IP Library Granted Patent US 11,649,400
Granted Patent B2
US 11,649,400 · App. 17/284,393 · Granted May 16, 2023

Polymer dispersion by controlled radical polymerization

Inventors: Zhenxing Cheng (Shanghai, CN); Zhihua Zhang (Singapore, SG); Man Chen (Shanghai, CN); Chee Fei Chin (Singapore, SG); David James Wilson (Coye la Foret, FR)
Assignee: ENERGY SOLUTIONS (US) LLC
C09K8/887C09K8/588C09K2208/28
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Quick Facts
Patent No.
US 11,649,400
App. No.
17/284,393
Granted
May 16, 2023
Kind
B2
Abstract

A polymer dispersion may include a water soluble copolymer, a water soluble salt, a polyol, and water. A method of preparing a polymer dispersion may include controlled radical polymerization. A method of using the polymer dispersion as a friction reducer in oil field processes.

Claims (71)

1. A fracturing fluid, comprising:

a polymer dispersion comprising:

a) 2 to 30 weight percentage of a water soluble copolymer;

b) 10 to 50 weight percentage of a water soluble salt;

c) 0 to 5 weight percentage of a polyol; and

d) water;

weight percentages are based on total weight of the polymer dispersion;

wherein the polymer dispersion is added to a fracturing fluid in an amount of between 100 to 2500 ppm based on the fracturing fluid,

wherein said water soluble copolymer is obtained by a process comprising steps of:

(A) an ionic charged polymeric dispersant is prepared from at least an ionic monomer in a presence of a radical polymerization control agent to obtain a living polymer,

(B) said living polymer is charged into an aqueous solution comprising a

nonionic monomer, and optionally an ionic monomer, a mixture of the living polymer and the aqueous solution is then subject to continuous polymerization to obtain said copolymer,

wherein said water soluble copolymer comprises (i) a block of an ionic charged polymeric dispersant at one terminal; and (ii) a block of a nonionic monomer, and

wherein the water soluble copolymer comprises 10 to 15 weight percentage of the block of the ionic charged polymeric dispersant.

2. The fracturing fluid according to claim 1 , wherein said radical polymerization control agent is a compound bearing a thiocarbonylthio group —S(C═S).

3. The fracturing fluid according to claim 1 , wherein said radical polymerization control agent is according to general formula (I):

wherein: Z represents:

a hydrogen atom,

a chlorine atom,

a alkyl or aryl radical,

a heterocycle,

a alkylthio radical,

a arylthio radical,

a alkoxy radical,

a aryloxy radical,

a amino radical,

a hydrazine radical,

a alkoxycarbonyl radical,

a aryloxycarbonyl radical,

a carboxyl or acyloxyl radical,

a aryloxy radical,

a carbamoyl radical,

a cyano radical,

a dialkyl- or diaryl-phosphonato radical,

a dialkyl-phosphinato or diaryl-phosphinato radical, or

a polymer chain;

and R1 represents:

an alkyl, acyl, aryl, aralkyl, alkene or alkyne group,

a saturated or unsaturated, aromatic, carbocycle or

heterocycle, or

a polymer chain.

4. The fracturing fluid according to claim 1 , wherein said radical polymerization control agent is a compound chosen from the group consisting of xanthate, trithiocarbonate, dithiocarbamate and dithiocarbazate.

5. A fracturing fluid, comprising:

a polymer dispersion comprising:

a) 2 to 30 weight percentage of a water soluble copolymer;

b) 10 to 50 weight percentage of a water soluble salt;

c) 0 to 5 weight percentage of a polyol; and

d) water;

weight percentages are based on total weight of the polymer dispersion;

wherein the polymer dispersion is added to a fracturing fluid in an amount of between 100 to 2500 ppm based on the fracturing fluid,

wherein said water soluble copolymer comprises (i) a block of an ionic charged polymeric dispersant at one terminal; and (ii) a block of a nonionic monomer, optionally containing an ionic monomer, and

wherein the water soluble copolymer comprises 10 to 15 weight percentage of the block of the ionic charged polymeric dispersant.

6. The fracturing fluid according to claim 5 , wherein said ionic charged polymeric dispersant is an anionic charged polymeric dispersant prepared from at least an anionic monomer according to general formula (II):

wherein:

R 3 is a hydrogen or a C 1 to C 5 alkyl or hydroxyalkyl;

R 4 and R 5 , independently, is a hydrogen or a C 1 to C 5 alkyl or hydroxyalkyl.

7. The fracturing fluid according to claim 5 , wherein said nonionic monomer is according to general formula (III):

wherein:

R 3 is a hydrogen or a C 1 to C 5 alkyl or hydroxyalkyl;

R 4 and R 5 , independently, is a hydrogen or a C 1 to C 5 alkyl or hydroxyalkyl.

8. A method for reducing friction resulting from turbulent flow in an aqueous fracturing fluid in an oil field fracturing process comprising adding to the aqueous fracturing fluid an effective friction-reducing amount of the polymer dispersion according to claim 1 .

9. A method for reducing friction resulting from turbulent flow in an aqueous fracturing fluid in an oil field fracturing process comprising adding to the aqueous fracturing fluid an effective friction-reducing amount of the polymer dispersion according to claim 5 .

10. The method according to claim 9 , wherein said ionic charged polymeric dispersant is an anionic charged polymeric dispersant prepared from at least an anionic monomer according to general formula (II):

wherein:

R 2 is a hydrogen or a C 1 to C 5 alkyl or hydroxyalkyl;

M is hydrogen, an alkali metal ion, or NH 4 + , or NR 4 + wherein R is a C 1 to C 5 alkyl or hydroxyalkyl.

11. The method according to claim 9 , wherein said nonionic monomer is according to general formula (III):

wherein:

R 3 is a hydrogen or a C 1 to C 5 alkyl or hydroxyalkyl;

R 4 and R 5 , independently, is a hydrogen or a C 1 to C 5 alkyl or hydroxyalkyl.

12. The method according to claim 8 , wherein said polymer dispersion is added to said aqueous fracturing fluid in an amount of from 100 to 2500 ppm.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 23, 2023
From: RHODIA OPERATIONS
To: ENERGY SOLUTIONS (US) LLC
Reel/Frame 063149/0540 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 1, 2021
From: CHEN, MAN
To: RHODIA OPERATIONS
Reel/Frame 057361/0163 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 28, 2021
From: CHENG, ZHENXING; ZHANG, ZHIHUA; CHIN, CHEE FEI; WILSON, DAVID JAMES
To: RHODIA OPERATIONS
Reel/Frame 056691/0866 →
Continuity (1)
Related Publication 20210340436A1 · Nov 4, 2021