CA2412191A1 - Improved high-solids coatings resins via controlled radical polymerization - Google Patents
Improved high-solids coatings resins via controlled radical polymerization Download PDFInfo
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- CA2412191A1 CA2412191A1 CA002412191A CA2412191A CA2412191A1 CA 2412191 A1 CA2412191 A1 CA 2412191A1 CA 002412191 A CA002412191 A CA 002412191A CA 2412191 A CA2412191 A CA 2412191A CA 2412191 A1 CA2412191 A1 CA 2412191A1
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- methacrylate
- alkyl
- acrylate
- alkoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
Abstract
Processes for the controlled radical polymerization of acrylic and related polymers to produce improved low VOC coating materials, or powder coating compositions, the novel polymers so produced, the catalyst systems employed, processes for application of the improved coatings , coatings so produced and objects coated on at least one surface with the novel coatings are disclosed.
Claims (2)
1. A process for the controlled free radical solution polymerization to a level of solids suitable for use as low volatile organic solvent coating compositions while maintaining viscosity suitable for such coatings of monomers comprising substituted or unsubstituted acrylic acid, or esters thereof in a solvent suitable for high solids coating application at a monomer concentration sufficient to give the desired polymer concentration which comprises treating said monomers in said solvent with a controlled free radical initiator selected from the group N,N-dialkyl-alkoxyamines having one hydrogen atom on one carbon atom in the a position of one alkyl group attached to the amino nitrogen, nitroxyl radicals having one hydrogen atom on one carbon atom in the a position of one alkyl group attached to the nitroxyl nitrogen and mixtures thereof.
2. A process as defined in claim 1 wherein the alkoxyamine has the structure II:
N O Z
(II) Wherein R1, R2, R3, R4,and R5 are independently selected from the group consisting of straight chain alkyl, branched chain alkyl and cyclic alkyl, substituted, or unsubstituted aralkyl, and substituted or unsubstituted aryl groups having from 1 to 50 carbon atoms, with the proviso that one of said R moieties be substituted with, or contain sulfur, or phosphorous and any two of R1, R2, R3, R4 and R5 which do not contain sulfur, or phosphorous, and which are attached.to the same carbon atom, may be concatenated to form, when taken together with the carbon atom to which they are attached, a cyclic alkyl group of from 5 to 20 carbon atoms and Z is selected from the following groups, wherein the dashed line attached to the carbon atom represents either a free electron or the point of attachment to the oxygen atom of the original alkoxyamine as appropriate:
a benzylic radical of the general formula Z1:
wherein Ar1 is an aryl group which may be substituted with halogen atoms, hydroxyl, alkoxy, ester, carboxy, acyl, amino, nitro, cyano, amido, sulfonyl, or phosphonyl groups and where Rz1 and R'z1 are independently selected from hydrogen atoms, or cyclic alkyl, straight chain alkyl, or branched chain alkyl groups, of from 1 to 50 carbon atoms and which alkyl groups may be unsubstituted or substituted with any of the above named substituent groups for Ar1 an ester type radical of general formula Z2:
Wherein Rz2, R'z2 and R"z2 are independently selected from straight chain alkyl, branched chain alkyl or cyclic alkyl groups of from 1 to 50 carbon atoms which alkyl groups may be unsubstituted or substituted with any of the above defined substituents for Ar1 and R"z2 may also be hydrogen.
a cyano radical of the general formula Z3:
wherein Rz3 and R'Z3 are independently selected from cyclic alkyl, straight chain alkyl, or branched chain alkyl groups of from 1 to 50 carbon atoms which alkyl groups may be unsubstituted or substituted with any of the named substituent groups for Ar1 and an alkyl radical of the general formula Z4:
wherein Rz4, R'z4 and R"z4 are independently selected from among the alkyl groups as defined for Rz3.
