Encapsulated activator and its use to trigger a gelling system by physical means

Patent metadata

Field	Value
Publication number	US-9499719-B2
Application number	US-201214004304-A
Country	US
Kind code	B2
Filing date	Mar 8, 2012
Priority date	Mar 11, 2011
Publication date	Nov 22, 2016
Grant date	Nov 22, 2016

Abstract

A process allowing the encapsulation of a polymerization accelerator comprising the steps of: a) providing an reverse emulsion containing, in an oil phase, a water solution/dispersion containing the polymerization activator, the oil phase including a heat curable mixture of an isocyanate and a polyalkyldiene hydroxylated or polyol, b) pouring the reverse emulsion in a water phase to make a multiple emulsion water/oil/water, containing drops of activators as the internal water phase, and then, c) heating the multiple emulsion obtained in step b) at a temperature of between 50 and 95° C., in order to cure the polyisocyanate in polyurethane and obtain drops of activator enclosed in shells of polyurethane dispersed in water.
The invention also relates to aqueous gelling systems comprising the encapsulated polymerization accelerator with water soluble or dispersable monomers and a polymerization initiator dispersed in said monomers, useful i.a. for sealing subterranean environments or consolidation of a soil or sealing of a subterranean structure.

First claim

The invention claimed is:

1. A process for the encapsulation of a polymerization accelerator of water soluble or water dispersable monomers, said process comprising the steps of:
a) providing a reverse emulsion containing, in an oil phase, a water solution or dispersion (W1) containing said polymerisation accelerator, the oil phase including a heat curable mixture of an isocyanate and a hydroxylated polyalkyldiene or polyol,
b) pouring the reverse emulsion of step a) in a water phase (W2) to make a water/oil/water multiple emulsion, containing drops of the water solution or dispersion comprising the accelerator as the internal water phase and, then,
c) heating the multiple emulsion obtained in step b) at a temperature of between 50 and 95° C., to cure the mixture of isocyanate and hydroxylated polyalkyldiene or polyol to obtain polyurethane and enclose the drops of the water solution or dispersion comprising the accelerator in shells of the polyurethane dispersed in water,
wherein the shells of polyurethane have an average diameter between 300 and 1500 μm.

2. The process of claim 1 , wherein in step a) a solvent or plasticizer is added to the oil phase.

3. The process of claim 2 , wherein the solvent or plasticizer is di-isobutyl ester of succinate, glutarate or adipate.

4. The process of claim 1 , wherein, in step a), a non-ionic surfactant is added to the water wherein said polymerisation accelerator is dispersed or in solution.

5. The process of claim 4 , wherein said non-ionic surfactant is a diC 1 -C 8 alkyl ester of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms.

6. The process of claim 1 , wherein the water phase of step b) contains a mineral salt.

7. The process of claim 1 , wherein the polymerisation accelerator is an alkylamine, polyalkyleneamine, or polyalkylenimine.

8. The process of claim 1 , wherein the hydroxylated polyalkyldiene or polyol is a hydroxylated polybutadiene.

9. The process as claimed in claim 1 , wherein the isocyanate is a trimer form of alpha, omega hexyldiisocynate.

10. The process of claim 9 , wherein the polymerisation accelerator is a polyethyleneimine (PEI).

11. The process of claim 1 , further comprising encapsulating a polymerization initiator with the polymerization accelerator, wherein the polymerization initiator is selected from the group consisting of water soluble persalts and/or peroxides.

12. The process of claim 1 , further comprising encapsulating a polymerization initiator with the polymerization accelerator.

13. The process of claim 1 , wherein the polymerisation accelerator is an alkylamine, polyalkyleneamine or polyalkylenimine comprising tertiary amino groups and whose alkyl or alkylen part comprises 2-4 carbon atoms.

14. The process as claimed in claim 1 , wherein the isocyanate is alpha, omega alkyldiisocynate.

15. The process as claimed in claim 1 , wherein the shells of polyurethane have an average diameter between 300 and 800 μm.

