Polymers for oilfield applications

1. A polymer having side chain groups comprising at least one of the following:

a) a group comprising a citrate ester in acid form, triammonium citrate ester, trisodium citrate ester, an aminoalkylphosphate ester, or an ammoniumalkylphosphate ester;

b) a group comprising an alkanolamino group, a fatty quaternary ammonium moiety, a heterocyclic ring moiety in which the ring is a pyridyl, pyrrolinyl, imidazolidinyl, 2-imidazolinyl, or oxazolidinyl moiety, or both a fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom;

c) a group comprising an alkylamino ethoxylate or an alkylamino propoxylate;

d) a group comprising a trialkylhexahydrotriazine moiety;

e) a group comprising a fatty alkyl ester; or

f) a group comprising (i) an ester of a polycarboxylic acid or polycarboxylate salt, an aminoalkylphosphate ester, or an ammoniumalkylphosphate ester, and (ii) a group comprising an alkanolamino group, a fatty quaternary ammonium moiety, a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom, or both a fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom.

2. A polymer as in claim 1 wherein said polymer is

a homopolymer which has side chain groups selected from a); b); c); or f); or

a bipolymer which has side chain groups selected from two different groups of a); a) and b); a) and c); a) and d); a) and e); b) and c); or

a terpolymer which has side chain groups selected from three different groups of b); two different groups of a) and one group of b); one group of a) and two different groups of b); a), b), and c); or a), b), and d).

3. A polymer as in claim 1 wherein said side chain groups are b); a) and b); one group of a) and two different groups of b); or a), b), and d).

4. A polymer as in any of claims 1 - 3 wherein

said group a) is a citrate ester in acid form, triammonium citrate ester, trisodium citrate ester, N,N-di(2-ethylphosphate)aminomethyl amide, or 1,3-bis[N,N,N-tri(2-ethylphosphate)ammonium chloride]propyl ester group; and/or

said group b) is a 2-imidazolinylmethyl ester, amino-2-imidazolidinyl, N-2-[3-(2-phenyl)-2-imidazolinyl]lethylamino methylamido, {N-2-[3-(2-phenyl)-(3-methylammonium)-2-imidazolinyl]lethyl}{(methylacrylamido)}dimethylammonium di(methylsulfate), N,N-bis(2-hydroxyethyl)aminomethyl amido, 2-(3-oxazolidinyl)ethyl ester, 2-{2-[methyl(2-pyrrolinyl)]3-oxazolidinyl}ethyl ester, or 2-{12-imido-3,6,9-triazatetracyclo[12.3.1.0 2,6 .0 9.13 ]octadeca-1(18),14,16-trien-3-yl}ethylamino methylamido group; and/or

said group c) is a N-(5-methylamido-1,3-dioxapentamethylene)amino methylamido group; and/or

said group d) is a 2-(hexahydro-3,5-dicyclohexyl-1,3,5-triazinyl)ethyl ester group; and/or

said groups e) are a mixture of groups having different chain lengths; and/or

said group f) is a 2-[(citratoyl)dimethylammonium chloride]ethyl ester group.

5. A polymer as in claim 1 wherein

said group a) is a citrate ester; and/or

said group b) comprises a heterocyclic ring moiety; and/or

said group d) is a trialkylhexahydrotriazine moiety having alkyl groups, which alkyl groups have two to about eight carbon atoms; and/or

said group e) is an eicosyl, docosyl, or tetracosyl ester, or a mixture comprising one or more of these; and/or

said group f) comprises (i) a citrate ester or salt thereof and (ii) a fatty quaternary ammonium moiety.

6. A polymer as in claim 1 wherein

said group b) comprises a heterocyclic ring moiety in which the ring is a pyridyl, pyrrolinyl, imidazolidinyl, 2-imidazolinyl, or oxazolidinyl moiety; and/or

said group f) comprises (i) a citrate ester or triammonium citrate ester and (ii) a fatty quaternary ammonium moiety.

