Utilizing aTREF data with chemometric analysis for determining the types of polyethylene present in polymer blends and multilayer films

Patent metadata

Field	Value
Publication number	US-11802865-B2
Application number	US-202117562224-A
Country	US
Kind code	B2
Filing date	Dec 27, 2021
Priority date	Dec 27, 2021
Publication date	Oct 31, 2023
Grant date	Oct 31, 2023

Abstract

A method of analyzing a polymer resin comprising: providing a polymer resin sample having two or more polymer components; subjecting the sample to aTREF analysis to yield aTREF elution trace by contacting the sample with aTREF solvent to form sample solution; introducing sample solution into aTREF column and allowing elution of polymer components at different elution rates along the column; eluting from the aTREF column an aTREF eluent comprising the polymer components eluting at different rates; and subjecting the aTREF eluent to IR detection to yield the aTREF elution trace; identifying the components of the sample to yield identified components by comparing the elution trace with an identification library that comprises a plurality of known polymer aTREF elution traces correlated with known polymer components characterized by identifying parameters (density, SCB, crystallization temperature, MI, HLMI, MWD); and quantifying each of the identified components to yield quantified polymer components via chemometric analysis.

First claim

What is claimed is:

1. A method of analyzing a polymer resin comprising:
(a) providing a polymer sample of the polymer resin, wherein the polymer sample comprises two or more polymer components;
(b) subjecting at least a portion of the polymer sample to analytical temperature rising elution fractionation (aTREF) analysis to yield an aTREF elution trace, wherein the subjecting comprises:
(i) contacting at least a portion of the polymer sample with an aTREF solvent to form a polymer sample solution;
(ii) introducing at least a portion of the polymer sample solution into an aTREF column and allowing the polymer sample solution to elute along the aTREF column, wherein the two or more polymer components elute at different elution rates along the aTREF column;
(iii) eluting an aTREF eluent from the aTREF column, wherein the aTREF eluent comprises the two or more polymer components eluting at the different elution rates from the aTREF column; and
(iv) subjecting at least a portion of the aTREF eluent to infrared (IR) detection to yield the aTREF elution trace;

(c) identifying the two or more polymer components of the polymer sample to yield two or more identified polymer components; wherein the identifying comprises comparing the aTREF elution trace with an identification library that comprises a plurality of known polymer aTREF elution traces, wherein each of the plurality of known polymer aTREF elution traces is correlated with a known polymer component, wherein the known polymer component is characterized by an identifying parameter, and wherein the identifying parameter is selected from the group consisting of density, short chain branching, crystallization temperature, melt index, high load melt index, molecular weight distribution, and combinations thereof; and
(d) quantifying an amount of each of the two or more identified polymer components in the polymer sample to yield two or more quantified polymer components, wherein the quantifying comprises chemometric analysis of the aTREF elution trace.

2. The method of claim 1 , wherein the step (ii) of introducing at least a portion of the polymer sample solution into an aTREF column and allowing the polymer sample solution to elute along the aTREF column comprises (1) at least a portion of the polymer in the polymer sample solution crystallizing out of the solution onto the aTREF column under substantially static conditions to yield a column-crystallized polymer; and (2) at least a portion of the column-crystallized polymer re-dissolving back into solution under flow conditions and eluting off the aTREF column with increasing a temperature in the aTREF column.

3. The method of claim 1 , wherein the aTREF analysis is performed on an analytical instrument selected from the group consisting of an aTREF instrument, a crystallization elution fractionation (CEF) instrument, a crystallization analysis fractionation (CRYSTAF)-aTREF instrument, an aTREF-gel permeation chromatography (GPC) instrument, and combinations thereof; wherein the analytical instrument comprises the aTREF column.

4. The method of claim 1 , wherein the chemometric analysis comprises pre-processing the aTREF elution trace to yield a pre-processed aTREF elution trace, wherein the pre-processing comprises baseline correction, mean centering (MC), normalization (N), baseline correction and MC, normalization and MC, or combinations thereof.

