Preparation of boron crosslinking agents for fracturing fluids
Methods for making polyaminoboric acid compounds are provided. The polyaminoboric acid compounds are made by reacting a polyamine with boric acid in the presence of a solvent to produce polyaminoboric acid compounds with more than one boron-nitrogen bond. The polyaminoboric acid compounds are useful as crosslinking agents for fracturing fluids.
1. A method of making a polyaminoboric acid compound comprising contacting boric acid with a polyamine in the presence of a solvent, wherein the polyaminoboric acid compound is:
or combinations thereof
wherein
X is —NH;
Y is a straight chain of (—CH 2 —), a straight chain with pendant(s), a straight chain with branching, aromatic ring(s) directly connected, aromatic ring(s) indirectly connected, fused aromatic rings, heterocyclic ring(s) directly connected, heterocyclic ring(s) indirectly connected, fused heterocyclic rings, aliphatic ring(s) directly connected, aliphatic ring(s) indirectly connected, fused aliphatic rings, or combinations thereof;
Z 1 is —CH, nitrogen, aromatic ring(s), aliphatic ring(s), heterocyclic ring(s) or a combination thereof; and Z 2 is silicon, oxygen, —NH, alkylene group, alkenyl group, alkynyl group, aromatic ring(s), aliphatic ring(s) or heterocyclic ring(s); and
x, y and z are 1, 2 or 3.
2. The method of claim 1 , wherein the polyaminoboric acid compound comprises:
or combinations thereof.
3. The method of claim 1 , wherein the polyamine comprises diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), 1,2-propylenediamine, 1,3-propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, ethylene propylene triamine, ethylene dipropylene tetramine, diethylene propylene tetramine, ethylene tripropylene pentamine, diethylene dipropylene pentamine, triethylene propylene pentamine, tris(2-aminoethyl)amine, or combinations thereof.
4. The method of claim 1 , wherein the solvent comprises methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol, ethylene glycol, toluene, N,N-dimethylformamide, dimethylsulfoxide, or combinations thereof.
5. A method of making a polyaminoboric acid compound comprising contacting a polyamine with boric acid in the presence of a solvent to produce the polyaminoboric compound, wherein the polyamine comprises diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), 1,2-propylenediamine, 1,3-propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, ethylene propylene triamine, ethylene dipropylene tetramine, diethylene propylene tetramine, ethylene tripropylene pentamine, diethylene dipropylene pentamine, triethylene propylene pentamine, tris(2-aminoethyl)amine, or combinations thereof.
6. The method of claim 5 , wherein the polyaminoboric acid compound comprises:
or combinations thereof,
X is —NH;
Y is a straight chain of (—CH 2 —), a straight chain with pendant(s), a straight chain with branching, aromatic ring(s) directly connected, aromatic ring(s) indirectly connected, fused aromatic rings, heterocyclic ring(s) directly connected, heterocyclic ring(s) indirectly connected, fused heterocyclic rings, aliphatic ring(s) directly connected, aliphatic ring(s) indirectly connected, fused aliphatic rings, or combinations thereof;
Z 1 is —CH, nitrogen, aromatic ring(s), aliphatic ring(s), heterocyclic ring(s) or a combination thereof; and Z 2 is silicon, oxygen, —NH, alkylene group, alkenyl group, alkynyl group, aromatic ring(s), aliphatic ring(s) or heterocyclic ring(s).
7. The method of claim 5 , wherein the solvent comprises methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol, ethylene glycol, toluene, N,N-dimethylformamide, dimethylsulfoxide, or combinations thereof.
8. A method of making a polyaminoboric acid compound comprising:
a. reacting a mixture of boric acid, a polyamine, and a solvent, wherein the polyamine comprises diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), 1,2-propylenediamine, 1,3-propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, ethylene propylene triamine, ethylene dipropylene tetramine, diethylene propylene tetramine, ethylene tripropylene pentamine, diethylene dipropylene pentamine, triethylene propylene pentamine, tris(2-aminoethyl)amine, or a combination thereof and;
b. removing water from the mixture to form the polyaminoboric acid compound.
9. The method of claim 8 , wherein the solvent comprises methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol, ethylene glycol, toluene, N,N-dimethylformamide, dimethylsulfoxide, or combinations thereof.
10. The method of claim 8 , wherein the polyaminoboric compound comprises at least two B—N bonds.
11. The method of claim 8 , wherein the polyaminoboric compound comprises an equivalent number of B—N bonds as N atoms in the polyamine.
12. The method of claim 8 , wherein the polyamine is tris(2-aminoethyl)amine.
13. The method of claim 8 , wherein the polyamine is tetraethylene pentamine.