7. A process for preparing polymers of claim 1 , which process comprises

1) bringing together at least one free radical initiator; a vinyl compound selected from an acrylic acid, acrylamide, vinylamine, or vinyl formamide; and optionally comprising at least one of the following:

A) an acryolyl ester of a polycarboxylic acid or polycarboxylate salt, an acryloyl or acrylamido aminoalkylphosphate ester, or an acryloyl or acrylamido ammoniumalkylphosphate ester;

B) an acryloyl alkanolamine, an acrylamido alkanolamine, an acryloyl fatty quaternary ammonium compound, an acrylamido fatty quaternary ammonium compound, an acryloyl or acrylamido compound comprising a heterocyclic ring moiety in which the ring is a pyridyl, pyrrolinyl, imidazolidinyl, 2-imidazolinyl, or oxazolidinyl moiety, a compound comprising both an acrylamido fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom;

C) an acryloyl alkylamino ethoxylate, an acryloyl alkylamino propoxylate, an acrylamido alkylamino ethoxylate, or an acrylamido alkylamino propoxylate;

D) an acryloyl trialkylhexahydrotriazine or an acrylamido trialkylhexahydrotriazine;

E) a fatty alkyl acrylate; or

F) an acryloyl or acrylamido compound comprising (I) an acryolyl ester of a polycarboxylic acid or polycarboxylate salt, an aminoalkylphosphate ester, or an ammoniumalkylphosphate ester, and (II) an alkanolamino group, a fatty quaternary ammonium moiety, a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom, or both a fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom,

to form a polymer-making mixture, which mixture is heated to a temperature of at least about 60° C. to form a polymer; and

2) bringing together at least a portion of the polymer formed in 1) and reagents suitable for forming a polymer having side chain groups as described above for a), b), c), d), e), and/or f) on the polymer.

8. A process as in claim 7 wherein said vinyl compound is vinyl formamide.

9. In a method for scale inhibition, corrosion inhibition, gas hydrate inhibition, hydrogen sulfide scavenging, and/or paraffin inhibition in a well, central treating area, or refinery, an improvement which comprises introducing a polymer of claim 1 to a refinery continuously; to a storage facility of a refinery; or to an exit of a de-salter unit in a refinery.

10. A method as in claim 9 wherein said polymer is

a homopolymer which has side chain groups selected from a); b); c); or f); or

a bipolymer which has side chain groups selected from two different groups of a); a) and b); a) and c); a) and d); a) and e); b) and c); or

a terpolymer which has side chain groups selected from three different groups of b); two different groups of a) and one group of b); one group of a) and two different groups of b); a), b), and c); or a), b), and d).

11. A method as in claim 9 wherein said side chain groups are b);

a) and b); one group of a) and two different groups of b); or a), b), and d).

12. A method as in any of claim 9 , 10 , or 11 wherein

said group a) is a citrate ester in acid form, triammonium citrate ester, trisodium citrate ester, N,N-di(2-ethylphosphate)aminomethyl amide, or 1,3-bis[N,N,N-tri(2-ethylphosphate)ammonium chloride]propyl ester group; and/or

said group b) is a 2-imidazolinylmethyl ester, amino-2-imidazolidinyl, N-2[3-(2-phenyl)-2-imidazolinyl]ethylamino methylamido, {N-2-[3-(2-phenyl)-(3-methylammonium)-2-imidazolinyl]ethyl} {(methylacrylamido)}dimethylammonium di(methylsulfate), N,N-bis(2-hydroxyethyl)aminomethyl amido, 2-(3-oxazolidinyl)ethyl ester, 2-{2-[methyl(2-pyrrolinyl)]3-oxazolidinyl}ethyl ester, or 2-{12-imido-3,6,9-triazatetracyclo[12.3.1.0 2.6 .0 9.13 ]octadeca-1(18),14,16-trien-3-yl}ethylamino methylamido group; and/or

said group c) is a N-(5-methylamido-1,3-dioxapentamethylene)amino methylamido group; and/or

said group d) is a 2-(hexahydro-3,5-dicyclohexyl-1,3,5-triazinyl)ethyl ester group; and/or

said groups e) are a mixture of groups having different chain lengths; and/or

said group f) is a 2-[(citratoyl)dimethylammonium chloride]lethyl ester group.