A process as defined in claim 1 wherein the nitroxyl radical has the structure I:
N O' (I) wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of straight chain alkyl, branched chain alkyl, cyclic alkyl, substituted, or unsubstituted aralkyl, or substituted, or unsubstituted aryl groups having from 1 to 50 carbon atoms, with the proviso that one of said R moieties be substituted with, or contain sulfur or phosphorous and any two of R1, R2, R3, R4 and R5 which do not contain sulfur, or phosphorous, and which are attached to the same carbon atom, may be concatenated to form, when taken together with the carbon atom to which they are attached, a cyclic alkyl group of from 5 to 20 carbon atoms.
4. A process as defined in claim 1 wherein the controlled free radical initiator is an alkoxyamine selected from the group consisting of methyl 2-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]propionate, 1-phenyl-1-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]ethane, 1,1-dimethyl-1-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]ethane, 1-methyl-1-cyano-1-[N-t-butyl-N-(1-diethyphosphono-2,2-dimethylpropyl)-N-oxy]ethane and mixtures thereof.
5. A process as defined in claim 1 wherein the controlled free radical initiator is the alkoxyamine methyl 2-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]propionate.
6. A process as defined in claim 1 wherein the controlled free radical initiator comprises a mixture of alkoxyamines as defined in claim 2 and nitroxyl radicals as defined in claim 3.
7. A process as defined in claim 4 wherein the controlled free radical initiator also includes nitroxyls derived from the alkoxyamine selected from the group defined in claim 4.
8. A process as defined in claim 5 wherein the controlled free radical initiator also includes a nitroxyl radical derived from the alkoxyamine.
9. A process as defined in claim 1 also including an organic peroxide initiator or an azonitrile initiator.
10. A process as defined in claim 1 wherein the monomers comprising substituted or unsubstituted acrylic acid or esters thereof are selected from the group consisting of (subgroup a) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acetoacetoxy ethyl acrylate, acetoacetoxy ethyl methacrylate and mixtures thereof, (subgroup b) methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, lauryl acrylate and mixtures thereof, (subgroup c) acrylic acid, methacrylic acid and mixtures thereof, (subgroup d) iso-octyl acrylate, diethylaminomethyl acrylate, diethylaminomethyl methacrylate, t-butylaminoethyl methacrylate, t-butylaminoethyl acrylate and mixtures thereof, with the proviso that at least one member of subgroup a and of subgroup b must be present.
11. A process as defined in claim 10 wherein a monomer selected from the group styrene, para-methyl styrene, vinyl acetate and mixtures thereof is also present.
12. A process as defined in claim 11 wherein the monomers comprise butyl acrylate, hydroxyethyl acrylate, styrene and acrylic acid.
13. A process as defined in 11 wherein the monomers comprise glycidyl methacrylate, butyl methacrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, methacrylic acid, hydroxypropyl acrylate, hydroxypropyl methacrylate, acetoacetoxy ethyl acrylate, acetoacetoxy ethyl methacrylate and mixtures thereof.
14. The product produced by a process as defined in claim 1.
15. A process for coating an object on at least one surface which comprises applying a product as defined in claim 14 to said at least one surface and treating said product after application on said at least one surface to sufficient heat for a sufficient time to evaporate the solvent contained in said product and crosslink the remaining material of said product on said at least one surface.
16. The coating produced by the process defined in claim 15.
17. The coated object produced by the process defined in claim 15.
18. A process as defined in claim 1 wherein the polymer so produced is recovered as a solvent free material.
19. A powder coating material prepared from the solvent free material prepared as defined in claim 18.
20. An object coated on at least one surface thereof with a coating formed by applying the powder coating material defined in claim 19 to the said at least one surface of said object and fusing said powder coating material into a coherent coating.
21. A process as defined in claim 2 wherein one of R1, R2, R3, R4, or R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from the group consisting of methyl, methoxy, ethoxy, n-propoxy, benzyloxy, dodecyloxy, phenyl and benzyl.
22. A process as defined in claim 3 wherein one of R1, R2, R3, R4, or R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from the group consisting of methyl, methoxy, ethoxy, n-propoxy, benzyloxy, dodecyloxy, phenyl and benzyl.
