Well cementing methods and compositions

A method of cementing a subterranean zone penetrated by a well bore comprising the steps of:

• (a) providing a cement composition comprising a hydraulic cement, sufficient water to form a pumpable slurry and a fluid loss control polymer additive comprised of:
• a) 5 to 93 weight % of monomers of the formula (Ia) or (Ib) or both
• 11
• wherein
• R1 is hydrogen or C1-C5 alkyl,
• R2 is C1-C20 alkylene, carboxy C1-C20 alkylene, carboamido C1-C20 alkylene or phenylene,
• M is hydrogen, ammonium or a metal cation in the oxidation state +I, +II or +III and
• x is 1 to 3;
• b) 1 to 50 weight % of monomers of the formula (IIa) or (IIb) or both
• 12
• wherein
• R3 and R4 are —COO−(Mx+)1/x or
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• R5 is —COO−(Mx+)1/x,
• M is hydrogen, ammonium or a metal cation in the oxidation state +I, +II or +III and
• x is 1 to 3;
• c) 5 to 93 weight % of a monomer of the formula (III)
• 14
• wherein
• R6 is hydrogen or C1-C5 alkyl,
• R7 and R8 are hydrogen, C1-C10 alkyl or —(CH2)y— and
• y is 3 to 7;
• and
• d) 1 to 25 weight % of monomers of the formula (IVa) or (IVb) or both
• 15
• wherein
• R9 is hydrogen or C1-C5 alkyl,
• R10 is C1-C10 alkyl, C1-C10 aminoalkyl, C1-C20 hydroxyalkyl, C1-C4 alkyl or hydroxyl terminated mono- or poly-C2-C3 alkylenoxy (with 1 to 400 alkylenoxy units), C7-C20 alkylaryl, C7-C20 hydroxyalkylaryl, C6-C10 aryl or C6-C10 hydroxyaryl,
• R11, R12 and R13 are hydrogen or C1-C5 alkyl and
• R14 is hydrogen, C1-C20 alkyl, C1-C10 aminoalkyl, C1-C20 hydroxyalkyl, C1-C4 alkyl- or hydroxyl terminated mono- or poly-C2-C3 alkylenoxy (with 1 to 400 alkylenoxy units), C7-C20 alkylaryl, C7-C20 hydroxyalkylaryl, C6-C10 aryl, C6-C10 hydroxyaryl or with hydroxyl substituted C1-C20 alkylensulfonic acids and their ammonium, alkali metal or alkaline earth metal salts;
• and
• wherein the monomers a) to d) add up to 100 weight %;
• (b) placing said composition in said subterranean zone to be cemented;
• and
• (c) allowing said cement composition to set into an impermeable solid mass therein.

A method of cementing a subterranean zone penetrated by a well bore comprising the steps of:

• (a) providing a cement composition comprising a hydraulic cement, sufficient water to form a pumpable slurry and a fluid loss control polymer additive comprised of 69 weight % of the calcium salt of 2-acrylamido-2-methyl propane sulfonic acid, 14 weight % of the calcium salt of maleic acid, 14 weight % of N-vinyl caprolactam and 3 weight % of 4-hydroxybutyl vinyl ether;
• (b) placing said composition in said subterranean zone to be cemented;
• and
• (c) allowing said cement composition to set into an impermeable solid mass therein.

A well cement composition comprising a hydraulic cement, sufficient water to form a pumpable slurry and a fluid loss control polymer additive comprised of:

• a) 5 to 93 weight % of monomers of the formula (Ia) or (Ib) or both
• 16
• wherein
• R1 is hydrogen or C1-C5 alkyl,
• R2 is C1-C20 alkylene, carboxy C1-C20 alkylene, carboamido C1-C20 alkylene or phenylene,
• M is hydrogen, ammonium or a metal cation in the oxidation state +I, +II or +III and
• x is 1 to 3;
• b) 1 to 50 weight % of monomers of the formula (IIa) or (IIb) or both
• 17
• wherein
• R3 and R4 are —COO−(Mx+)1/x or
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• R5 is —COO−(Mx+)1/x,
• M is hydrogen, ammonium or a metal cation in the oxidation state +I, +II or +III and
• x is 1 to 3;
• c) 5 to 93 weight % of a monomer of the formula (III)
• 19
• wherein
• R6 is hydrogen or C1-C5 alkyl,
• R7 and R8 are hydrogen, C1-C10 alkyl or —(CH2)y— and
• y is 3 to 7;
• and
• d) 1 to 25 weight % of monomers of the formula (IVa) or (IVb) or both
• 20
• wherein
• R9 is hydrogen or C1-C5 alkyl,
• R10 is C1-C10 alkyl, C1-C10 aminoalkyl, C1-C20 hydroxyalkyl, C1-C4 alkyl or hydroxyl terminated mono- or poly-C2-C3 alkylenoxy (with 1 to 400 alkylenoxy units), C7-C20 alkylaryl, C7-C20 hydroxyalkylaryl, C6-C10 aryl or C6-C10 hydlroxyaryl,
• R11, R12 and R13 are hydrogen or C1-C5 alkyl and
• R14 is hydrogen, C1-C20 alkyl, C1-C10 aminoalkyl, C1-C20 hydroxyalkyl, C1-C4 alkyl- or hydroxyl terminated mono- or poly-C2-C3 alkylenoxy (with 1 to 400 alkylenoxy units), C7-C20 alkylaryl, C7-C20 hydroxyalkylaryl, C6-C10 aryl, C6-C10 hydroxyaryl or with hydroxyl substituted C1-C20 alkylensulfonic acids and their ammonium, alkali metal or alkaline earth metal salts;
• and
• wherein the monomers a) to d) add up to 100 weight %.