# US 11,028,210 B2 · Core-shell flow improver

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- Number: US 11,028,210 B2
- Document ID: US11028210B2
- Status: Granted
- Kind: B2
- Application number: 15/210,918
- Filed: 2016-07-15
- Published: 2016-11-10
- Granted: 2021-06-08
- Earliest claimed: 2008-02-14
- Assignees: Liquidpower Specialty Products Inc.
- Applicants: Liquidpower Specialty Products Inc.
- Inventors: Wayne R. Dreher; Kenneth W. Smith; Stuart N. Milligan; Timothy L. Burden; William F. Harris; Ray L. Johnston; Wolfgang Klesse; Gerold Schmitt; John Wey
- Web page: https://patentgrep.com/patent/US11028210B2

## CPC

- C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof
- C08F 2/002: {Scale prevention in a polymerisation reactor or its auxiliary parts}
- C08F 2/22: Emulsion polymerisation
- C08F 265/04: on to polymers of esters
- C08L 51/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C08L51/04, C08L51/06 take precedence)}
- F17D 1/17: by mixing with another liquid {, i.e. diluting}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- F17D: PIPE-LINE SYSTEMS; PIPE-LINES (pumps or compressors F04; fluid dynamics F15D; valves or the like F16K; pipes, laying pipes, supports, joints, branches, repairing, work on the entire line, accessories F16L; steam traps or the like F16T; fluid-pressure electric cables H01B9/06)

## Abstract

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.

## Claims

### Claim 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.

### Claim 2 (depends on 1)

The flow improver of claim 1, wherein said hydrophobic compound is selected from the group consisting of:
wherein R1 is H or a C1-C10 alkyl radical, and R2 is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, an aryl-substituted C1-C10 alkyl radical, a —(CH2CH2O)x—RA or —(CH2CH(CH3)O)x—RA radical wherein x is in the range of from 1 to 50 and RA is H, a C1-C30 alkyl radical, or a C6-C30 alkylaryl radical;
R3-arene-R4 (B)
wherein arene is a phenyl, naphthyl, anthracenyl, or phenanthrenyl, R3 is CH═CH2 or CH3—C═CH2, and R4 is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, Cl, SO3, ORB, or COOR.sub.C, wherein RB is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, or an aryl-substituted C1-C10 alkyl radical, and wherein Rc is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, or an aryl-substituted C1-C10 alkyl radical;
wherein R5 is H, a C1-C30 alkyl radical, or a C6-C20 substituted or unsubstituted aryl radical;
wherein R6 is H, a C1-C30 alkyl radical, or a C.sub.6-C.sub.20 substituted or unsubstituted aryl radical;
wherein R7 is H or a C1-C18 alkyl radical, and R8 is H, a C1-C18 alkyl radical, or Cl;
wherein R9 and R10 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R11 and R12 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R13 and R14 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R15 is H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R16 is H, a C1-C30 alkyl radical, or a C6-C20 aryl radical;
wherein R17 and R18 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalky radical, or heterocyclic radicals; and
wherein R10 and R20 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 3)

The flow improver of claim 3, wherein said hydrophobic compound comprises an acrylate and/or methacrylate.

### Claim 5 (depends on 1)

The flow improver of claim 1, wherein said first amphiphilic compound is polyethylene glycol methacrylate and/or said hydrophobic compound is 2-ethylhexyl methacrylate.

### Claim 6 (depends on 1)

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.

### Claim 7 (depends on 1)

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.

### Claim 8 (depends on 1)

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.

### Claim 9 (depends on 1)

The flow improver of claim 1, wherein said hydrophobic compound is selected from the group consisting of:
wherein R16 is H, a C1-C30 alkyl radical, or a C6-C20 aryl radical;
wherein R17 and R18 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalky radical, or heterocyclic radicals; and
wherein R10 and R20 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.

### Claim 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.

### Claim 11 (depends on 10)

The flow improver of claim 10, wherein said hydrophobic monomer is a methacrylate or acrylate monomer.

