Rapid characterization of polymers

• US 6,406,632 B1
• Filed: 11/08/2000
• Issued: 06/18/2002
• Est. Priority Date: 04/03/1998
• Status: Expired due to Term

• Current Assignee: Intermolecular Incorporated (Merck & Co., Inc.)
• Original Assignee: Symyx Technologies Incorporated (Dassault Systemes SA)
• Inventors: Lee, Thomas S., Petro, Miroslav, Safir, Adam, Nielsen, Ralph B., Fréchet, Jean M. J.
• Primary Examiner(s): Drodge, Joseph W.
• Application Number:
  US09/710,801
• Time in Patent Office: 587 Days
• Field of Search: 210/94, 210/96.1, 210/137, 210/143, 210/198.2, 210/634, 210/635, 210/656, 210/739, 210/745, 210/659, 961/03, 961/05, 422/63, 422/67, 422/68.1, 422/70, 422/101, 436/161, 436/172, 436/174, 436/179, 436/180, 436/164, 73/615.2, 73/615.5, 73/615.6
• US Class Current: 506/7
• 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 19/0046 Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays synthesis methods per se C40B50/00
• 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 2030/324 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; Plastics; Rubber; Leather
• 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 436/25 : 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 characterizing a combinatorial library of non-biological polymer samples, the method comprising

providing a combinatorial library comprising four or more spatially separated non-biological polymer samples, the four or more polymer samples being polymerization polymer mixtures resulting from polymerization reactions that are varied with respect to a factor affecting polymerization,

serially injecting the four or more non-biological polymer samples into a mobile phase of a liquid chromatography system,

chromatographically separating at least one sample component or polymer molecule of each of the four or more injected polymer samples from other sample components or polymer molecules thereof, and

serially detecting a property of the four or more non-biological polymer samples or of components or polymer molecules thereof with a flow-through detector at an average sample throughput of not more than about 10 minutes per sample.

2. The method of claim 1 wherein the polymer samples are selected from the group consisting of polymer solutions, polymer emulsions and polymer dispersions.

3. The method of claim 1 wherein the four or more polymer samples comprise a polymer component, a monomer component and a continuous fluid phase.

4. The method of claim 1 wherein the four or more polymer samples comprise a copolymer component, a first comonomer component, a second comonomer component and a continuous fluid phase.

5. The method of claim 1 wherein the four or more polymer samples are 8 or more polymer samples.

6. The method of claim 1 wherein the four or more polymer samples are 40 or more polymer samples.

7. The method of claim 1 wherein the four or more polymer samples are 80 or more polymer samples.

8. The method of claim 1 wherein the four or more polymer samples are 150 or more polymer samples.

9. The method of claim 1 wherein the four or more polymer samples are 400 or more polymer samples.

10. The method of claim 1 wherein the four or more polymer samples are 1000 or more polymer samples.

11. The method of claim 1 wherein the four or more polymer samples are 2000 or more polymer samples.

12. The method of claim 1 wherein the four or more polymer samples are 5000 or more polymer samples.

13. The method of claim 1 wherein the four or more polymers samples ranges from about 8 polymer samples to about 10,000 polymer samples.

14. The method of claim 1 wherein the four or more polymer samples ranges from about 80 polymer samples to about 1500 polymer samples.

15. The method of claim 1 wherein the four or more polymer samples are 96*N polymer samples, where N is an integer ranging from 1 to about 100.

16. The method of claim 1 wherein the average sample-throughput is not more than about 8 minutes per sample.

17. The method of claim 1 wherein the average sample-throughput is not more than about 4 minutes per sample.

18. The method of claim 1 wherein the average sample-throughput is not more than about 2 minutes per sample.

19. The method of claim 1 wherein the average sample-throughput is not more than about 1 minute per sample.

20. The method of claim 1 wherein the average sample-throughput is not more than about 30 seconds per sample.

21. The method of claim 1 wherein the average sample-throughput is not more than about 20 seconds per sample.

22. The method of claim 1 wherein the average sample-throughput is not more than about 10 seconds per sample.

23. The method of claim 1 wherein the average sample-throughput ranges from about 10 minutes per sample to about 8 minutes per sample.