23. A process as defined in claim 6 wherein, independently in the alkoxyamine and the nitroxyl, one of R1, R2, R3, R4, or R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from the group consisting of methyl, methoxy, ethoxy, n-propoxy, benzyloxy, dodecyloxy, phenyl and benzyl.
24. A process as defined in claim 2 wherein R1, R2 and R3 are methyl, R4 is t-butyl and R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from straight chain alkyl, branched chain alkyl, or cyclic alkyl groups, aralkyl groups having straight chain alkyl, branched chain alkyl, or cyclic alkyl portions, straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy groups and aralkoxy groups having straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy portions and all of said groups may be unsubstituted or substituted with any functional group compatible with a nitroxyl radical.
25. A process as defined in claim 24 wherein R6 and R7 are linear alkoxy groups of from 1 to 20 carbon atoms.
26. A process as defined in claim 24 wherein R6 and R7 are ethoxy.
27. A process as defined in claim 3 wherein R1, R2 and R3 are methyl, R4 is t-butyl and R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from straight chain alkyl, branched chain alkyl, or cyclic alkyl groups, aralkyl groups having straight chain alkyl, branched chain alkyl, or cyclic alkyl portions, straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy groups and aralkoxy groups having straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy portions and all of said groups may be unsubstituted or substituted with any functional group compatible with a nitroxyl radical.
28. A process as defined in claim 27 wherein R6 and R7 are linear alkoxy groups of from 1 to 20 carbon atoms.
29. A process as defined in claim 27 wherein R6 and R7 are ethoxy.
30. A process as defined in claim 6 wherein R1, R2 and R3 are methyl, R4 is t-butyl and R5 is P(=O)R6R7 wherein R6 and R7 in the alkoxyamine and the nitroxyl are each independently selected from straight chain alkyl, branched chain alkyl, or cyclic alkyl groups, aralkyl groups having straight chain alkyl, branched chain alkyl, or cyclic alkyl portions, straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy groups and aralkoxy groups having straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy portions and all of said groups may be unsubstituted or substituted with any functional group compatible with a nitroxyl radical.
31. A process as defined in claim 30 wherein R6 and R7 are linear alkoxy groups of from 1 to 20 carbon atoms.
32. A process as defined in claim 30 wherein R6 and R7 are ethoxy.
N O Z
(II) Wherein R1, R2, R3, R4,and R5 are independently selected from the group consisting of straight chain alkyl, branched chain alkyl and cyclic alkyl, substituted, or unsubstituted aralkyl, and substituted or unsubstituted aryl groups having from 1 to 50 carbon atoms, with the proviso that one of said R moieties be substituted with, or contain sulfur, or phosphorous and any two of R1, R2, R3, R4 and R5 which do not contain sulfur, or phosphorous, and which are attached.to the same carbon atom, may be concatenated to form, when taken together with the carbon atom to which they are attached, a cyclic alkyl group of from 5 to 20 carbon atoms and Z is selected from the following groups, wherein the dashed line attached to the carbon atom represents either a free electron or the point of attachment to the oxygen atom of the original alkoxyamine as appropriate:
a benzylic radical of the general formula Z1:
wherein Ar1 is an aryl group which may be substituted with halogen atoms, hydroxyl, alkoxy, ester, carboxy, acyl, amino, nitro, cyano, amido, sulfonyl, or phosphonyl groups and where Rz1 and R'z1 are independently selected from hydrogen atoms, or cyclic alkyl, straight chain alkyl, or branched chain alkyl groups, of from 1 to 50 carbon atoms and which alkyl groups may be unsubstituted or substituted with any of the above named substituent groups for Ar1 an ester type radical of general formula Z2:
Wherein Rz2, R'z2 and R"z2 are independently selected from straight chain alkyl, branched chain alkyl or cyclic alkyl groups of from 1 to 50 carbon atoms which alkyl groups may be unsubstituted or substituted with any of the above defined substituents for Ar1 and R"z2 may also be hydrogen.
a cyano radical of the general formula Z3:
wherein Rz3 and R'Z3 are independently selected from cyclic alkyl, straight chain alkyl, or branched chain alkyl groups of from 1 to 50 carbon atoms which alkyl groups may be unsubstituted or substituted with any of the named substituent groups for Ar1 and an alkyl radical of the general formula Z4:
wherein Rz4, R'z4 and R"z4 are independently selected from among the alkyl groups as defined for Rz3.