13. A method as in claim 9 wherein

said group a) is a citrate ester; and/or

said group b) comprises a heterocyclic ring moiety in which the ring is a pyridyl, pyrrolinyl, imidazolidinyl, 2-imidazolinyl, or oxazolidinyl moiety; and/or

said group d) is a trialkylhexahydrotriazine moiety having alkyl groups, which alkyl groups have two to about eight carbon atoms; and/or

said group e) is an eicosyl, docosyl, or tetracosyl ester, or a mixture comprising one or more of these; and/or

said group f) comprises (i) a citrate ester or salt thereof and (ii) a fatty quaternary ammonium moiety.

14. A method as in claim 9 wherein

said group b) comprises a heterocyclic ring moiety in which the ring is a pyridyl, pyrrolinyl, imidazolidinyl, 2-imidazolinyl, or oxazolidinyl moiety; and/or

said group f) comprises (i) a citrate ester or triammonium citrate and (ii) a fatty quaternary ammonium moiety.

15. A process for preparing polymers, which process comprises bringing together at least one free radical initiator and monomer species comprising at least one of the following:

A) an acryolyl ester of a polycarboxylic acid or polycarboxylate salt, an acryloyl or acrylamido aminoalkylphosphate ester, or an acryloyl or acrylamido ammoniumalkylphosphate ester;

B) an acryloyl alkanolamine, an acrylamido alkanolamine, an acryloyl fatty quaternary ammonium compound, an acrylamido fatty quaternary ammonium compound, an acryloyl or acrylamido compound comprising a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom, a compound comprising both an acrylamido fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom;

C) an acryloyl alkylamino ethoxylate, an acryloyl alkylamino propoxylate, an acrylamido alkylamino ethoxylate, or an acrylamido alkylamino propoxylate;

D) an acryloyl trialkylhexahydrotriazine or an acrylamido trialkylhexahydrotriazine;

E) a fatty alkyl acrylate; or

F) an acryloyl or acrylamido compound comprising (I) an acryolyl ester of a polycarboxylic acid or polycarboxylate salt, an aminoalkylphosphate ester, or an ammoniumalkylphosphate ester, and (II) an alkanolamino group, a fatty quaternary ammonium moiety, a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom, or both a fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom,

to form a polymerization mixture, which polymerization reaction mixture is heated to a temperature of at least about 60° C. to form a polymer.

16. A process as in claim 15 or 7 wherein

said monomer species A) is an acryloyl citrate ester; and/or

said monomer species B) is an acryloyl or acrylamido compound that comprises a heterocyclic ring moiety; and/or

said monomer species D) is a trialkylhexahydrotriazine moiety having alkyl groups, which alkyl groups have two to about eight carbon atoms; and/or

said monomer species E) is eicosyl acrylate, docosyl acrylate, or tetracosyl acrylate, or a mixture comprising one or more of these; and/or

said monomer species F) comprises (I) an acryloyl citrate or salt thereof and (II) an imidazoline or a fatty quaternary ammonium moiety.

17. A process as in claim 15 or 7 wherein

said monomer species B) is an acryloyl or acrylamido compound that comprises a heterocyclic ring moiety in which the ring is a pyridyl, pyrrolinyl, imidazolidinyl, 2-imidazolinyl, or oxazolidinyl moiety; and/or

said monomer species F) comprises (I) an acryloyl citrate or triammonium acryloyl citrate and (II) a fatty quaternary ammonium moiety.

18. A process as in claim 15 or 7 wherein said free radical initiator is azobiscyanovaleric acid.

19. A process as in claim 15 or 7 further comprising contacting at least a portion of said polymer with a quaternizing agent.

20. A process as in claim 15 wherein

a homopolymer is formed, and the monomer species is A), B), C), or F); or a bipolymer is formed, and the monomer species are two different monomer species of A); A) and B); A) and C); A) and D); A) and E); B) and C); or a terpolymer is formed, and the monomer species are three different monomer species of B); two different monomer species of A) and one monomer species of B); one monomer species of A) and two different monomer species of B); A), B), and C); or A), B), and D).