16. A process for the encapsulation of a polymerization accelerator of water soluble or water dispersable monomers, said process comprising the steps of:
a) providing a reverse emulsion containing, in an oil phase, a water solution or dispersion (W1) containing said polymerisation accelerator, the oil phase including a heat curable mixture of an isocyanate and a hydroxylated polyalkyldiene or polyol,
b) pouring the reverse emulsion of step a) in a water phase (W2) to make a water/oil/water multiple emulsion, containing drops of the water solution or dispersion comprising the accelerator as the internal water phase and, then,
c) heating the multiple emulsion obtained in step b) at a temperature of between 50 and 95° C., to cure the mixture of isocyanate and hydroxylated polyalkyldiene or polyol to obtain polyurethane and enclose the drops of the water solution or dispersion comprising the accelerator in shells of the polyurethane dispersed in water,
wherein, in step a), a non-ionic surfactant is added to the water wherein said polymerisation accelerator is dispersed or in solution, wherein said non-ionic surfactant is a diC 1 -C 8 alkyl ester of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms.

17. The process of claim 16 , wherein the polymerisation accelerator is an alkylamine, polyalkyleneamine or polyalkylenimine comprising tertiary amino groups and whose alkyl or alkylen part comprises 2-4 carbon atoms.

18. A process for the encapsulation of a polymerization accelerator of water soluble or water dispersable monomers, said process comprising the steps of:
a) providing a reverse emulsion containing, in an oil phase, a water solution or dispersion (W1) containing said polymerisation accelerator, the oil phase including a heat curable mixture of an isocyanate and a hydroxylated polyalkyldiene or polyol,
b) pouring the reverse emulsion of step a) in a water phase (W2) to make a water/oil/water multiple emulsion, containing drops of the water solution or dispersion comprising the accelerator as the internal water phase and, then,
c) heating the multiple emulsion obtained in step b) at a temperature of between 50 and 95° C., to cure the mixture of isocyanate and hydroxylated polyalkyldiene or polyol to obtain polyurethane and enclose the drops of the water solution or dispersion comprising the accelerator in shells of the polyurethane dispersed in water,
wherein the polymerisation accelerator is a polyethyleneimine (PEI).

19. A process for the encapsulation of a polymerization accelerator of water soluble or water dispersable monomers, said process comprising the steps of:
a) providing a reverse emulsion containing, in an oil phase, a water solution or dispersion (W1) containing said polymerisation accelerator, the oil phase including a heat curable mixture of an isocyanate and a hydroxylated polyalkyldiene or polyol,
b) pouring the reverse emulsion of step a) in a water phase (W2) to make a water/oil/water multiple emulsion, containing drops of the water solution or dispersion comprising the accelerator as the internal water phase and, then,
c) heating the multiple emulsion obtained in step b) at a temperature of between 50 and 95° C., to cure the mixture of isocyanate and hydroxylated polyalkyldiene or polyol to obtain polyurethane and enclose the drops of the water solution or dispersion comprising the accelerator in shells of the polyurethane dispersed in water,
further comprising encapsulating a polymerization initiator with the polymerization accelerator, wherein the polymerization initiator is selected from the group consisting of water soluble persalts and/or peroxides.

20. The process of claim 19 , wherein the polymerisation accelerator is an alkylamine, polyalkyleneamine or polyalkylenimine comprising tertiary amino groups and whose alkyl or alkylen part comprises 2-4 carbon atoms.

Assignees

• Cadix Arnaud
• Rached Rabih
• Ardaud Pierre
• Rhodia Operations

Inventors

• Cadix Arnaud
• Rached Rabih
• Ardaud Pierre

Classifications

• F16L55/1645

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• C09K2208/14

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• E21B33/138

  Plastering the borehole wall; Injecting into the formation · CPC title

• C08G18/6423

  Polyalkylene polyamines; polyethylenimines; Derivatives thereof (polyamides or polyesteramides C08G18/60) · CPC title

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title