Expandable elastomeric material in the presence of water or oil

Patent metadata

Field	Value
Publication number	US-9303096-B2
Application number	US-79915310-A
Country	US
Kind code	B2
Filing date	Apr 20, 2010
Priority date	Apr 20, 2010
Publication date	Apr 5, 2016
Grant date	Apr 5, 2016

Abstract

A process for the preparation of an elastomer capable of swelling in oil and/or in water and brine comprising the steps of: a) making an aqueous inverse emulsion of particles of a polymer comprising a betaine group prepared by inverse emulsion polymerization of monomers A b comprising a betaine group, optionally other monomers B a and a small quantity of polyvalent, preferably divalent or trivalent monomers C a , comprised in an aqueous phase dispersed in the form of droplets in a hydrophobic external phase having hydrophobic surfactants, the molar ratio of the monomers A b to the optional monomers B a being between 4/96 and 40/60, preferably 7/93 and 30/70, the molar ratio of the polyvalent, preferably divalent or trivalent monomers C a per mole of polymer being between 1.5 and 10, preferably between 2 and 4, and b) compounding said elastomer with the aqueous inverse emulsion obtained by step a).

First claim

The invention claimed is:

1. A process for making an elastomer composition, comprising the steps of:
a) making an aqueous inverse emulsion of particles of a polymer by inverse emulsion polymerization of monomers A b comprising a betaine group, hydrophilic monomers B a , and polyvalent monomers C a , wherein the emulsion is in the form of droplets of an aqueous phase dispersed in a hydrophobic external phase, the hydrophobic external phase comprises hydrophobic surfactants, and the molar ratio of the monomers A b to monomers B a is between 4/96 and 40/60, and
b) compounding an elastomer with the aqueous inverse emulsion obtained by step a) to form the elastomer composition, wherein the aqueous inverse emulsion may, optionally, be partially or totally dewatered and de-oiled prior to said compounding,

wherein the elastomer composition is capable of swelling in oil and/or in water and brine.

2. A process according to claim 1 , wherein in step a), a reactive monomer to chemical functions present in the elastomer is added to the aqueous inverse emulsion before its addition to said elastomer.

3. A process according claim 1 , wherein the particles of polymer have a particle size of between 10 nm to 10,000 nm.

4. A process according to claim 1 , wherein the aqueous inverse emulsion a) is partially or totally the step of dehydrating and de-oiling the aqueous inverse emulsion to form of a dry solid comprising the particles of the polymer and the hydrophobic surfactants, and wherein the elastomer is compounded with the particles of the polymer by mixing the elastomer with the dry solid.

5. A process according to claim 4 , wherein the step of dehydrating and de-oiling the aqueous inverse emulsion is conducted by spray drying the aqueous inverse emulsion or by blowing hot air on the emulsion coated on a flat surface.

6. A process according to claim 1 , wherein the aqueous inverse emulsion comprises between 10 and 40% by weight of water and the elastomer is compounded with the particles of the polymer by compounding from 51 to 99% by weight of the elastomer with from 1 to 49% by weight of the aqueous inverse emulsion.

7. A process according to claim 1 , wherein the aqueous inverse emulsion of particles of a polymer is made by inverse emulsion polymerization of monomers A b , hydrophilic monomers B a , and polyvalent monomers C a , and the quantity of polyvalent monomers C a is between 0.001 and 0.1 mol % of monomers A b , B a , and C a .

8. A process according to claim 1 , wherein the polyvalent monomer is N,N′-methylenebisacrylamide (MBA) or triacryloylhexahydrotriazine (TAHT).

9. A process according to claim 1 , further comprising, prior to compounding the elastomer with the particles of the polymer, the step of dehydrating and de-oiling the aqueous inverse emulsion by mixing the inverse emulsion with a compound in which the polymer is not soluble and dissolving at least partially the other components of the inverse emulsion in the solvent to form a dry solid comprising the particles of the polymer, and wherein the elastomer is compounded with the particles of the polymer by mixing the elastomer with the dry solid.