21. A process as in claim 15 wherein said monomer species are B);

A) and B); one monomer species of A) and two different monomer species of B); or A), B), and D).

22. A process as in any of claims 15 - 21 wherein

said monomer species A) is acryloyl citrate, acryloyl triammonium citrate, acryloyl trisodium citrate, N,N-di(2-ethylphosphate)aminomethyl amide, or 1,3-bis[N,N,N-tri(2-ethylphosphate)ammonium chloride]propyl ester; and/or

said monomer species B) is 2-imidazolinylmethyl acrylate, 2-imidazolidinyl vinylamine, N-2-[3-(2-phenyl)-2-imidazolinyl]ethylamino methyl acrylamide, {N-2-[3-(2-phenyl)-(3-methylammonium)-2-imidazolinyl]ethyl} {(methylacrylamide)}dimethylammonium di(methylsulfate), N,N-bis(2-hydroxyethyl)aminomethyl acrylamide, 2-(3-oxazolidinyl)ethyl acrylate, 2-{2-[methyl(2-pyrrolinyl)]3-oxazolidinyl}ethyl acrylate, or 2-{12-imido-3,6,9-triazatetracyclo[12.3.1.0 2.6 .0 9.13 ]octadeca-1(18),14,16-trien-3-yl}ethylamino methylamide; and/or

said monomer species C) is N-(5-methylamido-1,3-dioxapentamethylene)amino methylacrylamide; and/or

said monomer species D) is 2-(hexahydro-3,5-dicyclohexyl-1,3,5-triazinyl)ethyl acrylate; and/or

said monomer species E) are a mixture of esters having different chain lengths; and/or

said monomer species F) is (acryloylethyl)(citratoyl)dimethylammonium chloride.

23. A composition of matter which is

A) an acryolyl ester of a polycarboxylic acid or polycarboxylate salt, an acryloyl or acrylamido aminoalkylphosphate ester, or an acryloyl or acrylamido ammoniumalkylphosphate ester; or

B) an acryloyl alkanolamine, an acrylamido alkanolamine, an acryloyl fatty quaternary ammonium compound, an acrylamido fatty quaternary ammonium compound, an acryloyl or acrylamido compound comprising a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom, a compound comprising both an acrylamido fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom; or

C) an acryloyl alkylamino ethoxylate, an acryloyl alkylamino propoxylate, an acrylamido alkylamino ethoxylate, or an acrylamido alkylamino propoxylate; or

D) an acryloyl trialkylhexahydrotriazine or an acrylamido trialkylhexahydrotriazine; or

E) a fatty alkyl acrylate; or

F) an acryloyl or acrylamido compound comprising (I) an acryolyl ester of a polycarboxylic acid or polycarboxylate salt, an aminoalkylphosphate ester, or an ammoniumalkylphosphate ester, and (II) an alkanolamino group, a fatty quaternary ammonium moiety, a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom, or both a fatty quaternary ammonium moiety and a heterocyclic ring moiety having at least five members, which ring has at least one nitrogen atom, said ring further comprising either unsaturation or at least one additional heteroatom.

24. A composition as in claim 23 wherein

A) is an acryloyl citrate ester;

B) is an acryloyl or acrylamido compound that comprises a heterocyclic ring moiety;

D) is a trialkylhexahydrotriazine moiety having alkyl groups, which alkyl groups have two to about eight carbon atoms;

E) is eicosyl acrylate, docosyl acrylate, or tetracosyl acrylate, or a mixture comprising one or more of these; or

F) comprises (I) an acryloyl citrate ester or salt thereof and (II) an imidazoline or a fatty quaternary ammonium moiety.

25. A composition as in claim 23 wherein

B) is an acryloyl or acrylamido compound that comprises a heterocyclic ring moiety in which the ring is a pyridyl, pyrrolinyl, imidazolidinyl, 2-imidazolinyl, or oxazolidinyl moiety;

F) comprises (I) acryloyl citrate or triammonium acryloyl citrate and (II) a fatty quaternary ammonium moiety.

