Apparatus and method for polymer characterization

Abstract

Apparatus for GPC/TREF and TREF/GPC characterization of a polymer sample. The apparatus provides for the automated and integrated use of multiple TREF columns and a GPC system employing a multiple flow through detectors. In addition, a method for TREF/GPC characterization of a polymer sample by GPC analysis of TREF fractions at increasing TREF elution temperatures from multiple TREF columns operated in a coordinated and synchronized temperature cycle for increased sample throughput. Also, a method for GPC/TREF characterization of a polymer sample by GPC fractionation followed by TREF fractionation of the GPC fractionations.

1 - 9 . (canceled) 
     
     
         10 . A method for TREF/GPC characterization of one or more polymer samples, comprising the steps of: (a) introducing a sample of a first polymer to be characterized into a stream of solvent flowing through a first TREF column; (b) stopping the flow of the solvent when the sample is in the first TREF column; (c) cooling the first TREF column to precipitate at least a portion of the sample in the TREF column; (d) heating the first TREF column to a first temperature to dissolve a portion of the sample precipitated in step (c) to form a first solution of dissolved first sample; and (e) analyzing the first solution of dissolved first sample by in-line gel permeation chromatography. 
     
     
         11 . The method of  claim 10 , further comprising the steps of: (f) introducing a sample of a second polymer to be characterized into a stream of solvent flowing through a second TREF column; (g) stopping the flow of the solvent when the sample is in the second TREF column; (h) cooling the second TREF column to precipitate at least a portion of the sample in the second TREF column; (i) heating the second TREF column to a first temperature to dissolve a portion of the sample precipitated in step (h) to form a first solution of dissolved second sample; and (j) analyzing the first solution of dissolved second sample by in-line gel permeation chromatography. 
     
     
         12 . The method of  claim 11 , further comprising the steps of: (k) heating the first TREF column to a second temperature higher than the first temperature to dissolve an additional portion of the sample precipitated in step (c) to form a second solution of dissolved first sample; (l) analyzing the second solution of dissolved first sample by gel permeation chromatography; (m) heating the second TREF column to a second temperature higher than the first temperature to dissolve an additional portion of the sample precipitated in step (h) to form a second solution of dissolved second sample; and (n) analyzing the second solution of dissolved second sample by in-line gel permeation chromatography. 
     
     
         13 . A method for TREF/GPC characterization of one or more polymer samples, comprising the steps of: (a) introducing a sample of a first polymer to be characterized into a stream of solvent flowing through a first TREF column; (b) stopping the flow of the solvent when the sample is in the first TREF column; (c) cooling the first TREF column to precipitate at least a portion of the sample in the TREF column; (d) heating the first TREF column to a first temperature to dissolve a portion of the sample precipitated in step (c) to form a first solution of dissolved first sample; and (e) analyzing the first solution of dissolved first sample by gel permeation chromatography;
 wherein the temperature of the solvent introduced into the TREF column is matched to the temperature of the TREF column during elution.   
     
     
         14 . The method of  claim 13 , further comprising the steps of: (f) introducing a sample of a second polymer to be characterized into a stream of solvent flowing through a second TREF column; (g) stopping the flow of the solvent when the sample is in the second TREF column; (h) cooling the second TREF column to precipitate at least a portion of the sample in the second TREF column; (i) heating the second TREF column to a first temperature to dissolve a portion of the sample precipitated in step (h) to form a first solution of dissolved second sample; and (j) analyzing the first solution of dissolved second sample by gel permeation chromatography. 
     
     
         15 . The method of  claim 14 , further comprising the steps of: (k) heating the first TREF column to a second temperature higher than the first temperature to dissolve an additional portion of the sample precipitated in step (c) to form a second solution of dissolved first sample; (l) analyzing the second solution of dissolved first sample by gel permeation chromatography; (m) heating the second TREF column to a second temperature higher than the first temperature to dissolve an additional portion of the sample precipitated in step (h) to form a second solution of dissolved second sample; and (n) analyzing the second solution of dissolved second sample by gel permeation chromatography. 
     
     
         16 . The method of  claim 13 , wherein the solvent introduced into the TREF column is directed through a temperature equilibration loop, and then through an oven. 
     
     
         17 . The method of  claim 13 , wherein the solvent is introduced into the TREF column using an equilibration loop contained in an oven. 
     
     
         18 . A method for GPC/TREF characterization of a polymer sample, comprising the steps of: (a) introducing a sample of a polymer to be characterized into a stream of eluent flowing through a gel permeation chromatography column to produce successive elution volumes from the gel permeation chromatography column, wherein the polymer sample elutes therefrom substantially according to the molecular size distribution of the polymer sample; (b) flowing a first elution volume from the gel permeation chromatography column into a first TREF column at an elevated temperature; (c) flowing a second elution volume from the gel permeation chromatography column into a second TREF column at an elevated temperature; (d) cooling the first TREF column to precipitate polymer in the first elution volume in the first TREF column; (e) cooling the second TREF column to precipitate polymer in the second elution volume in the second TREF column; (f) flowing a stream solvent through the second TREF column while heating the second TREF column to dissolve the polymer precipitated therein into the flowing stream of solvent; (g) flowing the stream of solvent from the second TREF column of step (f) through a flow through detector to detect the polymer in the stream of solvent as the polymer dissolves in the solvent as the second TREF column is heated; (h) flowing a stream solvent through the first TREF column while heating the first TREF column to dissolve the polymer precipitated therein into the flowing stream of solvent; (i) flowing the stream of solvent from the first TREF column of step (h) through a flow through detector to detect the polymer in the stream of solvent as the polymer dissolves in the solvent as the first TREF column is heated;
 wherein the temperature of the solvent introduced into the TREF column is matched to the temperature of the TREF column during elution.   
     
     
         19 . The method of  claim 18 , wherein the flow through detector is selected from the group consisting of an infrared detector, a light scattering detector and a viscosity detector. 
     
     
         20 . The method of  claim 19 , wherein the flow through detector is followed by two additional flow through detectors selected from the group consisting of an infrared detector, a light scattering detector and a viscosity detector. 
     
     
         21 . The method of  claim 18 , wherein the solvent introduced into the TREF column is directed through a temperature equilibration loop, and then through an oven. 
     
     
         22 . The method of  claim 18 , wherein the solvent is introduced into the TREF column using an equilibration loop contained in an oven. 
     
     
         23 . An apparatus for the method of TREF/GPC characterization of  claim 13 , which apparatus comprises at least one TREF column, which is in liquid communication with a gel permeation chromatography column, and wherein the at least one TREF column comprises a means for introducing a sample of a polymer to be characterized into a stream of solvent flowing through the TREF column, a means for stopping the flow of the solvent when the sample is in the TREF column, a means for cooling the TREF column to precipitate at least a portion of the sample in the TREF column, and a means for heating the TREF column to dissolve a portion of the precipitated sample to form a solution of dissolved first sample, and wherein said apparatus further comprises a means of equilibrating the temperature of the solvent introduced into the TREF column to the temperature of the TREF column during elution.