Encoding methods using up-converting phosphors for high-throughput screening of catalysts

• US 20020045190A1
• Filed: 07/11/2001
• Published: 04/18/2002
• Est. Priority Date: 07/11/2000
• Status: Abandoned Application

• Current Assignee: SRI International, Inc.
• Original Assignee: SRI International, Inc.
• Inventors: Wilson, Robert B. Jr., Tagge, Christopher D., Mufti, Naheed
• Application Number:
  US09/901,912
• Publication Number:
  US 20020045190A1
• Time in Patent Office: Days
• US Class Current: 435/7.1
• 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 2219/005 Beads
• CPC Class Codes: B01J 2219/00576 fluorophore
• CPC Class Codes: B01J 2219/00596 Solid-phase processes
• CPC Class Codes: B01J 2219/00702 Processes involving means for analysing and characterising the products
• CPC Class Codes: B01J 2219/00736 Non-biologic macromolecules, e.g. polymeric compounds
• CPC Class Codes: B01J 2219/00747 Catalysts
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 4/00 Polymerisation catalysts
• CPC Class Codes: C40B 20/04 Identifying library members by means of a tag, label, or other readable or detectable entity associated with the library members, e.g. decoding processes
• CPC Class Codes: C40B 30/08 by measuring catalytic activity
• CPC Class Codes: C40B 30/10 by measuring physical properties, e.g. mass
• CPC Class Codes: C40B 40/16 Libraries containing metal-containing organic compounds
• CPC Class Codes: C40B 40/18 Libraries containing only inorganic compounds or inorganic materials
• CPC Class Codes: C40B 60/10 for identifying library members
• CPC Class Codes: C40B 60/12 for screening libraries
• CPC Class Codes: C40B 70/00 Tags or labels specially adapted for combinatorial chemistry or libraries, e.g. fluorescent tags or bar codes

Abstract

This invention relates to encoding methods using up-converting phosphors for high-throughput screening of catalysts. In particular, the invention relates to polymerization catalysts. In one embodiment of the invention, a monomer is combined with at least one labeled catalyst particle. The labeled catalyst particle comprises an up-converting phosphor label and a catalyst. The up-converting phosphor label identifies a particular catalyst. The monomer is polymerized to form a polymer bead surrounding the labeled catalyst particle. According to the invention, it is possible to combine two or more labeled catalyst particles in a commercially relevant large scale reactor to obtain direct comparison of different catalysts, and to avoid reactor effects that may occur when performed on the microscale. After the reaction, the resulting polymer beads are sorted, based on their size and/or phosphor labels. The polymer beads may also be further characterized to determine various physical and chemical properties of the resultant polymer.

Claims

1. A method for polymerization, comprising the steps of:

combining a monomer with at least one labeled catalyst particle, wherein said labeled catalyst particle comprises at least one up-converting phosphor label and a catalyst,

wherein said up-converting phosphor label identifies said catalyst, and

comprises at least one rare earth ion and at least one phosphor host material;

and

polymerizing said monomer to form a polymer bead surrounding said labeled catalyst particle.

2. The method of claim 1, wherein said monomer is combined with at least two labeled catalyst particles.

3. The method of claim 2, wherein the wavelength of the excitation radiation of a first phosphor is about equal to the wavelength of the excitation radiation of a second phosphor, and wherein the wavelength of the emission radiation of said first phosphor is different from the wavelength of the emission radiation of said second phosphor.

4. The method of claim 2, wherein the wavelength of the excitation radiation of a first phosphor is different from the wavelength of the excitation radiation of a second phosphor, and wherein the wavelength of the emission radiation of said first phosphor is about the same as the wavelength of the emission radiation of said second phosphor.

5. The method of claim 2, wherein the wavelength of the excitation radiation of a first phosphor is different from the wavelength of the excitation radiation of a second phosphor, and wherein the wavelength of the emission radiation of the first phosphor is different from the wavelength of the emission radiation of the second phosphor.

6. The method of claim 1, further comprising, after the polymerizing step, a step of sorting said polymer beads.

7. The method of claim 6, wherein the sorting step comprises:

illuminating at least one polymer bead with excitation radiation;

detecting emission radiation of at least one emission wavelength; and

separating said polymer beads.

8. The method of claim 7, wherein said excitation radiation is near infrared radiation and said emission radiation is visible radiation.

9. The method of claim 7, wherein said up-converting phosphor label comprises a rare earth ion selected from the group consisting of ytterbium and erbium.

10. The method according to claim 9, wherein said up-converting phosphor label comprises sodium yttrium fluoride ytterbium erbium or yttrium ytterbium erbium oxysulfide.

11. The method of claim 1, wherein said phosphor host material is selected from the group consisting of barium-yttrium-fluoride, sodium yttrium fluoride (NaYF₄), lanthanum fluoride (LaF₃), lanthanum oxysulfide, yttrium oxysulfide, yttrium fluoride (YF₃), yttrium gallate, yttrium aluminum garnet, gadolinium fluoride (GdF₃), barium yttrium fluoride (BaYF₅, BaY₂F₈), gadolinium oxysulfide, lanthanum oxide, gadolinium oxide, alumina, aluminum oxysulfide, aluminum trifluoride, magnesium difluoride, magnesium dichloride and yttrium oxide;

and

wherein said rare earth ion is selected from the group consisting of an erbium ion, neodymium ion, a thulium ion, a holmium ion and a praseodymium ion.

12. The method of claim 1, wherein said monomer is polymerized in a gas phase or slurry phase, or via emulsion polymerization.