A process as defined in claim 1 wherein the nitroxyl radical has the structure I:
N O' (I) wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of straight chain alkyl, branched chain alkyl, cyclic alkyl, substituted, or unsubstituted aralkyl, or substituted, or unsubstituted aryl groups having from 1 to 50 carbon atoms, with the proviso that one of said R moieties be substituted with, or contain sulfur or phosphorous and any two of R1, R2, R3, R4 and R5 which do not contain sulfur, or phosphorous, and which are attached to the same carbon atom, may be concatenated to form, when taken together with the carbon atom to which they are attached, a cyclic alkyl group of from 5 to 20 carbon atoms.
4. A process as defined in claim 1 wherein the controlled free radical initiator is an alkoxyamine selected from the group consisting of methyl 2-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]propionate, 1-phenyl-1-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]ethane, 1,1-dimethyl-1-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]ethane, 1-methyl-1-cyano-1-[N-t-butyl-N-(1-diethyphosphono-2,2-dimethylpropyl)-N-oxy]ethane and mixtures thereof.
5. A process as defined in claim 1 wherein the controlled free radical initiator is the alkoxyamine methyl 2-[N-t-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxy]propionate.
6. A process as defined in claim 1 wherein the controlled free radical initiator comprises a mixture of alkoxyamines as defined in claim 2 and nitroxyl radicals as defined in claim 3.
7. A process as defined in claim 4 wherein the controlled free radical initiator also includes nitroxyls derived from the alkoxyamine selected from the group defined in claim 4.
8. A process as defined in claim 5 wherein the controlled free radical initiator also includes a nitroxyl radical derived from the alkoxyamine.
9. A process as defined in claim 1 also including an organic peroxide initiator or an azonitrile initiator.
10. A process as defined in claim 1 wherein the monomers comprising substituted or unsubstituted acrylic acid or esters thereof are selected from the group consisting of (subgroup a) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acetoacetoxy ethyl acrylate, acetoacetoxy ethyl methacrylate and mixtures thereof, (subgroup b) methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, lauryl acrylate and mixtures thereof, (subgroup c) acrylic acid, methacrylic acid and mixtures thereof, (subgroup d) iso-octyl acrylate, diethylaminomethyl acrylate, diethylaminomethyl methacrylate, t-butylaminoethyl methacrylate, t-butylaminoethyl acrylate and mixtures thereof, with the proviso that at least one member of subgroup a and of subgroup b must be present.
11. A process as defined in claim 10 wherein a monomer selected from the group styrene, para-methyl styrene, vinyl acetate and mixtures thereof is also present.
12. A process as defined in claim 11 wherein the monomers comprise butyl acrylate, hydroxyethyl acrylate, styrene and acrylic acid.
13. A process as defined in 11 wherein the monomers comprise glycidyl methacrylate, butyl methacrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, methacrylic acid, hydroxypropyl acrylate, hydroxypropyl methacrylate, acetoacetoxy ethyl acrylate, acetoacetoxy ethyl methacrylate and mixtures thereof.
14. The product produced by a process as defined in claim 1.
15. A process for coating an object on at least one surface which comprises applying a product as defined in claim 14 to said at least one surface and treating said product after application on said at least one surface to sufficient heat for a sufficient time to evaporate the solvent contained in said product and crosslink the remaining material of said product on said at least one surface.
16. The coating produced by the process defined in claim 15.
17. The coated object produced by the process defined in claim 15.
18. A process as defined in claim 1 wherein the polymer so produced is recovered as a solvent free material.
19. A powder coating material prepared from the solvent free material prepared as defined in claim 18.
20. An object coated on at least one surface thereof with a coating formed by applying the powder coating material defined in claim 19 to the said at least one surface of said object and fusing said powder coating material into a coherent coating.
