Indirect calibration of polymer characterization systems

• US 6,294,388 B1
• Filed: 04/02/1999
• Issued: 09/25/2001
• Est. Priority Date: 04/03/1998
• Status: Expired due to Term

• Current Assignee: Intermolecular Incorporated
• Original Assignee: Symyx Technologies Incorporated (Dassault Systemes SA)
• Inventors: Petro, Miroslav
• Primary Examiner(s): WALLENHORST, MAUREEN
• Application Number:
  US09/285,392
• Time in Patent Office: 907 Days
• Field of Search: 436/8, 436/19, 436/174, 435/DIG.1, 435/DIG.2, 435/DIG.9, 435/DIG.10, 435/DIG.29, 435/DIG.39, 702/22, 702/27, 702/29, 702/30
• US Class Current: 506/12
• CPC Class Codes: B01D 15/08 Selective adsorption, e.g. chromatography
• CPC Class Codes: B01D 15/14 relating to the introduction of the feed to the apparatus
• CPC Class Codes: B01D 15/1871 placed in series
• CPC Class Codes: B01D 15/1885 placed in parallel
• CPC Class Codes: B01D 15/34 Size selective separation, e.g. size exclusion chromatography, gel filtration, permeation
• CPC Class Codes: B01J 19/26 Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
• CPC Class Codes: B01J 2219/00274 Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
• CPC Class Codes: B01J 2219/00585 Parallel processes
• CPC Class Codes: B01J 2219/00587 High throughput processes
• CPC Class Codes: B01J 2219/00707 separated from the reactor apparatus
• CPC Class Codes: B01J 2219/00722 Nucleotides
• CPC Class Codes: C40B 40/14 Libraries containing macromolecular compounds and not covered by groups C40B40/06 - C40B40/12
• CPC Class Codes: G01N 15/0205 by optical means
• CPC Class Codes: G01N 2015/0288 Sorting the particles
• CPC Class Codes: G01N 2015/0294 Particle shape
• CPC Class Codes: G01N 2030/0045 normal, i.e. diffusion or thermal FFF
• CPC Class Codes: G01N 2030/324 speed, flow rate
• CPC Class Codes: G01N 30/02 Column chromatography
• CPC Class Codes: G01N 30/16 Injection G01N30/24 takes precedence
• CPC Class Codes: G01N 30/24 Automatic injection systems
• CPC Class Codes: G01N 30/30 : of temperature
• CPC Class Codes: G01N 30/461 : with serial coupling of separation columns
• CPC Class Codes: G01N 30/466 : with separation columns in parallel
• CPC Class Codes: G01N 30/54 : Temperature
• CPC Class Codes: G01N 30/6052 : body
• CPC Class Codes: G01N 30/88 : Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
• CPC Class Codes: G01N 33/44 : Resins; rubber; leather
• CPC Class Codes: G01N 33/442 : Resins, plastics
• CPC Class Codes: G01N 35/085 : Flow Injection Analysis
• CPC Class Codes: G01N 35/1097 : characterised by the valves valves in general F16K
• CPC Class Codes: Y10T 436/10 : Composition for standardization, calibration, simulation, stabilization, preparation or preservation; processes of use in preparation for chemical testing
• CPC Class Codes: Y10T 436/109163 : Inorganic standards or controls
• CPC Class Codes: Y10T 436/25 : including sample preparation

Abstract

Rapid characterization and screening of polymer samples to determine average molecular weight, molecular weight distribution and other properties is disclosed. Rapid flow characterization systems and methods, including liquid chromatography and flow-injection analysis systems and methods are preferably employed. High throughput, automated sampling systems and methods, high-temperature characterization systems and methods, and rapid, indirect calibration compositions and methods are also disclosed. The described methods, systems, and devices have primary applications in combinatorial polymer research and in industrial process control.

Claims

1. A method for preparing a composition for calibrating polymer characterization systems for characterization of a target polymer sample, the method comprising

injecting a plurality of target-polymer standards into a polymer characterization system, each of the plurality of target-polymer standards having a different known molecular weight and having a polydispersity index of more than about 1.10,

detecting the hydrodynamic volume of each of the injected target-polymer standards,

injecting a plurality of narrow-band polymer standards into the polymer characterization system, the narrow-band polymer standards comprising polymer molecules having a different repeat unit than polymer molecules of the target-polymer standards, each of the injected narrow-band polymer standards having a different known molecular weight and having a polydispersity index ranging from about 1.00 to about 1.10,

detecting the hydrodynamic volume of each of the injected narrow-band standards,

selecting narrow-band standards having a hydrodynamic volume substantially equivalent to the hydrodynamic volumes of the plurality of target-polymer standards, and forming a composition comprising the selected narrow-band standards.

2. The method of claim 1 wherein the composition formed consists essentially of the selected narrow-band standards and a continuous liquid phase.

3. The method of claim 1 wherein the polymer characterization system is a liquid chromatography system.

4. The method of claim 1 wherein the polymer characterization system is a liquid chromatography system comprising a chromatographic column having a stationary phase for size-exclusion chromatography.