13. The method of claim 1, wherein said monomer is selected from the group consisting of:

ethylene, propylene, cis-2-butene, butadiene, 1-hexene, 1-octene, 1-butene, 3 methyl-1-butene, 1,3-butadiene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1,4-hexadiene, 1,5-hexadiene, 1-octene, 1,6-octadiene, 1-nonene, 1-decene, 1,4-dodecadiene, 1-hexadecene, 1-octadecene, cyclopentene, 3-vinylcyclohexene, 5-vinyl-2-norbomene, 5-ethylidene-2-norbomene, dicyclopentadiene, 4-vinylbenzocyclobutane, tetracyclododecene, dimethano-octahydronaphthalene, 7-octenyl-9-borabicyclo-(3,3,1)nonane, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, m-chlorostyrene, p-chlorostyrene, p-fluorostyrene, indene, 4-vinylbiphenyl, acenaphthalene, vinylfluorene, vinylanthracene, vinylphenanthrene, vinylpyrene, methylmethacrylate, ethylacrylate, vinyl silane, phenyl silane, trimethylallyl silane, acrylonitrile, maleimide, vinyl chloride, vinylidene chloride, tetrafluoroethylene, isoprene, isobutylene, carbon monoxide, acrylic acid, 2-ethylhexylacrylate, methyl acrylate, methyl methacrylate, methacrylonitrile, methacrylic acid, vinyl acetate, norbornene, norbornadiene, and mixtures thereof.

14. The method of claim 1, wherein said catalyst is selected from the group consisting of Zieglar-Natta catalysts, metallocene catalysts, stereospecific catalysts, constrained geometry catalysts, single-site catalysts, late transition metal single-site catalysts, free radial initiators, living free radical initiators, cationic initiators, anionic initiators, and mixtures thereof.

15. The method of claim 1, wherein said labelled catalyst particle further comprises a solid support material selected from the group consisting of a porous resinous material and a solid inorganic oxide.

17. The method of claim 16, wherein the sorting step is accomplished through the use of a cytometer.

18. The method of claim 16, wherein the sorting step comprises distinguishing said polymer beads based upon size.

19. The method of claim 16, wherein the sorting step comprises:

illuminating at least one polymer bead with excitation radiation;

detecting emission radiation of at least one emission wavelength; and

classifying the polymer beads based on the up-converting phosphor label.

16. A method for screening a library of catalysts, comprising the steps of:

combining a monomer with at least two labeled catalyst particles, wherein each labeled catalyst particle comprises an up-converting phosphor label and a catalyst,

wherein said up-converting phosphor label identifies a particular catalyst, and comprises at least one rare earth ion and at least one phosphor host material;

polymerizing said monomer to form a polymer bead surrounding said labeled catalyst particle; and

sorting at least two of said polymer beads.

20. A method for screening a solid support material for a supported catalyst, comprising the steps of:

combining a monomer with at least one labeled catalyst particle, wherein said labeled catalyst particle comprises an up-converting phosphor label and a catalyst,

wherein said up-converting phosphor label identifies a particular support material, and comprises at least one rare earth ion and at least one phosphor host material; and

polymerizing said monomer to form a polymer bead surrounding said labeled catalyst particle.

21. A composition comprising a labeled catalyst particle which comprises an up-converting phosphor label and a catalyst, wherein said up-converting phosphor label comprises at least one rare earth ion and at least one phosphor host material.

22. The composition of claim 21, further comprising a solid support material selected from the group consisting of a porous resinous material and a solid inorganic oxide.

23. The composition of claim 21, wherein said up-converting phosphor further comprises at least one compound selected from the group consisting of:

Na(Y_xYb_yEr_z)F₄;

wherein x is 0.7 to 0.9, y is 0.09 to 0.29, and z is 0.05 to 0.01;

Na(Y_xYb_yHo_z)F₄;

wherein x is 0.7 to 0.9, y is 0.0995 to 0.2995, and z is 0.0005 to 0.001;

Na(Y_xYb_yPr_z)F₄;

wherein x is 0.7 to 0.9, y is 0.0995 to 0.2995, and z is 0.0005 to 0.001;

Na(Y_xYb_yTm_z)F₄;

wherein x is 0.7 to 0.9, y is 0.0995 to 0.2995, and z is 0.0005 to 0.001; and

(Y_xYb_yEr_z)O₂S;

wherein x is 0.7 to 0.9, y is 0.05 to 0.12;

z is 0.05 to 0.12.

24. A composition of claim 21, wherein said up-converting phosphor further comprises at least one compound selected from the group consisting of:

(Y_0.80Yb_0.18Er_0.02)F₃;

(Y_0.87Yb_0.13Tm_0.001)F;

(Y_0.80Yb_0.198Ho_0.002)F_3;

(Gd_0.08Yb_0.18Er_0.02)F₃;

(Gd_0.87Yb_0.13Tm_0.001)F₃;

(Gd_0.80Yb_0.198Ho_0.002)F_3;

(Y_0.86Yb_0.08Er_0.6)₂O₂S;

(Y_0.87Yb_0.13Tm_0.001)₂O₂S;

(Y_0.08Yb_0.198Ho_0.0022)O₂S;

(Gd_0.86Yb_0.08Er_0.06)₂O₂S;

(Gd_0.87Yb_0.13Tm_0.001)₂O₂S; and

(Gd_0.08Yb_0.198Ho_0.002)₂O₂S.

25. The composition of claim 21, wherein said catalyst is selected from the group consisting of Zieglar-Natta catalysts, metallocene catalysts, stereospecific catalysts, constrained geometry catalysts, single-site catalysts, late transition metal single-site catalysts, free radical initiators, living free radical initiators, cationic initiators, anionic initiators, and mixtures thereof.