21. A process as defined in claim 2 wherein one of R1, R2, R3, R4, or R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from the group consisting of methyl, methoxy, ethoxy, n-propoxy, benzyloxy, dodecyloxy, phenyl and benzyl.
22. A process as defined in claim 3 wherein one of R1, R2, R3, R4, or R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from the group consisting of methyl, methoxy, ethoxy, n-propoxy, benzyloxy, dodecyloxy, phenyl and benzyl.
23. A process as defined in claim 6 wherein, independently in the alkoxyamine and the nitroxyl, one of R1, R2, R3, R4, or R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from the group consisting of methyl, methoxy, ethoxy, n-propoxy, benzyloxy, dodecyloxy, phenyl and benzyl.
24. A process as defined in claim 2 wherein R1, R2 and R3 are methyl, R4 is t-butyl and R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from straight chain alkyl, branched chain alkyl, or cyclic alkyl groups, aralkyl groups having straight chain alkyl, branched chain alkyl, or cyclic alkyl portions, straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy groups and aralkoxy groups having straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy portions and all of said groups may be unsubstituted or substituted with any functional group compatible with a nitroxyl radical.
25. A process as defined in claim 24 wherein R6 and R7 are linear alkoxy groups of from 1 to 20 carbon atoms.
26. A process as defined in claim 24 wherein R6 and R7 are ethoxy.
27. A process as defined in claim 3 wherein R1, R2 and R3 are methyl, R4 is t-butyl and R5 is P(=O)R6R7 wherein R6 and R7 are independently selected from straight chain alkyl, branched chain alkyl, or cyclic alkyl groups, aralkyl groups having straight chain alkyl, branched chain alkyl, or cyclic alkyl portions, straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy groups and aralkoxy groups having straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy portions and all of said groups may be unsubstituted or substituted with any functional group compatible with a nitroxyl radical.
28. A process as defined in claim 27 wherein R6 and R7 are linear alkoxy groups of from 1 to 20 carbon atoms.
29. A process as defined in claim 27 wherein R6 and R7 are ethoxy.
30. A process as defined in claim 6 wherein R1, R2 and R3 are methyl, R4 is t-butyl and R5 is P(=O)R6R7 wherein R6 and R7 in the alkoxyamine and the nitroxyl are each independently selected from straight chain alkyl, branched chain alkyl, or cyclic alkyl groups, aralkyl groups having straight chain alkyl, branched chain alkyl, or cyclic alkyl portions, straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy groups and aralkoxy groups having straight chain alkoxy, branched chain alkoxy, or cyclic alkoxy portions and all of said groups may be unsubstituted or substituted with any functional group compatible with a nitroxyl radical.