24. The method of claim 1 wherein the average sample-throughput ranges from about 8 minutes per sample to about 2 minutes per sample.

25. The method of claim 1 wherein the average sample-throughput ranges from about 2 minutes per sample to about 1 minute per sample.

26. The method of claim 1 wherein the average sample-throughput ranges from about 1 minute per sample to about 30 seconds per sample.

27. The method of claim 1 wherein the average sample-throughput ranges from about 30 seconds per sample to about 10 seconds per sample.

28. The method of claim 1 wherein the four or more polymer samples are 8 or more polymer samples and the average sample-throughput is not more than about 8 minutes per sample.

29. The method of claim 1 wherein the four or more polymer samples are 16 or more polymer samples and the average sample-throughput is not more than about 4 minutes per sample.

30. The method of claim 1 wherein the four or more polymer samples are 48 or more polymer samples and the average sample-throughput is not more than about 4 minutes per sample.

31. The method of claim 1 wherein the four or more polymer samples are 96 or more polymer samples and the average sample-throughput is not more than about 4 minutes per sample.

32. The method of claim 1 wherein the four or more polymer samples are 96 or more polymer samples and the average sample-throughput is not more than about 2 minutes per sample.

33. The method of claim 1 wherein the four or more polymer samples are 96 or more polymer samples and the average sample-throughput is not more than about 1 minute per sample.

34. The method of claim 1 wherein the detected property is a chemical property.

35. The method of claim 1 wherein the detected property is a physical property.

36. The method of claim 1 wherein the detected property is an optical property.

37. The method of claim 1 wherein the detected property is selected from the group consisting of emitted light, refracted light, absorbed light and scattered light.

38. The method of claim 1 further comprising determining a property of interest from the detected property.

39. The method of claim 38 wherein the determined property is selected from the group consisting of weight-average molecular weight, number-average molecular weight, viscosity-average molecular weight, peak molecular weight, polydispersity index and molecular-weight-distribution shape.

40. The method of claim 38 wherein the determined property is selected from the group consisting of composition and conversion.

41. The method of claim 38 wherein the determined property is selected from the group consisting of hydrodynamic radius and radius of gyration.

42. The method of claim 38 wherein the determined property is molecular weight.

43. The method of claim 38 wherein the determined property is a weight-average molecular weight.

44. The method of claim 38 wherein the determined property is a composition.

45. The method of claim 38 wherein the determined property is a conversion value for a polymerization reaction from which the polymer sample was formed.

46. The method of claim 1 further comprising determining a molecular weight and a conversion value for a polymerization reaction from which the polymer sample was formed.

47. The method of claim 1 wherein the liquid chromatography system is a high-pressure liquid chromatography system.

48. The method of claim 1 wherein the liquid chromatography system comprises a chromatographic column having a separation medium for size exclusion chromatography.

49. The method of claim 1 wherein the liquid chromatography system comprises a chromatographic column having a separation medium for precipitation-redissolution chromatography.

50. The method of claim 1 wherein the liquid chromatography system comprises a chromatographic column having a separation medium for adsorption chromatography.

51. The method of claim 1 wherein the liquid chromatography system comprises a chromatographic column having a separation medium for reverse-phase chromatography.

52. The method of claim 1 wherein the property is detected with a detector selected from the group consisting of a refractive-index detector, an ultraviolet-visual detector, a photodiode array detector, a static-light-scattering detector, a dynamic-light-scattering detector, an evaporative-light-scattering detector and a capillary viscometer detector.