5. The method of claim 1 wherein the plurality of target-polymer standards comprises 5 or more target-polymer standards.

6. The method of claim 1 wherein the plurality of target-polymer standards comprises 10 or more target-polymer standards.

7. The method of claim 1 wherein the narrow-band polymer standards are polystyrene standards.

8. The method of claim 1 wherein the target-polymer standards are selected from the group consisting of polyisobutylene, polyethylene and polypropylene.

9. The method of claim 1 wherein the plurality of narrow-band standards each have a polydispersity index ranging from about 1.00 to about 1.05.

10. The composition prepared by the process of claim 1.

11. A method for preparing a correlation suitable for calibrating a polymer characterization system for characterization of a target polymer, the method comprising

injecting the composition of claim 10 into a polymer characterization system,

detecting a property of the narrow-band polymer standards of the injected composition, and

assigning the value for the detected property of each of the narrow-band polymer standards to the target-polymer standard having substantially equivalent hydrodynamic volume as the narrow-band polymer standard, to prepare the correlation.

22. A method for characterizing a plurality of target-polymer samples, the method comprising

calibrating a polymer characterization system with the composition of claim 10,

serially injecting a plurality of the target-polymer samples into the polymer characterization system, and

detecting a property of the injected target-polymer samples.

24. The method of claims 22 or 23 wherein the polymer characterization system is a high-performance liquid chromatography system.

25. The method of claims 22 or 23 wherein the polymer characterization system is a high-performance liquid chromatography system, and the target-polymer samples are non-biological polymer samples.

26. The method of claims 22 or 23 wherein the polymer characterization system is a flow-injection analysis system.

27. The method of claims 22 or 23 wherein the polymer characterization system is a flow-injection analysis system, and the target-polymer samples are non-biological polymer samples.

28. The method of claims 22 or 23 wherein the target-polymer samples are polymerization product mixtures.

29. The method of claims 22 or 23 wherein the target-polymer samples are polymerization product mixtures resulting from polymerization reactions that are varied with respect to reactant materials, catalysts, catalyst precursors, initiators, additives or the relative amounts thereof.

30. The method of claims 22 or 23 wherein the target-polymer samples are polymerization product mixtures resulting from polymerization reactions that are varied with respect to reaction conditions.

31. The method of claims 22 or 23 wherein the target-polymer samples are polymerization product mixtures resulting from synthesis in a parallel polymerization reaction.

32. The method of claims 22 or 23 wherein the target-polymer samples are included within a library of four or more target-polymer samples spatially separated on a common substrate.

12. A set of narrow-band polymer standards suitable for calibration of a polymer characterization system for characterization of a target polymer sample, the set consisting essentially of

a plurality of narrow-band polymer standards, each of the narrow-band polymer standards comprising polymer molecules having a different repeat unit than polymer molecules of the target polymer sample, each of the narrow-band polymer standards having a polydispersity index ranging from about 1.00 to about 1.10 and each having a hydrodynamic volume substantially equivalent to the hydrodynamic volume of one of a plurality of target-polymer standards, the target-polymer standards having different known molecular weights and having a polydispersity index of more than about 1.10.

13. The set of narrow-band polymer standards of claim 12 wherein the plurality of target-polymer standards comprises 5 or more target-polymer standards.

14. The set of narrow-band polymer standards of claim 12 wherein the plurality of target-polymer standards comprises 10 or more target-polymer standards.

15. The set of narrow-band polymer standards of claim 12 wherein the polydispersity index of the plurality of narrow-band polymer standards ranges from about 1.00 about 1.05.

16. The set of narrow-band polymer standards of claim 12 wherein the narrow-band polymer standards are polystyrene standards.

17. The set of narrow-band polymer standards of claim 12 wherein the plurality of target-polymer standards are selected from the group consisting of polyisobutylene, polyethylene and polypropylene.

18. A composition for calibrating polymer characterization systems, the composition consisting essentially of

the set of narrow-band polymer standards of claim 12, and

a continuous liquid phase in which each of the narrow-band standards are dissolved, dispersed or emulsified.

19. The composition of claim 18 wherein the polydispersity index of the narrow-band standards range from about 1.00 about 1.05.

20. The composition of claim 18 wherein the narrow-band polymer standards are polystyrene s tandards.

21. A method for preparing a correlation suitable for calibrating a polymer characterization system for characterization of a target polymer, the method comprising

injecting the composition of claim 18 into a polymer characterization system,

detecting a property of the narrow-band polymer standards of the injected composition, and assigning the value for the detected property of each of the narrow-band polymer standards to the target-polymer standard having substantially equivalent hydrodynamic volume as the narrow-band polymer standard, to prepare the correlation.

23. A method for characterizing a plurality of target-polymer samples, the method comprising

calibrating a polymer characterization system with the composition of claim 18,

serially injecting a plurality of the target-polymer samples into the polymer characterization system, and

detecting a property of the injected target-polymer samples.