26. A composition as in claim 23 wherein

A) is acryloyl citrate, acryloyl triammonium citrate, acryloyl trisodium citrate, N,N-di(2-ethylphosphate)aminomethyl amide, or 1,3-bis[N,N,N-tri(2-ethylphosphate)ammonium chloride]propyl ester;

B) is 2-imidazolinylmethyl acrylate, 2-imidazolidinyl vinylamine, N-2-[3-(2-phenyl)-2-imidazolinyl]ethylamino methyl acrylamide, {N-2-[3-(2-phenyl)-(3-methylammonium)-2-imidazolinyl]ethyl} {(methylacrylamide)}dimethylammonium di(methylsulfate), N,N-bis(2-hydroxyethyl)aminomethyl acrylamide, 2-(3-oxazolidinyl)ethyl acrylate, 2-{2-[methyl(2-pyrrolinyl)]3-oxazolidinyl}ethyl acrylate, or 2-{12-imido-3,6,9-triazatetracyclo[12.3.1.0 2.6 .0 9.13 ]octadeca-1(18),14,16-trien-3-yl}ethylamino methylamide;

C) is N-(5-methylamido-1,3-dioxapentamethylene)amino methylacrylamide;

D) is 2-(hexahydro-3,5-dicyclohexyl-1,3,5-triazinyl)ethyl acrylate;

E) is a mixture of esters having different chain lengths; or

F) is (acryloylethyl)(citratoyl)dimethylammonium chloride.

27. A method for preparing compositions as in claim 23 , which method comprises

when composition A) is an acryloyl or acrylamido aminoalkylphosphate ester, i) bringing together a dialkanolamine or a trialkanolamine and polyphosphoric acid, to form an alkylaminophosphate ester; and ii) bringing together at least a portion of an alkylaminophosphate ester formed in i), an acrylic reagent, and formaldehyde, forming the acryloyl or acrylamido aminoalkylphosphate ester;

when composition A) is an acryloyl or acrylamido ammoniumalkylphosphate ester, bringing together an acryloyl or acrylamido aminoalkylphosphate ester, an acrylic reagent, and an epoxide having a haloalkyl substituent, forming the acryloyl or acrylamido ammoniumalkylphosphate ester;

when the composition is C), i) bringing together an alkyl anhydride, an ethoxylated or propoxylated alkylamine, and a strong base, forming an ethoxylated or propoxylated alkylamino alkylamide; ii) bringing together at least a portion of the ethoxylated or propoxylated alkylamino alkylamide formed in i), an acrylic reagent, and optionally formaldehyde, forming an acryloyl or acrylamido alkylamino ethoxylate or propoxylate;

when the composition is D), i) bringing together a monoalkylamine, a monoalkanolamine, and formaldehyde, forming a 1-alkanol-3,5-dialkylhexahydrotriazine; ii) bringing together at least a portion of the a 1-alkanol-3,5-dialkylhexahydrotriazine formed in i) and an acrylic reagent, to form an acryloyl or acrylamido trialkylhexahydrotriazine;

when the composition is E), bringing together a fatty alkyl alcohol and an acrylic reagent, forming a fatty alkyl acrylate.

28. A method as in claim 27 wherein

when preparing a composition A) which is an acryloyl or acrylamido aminoalkylphosphate ester,

said dialkanolamine is diethanolamine, or said trialkanolamine is triethanolamine; and/or

said acrylic reagent is acrylic acid or acrylamide;

when preparing a composition A) which is an acryloyl or acrylamido ammoniumalkylphosphate ester,

said acrylic reagent is acrylic acid or acrylamide; and/or

said epoxide is epichlorohydrin;

when preparing a composition C),

said acrylic reagent is acrylamide;

said alkyl anhydride is acetic anhydride;

said ethoxylated or propoxylated alkylamine is triethylene glycol diamine; and/or

said base is sodium hydroxide is a preferred base;

when preparing a composition D),

said acrylic reagent is acrylic acid;

said monoalkylamine is cyclohexylamine; and/or

said monoalkanolamine is ethanolamine;

when preparing a composition E),

said fatty alcohol is eicosol, docosol, and tetracosol, or a mixture comprising one or more of these alcohols; and/or

said acrylic reagent is acrylic acid.