69. The method of claim 1 or 67 wherein the liquid chromatography system comprises a pump for providing flow of a mobile phase from a mobile-phase fluid source through one or more chromatography columns to a flow-through detector, an injection port, and optionally an injection valve, the injection port and optional injection valve being adaptable for fluid communication with the mobile phase for injecting the polymer samples into the mobile phase, the one or more chromatography columns being adapted to separate one or more components or polymer molecules of the polymer samples from other components or polymer molecules thereof, the flow-through detector being adapted to detect a property of the polymer samples or a component or polymer molecule thereof.

72. The method of claims 1 or 67 wherein the injected polymer samples are serially separated.

98. The method of claims 1, 64, 67 or 81 wherein the polymer samples are members of a combinatorial library comprising four or more different non-biological polymer samples on a common substrate.

99. The method of claims 1, 64, 67 or 81 wherein each of the four or more polymer samples of the library resides in a separate reaction vessel, the method further comprising withdrawing each of the four or more polymer samples from its reaction vessel.

100. The method of claims 1, 64, 67 or 81 wherein the polymer samples are members of a combinatorial library comprising twenty or more non-biological polymer samples and at least about 50% of the polymer samples included in the library are different from each other with regard to chemical structure of polymer molecules in the samples.

102. The method of claims 1, 64, 67 or 81 wherein the four or more polymer samples are polymerization product mixtures resulting from polymerization reactions that are varied with respect to reaction conditions.

103. The method of claims 1, 64, 67 or 81 wherein the four or more polymer samples are polymerization product mixtures resulting from synthesis in a parallel polymerization reaction.

104. The method of claims 1, 64, 67 or 81 wherein polymer molecules having the same repeat unit, but different molecular weights, are chromatographically separated from each other.

106. The method of claims 1 or 105 wherein

the liquid chromatography system comprises a pump for providing flow of a mobile phase from a mobile-phase fluid source through one or more chromatography columns to a flow-through detector, an injection port, and optionally an injection valve, the injection port and optional injection valve being internal to heated-environment enclosure and being adaptable for fluid communication with the mobile phase for injecting the polymer samples into the mobile phase, the one or more chromatography columns being internal to the heated-environment enclosure and being adapted to separate one or more components or polymer molecules of the polymer samples from other components or polymer molecules thereof, the flow-through detector being internal or external to the heated-environment enclosure and being adapted to detect a property of the polymer samples or a component or polymer molecule thereof, and

the samples are injected into the mobile phase using an injection probe of an autosampler, the injection probe and autosampler being external to the heated-environment enclosure, by inserting the injection probe from a position external to the heated-environment enclosure into the injection port within the heated-environment enclosure.

107. The method of claim 106 wherein the injection probe is a heated injection probe.

53. A method for characterizing a combinatorial library of non-biological polymer samples, the method comprising

providing a combinatorial library comprising a plurality of non-biological polymer samples, each of the plurality of polymer samples being polymerization polymer mixtures resulting from polymerization reactions that are varied with respect to a factor affecting polymerization and residing in separate sample containers,

withdrawing a first non-biological polymer sample from a first sample container,

injecting at least a portion of the withdrawn first sample into a mobile phase of a liquid chromatography system at a first injection time, t_LCI1,

chromatographically separating at least one sample component or polymer molecule of the injected first sample from other sample components or polymer molecules thereof in a chromatographic column,

detecting a property of at least one of the separated sample components or polymer molecules of the first sample,

withdrawing a second non-biological polymer sample from a second sample container,

injecting at least a portion of the withdrawn second sample into the mobile phase of the liquid chromatography system at a second injection time, t_LCI2, the difference in time, t_LCI2−

t_LCI1, being not more than about 10 minutes,

chromatographically separating at least one sample component or polymer molecule of the injected second sample from other sample components or polymer molecules thereof in the chromatographic column, and

detecting a property of at least one of the separated sample components or polymer molecules of the second sample.

54. the method of claim 53 wherein the chromatographic column comprises a stationary-phase and the sample components of the first and second samples are separated from other respective components thereof by introducing the samples onto the stationary phase and subsequently eluting the samples or components thereof from the stationary phase with an eluant, the method further comprising

controlling the column geometry, stationary-phase, eluant composition, eluant temperature or eluant flow rate such that the sample throughput is not more than about 10 minutes per sample.

