METHODS FOR PRODUCING VINYLAMINE-CONTAINING POLYMER SOLUTIONS AND VINYLAMINE-CONTAINING POLYMER SOLUTIONS PRODUCED THROUGH THE METHODS
Methods for producing a vinylamine-containing polymer solution and vinylamine-containing polymer solutions produced through the methods are provided herein. In an embodiment, a method for producing a vinylamine-containing polymer solution includes polymerizing N-vinylcarboxamide monomers and hydrolyzing a resulting intermediate polymer formulation. The method involves determining the amount of unreacted N-vinylcarboxamide monomers in the intermediate polymer formulation, modifying one or more process parameters of the polymerization step accordingly, and repeating the polymerization step with the modified process parameter(s). Methods of assessing the amount of unreacted monomers include directly measuring the amount of unreacted monomers in the intermediate, observing the color of the product, measuring the wavelength of the product, or measuring the dynamic viscosity of the product.
1 . A method of synthesizing a vinylamine-containing polymer solution, the method comprising the steps of:
(a) reacting a polymerization initiator, one or more N-vinylcarboxamide monomers, and optionally one or more additional vinyl monomers having a formula different from the N-vinylcarboxamide monomers, in a reaction mixture to create an intermediate polymer formulation comprising a poly(N-vinylcarboxamide) prepolymer, wherein the N-vinylcarboxamide monomers have the general formula I
wherein R 1 and R 2 , independently of one another, are H or C 1 to C 6 alkyl groups;
(b) hydrolyzing carboxamide groups in the poly(N-vinylcarboxamide) prepolymer to create a vinylamine-containing polymer solution comprising a vinyl-amine containing polymer;
(c) determining the intermediate polymer formulation to have an unacceptably high amount of unreacted N-vinylcarboxamide monomers;
(d) after step (c), modifying one or more process parameters of step (a); and
repeating step (a) after step (d) to form a modified intermediate polymer formulation.
2 . The method of claim 1 , further comprising:
(e) determining the amount of unreacted N-vinylcarboxamide monomers in the modified intermediate polymer formulation after repeating step (a) to be at or below a predetermined N-vinylcarboxamide threshold value.
3 . The method of claim 1 , wherein determining the intermediate polymer formulation to have an unacceptably high amount of unreacted N-vinylcarboxamide monomers comprises:
measuring the amount of unreacted N-vinylcarboxamide monomers in the intermediate polymer formulation;
comparing the amount of unreacted N-vinylcarboxamide monomers in the intermediate polymer formulation to a predetermined N-vinylcarboxamide threshold value; and
determining that the amount of unreacted N-vinylcarboxamide monomers in the intermediate polymer formulation is greater than the predetermined unreacted N-vinylcarboxamide threshold value.
4 . The method of claim 3 , wherein determining that the amount of unreacted N-vinylcarboxamide monomers is greater than the predetermined unreacted N-vinylcarboxamide threshold value comprises determining that the amount of unreacted N-vinylcarboxamide monomers is greater than about 0.03% by weight based on a total weight of the intermediate polymer formulation.
5 . The method of claim 3 , wherein determining that the amount of unreacted N-vinylcarboxamide monomers is greater than the predetermined unreacted N-vinylcarboxamide threshold value comprises determining that the amount of N-vinylcarboxamide monomers is greater than about 0.06% by weight based on a total weight of the intermediate polymer formulation.
6 . The method of claim 1 , wherein determining the intermediate polymer formulation to have an unacceptably high amount of unreacted N-vinylcarboxamide monomers comprises:
visually observing the color of the vinylamine-containing polymer solution after performing step (b); and
determining that the color of the vinylamine-containing polymer solution is dark yellow or higher wavelength in the electromagnetic spectrum.
7 . The method of claim 1 , wherein determining the intermediate polymer formulation to have an unacceptably high amount of unreacted N-vinylcarboxamide monomers comprises:
measuring the wavelength of the vinylamine-containing polymer solution; and
determining that the wavelength of the vinylamine-containing polymer solution is at least 600 nm using a spectrophotometer.
8 . The method of claim 7 , wherein the wavelength of the vinylamine-containing polymer solution is determined to be at least 575 nm.
9 . The method of claim 1 , wherein determining the intermediate polymer formulation to have an unacceptably high amount of unreacted N-vinylcarboxamide monomers comprises determining that a dynamic viscosity of the vinylamine-containing polymer solution exceeds a predetermined dynamic viscosity threshold value.
10 . The method of claim 9 , wherein determining that the dynamic viscosity of the vinylamine-containing polymer solution exceeds the predetermined dynamic viscosity threshold value comprises:
measuring the dynamic viscosity of the vinylamine-containing polymer solution, with total solids of 18%, using a Brookfield viscometer at 6 rpm using an LV spindle number 62 at 25° C.; and
determining that the dynamic viscosity of the vinylamine-containing polymer solution is greater than the predetermined dynamic viscosity threshold value.
11 . The method of claim 10 , wherein the predetermined dynamic viscosity threshold value is 700 cPs.
12 . The method of claim 10 , wherein the predetermined dynamic viscosity threshold value is 1100 cPs.
13 . The method of claim 1 , wherein the one or more process parameters of step (a) are chosen from the group of reaction time, temperature, pressure, pH, initiator concentration, monomer concentration, or purity of process water.
14 . The method of claim 1 , wherein hydrolyzing carboxamide groups in the poly(N-vinylcarboxamide) prepolymer to create a vinylamine-containing polymer solution comprises adding an acid or base to the reaction mixture.
15 . The method of claim 1 , wherein the polymerization initiator is an azo initiator.
16 . The method of claim 3 , wherein determining the intermediate polymer formulation to have an unacceptably high amount of unreacted vinylformamide monomers further comprises:
determining that the color of the vinylamine-containing polymer solution is visibly dark yellow or higher wavelength in the electromagnetic spectrum; and
determining that the dynamic viscosity of the vinylamine-containing polymer solution is greater than about 700 cPs.
17 . A vinylamine-containing polymer solution formed by:
(a) reacting one or more N-vinylcarboxamide monomers and a polymerization initiator in a reaction mixture to create an intermediate polymer formulation comprising a poly(N-vinylcarboxamide) prepolymer, wherein the N-vinylcarboxamide monomers have the general formula I;
(b) optionally adding one or more vinyl monomers having a formula different from formula I during step (a);
(c) hydrolyzing carboxamide groups in the poly(N-vinylcarboxamide) prepolymer to create a vinylamine-containing polymer solution comprising a vinyl-amine containing polymer;
(d) determining the intermediate polymer formulation to have an unacceptably high amount of unreacted N-vinylcarboxamide monomers;
(e) modifying one or more process parameters of step (a);
(f) repeating step (a) to form a modified intermediate polymer formulation;
(g) determining the amount of unreacted N-vinylcarboxamide monomers in the modified intermediate polymer formulation;
(h) repeating steps (a) and (g) until the amount of unreacted N-vinylcarboxamide monomers in the modified intermediate polymer formulation is at or below a predetermined N-vinylcarboxamide threshold value.