### Claim 12 (depends on 10)

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.

### Claim 13 (depends on 10)

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.

### Claim 14 (depends on 10)

The flow improver of claim 10, wherein said hydrophobic compound is selected from the group consisting of:
wherein R1 is H or a C1-C10 alkyl radical, and R2 is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, an aryl-substituted C1-C10 alkyl radical, a —(CH2CH2O)x—RA or —(CH2CH(CH3)O)x—RA radical wherein x is in the range of from 1 to 50 and RA is H, a C1-C30 alkyl radical, or a C6-C30 alkylaryl radical;
R3-arene-R4 (B)
wherein arene is a phenyl, naphthyl, anthracenyl, or phenanthrenyl, R3 is CH═CH2 or CH3—C═CH2, and R4 is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, Cl, SO3, ORB, or COOR.sub.C, wherein RB is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, or an aryl-substituted C1-C10 alkyl radical, and wherein Rc is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, or an aryl-substituted C1-C10 alkyl radical;
wherein R5 is H, a C1-C30 alkyl radical, or a C6-C20 substituted or unsubstituted aryl radical;
wherein R6 is H, a C1-C30 alkyl radical, or a C.sub.6-C.sub.20 substituted or unsubstituted aryl radical;
wherein R7 is H or a C1-C18 alkyl radical, and R8 is H, a C1-C18 alkyl radical, or Cl;
wherein R9 and R10 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R11 and R12 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R13 and R14 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals; and
wherein R15 is H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.

### Claim 15 (depends on 10)

The flow improver of claim 10, wherein said hydrophobic compound is selected from the group consisting of:
wherein R16 is H, a C1-C30 alkyl radical, or a C6-C20 aryl radical;
wherein R17 and R18 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalky radical, or heterocyclic radicals; and
wherein R10 and R20 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.

### Claim 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.

### Claim 17 (depends on 16)

The flow improver of claim 16, wherein said hydrophobic compound is selected from the group consisting of:
wherein R1 is H or a C1-C10 alkyl radical, and R2 is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, an aryl-substituted C1-C10 alkyl radical, a —(CH2CH2O)x—RA or —(CH2CH(CH3)O)x—RA radical wherein x is in the range of from 1 to 50 and RA is H, a C1-C30 alkyl radical, or a C6-C30 alkylaryl radical;
R3-arene-R4 (B)
wherein arene is a phenyl, naphthyl, anthracenyl, or phenanthrenyl, R3 is CH═CH2 or CH3—C═CH2, and R4 is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, Cl, SO3, ORB, or COOR.sub.C, wherein RB is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, or an aryl-substituted C1-C10 alkyl radical, and wherein Rc is H, a C1-C30 alkyl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, a C6-C20 substituted or unsubstituted aryl radical, or an aryl-substituted C1-C10 alkyl radical;
wherein R5 is H, a C1-C30 alkyl radical, or a C6-C20 substituted or unsubstituted aryl radical;
wherein R6 is H, a C1-C30 alkyl radical, or a C.sub.6-C.sub.20 substituted or unsubstituted aryl radical;
wherein R7 is H or a C1-C18 alkyl radical, and R8 is H, a C1-C18 alkyl radical, or Cl;
wherein R9 and R10 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R11 and R12 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals;
wherein R13 and R14 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals; and
wherein R15 is H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.

### Claim 18 (depends on 16)

The flow improver of claim 16, wherein said hydrophobic compound is selected from the group consisting of:
wherein R16 is H, a C1-C30 alkyl radical, or a C6−C20 aryl radical;
wherein R17 and R18 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalky radical, or heterocyclic radicals; and
wherein R19 and R20 are independently H, a C1-C30 alkyl radical, a C6-C20 substituted or unsubstituted aryl radical, a C5-C30 substituted or unsubstituted cycloalkyl radical, or heterocyclic radicals.

### Claim 19 (depends on 16)

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.

### Claim 20 (depends on 16)

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.