55. The method of claim 53 wherein the chromatographic column comprises a porous stationary-phase and has an aspect ratio ranging from about 0.1 to about 1.

56. The method of claim 53 wherein the first and second samples are withdrawn into an injection probe of an auto-sampler, the method further comprising

preparing the withdrawn first sample prior to injecting at least a portion thereof into the mobile-phase of the liquid chromatography system, and

preparing the withdrawn second sample prior to injecting at least a portion thereof into the mobile-phase of the liquid-chromatography system.

57. The method of claim 56 wherein the second withdrawn sample is prepared while separating or detecting the first withdrawn sample.

58. The method of claim 53 wherein the first and second samples are withdrawn into an injection probe of an auto-sampler, the method further comprising

cleaning the injection probe after injecting at least a portion of the first sample into the mobile phase of the liquid chromatography system and before withdrawing the second sample.

59. The method of claim 53 wherein the first and second samples are withdrawn into an injection probe of an auto-sampler, the method further comprising

preparing the withdrawn first sample prior to injecting at least a portion thereof into the mobile-phase of the liquid chromatography system,

cleaning the injection probe after injecting at least a portion of the first sample into the mobile-phase of the liquid chromatography system and before withdrawing the second sample, and

preparing the withdrawn second sample prior to injecting at least a portion thereof into the mobile-phase of the liquid chromatography system.

95. The method of claims 53, 60, 67 or 81 wherein the polymer sample is a polymerization product mixture that is untreated or pretreated only with one or more steps selected from the group consisting of non-chromatographic separation, dilution, mixing, and redissolution.

96. The method of claims 53, 67 or 81 wherein ten or more polymer samples are characterized, the ten or more polymer samples being members of a library of polymerization product mixtures.

97. The method of claims, 53, 60, 64 or 81 wherein at least one sample component or polymer molecule of the injected samples are separated from other sample components or polymer molecules thereof by size-exclusion chromatography.

60. A method for characterizing a combinatorial library of non-biological polymer samples, the method comprising

providing a combinatorial library comprising four or more different, spatially separated, non-biological polymer samples, the four or more polymer samples being polymerization polymer mixtures resulting from polymerization reactions that are varied with respect to a factor affecting polymerization,

serially injecting each of the forty-eight or more non-biological polymer samples into a mobile-phase of a liquid chromatography system, and

determining a weight-average molecular weight of at least one chromatographically separated component or polymer molecule of each of the forty-eight or more samples with the liquid chromatography system, the average sample-throughput being not more than about 10 minutes per sample.

61. The method of claim 60 wherein the average sample throughput is not more than about 8 minutes per sample.

62. The method of claim 60 wherein the average sample throughput is not more than about 4 minutes per sample.

63. The method of claim 60 wherein the average sample throughput is not more than about 2 minutes per sample.

64. A method for characterizing a plurality of non-biological polymer samples comprising a polymerization product mixture, the method comprising

(a) injecting a non-biological polymer sample into a mobile-phase of a liquid chromatography system,

(b) chromatographically separating a low molecular-weight fraction of the injected sample from a high molecular-weight fraction thereof in a chromatographic column having a stationary-phase, the low molecular-weight fraction comprising sample components having molecular weights of not more than about 1000 D, the high molecular-weight fraction comprising sample components having molecular weights of more than about 1000 D,

(c) passing the high molecular-weight fraction of the injected sample through the chromatographic column without substantial separation thereof,

(d) detecting a property of the high molecular-weight fraction or of a component thereof, and

(e) repeating steps (a), (b), (c) and (d) for the plurality of polymer samples.

65. The method of claim 64, wherein the stationary-phase is a porous medium having a range of pore sizes that facilitate passage of the high-molecular weight fraction and separation of the low molecular-weight fraction from the high molecular-weight fraction.

