Cementing compositions and methods

1. An epoxide resin cementing composition for use in a subterranean well, the composition comprising:

(a) a di- or poly epoxide resin;

(b) polyoxypropylenediamine, wherein the polyoxypropylenediamine is present from 5 wt % to 15 wt % based on the total weight of the composition; and

(c) a di- or polyfunctional alkylphosphonate ester fortifier, wherein the fortifier is present from 3 wt % to 15 wt % based on the total weight of the composition;

wherein the di- or polyfunctional alkylphosphonate ester is one or more compounds selected from the group consisting of:

hexa(methyl or ethyl) 1,2,3-propanetriyltrisphosphonate;

tetra(methyl or ethyl) 1,x-phenylenebis(methylene)diphosphonate, wherein x=2-4;

tetra(methyl or ethyl) 1,x-naphthalenediylbis(methylene)diphosphonate, wherein x=2-8;

tetra(methyl or ethyl) 2,x-pyridinediylbis(methylene)diphosphonate, wherein x=3-6;

tetra(methyl or ethyl) 2,5-furandiylbis(methylene)diphosphonate;

tetra(methyl or ethyl) 3-alkyl-2,5-furandiylbis (methylene) diphosphonate; and

tetra(methyl or ethyl) 3-alkyl-2,5-thiophenediylbis (methylene) diphosphonate

(d) a density modifier;

wherein the glass transition temperature of the composition is increased by the presence of the fortifier from 15° F. to 50° F. compared to the identical composition without the fortifier, and

wherein the composition has a viscosity of at least 5 Bc to 90 Bc prior to curing, and

wherein the composition does not comprise any Portland cement.

2. The composition according to claim 1 , wherein

(a) the di- or poly epoxide resin is one or more compounds selected from the group consisting of an epichlorohydrin adduct of a bisphenol, an epichlorohydrin adduct of a novolac, an epichlorohydrin adduct of an alkyl diol, and an epichlorohydrin adduct of a cycloalkyl diol.

3. The composition according to claim 2 , wherein

(a) the di- or poly epoxide resin is one or more compounds selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, an epoxy novolac resin, a diglycidyl ether of an aliphatic diol, a diglycidyl ether of a polyethylene glycol, a diglycidyl ether of a polypropylene glycol, a cyclohexanedimethanol diglycidyl ether, a butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, a hexanediol diglycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline, 4,4′-methylenebis(N,N-diglycidylaniline), neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, tetraphenylolethane glycidyl ether, tris(2,3-epoxypropyl) isocyanurate, and tris(4-hydroxyphenyl)methane triglycidyl ether.

4. The composition according to claim 3 , wherein

(a) the di- or poly epoxide resin is a bisphenol A diglycidyl ether resin and/or a cyclohexanedimethanol diglycidyl ether.

5. The composition according to claim 1 , wherein the di- or polyfunctional alkylphosphonate ester fortifier is an ethyl or methyl ester.

6. The composition according to claim 1 , wherein the di- or polyfunctional alkyl phosphonate ester is one or more compounds selected from the group consisting of:

wherein R is methyl or ethyl; and

R′ is a C 1 -C 15 aliphatic or branched alkyl, which may be optionally substituted.

7. The composition according to claim 1 , where (a) the di- or poly epoxide resin is in an amount of from 20 wt. % to 90 wt. %, based on the total weight of the composition.

8. The composition according to claim 1 , wherein (b) the amine hardener is in an amount of from 5 wt. % to 75 wt. %, based on the total weight of the epoxy resin.

9. The composition according to claim 1 , wherein the density modifier is barite.

10. The composition according to claim 1 , further comprising:

(e) a silane coupling agent, and (f) a diluent.

11. An epoxide resin cement composition for use in a subterranean well, the composition comprising:

(a) 30 wt. % to 90 wt. %, based on the total weight of the composition, of a bisphenol A diglycidyl ether resin and/or a cyclohexanedimethanol diglycidyl ether;

(b) 5 wt. % to 15 wt. %, based on the total weight of component (a), of polyoxypropylenediamine;

(c) 3 wt % to 15 wt % based on the total weight of the composition, of one or more di- or polyfunctional alkylphosphonate esters selected from the group consisting of:

hexa(methyl or ethyl) 1,2,3-propanetriyltrisphosphonate;

tetra(methyl or ethyl) 1,x-phenylenebis(methylene)diphosphonate, wherein x=2-4;

tetra(methyl or ethyl) 1,x-naphthalenediylbis(methylene)diphosphonate, wherein x=2-8;

tetra(methyl or ethyl) 2,x-pyridinediylbis(methylene)diphosphonate, wherein x=3-6;

tetra(methyl or ethyl) 2,5-furandiylbis(methylene)diphosphonate;

tetra(methyl or ethyl) 3-alkyl-2,5-furandiylbis(methylene)diphosphonate; and

tetra(methyl or ethyl) 3-alkyl-2,5-thiophenediylbis(methylene)diphosphonate;

(d) a density modifier;

(e) optionally a silane coupling agent; and

(f) optionally a diluent,

wherein the glass transition temperature of the composition is increased by the presence of the fortifier from 15° F. to 50° F. compared to the identical composition without the fortifier, and

wherein the composition has a viscosity of at least 5 Bc to 90 Bc prior to curing, and

wherein the composition does not comprise any Portland cement.

12. A system for cementing in a subterranean zone penetrated by a well bore comprising:

mixing equipment in which cement comprising a composition according to claim 1 is mixed; and

pumping equipment by which the mixed cement is placed in the subterranean zone.

13. A method of cementing in a subterranean zone penetrated by a well bore comprising:

(a) providing a composition according to claim 1 ;

(b) placing the composition in the subterranean zone using pumping equipment; and

(c) allowing the composition to fully cure.

14. A method of increasing the T g of a cured cement, plug, or seal used in a subterranean zone penetrated by a well bore comprising:

(a) dissolving a di- or polyfunctional alkylphosphonate ester fortifier in a di- or poly epoxide resin;

(b) adding polyoxypropylenediamine to the di- or poly epoxide resin having the di- or polyfunctional alkylphosphonate ester fortifier dissolved therein to form an uncured composition, wherein the polyoxypropylenediamine is present from 5 wt % to 15 wt % based on the total weight of the composition;

(c) pumping the uncured composition into a subterranean zone penetrated by a well bore; and

(d) allowing the uncured composition to cure and form a cured cement, plug, or seal having a T g higher than an otherwise identical cured cement, plug, or seal formed without addition of the di- or polyfunctional alkylphosphonate ester fortifier.