5. The method of claim 4 , wherein the pre-processed aTREF elution trace is subjected to principal components analysis (PCA) followed by partial least squares (PLS) regression analysis to predict the amount of each of the two or more polymer components in the polymer sample, thereby quantifying the amount of each of the two or more identified polymer components in the polymer sample.

6. The method of claim 5 , wherein PCA further comprises root mean square (RMS) analysis to determine a number of principal components (PCs) necessary to predict the amount of each of the two or more polymer components in the polymer sample; and wherein the number of PCs is an integer equal to or greater than 1.

7. The method of claim 1 , wherein the chemometric analysis further comprises employing a calibration set that comprises calibration data for known polymer resins having a known amount of each of the two or more identified polymer components.

8. The method of claim 1 , wherein the polymer resin comprises a semi-crystalline polymer, a polyethylene resin, a polypropylene resin, an ethylene-propylene copolymer, an isotactic polypropylene, a syndiotactic polypropylene, a syndiotactic polystyrene, or combinations thereof.

9. The method of claim 1 , wherein the two or more polymer components comprise a metallocene-catalyzed resin, a Ziegler-Natta (ZN)-catalyzed resin, a chromium-catalyzed resin, a non-metallocene single-site-catalyzed resin, a crosslinked resin, a peroxide-treated resin, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene-catalyzed linear low density polyethylene (mLLDPE), peroxide-treated linear low density polyethylene (pLLDPE), peroxide-treated metallocene-catalyzed linear low density polyethylene (pmLLDPE), ZN-catalyzed LLDPE, chromium-catalyzed LLDPE, non-metallocene single-site-catalyzed LLDPE, medium density polyethylene (MDPE), metallocene-catalyzed medium density polyethylene (mMDPE), high density polyethylene (HDPE), a plastomer, an elastomer, or combinations thereof.

10. The method of claim 1 , wherein the step (c) of identifying the two or more polymer components of the polymer sample accounts for the type of catalyst used for producing the two or more polymer components.

11. The method of claim 10 , wherein the two or more polymer components comprise Ziegler-Natta-catalyzed linear low density polyethylene (ZN-LLDPE) and metallocene-catalyzed linear low density polyethylene (mLLDPE).

12. The method of claim 1 , wherein the polymer resin is a polymer film, a multi-layer polymer film, a polymer blend, a unimodal polymer, a multimodal polymer, a bimodal polymer, a trimodal polymer, a terpolymer, or combinations thereof.

13. A method of producing a polymer resin comprising:
(a) providing a polymer sample of the polymer resin, wherein the polymer sample comprises two or more polymer components;
(b) subjecting at least a portion of the polymer sample to analytical temperature rising elution fractionation (aTREF) analysis to yield an aTREF elution trace;
(c) identifying the two or more polymer components of the polymer sample to yield two or more identified polymer components; wherein the identifying comprises comparing the aTREF elution trace with an identification library that comprises a plurality of known polymer aTREF elution traces, wherein each of the plurality of known polymer aTREF elution traces is correlated with a known polymer component, wherein the known polymer component is characterized by an identifying parameter, and wherein the identifying parameter is selected from the group consisting of density, short chain branching, crystallization temperature, melt index, high load melt index, molecular weight distribution, and combinations thereof;
(d) quantifying an amount of each of the two or more identified polymer components in the polymer sample to yield two or more quantified polymer components, wherein the quantifying comprises chemometric analysis of the aTREF elution trace; and
(e) producing the polymer resin by:
(i) responsive to step (c), selecting one or more monomers that can form the two or more identified polymer components; and polymerizing the one or more monomers to produce the polymer resin; wherein the polymerizing occurs under a plurality of polymerizati

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Dixon Janeille K
• Robinson Todd A
• Solis James A
• Kamplain Justin W

Classifications

• G01N33/442 Primary

  Resins; Plastics · CPC title

• C08F10/02

  Ethene · CPC title

• C08J99/00

  Subject matter not provided for in other groups of this subclass · CPC title

• G01N30/14

  by elimination of some components · CPC title

• G01N30/74

  Optical detectors {(measurement of intensity, velocity, spectral content, polarisation, or phase of infrared, visible or ultraviolet light G01J)} · CPC title