66. The method of claim 64 wherein the polymer samples are polymerization product mixtures resulting from polymerization reactions that are varied with respect to a factor affecting polymerization.

73. The method of claims 64 or 67 wherein the property is detected with a light-scattering detector.

74. The method of claim 73 wherein the property is detected with a static light-scattering detector.

75. The method of claim 73 wherein the property is detected with a dynamic light-scattering detector.

76. The method of claim 73 wherein the property is detected with a combination of detectors comprising a static light-scattering detector and a mass detector.

77. The method of claim 73 wherein the property is detected with a combination of detectors comprising a static-light-scattering detector and at least one of a refractive index detector or an evaporative light-scattering detector.

78. The method of claim 73 wherein the property is detected with a combination of detectors comprising the light-scattering detector and at least one of a UV-VIS detector or a photodiode array detector.

79. The method of claim 73 wherein the property is detected with a combination of detectors comprising the light-scattering detector and a viscometric detector.

80. The method of claims 64 or 67 wherein the sample concentration is known, and a property is detected with a refractive index detector.

101. The method of claims 64, 67 or 81 wherein the four or more polymer samples are polymerization product mixtures resulting from polymerization reactions that are varied with respect to one or more of (i) reactant materials, (ii) catalysts, (iii) catalyst precursors, (iv) initiators, (v) additives or (vi) the relative amounts of reactant materials, catalysts, catalyst precursors, initiators or additives.

67. A method for characterizing a combinatorial library of non-biological polymer samples, the method comprising

providing a combinatorial library comprising a plurality of non-biological polymer samples, each of the plurality of polymer samples being polymerization polymer mixtures resulting from polymerization reactions that are varied with respect to a factor affecting polymerization,

serially injecting the plurality of polymer samples into a mobile phase of a liquid chromatography system,

chromatographically separating at least one sample component or polymer molecule of the injected samples from other sample components or polymer molecules thereof in a chromatographic column having a stationary-phase and an aspect ratio ranging from about 0.1 to about 1, and

detecting a property of at least one of the separated components of the plurality of samples.

68. The method of claim 67 wherein the stationary-phase is a porous stationary phase.

70. The method of claim 67 wherein the at least one sample component or polymer molecule of the injected samples are separated from other sample components or polymer molecules thereof by size-exclusion chromatography.

71. The method of claim 67 wherein the at least one sample component or polymer molecule of the injected samples are separated from other sample components or polymer molecules thereof by size-exclusion chromatography together with one or more additional chromatographic methods selected from the group consisting of adsorption chromatography, reverse-phase chromatography, and precipitation-redissolution chromatography.

81. A method for characterizing a combinatorial library of non-biological polymer samples, the method comprising

providing a combinatorial library comprising four or more non-biological polymer samples, the four or more polymer samples being polymerization polymer mixtures resulting from polymerization reactions that are varied with respect to a factor affecting polymerization,

serially screening four or more non-biological polymer samples of the library for a first property of interest with a first flow characterization system, the first flow characterization system being a liquid chromatography system having an average sample throughput of not more than about 10 minutes per sample, the four or more polymer samples being screened by a method that includes injecting the four or more polymer samples into a mobile phase of the liquid chromatography system, chromatographically separating one or more components or polymer molecules of the four or more injected samples from other components or polymer molecules thereof, and detecting the first property of interest, and

screening at least one of the four or more samples screened with the first characterization system for a second property of interest with a second characterization system.

82. The method of claim 81 wherein the second characterization system has an average sample-throughput of not more than about 10 minutes per sample.

83. The method of claim 81 wherein the second property of interest is the same as the first property of interest.

84. The method of claim 81 wherein the second property of interest is different from the first property of interest.

85. The method of claim 81 wherein the second characterization system is a liquid chromatography system.

86. The method of claim 85 further comprising determining chemical composition from the first detected property and determining molecular weight from the second detected property.

87. The method of claim 85 further comprising determining molecular weight from the first detected property and determining chemical composition from the second detected property.