31. A process as defined in claim 30 wherein R6 and R7 are linear alkoxy groups of from 1 to 20 carbon atoms.
32. A process as defined in claim 30 wherein R6 and R7 are ethoxy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/061,423 | 2002-02-01 | ||
| US10/061,423 US6762263B2 (en) | 2002-02-01 | 2002-02-01 | High-solids coatings resins via controlled radical polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2412191A1 true CA2412191A1 (en) | 2003-08-01 |
| CA2412191C CA2412191C (en) | 2011-01-25 |
Family
ID=27658417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2412191A Expired - Lifetime CA2412191C (en) | 2002-02-01 | 2002-11-19 | Improved high-solids coatings resins via controlled radical polymerization |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6762263B2 (en) |
| EP (1) | EP1342735B1 (en) |
| JP (1) | JP4869542B2 (en) |
| AT (1) | ATE348846T1 (en) |
| AU (1) | AU2002301897B2 (en) |
| CA (1) | CA2412191C (en) |
| DE (1) | DE60310465T2 (en) |
| DK (1) | DK1342735T3 (en) |
| ES (1) | ES2279073T3 (en) |
| MX (1) | MXPA02011685A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293063A (en) * | 2014-10-14 | 2015-01-21 | 苏州洛特兰新材料科技有限公司 | Thermosetting acrylic resin powder coating for ceramic |
| CN110396147A (en) * | 2014-12-18 | 2019-11-01 | 阿科玛法国公司 | The low temperature free radical polymerization of alkoxyamine |
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|---|---|---|---|---|
| US7585924B2 (en) * | 2002-07-11 | 2009-09-08 | E. I. Du Pont De Nemours And Company | Pressurized high temperature polymerization process and polymerization system used therein |
| FR2843394B1 (en) * | 2002-08-07 | 2005-12-30 | Atofina | ALCOXYAMINES FROM NITROXIDES B-PHOSPHORUS, THEIR USE IN RADICAL POLYMERIZATION |
| US7074856B2 (en) * | 2002-12-20 | 2006-07-11 | The Sherwin-Williams Company | Moisture cure non-isocyanate acrylic coatings |
| EP1541339A1 (en) * | 2003-12-12 | 2005-06-15 | Arkema | Multilayer acrylate film with improved optical and mechanical properties |
| FR2866026B1 (en) * | 2004-02-06 | 2008-05-23 | Arkema | RADICAL EMULSION POLYMERIZATION PROCESS USING WATER-SOLUBLE ALCOXYAMINES |
| FR2870251B1 (en) * | 2004-05-11 | 2010-09-17 | Arkema | COMPOSITE MATERIALS BASED ON CARBON NANOTUBES AND POLYMERIC MATRICES AND METHODS OF OBTAINING THEM |
| EP1719616A1 (en) * | 2004-12-10 | 2006-11-08 | Arkema | Multilayer acrylate film with improved optical and mechanical properties |
| US20060173142A1 (en) * | 2005-02-01 | 2006-08-03 | Hildeberto Nava | Functionalized thermosetting resin systems |
| WO2007078819A2 (en) * | 2005-12-16 | 2007-07-12 | Arkema Inc. | Low surface energy block co-polymer preparation methods and applications |
| FR2898127B1 (en) * | 2006-03-02 | 2008-07-11 | Arkema Sa | PROCESS FOR THE CONTROLLED RADICAL POLYMERIZATION OR COPOLYMERIZATION OF ONE OR MORE MONOMERS IN THE PRESENCE OF AN ALCOXYAMINE STARTER |
| US7498398B2 (en) * | 2006-03-21 | 2009-03-03 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition, method of making, and articles formed therefrom |
| US20090065737A1 (en) * | 2007-09-11 | 2009-03-12 | Arkema Inc. | Polymerization controllers for composites cured by organic peroxide initiators |
| WO2009149001A1 (en) * | 2008-06-06 | 2009-12-10 | Union Carbide Chemicals & Plastics Technology Llc | Method for inhibiting scorch in crosslinkable compositions |
| CN112194753B (en) * | 2020-09-08 | 2022-07-08 | 莱阳千宝新材料制造有限公司 | Acrylic resin, low-VOC polypropylene coating material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4581429A (en) | 1983-07-11 | 1986-04-08 | Commonwealth Scientific And Industrial Research Organization | Polymerization process and polymers produced thereby |
