carried out to form said shell includes the use of a first non-ionic polymerizable surfactant and a second ionic polymerizable surfactant, wherein said shell comprises repeat units of said first polymerizable surfactant in an amount in the range of from about 2 to about 50 weight percent and repeat units of said second polymerizable surfactant in an amount in the range of from about 0.05 to about 30 weight percent.
13. The flow improver of claim 10 , wherein said plurality of polymeric particles have a mean particle size less than about 1 micron, wherein the average thickness of said shell is in the range of from about 0.5 to about 30 nanometers.
14. The flow improver of claim 10 , wherein said hydrophobic compound 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;
R 3 -arene-R 4 (B)
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.sub.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.sub.6-C.sub.20 substituted or unsubstituted aryl radical;
wherein R 7 is H or a C 1 -C 18 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.
15. The flow improver of claim 10 , wherein said hydrophobic compound 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 cycloalky radical, or heterocyclic radicals; and
wherein R 10 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.
16. A flow improver comprising:
a polymeric core comprising a drag reducing polymer; and
a polymeric shell at least partly surrounding said polymeric core, wherein said polymeric shell comprises a shell copolymer having repeat units of a hydrophobic compound and repeat units of a first amphiphilic compound.
17. The flow improver of claim 16 , wherein said hydrophobic compound 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;
R 3 -arene-R 4 (B)
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.sub.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.sub.6-C.sub.20 substituted or unsubstituted aryl radical;
wherein R 7 is H or a C 1 -C 18 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.
18. The flow improver of claim 16 , wherein said hydrophobic compound 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 cycloalky 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.
19. The flow improver of claim 16 , wherein said first amphiphilic compound is a polymerizable surfactant, wherein a weight ratio of repeat units of said hydrophobic compound to repeat units of said first amphiphilic compound in said shell copolymer is in the range of from about 0.5:1 to about 40:1.
20. The flow improver of claim 16 , wherein said shell copolymer further comprises repeat units of a second amphiphilic compound, wherein said first amphiphilic compound is a non-ionic polymerizable surfactant and said second amphiphilic compound is an ionic polymerizable surfactant, wherein a weight ratio of repeat units of said first amphiphilic compound to repeat units of said second amphiphilic compound in said shell copolymer is in the range of from about 0.25:1 to about 30:1.