Rheological agent, preparation methods and uses thereof
The present invention relates to a method to prepare a rheological agent comprising the polymerization of the following monomers: (a) at least one styrene-based monomer, (b) at least one (meth)acrylate-based monomer or butadiene, and (c) optionally a copolymerisable surfactant containing an optionally substituted vinyl function and moieties derived from propylene oxide and/or ethylene oxide, optionally in the presence of a non polymerisable surfactant containing moieties derived from propylene oxide and/or ethylene oxide, and optionally in the presence of another surfactant, wherein at least the copolymerisable surfactant or the non polymerisable surfactant is present during the said polymerization, as well as a rheological agent obtainable by said method, an oil-based drilling fluid containing such a rheological agent, the use of such a rheological agent as a thixotropic agent in an oil-based drilling fluid and a method of drilling using an oil-based drilling fluid containing such a rheological agent.
1. An oil-based drilling fluid comprising a rheological agent, said rheological agent being obtained by a polymerization of monomers to form the rheological agent, the monomers consisting of:
(a) styrene-based monomer(s) substituted on the phenyl moiety, wherein the styrene-based monomer(s) is chosen among meta-methyl-styrene, para-methyl-styrene, para-propyl-styrene, para-tert-butyl-styrene, para-cyclohexyl-styrene, para-dodecyl-styrene, 2-ethyl-4-benzyl-styrene, para-(phenylbutyl)-styrene, divinylbenzene and mixtures thereof,
(b) optionally (meth)acrylate-based monomer(s) or butadiene, wherein the (meth)acrylate-based monomer(s) is chosen among ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isobornyl methacrylate, isobornyl acrylate and mixtures thereof, (c) a copolymerisable surfactant having the following formula:
CHR′═CRL-(O—CHR 7n —CHR 8n ) n —X 1
wherein:
L represents a single bond or a linker,
R and R′ represent, independently of each other, H or a (C 1 -C 25 )alkyl,
n represents an integer of at least 1,
each R 7n and each R 8n represent, independently of each other, a hydrogen atom or a methyl group but R 7n and R 8n cannot both represent a methyl group, and
X 1 represents an —O-(optionally substituted aryl), —O(C 1 -C 25 )alkyl, —O—(C 1 -C 6 )alkanediyl-SO 3 H, —OH, —S(O) 2 (OH), —O—P(O)(OH) 2 group, or a salt thereof, and (d) optionally a crosslinking agent,
said polymerization being performed in the presence of a non polymerisable surfactant, the non polymerisable surfactant has the following formula:
X 3 —(OCH 2 CH 2 ) q —X 2
wherein:
q represents an integer comprised between 1 and 60,
X 3 represents a (C 8 -C 25 )alkyl chain or an aryl optionally substituted with a (C 1 -C 25 )alkyl, and
X 2 represents an —OH, —S(O) 2 (OH), —O—P(O)(OH) 2 or —O—S(O) 2 (OH) group, or a salt thereof, and
optionally in the presence of another surfactant.
2. The oil based drilling fluid according to claim 1 , wherein the copolymerisable surfactant is chosen among anionic and non-ionic surfactants.
3. The oil based drilling fluid according to claim 1 , wherein the styrene-based monomer(s) is chosen among para-tert-butyl-styrene (PTBS), para-methyl-styrene (PMS) and mixtures thereof.
4. The oil based drilling fluid according to claim 1 , wherein monomer (b) is (meth)acrylate-based monomer(s) chosen among isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), isobutyl methacrylate (IBMA), 2-ethylhexyl acrylate (2-EHA) and mixtures thereof.
5. The oil based drilling fluid according to claim 1 , wherein the ratio by weight of monomer (a) to monomer (b) is comprised between 100:0 and 10:90.
6. The oil based drilling fluid according to claim 5 , wherein the ratio by weight of monomer (a) to monomer (b) is comprised between 100:0 and 70:30.
7. The oil based drilling fluid according to claim 1 , wherein:
R and R′ represent, independently of each other, H or a (C 1 -C 6 )alkyl, and
n represents an integer comprised between 3 and 120.
8. The oil based drilling fluid according to claim 1 , wherein:
X 1 represents an —O-(optionally substituted aryl), —O(C 1 -C 25 )alkyl, —O—(C 1 -C 6 )alkanediyl-SO 3 H, —OH, —S(O) 2 (OH), —O—P(O)(OH) 2 or —O—S(O) 2 (OH) group, or a sodium, potassium or ammonium salt thereof,
R and R′ represent, independently of each other, H, and
n represents an integer comprised between 5 and 40.
9. The oil-based drilling fluid according to claim 1 , wherein X 1 represents an —O-(optionally substituted aryl), —O(C 1 -C 25 )alkyl, —O—(C 1 -C 6 )alkanediyl-SO 3 H, —OH, —S(O) 2 (OH), —O—P(O)(OH) 2 or —O—S(O) 2 (OH) group, or a sodium, potassium or ammonium salt thereof.
10. The oil based frilling fluid according to claim 1 , wherein q represents an integer comprised between 3 and 20, and wherein X 2 represents an —OH, —S(O) 2 (OH), —O—P(O)(OH) 2 or —O—S(O) 2 (OH) group, or a sodium, potassium or ammonium salt thereof.
11. The oil based drilling fluid according to claim 1 , wherein the polymerization is carried out in the presence of a crosslinking agent.
12. The oil based drilling fluid according to claim 1 , using 0.5 to 10 wt % relatively to the total weight of the rheological agent on a dry basis of the combination of the copolymerisable surfactant and the non polymerisable surfactant.
13. The oil based drilling fluid according to claim 10 , wherein the oil-based drilling fluid contains 0.1 to 10 ppb (0.285 to 28.5 kg/m 3 ) of the rheological agent.