10. A process according to claim 1 , wherein the monomer A b comprising the betaine group is chosen from:
alkylsulphonates or -phosphonates of dialkylammonioalkyl acrylates or methacrylates, -acrylamides or -methacrylamides,
heterocyclic betaine monomers,
alkylsulphonates or -phosphonates of dialkylammonioalkylallylics,
alkylsulphonates or -phosphonates of dialkylammonioalkylstyrenes,
betaines resulting from ethylenically unsaturated anhydrides and dienes, and
phosphobetaines.

11. A process according to claim 1 , wherein the monomer A b comprises a compound selected from the following compounds:

12. A process according to claim 1 , wherein the monomer A b comprises a compound according to the formula:

or the formula:

in which:
R 1 is hydrogen or methyl,
R 2 and R 3 , which are identical or different, are hydrogen or alkyls having from 1 to 6 carbon atoms,
Y 1 is a divalent group of formula —O— or NR 2 ,
Z − is SO 3 − ,
m is 2 or 3, and
n is 1-6.

13. A process according to claim 1 , wherein the monomer A b is selected from:
sulphopropyldimethylammonioethyl methacrylate (SPE),
sulphoethyldimethylammonioethyl methacrylate,
sulphobutyldimethylammonioethyl methacrylate,
sulphohydroxypropyldimethylammonioethyl methacrylate (SHPE),
sulphopropyldimethylammoniopropylacrylamide,
sulphopropyldimethylammoniopropylmethacrylamide (SPP),
sulphohydroxypropyldimethylammoniopropylmethacrylamide (SHPP),
sulphopropyldiethylammonioethyl methacrylate,
2-vinyl-1-(3-sulphopropyl)pyridinium betaine,
4-vinyl-1-(3-sulphopropyl)pyridinium betaine,
sulphopropyldimethylammonioethyl methacrylate,
1-vinyl-3-(3-sulphopropyl)imidazolium betaine, and
sulphopropylmethyldiallylammonium betaine.

14. A process according to claim 1 , wherein the monomer A b comprises one of the following compounds:

15. A process according to claim 1 , wherein the monomers B a used alone or in a polymerizable mixture are:
ethylenically unsaturated carboxylic acid and carboxylic acid anhydride;
ethylenically unsaturated carboxylic acid and carboxylic acid anhydride; or
ethylenically unsaturated amine and cationic monomers.

16. A process according to claim 15 , wherein the monomer B a comprises acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, 1-methylacrylic acid (crotonic acid), α-phenylacrylic acid, β-acryloxypropionic acid, sorbic acid, α-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, β-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene, 2-methyl-2-butene dicarboxylic acid, maleamic acid, N-phenyl maleamide, maleamide, maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, methyl itaconic anhydride, ethyl maleic anhydride, diethylmaleate, methylmaleate, maleic anhydride; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2.3-dihydroxypropyl acrylate, 2.3-dihydroxypropyl methacrylate, acrylamide (AM), methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, dimethylacrylamide, dimethylmethacrylamide, poly(ethylene and/or propylene oxide), α-acrylates or α-methacrylates, N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]acrylamide, N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]methacrylamide vinyl alcohol, vinylpyrrolidone, sodium(meth)acrylate, sodium itaconate, 2-acrylamido-2-methylpropane sulfonate, sodium styrene sulfonate, sodium vinylsulfonate, sodium allylsulfonate, sodium sulfomethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate or (meth)acrylamide, trimethylaminoethyl(meth)acrylate or (meth)acrylamide salts, dimethylaminopropyl(meth)acry

Assignees

• Adam Herve
• Cadix Arnaud
• Vuong Chi-Thanh
• Rhodia Operations

Inventors

• Adam Herve
• Cadix Arnaud
• Vuong Chi-Thanh

Classifications

• C08L33/26

  Homopolymers or copolymers of acrylamide or methacrylamide · CPC title

• C08L83/04

  Polysiloxanes · CPC title

• C08F2/32 Primary

  Polymerisation in water-in-oil emulsions · CPC title

• C08G18/69

  Polymers of conjugated dienes {(hydrogenated polymers of conjugated dienes C08G18/6208)} · CPC title

• C08L23/06

  Polyethylene · CPC title