88. The method of claim 81 wherein the second characterization system is a flow-injection analysis system.

89. The method of claim 81 wherein each of the four or more samples screened with the first characterization system are screened for the second property of interest with the second characterization system.

90. The method of claim 81 wherein each of the four or more samples screened with the first characterization system are screened for the second property of interest with the second characterization system, the second property of interest is different from the first property of interest, and the second characterization system has an average sample-throughput of not more than about 10 minutes per sample.

91. The method of claim 90 wherein the second characterization system is a liquid chromatography system, and the four or more samples are screened for the first and second properties with the first and second liquid chromatography systems by a protocol that includes

(a) withdrawing a polymer sample from a sample container,

(b) injecting a first portion of the withdrawn sample into a mobile-phase of the first liquid chromatography system,

(c) after step (b), injecting a second portion of the withdrawn sample into a mobile phase of the second liquid chromatography system,

(d) separating at least one sample component or polymer molecule of the sample injected in the mobile phase of the first liquid chromatography system from other sample components or polymer molecules thereof with a chromatographic column,

(e) separating at least one sample component or polymer molecule of the sample injected in the second liquid chromatography system from other sample components or polymer molecules thereof with a chromatographic column,

(f) detecting the first property of interest with a first detector in the first liquid chromatography system,

(g) detecting the second property of interest with a second detector in the second liquid chromatography system, and

(h) repeating steps (a) through (g) in series for the four or more samples.

92. The method of claim 81 further comprising

determining a figure of merit for the four or more samples based at least in part on the first property of interest,

comparing the determined figure of merit for the four or more samples with a predetermined threshold value for the figure of merit, and

screening those of the four or more samples that favorably compare with the predetermined threshold value for the figure of merit with the second characterization system.

93. The method of claim 92 wherein only those of the four or more samples that favorably compare with the predetermined threshold value for the figure of merit are screened with the second characterization system.

94. The method of claim 92 wherein the second characterization system is a liquid chromatography system, and the four or more samples are screened by a protocol that includes

(a) withdrawing a polymer sample from a sample container,

(b) injecting at least a portion of the withdrawn sample into a mobile phase of the first liquid chromatography system,

(c) separating at least one sample component or polymer molecule of the sample injected in the mobile phase of the first liquid chromatography system from other sample components or polymer molecules thereof with a chromatographic column,

(d) detecting the first property of interest with a detector of the first liquid chromatography system,

(e) determining a figure of merit based at least in part on the detected first property,

(f) comparing the determined figure of merit with a predetermined threshold value for the figure of merit,

(g) repeating steps (a) through (f) in series for the four or more samples,

(h) injecting those samples that favorably compare with the predetermined threshold value for the figure of merit into a mobile phase of the second liquid chromatography system,

(i) separating at least one sample component or polymer molecule of the samples injected in the mobile phase of the second liquid chromatography system from other sample components or polymer molecules thereof in a chromatographic column, and

(j) detecting the second property of interest with a detector of the second liquid chromatography system.

105. A method for characterizing a plurality of polymer samples comprising a polymerization product mixture, the method comprising

providing an array of four or more spatially separated polymer samples, and

serially detecting a property of the four or more polymer samples or of components thereof with a liquid chromatography system at an average sample-throughput ranging from about 1 minute per sample to about 30 seconds per sample.

112. The method of claims 105 or 108 wherein the polymer samples are a non-biological polymer sample.

108. A method for characterizing a plurality of polymer samples comprising a polymerization product mixture, the method comprising

providing an array of four or more spatially separated polymer samples, and

serially detecting a property of the four or more polymer samples or of components thereof with a liquid chromatography system at an average sample-throughput of not more than about 30 seconds per sample.

109. The method of claim 108 wherein the average sample-throughput is not more than about 20 seconds per sample.

110. The method of claim 108 wherein the average sample-throughput is not more than about 10 seconds per sample.

111. The method of claim 108 wherein the average sample-throughput ranges from about 30 seconds per sample to about 10 seconds per sample.