| US4777230A (en) | 1985-05-30 | 1988-10-11 | Pennwalt Corporation | Solution polymerization of acrylic acid derived monomers using tertiary alkyl(ηC5)hydroperoxides |
| US5322912A (en) | 1992-11-16 | 1994-06-21 | Xerox Corporation | Polymerization processes and toner compositions therefrom |
| FR2730240A1 (en) | 1995-02-07 | 1996-08-09 | Atochem Elf Sa | STABILIZATION OF A POLYMER BY A STABLE FREE RADICAL |
| US5627248A (en) | 1995-09-26 | 1997-05-06 | The Dow Chemical Company | Difunctional living free radical polymerization initiators |
| CA2259559C (en) | 1996-07-10 | 2004-11-09 | E.I. Du Pont De Nemours And Company | Polymerization with living characteristics |
| AU4773997A (en) | 1996-09-25 | 1998-04-17 | Akzo Nobel N.V. | No-compounds for pseudo-living radical polymerization |
| AU750626B2 (en) * | 1997-01-10 | 2002-07-25 | Commonwealth Scientific And Industrial Research Organisation | Method of controlling polymer molecular weight and structure |
| US6281311B1 (en) * | 1997-03-31 | 2001-08-28 | Pmd Holdings Corp. | Controlled free radical polymerization process |
| JP2001510208A (en) * | 1997-07-15 | 2001-07-31 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Polymerizable composition containing an alkoxyamine compound derived from a nitroso compound or a nitrone compound |
| FR2784111B1 (en) * | 1998-10-06 | 2003-08-01 | Atochem Elf Sa | RADICAL POLYMERISATIN IN THE PRESENCE OF MULTIPLE FREE STABLE RADICALS |
| FR2789991B1 (en) * | 1999-02-18 | 2002-02-22 | Atochem Elf Sa | ALCOXYAMINES FROM NITROXIDE BETA-PHOSPHORUS, THEIR USE IN RADICAL POLYMERIZATION |
| AU3733800A (en) | 1999-03-09 | 2000-09-28 | Symyx Technologies, Inc. | Controlled free radical emulsion and water-based polymerizations and seeded methodologies |
| FR2807439B1 (en) | 2000-04-07 | 2003-06-13 | Atofina | MULTIMODAL POLYMERS BY CONTROLLED RADICAL POLYMERIZATION IN THE PRESENCE OF ALCOXYAMINES |
| FR2853317B1 (en) * | 2003-04-01 | 2006-07-07 | Atofina | ALCOXYAMINES FROM NITROXIDES B-PHOSPHORES, THEIR USE FOR THE PREPARATION OF MONO OR POLYALCOXYAMINES, POLYMERIZED OR NOT |
-
2002
- 2002-02-01 US US10/061,423 patent/US6762263B2/en not_active Expired - Lifetime
- 2002-10-31 AU AU2002301897A patent/AU2002301897B2/en not_active Expired
- 2002-11-19 CA CA2412191A patent/CA2412191C/en not_active Expired - Lifetime
- 2002-11-26 MX MXPA02011685A patent/MXPA02011685A/en active IP Right Grant
-
2003
- 2003-01-21 EP EP03290146A patent/EP1342735B1/en not_active Expired - Lifetime
- 2003-01-21 DE DE60310465T patent/DE60310465T2/en not_active Expired - Lifetime
- 2003-01-21 DK DK03290146T patent/DK1342735T3/en active
- 2003-01-21 AT AT03290146T patent/ATE348846T1/en active
- 2003-01-21 ES ES03290146T patent/ES2279073T3/en not_active Expired - Lifetime
- 2003-01-29 JP JP2003020074A patent/JP4869542B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293063A (en) * | 2014-10-14 | 2015-01-21 | 苏州洛特兰新材料科技有限公司 | Thermosetting acrylic resin powder coating for ceramic |
| CN110396147A (en) * | 2014-12-18 | 2019-11-01 | 阿科玛法国公司 | The low temperature free radical polymerization of alkoxyamine |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1342735A2 (en) | 2003-09-10 |
| MXPA02011685A (en) | 2003-08-08 |
| US6762263B2 (en) | 2004-07-13 |
| CA2412191C (en) | 2011-01-25 |
| DE60310465D1 (en) | 2007-02-01 |
| AU2002301897B2 (en) | 2007-11-01 |
| EP1342735B1 (en) | 2006-12-20 |
| EP1342735A3 (en) | 2003-12-17 |
| JP2004002678A (en) | 2004-01-08 |
| US20030149205A1 (en) | 2003-08-07 |
| ATE348846T1 (en) | 2007-01-15 |
| DK1342735T3 (en) | 2007-04-30 |
| JP4869542B2 (en) | 2012-02-08 |
| DE60310465T2 (en) | 2007-09-27 |
| AU2002301897A1 (en) | 2003-08-21 |
| ES2279073T3 (en) | 2007-08-16 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20221121 |