Method for producing polyether polymers
View Patent ↗A method of making a polyether polymer comprises reacting a salt of a dihydroxy-substituted aromatic hydrocarbon with a substituted aromatic compound of formula (I) Z(A 1 —X 1 ) 2 (I) in the presence of a catalyst to form an intermediate polymer having endgroups, wherein the molar ratio of the salt of a dihydroxy-substituted aromatic hydrocarbon to the substituted aromatic compound is less than 1, Z is an activating radical, A 1 is an aromatic radical and X 1 is fluoro, chloro, bromo or nitro; determining the additional amount of the salt of a dihydroxy-substituted aromatic hydrocarbon needed to form a final polyether polymer with a predetermined molecular weight and adding the additional amount of the salt of a dihydroxy-substituted aromatic hydrocarbon to the intermediate polymer.
1. A method of making a polyether polymer comprising
reacting a salt of a dihydroxy-substituted aromatic hydrocarbon with a substituted aromatic compound of formula (I)
Z(A 1 —X 1 ) 2 (I)
in the presence of a catalyst to form an intermediate polymer having endgroups, wherein the molar ratio of the salt of a dihydroxy-substituted aromatic hydrocarbon to the substituted aromatic compound is less than 1, Z is an activating radical, A 1 is an aromatic radical and X 1 is fluoro, chloro, bromo or nitro;
determining the gram moles of endgroups per gram of polymer present on the intermediate polymer;
reacting the intermediate polymer with an additional amount of the salt of a dihydroxy-substituted aromatic hydrocarbon to form a final polymer having endgroups and a predetermined molecular weight wherein the additional amount of the salt of a dihydroxy-substituted aromatic hydrocarbon equals grams of final polymer X (gram moles of end groups per gram of polymer for the intermediate polymer - gram moles of end groups per gram of polymer for the final polymer)/2.
2. The method of claim 1 wherein the dihydroxy-substituted aromatic hydrocarbon has the formula
HO—A 2 —OH (II)
wherein A 2 is a divalent aromatic hydrocarbon radical.
3. The method of claim 2 wherein A 2 has the formula
—A 3 —Y—A 4 — (III)
wherein each of A 3 and A 4 may be a monocyclic divalent aromatic hydrocarbon radical and Y comprises methylene, cyclohexylmethylene, 2-[2.2.1]-bicycloheptylmethylene, ethylene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamantylidene.
4. The method of claim 1 , wherein the the dihydroxy-substituted aromatic hydrocarbon is bisphenol A.
5. The method of claim 1 , wherein the substituted aromatic compound comprises bis(arylene)sulfone, bis(arylene)ketone, tris(arylene)bis(sulfone), tris(arylene)bis(ketone), bis(arylene)benzo-1,2-diazine, bis(arylene)azoxy radical or a bis(ether imide) radical having the formula
wherein R 8 is a substituted or unsubstituted C 6-20 divalent aromatic hydrocarbon radical, or a C 2-22 alkylene or cycloalkylene radical.
6. The method of claim 1 , wherein the catalyst is a guanidinium salt.
7. The method of claim 1 , wherein the intermediate polymer has a weight average molecular weight of about 10,000 to about 40,000.
8. The method of claim 1 wherein the grams moles of end groups per gram of polymer is determined using the equation: absolute number average molecular weight equals 2×(1−weight fraction of cyclics)/gram moles of endgroups per gram of polymer.
9. The method of claim 8 wherein the absolute number average molecular weight is measured by gel permeation chromatography.
10. The method of claim 8 wherein the weight fraction of cyclics is measured by gel permeation chromatography.
11. The method of claim 1 further comprising monitoring the reaction progress with an in-situ viscosity meter.
12. The method of claim 1 wherein the final polymer has a molecular weight of about 42,000 to about 49,000.
13. The method of claim 1 wherein the final polymer has a molecular weight of about 49,000 to about 60,000.
14. A method of making a polyether polymer comprising
reacting a salt of a dihydroxy-substituted aromatic hydrocarbon with a substituted aromatic compound of formula (I)
Z(A 1 —X 1 ) 2 (I)
in the presence of a catalyst to form an intermediate polymer, wherein the molar ratio of the salt of a dihydroxy-substituted aromatic hydrocarbon to the substituted aromatic compound is less than 1, Z is an activating radical, A 1 is an aromatic radical and X 1 is fluoro, chloro, bromo or nitro;
determining the molecular weight of the intermediate polymer;
calculating the amount of the salt of a dihydroxy-substituted aromatic hydrocarbon used to form the intermediate polymer based on molecular weight achieved and an historical trend of molecular weight versus amount of salt used;
determining an additional amount of a salt of a dihydroxy-substituted aromatic hydrocarbon to obtain a final polymer having a predetermined weight from the intermediate polymer wherein the additional amount of equals (amount of salt of dihydroxy-substituted aromatic hydrocarbon needed per amount of final polymer - amount of the salt of a dihydroxy-substituted aromatic hydrocarbon used to form the intermediate polymer per amount of intermediate polymer) X amount of final polymer;
reacting the intermediate polymer with the additional amount of the salt of a dihydroxy-substituted aromatic hydrocarbon to form the final polymer.
15. The method of claim 14 wherein the dihydroxy-substituted aromatic hydrocarbon has the formula
HO—A 2 —OH (II)
wherein A 2 is a divalent aromatic hydrocarbon radical.
16. The method of claim 15 wherein A 2 has the formula
—A 3 —Y—A 4 — (III)
wherein each of A 3 and A 4 may be a monocyclic divalent aromatic hydrocarbon radical and Y comprises methylene, cyclohexylmethylene, 2-[2.2.1]-bicycloheptylmethylene, ethylene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamantylidene.
17. The method of claim 14 , wherein the the dihydroxy-substituted aromatic hydrocarbon is bisphenol A.
18. The method of claim 14 , wherein the substituted aromatic compound comprises bis(arylene)sulfone, bis(arylene)ketone, tris(arylene)bis(sulfone), tris(arylene)bis(ketone), bis(arylene)benzo-1,2-diazine, bis(arylene)azoxy radical or a bis(ether imide) radical having the formula
wherein R 8 is a substituted or unsubstituted C 6-20 divalent aromatic hydrocarbon radical, or a C 2-22 alkylene or cycloalkylene radical.
19. The method of claim 14 , wherein the catalyst is a guanidinium salt.
20. The method of claim 14 , wherein the intermediate polymer has a weight average molecular weight of about 10,000 to about 40,000.
21. The method of claim 14 further comprising monitoring the reaction progress with an in-situ viscosity meter.
22. The method of claim 14 wherein the final polymer has a molecular weight of about 42,000 to about 49,000.
23. The method of claim 14 wherein the final polymer has a molecular weight of about 49,000 to about 60,000.