Process to remove silanol from the preparation of a modified polymer
The invention provides a method for a preparation of a polymer selected from the following: (a) modified interpolymer comprising, in polymerized form, a conjugated diene and an aromatic alpha-olefin, or (b) a modified polymer comprising, in polymerized form, a conjugated diene; and wherein said method comprising at least the following steps: polymerizing monomers comprising at least one conjugated diene monomer in at least one polymerization reactor, in the presence of at least one solvent, to form the polymer, optionally coupling a fraction of the polymer chains using at least one coupling agent, modifying the polymer with at least one modifying agent, in at least one reactor, in the presence of the at least one solvent, to form a modified polymer solution; optionally, contacting the modified polymer solution with at least one proton donating compound; contacting the modified polymer solution with water; removing the at least one solvent; contacting the removed solvent with at least one material that will react with, and/or adsorb, silanol to form a purified solvent, recirculating the purified solvent back to the at least one polymerization reactor or to a storage container.
1. A method for a preparation of a polymer selected from the following: (a) modified interpolymer comprising, in polymerized form, a conjugated diene and an aromatic alpha-olefin, or (b) a modified polymer comprising, in polymerized form, a conjugated diene; and wherein said method comprising at least the following steps:
polymerizing monomers comprising at least one conjugated diene monomer in at least one polymerization reactor, in the presence of at least one solvent, to form the polymer,
optionally coupling a fraction of the polymer chains using at least one coupling agent,
modifying the polymer with at least one modifying agent, in at least one reactor, in the presence of the at least one solvent, to form a modified polymer solution;
optionally, contacting the modified polymer solution with at least one proton donating compound;
contacting the modified polymer solution with water to form a silanol;
removing the at least one solvent;
contacting the removed solvent with at least one material that will react with, and/or adsorb, the silanol to form a purified solvent, recirculating the purified solvent back to the at least one polymerization reactor or to a storage container.
2. The method of claim 1 , wherein the at least one solvent comprises cyclohexane.
3. The method of claim 1 , wherein the at least one solvent further comprises an alkane.
4. The method of claim 1 , wherein the polymer is a modified interpolymer comprising, in polymerized form, a conjugated diene and an aromatic alpha-olefin.
5. The method of claim 1 , wherein the polymerization takes place by a consecutive batch-wise polymerization or a continuous polymerization.
6. The method of claim 1 , wherein the material comprises alumina, silica, and/or aluminosilicates.
7. The method of claim 1 , wherein the at least one material is contained in a column.
8. The method of claim 1 , wherein the silanol is selected from a compound according to Formula 3:
wherein:
Si is silicon; O is oxygen; H is hydrogen;
R 1 , R 2 and R 3 are the same or different, and are each, independently, a group having from 1 to 80 nonhydrogen atoms, and which is hydrocarbyl, and wherein each hydrocarbyl group, independently, may be linear or branched, saturated or unsaturated, and wherein each hydrocarbyl group, independently, may be optionally substituted with a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or combinations thereof.
9. The method of claim 1 , wherein the silanol is selected from one or more of the following compounds:
10. The method of claim 1 , wherein the modified polymer is selected from a modified butadiene-styrene copolymer or a modified polybutadiene.
11. The method of claim 1 , wherein the modifying agent is selected from one or more of the following A) through E):
A) (R 1 O) 3 Si—R 4 —S—SiR 3 3 (Formula 8),
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen;
R 4 is a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl), and wherein each group is optionally substituted with at least one of the following: a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, an amine, a thioalkyl, or combinations thereof; and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 and R 3 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each, independently, selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 7 -C 16 ) aralkyl;
B) (R 13 O) 3 Si—R 9 —N(SiR 10 R 11 R 12 ) 2 (Formula 9),
wherein:
Si is silicon; S is sulfur; 0 is oxygen; N is nitrogen;
R 9 is a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl), and wherein each group is optionally substituted with at least one of the following: a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, an amine, a thioalkyl, or combinations thereof; and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 10 ,R 11 ,R 12 and R 13 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each, independently, selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 6 -C 16 ) aralkyl;
C) (R 1 O) x (R 2 ) y Si—R 4 —S—SiR 3 3 (Formula 10),
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen,
x is an integer selected from 1, and 2;
y is an integer selected from 1, and 2;
x+y=3;
R 4 is a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl), and wherein each group is optionally substituted with at least one of the following: a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, an amine, a thioalkyl, or combinations thereof; and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 1 , R 2 , and R 3 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each independently selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 7 -C 16 ) aralkyl;
D) (R 13 O) p (R 14 ) q Si—R 9 —N(SiR 10 R 11 R 12 ) 2 (Formula 11),
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen,
p is an integer selected from 1, and 2;
q is an integer selected from 1, and 2;
p+q =3;
R 9 is a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 1 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl), and wherein each group is optionally substituted with at least one of the following: a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, an amine, a thioalkyl, or combinations thereof; and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 10 ,R 11 ,R 12 ,R 13 ,R 14 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each, independently, selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, or a (C 7 -C 16 ) aralkyl;
E)
wherein:
Si is silicon; S is sulfur; O is oxygen; N is nitrogen,
R 15 is a group selected from a (C 7 -C 100 ) aralkyl, a (C 6 -C 100 ) aryl, a (C 2 -C 100 ) alkyl, or a (C 2 -C 100 ) dialkylether (alkyl-O-alkyl), and wherein each group is optionally substituted with at least one of the following: a (C 1 -C 4 ) alkyl, a (C 1 -C 4 ) alkoxy, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, an amine, a thioalkyl, or combinations thereof; and wherein each alkyl may be linear or branched, and saturated or unsaturated;
R 16 ,R 17 ,R 18 ,R 19 ,R 20 , and R 21 are the same or different, and are each, independently, selected from hydrogen (H), a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or a (C 3 -C 30 ) tri(hydrocarbyl)silyl, and wherein the hydrocarbyl groups are each independently selected from a (C 1 -C 16 ) alkyl, a (C 6 -C 16 ) aryl, a (C 7 -C 16 ) aralkyl, or combinations thereof.
12. The method of claim 1 , wherein the at least one solvent is passed through at least two columns connected in series.
13. The method of claim 12 , wherein, once a column is exhausted (capacity full), the flow of the at least one solvent by-passes this column, and flows into another column.
14. The method of claim 13 , wherein the exhausted column is regenerated or exchanged with new material, and wherein the flow of the at least one solvent is re-routed to again flow into this column.
15. The method of claim 1 , wherein the at least one solvent is recycled at a rate from 50 to 70 m 3 solvent per hour.